synthesis, properties, and structure of 1,3-dimethyl-2 (3h)-imidazolethione hydrogen bromide
TRANSCRIPT
Journal of Crystallographic and Spectroscopic Research, Vol. 16, No. 3, 1986
Synthesis, properties, and structure of 1,3-dimethyl- 2(3H)-imidazolethione hydrogen bromide
DANIEL J. WILLIAMS* and GUILLERMO RAMIREZ Department of Chemistry
Kennesaw College Marietta, Georgia 30061
and
DONALD VANDERVEER School of Chemistry Georgia Institute of Technology
Atlanta, Georgia 30332
(Received May 25, 1985)
Abstract
The compound dmit .HBr (dmit = 1,3-dimethyl-2(3H)-imidazolethione) has been synthesized and characterized. The crystal and molecular structure of dmit. HBr has also been determined. The compound, CsH9BrN2S, crystallizes in space group P21/c with four formula units in a cell of dimensions a = 7.331(1), b = 7.744(2), c = 14.626(4) ,~, and 13 = 99.56(2) ~ The calculated and observed densities are 1.678 and 1.68(2) g cm -3, respectively. X-ray re- suits along with physical characterization show this compound to be a molecular adduct of dmit and hydrogen bromide which is sensitive to air, light, and mois- ture. Specific conductivity (10 -3 M in PhNO2), infrared, and 1H-NMR data have also been obtained. X-ray results reveal intermolecular contracts between S and Br to be primarily van der Waals in nature. Molecular units are linked through long zigzag Br-S-Br-S chains.
Introduction
Addition products derived from adding acids to thioureas have been known for almost a century. These complexes were thought to be nonionic due to low conductivity and lack of other solution properties expected for ionic compounds
3o9
0277-8068/86/0600-0309505.00/0 �9 1986 Plenum Publishing Corporation
310 Williams et ai.
(Reid, 1963). In the process of attempting to generate 1 : 1 and 1 : 2 complexes of silicon tetrahalides and 1,3-dimethyl-2(3H)-imidazolethione (dmit), we syn- thesized the HBr adduct of this thiourea. The following is a report of the syn- thesis, characterization, and results of a single crystal X-ray study for dmit. HBr.
E x p e r i m e n t a l
Due to the hygroscopic nature of starting material and the adduct, all ma- nipulations were carried out in a polyethylene glove bag under a dry Nz atmo- sphere.
Spectra and conductivity
An infrared spectrum (4000-400 cm -1) was collected as a Nujol mull be- tween AgC1 plates on a Perkin-Elmer Model 735 infrared spectrophotometer. A proton magnetic resonance spectrum was recorded in CDC13 with TMS in- ternal reference on a Varian Model EM360A NMR spectrometer (60 MHz). Results are reported in ppm (6) relative to TMS. Conductivity data was col- lected as previously reported (Williams and Wynne 1976).
Chemicals
SiBr4 (Alfa) and spectral grade CHC13 (Fisher) were used as obtained with- out further purification. Dmit was prepared as previously reported (Ansell et al., 1970).
Analytical section
Bromine analysis was obtained in our laboratory by gravimetry with AgNO 3. C, H, and N analyses were obtained from Altlantic Microlabs, Inc.
1,2-Dimethyl-2 (3H)-imidazolethione hydrogen bromide
In 75ml CHC13 was dissolved 7.37 g dmit (57.6 mmol). To this solution was added 10.0 g SiBr 4 (28.8 mmol). The resultant turbid yellow solution was cooled for 24 h at O~ About 4.0 g of large pale yellow-green crystals were isolated and dried in vacuo. Yield: 33% based on dmit. Anal. Calcd. (%) for CsH9BrN2S: C, 28.71; H, 4.33; N, 13.39; Br, 38.21. Found: C, 28.17; H, 4.47; N, 13.11; Br, 37.45. Mp. 144~ M(ca. 10 -3 M in PhNO2) = 0.0 c m 2M-3 -1 Q. iH_NM R (CDC13): 63.75 (s, 3H, methyl), 66.80 (s, 1H, ethy- lenic). IR (mull): 3200w, 3160m, 1580s, 1238s, 1167s, 1095m, 725s,br(cm-l).
Structure of CsH9BrN2S 311
X-ray determination
A crystal with approximate dimensions 0.7 • 0.4 • 0.4 mm was mounted on a glass fiber using epoxy cement such that the longest crystal dimension was approximately parallel to the fiber axis.
Unit cell parameters and the orientation matrix were determined on a Syn- tex P21 four-circle diffractometer equipped with a graphite monochromator (Bragg 20 angle = 12.2 ~ using Mo Ko~ (2 = 0.71069 A) radiation at a takeoff angle of 6.75 ~ . Fifteen reflections whose 20 values ranged from 22.I ~ to 26.7 ~ were centered and used in least-squares refinement of the lattice parameters and orientation matrix. Omega scans of several low 20 angle reflections gave peak widths at half-height of less than 0.24 ~ indicating a satisfactory mosaic spread for the crystal.
Axial photographs indicated that the crystal belonged to the monoclinic system. Intensity data for zero and upper levels were collected at a rapid scan rate and the intensities examined carefully for systematic absences. The absence of hO1 (1 = 2n + 1) and 0k0 (k = 2n + 1) is consistent with only space group P2Jc (No. 14).
Intensity data were collected using 0-20 scans with X-ray source and monochromator settings identical to those used for determination of the unit cell parameters. A variable scan rate of from 2.02 to 29.3 o min-1 was used and a scan width of 2.2 o was sufficient to collect all of the peak intensity. Stationary background counts were measured at the beginning and at the end of each scan with a total background-to-scan time ratio of 1.0. No significant fluctuations were observed in the intensities of three standard reflections (700, 0010, 060) monitored every 97 reflections. Intensities were calculated from the total scan count and background counts by the usual relationship.
The intensities were assigned standard deviations according to the formula in the usual manner, and from a total of 1452 reflections collected in a complete quadrant (_+h + k + l) of data out to 20 = 50 ~ 1231 were accepted as statis- tically above background on the basis that F was greater than 3a (F). Lorentz and polarization corrections were made in the usual way. Absorption correc- tions were not applied.
Solution and refinement of the structure
Computations were performed using standard programs (Sheldrick, 1976), and were carried out on the CDC Cyber 74 System. For structure factor cal- culations the scattering factors were taken from the International Tables for X-Ray Crystallography (1974). The agreement factors are defined in the con- ventional way. In all least-squares refinements, the quantity minimized was r,
312 Williams et al.
(IFol - levi) 2. The weighting scheme based on counting statistics (w = 1.0/ ( o ( F f + 0.003 F2)) was employed for calculating Rw and in least-squares re- finement,
The structure was solved using a Patterson map. Hydrogen atoms with the
exception of the one attached to bromine were located from differential Fourier maps. The hydrogen coordinates were not varied during refinement. The proton could not be located. Final calculated values were R = 0.036 and Rw = 0.042. Table 1 lists crystal lographic data while Table 2 reports final posit ional param- eters for nonhydrogen atoms. Interatomic distances and angles are listed in Table 3.
R e s u l t s a n d d i s c u s s i o n
Addit ion of SiBr 4 to a CHC13 solution of dmit yielded stable delinquescent pale yel low-green crystals which darken in color upon prolonged exposure to light, and take on an opaque white coating on exposure to dry air. The com-
pound is somewhat soluble in a wide variety of nonpolar to slightly polar sol- vents. Solution state conductivity data shows the compound to be nonionic in nitrobenzene. Based on conductivity and general solubility plus other structural features noted below, the compound appears to be a molecular adduct of dmit and HBr. As additional proof of structure, the complex could also be synthe- sized merely by bubbling anhydrous HBr through a CHC13 solution of dmit, but the crystals obtained via this method were of poorer quality. The mechanism of reaction appears to proceed via electron transfer from the thione to SiBr 4, releasing B r - , and with abstraction of H possibly from CHC1 s to generate HBr.
Electron transfer properties of this thione are particularly pronounced due to the
Table 1. Crystallographic Data
Formula unit: CsHgBrN2S a = 7.331(2) ~ b = 7.744(2) c = 14.626(4) A, /3 = 99.56(2) ~ fw = 208.0 z = 4 space group P2 ~/c v = 818.8(4) A 3 PcaMca = 1.687 g/cm 3 Oob~d = 1.68(2) g/cm 3 by flotation (CCIJCHsl) radiation: Mo Ks X = 0.71069 A T = 295 K
aThe figures in parentheses are estimated standard deviations (esd's) of the least significant digit here and throughout the pa- per.
S t r u c t u r e o f CsHgBrN2S
T a b l e 2. Positional parameters (with esd's)
313
Atom x y z
Br(1) 0.71055(5) 0.32220(6) 0.08258(3) S - 0.0706( 1 ) 0.5219 ( 1 ) 0.29699 (7) N(1) 0.2476(4) 0.3631 (4) 0.3786(2) N(2) 0.2531(4) 0.4386(4) 0.2369(2) C(1) 0.1496(5) 0.4371(4) 0.3044(2) C(2) 0.4173(7) 0.3158(6) 0.3585(4) C(3) 0.4205(6) 0.3605(6) 0.2702(3) C(4) 0.1930(8) 0.3439(7) 0.4688(3) C(5) 0.2008(7) 0.5109(6) 0.1442(3)
subsequent formation of the 67r-electron imidazol ium cation (Arduengo and Burgess, 1977). The S" �9 �9 Br distances reported in Table 3 (3.62 and 3.73 A.) imply the normal closed-shell van der Waals contacts which are expected to range from 3.60 to 3.80 .~ for these atoms (Bondi, 1964). Figure 1 shows the linking of molecular units through long zig-zag B r - S - B r - S chains. The ster- eoscopic view seen in Fig. 2 shows the molecular packing for this complex with the S" " �9 Br contacts emphasized. The bromine proton could not be located probably due to the mobil i ty and proximity of the heavy atoms. The relative shortness o f the C - S bond (1.730 A ) compared to 1.757 A_ in the known ionic compound (dmi tCN)+Br - (Arduengo and Burgess, 1977) also supports the mo- lecular nature of the complex. It is interesting to note, however, that the C - S bond is elongated over that observed by Ansel l et at. (1970) for the free
Table 3. Interatomic distances (,~) and angles (deg) (with esd's) (see Fig. 1)
Interatomic distances
S-C(1) N(1)-C(2) N(2)-C(1) N(2)-C(5) S - ' " Br S " ' ' Br'
1.730(4) N(1)-C(1) 1.374(6) N(1)-C(4) 1.340(5) N(2)-C(3) 1.458(5) C(2)-C(3) 3.62(1)" 3.73(1)"
1.329(5) 1.449(6) 1.382(6) 1.341 (7)
Angles
C(2)-N(t)-C(1) C(4)-N(1)-C(2) C(5)-N(2)-C(1) N(1)-C(I)-S N(2)-C(1)-N(1) C(2)-C(3)-N(2) S - - " B r . . - S' Br ' ' - S . . . . Br'
109.0(3) 124.4(4) 126.4(3) 125.9(3) 108.1(3) 107.2(4) 71.4(1.0) a
148.3(1.0) a
C(4)-N(1)-C(1) C(3)-N(2)-C(1) C(5)-N(2)-C(3) N(2)-C(1)-S C(3)-C(2)-N(1)
126.5(3) 108.4(3) 125.2(3) 126.0(3) 107.4(4)
Nonbonding contacts. See text.
3 1 4 W i l l i a m s e t a l .
o
0)
[,,.
I I I
I
I I I I I
d d d d d d d d d I
Structure of CsHgBrN2S 315
Table 5. Calculated positions for hydrogen atoms and isotropic thermal parameters (with esd's)
Atom x y z U
HC(2) 0.50580 0.25960 0.41840 0.11(2) HC(3) 0.54000 0.33610 0.23320 0.08(2) HC(4) 0.05810 0.31780 0.46490 0.14(3) HC(4) 0.17360 0.47820 0.50900 0.31(8) HC(4) 0.28800 0.29500 0.51540 0.18(4) HC(5) 0.05550 0.49450 0.10550 0.16(3) HC(5) 0.18660 0.64240 0.14930 0.06(1) HC(5) 0.29520 0.49950 0.11690 0.05(1)
Table 6. Observed and calculated structure factors for dmit'HBr
h k l F o Fc h k l Fo F c
1 0 0 14 12 3 5 0 13 12 3 0 0 36 40 4 5 0 38 37 4 0 0 47 48 5 5 0 9 8 5 0 0 51 52 6 5 0 14 14 6 0 0 33 34 7 5 0 5 4 7 0 0 24 24 0 6 0 54 56 8 0 0 19 19 1 6 0 4 4 1 1 0 41 41 2 6 0 25 24 2 1 0 42 42 3 6 0 20 20 3 1 0 63 65 4 6 0 12 12 4 1 0 66 67 5 6 0 19 20 6 1 0 41 42 6 6 0 9 9 7 1 0 9 9 1 7 0 23 22 8 1 0 15 15 2 7 0 20 20 0 2 0 5 6 3 7 0 28 28 1 2 0 76 81 4 7 0 12 12 2 2 0 49 49 0 8 0 18 17 3 2 0 36 35 1 8 0 7 6 4 2 0 24 23 2 8 0 17 17 5 2 0 16 16 3 8 0 9 9 6 2 0 10 10 4 8 0 7 7 7 2 0 32 32 1 9 0 11 10 1 3 0 56 55 - 7 1 1 8 8 2 3 0 9 9 - 6 1 1 8 7 3 3 0 14 13 - 5 1 1 31 31 4 3 0 15 15 - 4 1 1 43 41 5 3 0 19 18 - 3 1 1 10 9 6 3 0 6 7 - 2 1 1 54 53 8 3 0 6 6 - 1 1 1 5 5 0 4 0 9 8 0 1 1 14 12 1 4 0 35 34 1 1 1 48 51 2 4 0 30 29 2 t 1 26 27 3 4 0 6 6 3 1 1 56 58 4 4 0 14 13 4 1 1 69 72 6 4 0 6 5 5 1 1 6 5 7 4 0 18 17 6 1 1 5 5 1 5 0 37 36 7 1 1 19 20
3 1 6 W i l l i a m s e t a l .
Table 6. Continued
l F o F c h
8 1 1 5 5
- 8 2 1 15 16 - 7 2 1 26 25 - 6 2 1 33 33 - 5 2 1 5 6 - 4 2 1 48 48 - 3 2 1 36 34 - 2 2 1 75 77 - 1 2 ! 65 72
0 2 1 89 100 2 2 1 30 29 3 2 1 54 55 4 2 1 11 11 5 2 1 29 28 6 2 1 17 17 7 2 1 18 18 8 2 1 12 13
- 8 3 1 18 18 - 7 3 1 14 14 - 6 3 1 19 20 - 5 3 1 38 37 - 4 3 1 10 11 - 3 3 1 102 110 - 2 3 1 18 17 - 1 3 1 34 36
0 3 1 49 51 1 3 1 19 18 2 3 1 62 64 3 3 1 13 11 4 3 1 29 28 5 3 1 57 59 6 3 1 23 24 7 3 1 24 25
- 7 4 1 6 5 6 4 1 33 33
- 4 4 1 37 36 - 3 4 1 12 13 - 2 4 1 38 38 - 1 4 1 55 57
0 4 1 41 44 1 4 1 68 71 2 4 1 27 27 3 4 1 63 64 4 4 1 17 18 5 4 1 28 28 6 4 1 16 16 7 4 1 6 3
- 7 5 1 14 14 - 6 5 1 11 11 - 5 5 1 30 30 - 4 5 1 5 7 - 3 5 1 21 20
l Fo F,
- 2 5 1 4 3 4 2 - 1 5 1 40 39
0 5 1 36 35 1 5 1 20 19 2 5 1 34 34 3 5 1 15 15 4 5 1 44 44 5 5 1 6 5 6 5 1 9 10 7 5 1 11 11
- 4 6 1 12 12 - 2 6 1 21 19 - 1 6 1 6 4
1 6 1 22 22 2 6 1 14 13 4 6 1 8 7 5 6 1 5 4 6 6 1 10 10
- 4 7 1 10 10 - 3 7 1 7 5 - 2 7 1 6 7 - 1 7 1 6 6
1 7 1 4 3 2 7 1 8 9 3 7 1 5 6 4 7 1 5 4
- 4 8 1 8 8 - 2 8 1 10 10
1 8 1 20 20 2 8 1 8 6 3 8 1 5 5 0 9 1 7 8
- 8 0 2 25 25 - 7 0 2 21 22 - 6 0 2 66 69 - 5 0 2 29 29 - 3 0 2 94 97 - 2 0 2 6 8
0 0 2 30 27 1 0 2 72 78 3 0 2 41 40 4 0 2 52 53 5 0 2 7 7 6 0 2 25 26 7 0 2 20 21 8 0 2 25 25
- 8 1 2 5 5 - 7 1 2 20 20 - 6 1 2 19 20 - 5 1 2 35 35 - 4 1 2 56 58 - 3 1 2 43 41
Structure of CsH9BrNzS 317
Table 6. Continued
h k l F o Pc h ~ t Fo F~
- 2 1 2 93 96 - 1 1 2 50 51
0 1 2 45 45 1 1 2 61 65 2 1 2 26 26 3 1 2 68 72 5 1 2 60 63 6 1 2 23 23 7 1 2 21 21 8 1 2 19 20
- 8 2 2 15 15 --5 2 2 49 51 - 4 2 2 23 22 --3 2 2 32 32 - 2 2 2 18 16 - 1 2 2 49 53
0 2 2 89 100 2 2 2 38 38 3 2 2 6 5 4 2 2 46 46 6 2 2 25 25
- 7 3 2 9 10 - 5 3 2 13 13 - 4 3 2 8 7 - 3 3 2 13 13 - 2 3 2 43 42 - 1 3 2 17 18
0 3 2 20 21 1 3 2 11 12 2 3 2 16 14 3 3 2 11 10 4 3 2 9 8 6 3 2 6 6 7 3 2 8 8
- 7 4 2 10 9 - 6 4 2 5 3 - 5 4 2 26 25 - 4 4 2 11 11 - 3 4 2 14 12 - 2 4 2 10 10 - 1 4 2 16 16
0 4 2 26 27 1 4 2 61 63 4 4 2 14 14 6 4 2 9 8 7 4 2 8 7
- 7 5 2 13 14 - 5 5 2 20 20 - 4 5 2 7 7 - 3 5 2 4 4 - 2 5 2 48 49 - 1 5 2 9 9
0 5 2 14 15 1 5 2 10 11 3 5 2 22 23 5 5 2 12 13 6 5 2 20 20 7 5 2 12 12
- 6 6 2 21 21 - 5 6 2 15 14 - 4 6 2 5 3 - 3 6 2 31 31 - 2 6 2 4 2 - 1 6 2 35 35
0 6 2 17 16 1 6 2 20 20 2 6 2 49 50 3 6 2 16 16 4 6 2 25 25 6 6 2 10 10
- 5 7 2 10 10 - 4 7 2 28 27 - 3 7 2 14 14 - 2 7 2 19 19 - 1 7 2 18 18
0 7 2 27 27 1 7 2 19 20 2 7 2 18 17 3 7 2 21 21 5 7 2 25 25
- 4 8 2 7 7 - 3 8 2 11 11 - 1 8 2 19 18
0 8 2 8 8 1 8 2 16 15 2 8 2 6 6 4 8 2 9 9 0 9 2 6 6 1 9 2 7 7
- 8 1 3 21 21 - 7 1 3 5 3 - 6 1 3 14 13 - 5 1 3 13 13 - 4 1 3 21 21 - 3 1 3 59 55 - 2 1 3 84 83 - 1 1 3 16 16
0 1 3 35 36 1 1 3 58 62 2 1 3 15 13 3 1 3 36 35 4 1 3 4 4 5 1 3 15 16 6 1 3 39 40
318 Wi l l iams et al.
Table 6. Continued
8 - 8 - 7 - 5 - 4 - 3 - 2 - I
0 l 2 3 4 5 7 8
- 8 - 7 - 6 - 5 - 4 - 3 - 2
0 1 2 3 4 5 6 7
- 7 - 5 - 4 - 3 - 2 - 1
0 1 2 3 4 5 7
- 7 - 6 - 5 - 4 - 3 - 2 - 1
0
t G F~ h
7 12 18 46 37 32 64 21 75 12 62 57 29 33 14 5 9 6
32 5
49 20 10 5
41 44 24 64 31 27 14 31 33 38 34 49 13 76 27 86 21 22 28 19 7
11 10 25 42 35 23
8
8 12 17 47 34 31 65 21 82 12 63 56 29 32 15 6 9 3
32 6
5O 20 l l 6
40 45 24 66 30 28 15 32 33 37 34 52 13 79 28 92 22 22 28 20
6 10 10 24 42 37 24
7
k t Fo F~
1 5 3 2 5 3 3 5 3 4 5 3 6 5 3
- 6 6 3 - 5 6 3 - 2 6 3 - 1 6 3
0 6 3 1 6 3 2 6 3 3 6 3 4 6 3 5 6 3
- 2 7 3 - 1 7 3
1 7 3 2 7 3 7 5 7
- 2 8 0 8 1 8 3 8
- 1 9 - 8 0 - 7 0 - 6 0 - 5 0 - 4 0 - 3 0 - 2 0 - 1 0
0 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0
- 8 1 - 7 1 - 6 1 - 5 1 - 4 1 - 3 1 - 2 1 - 1 1
0 1 1 1
35 12 28 15 27
8 10 8 6
17 4
10 22
6 9
12
3 3 3 3 3 3 3 3 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 ~ 4 4 4 4
34 12 28 15 27
11 8 5 9
10 9
14 6
10 14 7
23 18 21
101 25 61 88 39 48 68 53 53 25 13 11 16 25 14 41
3 70 54 79 76 18
8 10 8 5
17 3 9
22 5 8
12 11 8 5 8 9 9
14 6
11 14 8
23 18 21
103 23 60 91 39 49 69 53 52 26 12 11 15 24 14 42
2 68 54 84 84 16
Structure of CsHgBrN2S 319
Table 6. Continued
h k l F o
2 1 4 69 3 1 4 19 4 1 4 44 5 1 4 30 6 1 4 19 7 1 4 31
- 8 2 4 14 - 7 2 4 11 - 6 2 4 43 - 5 2 4 33 - 4 2 4 17 - 3 2 4 32 - 2 2 4 49 - 1 2 4 33
0 2 4 46 1 2 4 39 2 2 4 19 3 2 4 69 4 2 4 5 5 2 4 10 6 2 4 17
- 7 3 4 5 - 6 3 4 6 - 5 3 4 6 - 4 3 4 8 - 3 3 4 30 - 2 3 4 4 - 1 3 4 9
0 3 4 19 2 3 4 13 3 3 4 9 4 3 4 18 5 3 4 12 6 3 4 14
- 6 4 4 15 - 5 4 4 23 - 4 4 4 5 - 3 4 4 17 - 2 4 4 26 - 1 4 4 12
0 4 4 11 1 4 4 4 2 4 4 12 3 4 4 36 4 4 4 8
- 5 5 4 13 - 4 5 4 9 - 3 5 4 29 - 2 5 4 4 - 1 5 4 6
0 5 4 35 2 5 4 23
F c h k 1 F o Fc
71 3 5 4 21 22 18 4 5 4 17 17 45 5 5 4 25 25 31 6 5 4 16 16 19 - 6 6 4 14 14 33 - 4 6 4 35 35 14 - 2 6 4 21 22 11 - 1 6 4 30 31 43 0 6 4 22 22 33 1 6 4 43 44 17 2 6 4 21 21 32 3 6 4 20 19 50 4 6 4 11 11 32 5 6 4 13 12 47 - 5 7 4 16 15 37 - 4 7 4 5 3 19 - 3 7 4 18 20 71 - 2 7 4 24 24
5 - 1 7 4 30 30 9 0 7 4 19 18
16 2 7 4 26 25 4 4 7 4 19 19 5 - 3 8 4 9 8 7 - 2 8 4 12 12 8 - 1 8 4 6 6
30 1 8 4 14 14 3 2 8 4 12 12
10 3 8 4 18 18 19 - 8 1 5 13 13 12 - 7 1 5 6 5 8 - 6 1 5 16 15
17 - 5 1 5 28 27 12 - 4 1 5 4 5 14 - 3 1 5 9 7 15 - 2 1 5 4 4 22 - 1 1 5 61 62
3 0 1 5 84 91 17 1 1 5 9 9 26 3 1 5 26 25 11 4 1 5 14 14 10 5 1 5 28 28 3 7 1 5 5 3
13 - 8 2 5 14 14 35 - 7 2 5 13 14
8 - 6 2 5 28 27 12 - 5 2 5 29 29 9 - 4 2 5 22 20
29 - 3 2 5 71 71 2 - 2 2 5 6 4 7 - 1 2 5 60 64
36 0 2 5 49 49 24 1 2 5 46 45
3 2 0 W i l l i a m s e t al .
Table 6. Continued
h k t Fo Fc h k t Fo Fc
2 2 5 70 71 3 2 5 40 37 4 2 5 46 46 6 2 5 25 26 7 2 5 8 9
- 8 3 5 8 8 - 7 3 5 27 27 - 6 3 5 11 10 - 5 3 5 10 9 - 4 3 5 52 52 - 3 3 5 6 5 - 2 3 5 83 89 - 1 3 5 9 9
0 3 5 30 31 1 3 5 70 75 2 3 5 33 34 3 3 5 55 55 5 3 5 31 32 6 3 5 27 28 7 3 5 29 30
- 6 4 5 24 24 - 5 4 5 31 30 - 4 4 5 30 30 - 3 4 5 34 33 - 2 4 5 11 10 - 1 4 5 55 58
0 4 5 23 24 1 4 5 55 55 2 4 5 26 27 4 4 5 42 42 5 4 5 6 5 6 4 5 16 16 6 5 5 18 18 5 5 5 18 17 4 5 5 21 21 3 5 5 10 11 2 5 5 32 33 1 5 5 31 31 0 5 5 45 47 1 5 5 20 19 2 5 5 11 11 3 5 5 31 30 4 5 5 5 5 5 5 5 30 30
- 6 6 5 7 7 - 4 6 5 11 12 - 3 6 5 17 18 - 1 6 5 5 5
0 6 5 8 9 1 6 5 6 6 2 6 5 30 30 3 6 5 12 12
4 6 5 7 8 5 6 5 6 6
- 2 7 5 6 6 - 1 7 5 7 7
3 7 5 9 10 - 3 8 5 13 12 - 1 8 5 6 7
2 8 5 12 12 3 8 5 9 9
- 7 0 6 42 42 - 6 0 6 16 17 - 5 0 6 82 81 - 4 0 6 10 10 - 3 0 6 48 43 - 2 0 6 82 85 - 1 0 6 49 49
0 0 6 86 89 1 0 6 38 33 2 0 6 72 70 3 0 6 71 74 4 0 6 70 71 5 0 6 22 21 7 0 6 23 23
- 8 1 6 15 15 - 7 1 6 8 8 - 6 1 6 25 24 - 5 1 6 15 15 - 4 1 6 35 35 - 3 1 6 56 53 - 2 1 6 29 28 - 1 1 6 82 82
0 1 6 13 12 1 1 6 69 72 2 1 6 36 36 3 1 6 34 33 4 1 6 50 49 5 1 6 7 8 6 1 6 37 39
- 8 2 6 13 13 - 7 2 6 11 12 - 6 2 6 7 6 - 5 2 6 9 9 - 4 2 6 44 42 - 3 2 6 41 42 - 2 2 6 18 18
0 2 6 54 57 1 2 6 8 8 2 2 6 49 51 3 2 6 5 4 4 2 6 10 10 5 2 6 41 41 7 2 6 13 13
Structure of CsHgBrNzS 321
Table 6. Continued
h k l Fo
--7 3 6 12 - 6 3 6 14 - 5 3 6 7 - 4 3 6 19 - 3 3 6 7 - 2 3 6 16 - 1 3 6 33
0 3 6 10 1 3 6 14 2 3 6 II 3 3 6 23 5 3 6 13 6 3 6 5
- 4 4 6 16 - 3 4 6 34
0 4 6 23 ! 4 6 4 2 4 6 21 3 4 6 13 4 4 6 8 5 4 6 12 6 4 6 6
- 7 5 6 5 - 6 5 6 18 - 5 5 6 7 - 4 5 6 18 - 3 5 6 21 - 2 5 6 5 - 1 5 6 38
0 5 6 7 1 5 6 21 2 5 6 22 3 5 6 27 4 5 6 18 5 5 6 7 6 5 6 9
- 5 6 6 20 - 3 6 6 6 - 2 6 6 29 - 1 6 6 11
0 6 6 25 1 6 6 7 2 6 6 16 3 6 6 28 4 6 6 15 5 6 6 14
- 5 7 6 7 - 4 7 6 15 - 3 7 6 15 - 2 7 6 17 - 1 7 6 18
0 7 6 9
F~ h k l Fo F~
12 1 7 6 30 28 15 2 7 6 5 6 6 3 7 6 9 9
17 4 7 6 15 15 7 - 3 8 6 10 11
14 - 2 8 6 10 9 33 0 8 6 17 17 10 2 8 6 20 20 13 - 7 1 7 12 12 12 - 6 1 7 16 15 22 - 5 1 7 7 7 13 - 4 1 7 32 30
1 - 3 1 7 36 35 15 - 2 1 7 43 39 34 - 1 1 7 41 40 24 0 1 7 3 3 4 1 1 7 37 35
19 2 1 7 49 49 13 3 1 7 7 7 8 4 1 7 18 18
13 5 1 7 24 23 6 6 1 7 5 5 6 7 1 7 24 24
18 - 8 2 7 11 12 7 - 7 2 7 17 16
17 - 6 2 7 35 35 20 - 5 2 7 12 10
4 - 4 2 7 57 57 40 - 3 2 7 13 11
7 - 2 2 7 45 45 23 - 1 2 7 27 28 23 0 2 7 43 42 28 1 2 7 56 57 17 2 2 7 10 8 7 3 2 7 37 38 8 4 2 7 16 16
20 5 2 7 23 22 7 6 2 7 11 11
31 7 2 7 5 2 12 - 7 3 7 4 5 26 - 6 3 7 5 3
7 - 5 3 7 44 43 16 - 4 3 7 7 7 28 - 3 3 7 40 41 14 - 2 3 7 41 42 14 - 1 3 7 28 28 7 0 3 7 84 92
15 1 3 7 38 38 15 2 3 7 42 42 18 3 3 7 18 17 19 4 3 7 43 42 9 5 3 7 23 24
322 Williams et al.
Table 6, Continued
6 - 7 - 6 - 5 - 4 - 3 - 2 - 1
0 1 2 3 4 5 6
- 6 - 5 - 4 - 3 - 2 - 1
0 1 2 4 5
- 6 - 4 - 1
0 1 2 3 4
- 3 0 2 3
- 3 - 2 - 1
0 1
- 8 - 6 - 5 - 4 - 3 - 2 - 1
0 1
l Fo Fr h
7 18 19 2 7 12 12 3 7 20 20 4 7 6 7 5 7 26 26 6 7 33 32 - 7 7 44 45 - 6 7 28 30 - 5 7 17 19 - 4 7 48 49 - 2 7 10 10 - 1 7 49 51 0 7 18 18 1 7 18 18 2 7 24 24 3 7 11 12 4 7 14 14 5 7 6 6 6 7 33 34 - 7 7 10 10 - 6 7 35 35 - 5 7 17 17 - 4 7 4 5 - 3 7 35 36 - 2 7 14 14 - 1 7 7 7 0 7 6 6 1 7 20 20 2 7 17 17 4 7 8 7 5 7 13 12 6 7 8 8 - 7 7 8 9 - 5 7 9 9 - 4 7 5 5 - 3 7 5 4 - 1 7 6 6 1 7 6 5 2 7 5 5 3 7 5 3 - 7 7 7 8 - 6 7 8 7 - 5 7 8 6 - 4 8 29 29 - 3 8 37 38 2 8 35 35 - 1 8 25 24 0 8 78 75 2 8 42 39 3 8 33 32 4 8 32 35 5 8 70 70 6
k I Fo F~
0 8 48 48 0 8 27 26 0 8 23 22 0 8 31 32 0 8 30 30 1 8 13 12 1 8 19 18 1 8 13 13 1 8 41 40 1 8 78 78 1 8 42 38 1 8 68 70 1 8 54 53 1 8 25 24 1 8 54 54 1 8 5 6 1 8 38 39 1 8 11 12 2 8 12 13 2 8 20 20 2 8 25 25 2 8 23 21 2 8 21 21 2 8 29 29 2 8 54 57 2 8 7 7 2 8 17 17 2 8 44 42 2 8 54 54 2 8 12 12 2 8 9 9 3 8 14 15 3 8 7 7 3 8 4 5 3 8 13 13 3 8 9 8 3 8 14 13 3 8 14 14 3 8 6 6 4 8 7 7 4 8 17 16 4 8 7 7 4 8 16 16 4 8 7 8 4 8 6 7 4 8 21 21 4 8 11 12 4 8 12 12 4 8 8 8 4 8 16 16 4 8 7 8 4 8 5 4
S t r u c t u r e o f CsHgBrNzS 323
Table 6. Continued
h k 1 F o
- 5 5 8 5 - 4 5 8 15 - 3 5 8 7 - 2 5 8 21 - 1 5 8 11
0 5 8 12 1 5 8 29 2 5 8 20 3 5 8 9 5 5 8 14
- 5 6 8 18 - 4 6 8 6 - 3 6 8 32 - 2 6 8 7 - 1 6 8 20
0 6 8 15 1 6 8 22 2 6 8 24 3 6 8 8 4 6 8 16
- 4 7 8 11 - 2 7 8 21 - 1 7 8 8
0 7 8 26 1 7 8 9 3 7 8 21
- 2 8 8 6 - 1 8 8 11
0 8 8 9 - 8 1 9 7 - 5 1 9 29 - 4 1 9 32 - 3 1 9 12 - 2 1 9 7 - 1 1 9 49
0 1 9 17 1 1 9 60 3 1 9 8 4 1 9 26 5 1 9 20 6 1 9 9
- 7 2 9 21 - 6 2 9 8 - 5 2 9 38 - 4 2 9 12 - 3 2 9 20 - 2 2 9 37 - 1 2 9 14
0 2 9 29 1 2 9 8 2 2 9 38 3 2 9 30
F~ h k l F o F~
6 4 2 9 11 11 14 5 2 9 25 24 7 6 2 9 7 8
21 - 7 3 9 4 4 11 - 6 3 9 27 28 13 - 4 3 9 10 8 30 - 3 3 9 43 43 20 - 2 3 9 27 28
9 - 1 3 9 59 62 14 0 3 9 3 2 18 1 3 9 40 39 5 2 3 9 46 46
34 3 3 9 38 39 8 4 3 9 20 21
20 5 3 9 5 5 15 6 3 9 26 27 22 - 7 4 9 12 12 23 - 6 4 9 8 8
8 - 5 4 9 32 32 17 - 4 4 9 30 31 11 - 3 4 9 41 42 23 - 2 4 9 28 29
8 - 1 4 9 6 6 27 0 4 9 41 43
9 1 4 9 5 4 21 2 4 9 36 36
7 3 4 9 26 26 11 4 4 9 18 18 8 5 4 9 28 28 6 - 6 5 9 7 8
30 - 5 5 9 12 12 31 - 4 5 9 19 20 11 - 3 5 9 7 8 7 - 2 5 9 4 3
47 - 1 5 9 28 30 17 1 5 9 37 38 61 3 5 9 7 6
8 4 5 9 18 18 25 - 3 6 9 7 7 20 - 2 6 9 20 20 9 - 1 6 9 4 1
20 0 6 9 8 8 8 I 6 9 10 11
36 2 6 9 12 11 12 3 6 9 7 7 19 4 6 9 8 9 36 - 3 7 9 5 5 13 - 2 7 9 8 9 30 - 1 7 9 8 7
7 0 7 9 6 7 37 1 7 .9 7 7 30 2 7 9 5 4
324 W i l l i a m s et al .
Table 6. Continued
h k t Vo
- 7 0 10 7 - 6 0 10 31 - 5 0 10 25 - 4 0 10 48 - 3 0 10 14 - 2 0 10 23 - I 0 10 68
0 0 10 42 1 0 10 30 2 0 10 12 3 0 10 52 4 0 10 38 5 0 10 36 6 0 10 18
- 7 1 10 18 - 6 1 10 6 - 5 1 10 26 - 4 1 10 10 - 3 1 10 39 - 2 1 10 27 - 1 1 10 42
0 1 10 61 1 1 10 9 2 1 10 59 3 1 10 10 4 1 10 29 5 1 10 16 6 1 10 16
- 7 2 10 13 - 6 2 10 9 - 4 2 10 38 - 3 2 10 15 - 2 2 10 49 - 1 2 10 5
0 2 i0 4 1 2 10 39 2 2 10 13 3 2 10 25 4 2 10 5 5 2 10 6
- 5 3 10 6 - 2 3 10 17 - 1 3 10 8
0 3 10 12 1 3 10 12 3 3 10 11 4 3 10 8 5 3 10 5
- 4 4 10 15 - 3 4 10 4 - 2 4 10 21 - 1 4 10 13
Fc h k 1 eo F~
6 0 4 10 7 6 32 1 4 10 10 9 25 2 4 10 8 9 46 5 4 10 6 7 13 - 6 5 10 4 4 21 - 5 5 10 11 10 69 - 4 5 10 4 3 40 - 2 5 10 24 25 30 - 1 5 10 18 18 10 0 5 10 34 34 52 1 5 10 10 10 36 2 5 10 15 16 36 3 5 10 12 13 19 4 5 10 17 17 19 - 5 6 10 10 11 6 - 4 6 10 20 20
26 - 2 6 10 13 13 10 - 1 6 10 16 17 40 0 6 10 12 13 26 1 6 10 14 13 42 2 6 10 5 4 62 3 6 10 21 21 10 - 3 7 10 18 19 60 - 1 7 10 12 12
9 0 7 10 14 14 29 - 7 1 l l 12 11 15 - 6 1 11 15 15 15 - 5 1 l l 21 22 13 - 4 1 11 4 4 9 - 3 1 11 8 9
38 - 2 1 11 25 25 13 - 1 t 11 6 6 49 0 1 l l 13 14
4 1 1 l l 21 19 4 3 1 l l 36 36
38 4 1 11 12 12 13 - 6 2 11 12 12 24 - 5 2 11 19 18
4 - 4 2 l l 19 19 4 - 3 2 11 48 46 7 - 2 2 11 5 3
16 - 1 2 11 34 34 8 0 2 11 19 19
12 1 2 11 23 23 11 2 2 11 20 18 10 3 2 11 5 5 8 4 2 11 31 30 5 5 2 11 11 11
16 - 6 3 11 11 11 4 - 4 3 11 38 39
21 - 3 3 11 6 6 14 - 2 3 11 30 31
Structure of CsHgBrNzS 325
Table 6. Continued
h k l F o Fc h k l F o F c
- 1 3 11 27 27 0 3 11 54 55 1 3 11 46 45 2 3 11 35 35 3 3 11 26 26 4 3 11 8 7 5 3 11 27 28
- 6 4 11 19 19 - 5 4 11 12 12 - 4 4 11 20 21 - 3 4 11 24 24 - 2 4 11 4 5 - 1 4 11 31 31
0 4 11 13 13 1 4 11 11 10 2 4 11 30 30- 3 4 11 11 11 4 4 11 24 24
- 5 5 11 11 12 - 4 5 11 9 9 - 3 5 11 4 4 - 2 5 11 28 29
0 5 11 19 19 1 5 11 12 12 3 5 11 24 24
- 3 6 11 14 14 - 1 6 11 7 7
0 6 11 13 13 1 6 11 14 14 2 6 11 7 6
- 2 7 11 6 8 - 7 0 12 23 24 - 6 0 12 6 4 - 5 0 12 18 18 - 4 0 12 34 32 - 3 0 12 51 51 - 2 0 12 57 57 - 1 0 12 39 38
0 0 12 24 24 1 0 12 23 22 2 0 12 36 36 3 0 12 14 14 4 0 12 14 13 5 0 12 28 27
- 7 1 12 5 4 - 6 1 12 22 22 - 5 1 12 15 15 - 4 1 12 20 20 - 3 1 12 25 26 - 2 1 12 6 5 - 1 1 12 45 45
1 1 12 53 54
2 1 12 25 24 3 1 12 26 27 4 1 12 27 27 5 1 12 8 7
- 6 2 12 9 8 - 5 2 12 25 25 - 4 2 12 5 5 - 3 2 12 9 9 - 2 2 12 16 16 - 1 2 12 17 16
0 2 12 39 40 2 2 12 9 9 3 2 12 23 23 4 2 12 14 13
- 6 3 12 5 6 - 4 3 12 4 2 - 3 3 12 12 13 - 2 3 12 16 17 - 1 3 12 5 5
3 3 12 6 7 - 6 4 12 5 4 - 5 4 12 11 11 - 4 4 12 10 10 - 3 4 12 6 5 - 2 4 12 5 3 - 1 4 12 6 6
0 4 12 14 14 1 4 12 7 7 2 4 12 5 7 3 4 12 9 9
- 5 5 12 5 4 - 3 5 12 23 22 - 2 5 12 12 13 - 1 5 12 15 15
1 5 12 21 21 2 5 12 12 13 3 5 12 16 17
- 3 6 12 15 15 - 2 6 12 14 15
0 6 12 10 11 1 6 12 11 11
- 5 1 13 7 7 - 4 1 13 17 17 - 3 1 13 19 19 - 2 1 13 8 9 - 1 1 13 6 6
0 1 13 40 39 1 1 13 16 15 2 1 13 30 29 3 1 13 6 7
- 6 2 13 14 14 - 5 2 13 5 6
326 Williams et al.
Table 6. Continued
h k l F o Fc h k l Fo F~
- 4 2 13 22 21 - 5 2 14 4 4 - 2 2 13 33 32 - 4 2 14 5 5 - 1 2 13 20 19 - 3 2 14 31 30
0 2 13 16 17 - 1 2 14 29 29 1 2 13 17 16 0 2 14 4 4 2 2 13 9 9 2 2 14 22 23 3 2 13 19 19 3 2 14 10 11 4 2 13 11 9 - 4 3 14 7 6
- 6 3 13 11 11 - 3 3 14 8 8 - 5 3 13 28 27 - 3 4 14 10 10 - 3 3 13 16 17 - 2 4 14 8 8 - 2 3 1~ 27 28 - 1 4 14 7 7 - 1 3 13 29 30 0 4 14 4 5
0 3 13 21 21 2 4 14 9 9 1 3 13 6 6 - 3 5 14 7 8 2 3 13 35 36 - 2 5 14 6 6 3 3 13 15 15 - 1 5 14 10 9
- 4 4 13 21 21 0 5 14 11 11 - 3 4 13 8 7 - 4 1 15 14 13 - 2 4 13 22 23 - 3 1 15 6 6 - 1 4 13 23 24 - 1 1 15 28 28
0 4 13 6 5 0 1 15 13 13 1 4 13 33 34 1 1 15 6 5 3 4 13 16 17 2 1 15 9 8
- 4 5 13 6 7 3 1 15 9 9 - 3 5 13 18 19 - 5 2 15 9 9 - 2 5 13 4 3 - 4 2 15 12 12 - 1 5 13 7 8 - 3 2 15 12 13
0 5 13 19 20 - 2 2 15 13 13 1 5 13 8 9 0 2 15 19 19 2 5 13 17 17 1 2 15 14 14
- 2 6 13 5 6 2 2 15 17 17 - 1 6 13 8 8 - 4 3 15 16 16
O' 6 13 7 8 - 3 3 15 24 24 - 6 0 14 7 5 - 2 3 15 14 14 ~ 5 0 14 23 24 - 1 3 15 17 19 - 4 0 14 24 24 0 3 15 13 13 - 3 0 14 15 15 1 3 15 34 34 - 1 0 14 28 28 2 3 15 8 9
0 0 14 30 29 - 3 4 15 9 10 1 0 14 24 25 - 2 4 15 24 24 2 0 14 19 20 - 1 4 15 9 9 3 0 14 10 9 0 4 15 26 27
- 6 1 14 9 10 - 4 0 16 12 13 - 5 1 14 15 15 - 3 0 16 20 19 - 4 1 14 25 24 - 2 0 16 27 27 - 2 1 14 34 34 - 1 0 16 18 18 - 1 1 14 15 15 0 0 16 10 11
0 1 14 28 30 1 0 16 25 26 1 1 14 27 26 2 0 16 11 10 2 1 14 23 22 - 3 1 16 23 24 3 1 14 31 30 - 2 1 16 12 13
Structure of CsHgBrN2S 327
T a b l e 6. C o n t i n u e d
h k 1 F o Fc h k I F o Fr
- 1 1 16 16 16 0 2 16 9 9 0 1 16 23 23 1 2 16 17 17 1 1 16 7 7 - 3 3 16 5 2
- 4 2 16 16 16 - 2 3 16 8 7 - 3 2 16 4 3 - 2 1 17 14 15
- 2 2 16 7 7 - 1 1 17 8 7
- 1 2 16 16 16
T a b l e 7. S u m m a r y o f all i n t e r m o l e c u l a r con t ac t s f o r d m i t " Br
Br (1 ) x/a = 0 . 7 1 0 6 y/b = 0 . 3 2 2 2 z/c = 0 . 0 8 2 6 S " �9 " B r ( 1 ) 3 .623 1, - 1 .0000 , 0 . 0 0 0 0 , 0 . 0 0 0 0
H C ( 3 ) - - �9 Br (1 ) 2 . 7 1 0 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
H C ( 5 ) �9 �9 �9 Br (1 ) 2 . 8 3 0 1, - 1 . 0000 , 0 . 0 0 0 0 , 0 . 0 0 0 0 Br (1 ) x/a = 0 . 2 8 9 5 y/b = 0 . 6 7 7 8 z/c = 0 . 9 1 7 4
Br (1 ) x/a = 0 . 2 8 9 5 y/b = 0 . 8 2 2 2 z/c = 0 . 4 1 7 4 S �9 �9 �9 Br (1 ) 3 . 7 3 3 2, 1 .0000 , 0 . 0 0 0 0 , 0 . 0 0 0 0
Br (1 ) x/a = 0 . 7 1 0 6 y/b = 0 . 1 7 7 8 z/c = 0 . 5 8 2 6 H C ( 2 ) - . �9 Br (1 ) 2 . 6 8 8 - 2 , 0 . 0 0 0 0 , 1 . 0000 , 1 .0000
S x/a = 0 . 9 2 9 4 y/b = 0 . 5 2 1 9 z/c = 0 . 2 9 7 0 Br (1 ) - - - S 3 .623 1, 1 . 0000 , 0 . 0 0 0 0 , 0 . 0 0 0 0
N ( 1 ) - - �9 S 2 . 7 3 0 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
N ( 2 ) �9 �9 �9 S 2 .741 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
C ( 1 ) - - - S 1 .730 (0 .003 ) 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 C(4) �9 �9 �9 S 3 . 2 1 5 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
C ( 5 ) �9 �9 - S 3 .231 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
S x/a = 0 . 0 7 0 7 y/b = 0 . 4 7 8 1 z/c = 0 . 7 0 3 0 S x/a = 0 . 0 7 0 7 y/b = 0 . 0 2 1 9 z/c = 0 . 2 0 3 0
Br (1 ) - . �9 S 3 . 7 3 3 2 , 1 . 0000 , - 1 .0000 , 0 . 0 0 0 0 S x/a = 0 . 9 2 9 4 y/b = 0 . 9 7 8 1 z/c = 0 . 7 9 7 0
N ( 1 ) x/a = 0 . 2 4 7 6 y/b = 0 . 3 6 3 1 z/c = 0 . 3 7 8 6
S - �9 �9 N ( 1 ) 2 . 7 3 0 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 N ( 2 ) - - �9 N ( 1 ) 2 . 1 6 0 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
C ( 1 ) - - - N ( 1 ) 1 .329 ( 0 . 0 0 5 ) 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 C ( 2 ) - - - N ( 1 ) 1 .374 ( 0 . 0 0 6 ) 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 C ( 2 ) - N ( 1 ) - C ( 1 ) 109 .0 (0 .3) 1,
C ( 3 ) " " - N ( 1 ) 2 . 1 8 8 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
C ( 4 ) - - - N ( 1 ) 1 .449 (0 .006 ) 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 C ( 4 ) - N ( 1 ) - C ( 1 ) 126 .5 (0 .3 )
C ( 4 ) - N ( 1 ) - C ( 2 ) 124 .4 (0 .4 )
H C ( 2 ) - - �9 N ( 1 ) 2 . 0 4 9 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
H C ( 4 ) �9 �9 �9 N ( 1 ) 2 . 0 5 6 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 H C ( 4 ) �9 �9 �9 N ( 1 ) 2 . 2 5 2 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 H C ( 4 ) �9 �9 �9 N ( 1 ) 2 . 0 4 2 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 N ( 1 ) x/a = 0 . 7 5 2 4 y/b = 0 . 6 3 7 0 z/c = 0 . 6 2 1 4 N ( 1 ) x/a = 0 . 7 5 2 4 y/b = 0 . 8 6 3 1 z/c = 0 . 1 2 1 4 N ( 1 ) x/a = 0 . 2 4 7 6 y/b = 0 . 1 3 7 0 z/c = 0 . 8 7 8 6 N ( 2 ) x/a = 0 . 2 5 3 1 y/b = 0 . 4 3 8 6 z/c = 0 . 2 3 6 9
S �9 - - N ( 2 ) 2 .741 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 N ( 1 ) - �9 �9 N ( 2 ) 2 . 1 6 0 1, 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
328 Williams et al.
T a b l e 7. Cont inued
C ( 1 ) - - - N(2) 1 .340 (0 .005) 1, 0 . 0000 , 0 . 0000 , 0 . 0 0 0 0 C ( 2 ) ' " - N(2) 2 .191 1, 0 .0000 , 0 .0000 , 0 .0000 C ( 3 ) - - - N(2) 1 .382 (0 .006) 1, 0 , 0000 , 0 .0000 , 0 . 0 0 0 0 C ( 3 ) - N ( 2 ) - C ( 1 ) 108 .4(0 .3) C ( 5 ) - - - N ( 2 ) 1 .458 (0 .005) 1, 0 . 0000 , 0 .0000 , 0 . 0 0 0 0 C ( 5 ) - N ( 2 ) - C ( 1 ) 126 .4(0 .003) C ( 5 ) - N ( 2 ) - C ( 3 ) 125 .2(0 .3) HC(3) �9 �9 - N(2) 2 .257 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 NC(5) �9 - �9 N(2) 2 . 2 4 9 1, 0 .0000 , 0 . 0000 , 0 . 0 0 0 0 HC(5) . . . . N(2) 2 .041 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 HC(5) - - �9 N(2) 1.892 1, 0 . 0000 , 0 .0000 , 0 . 0 0 0 0 N(2) x/a = 0 . 7 4 6 9 y/b = 0 .5614 z/c = 0 .7631 N(2) x/a = 0 . 7 4 6 9 y/b = 0 . 9 3 8 6 z/c = 0 .2631 N(2) x/a = 0 .2531 y/b = 0 . 0 6 1 4 z/c = 0 . 7 3 6 9 C(1) x/a = 0 . 1 4 9 6 y/b = 0 .4371 z/c = 0 . 3 0 4 4 S - - - C ( I ) 1 .730 (0 .003) 1, 0 . 0000 , 0 .0000 , 0 . 0 0 0 0 N ( 1 ) - - - C ( 1 ) 1 .329 (0 .005) 1, 0 . 0000 , 0 .0000 , 0 .0000 N ( 1 ) - C ( 1 ) - S 125 .9(0 .3) N ( 2 ) - - - C ( 1 ) 1 .340 (0 .005) 1, 0 . 0000 , 0 . 0000 , 0 . 0 0 0 0 N ( 2 ) - C ( 1 ) - S 126 .0(0 .3) N ( 2 ) - C ( 1 ) - N ( 1 ) 108 .1(0 .3) C ( 2 ) " �9 �9 C(I ) 2 . 2 0 0 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 C(3 )" - - C(1) 2 .208 1, 0 . 0000 , 0 .0000 , 0 . 0 0 0 0 C ( 4 ) . �9 - C(1) 2 .481 1, 0 . 0000 , 0 .0000 , 0 . 0 0 0 0 C(5 ) - �9 �9 C(1) 2 . 4 9 9 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 C(1) x/a = 0 . 8 5 0 4 y/b = 0 . 5 6 2 9 z/c = 0 . 6 9 5 7 C(1) x/a = 0 . 8 5 0 4 y/b = 0 .9371 z/c = 0 . 1 9 5 7 C(I ) x/a = 0 . 1 4 9 6 y/b = 0 . 0 6 2 9 z/c = 0 . 8 0 4 4 C(2) x/a = 0 . 4 1 7 3 y/b = 0 . 3 1 5 8 z/c = 0 .3585 N ( 1 ) - - - C(2) 1 .374 (0 .006) 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 N(2 ) - - �9 C(2) 2 .191 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 C(1 ) - �9 - C(2) 2 . 2 0 0 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 C ( 3 ) - - - C ( 2 ) 1.341 (0 .007) 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 C ( 3 ) - C ( 2 ) - N ( 1 ) 107 .4(0 .4) C(4 ) - - �9 C(2) 2 . 4 9 7 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 H C ( 2 ) - - - C ( 2 ) 1.091 (0.005) 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 H C ( 2 ) - C ( 2 ) - N ( 1 ) 111 .9(0 .4) H C ( 2 ) - C ( 2 ) - C ( 3 ) 140 .6(0 .5) HC(3) - �9 �9 C(2) 2 . 1 7 7 1, 0 . 0000 , 0 .0000 , 0 . 0 0 0 0 C(2) x/a = 0 . 5 8 2 7 y/b = 0 . 6 8 4 2 z/c = 0 .6415 C(2) x/a = 0 .5827 y/b = 0 . 8 1 5 8 z/c = 0 .1415 C(2) x/a = 0 .4173 y/b = 0 .1842 z/c = 0 .8585 C(3) x/a = 0 . 4 2 0 5 y/b = 0 .3605 z/c = 0 .2702 N(1) �9 �9 �9 C(3) 2 .188 1, 0 .0000 , 0 . 0000 , 0 . 0 0 0 0 N ( 2 ) - - - C ( 3 ) 1 .382 (0.06) 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 C(1) �9 �9 �9 C(3) 2 . 2 0 8 1, 0 .0000 , 0 . 0000 , 0 . 0 0 0 0 C ( 2 ) - - - C ( 3 ) 1.341 (0 .007) 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 C ( 2 ) - C ( 3 ) - N ( 2 ) 107 .2(0 .4) C(5) �9 - �9 C(3) 2 .522 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 HC(2) �9 �9 �9 C(3) 2 .291 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 HC(3) - - - C(3) 1 .119 (0 .004) 1, 0 .0000 , 0 .0000 , 0 . 0 0 0 0 H C ( 3 ) - C ( 3 ) - N ( 2 ) 128 .6(0.4) H C ( 3 ) - C ( 3 ) - C ( 2 ) 1 2 4 . 2 ( 0 . 4 ) HC(5) �9 �9 �9 C(3) 2 . 5 1 9 1, 0 . 0000 , 0 .0000 , 0 . 0 0 0 0
Structure of CsHgBrN2S 329
T a b l e 7. Con t inued
C(3) x/a = 0 . 5 7 9 5 y/b = 0 .6395 C(3) x/a = 0 . 5 7 9 5 y/b = 0 . 8 6 0 5 C(3) x/a = 0 .4205 y/b = 0 . 1 3 9 5 C(4) x/a = 0 . 1 9 3 0 y/b = 0 . 3 4 3 9 S " �9 " C ( 4 ) 3 .215 1, N ( 1 ) - - - C ( 4 ) 1 .449 (0 .006) 1, C(1 ) " �9 �9 C(4) 2 .481 1, C ( 2 ) ' �9 �9 C(4) 2 . 4 9 7 1, H C ( 4 ) - - - C ( 4 ) 1 .002 (0 .006) 1, H C ( 4 ) - C ( 4 ) - N ( 1 ) 112 .8(0 .5) H C ( 4 ) - - - C ( 4 ) 1 .214 (0 .006) 1, H C ( 4 ) - C ( 4 ) - N ( 1 ) 115 .2(0 .4) H C ( 4 ) - C ( 4 ) - H C ( 4 ) 90 .4(0 .4) H C ( 4 ) - - - C(4) .967 (0 .005) 1, H C ( 4 ) - C ( 4 ) - N ( 1 ) 113 .9(0 .4) H C ( 4 ) - C ( 4 ) - H C ( 4 ) 123 .4(0 .5) H C ( 4 ) - C ( 4 ) - H C ( 4 ) 9 7 . 1 (0.5) C(4) x/a = 0 . 8 0 7 0 y/b = 0 .6561 C(4) x/a = 0 . 8 0 7 0 y/b = 0 . 8 4 3 9 C(4) x/a = 0 . 1 9 3 0 y/b = 0 .1561 C(5) x/a = 0 . 2 0 0 8 y/b = 0 . 5 1 0 9 S ' �9 "C(5 ) 3 .231 1, N ( 2 ) - - - C ( 5 ) 1 .458 (0 .005) 1, C(1 ) - �9 �9 C(5) 2 . 4 9 9 1, C(3 ) " - -C(5 ) 2 . 5 2 2 1, H C ( 5 ) - - - C ( 5 ) 1 .128 (0 .005) l , H C ( 5 ) - C ( 5 ) - N ( 2 ) 120 .3(0 .3) H C ( 5 ) - - - C ( 5 ) 1 .028 (0 .005) 1, H C ( 5 ) - C ( 5 ) - N ( 2 ) 109 . 1(0.4) H C ( 5 ) - C ( 5 ) - H C ( 5 ) 92 .8(0 .4) H C ( 5 ) - - - C ( 5 ) .859 (0 .004) 1, H C ( 5 ) - C ( 5 ) - N ( 2 ) 106 .6(0 .4) H C ( 5 ) - C ( 5 ) - H C ( 5 ) 121 .4(0 .5) H C ( 5 ) - C ( 5 ) - H C ( 5 ) 103 .6(0 .4) C(5) x/a = 0 . 7 9 9 2 y/b = 0 .4891 C(5) x/a = 0 . 7 9 9 2 y/b = 0 . 0 1 0 9 C(5) x/a = 0 . 2 0 0 8 y/b = 0 .9891 HC(2) x/a = 0 . 5 0 5 8 y/b = 0 . 2 5 9 6 N ( 1 ) - " �9 HC(2) 2 . 0 4 9 1, C ( 2 ) - - - H C ( 2 ) 1.091 (0 .005) 1, C(3) �9 �9 �9 HC(2) 2 .291 1, HC(2) x/a = 0 . 4 9 4 2 y/b = 0 . 7 4 0 4 HC(2) x/a = 0 . 4 9 4 2 y/b = 0 . 7 5 9 6 HC(2) x/a = 0 . 5 0 5 8 y/b = 0 . 2 4 0 4 Br(1) �9 �9 �9 HC(2) 2 . 6 8 8 - 2 , HC(3) x/a = 0 . 5 4 0 0 y/b = 0 .3361 Br(1) �9 �9 �9 HC(3) 2 . 7 1 0 1, N ( 2 ) - . - HC(3) 2 . 2 5 7 1, C(2 ) - - - HC(3) 2 . 1 7 7 1, C ( 3 ) - - - H C ( 3 ) 1 .119 (0 .004) 1, HC(3) x/a = 0 . 4 6 0 0 y/b = 0 . 6 6 3 9 HC(3) x/a = 0 . 4 6 0 0 y/b = 0 .8361 HC(3) x/a = 0 . 5 4 0 0 y/b = 0 . 1 6 3 9 HC(4) x/a = 0 .0581 y/b = 0 . 3 1 7 8
z/c = 0 . 7 2 9 8 z/c = 0 . 2 2 9 8 z/c = 0 . 7 7 0 2 z/c = 0 . 4 6 8 8
0 .0000 , 0 .0000 , 0 . 0 0 0 0 0 .0000 , 0 .0000 , 0 . 0 0 0 0 0 .0000 , 0 .0000 , 0 . 0 0 0 0 0 .0000 , 0 . 0000 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0000 , 0 . 0 0 0 0
0 .0000 , 0 .0000 , 0 . 0 0 0 0
0 .0000 , 0 .0000 , 0 . 0 0 0 0
z/c = 0 . 5 3 1 2 z/c = 0 . 0 3 1 2 z/c = 0 . 9 6 8 8 z/c = 0 . 1 4 4 2
0 . 0 0 0 0 , 0 . 0000 , 0 . 0 0 0 0 0 .0000 , 0 .0000 , 0 . 0 0 0 0 0 .0000 , 0 . 0000 , 0 . 0 0 0 0 0 .0000 , 0 .0000 , 0 . 0 0 0 0 0 .0000 , 0 . 0000 , 0 . 0 0 0 0
0 .0000 , 0 .0000 , 0 . 0 0 0 0
0 .0000 , 0 . 0 0 0 0 , 0 . 0 0 0 0
z/c = 0 . 8 5 5 8 z/c = 0 .3558 z/c = 0 .6442 z/c = 0 . 4 1 8 4
0 .0000 , 0 .0000 , 0 . 0 0 0 0 0 .0000 , 0 .0000 , 0 . 0 0 0 0 0 .0000 , 0 . 0000 , 0 . 0 0 0 0
z/c = 0 . 5 8 1 6 z/c = 0 . 0 8 1 6 z/c = 0 . 9 1 8 4
0 .0000 , 1 ,0000, 0 . 0 0 0 0 z/c = 0 . 2 3 3 2
0 .0000 , 0 .0000 , 0 . 0 0 0 0 0 .0000 , 0 .0000 , 0 . 0 0 0 0 0 .0000 . 0 .0000 , 0 . 0 0 0 0 0 .0000 , 0 . 0000 , 0 . 0 0 0 0
z/c = 0 . 7 6 6 8 z/c = 0 . 2 6 6 8 z/c = 0 . 7 3 3 2 z/c = 0 . 4 6 4 9
330 Will iams et al.
T a b l e 7. C o n t i n u e d
N ( 1 ) . �9 �9 H C ( 4 ) 2 . 0 5 6 1,
C ( 4 ) - - - H C ( 4 ) 1 .002 (0 .006 ) 1, H C ( 4 ) �9 �9 �9 H C ( 4 ) 1 .579 1,
H C ( 4 ) �9 �9 �9 H C ( 4 ) 1 .733 1,
H C ( 4 ) x/a = 0 . 9 4 1 9 y/b = 0 . 6 8 2 2 H C ( 4 ) x/a = 0 . 9 4 1 9 y/b = 0 . 8 1 7 8
H C ( 4 ) x/a = 0 . 0 5 8 1 y/b = 0 . 1 8 2 2
H C ( 4 ) x/a = 0 . 1 7 3 6 y/b = 0 . 4 7 8 2 N ( 1 ) ' �9 �9 H C ( 4 ) 2 . 2 5 2 1,
C ( 4 ) - - - H C ( 4 ) 1 .214 (0 .006 ) 1,
H C ( 4 ) - - - H C ( 4 ) 1 .579 1,
H C ( 4 ) - - - H C ( 4 ) 1 .643 1,
H C ( 4 ) x/a = 0 . 8 2 6 4 y/b = 0 . 5 2 1 8 H C ( 4 ) x/a = 0 . 8 2 6 4 y/b = 0 . 9 7 8 2
H C ( 4 ) x/a = 0 . 1 7 3 6 y/b = 0 . 0 2 1 8
H C ( 4 ) x/a = 0 . 2 8 8 0 y/b = 0 . 2 9 5 0 N ( 1 ) ' �9 �9 H E ( 4 ) 2 . 0 4 2 1,
C ( 4 ) - - - H C ( 4 ) 0 . 9 6 7 (0 .005 ) 1,
H C ( 4 ) �9 �9 �9 n c ( 4 ) 1 .733 1,
H C ( 4 ) - �9 �9 H C ( 4 ) 1 .643 1, H C ( 4 ) x/a = 0 . 7 1 2 0 y/b = 0 . 7 0 5 0
H C ( 4 ) x/a = 0 . 7 1 2 0 y/b = 0 . 7 9 5 0 H C ( 4 ) x/a = 0 . 2 8 8 0 y/b = 0 . 2 0 5 0
H C ( 5 ) x/a = 0 . 0 5 5 5 y/b = 0 . 4 9 4 5
B r ( 1 ) - - - H C ( 5 ) 2 . 8 3 0 1, N ( 2 ) ' �9 �9 H C ( 5 ) 2 . 2 4 9 1, C ( 5 ) - - - H C ( 5 ) 1 .128 (0 .005 ) 1,
H C ( 5 ) �9 �9 �9 H C ( 5 ) 1 .562 1, H C ( 5 ) �9 �9 �9 H C ( 5 ) 1 .738 1,
H C ( 5 ) x/a = 0 . 9 4 4 5 y/b = 0 . 5 0 5 5
H C ( 5 ) x/a = 0 . 9 4 4 5 y/b = 0 . 9 9 4 5 H C ( 5 ) x/a = 0 . 0 5 5 5 y/b = 0 . 0 0 5 5
H C ( 5 ) x/a = 0 . 1 8 6 6 y/b = 0 . 6 4 2 4
N ( 2 ) . �9 �9 H C ( 5 ) 2 .041 1, C ( 5 ) - - - H C ( 5 ) 1 .028 (0 .005 ) 1,
H C ( 5 ) �9 �9 �9 H C ( 5 ) 1 .562 1,
H C ( 5 ) - - �9 H C ( 5 ) 1 .486 1, H C ( 5 ) x/a = 0 . 8 1 3 4 y/b = 0 . 3 5 7 6 H C ( 5 ) x/a = 0 . 8 1 3 4 y/b = 0 . 1 4 2 4
H C ( 5 ) x/a = 0 . 1 8 6 6 y/b = 0 . 8 5 7 6 H C ( 5 ) x/a = 0 . 2 9 5 2 y/b = 0 . 4 9 9 5 N ( 2 ) " - - H C ( 5 ) 1 .892 1, C ( 3 ) " - - H C ( 5 ) 2 . 5 1 9 1, C ( 5 ) - - - H C ( 5 ) 0 . 8 5 9 (0 .004 ) 1,
H C ( 5 ) - - �9 H C ( 5 ) 1 .738 1, H C ( 5 ) �9 �9 �9 n c ( 5 ) 1 .486 1, H C ( 5 ) x/a = 0 . 7 0 4 8 y/b = 0 . 5 0 0 5 H C ( 5 ) x/a = 0 . 7 0 4 8 y/b = 0 . 9 9 9 5 H C ( 5 ) x/a = 0 . 2 9 5 2 y/b = 0 . 0 0 0 5
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
z/c = 0 . 5 3 5 1
z/c = 0 . 0 3 5 1 z/c = 0 . 9 6 4 9
z/c = 0 . 5 0 9 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
z/c = 0 . 4 9 1 0 z/c = 0 . 9 9 1 0 z/c = 0 . 0 0 9 0
z/c = 0 . 5 1 5 4 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 z/c = 0 . 4 8 4 6
z/c = 0 . 9 8 4 6
z/c = 0 . 0 1 5 4 z/c = 0 . 1 0 5 5
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
z/c = 0 . 8 9 4 5
z/c = 0 . 3 9 4 5
z/c = 0 . 6 0 5 5 z/c = 0 . 1 4 9 3
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
z/c = 0 . 8 5 0 7 z/c = 0 . 3 5 0 7 z/c = 0 . 6 4 9 3
z/c = 0 . 1 1 6 9 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0 0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
0 . 0 0 0 0 , 0 . 0 0 0 0 , 0 . 0 0 0 0
z/c = 0 . 8 8 3 1 z/c = 0 . 3 8 3 1 z/c = 0 . 6 1 6 9
Structure of CsHgBrN2S 331
C4~N~I~G3
Br' ~ Fig. 1. View of dmit ,HBr showing Br-S-Br-S chain. Thermal ellipsoids are drawn at 50% prob-
ability.
Fig. 2. Stereoview of the unit cell. The view is through b with a running horizontally and c ver tically. Thermal ellipsoids are drawn at the 50% probability level.
332 Williams et al.
ligand (1.695 A), but similar elongation is noted for several other molecular adducts of dmit with various acceptors (Arduengo and Burgess, 1977; Williams et a l . , 1978; Rubin et al. 1981).
Spectral data also appear to support a molecular association based on com- parisons with known molecular adducts of this ligand. 1H-NMR data show downfield shifts of both signals compared to those for the free ligand in the same solvent (cf. complex: 63.75 and 66.80; free ligand: 63.58 and 66.67). Similar shifts are observed for other molecular thiourea adducts (Williams and Wynn, 1978; Wynne and Pearson, 1971). Notably absent from the proton NMR spectrum is the bromine proton. Possible averaging and broadening due to ex- change with unreacted thione may be one explanation for the absence. No sig- nificant changes were noted in the solid-state IR spectrum of dmit-HBr relative to the free ligand other than a slight shift in the N-C-N antisymmetric stretching frequency which appears at 1580 cm -~ in the complex (cf. 1570 cm -1 for free dmit) (Williams and Wynne; 1978). Much more dramatic shifts (ca. 90 cm-l ) are noted for acyclic thioureas in going from free to coordinated state (Williams and Wynne, 1978; Wynne et a l . , 1972).
In conclusion, the results show that the complex dmit 'HBr is indeed a molecular adduct and lends further evidence to the assumption that addition compounds generated by adding acid to thioureas are nonionic.
Acknowledgment
We wish to thank the Kennesaw College Faculty Development Fund for partial support of this research.
References
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