Pentane-1,5-diaminium dibromide

Charmaine Arderne

Department of Chemistry, University of Johannesburg, PO Box 524, Auckland Park,

Johannesburg 2006, South Africa

Correspondence e-mail: carderne@uj.ac.za

Received 30 January 2013

Accepted 20 March 2013

The crystal structure of the title salt, C5H16N22+�2Br�, with

Z = 12 and more unusually Z0 = 3, forms part of a small group

of crystal structures in the Cambridge Structural Database

that are ammonium bromide salts. One of the diaminium

cation chains in the asymmetric unit exhibits positional

disorder, which was modelled using a suitable disorder model.

This compound also exhibits organic–inorganic layering in its

packing arrangement that is typical of this class of compound.

An extensive complex three-dimensional hydrogen-bonding

network is also identified. The hydrogen bonds evident in this

crystal structure were identified as being most likely strong

charge-assisted hydrogen bonds.

Comment

The crystal structure of pentane-1,5-diaminium dibromide, (I),

was determined as part of an ongoing study of the structural

characteristics and noncovalent interactions of organic–inor-

ganic hybrid salts. A search of the Cambridge Structural

Database (CSD, Version 5.33, August 2012 update; Allen,

2002) revealed that this compound had not been determined

previously, so it is presented here.

The asymmetric unit of (I) contains three diaminium cations

and six bromide anions with Z = 12 and Z0 = 3. Since structures

with Z0 > 1 are not a common occurrence, a search was carried

out to determine the number of structures in the CSD with

Z0 = 3, limited to organic crystal structures and also only those

structures that contain C, H, N and Br. This search resulted in

11 hits, only five of which are ammonium bromide salts,

namely dimethyldi-n-propylammonium bromide (CSD

refcode CANYOG; Busi et al., 2005), 1-isopropyl-3-methyl-

imidazol-3-ium bromide (JIRCAP01; Kawahata et al., 2009),

1-decyl-1-methylpyrrolidinium bromide (YUHFUD; Getsis &

Mudring, 2009), 1-dodecyl-1-methylpyrrolidinium bromide

(YUHGAK; Getsis & Mudring, 2009) and propane-1,3-bis(N-

methylpyrrolidinium) dibromide (FELCOP; Anderson et al.,

2005). Interestingly, the title salt, (I), is only the second

diaminium dibromide salt with similar crystallographic prop-

erties, i.e. Z0 = 3.

One of the diaminium cations of (I) was found to be

disordered and a suitable model was used to resolve the

disorder. This entire diaminium chain is disordered over two

positions, with occupancies of 0.552 (10) and 0.449 (8). The

disordered atoms were refined anisotropically with inter-

atomic distance restraints and displacement-parameter

constraints. Fig. 1 shows the molecular structure of (I) and also

only depicts the minor component of the disordered cation

chain. As a result of this disorder, the diaminium cation chain

deviates substantially from planarity, as is evident in the

torsion angles along the chain (Table 1 lists selected torsion

angles for both disordered cation models).

The other two (ordered) diaminium cations also deviate

slightly from planarity and have a bowed zigzag configuration.

This is particularly noticeable in the centre of the cation

chains, where the C1A—C2A—C3A—C4A torsion angle is

166.3 (3)� and the C2B—C3B—C4B—C5B torsion angle is

169.4 (3)� (see Table 1).

These n-alkyldiaminium dihalide salts usually exhibit an

organic–inorganic layering effect, where the organic diami-

nium cation layers are sandwiched between inorganic anion

layers (consisting of counter-anions, in this case bromide

anions). This phenomenon has been demonstrated in our

previous work (van Blerk & Kruger, 2007a,b, 2009; Arderne &

Kruger, 2011; Arderne, 2011) and in work done by our

colleagues (Lemmerer & Billing, 2006; Rademeyer, 2006). Salt

(I) clearly shows this layering effect (Fig. 2), which is evident

primarily because of the intricate and complex three-dimen-

sional hydrogen-bonding network that is present in this crystal

structure, consisting entirely of N—H� � �Br hydrogen bonds.

This means that the distance between the organic and inor-

ganic layers will be approximately equal to the N� � �Br

organic compounds

526 # 2013 International Union of Crystallography doi:10.1107/S0108270113007762 Acta Cryst. (2013). C69, 526–528

Acta Crystallographica Section C

Crystal StructureCommunications

ISSN 0108-2701

Figure 1The molecular structure of the title compound, showing the atomicnumbering scheme. Displacement ellipsoids are drawn at the 50%probability level. Only the minor component of the one disorderedpentane-1,5-diaminium cation chain is shown. Selected hydrogen bondsare indicated by dashed lines.

distance (on average, this distance is around 3.3 A). One of the

interlayer distances (i.e. the distance between the two inor-

ganic layers) is 4.597 A (Mercury; Macrae et al., 2008) (Fig. 3).

The N—H� � �Br hydrogen bonds are postulated to be rela-

tively strong charge-assisted hydrogen bonds because of their

directionality (many of them are close to 180�) and their

relatively short H� � �A distances.

This organic–inorganic layering effect is also evident in two

of the crystal structures found in the CSD search, namely

YUHFUD and YUHGAK. The layering effect was not

evident in CANYOG, JIRCAP01 and FELCOP. In the case of

YUHFUD and YUHGAK, the layering effect is evident not

as a result of hydrogen bonding, but primarily as a result of

hydrocarbon chain stacking, since YUHFUD and YUHGAK

have 10- and 12-carbon hydrocarbon chains, respectively. This

chain stacking is common in hydrocarbon-type materials and

is a result of weak van der Waals interactions between the

layers (Dorset, 2005).

Experimental

The title compound was prepared by adding butane-1,5-diamine

(0.050 g, 0.489 mmol) to 47% hydrobromic acid (2 ml, 37 mmol) in a

sample vial. The mixture was then refluxed at 363 K for 2 h. The

solution was cooled slowly at a rate of 2 K h�1 to room temperature.

Colourless crystals of butane-1,5-diaminium dibromide, (I), were

collected.

Crystal data

C5H16N22+�2Br�

Mr = 264.02Monoclinic, P21=ca = 4.5971 (3) Ab = 15.4607 (11) Ac = 41.389 (3) A� = 90.310 (5)�

V = 2941.7 (4) A3

Z = 12Mo K� radiation� = 8.20 mm�1

T = 150 K0.26 � 0.15 � 0.08 mm

Data collection

Oxford Xcalibur2 diffractometerAbsorption correction: multi-scan

(CrysAlis RED; OxfordDiffraction, 2006)Tmin = 0.225, Tmax = 0.546

17961 measured reflections6280 independent reflections4223 reflections with I > 2�(I)Rint = 0.038

Refinement

R[F 2 > 2�(F 2)] = 0.030wR(F 2) = 0.049S = 0.896280 reflections316 parameters

298 restraintsH-atom parameters constrained��max = 0.72 e A�3

��min = �0.61 e A�3

One of the cations in (I) is completely disordered over two posi-

tions. The occupation factor of the major orientation of this cation

refined to 0.552 (10). The N—C distances in the disordered cation

were restrained to be similar, with a restraint s.u. value of 0.01 A,

while rigid-bond and similarity restraints were applied to the aniso-

tropic displacement parameters of neighbouring disordered atoms

within and between the two orientations. Atom N2CB was also

restrained to be pseudo-isotropic. All H atoms were placed in idea-

organic compounds

Acta Cryst. (2013). C69, 526–528 Charmaine Arderne � C5H16N22+�2Br� 527

Figure 2A packing diagram for (I), viewed down the b axis, clearly showing theorganic–inorganic layering effect.

Figure 3A packing diagram for (I), viewed down the b axis, showing the inorganic interlayer distance of 4.597 A (highlighted with a dotted line).

Table 1Selected torsion angles (�).

C1A—C2A—C3A—C4A 166.3 (3)C2B—C3B—C4B—C5B 169.4 (3)C1CB—C2CB—C3CB—C4CB �74.4 (19)C3CB—C4CB—C5CA—N2CB 71.7 (18)N2CA—C5CB—C4CA—C3CA �81.0 (15)C1CA—C2CA—C3CA—C4CA 69.5 (16)

lized positions and refined using a riding model, with N—H = 0.91 A

and C—H = 0.99 A, and with Uiso(H) = 1.2Ueq(parent atom).

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell

refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduc-

tion: CrysAlis RED; program(s) used to solve structure: SHELXS97

(Sheldrick, 2008); program(s) used to refine structure: SHELXL97

(Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al.,

2009); software used to prepare material for publication: OLEX2,

PLATON (Spek, 2009) and publCIF (Westrip, 2010).

The Department of Chemistry at the University of Kwa-

Zulu Natal (UKZN), Pietermaritzburg Campus, is acknowl-

edged for the use of facilities for the data collection for this

crystal structure. Dr Melanie Rademeyer is acknowledged for

her assistance with the use of the instrument during her time

at UKZN. The University of Johannesburg is gratefully

acknowledged for funding for this research project. Dr Ilia A.

Guzei is gratefully acknowledged for his assistance with the

disorder modelling in this crystal structure.

Supplementary data for this paper are available from the IUCr electronicarchives (Reference: FN3129). Services for accessing these data aredescribed at the back of the journal.

References

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Soc. 127, 593–604.Arderne, C. (2011). Acta Cryst. E67, o2183.Arderne, C. & Kruger, G. J. (2011). Acta Cryst. E67, o1060.Blerk, C. van & Kruger, G. J. (2007a). Acta Cryst. E63, o342–o344.Blerk, C. van & Kruger, G. J. (2007b). Acta Cryst. E63, o4289.Blerk, C. van & Kruger, G. J. (2009). Acta Cryst. E65, o1008.Busi, S., Lahtinen, M., Mansikkamaki, H., Valkonen, J. & Rissanen, K. (2005).

J. Solid State Chem. 178, 1722–1737.Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,

H. (2009). J. Appl. Cryst. 42, 339–341.Dorset, D. (2005). Crystallography of the Polymethylene Chain, pp. 1–6. New

York: International Union of Crystallography and Oxford University Press.Getsis, A. & Mudring, A.-V. (2009). Z. Anorg. Allg. Chem. 635, 2214–2221.Kawahata, M., Endo, T., Seki, H., Nishikawa, K. & Yamaguchi, K. (2009).

Chem. Lett. 38, 1136–1137.Lemmerer, A. & Billing, D. G. (2006). Acta Cryst. E62, o1954–o1956.Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P.,

Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood,P. A. (2008). J. Appl. Cryst. 41, 466–470.

Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. OxfordDiffraction Ltd, Abingdon, Oxfordshire, England.

Rademeyer, M. (2006). Acta Cryst. E62, o5767–o5769.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Spek, A. L. (2009). Acta Cryst. D65, 148–155.Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

organic compounds

528 Charmaine Arderne � C5H16N22+�2Br� Acta Cryst. (2013). C69, 526–528

Table 2Hydrogen-bond geometry (A, �).

D—H� � �A D—H H� � �A D� � �A D—H� � �A

N1A—H1AA� � �Br5 0.91 2.47 3.318 (3) 154N1A—H1AB� � �Br1 0.91 2.55 3.310 (3) 141N1A—H1AC� � �Br1i 0.91 2.53 3.352 (3) 151N2A—H2AA� � �Br2 0.91 2.49 3.351 (3) 159N2A—H2AB� � �Br1ii 0.91 2.51 3.403 (3) 167N2A—H2AC� � �Br3 0.91 2.39 3.284 (3) 166N1B—H1BA� � �Br2iii 0.91 2.75 3.553 (3) 148N1B—H1BB� � �Br3iii 0.91 2.41 3.280 (2) 161N1B—H1BC� � �Br1i 0.91 2.46 3.369 (3) 179N2B—H2BA� � �Br4 0.91 2.49 3.361 (3) 161N2B—H2BB� � �Br4iv 0.91 2.84 3.618 (3) 144N2B—H2BC� � �Br6 0.91 2.44 3.351 (3) 175N1CB—H1CA� � �Br4v 0.91 2.50 3.37 (2) 161N1CB—H1CB� � �Br2i 0.91 3.04 3.52 (2) 115N1CB—H1CB� � �Br4vi 0.91 2.62 3.29 (3) 131N1CB—H1CC� � �Br2 0.91 2.53 3.40 (3) 160N2CB—H2CA� � �Br6 0.91 2.64 3.41 (3) 142N2CB—H2CB� � �Br5 0.91 2.50 3.26 (2) 142N2CB—H2CC� � �Br5i 0.91 2.43 3.29 (3) 159N1CA—H1CF� � �Br4vi 0.91 2.63 3.34 (2) 136N1CA—H1CG� � �Br2i 0.91 2.33 3.22 (2) 167N1CA—H1CH� � �Br2 0.91 2.38 3.25 (2) 160N2CA—H2CF� � �Br6 0.91 2.39 3.29 (2) 172N2CA—H2CG� � �Br5 0.91 2.62 3.361 (18) 139N2CA—H2CH� � �Br5i 0.91 2.95 3.41 (2) 113N2CA—H2CH� � �Br6i 0.91 2.62 3.37 (2) 141

Symmetry codes: (i) x� 1; y; z; (ii) �xþ 2; y� 12;�zþ 3

2; (iii) x; yþ 1; z; (iv)�xþ 2;�yþ 2;�zþ 1; (v) �xþ 2;�yþ 1;�zþ 1; (vi) �xþ 1;�yþ 1;�zþ 1.

supplementary materials

sup-1Acta Cryst. (2013). C69, 526-528

supplementary materials

Acta Cryst. (2013). C69, 526-528 [doi:10.1107/S0108270113007762]

Pentane-1,5-diaminium dibromide

Charmaine Arderne

Pentane-1,5-diaminium dibromide

Crystal data

C5H16N22+·2Br−

Mr = 264.02Monoclinic, P21/ca = 4.5971 (3) Åb = 15.4607 (11) Åc = 41.389 (3) Åβ = 90.310 (5)°V = 2941.7 (4) Å3

Z = 12

F(000) = 1560Dx = 1.788 Mg m−3

Mo Kα radiation, λ = 0.71073 ÅCell parameters from 8965 reflectionsθ = 3.9–28.0°µ = 8.20 mm−1

T = 150 KFlat plate, colourless0.26 × 0.15 × 0.08 mm

Data collection

Oxford Xcalibur2 diffractometer

Radiation source: fine-focus sealed tubeGraphite monochromatorDetector resolution: 8.4190 pixels mm-1

φ and ω scansAbsorption correction: multi-scan

(CrysAlis RED; Oxford Diffraction, 2006)Tmin = 0.225, Tmax = 0.546

17961 measured reflections6280 independent reflections4223 reflections with I > 2σ(I)Rint = 0.038θmax = 27.0°, θmin = 3.9.939°h = −4→5k = −18→19l = −47→52

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.030wR(F2) = 0.049S = 0.896280 reflections316 parameters298 restraintsPrimary atom site location: structure-invariant

direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrainedw = 1/[σ2(Fo

2) + (0.0187P)2], where P = (Fo

2 + 2Fc2)/3

(Δ/σ)max = 0.003Δρmax = 0.72 e Å−3

Δρmin = −0.60 e Å−3

Special details

Experimental. Absorption correction: CrysAlis RED, (Oxford Diffraction, 2006), Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (Blessing, 1995).Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

supplementary materials

sup-2Acta Cryst. (2013). C69, 526-528

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.The crystal structure was refined in OLEX2 (Dolomanov et. al., 2009) as follows:1. Fixed Uiso At 1.2 times of: {H1AA,H1AB,H1AC} of N1A, {H4CC,H4CD} of C4CA, {H5CA,H5CB} of C5CA, {H3CC, H3CD} of C3CA, {H3BA,H3BB} of C3B, {H2AA,H2AB,H2AC} of N2A, {H1AD,H1AE} of C1A, {H2AD,H2AE} of C2A, {H1BA,H1BB,H1BC} of N1B, {H5AA,H5AB} of C5A, {H2BA, H2BB,H2BC} of N2B, {H2BD,H2BE} of C2B, {H3AA,H3AB} of C3A, {H1BD,H1BE} of C1B, {H4AA,H4AB} of C4A, {H5CC,H5CD} of C5CB, {H4CA,H4CB} of C4CB, {H3CA,H3CB} of C3CB, {H1CF,H1CG,H1CH} of N1CA, {H2CD,H2CE} of C2CB, {H1CI,H1CJ} of C1CA, {H2CI,H2CJ} of C2CA, {H2CF,H2CG,H2CH} of N2CA, {H1CA,H1CB,H1CC} of N1CB, {H2CA,H2CB,H2CC} of N2CB, {H1CD,H1CE} of C1CB, {H4BA,H4BB} of C4B, {H5BA, H5BB} of C5B2. Restrained distances N1CA-C1CA, N1CB-C1CB, N2CB-C5CA, N2CA-C5CB with sigma of 0.013. Rigid bond restraints N2CB, N2CA, C5CB, C5CA, C4CB, C4CA, C2CB, C3CB, C2CA, C3CA, C1CB, C1CA, N1CB, N1CA with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.014. Uiso/Uaniso restraints and constraints N2CB, N2CA, C5CB, C5CA, C4CB, C4CA, C3CB, C3CA, C2CB, C2CA, C1CB, C1CA, N1CB N1CA: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 Uanis(N1CB) Ueq, Uanis(C1CB) Ueq, Uanis(C2CB) Ueq, Uanis(C3CB) Ueq, Uanis(C4CB) Ueq, Uanis(C5CB) Ueq, Uanis(N1CA) Ueq, Uanis(N2CA) Ueq, Uanis(C1CA) Ueq, Uanis(C2CA) Ueq, Uanis(C3CA) Ueq, Uanis(C4CA) Ueq, Uanis(C5CA) Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01 Uanis(N2CB) Ueq: with sigma of 0.0025 and sigma for terminal atoms of 0.0055. Others 1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1- Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1- Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1- Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=Sof(N1CA)=Sof(H1CF)= Sof(H1CG)=Sof(H1CH)=Sof(N2CA)=Sof(H2CF)=Sof(H2CG)=Sof(H2CH)=Sof(C1CA)= Sof(H1CI)=Sof(H1CJ)=Sof(C2CA)=Sof(H2CI)=Sof(H2CJ)=Sof(C3CA)=Sof(H3CC)= Sof(H3CD)=Sof(C4CA)=Sof(H4CC)=Sof(H4CD)=Sof(C5CA)=Sof(H5CA)=Sof(H5CB)6.a Secondary CH2 refined with riding coordinates: C1A(H1AD,H1AE), C2A(H2AD,H2AE), C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA, H5AB), C1B(H1BD,H1BE), C2B(H2BD,H2BE), C3B(H3BA,H3BB), C4B(H4BA,H4BB), C5B(H5BA,H5BB), C1CB(H1CD,H1CE), C2CB(H2CD,H2CE), C3CB(H3CA,H3CB), C4CB(H4CA, H4CB), C5CB(H5CC,H5CD), C1CA(H1CI,H1CJ), C2CA(H2CI,H2CJ), C3CA(H3CC,H3CD), C4CA(H4CC,H4CD), C5CA(H5CA,H5CB)6.b Idealised Me refined as rotating group: N1A(H1AA,H1AB,H1AC), N2A(H2AA,H2AB,H2AC), N1B(H1BA,H1BB,H1BC), N2B(H2BA,H2BB, H2BC), N1CB(H1CA,H1CB,H1CC), N2CB(H2CA,H2CB,H2CC), N1CA(H1CF,H1CG,H1CH), N2CA(H2CF,H2CG,H2CH)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq Occ. (<1)

Br1 1.47772 (7) 0.75787 (2) 0.71013 (2) 0.02154 (9)Br2 0.59461 (7) 0.12633 (3) 0.64898 (2) 0.02762 (10)Br3 1.33274 (7) 0.02700 (2) 0.73833 (2) 0.01994 (9)Br4 1.37893 (7) 0.92942 (2) 0.45899 (2) 0.02096 (9)Br5 0.51019 (7) 0.64105 (3) 0.61085 (2) 0.02760 (10)Br6 0.49897 (8) 0.68026 (3) 0.50448 (2) 0.03657 (12)N1A 0.9825 (5) 0.64060 (18) 0.67175 (7) 0.0237 (7)H1AA 0.9066 0.6354 0.6515 0.028*H1AB 1.1168 0.6839 0.6720 0.028*H1AC 0.8377 0.6531 0.6859 0.028*

supplementary materials

sup-3Acta Cryst. (2013). C69, 526-528

N2A 0.8478 (5) 0.17742 (18) 0.72262 (6) 0.0194 (7)H2AA 0.7345 0.1600 0.7057 0.023*H2AB 0.7327 0.1963 0.7390 0.023*H2AC 0.9580 0.1322 0.7296 0.023*C1A 1.1242 (6) 0.5577 (2) 0.68127 (8) 0.0197 (8)H1AD 1.2047 0.5636 0.7034 0.024*H1AE 1.2884 0.5462 0.6665 0.024*C2A 0.9181 (6) 0.4814 (2) 0.68041 (8) 0.0181 (8)H2AD 0.8495 0.4715 0.6580 0.022*H2AE 0.7466 0.4936 0.6940 0.022*C3A 1.0739 (7) 0.4013 (2) 0.69283 (8) 0.0203 (8)H3AA 1.2155 0.3820 0.6764 0.024*H3AB 1.1842 0.4166 0.7126 0.024*C4A 0.8703 (6) 0.3270 (2) 0.70043 (8) 0.0195 (8)H4AA 0.7574 0.3116 0.6808 0.023*H4AB 0.7315 0.3451 0.7173 0.023*C5A 1.0406 (6) 0.2487 (2) 0.71204 (8) 0.0195 (8)H5AA 1.1664 0.2278 0.6943 0.023*H5AB 1.1681 0.2660 0.7303 0.023*N1B 0.8432 (5) 0.93923 (18) 0.69062 (6) 0.0201 (7)H1BA 0.7166 0.9827 0.6858 0.024*H1BB 0.9589 0.9555 0.7075 0.024*H1BC 0.7420 0.8909 0.6961 0.024*N2B 0.8828 (5) 0.86320 (19) 0.51298 (6) 0.0250 (7)H2BA 1.0029 0.8692 0.4957 0.030*H2BB 0.7509 0.9071 0.5130 0.030*H2BC 0.7877 0.8117 0.5116 0.030*C1B 1.0274 (6) 0.9206 (2) 0.66181 (7) 0.0180 (8)H1BD 1.1725 0.8758 0.6675 0.022*H1BE 1.1343 0.9737 0.6557 0.022*C2B 0.8487 (6) 0.8899 (2) 0.63327 (7) 0.0174 (8)H2BD 0.6929 0.9324 0.6286 0.021*H2BE 0.7557 0.8340 0.6386 0.021*C3B 1.0385 (6) 0.8789 (2) 0.60342 (7) 0.0199 (8)H3BA 1.1520 0.9326 0.6000 0.024*H3BB 1.1780 0.8312 0.6073 0.024*C4B 0.8654 (6) 0.8597 (2) 0.57326 (7) 0.0180 (8)H4BA 0.7024 0.9012 0.5714 0.022*H4BB 0.7821 0.8008 0.5748 0.022*C5B 1.0560 (6) 0.8658 (2) 0.54313 (7) 0.0198 (8)H5BA 1.1682 0.9205 0.5439 0.024*H5BB 1.1965 0.8173 0.5431 0.024*N1CB 0.111 (6) 0.1629 (12) 0.5880 (7) 0.021 (4) 0.448 (10)H1CA 0.2378 0.1488 0.5720 0.025* 0.448 (10)H1CB −0.0398 0.1249 0.5879 0.025* 0.448 (10)H1CC 0.2046 0.1605 0.6074 0.025* 0.448 (10)N2CB 0.013 (5) 0.5938 (10) 0.5573 (6) 0.022 (5) 0.449 (8)H2CA 0.0573 0.6288 0.5403 0.026* 0.448 (10)H2CB 0.1778 0.5809 0.5685 0.026* 0.448 (10)

supplementary materials

sup-4Acta Cryst. (2013). C69, 526-528

H2CC −0.1148 0.6214 0.5705 0.026* 0.448 (10)C1CB −0.001 (3) 0.2523 (11) 0.5826 (5) 0.025 (3) 0.448 (10)H1CD −0.1828 0.2600 0.5950 0.030* 0.448 (10)H1CE −0.0493 0.2594 0.5594 0.030* 0.448 (10)C2CB 0.212 (3) 0.3211 (10) 0.5923 (4) 0.024 (3) 0.448 (10)H2CD 0.3920 0.3150 0.5796 0.029* 0.448 (10)H2CE 0.2624 0.3143 0.6155 0.029* 0.448 (10)C3CB 0.076 (3) 0.4131 (13) 0.5865 (5) 0.033 (4) 0.448 (10)H3CA −0.1240 0.4141 0.5953 0.039* 0.448 (10)H3CB 0.1921 0.4566 0.5984 0.039* 0.448 (10)C4CB 0.065 (2) 0.4380 (7) 0.5513 (3) 0.027 (2) 0.448 (10)H4CA 0.2641 0.4514 0.5439 0.032* 0.448 (10)H4CB −0.0072 0.3881 0.5386 0.032* 0.448 (10)C5CB −0.008 (3) 0.5031 (8) 0.5428 (3) 0.020 (3) 0.449 (8)H5CC 0.1798 0.4879 0.5327 0.024* 0.448 (10)H5CD −0.1577 0.5006 0.5256 0.024* 0.448 (10)N1CA 0.087 (4) 0.1535 (10) 0.5948 (6) 0.024 (4) 0.552 (10)H1CF 0.0550 0.1120 0.5796 0.029* 0.552 (10)H1CG −0.0627 0.1541 0.6091 0.029* 0.552 (10)H1CH 0.2562 0.1418 0.6056 0.029* 0.552 (10)N2CA 0.014 (5) 0.5954 (9) 0.5533 (5) 0.036 (5) 0.552 (10)H2CF 0.1525 0.6228 0.5414 0.043* 0.552 (10)H2CG 0.0647 0.5976 0.5746 0.043* 0.552 (10)H2CH −0.1602 0.6220 0.5504 0.043* 0.552 (10)C1CA 0.110 (2) 0.2399 (9) 0.5788 (4) 0.024 (3) 0.552 (10)H1CI −0.0614 0.2485 0.5645 0.029* 0.552 (10)H1CJ 0.2858 0.2411 0.5651 0.029* 0.552 (10)C2CA 0.125 (3) 0.3125 (8) 0.6027 (3) 0.028 (3) 0.552 (10)H2CI 0.2840 0.3007 0.6184 0.034* 0.552 (10)H2CJ −0.0595 0.3150 0.6149 0.034* 0.552 (10)C3CA 0.179 (2) 0.4006 (9) 0.5866 (4) 0.020 (3) 0.552 (10)H3CC 0.2246 0.4441 0.6034 0.024* 0.552 (10)H3CD 0.3502 0.3961 0.5722 0.024* 0.552 (10)C4CA −0.079 (2) 0.4303 (5) 0.5673 (2) 0.034 (2) 0.552 (10)H4CC −0.2302 0.4513 0.5823 0.040* 0.552 (10)H4CD −0.1604 0.3803 0.5554 0.040* 0.552 (10)C5CA −0.122 (2) 0.5124 (6) 0.5450 (2) 0.030 (2) 0.552 (10)H5CA −0.3122 0.5036 0.5555 0.036* 0.552 (10)H5CB −0.1561 0.5176 0.5214 0.036* 0.552 (10)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Br1 0.02310 (18) 0.0219 (2) 0.0196 (2) −0.00424 (16) −0.00119 (15) 0.00108 (17)Br2 0.0354 (2) 0.0298 (3) 0.0177 (2) −0.00330 (18) −0.00635 (16) 0.00320 (18)Br3 0.01884 (17) 0.0231 (2) 0.0179 (2) −0.00097 (16) −0.00081 (14) 0.00046 (17)Br4 0.01968 (18) 0.0250 (2) 0.0182 (2) −0.00122 (16) −0.00010 (14) 0.00041 (17)Br5 0.02360 (19) 0.0393 (3) 0.0200 (2) −0.00110 (18) 0.00088 (15) 0.00088 (18)Br6 0.0310 (2) 0.0537 (3) 0.0250 (2) −0.0188 (2) −0.00533 (17) 0.0109 (2)

supplementary materials

sup-5Acta Cryst. (2013). C69, 526-528

N1A 0.0173 (15) 0.021 (2) 0.0327 (19) −0.0016 (14) −0.0035 (13) −0.0032 (15)N2A 0.0184 (15) 0.0182 (19) 0.0216 (17) 0.0022 (13) −0.0008 (12) 0.0007 (14)C1A 0.0173 (18) 0.018 (2) 0.023 (2) 0.0041 (16) −0.0005 (15) 0.0023 (17)C2A 0.0179 (17) 0.019 (2) 0.017 (2) 0.0010 (16) 0.0019 (14) 0.0002 (16)C3A 0.0191 (18) 0.018 (2) 0.024 (2) 0.0018 (16) 0.0003 (15) 0.0023 (17)C4A 0.0169 (18) 0.020 (2) 0.022 (2) −0.0002 (16) −0.0030 (15) −0.0002 (17)C5A 0.0189 (18) 0.022 (2) 0.018 (2) −0.0033 (17) −0.0011 (15) 0.0012 (17)N1B 0.0222 (15) 0.0202 (19) 0.0180 (17) −0.0070 (13) −0.0013 (12) −0.0020 (14)N2B 0.0219 (15) 0.041 (2) 0.0118 (16) −0.0069 (15) 0.0018 (12) 0.0034 (15)C1B 0.0159 (17) 0.022 (2) 0.0159 (19) 0.0012 (16) 0.0023 (14) 0.0008 (17)C2B 0.0196 (18) 0.021 (2) 0.0121 (19) 0.0011 (16) −0.0024 (14) 0.0011 (16)C3B 0.0169 (18) 0.028 (2) 0.015 (2) 0.0017 (16) −0.0006 (15) −0.0020 (17)C4B 0.0170 (17) 0.024 (2) 0.0129 (19) −0.0009 (16) −0.0019 (14) 0.0004 (16)C5B 0.0152 (17) 0.025 (2) 0.019 (2) 0.0015 (16) −0.0044 (15) −0.0040 (17)N1CB 0.018 (6) 0.029 (7) 0.016 (8) −0.009 (6) 0.005 (5) −0.014 (7)N2CB 0.014 (5) 0.030 (4) 0.018 (5) −0.006 (4) 0.010 (4) −0.003 (3)C1CB 0.019 (8) 0.031 (6) 0.025 (7) −0.003 (6) −0.001 (6) 0.005 (5)C2CB 0.015 (6) 0.025 (6) 0.032 (8) −0.002 (5) 0.002 (5) −0.006 (6)C3CB 0.028 (9) 0.031 (6) 0.039 (6) 0.000 (7) −0.003 (8) −0.006 (5)C4CB 0.026 (5) 0.032 (6) 0.021 (5) −0.003 (4) 0.006 (4) −0.007 (4)C5CB 0.019 (4) 0.026 (4) 0.018 (4) 0.004 (4) −0.003 (4) −0.001 (3)N1CA 0.013 (6) 0.022 (5) 0.037 (11) 0.001 (4) −0.006 (5) 0.004 (5)N2CA 0.021 (5) 0.062 (8) 0.026 (8) −0.012 (3) 0.012 (4) −0.010 (4)C1CA 0.021 (6) 0.028 (6) 0.025 (5) −0.006 (6) 0.001 (5) 0.005 (4)C2CA 0.025 (6) 0.028 (5) 0.032 (7) 0.000 (5) 0.000 (4) 0.004 (4)C3CA 0.020 (6) 0.020 (6) 0.019 (4) −0.002 (5) −0.007 (5) 0.002 (4)C4CA 0.031 (5) 0.039 (5) 0.031 (5) 0.010 (4) −0.008 (4) 0.003 (4)C5CA 0.031 (5) 0.037 (6) 0.023 (5) −0.012 (4) 0.009 (4) −0.004 (4)

Geometric parameters (Å, º)

N1A—H1AA 0.9100 N1CB—H1CA 0.9100N1A—H1AB 0.9100 N1CB—H1CB 0.9100N1A—H1AC 0.9100 N1CB—H1CC 0.9100N1A—C1A 1.490 (4) N1CB—C1CB 1.492 (8)N2A—H2AA 0.9100 N2CB—H2CA 0.9100N2A—H2AB 0.9100 N2CB—H2CB 0.9100N2A—H2AC 0.9100 N2CB—H2CC 0.9100N2A—C5A 1.482 (4) N2CB—C5CA 1.490 (8)C1A—H1AD 0.9900 C1CB—H1CD 0.9900C1A—H1AE 0.9900 C1CB—H1CE 0.9900C1A—C2A 1.514 (4) C1CB—C2CB 1.50 (2)C2A—H2AD 0.9900 C2CB—H2CD 0.9900C2A—H2AE 0.9900 C2CB—H2CE 0.9900C2A—C3A 1.519 (4) C2CB—C3CB 1.57 (2)C3A—H3AA 0.9900 C3CB—H3CA 0.9900C3A—H3AB 0.9900 C3CB—H3CB 0.9900C3A—C4A 1.515 (4) C3CB—C4CB 1.51 (2)C4A—H4AA 0.9900 C4CB—H4CA 0.9900C4A—H4AB 0.9900 C4CB—H4CB 0.9900

supplementary materials

sup-6Acta Cryst. (2013). C69, 526-528

C4A—C5A 1.518 (4) C4CB—C5CA 1.457 (13)C5A—H5AA 0.9900 C5CB—H5CC 0.9900C5A—H5AB 0.9900 C5CB—H5CD 0.9900N1B—H1BA 0.9100 C5CB—N2CA 1.494 (8)N1B—H1BB 0.9100 C5CB—C4CA 1.550 (14)N1B—H1BC 0.9100 N1CA—H1CF 0.9100N1B—C1B 1.494 (4) N1CA—H1CG 0.9100N2B—H2BA 0.9100 N1CA—H1CH 0.9100N2B—H2BB 0.9100 N1CA—C1CA 1.496 (8)N2B—H2BC 0.9100 N2CA—H2CF 0.9100N2B—C5B 1.477 (4) N2CA—H2CG 0.9100C1B—H1BD 0.9900 N2CA—H2CH 0.9100C1B—H1BE 0.9900 C1CA—H1CI 0.9900C1B—C2B 1.512 (4) C1CA—H1CJ 0.9900C2B—H2BD 0.9900 C1CA—C2CA 1.50 (2)C2B—H2BE 0.9900 C2CA—H2CI 0.9900C2B—C3B 1.526 (4) C2CA—H2CJ 0.9900C3B—H3BA 0.9900 C2CA—C3CA 1.538 (18)C3B—H3BB 0.9900 C3CA—H3CC 0.9900C3B—C4B 1.506 (4) C3CA—H3CD 0.9900C4B—H4BA 0.9900 C3CA—C4CA 1.500 (12)C4B—H4BB 0.9900 C4CA—H4CC 0.9900C4B—C5B 1.531 (4) C4CA—H4CD 0.9900C5B—H5BA 0.9900 C5CA—H5CA 0.9900C5B—H5BB 0.9900 C5CA—H5CB 0.9900

H1AA—N1A—H1AB 109.5 H1CA—N1CB—H1CB 109.5H1AA—N1A—H1AC 109.5 H1CA—N1CB—H1CC 109.5H1AB—N1A—H1AC 109.5 H1CB—N1CB—H1CC 109.5C1A—N1A—H1AA 109.5 C1CB—N1CB—H1CA 109.5C1A—N1A—H1AB 109.5 C1CB—N1CB—H1CB 109.5C1A—N1A—H1AC 109.5 C1CB—N1CB—H1CC 109.5H2AA—N2A—H2AB 109.5 H2CA—N2CB—H2CB 109.5H2AA—N2A—H2AC 109.5 H2CA—N2CB—H2CC 109.5H2AB—N2A—H2AC 109.5 H2CB—N2CB—H2CC 109.5C5A—N2A—H2AA 109.5 C5CA—N2CB—H2CA 109.5C5A—N2A—H2AB 109.5 C5CA—N2CB—H2CB 109.5C5A—N2A—H2AC 109.5 C5CA—N2CB—H2CC 109.5N1A—C1A—H1AD 109.0 N1CB—C1CB—H1CD 109.0N1A—C1A—H1AE 109.0 N1CB—C1CB—H1CE 109.0N1A—C1A—C2A 113.1 (2) N1CB—C1CB—C2CB 113.0 (16)H1AD—C1A—H1AE 107.8 H1CD—C1CB—H1CE 107.8C2A—C1A—H1AD 109.0 C2CB—C1CB—H1CD 109.0C2A—C1A—H1AE 109.0 C2CB—C1CB—H1CE 109.0C1A—C2A—H2AD 109.8 C1CB—C2CB—H2CD 109.6C1A—C2A—H2AE 109.8 C1CB—C2CB—H2CE 109.6C1A—C2A—C3A 109.5 (2) C1CB—C2CB—C3CB 110.1 (13)H2AD—C2A—H2AE 108.2 H2CD—C2CB—H2CE 108.2C3A—C2A—H2AD 109.8 C3CB—C2CB—H2CD 109.6

supplementary materials

sup-7Acta Cryst. (2013). C69, 526-528

C3A—C2A—H2AE 109.8 C3CB—C2CB—H2CE 109.6C2A—C3A—H3AA 108.9 C2CB—C3CB—H3CA 109.0C2A—C3A—H3AB 108.9 C2CB—C3CB—H3CB 109.0H3AA—C3A—H3AB 107.7 H3CA—C3CB—H3CB 107.8C4A—C3A—C2A 113.4 (3) C4CB—C3CB—C2CB 113.1 (15)C4A—C3A—H3AA 108.9 C4CB—C3CB—H3CA 109.0C4A—C3A—H3AB 108.9 C4CB—C3CB—H3CB 109.0C3A—C4A—H4AA 109.5 C3CB—C4CB—H4CA 108.9C3A—C4A—H4AB 109.5 C3CB—C4CB—H4CB 108.9C3A—C4A—C5A 110.6 (3) H4CA—C4CB—H4CB 107.8H4AA—C4A—H4AB 108.1 C5CA—C4CB—C3CB 113.2 (11)C5A—C4A—H4AA 109.5 C5CA—C4CB—H4CA 108.9C5A—C4A—H4AB 109.5 C5CA—C4CB—H4CB 108.9N2A—C5A—C4A 112.2 (2) H5CC—C5CB—H5CD 106.8N2A—C5A—H5AA 109.2 N2CA—C5CB—H5CC 107.0N2A—C5A—H5AB 109.2 N2CA—C5CB—H5CD 107.0C4A—C5A—H5AA 109.2 N2CA—C5CB—C4CA 121.2 (12)C4A—C5A—H5AB 109.2 C4CA—C5CB—H5CC 107.0H5AA—C5A—H5AB 107.9 C4CA—C5CB—H5CD 107.0H1BA—N1B—H1BB 109.5 H1CF—N1CA—H1CG 109.5H1BA—N1B—H1BC 109.5 H1CF—N1CA—H1CH 109.5H1BB—N1B—H1BC 109.5 H1CG—N1CA—H1CH 109.5C1B—N1B—H1BA 109.5 C1CA—N1CA—H1CF 109.5C1B—N1B—H1BB 109.5 C1CA—N1CA—H1CG 109.5C1B—N1B—H1BC 109.5 C1CA—N1CA—H1CH 109.5H2BA—N2B—H2BB 109.5 C5CB—N2CA—H2CF 109.5H2BA—N2B—H2BC 109.5 C5CB—N2CA—H2CG 109.5H2BB—N2B—H2BC 109.5 C5CB—N2CA—H2CH 109.5C5B—N2B—H2BA 109.5 H2CF—N2CA—H2CG 109.5C5B—N2B—H2BB 109.5 H2CF—N2CA—H2CH 109.5C5B—N2B—H2BC 109.5 H2CG—N2CA—H2CH 109.5N1B—C1B—H1BD 109.2 N1CA—C1CA—H1CI 109.2N1B—C1B—H1BE 109.2 N1CA—C1CA—H1CJ 109.2N1B—C1B—C2B 112.1 (2) N1CA—C1CA—C2CA 112.2 (14)H1BD—C1B—H1BE 107.9 H1CI—C1CA—H1CJ 107.9C2B—C1B—H1BD 109.2 C2CA—C1CA—H1CI 109.2C2B—C1B—H1BE 109.2 C2CA—C1CA—H1CJ 109.2C1B—C2B—H2BD 109.5 C1CA—C2CA—H2CI 109.1C1B—C2B—H2BE 109.5 C1CA—C2CA—H2CJ 109.1C1B—C2B—C3B 110.9 (2) C1CA—C2CA—C3CA 112.5 (11)H2BD—C2B—H2BE 108.0 H2CI—C2CA—H2CJ 107.8C3B—C2B—H2BD 109.5 C3CA—C2CA—H2CI 109.1C3B—C2B—H2BE 109.5 C3CA—C2CA—H2CJ 109.1C2B—C3B—H3BA 109.0 C2CA—C3CA—H3CC 109.2C2B—C3B—H3BB 109.0 C2CA—C3CA—H3CD 109.2H3BA—C3B—H3BB 107.8 H3CC—C3CA—H3CD 107.9C4B—C3B—C2B 113.0 (2) C4CA—C3CA—C2CA 111.9 (11)C4B—C3B—H3BA 109.0 C4CA—C3CA—H3CC 109.2C4B—C3B—H3BB 109.0 C4CA—C3CA—H3CD 109.2

supplementary materials

sup-8Acta Cryst. (2013). C69, 526-528

C3B—C4B—H4BA 109.4 C5CB—C4CA—H4CC 108.8C3B—C4B—H4BB 109.4 C5CB—C4CA—H4CD 108.8C3B—C4B—C5B 111.1 (2) C3CA—C4CA—C5CB 113.6 (9)H4BA—C4B—H4BB 108.0 C3CA—C4CA—H4CC 108.8C5B—C4B—H4BA 109.4 C3CA—C4CA—H4CD 108.8C5B—C4B—H4BB 109.4 H4CC—C4CA—H4CD 107.7N2B—C5B—C4B 112.2 (2) N2CB—C5CA—H5CA 109.4N2B—C5B—H5BA 109.2 N2CB—C5CA—H5CB 109.4N2B—C5B—H5BB 109.2 C4CB—C5CA—N2CB 111.2 (12)C4B—C5B—H5BA 109.2 C4CB—C5CA—H5CA 109.4C4B—C5B—H5BB 109.2 C4CB—C5CA—H5CB 109.4H5BA—C5B—H5BB 107.9 H5CA—C5CA—H5CB 108.0

N1A—C1A—C2A—C3A −175.8 (3) N1CB—C1CB—C2CB—C3CB −178.9 (15)C1A—C2A—C3A—C4A 166.3 (3) C1CB—C2CB—C3CB—C4CB −74.4 (19)C2A—C3A—C4A—C5A 178.9 (3) C2CB—C3CB—C4CB—C5CA 165.9 (11)C3A—C4A—C5A—N2A 174.7 (3) C3CB—C4CB—C5CA—N2CB 71.7 (18)N1B—C1B—C2B—C3B 175.1 (3) N1CA—C1CA—C2CA—C3CA 174.2 (11)C1B—C2B—C3B—C4B −172.5 (3) N2CA—C5CB—C4CA—C3CA −81.0 (15)C2B—C3B—C4B—C5B 169.4 (3) C1CA—C2CA—C3CA—C4CA 69.5 (16)C3B—C4B—C5B—N2B −169.5 (3) C2CA—C3CA—C4CA—C5CB −163.0 (10)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1A—H1AA···Br5 0.91 2.47 3.318 (3) 154N1A—H1AB···Br1 0.91 2.55 3.310 (3) 141N1A—H1AC···Br1i 0.91 2.53 3.352 (3) 151N2A—H2AA···Br2 0.91 2.49 3.351 (3) 159N2A—H2AB···Br1ii 0.91 2.51 3.403 (3) 167N2A—H2AC···Br3 0.91 2.39 3.284 (3) 166N1B—H1BA···Br2iii 0.91 2.75 3.553 (3) 148N1B—H1BB···Br3iii 0.91 2.41 3.280 (2) 161N1B—H1BC···Br1i 0.91 2.46 3.369 (3) 179N2B—H2BA···Br4 0.91 2.49 3.361 (3) 161N2B—H2BB···Br4iv 0.91 2.84 3.618 (3) 144N2B—H2BC···Br6 0.91 2.44 3.351 (3) 175N1CB—H1CA···Br4v 0.91 2.50 3.37 (2) 161N1CB—H1CB···Br2i 0.91 3.04 3.52 (2) 115N1CB—H1CB···Br4vi 0.91 2.62 3.29 (3) 131N1CB—H1CC···Br2 0.91 2.53 3.40 (3) 160N2CB—H2CA···Br6 0.91 2.64 3.41 (3) 142N2CB—H2CB···Br5 0.91 2.50 3.26 (2) 142N2CB—H2CC···Br5i 0.91 2.43 3.29 (3) 159N1CA—H1CF···Br4vi 0.91 2.63 3.34 (2) 136N1CA—H1CG···Br2i 0.91 2.33 3.22 (2) 167N1CA—H1CH···Br2 0.91 2.38 3.25 (2) 160N2CA—H2CF···Br6 0.91 2.39 3.29 (2) 172N2CA—H2CG···Br5 0.91 2.62 3.361 (18) 139

supplementary materials

sup-9Acta Cryst. (2013). C69, 526-528

N2CA—H2CH···Br5i 0.91 2.95 3.41 (2) 113N2CA—H2CH···Br6i 0.91 2.62 3.37 (2) 141

Symmetry codes: (i) x−1, y, z; (ii) −x+2, y−1/2, −z+3/2; (iii) x, y+1, z; (iv) −x+2, −y+2, −z+1; (v) −x+2, −y+1, −z+1; (vi) −x+1, −y+1, −z+1.