modulation of the nuclearity of molecular mg(ii)solid-state … · 2019. 5. 16. · s1 . electronic...
TRANSCRIPT
S1
Electronic Supplementary Information
for
Modulation of the Nuclearity of Molecular Mg(II)-Phosphates: Solid-State
Structural Change Involving Coordinating Solvents
Biswajit Santra,a Ramakirushnan Suriya Narayanan,a Pankaj Kalita,b Debdeep Mandal,a Vivek Gupta,a Michael
Zimmer,c Volker Huch,c Vadapalli Chandrasekhar,*a,d David Scheschkewitz,*c Carola Schulzke*e and Anukul Jana*a
1. Content S1 2. General Considerations S2 3. Experimental Details S2 4. Crystallographic Details S6 5. Molecular Structures of Mg-Phosphate Monoesters S9 6. H-Bonded Molecular Structures of Mg-Phosphate Monoesters S10 7. H-Bonded Chemical Structures of Mg-Phosphate Monoesters S15 8. NMR Spectra S16 9. ESI-MS Data S23 10. FT-IR Data S26 11. CHN Data S30 12. References S31
aTata Institute of Fundamental Research Hyderabad, Gopanpally, Hyderabad-500107, Telangana, India E-mail: [email protected] bSchool of Chemical Sciences, National Institute of Science Education and Research, HBNI, Bhubaneswar-752050, India cKrupp-Chair of General and Inorganic Chemistry, Saarland University, 66123 Saarbrücken, Germany E-mail: [email protected] dDepartment of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India E-mail: [email protected] eInstitut für Biochemie, Universität Greifswald, Felix-Hausdorff-Straße 4, D-17487 Greifswald, Germany E-mail: [email protected]
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2019
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General Considerations
Crystallographic Details
Single crystal X-ray diffraction data of 2, 3, 4a, 4b, 5, 6, and 7 were collected at low temperature (120 K) using a Rigaku
diffractometer with graphite-monochromated molybdenum Kα radiation, λ = 0.71073 Å. Data integration and reduction were
processed with CrysAlisPro software.S2 An empirical absorption correction was applied to the collected reflections with SCALE3
ABSPACK integrated within CrysAlisPro. The structures were solved by direct methods using the SHELXTS3 program and refined
by full matrix least-squares method based on F2 by using the SHELXLS4 program through the Olex2S5 interface. All non-hydrogen-
atoms were refined with anisotropic displacement parameters. The hydrogen atoms (except those of water) were refined
isotropically on calculated positions using a riding model with their Uiso values constrained to 1.5 Ueq of their pivot atoms for
terminal sp3 carbon atoms and 1.2 times for the aromatic carbon atoms.
For 7, the water molecule was constraint with DFIX for O-H and H…H distances. For 2, the lattice solvent molecule present in
the structure is heavily disordered. The PLATON/SQUEEZES6 program was used to get rid of the respective electron density
entirely. This yielded a total of 161 electrons per unit cell and total void volume of 739 Å3 which corresponds to one DMF
molecule per formula. Further, two disorders were taken care of in this structure. One DMF is disordered completely over two
positions (flipped) with occupancies of 80% and 20% respectively. The two partially occupied molecules were constrained using
SAME/SIMU/DELU. The tBu group of one phosphate ligand is disordered over two positions, again with ca. 80% to 20%
occupancies. All atoms of the tBu group were constrained using SIMU/DELU. For 3, the presence of disordered lattice solvent
molecules resulted in large total void volume in the structure. The PLATON/SQUEEZES6 program was used to get rid of the
respective diffuse electron density which yielded in total 41 electrons per unit cell and total void volume of 1538 Å3. This would
fit a bit more than two waters per unit cell, i.e. 2/3 per formula. For 4a, the tBu group is disordered over two positions. This was
modelled with occupancies of ca. 82% and 18%. Restraints or constraints were not needed in this structure.
For 5, both the tBu groups are disordered, as is one phenyl substituent and the entire chloroform. The present four individual
disorders were treated with a combination of SAME/SIMU/DELU constraints or with SADI/SIMU/DELU constraints. There exists
further some electron density which did not make sense at all. The extra electron density was therefore again SQUEEZED.
For 6, SQUEEZE was used to get rid of electron density which could not be refined sufficiently well to result in chemically
reasonable ions or molecules. The SQUEEZE/PLATONS6 routine yielded in total 1849 electrons per unit cell and total void
volume of 5503 Å3. This would fit roughly 100 water molecules per unit cell which is a comparatively large value (these are
roughly fife water per Mg, in addition to the coordinated ones). Also, one of the tBu groups is disordered (ca. 76% vs. 24%,
treated with constraints: SADI/SIMU/DELU). This time it is disordered not by rotation but by a bend, which does not make much
sense chemically. It could be argued that this is due to the very high symmetry and slight deviations of the atom positions on
symmetry generated atoms and that it might be better to go to a space group with lower symmetry. All hydrogen atoms on the
coordinated and lattice water molecules were located but then constrained with respect to the O-H and H…H distances and
with respect to their displacement parameters which were made dependent on their parent oxygen atoms (1.5 times). The
hydrogen atoms on O18 are the most precarious ones. The O18 resides at a special crystallographic position and is ‘rotating’ by
90° so that the hydrogen atoms are in two different orientations with half occupancy each (all four generated from one H in the
asymmetric unit).
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All crystallographic data were deposited with the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge
CB21EZ, UK. These data can be obtained free of charge on quoting the depository number as listed in the crystallographic table
by FAX (+44-1223-336-033), email ([email protected]) or their web interface (at http://www.ccdc.cam.ac.uk). Crystal and
refinement data for compounds 2, 3, 4a, 4b, 5, 6, and 7 are in Table S1.
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Table S1. Crystal and refinement data for compounds 2, 3, 4a, 4b, 5, 6 and 7.
Compound 2 3 4a 4b 5 6 7
Code No aj0073 aj0008
aj0116 aj0120 aj0477 aj0270 aj0215
CCDC number 1866871 1866862
1866872 1866873 1866875 1866874 1866861
Empirical formula C168H188Mg4 N8O24P4
C252H318Mg6N12O54P6
C78H95Mg2N2O18P2 C41H50MgNO8P C158 H210 Cl6 Mg4N4O44P4
C288H354Cl2Mg9O77P8 C108H114Mg2N8O14P2
Fw 2924.37 4710.85 1459.11 740.10 3303.11 5585.14 1858.63
Temp. (K) 120.00(10) 120.00(10) 119(2) 120.(2) 148(2) K 120 .00(2) 120.(2)
Crystal system Monoclinic Trigonal Monoclinic Monoclinic Triclinic tetragonal Monoclinic
space group C2/c R-3 P21/c P21/n P-1 P4/n P21/n
a (Å) 29.9635(10) 35.8954(11) 31.610(6) 18.4495(10) 10.49570(10) 29.2437(5) 18.6977(5)
b (Å) 18.7967(5) 35.8954(11) 10.344(2) 10.4526(4) 20.6949(3) 29.2437(5) 13.5431(4)
c (Å) 32.9183(11) 17.7162(5) 23.225(5) 21.1252(10) 21.1795(3) 22.0280(5) 19.4511(6)
α (°) 90 90 90 90 87.4830(10) 90 90
β (°) 120.910(5) 90 91.52(3) 108.412(6) 76.5730(10) 90 104.515(3)
γ (°) 90 120 90 90 83.5070(10) 90 90
V (Å3) 15906.9(11) 19768.7(13) 7591(3) 3865.4(3) 4445.16(10) 18838.2(8) 4768.3(2)
Z 4 3 4 4 1 2 2
Dcalcd(Mg m−3) 1.221 1.187 1.277 1.272 1.234 0.985 1.295
μ (mm−1) 0.133 0.130 0.144 0.140 0.221 0.129 0.129
2θ range (°) 5.206 to 52.998 5.724 to 58.366 5.76 to 50.998 5.122 to 52.998 4.948 to 58.2 5.352 to 53 5.27 to 52.998
Reflections collected
75276 39891 26413 36715 100352 139116 51169
Independent reflections
16454 10049 12928 7984 20783 19503 9858
Data/ restraints/ parameters
16454 / 174 / 1030
10049/0/527 12928/99/1024 7984/0/504 20783 / 627 / 1254 19503 / 159 / 976 9858/3/619
GOF 1.039 1.038 1.214 1.074 1.090 1.031 1.036
R1[I0>2σ(I0)] 0.0540 0.0478 0.1476 0.0456 0.0412 0.0829 0.0412
wR2(all data) 0.1459 0.1115 0.3547 0.1159 0.1057 0.2124 0.0984
Largest diff. peak and hole (e Å−3 )
0.640 and -0.66
0.87 and -0.42 0.83 and -1.15 0.414 and -0.552 0.47 and -0.33 0.614 and -0.415 0.38 and -0.39
S5
Molecular Structures of Mg-Phosphate Monoesters
Figure S1. Molecular structure of 4b at the 50 % probability level. All H-atoms except those of water, two o-CHPh2, and p-tBu moieties were omitted for clarity reasons.
Figure S2. Molecular structures of tetranuclear Mg(II)-phosphate with the encapsulated chloride ion (top), mononuclear Mg(II)-phosphate (bottom left), and chloromagnesium cation (bottom right) as components of 6 at the 50 % probability level. All H-atoms except those on water, two o-CHPh2, and p- tBu moieties were omitted for clarity reasons.
S6
H-Bonded Molecular Structures of Mg-Phosphate Monoesters
Figure S4. open caged dodecanuclear water cluster inside the 3.
Figure S5. Icosahedral water cluster inside the 3 ring.
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Figure S6. Molecular structure of 3 with six non-coordinating water molecules.
Figure S7. Molecular structure of 3 with six non-coordinating water molecules where all the organic part of the ligands have been removed for clarity.
S8
Figure S8. Complete molecular structure of 6 comprising ring tetranuclear Mg-phosphate monoester, encapsulated chloride anion, Mg(II)-monochloride cation, and four mononuclear Mg-phosphate monoester.
Figure S9. H-bonded molecular structures of ring tetranuclear Mg-phosphate monoester with encapsulated chloride anion with the organic part of the ligand (left) and without the organic part of the ligand (right) of 6.
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Figure S10. Different view of H-bonded molecular structures of ring tetranuclear Mg-phosphate monoester with encapsulated chloride anion with the organic part of the ligand of 6.
Figure S11. H-bonded molecular structures of Mg(II)-monochloride cation stabilized by four mononuclear Mg-phosphate monoester of 6.
S10
Figure S12. Solid state pi-pi stacking interaction in complex 7 leading to 1D polymeric chain.
S11
H-Bonded Chemical Structures of Mg-Phosphate Monoesters
ArOP
OO
O
ArOPO
O
O
ArO
P
O
O
O
ArOP
Ow
OO
Mg
Mg
Mg
Mg
Od
Od
Ow
Od
Od
O
Ow
ArO
P O
O O
Mg
Mg
ArO P O
O
O
Od
Ow
Od Ow
Ow
Od
Od
Od
OdOd
Od
Ow
Ow
Ow
Ow
Ow
Ow
Ow
Ow
Ow
Ow
Ow
Ow
Scheme S1. H-bonded chemical structures of 3 (Od = DMF, Ow = water).
ArO P
O
O
O
ArOP
O
O
O
ArO
P OO
O
ArO
P
Ow1
O
O
MgMg
Mg
Mg
Ow1
Ow1
Ow1
Ow1
Ow3
O
Ow1
Mg
Mg
ArO
PO
OOOw1
Ow1
Ow2 Ow2
Ow3
Ow1
Ow1
Ow1
Ow1Ow3
Ow2
Ow2
Ow3
Ow1
Ow1
Ow1
Ow1
Cl
Ow2Cl
Ow3
Mg
ArO
PO
O
O
Ow2
Ow2
Ow2
Ow2Ow2
Mg
Ar
O
P
O
OO
Ow2
Ow2
Ow2
Ow2
Ow2
Mg
ArO
P O
O
O
Ow2
Ow2
Ow2 Ow2
Ow2
Ow2
Ow2
Ow2
Ow2
Ow2Ow2
Ow2
Ow2
Scheme S2. H-bonded chemical structures of 6, ring tetranuclear Mg-phosphate monoester with encapsulated chloride anion (left) and Mg(II)-monochloride cation stabilized by four mononuclear Mg-phosphate monoester (right) (Ow = water).
S12
NMR Spectra
Figure S12: 31P{1H} NMR spectrum of 2 in CDCl3 at room temperature.
Figure S13. CP-MAS 31P{1H} NMR spectrum of 2 at room temperature.
S13
Figure S14. 31P{1H} NMR spectrum of 3 in CDCl3 at room temperature.
Figure S15. CP-MAS 31P{1H} NMR spectrum of 3 at room temperature.
S14
Figure S16. 31P{1H} NMR spectrum of 4 in CDCl3 at room temperature.
Figure S17. 31P{1H} NMR spectrum of 4 in CDCl3 at room temperature.
S15
Figure S18. CP-MAS 31P{1H} NMR spectrum of 4 at room temperature.
Figure S19. 31P{1H} NMR spectrum of 5 in CDCl3 at room temperature.
S16
Figure S20. CP-MAS 31P{1H} NMR spectrum of 5 at room temperature.
Figure S21. 31P{1H} NMR spectrum of 6 in CDCl3 at room temperature.
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Figure S22. CP-MAS 31P{1H} NMR spectrum of 6 at room temperature.
Figure S23. 31P{1H} NMR spectrum of 7 in CDCl3 at room temperature.
S18
Figure S24. CP-MAS 31P{1H} NMR spectrum of 7 at room temperature.
S19
ESI-MS
Figure S25. ESI-MS of 3.
Figure S26. ESI-MS of 4.
S20
Figure S27. ESI-MS of 4.
Figure S28. ESI-MS of 5.
S21
Figure S29. ESI-MS of 6.
Figure S30. ESI-MS of 6.
S22
FT-IR Spectra
Figure S31. FT-IR spectrum of 2.
Figure S32. FT-IR spectrum of 3.
S23
Figure S33. FT-IR spectrum of 4a.
Figure S34. FT-IR spectrum of 4b.
S24
Figure S35. FT-IR spectrum of 5.
Figure S36. FT-IR spectrum of 6.
S25
Figure S37: FT-IR spectrum of 7.
S26
Elemental Analysis
Figure S59: CHN data for 3 (BS-271A, top), 2 (BS-299C, middle), 4b (BS-299M, middle), 7 (BS-298A, middle), 6 (BS-299BS, middle), 4a (BS-280A, bottom), 5 (BS-306, bottom).
S27
REFERENCES
S1 D. Mandal, B. Santra, P. Kalita, N. Chrysochos, A. Malakar, R. S. Narayanan, S. Biswas, C. Schulzke, V. Chandrasekhar and
A. Jana, Chemistry Select 2017, 2, 8898–8910.
S2 CrysAlisPro: Rigaku Oxford Diffraction (1995-2017). Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
S3 G. M. Sheldrick, Acta Cryst. 2015, A71, 3‒8.
S4 G. M. Sheldrick, Acta Cryst. 2015, C71, 3‒8.
S5 O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, J. Appl. Crystallogr. 2009, 42, 339‒341.
S6 A. L. Spek, J. Appl. Cryst., 2003, 36, 7‒13.