![](/logos/buttonlogos/cross.png)
![](/logos/buttonlogos/cross.png)
metal-organic compounds
Bis(tetramethylammonium) tetrachloridozincate(II), phase VI
aDepartment of Chemistry, University of Texas San Antonio, One UTSA Circle, San Antonio, TX 78249-0698, USA, and bDepartment of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Room 208, Norman, OK 73019-3051, USA
*Correspondence e-mail: ghezai.musie@utsa.edu
Phase VI of bis(tetramethylammonium) tetrachlorozincate(II), (C4H12N)2[ZnCl4], contains three formula units per Several short C—H⋯Cl contacts [2.70 (3) and 2.72 (4) Å] are observed, but they are believed to participate only in van der Waals interactions. The crystal studied exhibited inversion twinning.
Related literature
For related literature, see: Madariaga et al. (1987); Ruiz-Larrea et al. (1981
); Wiesner et al. (1967
); Zuñiga et al. (1989
); Zhang & Bordwell (1994
).
Experimental
Crystal data
|
|
Data collection: SMART (Bruker, 1998); cell SAINT (Bruker, 1998
); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000
); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536807065828/mg2041sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807065828/mg2041Isup2.hkl
Single crystals of bis(tetramethylammonium) tetrachlorozincate(II) were grown by slow diffusion of diethyl ether into a methanol solution of ZnCl2 and N(CH3)4OH in a 1:3 mole ratio over the course of three days.
The methyl H atoms were initially located by geometry. The H atoms were then refined with distances of 0.98 Å and Uiso(H) = 1.5Ueq(C), but each methyl group was allowed to rotate freely about its N—C bond.
The refined
indicated racemic in the sample.Bis(tetramethylammonium) tetrachlorozincate(II) undergoes five solid-solid phase transitions with decreasing temperature according to a calorimetric study by Ruiz-Larrea et al. (1981). The room temperature phase I crystallized in the
Pnma with a = 12.276 (2), b = 8.998 (2), and c = 15.541 (2) Å (Wiesner et al., 1967). Weak incommensurate lattice spots in phases II, III, and IV have shown that these two phases are small distortions of the room temperature phase (Madariaga et al., 1987). Similarly, phase V was found to be an incommensurately modulated structure related to phase I (Zuñiga et al., 1989).No evidence of
spots were observed in the frame data for phase VI. Short C—H···Cl contacts were observed, but because of the very large estimated pKa of 42 for the protons of the cations (Zhang & Bordwell, 1994), it is unlikely that any of these contacts are weak hydrogen bonds. There were three formula units in the of the cell (Fig. 1).For related literature, see: Madariaga et al. (1987); Ruiz-Larrea et al. (1981); Wiesner et al. (1967); Zuñiga et al. (1989); Zhang & Bordwell (1994).
Data collection: SMART (Bruker, 1998); cell
SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL (Sheldrick, 2000); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2000). ![]() | Fig. 1. View of the unique atoms showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. |
(C4H12N)2[ZnCl4] | F(000) = 2208 |
Mr = 355.46 | Dx = 1.442 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 6850 reflections |
a = 8.9114 (18) Å | θ = 2.5–28.2° |
b = 15.105 (3) Å | µ = 2.13 mm−1 |
c = 36.493 (7) Å | T = 100 K |
V = 4912.2 (17) Å3 | Plate, colourless |
Z = 12 | 0.36 × 0.24 × 0.04 mm |
Bruker APEX CCD diffractometer | 9616 independent reflections |
Radiation source: fine-focus sealed tube | 9039 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
\ scans | θmax = 26.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −10→10 |
Tmin = 0.512, Tmax = 0.918 | k = −18→18 |
32538 measured reflections | l = −44→45 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.055 | w = 1/[σ2(Fo2) + (0.022P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
9616 reflections | Δρmax = 0.43 e Å−3 |
407 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.611 (6) |
(C4H12N)2[ZnCl4] | V = 4912.2 (17) Å3 |
Mr = 355.46 | Z = 12 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.9114 (18) Å | µ = 2.13 mm−1 |
b = 15.105 (3) Å | T = 100 K |
c = 36.493 (7) Å | 0.36 × 0.24 × 0.04 mm |
Bruker APEX CCD diffractometer | 9616 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 9039 reflections with I > 2σ(I) |
Tmin = 0.512, Tmax = 0.918 | Rint = 0.038 |
32538 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.055 | Δρmax = 0.43 e Å−3 |
S = 1.00 | Δρmin = −0.29 e Å−3 |
9616 reflections | Absolute structure: Flack (1983) |
407 parameters | Absolute structure parameter: 0.611 (6) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1A | 0.22269 (3) | 0.833130 (18) | 0.249954 (7) | 0.01451 (7) | |
Cl1A | 0.27151 (7) | 0.83942 (4) | 0.311249 (16) | 0.01927 (14) | |
Cl2A | 0.42172 (7) | 0.89470 (4) | 0.220415 (17) | 0.02094 (15) | |
Cl3A | 0.01026 (7) | 0.91090 (4) | 0.236224 (17) | 0.02043 (14) | |
Cl4A | 0.18901 (8) | 0.69109 (4) | 0.231878 (17) | 0.02295 (15) | |
Zn1B | 0.80374 (3) | 0.648812 (18) | 0.085633 (7) | 0.01432 (7) | |
Cl1B | 0.78781 (7) | 0.67180 (4) | 0.024348 (16) | 0.01814 (13) | |
Cl2B | 0.99810 (7) | 0.55514 (4) | 0.098555 (17) | 0.01982 (15) | |
Cl3B | 0.58278 (8) | 0.59089 (4) | 0.106043 (18) | 0.02098 (15) | |
Cl4B | 0.84775 (8) | 0.77752 (4) | 0.115946 (17) | 0.01842 (14) | |
Zn1C | 0.27960 (3) | 0.148178 (18) | 0.084326 (7) | 0.01390 (7) | |
Cl1C | 0.30736 (7) | 0.14537 (4) | 0.145927 (16) | 0.01915 (14) | |
Cl2C | 0.32460 (8) | 0.28462 (4) | 0.060498 (18) | 0.02114 (15) | |
Cl3C | 0.44003 (8) | 0.04975 (4) | 0.057901 (18) | 0.02362 (16) | |
Cl4C | 0.04001 (7) | 0.10798 (4) | 0.069889 (17) | 0.02188 (15) | |
N1D | 0.7769 (2) | 0.34272 (13) | 0.04975 (5) | 0.0161 (5) | |
C1D | 0.7608 (3) | 0.34836 (17) | 0.09057 (6) | 0.0214 (6) | |
H1D1 | 0.6561 | 0.3374 | 0.0974 | 0.032* | |
H1D2 | 0.7906 | 0.4075 | 0.0989 | 0.032* | |
H1D3 | 0.8253 | 0.3039 | 0.1021 | 0.032* | |
C2D | 0.7222 (3) | 0.25421 (16) | 0.03673 (7) | 0.0222 (6) | |
H2D1 | 0.7274 | 0.2518 | 0.0099 | 0.033* | |
H2D2 | 0.6181 | 0.2455 | 0.0446 | 0.033* | |
H2D3 | 0.7854 | 0.2074 | 0.0471 | 0.033* | |
C3D | 0.6849 (3) | 0.41380 (17) | 0.03245 (7) | 0.0268 (7) | |
H3D1 | 0.6954 | 0.4106 | 0.0058 | 0.040* | |
H3D2 | 0.7197 | 0.4717 | 0.0411 | 0.040* | |
H3D3 | 0.5793 | 0.4058 | 0.0391 | 0.040* | |
C4D | 0.9376 (3) | 0.35435 (19) | 0.03958 (7) | 0.0248 (6) | |
H4D1 | 0.9967 | 0.3053 | 0.0496 | 0.037* | |
H4D2 | 0.9747 | 0.4104 | 0.0496 | 0.037* | |
H4D3 | 0.9473 | 0.3550 | 0.0128 | 0.037* | |
N1E | 0.2499 (2) | 0.40749 (14) | 0.17102 (5) | 0.0148 (5) | |
C1E | 0.1088 (3) | 0.36434 (17) | 0.15805 (8) | 0.0252 (7) | |
H1E1 | 0.0675 | 0.3979 | 0.1374 | 0.038* | |
H1E2 | 0.0355 | 0.3631 | 0.1781 | 0.038* | |
H1E3 | 0.1306 | 0.3037 | 0.1502 | 0.038* | |
C2E | 0.3602 (3) | 0.41315 (18) | 0.14052 (7) | 0.0278 (7) | |
H2E1 | 0.3172 | 0.4477 | 0.1204 | 0.042* | |
H2E2 | 0.3842 | 0.3534 | 0.1318 | 0.042* | |
H2E3 | 0.4520 | 0.4420 | 0.1493 | 0.042* | |
C3E | 0.2129 (3) | 0.49855 (16) | 0.18458 (7) | 0.0218 (6) | |
H3E1 | 0.3047 | 0.5277 | 0.1931 | 0.033* | |
H3E2 | 0.1412 | 0.4943 | 0.2049 | 0.033* | |
H3E3 | 0.1685 | 0.5332 | 0.1646 | 0.033* | |
C4E | 0.3153 (3) | 0.35468 (17) | 0.20164 (7) | 0.0233 (6) | |
H4E1 | 0.3432 | 0.2958 | 0.1926 | 0.035* | |
H4E2 | 0.2410 | 0.3487 | 0.2213 | 0.035* | |
H4E3 | 0.4046 | 0.3848 | 0.2111 | 0.035* | |
N1F | 0.2919 (3) | 0.82358 (13) | 0.11507 (5) | 0.0179 (5) | |
C1F | 0.2556 (3) | 0.74168 (17) | 0.13618 (8) | 0.0279 (7) | |
H1F1 | 0.2800 | 0.7508 | 0.1621 | 0.042* | |
H1F2 | 0.3146 | 0.6921 | 0.1266 | 0.042* | |
H1F3 | 0.1485 | 0.7284 | 0.1337 | 0.042* | |
C2F | 0.4559 (3) | 0.84202 (19) | 0.11789 (8) | 0.0283 (7) | |
H2F1 | 0.4800 | 0.8957 | 0.1040 | 0.042* | |
H2F2 | 0.5124 | 0.7919 | 0.1079 | 0.042* | |
H2F3 | 0.4831 | 0.8506 | 0.1437 | 0.042* | |
C3F | 0.2049 (3) | 0.89951 (17) | 0.13031 (8) | 0.0284 (7) | |
H3F1 | 0.0973 | 0.8864 | 0.1288 | 0.043* | |
H3F2 | 0.2269 | 0.9530 | 0.1161 | 0.043* | |
H3F3 | 0.2332 | 0.9089 | 0.1560 | 0.043* | |
C4F | 0.2506 (3) | 0.8116 (2) | 0.07569 (7) | 0.0379 (8) | |
H4F1 | 0.2741 | 0.8658 | 0.0621 | 0.057* | |
H4F2 | 0.1429 | 0.7992 | 0.0738 | 0.057* | |
H4F3 | 0.3075 | 0.7620 | 0.0654 | 0.057* | |
N1G | 0.7277 (2) | 0.63485 (14) | 0.21747 (5) | 0.0161 (5) | |
C1G | 0.5783 (3) | 0.5939 (2) | 0.21077 (8) | 0.0304 (7) | |
H1G1 | 0.5017 | 0.6258 | 0.2248 | 0.046* | |
H1G2 | 0.5805 | 0.5318 | 0.2185 | 0.046* | |
H1G3 | 0.5544 | 0.5973 | 0.1846 | 0.046* | |
C2G | 0.7243 (4) | 0.73057 (17) | 0.20696 (7) | 0.0286 (7) | |
H2G1 | 0.8219 | 0.7576 | 0.2122 | 0.043* | |
H2G2 | 0.6461 | 0.7610 | 0.2210 | 0.043* | |
H2G3 | 0.7026 | 0.7359 | 0.1807 | 0.043* | |
C3G | 0.8431 (3) | 0.58795 (18) | 0.19485 (7) | 0.0244 (7) | |
H3G1 | 0.8174 | 0.5935 | 0.1688 | 0.037* | |
H3G2 | 0.8456 | 0.5252 | 0.2017 | 0.037* | |
H3G3 | 0.9419 | 0.6145 | 0.1992 | 0.037* | |
C4G | 0.7650 (3) | 0.62664 (18) | 0.25733 (7) | 0.0249 (7) | |
H4G1 | 0.6886 | 0.6574 | 0.2719 | 0.037* | |
H4G2 | 0.8634 | 0.6532 | 0.2620 | 0.037* | |
H4G3 | 0.7673 | 0.5639 | 0.2642 | 0.037* | |
N1H | 0.2840 (2) | 0.56575 (13) | −0.00491 (5) | 0.0147 (5) | |
C1H | 0.2778 (3) | 0.46942 (16) | 0.00445 (7) | 0.0219 (6) | |
H1H1 | 0.2724 | 0.4624 | 0.0311 | 0.033* | |
H1H2 | 0.3682 | 0.4400 | −0.0048 | 0.033* | |
H1H3 | 0.1889 | 0.4428 | −0.0068 | 0.033* | |
C2H | 0.1461 (3) | 0.61057 (18) | 0.00861 (8) | 0.0264 (7) | |
H2H1 | 0.0579 | 0.5847 | −0.0033 | 0.040* | |
H2H2 | 0.1515 | 0.6739 | 0.0029 | 0.040* | |
H2H3 | 0.1381 | 0.6027 | 0.0352 | 0.040* | |
C3H | 0.2935 (3) | 0.57694 (17) | −0.04539 (6) | 0.0230 (6) | |
H3H1 | 0.3835 | 0.5470 | −0.0546 | 0.035* | |
H3H2 | 0.2988 | 0.6401 | −0.0513 | 0.035* | |
H3H3 | 0.2043 | 0.5510 | −0.0569 | 0.035* | |
C4H | 0.4208 (3) | 0.60584 (18) | 0.01198 (8) | 0.0301 (7) | |
H4H1 | 0.5105 | 0.5767 | 0.0022 | 0.045* | |
H4H2 | 0.4172 | 0.5980 | 0.0386 | 0.045* | |
H4H3 | 0.4244 | 0.6692 | 0.0062 | 0.045* | |
N1I | 0.7744 (2) | 1.07188 (13) | 0.16264 (5) | 0.0150 (5) | |
C1I | 0.9184 (3) | 1.11122 (17) | 0.17517 (7) | 0.0216 (6) | |
H1I1 | 0.9615 | 1.0744 | 0.1946 | 0.032* | |
H1I2 | 0.9002 | 1.1710 | 0.1846 | 0.032* | |
H1I3 | 0.9886 | 1.1143 | 0.1545 | 0.032* | |
C2I | 0.6673 (3) | 1.06734 (18) | 0.19391 (7) | 0.0260 (7) | |
H2I1 | 0.7082 | 1.0285 | 0.2130 | 0.039* | |
H2I2 | 0.5711 | 1.0437 | 0.1854 | 0.039* | |
H2I3 | 0.6523 | 1.1268 | 0.2040 | 0.039* | |
C3I | 0.8031 (4) | 0.98137 (16) | 0.14806 (7) | 0.0286 (7) | |
H3I1 | 0.8714 | 0.9851 | 0.1271 | 0.043* | |
H3I2 | 0.7081 | 0.9547 | 0.1403 | 0.043* | |
H3I3 | 0.8487 | 0.9448 | 0.1672 | 0.043* | |
C4I | 0.7082 (3) | 1.12811 (17) | 0.13312 (7) | 0.0233 (6) | |
H4I1 | 0.7788 | 1.1323 | 0.1126 | 0.035* | |
H4I2 | 0.6880 | 1.1875 | 0.1428 | 0.035* | |
H4I3 | 0.6142 | 1.1014 | 0.1246 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1A | 0.01419 (16) | 0.01415 (15) | 0.01521 (15) | 0.00001 (13) | 0.00065 (12) | 0.00035 (12) |
Cl1A | 0.0185 (3) | 0.0239 (3) | 0.0154 (3) | −0.0007 (3) | −0.0014 (3) | 0.0007 (3) |
Cl2A | 0.0165 (3) | 0.0255 (4) | 0.0209 (3) | −0.0037 (3) | 0.0028 (3) | 0.0024 (3) |
Cl3A | 0.0162 (3) | 0.0223 (3) | 0.0227 (3) | 0.0038 (3) | −0.0018 (3) | 0.0021 (3) |
Cl4A | 0.0318 (4) | 0.0155 (3) | 0.0215 (3) | −0.0028 (3) | −0.0004 (3) | −0.0019 (3) |
Zn1B | 0.01474 (15) | 0.01379 (14) | 0.01444 (14) | −0.00018 (13) | 0.00038 (13) | 0.00079 (12) |
Cl1B | 0.0189 (3) | 0.0207 (3) | 0.0149 (3) | 0.0009 (3) | −0.0001 (3) | 0.0016 (3) |
Cl2B | 0.0205 (4) | 0.0189 (3) | 0.0201 (3) | 0.0046 (3) | −0.0015 (3) | 0.0023 (3) |
Cl3B | 0.0177 (4) | 0.0240 (3) | 0.0212 (3) | −0.0048 (3) | 0.0029 (3) | 0.0013 (3) |
Cl4B | 0.0204 (4) | 0.0157 (3) | 0.0192 (3) | −0.0012 (3) | −0.0008 (3) | −0.0020 (3) |
Zn1C | 0.01250 (15) | 0.01516 (14) | 0.01404 (14) | 0.00037 (13) | 0.00063 (13) | −0.00004 (12) |
Cl1C | 0.0193 (3) | 0.0243 (3) | 0.0138 (3) | 0.0011 (3) | −0.0003 (3) | −0.0010 (3) |
Cl2C | 0.0212 (4) | 0.0187 (3) | 0.0235 (3) | −0.0020 (3) | −0.0005 (3) | 0.0038 (3) |
Cl3C | 0.0237 (4) | 0.0247 (4) | 0.0225 (3) | 0.0072 (3) | 0.0054 (3) | −0.0017 (3) |
Cl4C | 0.0145 (4) | 0.0288 (4) | 0.0224 (3) | −0.0039 (3) | −0.0024 (3) | −0.0007 (3) |
N1D | 0.0156 (11) | 0.0178 (11) | 0.0150 (11) | −0.0001 (10) | 0.0002 (9) | −0.0003 (9) |
C1D | 0.0268 (16) | 0.0229 (14) | 0.0146 (13) | −0.0023 (12) | 0.0036 (11) | −0.0007 (11) |
C2D | 0.0252 (16) | 0.0192 (14) | 0.0221 (15) | −0.0005 (13) | −0.0004 (13) | −0.0040 (11) |
C3D | 0.0293 (19) | 0.0248 (15) | 0.0262 (16) | 0.0108 (14) | −0.0038 (14) | 0.0033 (12) |
C4D | 0.0153 (15) | 0.0317 (16) | 0.0274 (15) | −0.0029 (13) | 0.0060 (12) | 0.0017 (13) |
N1E | 0.0126 (13) | 0.0169 (11) | 0.0150 (11) | 0.0003 (9) | 0.0010 (9) | −0.0013 (9) |
C1E | 0.0142 (15) | 0.0238 (15) | 0.0377 (17) | −0.0041 (12) | −0.0099 (13) | 0.0033 (13) |
C2E | 0.0288 (18) | 0.0265 (16) | 0.0280 (16) | −0.0022 (14) | 0.0104 (14) | −0.0014 (13) |
C3E | 0.0208 (16) | 0.0181 (14) | 0.0265 (15) | 0.0017 (13) | −0.0006 (13) | −0.0041 (12) |
C4E | 0.0224 (16) | 0.0277 (15) | 0.0200 (14) | 0.0081 (14) | −0.0014 (12) | 0.0011 (12) |
N1F | 0.0177 (12) | 0.0198 (11) | 0.0163 (11) | −0.0004 (11) | −0.0012 (10) | −0.0019 (9) |
C1F | 0.0236 (17) | 0.0210 (15) | 0.0392 (18) | 0.0014 (12) | 0.0038 (14) | 0.0097 (13) |
C2F | 0.0157 (15) | 0.0356 (17) | 0.0336 (16) | −0.0034 (14) | −0.0017 (12) | 0.0066 (14) |
C3F | 0.0269 (17) | 0.0231 (15) | 0.0352 (17) | 0.0040 (14) | −0.0053 (15) | −0.0052 (13) |
C4F | 0.035 (2) | 0.060 (2) | 0.0189 (16) | −0.0039 (16) | −0.0039 (13) | −0.0064 (15) |
N1G | 0.0156 (12) | 0.0180 (11) | 0.0146 (11) | 0.0013 (10) | −0.0001 (9) | 0.0000 (9) |
C1G | 0.0191 (16) | 0.0458 (19) | 0.0265 (16) | −0.0087 (15) | −0.0016 (13) | 0.0008 (14) |
C2G | 0.044 (2) | 0.0162 (14) | 0.0253 (16) | 0.0071 (14) | 0.0024 (15) | 0.0030 (12) |
C3G | 0.0211 (16) | 0.0253 (15) | 0.0269 (16) | 0.0051 (13) | 0.0043 (13) | −0.0059 (13) |
C4G | 0.0328 (18) | 0.0256 (15) | 0.0164 (14) | −0.0001 (13) | −0.0070 (12) | 0.0015 (12) |
N1H | 0.0152 (12) | 0.0142 (10) | 0.0148 (11) | −0.0031 (10) | −0.0011 (10) | 0.0020 (9) |
C1H | 0.0238 (16) | 0.0156 (13) | 0.0263 (15) | 0.0000 (13) | 0.0017 (13) | 0.0049 (11) |
C2H | 0.0246 (17) | 0.0232 (15) | 0.0313 (16) | 0.0063 (13) | 0.0131 (13) | −0.0006 (13) |
C3H | 0.0274 (17) | 0.0254 (15) | 0.0163 (13) | −0.0005 (14) | 0.0027 (13) | 0.0053 (11) |
C4H | 0.0286 (18) | 0.0240 (16) | 0.0377 (18) | −0.0052 (14) | −0.0139 (14) | 0.0024 (14) |
N1I | 0.0118 (11) | 0.0180 (11) | 0.0153 (11) | −0.0013 (9) | −0.0015 (9) | −0.0001 (9) |
C1I | 0.0171 (15) | 0.0231 (15) | 0.0246 (15) | −0.0039 (13) | −0.0024 (12) | −0.0027 (12) |
C2I | 0.0228 (17) | 0.0345 (17) | 0.0207 (15) | −0.0058 (14) | 0.0032 (13) | 0.0023 (13) |
C3I | 0.0325 (19) | 0.0198 (14) | 0.0336 (17) | 0.0005 (14) | −0.0048 (15) | −0.0094 (13) |
C4I | 0.0198 (15) | 0.0262 (15) | 0.0238 (14) | 0.0029 (13) | −0.0002 (13) | 0.0043 (12) |
Zn1A—Cl4A | 2.2645 (8) | C3F—H3F1 | 0.9800 |
Zn1A—Cl2A | 2.2743 (8) | C3F—H3F2 | 0.9800 |
Zn1A—Cl1A | 2.2807 (8) | C3F—H3F3 | 0.9800 |
Zn1A—Cl3A | 2.2836 (8) | C4F—H4F1 | 0.9800 |
Zn1B—Cl1B | 2.2677 (8) | C4F—H4F2 | 0.9800 |
Zn1B—Cl4B | 2.2709 (7) | C4F—H4F3 | 0.9800 |
Zn1B—Cl3B | 2.2797 (8) | N1G—C1G | 1.488 (3) |
Zn1B—Cl2B | 2.2857 (8) | N1G—C2G | 1.496 (3) |
Zn1C—Cl1C | 2.2620 (8) | N1G—C3G | 1.497 (3) |
Zn1C—Cl2C | 2.2726 (8) | N1G—C4G | 1.497 (3) |
Zn1C—Cl3C | 2.2770 (8) | C1G—H1G1 | 0.9800 |
Zn1C—Cl4C | 2.2814 (8) | C1G—H1G2 | 0.9800 |
N1D—C4D | 1.490 (3) | C1G—H1G3 | 0.9800 |
N1D—C3D | 1.491 (3) | C2G—H2G1 | 0.9800 |
N1D—C1D | 1.499 (3) | C2G—H2G2 | 0.9800 |
N1D—C2D | 1.500 (3) | C2G—H2G3 | 0.9800 |
C1D—H1D1 | 0.9800 | C3G—H3G1 | 0.9800 |
C1D—H1D2 | 0.9800 | C3G—H3G2 | 0.9800 |
C1D—H1D3 | 0.9800 | C3G—H3G3 | 0.9800 |
C2D—H2D1 | 0.9800 | C4G—H4G1 | 0.9800 |
C2D—H2D2 | 0.9800 | C4G—H4G2 | 0.9800 |
C2D—H2D3 | 0.9800 | C4G—H4G3 | 0.9800 |
C3D—H3D1 | 0.9800 | N1H—C2H | 1.487 (3) |
C3D—H3D2 | 0.9800 | N1H—C3H | 1.489 (3) |
C3D—H3D3 | 0.9800 | N1H—C4H | 1.494 (3) |
C4D—H4D1 | 0.9800 | N1H—C1H | 1.496 (3) |
C4D—H4D2 | 0.9800 | C1H—H1H1 | 0.9800 |
C4D—H4D3 | 0.9800 | C1H—H1H2 | 0.9800 |
N1E—C2E | 1.488 (3) | C1H—H1H3 | 0.9800 |
N1E—C4E | 1.491 (3) | C2H—H2H1 | 0.9800 |
N1E—C1E | 1.494 (3) | C2H—H2H2 | 0.9800 |
N1E—C3E | 1.498 (3) | C2H—H2H3 | 0.9800 |
C1E—H1E1 | 0.9800 | C3H—H3H1 | 0.9800 |
C1E—H1E2 | 0.9800 | C3H—H3H2 | 0.9800 |
C1E—H1E3 | 0.9800 | C3H—H3H3 | 0.9800 |
C2E—H2E1 | 0.9800 | C4H—H4H1 | 0.9800 |
C2E—H2E2 | 0.9800 | C4H—H4H2 | 0.9800 |
C2E—H2E3 | 0.9800 | C4H—H4H3 | 0.9800 |
C3E—H3E1 | 0.9800 | N1I—C1I | 1.486 (3) |
C3E—H3E2 | 0.9800 | N1I—C3I | 1.489 (3) |
C3E—H3E3 | 0.9800 | N1I—C2I | 1.490 (3) |
C4E—H4E1 | 0.9800 | N1I—C4I | 1.493 (3) |
C4E—H4E2 | 0.9800 | C1I—H1I1 | 0.9800 |
C4E—H4E3 | 0.9800 | C1I—H1I2 | 0.9800 |
N1F—C2F | 1.491 (3) | C1I—H1I3 | 0.9800 |
N1F—C3F | 1.492 (3) | C2I—H2I1 | 0.9800 |
N1F—C1F | 1.493 (3) | C2I—H2I2 | 0.9800 |
N1F—C4F | 1.494 (3) | C2I—H2I3 | 0.9800 |
C1F—H1F1 | 0.9800 | C3I—H3I1 | 0.9800 |
C1F—H1F2 | 0.9800 | C3I—H3I2 | 0.9800 |
C1F—H1F3 | 0.9800 | C3I—H3I3 | 0.9800 |
C2F—H2F1 | 0.9800 | C4I—H4I1 | 0.9800 |
C2F—H2F2 | 0.9800 | C4I—H4I2 | 0.9800 |
C2F—H2F3 | 0.9800 | C4I—H4I3 | 0.9800 |
Cl4A—Zn1A—Cl2A | 110.65 (3) | N1F—C3F—H3F3 | 109.5 |
Cl4A—Zn1A—Cl1A | 110.51 (3) | H3F1—C3F—H3F3 | 109.5 |
Cl2A—Zn1A—Cl1A | 107.40 (3) | H3F2—C3F—H3F3 | 109.5 |
Cl4A—Zn1A—Cl3A | 108.27 (3) | N1F—C4F—H4F1 | 109.5 |
Cl2A—Zn1A—Cl3A | 109.40 (3) | N1F—C4F—H4F2 | 109.5 |
Cl1A—Zn1A—Cl3A | 110.60 (3) | H4F1—C4F—H4F2 | 109.5 |
Cl1B—Zn1B—Cl4B | 111.11 (3) | N1F—C4F—H4F3 | 109.5 |
Cl1B—Zn1B—Cl3B | 109.08 (3) | H4F1—C4F—H4F3 | 109.5 |
Cl4B—Zn1B—Cl3B | 108.58 (3) | H4F2—C4F—H4F3 | 109.5 |
Cl1B—Zn1B—Cl2B | 110.23 (3) | C1G—N1G—C2G | 109.9 (2) |
Cl4B—Zn1B—Cl2B | 107.37 (3) | C1G—N1G—C3G | 109.1 (2) |
Cl3B—Zn1B—Cl2B | 110.46 (3) | C2G—N1G—C3G | 109.3 (2) |
Cl1C—Zn1C—Cl2C | 112.21 (3) | C1G—N1G—C4G | 108.9 (2) |
Cl1C—Zn1C—Cl3C | 109.88 (3) | C2G—N1G—C4G | 109.50 (19) |
Cl2C—Zn1C—Cl3C | 108.62 (3) | C3G—N1G—C4G | 110.1 (2) |
Cl1C—Zn1C—Cl4C | 109.08 (3) | N1G—C1G—H1G1 | 109.5 |
Cl2C—Zn1C—Cl4C | 108.55 (3) | N1G—C1G—H1G2 | 109.5 |
Cl3C—Zn1C—Cl4C | 108.42 (3) | H1G1—C1G—H1G2 | 109.5 |
C4D—N1D—C3D | 109.7 (2) | N1G—C1G—H1G3 | 109.5 |
C4D—N1D—C1D | 109.4 (2) | H1G1—C1G—H1G3 | 109.5 |
C3D—N1D—C1D | 109.11 (19) | H1G2—C1G—H1G3 | 109.5 |
C4D—N1D—C2D | 109.8 (2) | N1G—C2G—H2G1 | 109.5 |
C3D—N1D—C2D | 109.2 (2) | N1G—C2G—H2G2 | 109.5 |
C1D—N1D—C2D | 109.54 (19) | H2G1—C2G—H2G2 | 109.5 |
N1D—C1D—H1D1 | 109.5 | N1G—C2G—H2G3 | 109.5 |
N1D—C1D—H1D2 | 109.5 | H2G1—C2G—H2G3 | 109.5 |
H1D1—C1D—H1D2 | 109.5 | H2G2—C2G—H2G3 | 109.5 |
N1D—C1D—H1D3 | 109.5 | N1G—C3G—H3G1 | 109.5 |
H1D1—C1D—H1D3 | 109.5 | N1G—C3G—H3G2 | 109.5 |
H1D2—C1D—H1D3 | 109.5 | H3G1—C3G—H3G2 | 109.5 |
N1D—C2D—H2D1 | 109.5 | N1G—C3G—H3G3 | 109.5 |
N1D—C2D—H2D2 | 109.5 | H3G1—C3G—H3G3 | 109.5 |
H2D1—C2D—H2D2 | 109.5 | H3G2—C3G—H3G3 | 109.5 |
N1D—C2D—H2D3 | 109.5 | N1G—C4G—H4G1 | 109.5 |
H2D1—C2D—H2D3 | 109.5 | N1G—C4G—H4G2 | 109.5 |
H2D2—C2D—H2D3 | 109.5 | H4G1—C4G—H4G2 | 109.5 |
N1D—C3D—H3D1 | 109.5 | N1G—C4G—H4G3 | 109.5 |
N1D—C3D—H3D2 | 109.5 | H4G1—C4G—H4G3 | 109.5 |
H3D1—C3D—H3D2 | 109.5 | H4G2—C4G—H4G3 | 109.5 |
N1D—C3D—H3D3 | 109.5 | C2H—N1H—C3H | 108.9 (2) |
H3D1—C3D—H3D3 | 109.5 | C2H—N1H—C4H | 110.7 (2) |
H3D2—C3D—H3D3 | 109.5 | C3H—N1H—C4H | 108.5 (2) |
N1D—C4D—H4D1 | 109.5 | C2H—N1H—C1H | 109.7 (2) |
N1D—C4D—H4D2 | 109.5 | C3H—N1H—C1H | 109.81 (19) |
H4D1—C4D—H4D2 | 109.5 | C4H—N1H—C1H | 109.3 (2) |
N1D—C4D—H4D3 | 109.5 | N1H—C1H—H1H1 | 109.5 |
H4D1—C4D—H4D3 | 109.5 | N1H—C1H—H1H2 | 109.5 |
H4D2—C4D—H4D3 | 109.5 | H1H1—C1H—H1H2 | 109.5 |
C2E—N1E—C4E | 109.5 (2) | N1H—C1H—H1H3 | 109.5 |
C2E—N1E—C1E | 110.2 (2) | H1H1—C1H—H1H3 | 109.5 |
C4E—N1E—C1E | 109.4 (2) | H1H2—C1H—H1H3 | 109.5 |
C2E—N1E—C3E | 109.9 (2) | N1H—C2H—H2H1 | 109.5 |
C4E—N1E—C3E | 109.25 (19) | N1H—C2H—H2H2 | 109.5 |
C1E—N1E—C3E | 108.6 (2) | H2H1—C2H—H2H2 | 109.5 |
N1E—C1E—H1E1 | 109.5 | N1H—C2H—H2H3 | 109.5 |
N1E—C1E—H1E2 | 109.5 | H2H1—C2H—H2H3 | 109.5 |
H1E1—C1E—H1E2 | 109.5 | H2H2—C2H—H2H3 | 109.5 |
N1E—C1E—H1E3 | 109.5 | N1H—C3H—H3H1 | 109.5 |
H1E1—C1E—H1E3 | 109.5 | N1H—C3H—H3H2 | 109.5 |
H1E2—C1E—H1E3 | 109.5 | H3H1—C3H—H3H2 | 109.5 |
N1E—C2E—H2E1 | 109.5 | N1H—C3H—H3H3 | 109.5 |
N1E—C2E—H2E2 | 109.5 | H3H1—C3H—H3H3 | 109.5 |
H2E1—C2E—H2E2 | 109.5 | H3H2—C3H—H3H3 | 109.5 |
N1E—C2E—H2E3 | 109.5 | N1H—C4H—H4H1 | 109.5 |
H2E1—C2E—H2E3 | 109.5 | N1H—C4H—H4H2 | 109.5 |
H2E2—C2E—H2E3 | 109.5 | H4H1—C4H—H4H2 | 109.5 |
N1E—C3E—H3E1 | 109.5 | N1H—C4H—H4H3 | 109.5 |
N1E—C3E—H3E2 | 109.5 | H4H1—C4H—H4H3 | 109.5 |
H3E1—C3E—H3E2 | 109.5 | H4H2—C4H—H4H3 | 109.5 |
N1E—C3E—H3E3 | 109.5 | C1I—N1I—C3I | 109.2 (2) |
H3E1—C3E—H3E3 | 109.5 | C1I—N1I—C2I | 109.63 (19) |
H3E2—C3E—H3E3 | 109.5 | C3I—N1I—C2I | 110.0 (2) |
N1E—C4E—H4E1 | 109.5 | C1I—N1I—C4I | 109.6 (2) |
N1E—C4E—H4E2 | 109.5 | C3I—N1I—C4I | 109.4 (2) |
H4E1—C4E—H4E2 | 109.5 | C2I—N1I—C4I | 109.0 (2) |
N1E—C4E—H4E3 | 109.5 | N1I—C1I—H1I1 | 109.5 |
H4E1—C4E—H4E3 | 109.5 | N1I—C1I—H1I2 | 109.5 |
H4E2—C4E—H4E3 | 109.5 | H1I1—C1I—H1I2 | 109.5 |
C2F—N1F—C3F | 109.9 (2) | N1I—C1I—H1I3 | 109.5 |
C2F—N1F—C1F | 109.4 (2) | H1I1—C1I—H1I3 | 109.5 |
C3F—N1F—C1F | 109.4 (2) | H1I2—C1I—H1I3 | 109.5 |
C2F—N1F—C4F | 109.3 (2) | N1I—C2I—H2I1 | 109.5 |
C3F—N1F—C4F | 108.9 (2) | N1I—C2I—H2I2 | 109.5 |
C1F—N1F—C4F | 110.0 (2) | H2I1—C2I—H2I2 | 109.5 |
N1F—C1F—H1F1 | 109.5 | N1I—C2I—H2I3 | 109.5 |
N1F—C1F—H1F2 | 109.5 | H2I1—C2I—H2I3 | 109.5 |
H1F1—C1F—H1F2 | 109.5 | H2I2—C2I—H2I3 | 109.5 |
N1F—C1F—H1F3 | 109.5 | N1I—C3I—H3I1 | 109.5 |
H1F1—C1F—H1F3 | 109.5 | N1I—C3I—H3I2 | 109.5 |
H1F2—C1F—H1F3 | 109.5 | H3I1—C3I—H3I2 | 109.5 |
N1F—C2F—H2F1 | 109.5 | N1I—C3I—H3I3 | 109.5 |
N1F—C2F—H2F2 | 109.5 | H3I1—C3I—H3I3 | 109.5 |
H2F1—C2F—H2F2 | 109.5 | H3I2—C3I—H3I3 | 109.5 |
N1F—C2F—H2F3 | 109.5 | N1I—C4I—H4I1 | 109.5 |
H2F1—C2F—H2F3 | 109.5 | N1I—C4I—H4I2 | 109.5 |
H2F2—C2F—H2F3 | 109.5 | H4I1—C4I—H4I2 | 109.5 |
N1F—C3F—H3F1 | 109.5 | N1I—C4I—H4I3 | 109.5 |
N1F—C3F—H3F2 | 109.5 | H4I1—C4I—H4I3 | 109.5 |
H3F1—C3F—H3F2 | 109.5 | H4I2—C4I—H4I3 | 109.5 |
Experimental details
Crystal data | |
Chemical formula | (C4H12N)2[ZnCl4] |
Mr | 355.46 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 8.9114 (18), 15.105 (3), 36.493 (7) |
V (Å3) | 4912.2 (17) |
Z | 12 |
Radiation type | Mo Kα |
µ (mm−1) | 2.13 |
Crystal size (mm) | 0.36 × 0.24 × 0.04 |
Data collection | |
Diffractometer | Bruker APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.512, 0.918 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32538, 9616, 9039 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.055, 1.00 |
No. of reflections | 9616 |
No. of parameters | 407 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.29 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.611 (6) |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2000).
Zn1A—Cl4A | 2.2645 (8) | N1E—C1E | 1.494 (3) |
Zn1A—Cl2A | 2.2743 (8) | N1E—C3E | 1.498 (3) |
Zn1A—Cl1A | 2.2807 (8) | N1F—C2F | 1.491 (3) |
Zn1A—Cl3A | 2.2836 (8) | N1F—C3F | 1.492 (3) |
Zn1B—Cl1B | 2.2677 (8) | N1F—C1F | 1.493 (3) |
Zn1B—Cl4B | 2.2709 (7) | N1F—C4F | 1.494 (3) |
Zn1B—Cl3B | 2.2797 (8) | N1G—C1G | 1.488 (3) |
Zn1B—Cl2B | 2.2857 (8) | N1G—C2G | 1.496 (3) |
Zn1C—Cl1C | 2.2620 (8) | N1G—C3G | 1.497 (3) |
Zn1C—Cl2C | 2.2726 (8) | N1G—C4G | 1.497 (3) |
Zn1C—Cl3C | 2.2770 (8) | N1H—C2H | 1.487 (3) |
Zn1C—Cl4C | 2.2814 (8) | N1H—C3H | 1.489 (3) |
N1D—C4D | 1.490 (3) | N1H—C4H | 1.494 (3) |
N1D—C3D | 1.491 (3) | N1H—C1H | 1.496 (3) |
N1D—C1D | 1.499 (3) | N1I—C1I | 1.486 (3) |
N1D—C2D | 1.500 (3) | N1I—C3I | 1.489 (3) |
N1E—C2E | 1.488 (3) | N1I—C2I | 1.490 (3) |
N1E—C4E | 1.491 (3) | N1I—C4I | 1.493 (3) |
Cl4A—Zn1A—Cl2A | 110.65 (3) | C2E—N1E—C3E | 109.9 (2) |
Cl4A—Zn1A—Cl1A | 110.51 (3) | C4E—N1E—C3E | 109.25 (19) |
Cl2A—Zn1A—Cl1A | 107.40 (3) | C1E—N1E—C3E | 108.6 (2) |
Cl4A—Zn1A—Cl3A | 108.27 (3) | C2F—N1F—C3F | 109.9 (2) |
Cl2A—Zn1A—Cl3A | 109.40 (3) | C2F—N1F—C1F | 109.4 (2) |
Cl1A—Zn1A—Cl3A | 110.60 (3) | C3F—N1F—C1F | 109.4 (2) |
Cl1B—Zn1B—Cl4B | 111.11 (3) | C2F—N1F—C4F | 109.3 (2) |
Cl1B—Zn1B—Cl3B | 109.08 (3) | C3F—N1F—C4F | 108.9 (2) |
Cl4B—Zn1B—Cl3B | 108.58 (3) | C1F—N1F—C4F | 110.0 (2) |
Cl1B—Zn1B—Cl2B | 110.23 (3) | C1G—N1G—C2G | 109.9 (2) |
Cl4B—Zn1B—Cl2B | 107.37 (3) | C1G—N1G—C3G | 109.1 (2) |
Cl3B—Zn1B—Cl2B | 110.46 (3) | C2G—N1G—C3G | 109.3 (2) |
Cl1C—Zn1C—Cl2C | 112.21 (3) | C1G—N1G—C4G | 108.9 (2) |
Cl1C—Zn1C—Cl3C | 109.88 (3) | C2G—N1G—C4G | 109.50 (19) |
Cl2C—Zn1C—Cl3C | 108.62 (3) | C3G—N1G—C4G | 110.1 (2) |
Cl1C—Zn1C—Cl4C | 109.08 (3) | C2H—N1H—C3H | 108.9 (2) |
Cl2C—Zn1C—Cl4C | 108.55 (3) | C2H—N1H—C4H | 110.7 (2) |
Cl3C—Zn1C—Cl4C | 108.42 (3) | C3H—N1H—C4H | 108.5 (2) |
C4D—N1D—C3D | 109.7 (2) | C2H—N1H—C1H | 109.7 (2) |
C4D—N1D—C1D | 109.4 (2) | C3H—N1H—C1H | 109.81 (19) |
C3D—N1D—C1D | 109.11 (19) | C1I—N1I—C3I | 109.2 (2) |
C4D—N1D—C2D | 109.8 (2) | C1I—N1I—C2I | 109.63 (19) |
C3D—N1D—C2D | 109.2 (2) | C3I—N1I—C2I | 110.0 (2) |
C1D—N1D—C2D | 109.54 (19) | C1I—N1I—C4I | 109.6 (2) |
C2E—N1E—C4E | 109.5 (2) | C3I—N1I—C4I | 109.4 (2) |
C2E—N1E—C1E | 110.2 (2) | C2I—N1I—C4I | 109.0 (2) |
C4E—N1E—C1E | 109.4 (2) |
Acknowledgements
Financial support from the Welch Foundation in the form of grant No. AX-1540 is greatly appreciated. The authors thank the National Science Foundation (grant No. CHE-0130835) and the University of Oklahoma for funds to acquire the diffractometer and computers used in this work.
References
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Madariaga, G., Zuñiga, F. J., Pérez-Mato, J. M. & Tello, M. J. (1987). Acta Cryst. B43, 356–368. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Ruiz-Larrea, I., Lopez-Echarri, A. & Tello, M. J. (1981). J. Phys. C Solid State Phys. 14, 3171–3176. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2007). SADABS. Version 2007/4. University of Göttingen, Germany. Google Scholar
Wiesner, J. R., Srivastava, R. C., Kennard, C. H. L., Di Vaira, M. & Lingafelter, E. C. (1967). Acta Cryst. 23, 565–574. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Zhang, X.-M. & Bordwell, F. C. (1994). J. Am. Chem. Soc. 116, 968–972. CrossRef CAS Web of Science Google Scholar
Zuñiga, F. J., Madariaga, G. & Pérez-Mato, J. M. (1989). Acta Cryst. B45, 462–466. CSD CrossRef Web of Science IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Bis(tetramethylammonium) tetrachlorozincate(II) undergoes five solid-solid phase transitions with decreasing temperature according to a calorimetric study by Ruiz-Larrea et al. (1981). The room temperature phase I crystallized in the space group Pnma with a = 12.276 (2), b = 8.998 (2), and c = 15.541 (2) Å (Wiesner et al., 1967). Weak incommensurate lattice spots in phases II, III, and IV have shown that these two phases are small distortions of the room temperature phase (Madariaga et al., 1987). Similarly, phase V was found to be an incommensurately modulated structure related to phase I (Zuñiga et al., 1989).
No evidence of superlattice spots were observed in the frame data for phase VI. Short C—H···Cl contacts were observed, but because of the very large estimated pKa of 42 for the protons of the cations (Zhang & Bordwell, 1994), it is unlikely that any of these contacts are weak hydrogen bonds. There were three formula units in the asymmetric unit of the cell (Fig. 1).