
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054098/wm2156sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054098/wm2156Isup2.hkl |
CCDC reference: 672598
The compound was prepared according to literature (Van Oort, 1988) and crystallized at room temperature by diffusing diethyl ether vapour into an ethanolic solution. A suitable emerald green crystal was quickly covered in oil and transferred to the cold nitrogen stream of the diffractometer.
All H atoms were positioned geometrically (C—H = 0.98 and 0.99 Å for CH3 and CH2, respectively; and N—H = 0.92 Å) and constrained to ride on their parent atoms; Uiso(H) values were set at 1.2 times Ueq(C,N) for CH2 or NH2 and 1.5 times Ueq(C) for CH3.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Atwood & Barbour, 2003 and Barbour, 2001); software used to prepare material for publication: X-SEED.
(C4H12N)2[CuCl4] | F(000) = 2196 |
Mr = 353.63 | Dx = 1.435 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7081 reflections |
a = 7.315 (4) Å | θ = 2.3–26.4° |
b = 14.843 (8) Å | µ = 1.96 mm−1 |
c = 45.24 (2) Å | T = 100 K |
β = 90.258 (9)° | Block, green |
V = 4912 (5) Å3 | 0.45 × 0.25 × 0.15 mm |
Z = 12 |
Bruker APEX CCD area detector diffractometer | 10012 independent reflections |
Radiation source: fine-focus sealed tube | 8231 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ω–scans | θmax = 26.6°, θmin = 0.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −7→9 |
Tmin = 0.421, Tmax = 0.742 | k = −18→18 |
28089 measured reflections | l = −56→50 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0356P)2 + 2.1467P] where P = (Fo2 + 2Fc2)/3 |
10012 reflections | (Δ/σ)max = 0.001 |
418 parameters | Δρmax = 0.78 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
(C4H12N)2[CuCl4] | V = 4912 (5) Å3 |
Mr = 353.63 | Z = 12 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.315 (4) Å | µ = 1.96 mm−1 |
b = 14.843 (8) Å | T = 100 K |
c = 45.24 (2) Å | 0.45 × 0.25 × 0.15 mm |
β = 90.258 (9)° |
Bruker APEX CCD area detector diffractometer | 10012 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 8231 reflections with I > 2σ(I) |
Tmin = 0.421, Tmax = 0.742 | Rint = 0.055 |
28089 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.78 e Å−3 |
10012 reflections | Δρmin = −0.49 e Å−3 |
418 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.50841 (5) | 0.74787 (2) | 0.084049 (8) | 0.02153 (10) | |
Cu2 | 0.92389 (5) | 0.24762 (2) | 0.083225 (8) | 0.01820 (10) | |
Cu3 | 0.46748 (5) | 0.24221 (2) | 0.255011 (8) | 0.02002 (10) | |
Cl11 | 0.58990 (12) | 0.62256 (5) | 0.059822 (18) | 0.03125 (19) | |
Cl12 | 0.42965 (12) | 0.67724 (5) | 0.126298 (19) | 0.0324 (2) | |
Cl13 | 0.60562 (11) | 0.87259 (5) | 0.107010 (18) | 0.03002 (19) | |
Cl14 | 0.40684 (11) | 0.81893 (5) | 0.043124 (19) | 0.0313 (2) | |
Cl21 | 0.92291 (11) | 0.38662 (5) | 0.062999 (17) | 0.02863 (18) | |
Cl22 | 0.91811 (11) | 0.18729 (5) | 0.036970 (17) | 0.02770 (18) | |
Cl23 | 0.91308 (12) | 0.10889 (5) | 0.103458 (17) | 0.02896 (19) | |
Cl24 | 0.92597 (11) | 0.30808 (5) | 0.129495 (17) | 0.02811 (18) | |
Cl31 | 0.41369 (12) | 0.11216 (5) | 0.231532 (18) | 0.0319 (2) | |
Cl32 | 0.60609 (13) | 0.30356 (5) | 0.215033 (19) | 0.0367 (2) | |
Cl33 | 0.41713 (12) | 0.38062 (5) | 0.274342 (18) | 0.0331 (2) | |
Cl34 | 0.42615 (11) | 0.17926 (5) | 0.300217 (17) | 0.02779 (18) | |
N1 | 0.6974 (3) | 0.49583 (16) | 0.11481 (6) | 0.0214 (5) | |
H1B | 0.7653 | 0.4542 | 0.1046 | 0.026* | |
H1A | 0.6597 | 0.5391 | 0.1016 | 0.026* | |
N2 | 0.3228 (3) | 0.84386 (16) | 0.16754 (6) | 0.0224 (6) | |
H2A | 0.3656 | 0.8015 | 0.1545 | 0.027* | |
H2B | 0.2474 | 0.8148 | 0.1807 | 0.027* | |
N3 | 0.6853 (3) | 1.00067 (16) | 0.05136 (5) | 0.0209 (5) | |
H3A | 0.6517 | 0.9579 | 0.0650 | 0.025* | |
H3B | 0.7567 | 1.0426 | 0.0610 | 0.025* | |
N4 | 0.3125 (3) | 0.65577 (16) | −0.00079 (5) | 0.0202 (5) | |
H4A | 0.3491 | 0.6967 | 0.0133 | 0.024* | |
H4B | 0.2415 | 0.6860 | −0.0144 | 0.024* | |
N5 | 0.6930 (3) | 0.15370 (16) | 0.16653 (5) | 0.0216 (6) | |
H5A | 0.7597 | 0.1827 | 0.1522 | 0.026* | |
H5B | 0.6629 | 0.1956 | 0.1807 | 0.026* | |
N6 | 0.3193 (3) | 0.49932 (16) | 0.21770 (6) | 0.0215 (6) | |
H6B | 0.3507 | 0.4604 | 0.2327 | 0.026* | |
H6A | 0.2478 | 0.5441 | 0.2257 | 0.026* | |
C11 | 0.4155 (5) | 0.4129 (2) | 0.10258 (8) | 0.0362 (8) | |
H11A | 0.3791 | 0.4619 | 0.0893 | 0.054* | |
H11B | 0.3062 | 0.3848 | 0.1110 | 0.054* | |
H11C | 0.4850 | 0.3678 | 0.0915 | 0.054* | |
C12 | 0.5325 (4) | 0.4500 (2) | 0.12712 (7) | 0.0254 (7) | |
H12A | 0.4606 | 0.4935 | 0.1389 | 0.031* | |
H12B | 0.5712 | 0.4004 | 0.1404 | 0.031* | |
C13 | 0.8173 (4) | 0.5392 (2) | 0.13752 (7) | 0.0281 (7) | |
H13A | 0.8636 | 0.4930 | 0.1515 | 0.034* | |
H13B | 0.7460 | 0.5839 | 0.1489 | 0.034* | |
C14 | 0.9751 (5) | 0.5849 (3) | 0.12256 (9) | 0.0465 (10) | |
H14A | 1.0440 | 0.5405 | 0.1111 | 0.070* | |
H14B | 1.0554 | 0.6119 | 0.1375 | 0.070* | |
H14C | 0.9288 | 0.6321 | 0.1093 | 0.070* | |
C21 | 0.0591 (5) | 0.8678 (3) | 0.13455 (10) | 0.0476 (10) | |
H21A | 0.1081 | 0.8253 | 0.1200 | 0.071* | |
H21B | −0.0128 | 0.9141 | 0.1243 | 0.071* | |
H21C | −0.0191 | 0.8355 | 0.1485 | 0.071* | |
C22 | 0.2136 (4) | 0.9113 (2) | 0.15093 (7) | 0.0288 (7) | |
H22A | 0.2935 | 0.9431 | 0.1367 | 0.035* | |
H22B | 0.1642 | 0.9565 | 0.1649 | 0.035* | |
C23 | 0.4815 (4) | 0.8823 (2) | 0.18419 (8) | 0.0295 (8) | |
H23A | 0.4376 | 0.9293 | 0.1979 | 0.035* | |
H23B | 0.5673 | 0.9108 | 0.1702 | 0.035* | |
C24 | 0.5795 (5) | 0.8103 (3) | 0.20133 (9) | 0.0491 (11) | |
H24A | 0.4940 | 0.7813 | 0.2150 | 0.074* | |
H24B | 0.6802 | 0.8374 | 0.2126 | 0.074* | |
H24C | 0.6283 | 0.7653 | 0.1876 | 0.074* | |
C31 | 0.9615 (5) | 0.9117 (3) | 0.04137 (8) | 0.0411 (9) | |
H31A | 1.0374 | 0.9571 | 0.0513 | 0.062* | |
H31B | 1.0326 | 0.8824 | 0.0258 | 0.062* | |
H31C | 0.9221 | 0.8666 | 0.0558 | 0.062* | |
C32 | 0.7971 (4) | 0.9564 (2) | 0.02798 (7) | 0.0258 (7) | |
H32A | 0.8368 | 1.0020 | 0.0134 | 0.031* | |
H32B | 0.7220 | 0.9109 | 0.0175 | 0.031* | |
C33 | 0.5180 (4) | 1.0460 (2) | 0.04010 (7) | 0.0251 (7) | |
H33A | 0.4438 | 1.0026 | 0.0286 | 0.030* | |
H33B | 0.5528 | 1.0960 | 0.0268 | 0.030* | |
C34 | 0.4059 (5) | 1.0825 (2) | 0.06546 (8) | 0.0357 (8) | |
H34A | 0.3667 | 1.0326 | 0.0781 | 0.054* | |
H34B | 0.2981 | 1.1138 | 0.0576 | 0.054* | |
H34C | 0.4802 | 1.1247 | 0.0771 | 0.054* | |
C41 | 0.0368 (5) | 0.6264 (3) | 0.02894 (9) | 0.0453 (10) | |
H41A | 0.0792 | 0.6670 | 0.0446 | 0.068* | |
H41B | −0.0378 | 0.5784 | 0.0376 | 0.068* | |
H41C | −0.0367 | 0.6603 | 0.0146 | 0.068* | |
C42 | 0.1987 (4) | 0.5856 (2) | 0.01366 (7) | 0.0272 (7) | |
H42A | 0.2740 | 0.5523 | 0.0283 | 0.033* | |
H42B | 0.1556 | 0.5421 | −0.0014 | 0.033* | |
C43 | 0.4786 (4) | 0.6202 (2) | −0.01612 (7) | 0.0254 (7) | |
H43A | 0.4407 | 0.5799 | −0.0325 | 0.031* | |
H43B | 0.5529 | 0.5846 | −0.0020 | 0.031* | |
C44 | 0.5921 (5) | 0.6961 (2) | −0.02826 (8) | 0.0366 (8) | |
H44A | 0.5201 | 0.7300 | −0.0428 | 0.055* | |
H44B | 0.7014 | 0.6715 | −0.0378 | 0.055* | |
H44C | 0.6288 | 0.7364 | −0.0121 | 0.055* | |
C51 | 0.4105 (5) | 0.1946 (2) | 0.14004 (8) | 0.0354 (8) | |
H51A | 0.3785 | 0.2372 | 0.1557 | 0.053* | |
H51B | 0.2985 | 0.1703 | 0.1311 | 0.053* | |
H51C | 0.4821 | 0.2256 | 0.1249 | 0.053* | |
C52 | 0.5214 (4) | 0.1188 (2) | 0.15287 (7) | 0.0247 (7) | |
H52A | 0.4486 | 0.0870 | 0.1680 | 0.030* | |
H52B | 0.5519 | 0.0752 | 0.1371 | 0.030* | |
C53 | 0.8102 (4) | 0.0835 (2) | 0.18044 (7) | 0.0272 (7) | |
H53A | 0.8341 | 0.0349 | 0.1660 | 0.033* | |
H53B | 0.7458 | 0.0569 | 0.1976 | 0.033* | |
C54 | 0.9882 (4) | 0.1238 (3) | 0.19054 (8) | 0.0362 (9) | |
H54A | 1.0541 | 0.1478 | 0.1735 | 0.054* | |
H54B | 1.0625 | 0.0773 | 0.2002 | 0.054* | |
H54C | 0.9641 | 0.1726 | 0.2046 | 0.054* | |
C61 | 0.0415 (5) | 0.4100 (3) | 0.20903 (10) | 0.0479 (10) | |
H61A | 0.0772 | 0.3666 | 0.2243 | 0.072* | |
H61B | −0.0318 | 0.3796 | 0.1938 | 0.072* | |
H61C | −0.0307 | 0.4584 | 0.2180 | 0.072* | |
C62 | 0.2104 (4) | 0.4494 (2) | 0.19511 (7) | 0.0285 (7) | |
H62A | 0.2856 | 0.4005 | 0.1866 | 0.034* | |
H62B | 0.1748 | 0.4909 | 0.1789 | 0.034* | |
C63 | 0.4895 (4) | 0.5406 (2) | 0.20549 (7) | 0.0262 (7) | |
H63A | 0.4566 | 0.5875 | 0.1908 | 0.031* | |
H63B | 0.5623 | 0.4939 | 0.1953 | 0.031* | |
C64 | 0.6021 (5) | 0.5821 (2) | 0.23000 (8) | 0.0366 (9) | |
H64A | 0.5303 | 0.6289 | 0.2399 | 0.055* | |
H64B | 0.7130 | 0.6089 | 0.2217 | 0.055* | |
H64C | 0.6359 | 0.5354 | 0.2443 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0198 (2) | 0.0189 (2) | 0.0259 (2) | 0.00035 (14) | 0.00180 (16) | 0.00107 (15) |
Cu2 | 0.01714 (19) | 0.01684 (19) | 0.0206 (2) | 0.00001 (14) | 0.00077 (15) | 0.00040 (14) |
Cu3 | 0.0188 (2) | 0.0190 (2) | 0.0223 (2) | 0.00079 (14) | 0.00224 (15) | 0.00094 (15) |
Cl11 | 0.0407 (5) | 0.0278 (4) | 0.0252 (4) | 0.0129 (3) | 0.0024 (4) | 0.0007 (3) |
Cl12 | 0.0428 (5) | 0.0199 (4) | 0.0346 (5) | 0.0009 (3) | 0.0175 (4) | 0.0015 (3) |
Cl13 | 0.0354 (5) | 0.0291 (4) | 0.0256 (4) | −0.0127 (3) | −0.0006 (3) | 0.0011 (3) |
Cl14 | 0.0381 (5) | 0.0198 (4) | 0.0360 (5) | 0.0020 (3) | −0.0144 (4) | −0.0002 (3) |
Cl21 | 0.0430 (5) | 0.0187 (4) | 0.0242 (4) | 0.0008 (3) | 0.0026 (3) | 0.0011 (3) |
Cl22 | 0.0413 (5) | 0.0202 (4) | 0.0215 (4) | 0.0007 (3) | 0.0003 (3) | −0.0010 (3) |
Cl23 | 0.0449 (5) | 0.0184 (4) | 0.0236 (4) | −0.0014 (3) | 0.0007 (4) | 0.0012 (3) |
Cl24 | 0.0419 (5) | 0.0205 (4) | 0.0220 (4) | 0.0003 (3) | 0.0013 (3) | −0.0009 (3) |
Cl31 | 0.0396 (5) | 0.0295 (4) | 0.0268 (4) | −0.0120 (3) | 0.0053 (4) | −0.0045 (3) |
Cl32 | 0.0499 (5) | 0.0248 (4) | 0.0355 (5) | −0.0058 (4) | 0.0233 (4) | −0.0019 (4) |
Cl33 | 0.0516 (5) | 0.0204 (4) | 0.0275 (4) | 0.0072 (3) | 0.0124 (4) | 0.0031 (3) |
Cl34 | 0.0397 (5) | 0.0202 (4) | 0.0235 (4) | 0.0014 (3) | 0.0037 (3) | 0.0022 (3) |
N1 | 0.0226 (13) | 0.0204 (13) | 0.0212 (14) | 0.0021 (10) | 0.0011 (11) | −0.0010 (10) |
N2 | 0.0226 (13) | 0.0171 (13) | 0.0275 (15) | 0.0012 (10) | 0.0021 (11) | 0.0013 (11) |
N3 | 0.0218 (13) | 0.0186 (13) | 0.0222 (14) | −0.0012 (10) | 0.0004 (11) | −0.0008 (10) |
N4 | 0.0196 (13) | 0.0180 (13) | 0.0228 (14) | −0.0010 (10) | −0.0018 (10) | 0.0003 (10) |
N5 | 0.0226 (13) | 0.0193 (13) | 0.0231 (14) | −0.0002 (10) | 0.0025 (11) | 0.0019 (10) |
N6 | 0.0208 (13) | 0.0201 (13) | 0.0235 (14) | 0.0003 (10) | 0.0029 (11) | 0.0014 (11) |
C11 | 0.0309 (19) | 0.035 (2) | 0.043 (2) | −0.0107 (15) | 0.0002 (16) | 0.0034 (17) |
C12 | 0.0269 (17) | 0.0230 (16) | 0.0265 (18) | −0.0017 (13) | 0.0078 (14) | 0.0009 (13) |
C13 | 0.0311 (18) | 0.0268 (17) | 0.0263 (18) | −0.0021 (14) | −0.0046 (14) | −0.0030 (14) |
C14 | 0.036 (2) | 0.053 (3) | 0.050 (3) | −0.0169 (18) | 0.0004 (19) | −0.011 (2) |
C21 | 0.035 (2) | 0.049 (2) | 0.058 (3) | 0.0062 (18) | −0.0163 (19) | 0.005 (2) |
C22 | 0.0315 (18) | 0.0235 (17) | 0.0313 (19) | 0.0067 (13) | 0.0047 (15) | 0.0017 (14) |
C23 | 0.0255 (17) | 0.0294 (18) | 0.034 (2) | −0.0055 (14) | −0.0036 (14) | −0.0018 (15) |
C24 | 0.041 (2) | 0.051 (3) | 0.055 (3) | 0.0009 (19) | −0.020 (2) | 0.004 (2) |
C31 | 0.038 (2) | 0.048 (2) | 0.038 (2) | 0.0141 (17) | 0.0055 (17) | −0.0007 (18) |
C32 | 0.0262 (17) | 0.0261 (17) | 0.0252 (18) | −0.0011 (13) | 0.0061 (14) | −0.0044 (13) |
C33 | 0.0232 (16) | 0.0216 (16) | 0.0305 (18) | 0.0025 (12) | −0.0042 (14) | 0.0029 (13) |
C34 | 0.0295 (19) | 0.038 (2) | 0.040 (2) | 0.0097 (15) | 0.0059 (16) | 0.0069 (17) |
C41 | 0.033 (2) | 0.047 (2) | 0.057 (3) | −0.0060 (17) | 0.0129 (19) | 0.004 (2) |
C42 | 0.0285 (17) | 0.0227 (16) | 0.0304 (19) | −0.0058 (13) | 0.0038 (14) | 0.0041 (14) |
C43 | 0.0252 (17) | 0.0270 (17) | 0.0241 (17) | 0.0054 (13) | 0.0021 (13) | −0.0028 (13) |
C44 | 0.0309 (19) | 0.036 (2) | 0.043 (2) | 0.0006 (15) | 0.0079 (16) | −0.0037 (17) |
C51 | 0.0267 (18) | 0.036 (2) | 0.043 (2) | 0.0001 (15) | −0.0014 (16) | −0.0009 (17) |
C52 | 0.0220 (16) | 0.0248 (17) | 0.0272 (18) | −0.0047 (12) | 0.0029 (13) | 0.0006 (13) |
C53 | 0.0292 (18) | 0.0242 (17) | 0.0284 (18) | 0.0043 (13) | 0.0028 (14) | 0.0042 (14) |
C54 | 0.0283 (19) | 0.047 (2) | 0.033 (2) | 0.0048 (16) | −0.0033 (16) | 0.0059 (17) |
C61 | 0.036 (2) | 0.051 (2) | 0.057 (3) | −0.0185 (18) | −0.0003 (19) | −0.003 (2) |
C62 | 0.0283 (18) | 0.0282 (18) | 0.0291 (19) | −0.0026 (14) | −0.0022 (14) | −0.0050 (14) |
C63 | 0.0235 (17) | 0.0276 (17) | 0.0276 (18) | −0.0024 (13) | 0.0072 (14) | 0.0029 (14) |
C64 | 0.0328 (19) | 0.037 (2) | 0.040 (2) | −0.0112 (15) | −0.0024 (16) | 0.0079 (17) |
Cu1—Cl13 | 2.2371 (12) | C23—C24 | 1.500 (5) |
Cu1—Cl11 | 2.2410 (12) | C23—H23A | 0.9900 |
Cu1—Cl14 | 2.2540 (12) | C23—H23B | 0.9900 |
Cu1—Cl12 | 2.2570 (13) | C24—H24A | 0.9800 |
Cu2—Cl23 | 2.2550 (13) | C24—H24B | 0.9800 |
Cu2—Cl21 | 2.2570 (13) | C24—H24C | 0.9800 |
Cu2—Cl22 | 2.2764 (13) | C31—C32 | 1.498 (5) |
Cu2—Cl24 | 2.2775 (13) | C31—H31A | 0.9800 |
Cu3—Cl31 | 2.2372 (13) | C31—H31B | 0.9800 |
Cu3—Cl33 | 2.2636 (13) | C31—H31C | 0.9800 |
Cu3—Cl32 | 2.2683 (12) | C32—H32A | 0.9900 |
Cu3—Cl34 | 2.2700 (13) | C32—H32B | 0.9900 |
N1—C13 | 1.493 (4) | C33—C34 | 1.514 (5) |
N1—C12 | 1.495 (4) | C33—H33A | 0.9900 |
N1—H1B | 0.9200 | C33—H33B | 0.9900 |
N1—H1A | 0.9200 | C34—H34A | 0.9800 |
N2—C22 | 1.483 (4) | C34—H34B | 0.9800 |
N2—C23 | 1.494 (4) | C34—H34C | 0.9800 |
N2—H2A | 0.9200 | C41—C42 | 1.501 (5) |
N2—H2B | 0.9200 | C41—H41A | 0.9800 |
N3—C33 | 1.485 (4) | C41—H41B | 0.9800 |
N3—C32 | 1.493 (4) | C41—H41C | 0.9800 |
N3—H3A | 0.9200 | C42—H42A | 0.9900 |
N3—H3B | 0.9200 | C42—H42B | 0.9900 |
N4—C42 | 1.487 (4) | C43—C44 | 1.505 (5) |
N4—C43 | 1.498 (4) | C43—H43A | 0.9900 |
N4—H4A | 0.9200 | C43—H43B | 0.9900 |
N4—H4B | 0.9200 | C44—H44A | 0.9800 |
N5—C53 | 1.487 (4) | C44—H44B | 0.9800 |
N5—C52 | 1.490 (4) | C44—H44C | 0.9800 |
N5—H5A | 0.9200 | C51—C52 | 1.501 (4) |
N5—H5B | 0.9200 | C51—H51A | 0.9800 |
N6—C62 | 1.490 (4) | C51—H51B | 0.9800 |
N6—C63 | 1.496 (4) | C51—H51C | 0.9800 |
N6—H6B | 0.9200 | C52—H52A | 0.9900 |
N6—H6A | 0.9200 | C52—H52B | 0.9900 |
C11—C12 | 1.503 (4) | C53—C54 | 1.502 (4) |
C11—H11A | 0.9800 | C53—H53A | 0.9900 |
C11—H11B | 0.9800 | C53—H53B | 0.9900 |
C11—H11C | 0.9800 | C54—H54A | 0.9800 |
C12—H12A | 0.9900 | C54—H54B | 0.9800 |
C12—H12B | 0.9900 | C54—H54C | 0.9800 |
C13—C14 | 1.503 (5) | C61—C62 | 1.507 (5) |
C13—H13A | 0.9900 | C61—H61A | 0.9800 |
C13—H13B | 0.9900 | C61—H61B | 0.9800 |
C14—H14A | 0.9800 | C61—H61C | 0.9800 |
C14—H14B | 0.9800 | C62—H62A | 0.9900 |
C14—H14C | 0.9800 | C62—H62B | 0.9900 |
C21—C22 | 1.495 (5) | C63—C64 | 1.510 (4) |
C21—H21A | 0.9800 | C63—H63A | 0.9900 |
C21—H21B | 0.9800 | C63—H63B | 0.9900 |
C21—H21C | 0.9800 | C64—H64A | 0.9800 |
C22—H22A | 0.9900 | C64—H64B | 0.9800 |
C22—H22B | 0.9900 | C64—H64C | 0.9800 |
Cl13—Cu1—Cl11 | 146.02 (4) | C23—C24—H24C | 109.5 |
Cl13—Cu1—Cl14 | 95.57 (5) | H24A—C24—H24C | 109.5 |
Cl11—Cu1—Cl14 | 94.24 (5) | H24B—C24—H24C | 109.5 |
Cl13—Cu1—Cl12 | 94.18 (5) | C32—C31—H31A | 109.5 |
Cl11—Cu1—Cl12 | 95.64 (5) | C32—C31—H31B | 109.5 |
Cl14—Cu1—Cl12 | 145.95 (4) | H31A—C31—H31B | 109.5 |
Cl23—Cu2—Cl21 | 177.81 (4) | C32—C31—H31C | 109.5 |
Cl23—Cu2—Cl22 | 90.77 (4) | H31A—C31—H31C | 109.5 |
Cl21—Cu2—Cl22 | 89.25 (4) | H31B—C31—H31C | 109.5 |
Cl23—Cu2—Cl24 | 89.24 (4) | N3—C32—C31 | 110.5 (3) |
Cl21—Cu2—Cl24 | 90.72 (4) | N3—C32—H32A | 109.6 |
Cl22—Cu2—Cl24 | 179.32 (3) | C31—C32—H32A | 109.6 |
Cl31—Cu3—Cl33 | 159.70 (4) | N3—C32—H32B | 109.6 |
Cl31—Cu3—Cl32 | 92.64 (5) | C31—C32—H32B | 109.6 |
Cl33—Cu3—Cl32 | 91.02 (4) | H32A—C32—H32B | 108.1 |
Cl31—Cu3—Cl34 | 92.80 (5) | N3—C33—C34 | 110.5 (3) |
Cl33—Cu3—Cl34 | 90.17 (4) | N3—C33—H33A | 109.5 |
Cl32—Cu3—Cl34 | 160.99 (4) | C34—C33—H33A | 109.5 |
C13—N1—C12 | 114.3 (2) | N3—C33—H33B | 109.5 |
C13—N1—H1B | 108.7 | C34—C33—H33B | 109.5 |
C12—N1—H1B | 108.7 | H33A—C33—H33B | 108.1 |
C13—N1—H1A | 108.7 | C33—C34—H34A | 109.5 |
C12—N1—H1A | 108.7 | C33—C34—H34B | 109.5 |
H1B—N1—H1A | 107.6 | H34A—C34—H34B | 109.5 |
C22—N2—C23 | 114.4 (2) | C33—C34—H34C | 109.5 |
C22—N2—H2A | 108.7 | H34A—C34—H34C | 109.5 |
C23—N2—H2A | 108.7 | H34B—C34—H34C | 109.5 |
C22—N2—H2B | 108.7 | C42—C41—H41A | 109.5 |
C23—N2—H2B | 108.7 | C42—C41—H41B | 109.5 |
H2A—N2—H2B | 107.6 | H41A—C41—H41B | 109.5 |
C33—N3—C32 | 114.2 (2) | C42—C41—H41C | 109.5 |
C33—N3—H3A | 108.7 | H41A—C41—H41C | 109.5 |
C32—N3—H3A | 108.7 | H41B—C41—H41C | 109.5 |
C33—N3—H3B | 108.7 | N4—C42—C41 | 111.4 (3) |
C32—N3—H3B | 108.7 | N4—C42—H42A | 109.4 |
H3A—N3—H3B | 107.6 | C41—C42—H42A | 109.4 |
C42—N4—C43 | 114.5 (2) | N4—C42—H42B | 109.4 |
C42—N4—H4A | 108.6 | C41—C42—H42B | 109.4 |
C43—N4—H4A | 108.6 | H42A—C42—H42B | 108.0 |
C42—N4—H4B | 108.6 | N4—C43—C44 | 110.8 (3) |
C43—N4—H4B | 108.6 | N4—C43—H43A | 109.5 |
H4A—N4—H4B | 107.6 | C44—C43—H43A | 109.5 |
C53—N5—C52 | 114.6 (2) | N4—C43—H43B | 109.5 |
C53—N5—H5A | 108.6 | C44—C43—H43B | 109.5 |
C52—N5—H5A | 108.6 | H43A—C43—H43B | 108.1 |
C53—N5—H5B | 108.6 | C43—C44—H44A | 109.5 |
C52—N5—H5B | 108.6 | C43—C44—H44B | 109.5 |
H5A—N5—H5B | 107.6 | H44A—C44—H44B | 109.5 |
C62—N6—C63 | 113.2 (2) | C43—C44—H44C | 109.5 |
C62—N6—H6B | 108.9 | H44A—C44—H44C | 109.5 |
C63—N6—H6B | 108.9 | H44B—C44—H44C | 109.5 |
C62—N6—H6A | 108.9 | C52—C51—H51A | 109.5 |
C63—N6—H6A | 108.9 | C52—C51—H51B | 109.5 |
H6B—N6—H6A | 107.8 | H51A—C51—H51B | 109.5 |
C12—C11—H11A | 109.5 | C52—C51—H51C | 109.5 |
C12—C11—H11B | 109.5 | H51A—C51—H51C | 109.5 |
H11A—C11—H11B | 109.5 | H51B—C51—H51C | 109.5 |
C12—C11—H11C | 109.5 | N5—C52—C51 | 110.7 (3) |
H11A—C11—H11C | 109.5 | N5—C52—H52A | 109.5 |
H11B—C11—H11C | 109.5 | C51—C52—H52A | 109.5 |
N1—C12—C11 | 110.4 (3) | N5—C52—H52B | 109.5 |
N1—C12—H12A | 109.6 | C51—C52—H52B | 109.5 |
C11—C12—H12A | 109.6 | H52A—C52—H52B | 108.1 |
N1—C12—H12B | 109.6 | N5—C53—C54 | 110.3 (3) |
C11—C12—H12B | 109.6 | N5—C53—H53A | 109.6 |
H12A—C12—H12B | 108.1 | C54—C53—H53A | 109.6 |
N1—C13—C14 | 109.5 (3) | N5—C53—H53B | 109.6 |
N1—C13—H13A | 109.8 | C54—C53—H53B | 109.6 |
C14—C13—H13A | 109.8 | H53A—C53—H53B | 108.1 |
N1—C13—H13B | 109.8 | C53—C54—H54A | 109.5 |
C14—C13—H13B | 109.8 | C53—C54—H54B | 109.5 |
H13A—C13—H13B | 108.2 | H54A—C54—H54B | 109.5 |
C13—C14—H14A | 109.5 | C53—C54—H54C | 109.5 |
C13—C14—H14B | 109.5 | H54A—C54—H54C | 109.5 |
H14A—C14—H14B | 109.5 | H54B—C54—H54C | 109.5 |
C13—C14—H14C | 109.5 | C62—C61—H61A | 109.5 |
H14A—C14—H14C | 109.5 | C62—C61—H61B | 109.5 |
H14B—C14—H14C | 109.5 | H61A—C61—H61B | 109.5 |
C22—C21—H21A | 109.5 | C62—C61—H61C | 109.5 |
C22—C21—H21B | 109.5 | H61A—C61—H61C | 109.5 |
H21A—C21—H21B | 109.5 | H61B—C61—H61C | 109.5 |
C22—C21—H21C | 109.5 | N6—C62—C61 | 110.0 (3) |
H21A—C21—H21C | 109.5 | N6—C62—H62A | 109.7 |
H21B—C21—H21C | 109.5 | C61—C62—H62A | 109.7 |
N2—C22—C21 | 111.3 (3) | N6—C62—H62B | 109.7 |
N2—C22—H22A | 109.4 | C61—C62—H62B | 109.7 |
C21—C22—H22A | 109.4 | H62A—C62—H62B | 108.2 |
N2—C22—H22B | 109.4 | N6—C63—C64 | 110.3 (3) |
C21—C22—H22B | 109.4 | N6—C63—H63A | 109.6 |
H22A—C22—H22B | 108.0 | C64—C63—H63A | 109.6 |
N2—C23—C24 | 110.9 (3) | N6—C63—H63B | 109.6 |
N2—C23—H23A | 109.5 | C64—C63—H63B | 109.6 |
C24—C23—H23A | 109.5 | H63A—C63—H63B | 108.1 |
N2—C23—H23B | 109.5 | C63—C64—H64A | 109.5 |
C24—C23—H23B | 109.5 | C63—C64—H64B | 109.5 |
H23A—C23—H23B | 108.0 | H64A—C64—H64B | 109.5 |
C23—C24—H24A | 109.5 | C63—C64—H64C | 109.5 |
C23—C24—H24B | 109.5 | H64A—C64—H64C | 109.5 |
H24A—C24—H24B | 109.5 | H64B—C64—H64C | 109.5 |
C13—N1—C12—C11 | 176.9 (3) | C43—N4—C42—C41 | 179.1 (3) |
C12—N1—C13—C14 | −178.5 (3) | C42—N4—C43—C44 | −176.1 (3) |
C23—N2—C22—C21 | 179.2 (3) | C53—N5—C52—C51 | 178.7 (3) |
C22—N2—C23—C24 | 177.6 (3) | C52—N5—C53—C54 | 173.8 (3) |
C33—N3—C32—C31 | −179.4 (3) | C63—N6—C62—C61 | −179.9 (3) |
C32—N3—C33—C34 | 175.5 (3) | C62—N6—C63—C64 | −174.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl11 | 0.92 | 2.31 | 3.214 (3) | 166 |
N1—H1B···Cl21 | 0.92 | 2.43 | 3.298 (3) | 158 |
N2—H2A···Cl12 | 0.92 | 2.29 | 3.197 (3) | 168 |
N3—H3A···Cl13 | 0.92 | 2.31 | 3.210 (3) | 166 |
N3—H3B···Cl23i | 0.92 | 2.44 | 3.298 (3) | 155 |
N4—H4A···Cl14 | 0.92 | 2.30 | 3.205 (3) | 169 |
N4—H4B···Cl22ii | 0.92 | 2.44 | 3.306 (3) | 158 |
N5—H5A···Cl24 | 0.92 | 2.45 | 3.315 (3) | 156 |
N5—H5B···Cl32 | 0.92 | 2.27 | 3.190 (3) | 176 |
N6—H6A···Cl31iii | 0.92 | 2.49 | 3.320 (3) | 151 |
N6—H6B···Cl33 | 0.92 | 2.28 | 3.188 (3) | 172 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z; (iii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C4H12N)2[CuCl4] |
Mr | 353.63 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 7.315 (4), 14.843 (8), 45.24 (2) |
β (°) | 90.258 (9) |
V (Å3) | 4912 (5) |
Z | 12 |
Radiation type | Mo Kα |
µ (mm−1) | 1.96 |
Crystal size (mm) | 0.45 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Bruker APEX CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.421, 0.742 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28089, 10012, 8231 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.629 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.111, 1.09 |
No. of reflections | 10012 |
No. of parameters | 418 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.78, −0.49 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Atwood & Barbour, 2003 and Barbour, 2001), X-SEED.
Cu1—Cl13 | 2.2371 (12) | Cu2—Cl22 | 2.2764 (13) |
Cu1—Cl11 | 2.2410 (12) | Cu2—Cl24 | 2.2775 (13) |
Cu1—Cl14 | 2.2540 (12) | Cu3—Cl31 | 2.2372 (13) |
Cu1—Cl12 | 2.2570 (13) | Cu3—Cl33 | 2.2636 (13) |
Cu2—Cl23 | 2.2550 (13) | Cu3—Cl32 | 2.2683 (12) |
Cu2—Cl21 | 2.2570 (13) | Cu3—Cl34 | 2.2700 (13) |
Cl13—Cu1—Cl11 | 146.02 (4) | Cl23—Cu2—Cl24 | 89.24 (4) |
Cl13—Cu1—Cl14 | 95.57 (5) | Cl21—Cu2—Cl24 | 90.72 (4) |
Cl11—Cu1—Cl14 | 94.24 (5) | Cl22—Cu2—Cl24 | 179.32 (3) |
Cl13—Cu1—Cl12 | 94.18 (5) | Cl31—Cu3—Cl33 | 159.70 (4) |
Cl11—Cu1—Cl12 | 95.64 (5) | Cl31—Cu3—Cl32 | 92.64 (5) |
Cl14—Cu1—Cl12 | 145.95 (4) | Cl33—Cu3—Cl32 | 91.02 (4) |
Cl23—Cu2—Cl21 | 177.81 (4) | Cl31—Cu3—Cl34 | 92.80 (5) |
Cl23—Cu2—Cl22 | 90.77 (4) | Cl33—Cu3—Cl34 | 90.17 (4) |
Cl21—Cu2—Cl22 | 89.25 (4) | Cl32—Cu3—Cl34 | 160.99 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl11 | 0.92 | 2.31 | 3.214 (3) | 165.8 |
N1—H1B···Cl21 | 0.92 | 2.43 | 3.298 (3) | 158.1 |
N2—H2A···Cl12 | 0.92 | 2.29 | 3.197 (3) | 168.4 |
N3—H3A···Cl13 | 0.92 | 2.31 | 3.210 (3) | 166.2 |
N3—H3B···Cl23i | 0.92 | 2.44 | 3.298 (3) | 155.2 |
N4—H4A···Cl14 | 0.92 | 2.30 | 3.205 (3) | 168.6 |
N4—H4B···Cl22ii | 0.92 | 2.44 | 3.306 (3) | 157.8 |
N5—H5A···Cl24 | 0.92 | 2.45 | 3.315 (3) | 156.4 |
N5—H5B···Cl32 | 0.92 | 2.27 | 3.190 (3) | 176.3 |
N6—H6A···Cl31iii | 0.92 | 2.49 | 3.320 (3) | 150.6 |
N6—H6B···Cl33 | 0.92 | 2.28 | 3.188 (3) | 171.7 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z; (iii) −x+1/2, y+1/2, −z+1/2. |
In the course of an experiment in the inorganic chemistry practical at our university the thermochromic behaviour of diethylammonium tetrachloridocuprate(II) (I) is studied. Surprisingly, atomic coordinates of the low-temperature phase have only been presented at a meeting of the American Crystallographic Association (Simonsen & Harlow, 1977), but not published in a journal or deposited in a data base. However, the structure is briefly discussed in a later publication together with the high-temperature phase (Bloomquist et al., 1988). Redetermination of the crystal and molecular structure was now done at 100 K from a crystal obtained at 293 K.
The molecular and crystal structures of both high- and low-temperature phases of other dialkylammonium tetrachlorocuprates(II), the anion being approximately tetrahedral and square-planar, respectively, have been determined, for example the dipropylammonium analogue (Bond et al., 1988).
The asymmetric unit of (I) is shown in Figure 1. The compound consists of three crystallographically independent formula units of which the anion containing Cu2 is virtually square-planar, the others show a certain degree of distortion towards tetrahedral. The r.m.s. deviations of the atoms constituting the anions from a plane fitted to them is 0.588, 0.017 and 0.344 Å for Cu1, Cu2 and Cu3, respectively. Except for N2 which only engages in one hydrogen bond to Cl12, the other five diethylammonium cations each link two tetrachlorocuprate anions to form a two-dimensional hydrogen-bond network in the (101) plane. Likewise, all chlorine atoms of the anions are hydrogen bond acceptors with the exception of Cl34 (see Table). The connectivity of the hydrogen bonds is shown in Figure 2, a perspective view in Figure 3. Bond lengths and angles are unexceptional.