Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009489/gg1063sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009489/gg1063Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009489/gg1063IIsup3.hkl |
CCDC references: 173346; 173347
Complexes (I) and (II) were prepared by mixing boiling solutions of 50/50 aqueous ethanol separately containing CuCl2 and either 2-amino-5-methyl-1,3,4-thiadiazole, (I), or 2-amino-5-ethyl-1,3,4-thiadiazole, (II). Upon cooling, the mixtures were filtered and allowed to evaporate to dryness. Crystals of (I) and (II) were separated from the resultant mass that also included crystals of the unreacted starting materials.
All H atoms except for the water protons were included in the refinement, at calculated positions, as riding models with C—H set to either 0.98 Å (CH3) or 0.99 Å (CH2) and N—H set to 0.88 Å. The two water protons were located on difference syntheses and both position and displacement parameters refined. The OW—H distances are 0.83 and 0.89 Å.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998) for (I); DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998) for (II). For both compounds, cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1997); software used to prepare material for publication: SHELXL97.
[CuCl(C3H5N3S)4]Cl·H2O | F(000) = 1252 |
Mr = 613.15 | Dx = 1.623 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.7183 (2) Å | Cell parameters from 8104 reflections |
b = 15.3106 (3) Å | θ = 2.9–27.5° |
c = 12.8865 (2) Å | µ = 1.45 mm−1 |
β = 90.4820 (9)° | T = 150 K |
V = 2509.23 (7) Å3 | Prism, green |
Z = 4 | 0.25 × 0.18 × 0.05 mm |
Enraf Nonius KappaCCD area detector diffractometer | 5620 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 4500 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
Phi and ω scans | h = −16→15 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −19→19 |
Tmin = 0.714, Tmax = 0.931 | l = −14→16 |
19695 measured reflections |
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)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0629P)2 + 3.8292P] where P = (Fo2 + 2Fc2)/3 |
S = 0.85 | (Δ/σ)max = 0.003 |
5620 reflections | Δρmax = 0.73 e Å−3 |
302 parameters | Δρmin = −0.77 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0028 (4) |
[CuCl(C3H5N3S)4]Cl·H2O | V = 2509.23 (7) Å3 |
Mr = 613.15 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.7183 (2) Å | µ = 1.45 mm−1 |
b = 15.3106 (3) Å | T = 150 K |
c = 12.8865 (2) Å | 0.25 × 0.18 × 0.05 mm |
β = 90.4820 (9)° |
Enraf Nonius KappaCCD area detector diffractometer | 5620 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 4500 reflections with I > 2σ(I) |
Tmin = 0.714, Tmax = 0.931 | Rint = 0.050 |
19695 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | Δρmax = 0.73 e Å−3 |
5620 reflections | Δρmin = −0.77 e Å−3 |
302 parameters |
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. |
Geometry. Mean plane data ex SHELXL97 for molecule (I) ############################################ Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 10.6836 (0.0081) x + 2.6267 (0.0170) y + 6.5416 (0.0111) z = 5.0130 (0.0047) * 0.0164 (0.0012) S1A * -0.0187 (0.0015) C2A * 0.0123 (0.0016) N3A * 0.0048 (0.0016) N4A * -0.0148 (0.0015) C5A -0.0929 (0.0042) N21A -0.1123 (0.0048) C51A Rms deviation of fitted atoms = 0.0142 - 2.3437 (0.0099) x + 4.1620 (0.0182) y + 12.1913 (0.0051) z = 3.1329 (0.0060) Angle to previous plane (with approximate e.s.d.) = 67.79 (0.07) * 0.0026 (0.0011) S1B * -0.0010 (0.0014) C2B * -0.0014 (0.0015) N3B * 0.0041 (0.0015) N4B * -0.0043 (0.0014) C5B -0.0160 (0.0043) N21B -0.0062 (0.0046) C51B Rms deviation of fitted atoms = 0.0030 12.0023 (0.0056) x + 4.9905 (0.0188) y + 0.6237 (0.0109) z = 4.2378 (0.0013) Angle to previous plane (with approximate e.s.d.) = 88.16 (0.07) * 0.0045 (0.0012) S1C * -0.0016 (0.0015) C2C * -0.0028 (0.0016) N3C * 0.0076 (0.0016) N4C * -0.0077 (0.0016) C5C 0.0024 (0.0042) N21C -0.0569 (0.0053) C51C Rms deviation of fitted atoms = 0.0054 - 0.7523 (0.0098) x - 7.6151 (0.0164) y + 11.1595 (0.0080) z = 1.7041 (0.0022) Angle to previous plane (with approximate e.s.d.) = 80.26 (0.07) * -0.0109 (0.0011) S1D * 0.0124 (0.0014) C2D * -0.0079 (0.0015) N3D * -0.0036 (0.0015) N4D * 0.0100 (0.0014) C5D 0.0243 (0.0040) N21D 0.0576 (0.0045) C51D Rms deviation of fitted atoms = 0.0095 |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.26304 (2) | 0.088224 (19) | 0.25913 (2) | 0.01566 (11) | |
Cl1 | 0.25140 (5) | 0.25576 (4) | 0.27156 (5) | 0.02003 (15) | |
Cl2 | 0.18676 (6) | 0.72637 (5) | 0.09052 (6) | 0.0365 (2) | |
S1A | 0.13011 (5) | −0.01378 (4) | 0.56186 (5) | 0.02285 (16) | |
C2A | 0.1995 (2) | −0.01996 (17) | 0.44566 (19) | 0.0200 (5) | |
N21A | 0.2332 (2) | −0.09547 (14) | 0.40964 (19) | 0.0262 (5) | |
H21A | 0.2668 | −0.0976 | 0.3503 | 0.033* | |
H22A | 0.2220 | −0.1437 | 0.4450 | 0.033* | |
N3A | 0.21017 (17) | 0.05756 (14) | 0.40184 (16) | 0.0193 (5) | |
N4A | 0.16010 (17) | 0.12479 (14) | 0.45547 (17) | 0.0203 (5) | |
C5A | 0.1142 (2) | 0.09743 (17) | 0.5383 (2) | 0.0211 (6) | |
C51A | 0.0494 (2) | 0.15447 (19) | 0.6065 (2) | 0.0277 (6) | |
H51A | −0.0197 | 0.1275 | 0.6167 | 0.035* | |
H52A | 0.0404 | 0.2118 | 0.5737 | 0.035* | |
H53A | 0.0848 | 0.1616 | 0.6738 | 0.035* | |
S1B | 0.60995 (5) | 0.07706 (5) | 0.34814 (6) | 0.02764 (18) | |
C2B | 0.4958 (2) | 0.12962 (17) | 0.3080 (2) | 0.0213 (5) | |
N21B | 0.4938 (2) | 0.21303 (15) | 0.2779 (2) | 0.0333 (6) | |
H21B | 0.4342 | 0.2369 | 0.2573 | 0.042* | |
H22B | 0.5520 | 0.2441 | 0.2785 | 0.042* | |
N3B | 0.41291 (17) | 0.07819 (14) | 0.30955 (17) | 0.0190 (5) | |
N4B | 0.43585 (17) | −0.00594 (14) | 0.34313 (17) | 0.0214 (5) | |
C5B | 0.5339 (2) | −0.01633 (17) | 0.3648 (2) | 0.0226 (6) | |
C51B | 0.5797 (2) | −0.10071 (19) | 0.4023 (2) | 0.0293 (6) | |
H51B | 0.6099 | −0.0925 | 0.4718 | 0.037* | |
H52B | 0.6348 | −0.1197 | 0.3547 | 0.037* | |
H53B | 0.5243 | −0.1452 | 0.4049 | 0.037* | |
S1C | 0.33157 (6) | 0.06330 (5) | −0.08539 (5) | 0.02568 (17) | |
C2C | 0.3014 (2) | 0.12063 (17) | 0.02716 (19) | 0.0189 (5) | |
N21C | 0.2675 (2) | 0.20309 (15) | 0.02633 (18) | 0.0267 (5) | |
H21C | 0.2535 | 0.2298 | 0.0851 | 0.033* | |
H22C | 0.2591 | 0.2308 | −0.0330 | 0.033* | |
N3C | 0.31609 (17) | 0.07445 (14) | 0.11166 (16) | 0.0186 (5) | |
N4C | 0.35293 (18) | −0.00963 (14) | 0.09197 (17) | 0.0213 (5) | |
C5C | 0.3631 (2) | −0.02505 (18) | −0.0057 (2) | 0.0239 (6) | |
C51C | 0.3971 (3) | −0.1113 (2) | −0.0483 (2) | 0.0356 (7) | |
H51C | 0.4605 | −0.1033 | −0.0900 | 0.044* | |
H52C | 0.3408 | −0.1355 | −0.0919 | 0.044* | |
H53C | 0.4124 | −0.1515 | 0.0091 | 0.044* | |
S1D | −0.08151 (5) | 0.04405 (5) | 0.17629 (5) | 0.02463 (17) | |
C2D | 0.0249 (2) | 0.10239 (17) | 0.2254 (2) | 0.0204 (5) | |
N21D | 0.01343 (19) | 0.17733 (15) | 0.27680 (18) | 0.0258 (5) | |
H21D | 0.0692 | 0.2058 | 0.2995 | 0.032* | |
H22D | −0.0499 | 0.1983 | 0.2880 | 0.032* | |
N3D | 0.11568 (17) | 0.06506 (14) | 0.20419 (16) | 0.0195 (5) | |
N4D | 0.10534 (18) | −0.01330 (14) | 0.15040 (17) | 0.0219 (5) | |
C5D | 0.0090 (2) | −0.03344 (18) | 0.1314 (2) | 0.0226 (6) | |
C51D | −0.0263 (2) | −0.11442 (19) | 0.0780 (2) | 0.0277 (6) | |
H51D | −0.0626 | −0.0991 | 0.0132 | 0.035* | |
H52D | −0.0744 | −0.1466 | 0.1231 | 0.035* | |
H53D | 0.0349 | −0.1510 | 0.0626 | 0.035* | |
O1W | 0.66078 (18) | 0.33564 (14) | 0.27617 (17) | 0.0280 (5) | |
H1W | 0.653 (3) | 0.382 (3) | 0.308 (3) | 0.059 (13)* | |
H2W | 0.712 (4) | 0.311 (3) | 0.311 (3) | 0.060 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01624 (18) | 0.01742 (18) | 0.01333 (16) | 0.00005 (11) | 0.00023 (12) | 0.00026 (11) |
Cl1 | 0.0230 (3) | 0.0180 (3) | 0.0192 (3) | −0.0001 (2) | 0.0007 (2) | −0.0006 (2) |
Cl2 | 0.0310 (4) | 0.0298 (4) | 0.0488 (5) | −0.0046 (3) | 0.0117 (3) | −0.0145 (3) |
S1A | 0.0257 (4) | 0.0243 (3) | 0.0186 (3) | −0.0005 (3) | 0.0047 (3) | 0.0033 (3) |
C2A | 0.0179 (13) | 0.0255 (14) | 0.0167 (12) | −0.0017 (10) | 0.0004 (10) | 0.0028 (11) |
N21A | 0.0325 (14) | 0.0214 (11) | 0.0249 (12) | 0.0018 (10) | 0.0090 (10) | 0.0008 (9) |
N3A | 0.0200 (11) | 0.0203 (11) | 0.0174 (10) | 0.0005 (9) | 0.0011 (9) | 0.0013 (9) |
N4A | 0.0220 (11) | 0.0214 (11) | 0.0175 (10) | 0.0014 (9) | 0.0011 (9) | −0.0008 (9) |
C5A | 0.0216 (14) | 0.0232 (13) | 0.0184 (13) | −0.0016 (10) | −0.0004 (10) | −0.0003 (10) |
C51A | 0.0270 (15) | 0.0303 (14) | 0.0258 (14) | −0.0043 (12) | 0.0066 (12) | −0.0062 (12) |
S1B | 0.0176 (3) | 0.0304 (4) | 0.0348 (4) | −0.0006 (3) | −0.0047 (3) | 0.0021 (3) |
C2B | 0.0186 (13) | 0.0246 (13) | 0.0208 (13) | 0.0007 (11) | 0.0001 (10) | −0.0009 (11) |
N21B | 0.0215 (13) | 0.0259 (13) | 0.0525 (17) | −0.0038 (10) | −0.0023 (12) | 0.0096 (12) |
N3B | 0.0179 (11) | 0.0206 (11) | 0.0185 (11) | 0.0002 (9) | −0.0011 (9) | −0.0005 (9) |
N4B | 0.0222 (12) | 0.0216 (11) | 0.0203 (11) | 0.0014 (9) | −0.0003 (9) | 0.0001 (9) |
C5B | 0.0258 (15) | 0.0232 (13) | 0.0187 (12) | 0.0024 (11) | −0.0007 (11) | −0.0016 (11) |
C51B | 0.0304 (16) | 0.0287 (15) | 0.0287 (15) | 0.0079 (12) | −0.0031 (12) | −0.0002 (12) |
S1C | 0.0357 (4) | 0.0262 (3) | 0.0151 (3) | 0.0036 (3) | 0.0021 (3) | −0.0019 (3) |
C2C | 0.0190 (13) | 0.0223 (13) | 0.0156 (12) | −0.0004 (10) | 0.0007 (10) | 0.0011 (10) |
N21C | 0.0440 (15) | 0.0195 (11) | 0.0165 (11) | 0.0070 (10) | −0.0019 (10) | 0.0002 (9) |
N3C | 0.0218 (11) | 0.0175 (10) | 0.0167 (10) | 0.0021 (9) | 0.0020 (9) | 0.0008 (9) |
N4C | 0.0235 (12) | 0.0198 (11) | 0.0207 (11) | 0.0047 (9) | 0.0039 (9) | −0.0003 (9) |
C5C | 0.0266 (15) | 0.0234 (14) | 0.0218 (13) | 0.0019 (11) | 0.0016 (11) | −0.0016 (11) |
C51C | 0.049 (2) | 0.0305 (16) | 0.0275 (16) | 0.0088 (14) | 0.0057 (14) | −0.0061 (13) |
S1D | 0.0187 (3) | 0.0313 (4) | 0.0239 (3) | −0.0028 (3) | −0.0007 (3) | −0.0008 (3) |
C2D | 0.0188 (13) | 0.0271 (13) | 0.0154 (12) | −0.0006 (11) | −0.0004 (10) | 0.0032 (11) |
N21D | 0.0195 (12) | 0.0280 (12) | 0.0297 (13) | 0.0010 (9) | 0.0021 (10) | −0.0041 (10) |
N3D | 0.0201 (11) | 0.0221 (11) | 0.0163 (10) | −0.0011 (9) | −0.0021 (9) | −0.0020 (9) |
N4D | 0.0227 (12) | 0.0207 (11) | 0.0223 (11) | −0.0023 (9) | −0.0004 (9) | −0.0007 (9) |
C5D | 0.0265 (15) | 0.0246 (13) | 0.0166 (12) | −0.0016 (11) | −0.0008 (11) | 0.0028 (11) |
C51D | 0.0279 (15) | 0.0275 (14) | 0.0277 (15) | −0.0065 (12) | −0.0026 (12) | −0.0003 (12) |
O1W | 0.0301 (12) | 0.0223 (11) | 0.0317 (11) | 0.0001 (9) | 0.0015 (9) | 0.0002 (9) |
Cu1—N3A | 2.019 (2) | C51B—H53B | 0.98 |
Cu1—N3B | 2.014 (2) | S1C—C2C | 1.741 (3) |
Cu1—N3C | 2.033 (2) | S1C—C5C | 1.743 (3) |
Cu1—N3D | 2.029 (2) | C2C—N3C | 1.310 (3) |
Cu1—Cl1 | 2.5744 (7) | C2C—N21C | 1.334 (3) |
S1A—C5A | 1.741 (3) | N21C—H21C | 0.88 |
S1A—C2A | 1.747 (2) | N21C—H22C | 0.88 |
C2A—N21A | 1.318 (3) | N3C—N4C | 1.394 (3) |
C2A—N3A | 1.322 (3) | N4C—C5C | 1.288 (3) |
N21A—H21A | 0.88 | C5C—C51C | 1.495 (4) |
N21A—H22A | 0.88 | C51C—H51C | 0.98 |
N3A—N4A | 1.396 (3) | C51C—H52C | 0.98 |
N4A—C5A | 1.291 (3) | C51C—H53C | 0.98 |
C5A—C51A | 1.492 (4) | S1D—C2D | 1.737 (3) |
C51A—H51A | 0.98 | S1D—C5D | 1.755 (3) |
C51A—H52A | 0.98 | C2D—N3D | 1.318 (3) |
C51A—H53A | 0.98 | C2D—N21D | 1.334 (3) |
S1B—C2B | 1.735 (3) | N21D—H21D | 0.88 |
S1B—C5B | 1.741 (3) | N21D—H22D | 0.88 |
C2B—N3B | 1.316 (3) | N3D—N4D | 1.391 (3) |
C2B—N21B | 1.335 (4) | N4D—C5D | 1.285 (4) |
N21B—H21B | 0.88 | C5D—C51D | 1.486 (4) |
N21B—H22B | 0.88 | C51D—H51D | 0.98 |
N3B—N4B | 1.389 (3) | C51D—H52D | 0.98 |
N4B—C5B | 1.286 (4) | C51D—H53D | 0.98 |
C5B—C51B | 1.495 (4) | O1W—H1W | 0.83 (5) |
C51B—H51B | 0.98 | O1W—H2W | 0.88 (5) |
C51B—H52B | 0.98 | ||
N3A—Cu1—N3B | 90.57 (9) | H51B—C51B—H52B | 109.5 |
N3A—Cu1—N3C | 160.59 (9) | C5B—C51B—H53B | 109.5 |
N3A—Cu1—N3D | 87.91 (9) | H51B—C51B—H53B | 109.5 |
N3B—Cu1—N3C | 88.45 (9) | H52B—C51B—H53B | 109.5 |
N3B—Cu1—N3D | 165.44 (9) | C2C—S1C—C5C | 87.24 (12) |
N3C—Cu1—N3D | 88.20 (9) | N3C—C2C—N21C | 124.1 (2) |
N3A—Cu1—Cl1 | 98.94 (6) | N3C—C2C—S1C | 112.91 (19) |
N3B—Cu1—Cl1 | 96.36 (6) | N21C—C2C—S1C | 122.95 (19) |
N3C—Cu1—Cl1 | 100.44 (6) | C2C—N21C—H21C | 120.0 |
N3D—Cu1—Cl1 | 98.19 (6) | C2C—N21C—H22C | 120.0 |
C5A—S1A—C2A | 87.85 (12) | H21C—N21C—H22C | 120.0 |
N21A—C2A—N3A | 127.0 (2) | C2C—N3C—N4C | 113.1 (2) |
N21A—C2A—S1A | 121.1 (2) | C2C—N3C—Cu1 | 132.42 (18) |
N3A—C2A—S1A | 111.83 (19) | N4C—N3C—Cu1 | 112.37 (15) |
C2A—N21A—H21A | 120.0 | C5C—N4C—N3C | 112.6 (2) |
C2A—N21A—H22A | 120.0 | N4C—C5C—C51C | 123.5 (3) |
H21A—N21A—H22A | 120.0 | N4C—C5C—S1C | 114.1 (2) |
C2A—N3A—N4A | 113.7 (2) | C51C—C5C—S1C | 122.3 (2) |
C2A—N3A—Cu1 | 129.36 (18) | C5C—C51C—H51C | 109.5 |
N4A—N3A—Cu1 | 115.86 (16) | C5C—C51C—H52C | 109.5 |
C5A—N4A—N3A | 112.4 (2) | H51C—C51C—H52C | 109.5 |
N4A—C5A—C51A | 123.6 (2) | C5C—C51C—H53C | 109.5 |
N4A—C5A—S1A | 114.1 (2) | H51C—C51C—H53C | 109.5 |
C51A—C5A—S1A | 122.3 (2) | H52C—C51C—H53C | 109.5 |
C5A—C51A—H51A | 109.5 | C2D—S1D—C5D | 87.48 (13) |
C5A—C51A—H52A | 109.5 | N3D—C2D—N21D | 125.1 (3) |
H51A—C51A—H52A | 109.5 | N3D—C2D—S1D | 112.5 (2) |
C5A—C51A—H53A | 109.5 | N21D—C2D—S1D | 122.3 (2) |
H51A—C51A—H53A | 109.5 | C2D—N21D—H21D | 120.0 |
H52A—C51A—H53A | 109.5 | C2D—N21D—H22D | 120.0 |
C2B—S1B—C5B | 87.35 (13) | H21D—N21D—H22D | 120.0 |
N3B—C2B—N21B | 124.3 (3) | C2D—N3D—N4D | 113.4 (2) |
N3B—C2B—S1B | 112.7 (2) | C2D—N3D—Cu1 | 131.27 (19) |
N21B—C2B—S1B | 123.0 (2) | N4D—N3D—Cu1 | 114.06 (16) |
C2B—N21B—H21B | 120.0 | C5D—N4D—N3D | 112.8 (2) |
C2B—N21B—H22B | 120.0 | N4D—C5D—C51D | 124.9 (3) |
H21B—N21B—H22B | 120.0 | N4D—C5D—S1D | 113.7 (2) |
C2B—N3B—N4B | 113.2 (2) | C51D—C5D—S1D | 121.4 (2) |
C2B—N3B—Cu1 | 134.85 (19) | C5D—C51D—H51D | 109.5 |
N4B—N3B—Cu1 | 111.52 (16) | C5D—C51D—H52D | 109.5 |
C5B—N4B—N3B | 112.5 (2) | H51D—C51D—H52D | 109.5 |
N4B—C5B—C51B | 123.5 (3) | C5D—C51D—H53D | 109.5 |
N4B—C5B—S1B | 114.2 (2) | H51D—C51D—H53D | 109.5 |
C51B—C5B—S1B | 122.3 (2) | H52D—C51D—H53D | 109.5 |
C5B—C51B—H51B | 109.5 | H1W—O1W—H2W | 103 (4) |
C5B—C51B—H52B | 109.5 | ||
C5A—S1A—C2A—N21A | −175.9 (2) | C5C—S1C—C2C—N3C | 0.4 (2) |
C5A—S1A—C2A—N3A | 2.9 (2) | C5C—S1C—C2C—N21C | −179.9 (2) |
N21A—C2A—N3A—N4A | 176.0 (3) | N21C—C2C—N3C—N4C | −179.3 (2) |
S1A—C2A—N3A—N4A | −2.7 (3) | S1C—C2C—N3C—N4C | 0.3 (3) |
N21A—C2A—N3A—Cu1 | 8.7 (4) | N21C—C2C—N3C—Cu1 | 18.6 (4) |
S1A—C2A—N3A—Cu1 | −170.01 (13) | S1C—C2C—N3C—Cu1 | −161.75 (15) |
N3B—Cu1—N3A—C2A | −81.6 (2) | N3B—Cu1—N3C—C2C | −128.1 (3) |
N3D—Cu1—N3A—C2A | 83.9 (2) | N3A—Cu1—N3C—C2C | 144.6 (3) |
N3C—Cu1—N3A—C2A | 5.3 (4) | N3D—Cu1—N3C—C2C | 66.1 (3) |
Cl1—Cu1—N3A—C2A | −178.2 (2) | Cl1—Cu1—N3C—C2C | −31.9 (3) |
N3B—Cu1—N3A—N4A | 111.27 (18) | N3B—Cu1—N3C—N4C | 69.74 (17) |
N3D—Cu1—N3A—N4A | −83.21 (18) | N3A—Cu1—N3C—N4C | −17.6 (4) |
N3C—Cu1—N3A—N4A | −161.8 (2) | N3D—Cu1—N3C—N4C | −96.09 (18) |
Cl1—Cu1—N3A—N4A | 14.75 (18) | Cl1—Cu1—N3C—N4C | 165.92 (16) |
C2A—N3A—N4A—C5A | 0.8 (3) | C2C—N3C—N4C—C5C | −1.1 (3) |
Cu1—N3A—N4A—C5A | 169.91 (18) | Cu1—N3C—N4C—C5C | 164.60 (19) |
N3A—N4A—C5A—C51A | −176.1 (2) | N3C—N4C—C5C—C51C | −177.4 (3) |
N3A—N4A—C5A—S1A | 1.5 (3) | N3C—N4C—C5C—S1C | 1.5 (3) |
C2A—S1A—C5A—N4A | −2.5 (2) | C2C—S1C—C5C—N4C | −1.1 (2) |
C2A—S1A—C5A—C51A | 175.1 (2) | C2C—S1C—C5C—C51C | 177.8 (3) |
C5B—S1B—C2B—N3B | 0.3 (2) | C5D—S1D—C2D—N3D | 1.9 (2) |
C5B—S1B—C2B—N21B | −179.1 (3) | C5D—S1D—C2D—N21D | −179.2 (2) |
N21B—C2B—N3B—N4B | 179.5 (2) | N21D—C2D—N3D—N4D | 179.4 (2) |
S1B—C2B—N3B—N4B | 0.1 (3) | S1D—C2D—N3D—N4D | −1.8 (3) |
N21B—C2B—N3B—Cu1 | 8.1 (4) | N21D—C2D—N3D—Cu1 | 13.1 (4) |
S1B—C2B—N3B—Cu1 | −171.21 (14) | S1D—C2D—N3D—Cu1 | −168.06 (14) |
N3A—Cu1—N3B—C2B | −126.3 (3) | N3B—Cu1—N3D—C2D | 145.4 (3) |
N3D—Cu1—N3B—C2B | 149.9 (3) | N3A—Cu1—N3D—C2D | 61.1 (2) |
N3C—Cu1—N3B—C2B | 73.1 (3) | N3C—Cu1—N3D—C2D | −137.9 (2) |
Cl1—Cu1—N3B—C2B | −27.2 (3) | Cl1—Cu1—N3D—C2D | −37.6 (2) |
N3A—Cu1—N3B—N4B | 62.29 (17) | N3B—Cu1—N3D—N4D | −20.9 (4) |
N3D—Cu1—N3B—N4B | −21.6 (4) | N3A—Cu1—N3D—N4D | −105.08 (17) |
N3C—Cu1—N3B—N4B | −98.32 (16) | N3C—Cu1—N3D—N4D | 55.90 (17) |
Cl1—Cu1—N3B—N4B | 161.35 (15) | Cl1—Cu1—N3D—N4D | 156.19 (15) |
C2B—N3B—N4B—C5B | −0.6 (3) | C2D—N3D—N4D—C5D | 0.4 (3) |
Cu1—N3B—N4B—C5B | 172.80 (17) | Cu1—N3D—N4D—C5D | 169.20 (18) |
N3B—N4B—C5B—C51B | −179.8 (2) | N3D—N4D—C5D—C51D | −178.1 (2) |
N3B—N4B—C5B—S1B | 0.8 (3) | N3D—N4D—C5D—S1D | 1.1 (3) |
C2B—S1B—C5B—N4B | −0.6 (2) | C2D—S1D—C5D—N4D | −1.7 (2) |
C2B—S1B—C5B—C51B | 179.9 (2) | C2D—S1D—C5D—C51D | 177.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21A—H21A···O1Wi | 0.88 | 2.14 | 2.953 (3) | 154 |
N21A—H21A···N4B | 0.88 | 2.57 | 3.049 (3) | 115 |
N21A—H22A···Cl2ii | 0.88 | 2.31 | 3.134 (2) | 156 |
N21B—H21B···Cl1 | 0.88 | 2.35 | 3.152 (3) | 151 |
N21B—H22B···O1W | 0.88 | 1.97 | 2.835 (3) | 167 |
N21C—H21C···Cl1 | 0.88 | 2.44 | 3.269 (2) | 158 |
N21C—H22C···Cl1iii | 0.88 | 2.53 | 3.348 (2) | 155 |
N21C—H22C···N4Aiii | 0.88 | 2.55 | 3.102 (3) | 122 |
N21D—H21D···Cl1 | 0.88 | 2.47 | 3.257 (2) | 149 |
N21D—H21D···N4A | 0.88 | 2.62 | 3.059 (3) | 112 |
N21D—H22D···Cl2iv | 0.88 | 2.39 | 3.169 (2) | 148 |
O1W—H1W···N4Cv | 0.83 (5) | 2.10 (5) | 2.921 (3) | 170 (4) |
O1W—H2W···Cl2i | 0.88 (5) | 2.21 (5) | 3.075 (3) | 167 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x, y−1/2, −z+1/2; (v) −x+1, y+1/2, −z+1/2. |
[CuCl(C4H7N3S)4]Cl | Melting point: ? K K |
Mr = 651.23 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4/ncc | Cell parameters from 6958 reflections |
a = 12.3273 (17) Å | θ = 2.9–27.5° |
c = 17.705 (4) Å | µ = 1.35 mm−1 |
V = 2690.5 (7) Å3 | T = 150 K |
Z = 4 | Plate, green |
F(000) = 1340 | 0.30 × 0.15 × 0.08 mm |
Dx = 1.608 Mg m−3 |
Enraf Nonius KappaCCD area detector diffractometer | 1531 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 1303 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.9° |
Phi and ω scans | h = −15→15 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −15→15 |
Tmin = 0.687, Tmax = 0.905 | l = −22→21 |
15487 measured reflections |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0565P)2 + 0.8119P] where P = (Fo2 + 2Fc2)/3 |
1531 reflections | (Δ/σ)max < 0.001 |
84 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
[CuCl(C4H7N3S)4]Cl | Z = 4 |
Mr = 651.23 | Mo Kα radiation |
Tetragonal, P4/ncc | µ = 1.35 mm−1 |
a = 12.3273 (17) Å | T = 150 K |
c = 17.705 (4) Å | 0.30 × 0.15 × 0.08 mm |
V = 2690.5 (7) Å3 |
Enraf Nonius KappaCCD area detector diffractometer | 1531 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1303 reflections with I > 2σ(I) |
Tmin = 0.687, Tmax = 0.905 | Rint = 0.051 |
15487 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.54 e Å−3 |
1531 reflections | Δρmin = −0.65 e Å−3 |
84 parameters |
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. |
Geometry. Mean plane data ex SHELXL97 for molecule (II) ############################################# Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 1.2389 (0.0065) x + 11.8149 (0.0038) y - 4.7278 (0.0146) z = 2.3700(0.0034) * -0.0031 (0.0007) S1 * 0.0015 (0.0009) C2 * 0.0012 (0.0010) N3 * -0.0045 (0.0010) N4 * 0.0049 (0.0009) C5 0.0002 (0.0029) N21 0.0308 (0.0031) C51 0.2043 (0.0039) C52 Rms deviation of fitted atoms = 0.0034 |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.2500 | 0.2500 | 0.09476 (2) | 0.01374 (16) | |
Cl1 | 0.2500 | 0.2500 | 0.23604 (5) | 0.0180 (2) | |
Cl2 | 0.7500 | 0.2500 | 0.2500 | 0.0247 (2) | |
S1 | 0.60241 (3) | 0.16010 (4) | 0.05732 (3) | 0.02213 (17) | |
C2 | 0.49154 (14) | 0.19444 (14) | 0.11310 (10) | 0.0183 (4) | |
N21 | 0.50103 (13) | 0.22228 (15) | 0.18546 (9) | 0.0256 (4) | |
H21 | 0.4429 | 0.2389 | 0.2119 | 0.032* | |
H22 | 0.5654 | 0.2241 | 0.2068 | 0.032* | |
N3 | 0.39937 (12) | 0.18910 (12) | 0.07565 (8) | 0.0178 (3) | |
N4 | 0.41141 (12) | 0.15744 (11) | 0.00091 (8) | 0.0191 (3) | |
C5 | 0.51070 (14) | 0.14056 (14) | −0.01725 (10) | 0.0185 (4) | |
C51 | 0.54716 (16) | 0.10795 (15) | −0.09468 (10) | 0.0229 (4) | |
H51 | 0.5784 | 0.0340 | −0.0925 | 0.029* | |
H52 | 0.6049 | 0.1581 | −0.1118 | 0.029* | |
C52 | 0.45463 (18) | 0.10947 (18) | −0.15181 (10) | 0.0303 (5) | |
H53 | 0.4220 | 0.1819 | −0.1531 | 0.038* | |
H54 | 0.3996 | 0.0561 | −0.1371 | 0.038* | |
H55 | 0.4828 | 0.0913 | −0.2020 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01263 (19) | 0.01263 (19) | 0.0160 (2) | 0.000 | 0.000 | 0.000 |
Cl1 | 0.0190 (3) | 0.0190 (3) | 0.0160 (4) | 0.000 | 0.000 | 0.000 |
Cl2 | 0.0204 (3) | 0.0204 (3) | 0.0335 (5) | −0.0018 (3) | 0.000 | 0.000 |
S1 | 0.0151 (3) | 0.0277 (3) | 0.0236 (3) | 0.00169 (18) | 0.00121 (17) | −0.00118 (18) |
C2 | 0.0160 (8) | 0.0170 (8) | 0.0219 (9) | −0.0016 (7) | 0.0007 (7) | 0.0010 (7) |
N21 | 0.0166 (8) | 0.0392 (10) | 0.0211 (8) | −0.0006 (7) | 0.0001 (6) | −0.0042 (7) |
N3 | 0.0164 (7) | 0.0176 (7) | 0.0195 (7) | 0.0021 (6) | 0.0013 (6) | −0.0012 (6) |
N4 | 0.0200 (8) | 0.0191 (8) | 0.0183 (8) | 0.0018 (6) | 0.0007 (6) | −0.0012 (6) |
C5 | 0.0186 (9) | 0.0159 (9) | 0.0211 (9) | 0.0006 (7) | 0.0002 (7) | 0.0001 (7) |
C51 | 0.0260 (10) | 0.0216 (10) | 0.0211 (10) | 0.0025 (8) | 0.0038 (7) | −0.0012 (7) |
C52 | 0.0335 (12) | 0.0362 (12) | 0.0213 (9) | 0.0069 (10) | −0.0009 (8) | −0.0004 (8) |
Cu1—N3i | 2.0171 (15) | N21—H22 | 0.88 |
Cu1—N3ii | 2.0171 (15) | N3—N4 | 1.388 (2) |
Cu1—N3iii | 2.0171 (15) | N4—C5 | 1.282 (2) |
Cu1—N3 | 2.0171 (15) | C5—C51 | 1.498 (2) |
Cu1—Cl1 | 2.5013 (10) | C51—C52 | 1.525 (3) |
S1—C2 | 1.7385 (18) | C51—H51 | 0.99 |
S1—C5 | 1.7548 (18) | C51—H52 | 0.99 |
C2—N3 | 1.317 (2) | C52—H53 | 0.98 |
C2—N21 | 1.331 (2) | C52—H54 | 0.98 |
N21—H21 | 0.88 | C52—H55 | 0.98 |
N3i—Cu1—N3ii | 160.69 (9) | C2—N3—Cu1 | 133.19 (12) |
N3i—Cu1—N3iii | 88.388 (14) | N4—N3—Cu1 | 111.24 (11) |
N3ii—Cu1—N3iii | 88.387 (14) | C5—N4—N3 | 112.76 (14) |
N3i—Cu1—N3 | 88.387 (14) | N4—C5—C51 | 124.02 (16) |
N3ii—Cu1—N3 | 88.387 (14) | N4—C5—S1 | 113.82 (13) |
N3iii—Cu1—N3 | 160.69 (9) | C51—C5—S1 | 122.16 (13) |
N3i—Cu1—Cl1 | 99.66 (4) | C5—C51—C52 | 112.30 (16) |
N3ii—Cu1—Cl1 | 99.66 (4) | C5—C51—H51 | 109.1 |
N3iii—Cu1—Cl1 | 99.66 (4) | C52—C51—H51 | 109.1 |
N3—Cu1—Cl1 | 99.66 (4) | C5—C51—H52 | 109.1 |
C2—S1—C5 | 87.39 (8) | C52—C51—H52 | 109.1 |
N3—C2—N21 | 124.96 (16) | H51—C51—H52 | 107.9 |
N3—C2—S1 | 112.34 (13) | C51—C52—H53 | 109.5 |
N21—C2—S1 | 122.70 (14) | C51—C52—H54 | 109.5 |
C2—N21—H21 | 120.0 | H53—C52—H54 | 109.5 |
C2—N21—H22 | 120.0 | C51—C52—H55 | 109.5 |
H21—N21—H22 | 120.0 | H53—C52—H55 | 109.5 |
C2—N3—N4 | 113.69 (14) | H54—C52—H55 | 109.5 |
C5—S1—C2—N3 | 0.33 (14) | N3ii—Cu1—N3—N4 | 66.82 (11) |
C5—S1—C2—N21 | −179.91 (17) | N3iii—Cu1—N3—N4 | −13.66 (10) |
N21—C2—N3—N4 | −179.67 (17) | Cl1—Cu1—N3—N4 | 166.34 (10) |
S1—C2—N3—N4 | 0.09 (18) | C2—N3—N4—C5 | −0.6 (2) |
N21—C2—N3—Cu1 | 17.7 (3) | Cu1—N3—N4—C5 | 165.87 (12) |
S1—C2—N3—Cu1 | −162.58 (10) | N3—N4—C5—C51 | −178.65 (16) |
N3i—Cu1—N3—C2 | 68.84 (19) | N3—N4—C5—S1 | 0.91 (18) |
N3ii—Cu1—N3—C2 | −130.20 (16) | C2—S1—C5—N4 | −0.72 (14) |
N3iii—Cu1—N3—C2 | 149.32 (17) | C2—S1—C5—C51 | 178.85 (16) |
Cl1—Cu1—N3—C2 | −30.68 (17) | N4—C5—C51—C52 | 6.5 (3) |
N3i—Cu1—N3—N4 | −94.13 (10) | S1—C5—C51—C52 | −173.03 (14) |
Symmetry codes: (i) −y+1/2, x, z; (ii) y, −x+1/2, z; (iii) −x+1/2, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···Cl1 | 0.88 | 2.42 | 3.2396 (16) | 155 |
N21—H22···Cl2 | 0.88 | 2.42 | 3.2928 (16) | 171 |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [CuCl(C3H5N3S)4]Cl·H2O | [CuCl(C4H7N3S)4]Cl |
Mr | 613.15 | 651.23 |
Crystal system, space group | Monoclinic, P21/c | Tetragonal, P4/ncc |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 12.7183 (2), 15.3106 (3), 12.8865 (2) | 12.3273 (17), 12.3273 (17), 17.705 (4) |
α, β, γ (°) | 90, 90.4820 (9), 90 | 90, 90, 90 |
V (Å3) | 2509.23 (7) | 2690.5 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.45 | 1.35 |
Crystal size (mm) | 0.25 × 0.18 × 0.05 | 0.30 × 0.15 × 0.08 |
Data collection | ||
Diffractometer | Enraf Nonius KappaCCD area detector diffractometer | Enraf Nonius KappaCCD area detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.714, 0.931 | 0.687, 0.905 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19695, 5620, 4500 | 15487, 1531, 1303 |
Rint | 0.050 | 0.051 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.105, 0.85 | 0.032, 0.088, 1.04 |
No. of reflections | 5620 | 1531 |
No. of parameters | 302 | 84 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.73, −0.77 | 0.54, −0.65 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1997), SHELXL97.
Cu1—N3A | 2.019 (2) | Cu1—N3D | 2.029 (2) |
Cu1—N3B | 2.014 (2) | Cu1—Cl1 | 2.5744 (7) |
Cu1—N3C | 2.033 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21A—H21A···O1Wi | 0.88 | 2.14 | 2.953 (3) | 154 |
N21A—H21A···N4B | 0.88 | 2.57 | 3.049 (3) | 115 |
N21A—H22A···Cl2ii | 0.88 | 2.31 | 3.134 (2) | 156 |
N21B—H21B···Cl1 | 0.88 | 2.35 | 3.152 (3) | 151 |
N21B—H22B···O1W | 0.88 | 1.97 | 2.835 (3) | 167 |
N21C—H21C···Cl1 | 0.88 | 2.44 | 3.269 (2) | 158 |
N21C—H22C···Cl1iii | 0.88 | 2.53 | 3.348 (2) | 155 |
N21C—H22C···N4Aiii | 0.88 | 2.55 | 3.102 (3) | 122 |
N21D—H21D···Cl1 | 0.88 | 2.47 | 3.257 (2) | 149 |
N21D—H21D···N4A | 0.88 | 2.62 | 3.059 (3) | 112 |
N21D—H22D···Cl2iv | 0.88 | 2.39 | 3.169 (2) | 148 |
O1W—H1W···N4Cv | 0.83 (5) | 2.10 (5) | 2.921 (3) | 170 (4) |
O1W—H2W···Cl2i | 0.88 (5) | 2.21 (5) | 3.075 (3) | 167 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x, y−1/2, −z+1/2; (v) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···Cl1 | 0.88 | 2.42 | 3.2396 (16) | 155 |
N21—H22···Cl2 | 0.88 | 2.42 | 3.2928 (16) | 171 |
2-Amino-1,3-thiazoles have many applications in both human and veterinary medicine as well as materials science (Lynch et al., 1999). The mode of action for several 2-aminothiazole derivatives depends on metal-ligand binding, such as in the case of 2-amino-4,5-dihydro-1,3-thiazole which possibly induces the transformation of tumor cells (Kubiak et al., 1983; Kubiak & Glowiak, 1984). 2-Aminothiazoles contain three donor sites available for co-ordination to a metal species, the amine N and the heterocyclic N and S atoms. However, structural studies of metal complexes containing 2-aminothiazoles have shown that the predominant point for metal attachment is to the heterocyclic N. As a derivative of 2-aminothiazoles, 2-amino-1,3,4-thiadiazoles contain two heterocyclic N atoms available for metal complexation and have been studied as corrosion inhibitors (Downie et al., 1972), for potential antiviral activity (Saramet, 1975; Tonew & Limki, 1974), and as an inhibitor of carbonic anhydrase (Pedregosa et al., 1993).
Four structural examples of metal complexes of substituted 2-amino-1,3,4-thiadiazoles are known; they display varying co-ordination geometries. The copper(I) chloride complex of 2-amino-5-methyl-1,3,4-thiadiazole (Neverov et al., 1986) forms linear polymers with planar units of two Cu atoms bridged by two thiadiazole molecules which then propagate via two bridging Cl atoms to the next Cu (Fig. 1). For the thiadiazoles in this structure, Cu atoms bind both heterocyclic N atoms. However, in the known metal(II) halide complexes of thiadiazole derivatives (Mn: Fabretti et al., 1993; Zn: Khusenov et al., 1997; Hg: Antolini et al., 1988) only one N atom is involved in metal co-ordination. In each case there are two thiadiazoles per metal and for the ZnCl2 and HgBr2 complexes the geometry is tetrahedral whereas the addition of two water molecules in the MnCl2 complex results in octahedral geometry. We have instigated a series of studies covering the syntheses of metal halide complexes of substituted 2-amino-1,3,4-thiadiazoles to determine the role, if any, of the exocyclic N atom in determining the metal co-ordination and/or the overall packing structure. If this N atom is not metal bound it is still available for hydrogen-bonding interactions if considering the presence of the 2-amino groups. For this particular study we chose to use the same thiadiazole derivative, as well as the ethyl analogue, that produced the Neverov et al. (1986) structure. However, complexation of 2-amino-5-methyl-1,3,4-thiadiazole, (I), and 2-amino-5-ethyl-1,3,4-thiadiazole, (II), with CuCl2 yielded square pyramidal Cu complexes containing four bound thiadiazoles, one bound Cl and the other in the lattice as a counter ion. Complex (I) was characterized as a hydrate. \sch
The structures of (I) and (II) are shown in Figs. 2 and 3 while selected Cu bonds for both complexes are listed in Table 1 and hydrogen-bonding geometries are given in Table 2. For any 2-aminothiazole derivative, (I) and (II) are the first examples of five-coordinate square-pyramidal geometry. In both (I) and (II) the thiadiazoles are singly bound at N3 and occupy the four square planar positions but differences between the two structures occur in the specific orientations of the organic ligands. In the structure of (I) there are four unique heterocyclics with ligand A opposing the similar orientations of groups B, C and D whereas for (II) all four thiadiazoles are symmetry related around the Cu atom. In both complexes the amino groups are orientated in the same direction as the Cu—Cl1 bond such that all, except for ligand A in (I), are involved with N—H···Cl hydrogen-bonding associations. The Cl2 atoms also participate in N—H···Cl associations but only in (I) are the N4 atoms used as hydrogen-bonding acceptors. The rotation of the A moiety in (I) is interesting because if it were orientated the same as thiadiazoles B - D then it would associate to Cl1. Instead N21A associates with O1W and N4B while the second N21B H atom, from an adjacent molecule, slots in to associate with Cl1 (Fig. 4). The availability of the N4 atoms for hydrogen bonding, combined with the presence of Cl2, creates five free acceptor elements, in comparison to the four free 2-amino H atoms, but a water molecule is still required to complete the hydrogen-bonding network; most probably because Cl2 is a multi-point hydrogen-bonding acceptor. For (II) the unique position of Cl2 satisfies the hydrogen-bonding requirements of the second 2-amino H atom; thus, in this structure all hydrogen-bonding elements are either complimented or structurally hindered (Fig. 5).
The general conformations of the Cu complexes in (I) and (II) are such that the S atom in each thiadiazole ring faces outwards, away from the metal centre. This specific ligand orientation generates several S···Cl and S···S short contacts. In (I), the S1A···Cl2 (x, 1/2 - y, 1/2 + z) distance is 3.351 (3) Å, the S1B···Cl2 (1 - x, -1/2 + y, 1/2 - z) distance is 3.534 (3) Å, the S1C···Cl1 (x, 1/2 - y, 1/2 + z) distance is 3.476 (3) Å, and the S1A···S1D (-x, -y, 1 - z) distance is 3.465 (3) Å while the slightly longer contacts are S1A···S1B [1 - x, -y, 1 - z; 3.626 (3) Å] and S1C···S1D [-x, -y, -z; 3.760 (3) Å]. In (II), the S1···S1 (1/2 + y, 1 - x, -z) distance is 3.633 (2) Å. A CSD search (Fletcher et al., 1996) on five-coordinate Cu complexes with at least one bound Cl atom gave 315 hits, of which 286 were CuII. Of the CuII complexes, only one of these was found with four separate N-bound ligands and, similar to complexes (I) and (II), the two conformations of tetra(pyridine-N)chlorocopper(II) in tetrakis(chlorotetrapyridinecopper)dotriacontaoxo-decatungsten pyridine solvated trihydrate (Gongdu et al., 1987), were square pyramidal. Analysis of the angle between the pyridine rings and the Cu—Cl bonds gave values of 22.5 (6), 23.4 (6), 31.5 (6), 50.9 (6)° and 16.1 (6), 29.1 (6), 29.4 (6), 49.8 (6)°. For comparison, these same values in (I) and (II) are 15.9 (1), 8.6 (1), 26.0 (1), 19.9 (1) and 15.5 (2)°, respectively. Given the CSD search parameters, complexes (I) and (II) have proved to be novel in their specific molecular construction whereas complex (II) is certainly unique with respect to its existence in a high symmetry space group given the near identical similarity of the thiadiazole in complex (I).