X-ray diffraction study of copper(I) thiourea complexes formed in sulfate-containing acid solutions
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768100008028/ca0005sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768100008028/ca0005sulphsup2.hkl |
CCDC reference: 156653
Data collection: Enraf-Nonius CAD4; cell refinement: Enraf-Nonius CAD4; data reduction: SDP (Frenz, 1983); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL93 (Sheldrick, 1993).
[Cu2(CH4N2S)6](SO4)·H2O | Z = 2 |
Mr = 697.89 | F(000) = 712 |
Triclinic, P1 | Dx = 1.847 Mg m−3 |
a = 11.079 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.262 (1) Å | Cell parameters from 23 reflections |
c = 12.195 (2) Å | θ = 13.5–21.7° |
α = 64.843 (10)° | µ = 2.32 mm−1 |
β = 76.119 (10)° | T = 293 K |
γ = 66.059 (10)° | Prism, colourless |
V = 1254.6 (3) Å3 | 0.40 × 0.24 × 0.16 mm |
Enraf-Nonius CAD4 diffractometer | 5184 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 28.0°, θmin = 1.9° |
ω–2θ scans | h = −13→14 |
Absorption correction: numerical ? | k = −13→14 |
Tmin = 0.570, Tmax = 0.734 | l = 0→16 |
6343 measured reflections | 1 standard reflections every 30 min |
5781 independent reflections | intensity decay: 1.4% |
Refinement on F2 | Primary atom site location: Patterson |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.068 | Isotropic |
S = 1.08 | Calculated w = 1/[σ2(Fo2) + (0.0331P)2 + 0.741P] where P = (Fo2 + 2Fc2)/3' |
5781 reflections | (Δ/σ)max = −0.005 |
393 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.72 e Å−3 |
[Cu2(CH4N2S)6](SO4)·H2O | γ = 66.059 (10)° |
Mr = 697.89 | V = 1254.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.079 (2) Å | Mo Kα radiation |
b = 11.262 (1) Å | µ = 2.32 mm−1 |
c = 12.195 (2) Å | T = 293 K |
α = 64.843 (10)° | 0.40 × 0.24 × 0.16 mm |
β = 76.119 (10)° |
Enraf-Nonius CAD4 diffractometer | 5184 reflections with I > 2σ(I) |
Absorption correction: numerical ? | Rint = 0.022 |
Tmin = 0.570, Tmax = 0.734 | 1 standard reflections every 30 min |
6343 measured reflections | intensity decay: 1.4% |
5781 independent reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.068 | Isotropic |
S = 1.08 | Δρmax = 0.51 e Å−3 |
5781 reflections | Δρmin = −0.72 e Å−3 |
393 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 on F2 for ALL reflections except for 0 with very negative F2= or flagged by the user for potential systematic errors. Weighted R-factors= wR and all goodnesses of fit S are based on F2, conventional R-factors R= are based on F, with F set to zero for negative F2. The observed= criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | 0.36373 (2) | 0.09604 (3) | 0.25273 (2) | 0.02625 (7) | |
Cu2 | 0.61892 (2) | 0.21689 (3) | 0.40109 (2) | 0.02576 (7) | |
S1 | 0.43116 (4) | 0.20730 (5) | 0.34944 (4) | 0.01967 (9) | |
C1 | 0.3067 (2) | 0.2259 (2) | 0.4656 (2) | 0.0198 (3) | |
N11 | 0.3264 (2) | 0.1354 (2) | 0.5770 (2) | 0.0253 (3) | |
H11 | 0.389 (3) | 0.066 (3) | 0.590 (3) | 0.032 (7)* | |
H11' | 0.267 (3) | 0.144 (3) | 0.632 (2) | 0.027 (6)* | |
N12 | 0.1935 (2) | 0.3305 (2) | 0.4428 (2) | 0.0372 (5) | |
H12 | 0.178 (3) | 0.392 (3) | 0.370 (3) | 0.032 (7)* | |
H12' | 0.133 (3) | 0.335 (3) | 0.493 (3) | 0.036 (7)* | |
S2 | 0.38331 (5) | −0.13383 (5) | 0.38708 (4) | 0.02166 (10) | |
C2 | 0.2514 (2) | −0.1741 (2) | 0.3785 (2) | 0.0229 (4) | |
N21 | 0.1358 (2) | −0.0767 (3) | 0.3506 (3) | 0.0530 (7) | |
H21 | 0.124 (3) | 0.005 (4) | 0.339 (3) | 0.056 (10)* | |
H21' | 0.071 (3) | −0.093 (3) | 0.346 (3) | 0.048 (9)* | |
N22 | 0.2664 (2) | −0.3033 (2) | 0.4010 (2) | 0.0318 (4) | |
H22 | 0.203 (3) | −0.323 (3) | 0.399 (3) | 0.038 (7)* | |
H22' | 0.344 (3) | −0.367 (3) | 0.414 (3) | 0.049 (9)* | |
S3 | 0.56537 (5) | 0.46395 (5) | 0.32683 (5) | 0.02554 (11) | |
C3 | 0.6995 (2) | 0.5131 (2) | 0.3072 (2) | 0.0267 (4) | |
N31 | 0.8220 (2) | 0.4318 (3) | 0.2874 (2) | 0.0395 (5) | |
H31 | 0.832 (3) | 0.354 (3) | 0.300 (3) | 0.042 (8)* | |
H31' | 0.881 (4) | 0.461 (4) | 0.280 (4) | 0.078 (12)* | |
N32 | 0.6806 (2) | 0.6345 (3) | 0.3086 (3) | 0.0464 (6) | |
H32 | 0.608 (3) | 0.680 (3) | 0.321 (3) | 0.045 (9)* | |
H32' | 0.750 (4) | 0.666 (4) | 0.289 (3) | 0.061 (10)* | |
S4 | 0.15999 (5) | 0.25658 (6) | 0.19267 (5) | 0.02974 (12) | |
C4 | 0.1302 (2) | 0.2588 (2) | 0.0600 (2) | 0.0243 (4) | |
N41 | 0.2148 (2) | 0.1754 (2) | 0.0050 (2) | 0.0367 (5) | |
H41 | 0.285 (3) | 0.130 (3) | 0.027 (3) | 0.040 (8)* | |
H41' | 0.199 (3) | 0.180 (4) | −0.062 (3) | 0.057 (10)* | |
N42 | 0.0176 (2) | 0.3486 (2) | 0.0107 (2) | 0.0336 (4) | |
H42 | −0.031 (3) | 0.393 (3) | 0.045 (3) | 0.033 (8)* | |
H42' | 0.001 (3) | 0.357 (3) | −0.055 (3) | 0.046 (8)* | |
S5 | 0.81648 (5) | 0.10555 (5) | 0.31497 (4) | 0.02552 (11) | |
C5 | 0.8032 (2) | 0.1776 (2) | 0.1611 (2) | 0.0253 (4) | |
N51 | 0.8813 (2) | 0.1086 (2) | 0.0918 (2) | 0.0360 (5) | |
H51 | 0.931 (3) | 0.029 (3) | 0.120 (3) | 0.034 (7)* | |
H51' | 0.871 (3) | 0.144 (3) | 0.019 (3) | 0.038 (8)* | |
N52 | 0.7167 (2) | 0.3037 (2) | 0.1105 (2) | 0.0371 (5) | |
H52 | 0.705 (3) | 0.340 (3) | 0.036 (3) | 0.030 (7)* | |
H52' | 0.671 (3) | 0.343 (3) | 0.150 (3) | 0.033 (7)* | |
S6 | 0.54034 (6) | 0.04699 (6) | 0.11653 (5) | 0.03014 (12) | |
C6 | 0.5426 (2) | 0.1959 (2) | −0.0033 (2) | 0.0276 (4) | |
N61 | 0.6394 (3) | 0.1920 (3) | −0.0919 (2) | 0.0458 (6) | |
H61 | 0.646 (3) | 0.274 (4) | −0.139 (3) | 0.059 (10)* | |
H61' | 0.698 (3) | 0.119 (4) | −0.086 (3) | 0.045 (9)* | |
N62 | 0.4501 (2) | 0.3185 (2) | −0.0135 (2) | 0.0431 (5) | |
H62 | 0.388 (4) | 0.324 (4) | 0.047 (3) | 0.058 (10)* | |
H62' | 0.454 (4) | 0.393 (4) | −0.070 (3) | 0.063 (10)* | |
S | 0.00488 (4) | 0.71477 (5) | 0.25222 (4) | 0.01961 (9) | |
O1 | 0.02456 (15) | 0.6791 (2) | 0.37890 (13) | 0.0317 (3) | |
O2 | 0.0715 (2) | 0.8136 (2) | 0.17049 (14) | 0.0335 (3) | |
O3 | 0.0593 (2) | 0.5864 (2) | 0.2242 (2) | 0.0393 (4) | |
O4 | −0.13794 (14) | 0.7783 (2) | 0.23400 (14) | 0.0297 (3) | |
OW | 0.3260 (2) | 0.5319 (2) | 0.1455 (2) | 0.0470 (5) | |
H1W | 0.357 (4) | 0.463 (4) | 0.182 (3) | 0.052 (11)* | |
H2W | 0.248 (4) | 0.547 (4) | 0.170 (4) | 0.067 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02406 (13) | 0.03033 (14) | 0.02298 (12) | −0.00904 (10) | −0.00161 (9)= | −0.00908 (10) |
Cu2 | 0.02275 (13) | 0.03343 (14) | 0.02302 (12) | −0.01034 (10) | −0.00009 (9)= | −0.01250 (10) |
S1 | 0.0166 (2) | 0.0265 (2) | 0.0200 (2) | −0.0091 (2) | 0.0003 (2) | −0.0116 (2) |
C1 | 0.0185 (8) | 0.0224 (9) | 0.0226 (9) | −0.0100 (7) | 0.0003 (7) | −0.0102 (7) |
N11 | 0.0227 (8) | 0.0239 (9) | 0.0221 (8) | −0.0062 (7) | 0.0018 (7) | −0.0057 (7) |
N12 | 0.0242 (9) | 0.0386 (11) | 0.0246 (9) | 0.0017 (8) | 0.0033 (8) | −0.0045 (8) |
S2 | 0.0214 (2) | 0.0266 (2) | 0.0187 (2) | −0.0131 (2) | −0.0046 (2) | −0.0038 (2) |
C2 | 0.0202 (9) | 0.0319 (10) | 0.0210 (9) | −0.0113 (8) | −0.0022 (7) | −0.0113 (8) |
N21 | 0.0253 (11) | 0.0417 (13) | 0.101 (2) | −0.0055 (10) | −0.0227 (12) | −0.0305 (14) |
N22 | 0.0278 (10) | 0.0342 (10) | 0.0392 (11) | −0.0156 (9) | −0.0092 (8) | −0.0107 (8) |
S3 | 0.0212 (2) | 0.0210 (2) | 0.0348 (3) | −0.0091 (2) | −0.0032 (2) | −0.0086 (2) |
C3 | 0.0278 (10) | 0.0287 (10) | 0.0268 (10) | −0.0136 (8) | −0.0008 (8) | −0.0103 (8) |
N31 | 0.0254 (10) | 0.0403 (12) | 0.0586 (14) | −0.0140 (9) | 0.0028 (9) | −0.0241 (11) |
N32 | 0.0322 (11) | 0.0415 (12) | 0.081 (2) | −0.0201 (10) | 0.0067 (11) | −0.0353 (13) |
S4 | 0.0256 (2) | 0.0342 (3) | 0.0315 (3) | −0.0012 (2) | −0.0085 (2) | −0.0193 (2) |
C4 | 0.0247 (9) | 0.0225 (9) | 0.0285 (10) | −0.0099 (8) | −0.0039 (8) | −0.0096 (8) |
N41 | 0.0313 (11) | 0.0461 (12) | 0.0377 (11) | −0.0037 (9) | −0.0074 (9) | −0.0266 (10) |
N42 | 0.0312 (10) | 0.0335 (10) | 0.0369 (11) | −0.0019 (8) | −0.0140 (9) | −0.0166 (9) |
S5 | 0.0200 (2) | 0.0272 (2) | 0.0223 (2) | −0.0036 (2) | −0.0003 (2) | −0.0079 (2) |
C5 | 0.0272 (10) | 0.0280 (10) | 0.0237 (9) | −0.0153 (8) | 0.0028 (8) | −0.0094 (8) |
N51 | 0.0456 (12) | 0.0303 (11) | 0.0258 (10) | −0.0099 (9) | 0.0058 (9) | −0.0122 (8) |
N52 | 0.0451 (12) | 0.0319 (10) | 0.0218 (9) | −0.0032 (9) | −0.0038 (9) | −0.0076 (8) |
S6 | 0.0315 (3) | 0.0248 (2) | 0.0237 (2) | −0.0054 (2) | 0.0060 (2) | −0.0080 (2) |
C6 | 0.0316 (11) | 0.0320 (11) | 0.0221 (9) | −0.0165 (9) | 0.0023 (8) | −0.0097 (8) |
N61 | 0.0508 (14) | 0.0487 (14) | 0.0355 (12) | −0.0270 (12) | 0.0185 (10) | −0.0159 (11) |
N62 | 0.0442 (13) | 0.0293 (11) | 0.0390 (12) | −0.0123 (9) | 0.0044 (10) | −0.0021 (9) |
S | 0.0182 (2) | 0.0242 (2) | 0.0191 (2) | −0.0088 (2) | −0.0007 (2) | −0.0094 (2) |
O1 | 0.0276 (8) | 0.0527 (10) | 0.0197 (7) | −0.0210 (7) | 0.0005 (6) | −0.0124 (7) |
O2 | 0.0310 (8) | 0.0414 (9) | 0.0284 (8) | −0.0218 (7) | 0.0048 (6) | −0.0081 (7) |
O3 | 0.0444 (10) | 0.0283 (8) | 0.0464 (10) | −0.0005 (7) | −0.0133 (8) | −0.0211 (7) |
O4 | 0.0195 (7) | 0.0386 (8) | 0.0340 (8) | −0.0098 (6) | −0.0038 (6) | −0.0154 (7) |
OW | 0.0388 (11) | 0.0413 (11) | 0.0379 (10) | −0.0108 (9) | −0.0018 (9) | 0.0024 (9) |
Cu1—S6 | 2.2882 (7) | C3—N32 | 1.303 (3) |
Cu1—S4 | 2.2925 (7) | C3—N31 | 1.327 (3) |
Cu1—S2 | 2.3542 (6) | S4—C4 | 1.715 (2) |
Cu1—S1 | 2.4409 (6) | C4—N41 | 1.316 (3) |
Cu2—S5 | 2.2924 (7) | C4—N42 | 1.326 (3) |
Cu2—S2i | 2.3414 (7) | S5—C5 | 1.716 (2) |
Cu2—S1 | 2.3674 (6) | C5—N51 | 1.314 (3) |
Cu2—S3 | 2.3853 (6) | C5—N52 | 1.323 (3) |
S1—C1 | 1.741 (2) | S6—C6 | 1.698 (2) |
C1—N11 | 1.310 (3) | C6—N62 | 1.319 (3) |
C1—N12 | 1.314 (3) | C6—N61 | 1.328 (3) |
S2—C2 | 1.734 (2) | S—O2 | 1.466 (2) |
S2—Cu2i | 2.3414 (7) | S—O4 | 1.476 (2) |
C2—N22 | 1.306 (3) | S—O3 | 1.478 (2) |
C2—N21 | 1.308 (3) | S—O1 | 1.4690 (15) |
S3—C3 | 1.719 (2) | ||
S6—Cu1—S4 | 122.34 (3) | N21—C2—S2 | 120.8 (2) |
S6—Cu1—S2 | 99.03 (2) | C3—S3—Cu2 | 113.50 (8) |
S4—Cu1—S2 | 120.02 (3) | N32—C3—N31 | 119.0 (2) |
S6—Cu1—S1 | 103.12 (2) | N32—C3—S3 | 119.5 (2) |
S4—Cu1—S1 | 101.74 (2) | N31—C3—S3 | 121.5 (2) |
S2—Cu1—S1 | 109.25 (2) | C4—S4—Cu1 | 110.77 (7) |
S5—Cu2—S2i | 111.98 (2) | N41—C4—N42 | 118.7 (2) |
S5—Cu2—S1 | 114.10 (2) | N41—C4—S4 | 122.6 (2) |
S2i—Cu2—S1 | 109.36 (2) | N42—C4—S4 | 118.7 (2) |
S5—Cu2—S3 | 113.14 (2) | C5—S5—Cu2 | 106.51 (8) |
S2i—Cu2—S3 | 107.47 (2) | N51—C5—N52 | 119.3 (2) |
S1—Cu2—S3 | 100.00 (2) | N51—C5—S5 | 120.0 (2) |
C1—S1—Cu2 | 107.18 (6) | N52—C5—S5 | 120.6 (2) |
C1—S1—Cu1 | 103.45 (6) | C6—S6—Cu1 | 110.18 (8) |
Cu2—S1—Cu1 | 142.98 (2) | N62—C6—N61 | 117.3 (2) |
N11—C1—N12 | 119.6 (2) | N62—C6—S6 | 122.4 (2) |
N11—C1—S1 | 119.7 (2) | N61—C6—S6 | 120.3 (2) |
N12—C1—S1 | 120.7 (2) | O2—S—O1 | 109.69 (9) |
C2—S2—Cu2i | 98.68 (7) | O2—S—O4 | 109.43 (10) |
C2—S2—Cu1 | 110.08 (7) | O1—S—O4 | 110.08 (9) |
Cu2i—S2—Cu1 | 125.78 (2) | O2—S—O3 | 109.95 (11) |
N22—C2—N21 | 119.2 (2) | O1—S—O3 | 109.54 (10) |
N22—C2—S2 | 120.0 (2) | O4—S—O3 | 108.14 (10) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···S1i | 0.792 | 2.789 | 3.566 | 167 |
N11—H11′···O4ii | 0.829 | 2.131 | 2.927 | 160 |
N12—H12···O3 | 0.866 | 2.274 | 3.085 | 156 |
N12—H12′···O1ii | 0.791 | 2.054 | 2.840 | 171 |
N21—H21···S4 | 0.831 | 2.763 | 3.506 | 150 |
N21—H21′···S5iii | 0.823 | 2.789 | 3.317 | 123 |
N22—H22···O1iv | 0.826 | 2.040 | 2.849 | 166 |
N22—H22′···S3iv | 0.859 | 2.736 | 3.492 | 148 |
N32—H32···S2v | 0.782 | 2.732 | 3.494 | 166 |
N32—H32′···O4vi | 0.916 | 1.934 | 2.830 | 166 |
N41—H41′···O4vii | 0.853 | 2.159 | 3.006 | 172 |
N42—H42′···O3vii | 0.820 | 2.078 | 2.890 | 170 |
N51—H51···O2viii | 0.804 | 2.198 | 2.996 | 172 |
N51—H51′···O2ix | 0.818 | 2.140 | 2.909 | 156 |
N52—H52···OWix | 0.842 | 2.085 | 2.913 | 168 |
N52—H52′···S3 | 0.758 | 2.799 | 3.535 | 164 |
OW—H1W···S1 | 0.697 | 2.647 | 3.333 | 169 |
OW—H2W···O3 | 0.813 | 1.961 | 2.774 | 178 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) x, y−1, z; (v) x, y+1, z; (vi) x+1, y, z; (vii) −x, −y+1, −z; (viii) x+1, y−1, z; (ix) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(CH4N2S)6](SO4)·H2O |
Mr | 697.89 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.079 (2), 11.262 (1), 12.195 (2) |
α, β, γ (°) | 64.843 (10), 76.119 (10), 66.059 (10) |
V (Å3) | 1254.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.32 |
Crystal size (mm) | 0.40 × 0.24 × 0.16 |
Data collection | |
Diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | Numerical |
Tmin, Tmax | 0.570, 0.734 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6343, 5781, 5184 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.068, 1.08 |
No. of reflections | 5781 |
No. of parameters | 393 |
H-atom treatment | Isotropic |
Δρmax, Δρmin (e Å−3) | 0.51, −0.72 |
Computer programs: Enraf-Nonius CAD4, SDP (Frenz, 1983), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), ORTEP (Johnson, 1965).
Cu1—S6 | 2.2882 (7) | Cu2—S5 | 2.2924 (7) |
Cu1—S4 | 2.2925 (7) | Cu2—S2i | 2.3414 (7) |
Cu1—S2 | 2.3542 (6) | Cu2—S1 | 2.3674 (6) |
Cu1—S1 | 2.4409 (6) | Cu2—S3 | 2.3853 (6) |
S6—Cu1—S4 | 122.34 (3) | S5—Cu2—S1 | 114.10 (2) |
S6—Cu1—S2 | 99.03 (2) | S2i—Cu2—S1 | 109.36 (2) |
S4—Cu1—S2 | 120.02 (3) | S5—Cu2—S3 | 113.14 (2) |
S6—Cu1—S1 | 103.12 (2) | S2i—Cu2—S3 | 107.47 (2) |
S4—Cu1—S1 | 101.74 (2) | S1—Cu2—S3 | 100.00 (2) |
S2—Cu1—S1 | 109.25 (2) | Cu2—S1—Cu1 | 142.98 (2) |
S5—Cu2—S2i | 111.98 (2) | Cu2i—S2—Cu1 | 125.78 (2) |
Symmetry code: (i) −x+1, −y, −z+1. |
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