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The formation of three different copper(I) thiourea complexes in sulfate-containing acid solutions was observed. The ratio between CuI and thiourea (tu) in these complexes depends on the amount of thiourea and copper sulfate in the solution. The crystal and molecular structure of a new complex, [Cu_2(tu)_6](SO_4)\cdotH_2O, was determined, and the formation and structures of [Cu_2(tu)_5](SO_4)\cdot3H_2O and [Cu_4(tu)_7](SO_4)_2\cdotH_2O were confirmed. The compound [Cu_2(tu)_6](SO_4)\cdotH_2O crystallizes in the P\overline 1 space group, with a = 11.079 (2), b = 11.262 (1), c = 12.195 (2) Å, \alpha = 64.84 (1), \beta = 76.12 (1), \gamma = 66.06 (1)°, and Z = 2. The Cu-thiourea complex is arranged as a CuI tetranuclear ion, [Cu_4(tu)_{12}]^{4+}, sited on a crystallographic inversion center. All copper ions are in a tetrahedral coordination with thiourea ligands and located at alternate sites on an eight-membered, crown-like ring.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768100008028/ca0005sup1.cif
Contains datablocks global, sulph

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768100008028/ca0005sulphsup2.hkl
Contains datablock s93

CCDC reference: 156653

Computing details top

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).

hexa(thiourea)dicopper(I) sulfate monohydrate top
Crystal data top
[Cu2(CH4N2S)6](SO4)·H2OZ = 2
Mr = 697.89F(000) = 712
Triclinic, P1Dx = 1.847 Mg m3
a = 11.079 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.262 (1) ÅCell parameters from 23 reflections
c = 12.195 (2) Åθ = 13.5–21.7°
α = 64.843 (10)°µ = 2.32 mm1
β = 76.119 (10)°T = 293 K
γ = 66.059 (10)°Prism, colourless
V = 1254.6 (3) Å30.40 × 0.24 × 0.16 mm
Data collection top
Enraf-Nonius CAD4
diffractometer
5184 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 28.0°, θmin = 1.9°
ω–2θ scansh = 1314
Absorption correction: numerical
?
k = 1314
Tmin = 0.570, Tmax = 0.734l = 016
6343 measured reflections1 standard reflections every 30 min
5781 independent reflections intensity decay: 1.4%
Refinement top
Refinement on F2Primary atom site location: Patterson
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: difference Fourier map
wR(F2) = 0.068Isotropic
S = 1.08Calculated w = 1/[σ2(Fo2) + (0.0331P)2 + 0.741P]
where P = (Fo2 + 2Fc2)/3'
5781 reflections(Δ/σ)max = 0.005
393 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.72 e Å3
Crystal data top
[Cu2(CH4N2S)6](SO4)·H2Oγ = 66.059 (10)°
Mr = 697.89V = 1254.6 (3) Å3
Triclinic, P1Z = 2
a = 11.079 (2) ÅMo Kα radiation
b = 11.262 (1) ŵ = 2.32 mm1
c = 12.195 (2) ÅT = 293 K
α = 64.843 (10)°0.40 × 0.24 × 0.16 mm
β = 76.119 (10)°
Data collection top
Enraf-Nonius CAD4
diffractometer
5184 reflections with I > 2σ(I)
Absorption correction: numerical
?
Rint = 0.022
Tmin = 0.570, Tmax = 0.7341 standard reflections every 30 min
6343 measured reflections intensity decay: 1.4%
5781 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.068Isotropic
S = 1.08Δρmax = 0.51 e Å3
5781 reflectionsΔρmin = 0.72 e Å3
393 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.36373 (2)0.09604 (3)0.25273 (2)0.02625 (7)
Cu20.61892 (2)0.21689 (3)0.40109 (2)0.02576 (7)
S10.43116 (4)0.20730 (5)0.34944 (4)0.01967 (9)
C10.3067 (2)0.2259 (2)0.4656 (2)0.0198 (3)
N110.3264 (2)0.1354 (2)0.5770 (2)0.0253 (3)
H110.389 (3)0.066 (3)0.590 (3)0.032 (7)*
H11'0.267 (3)0.144 (3)0.632 (2)0.027 (6)*
N120.1935 (2)0.3305 (2)0.4428 (2)0.0372 (5)
H120.178 (3)0.392 (3)0.370 (3)0.032 (7)*
H12'0.133 (3)0.335 (3)0.493 (3)0.036 (7)*
S20.38331 (5)0.13383 (5)0.38708 (4)0.02166 (10)
C20.2514 (2)0.1741 (2)0.3785 (2)0.0229 (4)
N210.1358 (2)0.0767 (3)0.3506 (3)0.0530 (7)
H210.124 (3)0.005 (4)0.339 (3)0.056 (10)*
H21'0.071 (3)0.093 (3)0.346 (3)0.048 (9)*
N220.2664 (2)0.3033 (2)0.4010 (2)0.0318 (4)
H220.203 (3)0.323 (3)0.399 (3)0.038 (7)*
H22'0.344 (3)0.367 (3)0.414 (3)0.049 (9)*
S30.56537 (5)0.46395 (5)0.32683 (5)0.02554 (11)
C30.6995 (2)0.5131 (2)0.3072 (2)0.0267 (4)
N310.8220 (2)0.4318 (3)0.2874 (2)0.0395 (5)
H310.832 (3)0.354 (3)0.300 (3)0.042 (8)*
H31'0.881 (4)0.461 (4)0.280 (4)0.078 (12)*
N320.6806 (2)0.6345 (3)0.3086 (3)0.0464 (6)
H320.608 (3)0.680 (3)0.321 (3)0.045 (9)*
H32'0.750 (4)0.666 (4)0.289 (3)0.061 (10)*
S40.15999 (5)0.25658 (6)0.19267 (5)0.02974 (12)
C40.1302 (2)0.2588 (2)0.0600 (2)0.0243 (4)
N410.2148 (2)0.1754 (2)0.0050 (2)0.0367 (5)
H410.285 (3)0.130 (3)0.027 (3)0.040 (8)*
H41'0.199 (3)0.180 (4)0.062 (3)0.057 (10)*
N420.0176 (2)0.3486 (2)0.0107 (2)0.0336 (4)
H420.031 (3)0.393 (3)0.045 (3)0.033 (8)*
H42'0.001 (3)0.357 (3)0.055 (3)0.046 (8)*
S50.81648 (5)0.10555 (5)0.31497 (4)0.02552 (11)
C50.8032 (2)0.1776 (2)0.1611 (2)0.0253 (4)
N510.8813 (2)0.1086 (2)0.0918 (2)0.0360 (5)
H510.931 (3)0.029 (3)0.120 (3)0.034 (7)*
H51'0.871 (3)0.144 (3)0.019 (3)0.038 (8)*
N520.7167 (2)0.3037 (2)0.1105 (2)0.0371 (5)
H520.705 (3)0.340 (3)0.036 (3)0.030 (7)*
H52'0.671 (3)0.343 (3)0.150 (3)0.033 (7)*
S60.54034 (6)0.04699 (6)0.11653 (5)0.03014 (12)
C60.5426 (2)0.1959 (2)0.0033 (2)0.0276 (4)
N610.6394 (3)0.1920 (3)0.0919 (2)0.0458 (6)
H610.646 (3)0.274 (4)0.139 (3)0.059 (10)*
H61'0.698 (3)0.119 (4)0.086 (3)0.045 (9)*
N620.4501 (2)0.3185 (2)0.0135 (2)0.0431 (5)
H620.388 (4)0.324 (4)0.047 (3)0.058 (10)*
H62'0.454 (4)0.393 (4)0.070 (3)0.063 (10)*
S0.00488 (4)0.71477 (5)0.25222 (4)0.01961 (9)
O10.02456 (15)0.6791 (2)0.37890 (13)0.0317 (3)
O20.0715 (2)0.8136 (2)0.17049 (14)0.0335 (3)
O30.0593 (2)0.5864 (2)0.2242 (2)0.0393 (4)
O40.13794 (14)0.7783 (2)0.23400 (14)0.0297 (3)
OW0.3260 (2)0.5319 (2)0.1455 (2)0.0470 (5)
H1W0.357 (4)0.463 (4)0.182 (3)0.052 (11)*
H2W0.248 (4)0.547 (4)0.170 (4)0.067 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02406 (13)0.03033 (14)0.02298 (12)0.00904 (10)0.00161 (9)=0.00908 (10)
Cu20.02275 (13)0.03343 (14)0.02302 (12)0.01034 (10)0.00009 (9)=0.01250 (10)
S10.0166 (2)0.0265 (2)0.0200 (2)0.0091 (2)0.0003 (2)0.0116 (2)
C10.0185 (8)0.0224 (9)0.0226 (9)0.0100 (7)0.0003 (7)0.0102 (7)
N110.0227 (8)0.0239 (9)0.0221 (8)0.0062 (7)0.0018 (7)0.0057 (7)
N120.0242 (9)0.0386 (11)0.0246 (9)0.0017 (8)0.0033 (8)0.0045 (8)
S20.0214 (2)0.0266 (2)0.0187 (2)0.0131 (2)0.0046 (2)0.0038 (2)
C20.0202 (9)0.0319 (10)0.0210 (9)0.0113 (8)0.0022 (7)0.0113 (8)
N210.0253 (11)0.0417 (13)0.101 (2)0.0055 (10)0.0227 (12)0.0305 (14)
N220.0278 (10)0.0342 (10)0.0392 (11)0.0156 (9)0.0092 (8)0.0107 (8)
S30.0212 (2)0.0210 (2)0.0348 (3)0.0091 (2)0.0032 (2)0.0086 (2)
C30.0278 (10)0.0287 (10)0.0268 (10)0.0136 (8)0.0008 (8)0.0103 (8)
N310.0254 (10)0.0403 (12)0.0586 (14)0.0140 (9)0.0028 (9)0.0241 (11)
N320.0322 (11)0.0415 (12)0.081 (2)0.0201 (10)0.0067 (11)0.0353 (13)
S40.0256 (2)0.0342 (3)0.0315 (3)0.0012 (2)0.0085 (2)0.0193 (2)
C40.0247 (9)0.0225 (9)0.0285 (10)0.0099 (8)0.0039 (8)0.0096 (8)
N410.0313 (11)0.0461 (12)0.0377 (11)0.0037 (9)0.0074 (9)0.0266 (10)
N420.0312 (10)0.0335 (10)0.0369 (11)0.0019 (8)0.0140 (9)0.0166 (9)
S50.0200 (2)0.0272 (2)0.0223 (2)0.0036 (2)0.0003 (2)0.0079 (2)
C50.0272 (10)0.0280 (10)0.0237 (9)0.0153 (8)0.0028 (8)0.0094 (8)
N510.0456 (12)0.0303 (11)0.0258 (10)0.0099 (9)0.0058 (9)0.0122 (8)
N520.0451 (12)0.0319 (10)0.0218 (9)0.0032 (9)0.0038 (9)0.0076 (8)
S60.0315 (3)0.0248 (2)0.0237 (2)0.0054 (2)0.0060 (2)0.0080 (2)
C60.0316 (11)0.0320 (11)0.0221 (9)0.0165 (9)0.0023 (8)0.0097 (8)
N610.0508 (14)0.0487 (14)0.0355 (12)0.0270 (12)0.0185 (10)0.0159 (11)
N620.0442 (13)0.0293 (11)0.0390 (12)0.0123 (9)0.0044 (10)0.0021 (9)
S0.0182 (2)0.0242 (2)0.0191 (2)0.0088 (2)0.0007 (2)0.0094 (2)
O10.0276 (8)0.0527 (10)0.0197 (7)0.0210 (7)0.0005 (6)0.0124 (7)
O20.0310 (8)0.0414 (9)0.0284 (8)0.0218 (7)0.0048 (6)0.0081 (7)
O30.0444 (10)0.0283 (8)0.0464 (10)0.0005 (7)0.0133 (8)0.0211 (7)
O40.0195 (7)0.0386 (8)0.0340 (8)0.0098 (6)0.0038 (6)0.0154 (7)
OW0.0388 (11)0.0413 (11)0.0379 (10)0.0108 (9)0.0018 (9)0.0024 (9)
Geometric parameters (Å, º) top
Cu1—S62.2882 (7)C3—N321.303 (3)
Cu1—S42.2925 (7)C3—N311.327 (3)
Cu1—S22.3542 (6)S4—C41.715 (2)
Cu1—S12.4409 (6)C4—N411.316 (3)
Cu2—S52.2924 (7)C4—N421.326 (3)
Cu2—S2i2.3414 (7)S5—C51.716 (2)
Cu2—S12.3674 (6)C5—N511.314 (3)
Cu2—S32.3853 (6)C5—N521.323 (3)
S1—C11.741 (2)S6—C61.698 (2)
C1—N111.310 (3)C6—N621.319 (3)
C1—N121.314 (3)C6—N611.328 (3)
S2—C21.734 (2)S—O21.466 (2)
S2—Cu2i2.3414 (7)S—O41.476 (2)
C2—N221.306 (3)S—O31.478 (2)
C2—N211.308 (3)S—O11.4690 (15)
S3—C31.719 (2)
S6—Cu1—S4122.34 (3)N21—C2—S2120.8 (2)
S6—Cu1—S299.03 (2)C3—S3—Cu2113.50 (8)
S4—Cu1—S2120.02 (3)N32—C3—N31119.0 (2)
S6—Cu1—S1103.12 (2)N32—C3—S3119.5 (2)
S4—Cu1—S1101.74 (2)N31—C3—S3121.5 (2)
S2—Cu1—S1109.25 (2)C4—S4—Cu1110.77 (7)
S5—Cu2—S2i111.98 (2)N41—C4—N42118.7 (2)
S5—Cu2—S1114.10 (2)N41—C4—S4122.6 (2)
S2i—Cu2—S1109.36 (2)N42—C4—S4118.7 (2)
S5—Cu2—S3113.14 (2)C5—S5—Cu2106.51 (8)
S2i—Cu2—S3107.47 (2)N51—C5—N52119.3 (2)
S1—Cu2—S3100.00 (2)N51—C5—S5120.0 (2)
C1—S1—Cu2107.18 (6)N52—C5—S5120.6 (2)
C1—S1—Cu1103.45 (6)C6—S6—Cu1110.18 (8)
Cu2—S1—Cu1142.98 (2)N62—C6—N61117.3 (2)
N11—C1—N12119.6 (2)N62—C6—S6122.4 (2)
N11—C1—S1119.7 (2)N61—C6—S6120.3 (2)
N12—C1—S1120.7 (2)O2—S—O1109.69 (9)
C2—S2—Cu2i98.68 (7)O2—S—O4109.43 (10)
C2—S2—Cu1110.08 (7)O1—S—O4110.08 (9)
Cu2i—S2—Cu1125.78 (2)O2—S—O3109.95 (11)
N22—C2—N21119.2 (2)O1—S—O3109.54 (10)
N22—C2—S2120.0 (2)O4—S—O3108.14 (10)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···S1i0.7922.7893.566167
N11—H11···O4ii0.8292.1312.927160
N12—H12···O30.8662.2743.085156
N12—H12···O1ii0.7912.0542.840171
N21—H21···S40.8312.7633.506150
N21—H21···S5iii0.8232.7893.317123
N22—H22···O1iv0.8262.0402.849166
N22—H22···S3iv0.8592.7363.492148
N32—H32···S2v0.7822.7323.494166
N32—H32···O4vi0.9161.9342.830166
N41—H41···O4vii0.8532.1593.006172
N42—H42···O3vii0.8202.0782.890170
N51—H51···O2viii0.8042.1982.996172
N51—H51···O2ix0.8182.1402.909156
N52—H52···OWix0.8422.0852.913168
N52—H52···S30.7582.7993.535164
OW—H1W···S10.6972.6473.333169
OW—H2W···O30.8131.9612.774178
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1, z+1; (iii) x1, y, z; (iv) x, y1, z; (v) x, y+1, z; (vi) x+1, y, z; (vii) x, y+1, z; (viii) x+1, y1, z; (ix) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu2(CH4N2S)6](SO4)·H2O
Mr697.89
Crystal system, space groupTriclinic, 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)
V3)1254.6 (3)
Z2
Radiation typeMo Kα
µ (mm1)2.32
Crystal size (mm)0.40 × 0.24 × 0.16
Data collection
DiffractometerEnraf-Nonius CAD4
diffractometer
Absorption correctionNumerical
Tmin, Tmax0.570, 0.734
No. of measured, independent and
observed [I > 2σ(I)] reflections
6343, 5781, 5184
Rint0.022
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.068, 1.08
No. of reflections5781
No. of parameters393
H-atom treatmentIsotropic
Δρmax, Δρmin (e Å3)0.51, 0.72

Computer programs: Enraf-Nonius CAD4, SDP (Frenz, 1983), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), ORTEP (Johnson, 1965).

Selected geometric parameters (Å, º) top
Cu1—S62.2882 (7)Cu2—S52.2924 (7)
Cu1—S42.2925 (7)Cu2—S2i2.3414 (7)
Cu1—S22.3542 (6)Cu2—S12.3674 (6)
Cu1—S12.4409 (6)Cu2—S32.3853 (6)
S6—Cu1—S4122.34 (3)S5—Cu2—S1114.10 (2)
S6—Cu1—S299.03 (2)S2i—Cu2—S1109.36 (2)
S4—Cu1—S2120.02 (3)S5—Cu2—S3113.14 (2)
S6—Cu1—S1103.12 (2)S2i—Cu2—S3107.47 (2)
S4—Cu1—S1101.74 (2)S1—Cu2—S3100.00 (2)
S2—Cu1—S1109.25 (2)Cu2—S1—Cu1142.98 (2)
S5—Cu2—S2i111.98 (2)Cu2i—S2—Cu1125.78 (2)
Symmetry code: (i) x+1, y, z+1.
 

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