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metal-organic compounds
Tetraaquabis(thiourea-κS)cadmium(II) triaquatris(thiourea-κS)cadmium(II) disulfate
aDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
*Correspondence e-mail: faridehj@ucalgary.ca
The title compound, [Cd(CH4N2S)2(H2O)4][Cd(CH4N2S)3(H2O)3](SO4)2, contains two molecules of each of the Cd complexes and four sulfate ions in the all the Cd atoms exhibit distorted octahedral geometries. The Cd—S and Cd—O bond lengths around the Cd atoms in the bis(thiourea) cations are in the ranges 2.580 (4)–2.599 (4) and 2.323 (8)–2.421 (9) Å, respectively, and the S atoms are in a cis orientation. In the tris(thiourea) cations, the corresponding bond lengths around the Cd atoms are slightly longer and are in the ranges 2.559 (4)–2.706 (3) and 2.303 (7)–2.480 (10) Å, respectively, and the S atoms are in a fac disposition. The features numerous N—H⋯O, N—H⋯N, O—H⋯O and O—H⋯N hydrogen bonds. Two O atoms of a sulfate anion were found to be disordered over two orientations in a 0.620 (9):0.380 (9) ratio. The crystal studied was a racemic twin with BASF = 0.17 (5)
Related literature
For the structures of other cadmium–sulfate–thiourea compounds, see: Cavaica et al. (1970); Corao & Baggio (1969
); Oussaid et al. (2000
). For the NMR measurement, see: Jalilehvand et al. (2012
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: COLLECT (Hooft, 1998); cell DENZO (Otwinowski & Minor, 1997
); data reduction: SCALEPACK (Otwinowski & Minor, 1997
); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997
); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536812026682/hb6807sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026682/hb6807Isup2.hkl
A colorless solution containing a mixture of CdSO4.8/3(H2O) (1.505 g, 5.87 mmol) and thiourea (1.340 g, 22.33 mmol) in hot water (10 ml) was prepared. Slow evaporation of this solution resulted in an inhomogeneous mixture of colorless crystals, mainly consisting of [Cd(TU)3(SO4)] complex, as well as cis-[Cd(TU)2(H2O)4](SO4) and fac-[Cd(TU)3(H2O)3](SO4) complexes that were co-crystallized in the same unit cell.
All H atoms were positioned geometrically and refined using a riding model, and the Uiso(H) were allowed at 1.2Ueq(parent atom). Water H-atoms were contrained at distances O—H = 0.82 Å and EADP commands were used to model the disorder. An
using Flack method was not determined as the crystals were composed of racemic twins with BASF = 0.17 (5); Fridel pairs were merged. Two oxygen atoms of a sulfate anion were disordered over two sites each in a ratio 0.620 (9):0.380 (9). A of the structure with half the current length of the cell axis-b, allowing half of the contents of the resulted in a grossly disordered model which was therefore ruled out as the Therefore, the model was refined in the current presented in this paper.A survey in the
database shows that mixing cadmium sulfate (CdSO4) with thiourea (TU) in the mole ratio 1:3 results in either monomeric [Cd(TU)3(SO4)] (Oussaid et al., 2000; Cavaica et al., 1970), (or dimeric [Cd(µ-TU)(TU)2(SO4)]2 complexes (Corao & Baggio, 1969) with the cadmium ion coordinating four (CdS3O) or five (CdS4O) ligand atoms, respectively.With intention to prepare the mononuclear [Cd(TU)3(SO4)] complex for a solid state 113Cd NMR measurement (Jalilehvand et al., 2012), a solution was prepared of a mixture of CdSO4.8/3H2O and thiourea in 1:3.8 mole ratio in hot water, and slowly evaporated resulting in colorless crystals. Elemental analysis of a ground sample (i) used for the solid state 113Cd NMR spectroscopy showed that the bulk of the crystalline solid mainly consisted of the [Cd(TU)3(SO4)] complex (see Special details section). However, elemental analyses of two random samples of the colorless crystals (ii and iii) showed that the sample was inhomogeneous. An X-ray crystallographic
of the colorless crystal, revealed that cis-[Cd(TU)2(H2O)4]2+ and fac-[Cd(TU)3(H2O)3]2+ complexes had co-crystallized in the crystal. To our knowledge, this is the first report on the structure of hydrated Cd(II) thiourea complexes.The
of the title contains two cadmium(II) complexes of each type together with four sulfate ions (Fig. 1). All Cd atoms exhibit distorted octahedral geometry. The Cd–S and Cd–O distances around Cd1 and Cd2 atoms in the bis(thiourea) complex, cis-[Cd(TU)2(H2O)4]2+, lie in the ranges 2.580 (4) - 2.599 (4) Å and 2.323 (8) - 2.421 (9) Å, respectively. In the tris(thiourea) complex, fac-[Cd(TU)3(H2O)3]2+, the corresponding bond lengths around Cd3 and Cd4 atoms are slightly longer and lie in the ranges 2.559 (4) - 2.706 (3) Å and 2.303 (7) - 2.480 (10) Å, respectively. The is stabilized by strong hydrogen bonds (Tab. 1).For the structures of other cadmium–sulfate–thiourea compounds, see: Cavaica et al. (1970); Corao & Baggio (1969); Oussaid et al. (2000).c/fg3255/trash
Data collection: COLLECT (Hooft, 1998); cell
DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).[Cd(CH4N2S)2(H2O)4][Cd(CH4N2S)3(H2O)3](SO4)2 | F(000) = 1848 |
Mr = 923.64 | Dx = 2.000 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yc | Cell parameters from 2175 reflections |
a = 10.9941 (3) Å | θ = 3.4–30.0° |
b = 11.7602 (3) Å | µ = 1.94 mm−1 |
c = 24.0100 (5) Å | T = 173 K |
β = 98.9169 (12)° | Prism, colorless |
V = 3066.80 (13) Å3 | 0.07 × 0.06 × 0.05 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 9995 independent reflections |
Radiation source: fine-focus sealed tube | 8817 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω and φ scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −12→13 |
Tmin = 0.876, Tmax = 0.909 | k = −13→13 |
16186 measured reflections | l = −28→28 |
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)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0102P)2 + 30.5291P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.004 |
9995 reflections | Δρmax = 0.78 e Å−3 |
453 parameters | Δρmin = −0.64 e Å−3 |
2 restraints | Absolute structure: Flack, H. D. (1983). Acta Cryst. A39, 876–881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.15 (5) |
[Cd(CH4N2S)2(H2O)4][Cd(CH4N2S)3(H2O)3](SO4)2 | V = 3066.80 (13) Å3 |
Mr = 923.64 | Z = 4 |
Monoclinic, Pc | Mo Kα radiation |
a = 10.9941 (3) Å | µ = 1.94 mm−1 |
b = 11.7602 (3) Å | T = 173 K |
c = 24.0100 (5) Å | 0.07 × 0.06 × 0.05 mm |
β = 98.9169 (12)° |
Nonius KappaCCD diffractometer | 9995 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 8817 reflections with I > 2σ(I) |
Tmin = 0.876, Tmax = 0.909 | Rint = 0.037 |
16186 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0102P)2 + 30.5291P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | Δρmax = 0.78 e Å−3 |
9995 reflections | Δρmin = −0.64 e Å−3 |
453 parameters | Absolute structure: Flack, H. D. (1983). Acta Cryst. A39, 876–881 |
2 restraints | Absolute structure parameter: 0.15 (5) |
Experimental. Elemental analysis of a ground sample (i) used for the solid state 113Cd NMR spectroscopy: C = 8.44%, H = 2.62%, N = 19.27% (calculated for [Cd(TU)3(SO4)]: CdC3H12N6O4S4 (M.W. = 436.7), C = 8.24%, H = 2.75%, N = 19.23%). Elemental analyses of two random samples of the colorless crystals: (ii) exp.: C = 8.23%, H = 2.68%, N = 19.08%, and (iii) exp.: C = 7.44%, H = 3.01%, N = 17.22% (calculated for [Cd(TU)3(H2O)3](SO4): CdC3H18N6O7S4 (M.W. = 490.7), C = 7.33%, H = 3.67%, N = 17.12%). |
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 | Occ. (<1) | |
Cd1 | 0.43936 (7) | 0.41388 (8) | 0.00967 (3) | 0.0175 (3) | |
S1 | 0.6026 (4) | 0.3423 (3) | −0.04845 (17) | 0.0207 (9) | |
S2 | 0.6146 (3) | 0.4338 (3) | 0.09512 (14) | 0.0282 (6) | |
C1 | 0.7138 (13) | 0.4492 (12) | −0.0421 (5) | 0.0176 (17) | |
C2 | 0.5530 (9) | 0.4611 (8) | 0.1553 (4) | 0.0176 (17) | |
N1 | 0.8306 (12) | 0.4197 (10) | −0.0393 (5) | 0.0261 (12) | |
H1A | 0.8882 | 0.4724 | −0.0362 | 0.031* | |
H1B | 0.8509 | 0.3475 | −0.0405 | 0.031* | |
N2 | 0.6847 (11) | 0.5571 (11) | −0.0403 (5) | 0.0261 (12) | |
H2A | 0.7428 | 0.6093 | −0.0372 | 0.031* | |
H2B | 0.6071 | 0.5774 | −0.0421 | 0.031* | |
N3 | 0.6216 (8) | 0.5129 (8) | 0.1981 (4) | 0.0261 (12) | |
H3A | 0.5922 | 0.5247 | 0.2297 | 0.031* | |
H3B | 0.6965 | 0.5356 | 0.1950 | 0.031* | |
N4 | 0.4413 (8) | 0.4275 (8) | 0.1604 (4) | 0.0261 (12) | |
H4A | 0.4124 | 0.4395 | 0.1921 | 0.031* | |
H4B | 0.3953 | 0.3930 | 0.1321 | 0.031* | |
O1 | 0.4217 (8) | 0.5795 (8) | −0.0511 (4) | 0.0227 (9) | |
H11 | 0.4015 | 0.5634 | −0.0844 | 0.027* | |
H12 | 0.3894 | 0.6411 | −0.0460 | 0.027* | |
O2 | 0.2817 (7) | 0.5077 (6) | 0.0450 (3) | 0.0227 (9) | |
H21 | 0.2345 | 0.5180 | 0.0155 | 0.027* | |
H22 | 0.3234 | 0.5657 | 0.0511 | 0.027* | |
O3 | 0.3575 (7) | 0.2714 (6) | 0.0616 (3) | 0.0227 (9) | |
H31 | 0.4142 | 0.2255 | 0.0699 | 0.027* | |
H32 | 0.2932 | 0.2347 | 0.0591 | 0.027* | |
O4 | 0.3053 (9) | 0.3178 (7) | −0.0617 (4) | 0.0227 (9) | |
H41 | 0.2319 | 0.3144 | −0.0588 | 0.027* | |
H42 | 0.3123 | 0.3608 | −0.0875 | 0.027* | |
Cd2 | 0.94999 (7) | 0.83626 (9) | 0.28083 (3) | 0.0174 (3) | |
S3 | 0.7784 (3) | 0.8140 (3) | 0.19488 (14) | 0.0285 (6) | |
S4 | 0.7831 (4) | 0.9044 (3) | 0.33779 (17) | 0.0196 (9) | |
C3 | 0.8400 (10) | 0.7856 (9) | 0.1342 (4) | 0.024 (2) | |
C4 | 0.6721 (13) | 0.7993 (12) | 0.3289 (5) | 0.015 (2) | |
N5 | 0.7722 (8) | 0.7352 (7) | 0.0914 (4) | 0.0238 (11) | |
H5A | 0.8036 | 0.7198 | 0.0607 | 0.029* | |
H5B | 0.6954 | 0.7168 | 0.0935 | 0.029* | |
N6 | 0.9549 (8) | 0.8122 (7) | 0.1300 (4) | 0.0238 (11) | |
H6A | 0.9846 | 0.7961 | 0.0989 | 0.029* | |
H6B | 1.0017 | 0.8459 | 0.1582 | 0.029* | |
N7 | 0.7024 (10) | 0.6918 (11) | 0.3256 (5) | 0.0238 (11) | |
H7A | 0.6452 | 0.6389 | 0.3227 | 0.029* | |
H7B | 0.7800 | 0.6726 | 0.3263 | 0.029* | |
N8 | 0.5568 (12) | 0.8291 (10) | 0.3279 (5) | 0.0238 (11) | |
H8A | 0.4989 | 0.7768 | 0.3250 | 0.029* | |
H8B | 0.5373 | 0.9013 | 0.3301 | 0.029* | |
O5 | 0.9699 (8) | 0.6725 (8) | 0.3411 (4) | 0.0275 (10) | |
H51 | 0.9203 | 0.6571 | 0.3638 | 0.033* | |
H52 | 1.0087 | 0.6135 | 0.3386 | 0.033* | |
O6 | 1.1097 (7) | 0.7376 (7) | 0.2461 (3) | 0.0275 (10) | |
H61 | 1.0851 | 0.6714 | 0.2438 | 0.033* | |
H62 | 1.1831 | 0.7350 | 0.2601 | 0.033* | |
O7 | 1.0359 (7) | 0.9713 (6) | 0.2252 (3) | 0.0275 (10) | |
H71 | 1.0057 | 1.0222 | 0.2418 | 0.033* | |
H72 | 1.1109 | 0.9747 | 0.2344 | 0.033* | |
O8 | 1.0807 (10) | 0.9404 (8) | 0.3495 (4) | 0.0275 (10) | |
H81 | 1.0944 | 0.9406 | 0.3842 | 0.033* | |
H82 | 1.0377 | 0.9954 | 0.3398 | 0.033* | |
Cd3 | 0.95867 (7) | 0.33264 (8) | 0.27590 (3) | 0.0184 (3) | |
S5 | 0.7880 (4) | 0.4025 (3) | 0.32882 (17) | 0.0185 (8) | |
S6 | 0.8492 (3) | 0.1824 (3) | 0.20761 (14) | 0.0264 (6) | |
S7 | 0.9420 (3) | 0.5165 (2) | 0.20781 (14) | 0.0225 (6) | |
C5 | 0.6854 (14) | 0.2918 (12) | 0.3271 (6) | 0.0196 (14) | |
C6 | 0.9099 (10) | 0.1920 (9) | 0.1457 (4) | 0.0196 (14) | |
C7 | 0.9997 (10) | 0.4949 (9) | 0.1465 (4) | 0.0196 (14) | |
N9 | 0.5673 (12) | 0.3151 (12) | 0.3264 (5) | 0.0306 (10) | |
H9A | 0.5142 | 0.2595 | 0.3277 | 0.037* | |
H9B | 0.5419 | 0.3861 | 0.3247 | 0.037* | |
N10 | 0.7216 (11) | 0.1847 (12) | 0.3297 (5) | 0.0306 (10) | |
H10A | 0.6675 | 0.1299 | 0.3309 | 0.037* | |
H10B | 0.7997 | 0.1680 | 0.3302 | 0.037* | |
N11 | 1.0266 (9) | 0.2179 (8) | 0.1451 (4) | 0.0306 (10) | |
H11A | 1.0559 | 0.2182 | 0.1130 | 0.037* | |
H11B | 1.0750 | 0.2349 | 0.1767 | 0.037* | |
N12 | 0.8397 (9) | 0.1671 (9) | 0.0984 (4) | 0.0306 (10) | |
H12A | 0.8702 | 0.1677 | 0.0666 | 0.037* | |
H12B | 0.7618 | 0.1497 | 0.0983 | 0.037* | |
N13 | 1.1188 (9) | 0.5005 (8) | 0.1441 (4) | 0.0306 (10) | |
H13A | 1.1453 | 0.4926 | 0.1116 | 0.037* | |
H13B | 1.1716 | 0.5121 | 0.1751 | 0.037* | |
N14 | 0.9224 (9) | 0.4772 (9) | 0.0987 (4) | 0.0306 (10) | |
H14A | 0.9512 | 0.4695 | 0.0667 | 0.037* | |
H14B | 0.8427 | 0.4731 | 0.0992 | 0.037* | |
O9 | 1.1578 (7) | 0.3016 (6) | 0.2561 (3) | 0.0205 (10) | |
H91 | 1.1995 | 0.3594 | 0.2624 | 0.025* | |
H92 | 1.1970 | 0.2495 | 0.2732 | 0.025* | |
O10 | 0.9931 (7) | 0.1753 (7) | 0.3437 (4) | 0.0205 (10) | |
H101 | 1.0583 | 0.1809 | 0.3319 | 0.025* | |
H102 | 1.0039 | 0.1975 | 0.3765 | 0.025* | |
O11 | 1.0797 (9) | 0.4490 (8) | 0.3510 (4) | 0.0205 (10) | |
H111 | 1.0876 | 0.4327 | 0.3847 | 0.025* | |
H112 | 1.1392 | 0.4880 | 0.3467 | 0.025* | |
Cd4 | 0.42807 (7) | 0.91384 (8) | 0.01451 (3) | 0.0159 (3) | |
S8 | 0.4471 (3) | 0.7294 (2) | 0.08265 (13) | 0.0222 (6) | |
S9 | 0.5445 (3) | 1.0590 (2) | 0.08499 (14) | 0.0226 (6) | |
S10 | 0.6009 (4) | 0.8462 (3) | −0.03811 (18) | 0.0202 (9) | |
C8 | 0.3906 (10) | 0.7517 (8) | 0.1463 (4) | 0.0199 (14) | |
C9 | 0.4804 (10) | 1.0523 (8) | 0.1473 (4) | 0.0199 (14) | |
C10 | 0.7041 (15) | 0.9583 (12) | −0.0345 (6) | 0.0199 (14) | |
N15 | 0.4670 (9) | 0.7666 (8) | 0.1924 (4) | 0.0249 (9) | |
H15A | 0.4394 | 0.7724 | 0.2248 | 0.030* | |
H15B | 0.5465 | 0.7708 | 0.1914 | 0.030* | |
N16 | 0.2711 (9) | 0.7451 (7) | 0.1469 (4) | 0.0249 (9) | |
H16A | 0.2422 | 0.7509 | 0.1790 | 0.030* | |
H16B | 0.2202 | 0.7350 | 0.1152 | 0.030* | |
N17 | 0.5546 (9) | 1.0710 (8) | 0.1947 (4) | 0.0249 (9) | |
H17A | 0.5261 | 1.0687 | 0.2269 | 0.030* | |
H17B | 0.6329 | 1.0857 | 0.1942 | 0.030* | |
N18 | 0.3642 (8) | 1.0303 (7) | 0.1464 (4) | 0.0249 (9) | |
H18A | 0.3334 | 1.0275 | 0.1781 | 0.030* | |
H18B | 0.3162 | 1.0181 | 0.1140 | 0.030* | |
N19 | 0.8225 (12) | 0.9344 (10) | −0.0319 (5) | 0.0249 (9) | |
H19A | 0.8769 | 0.9898 | −0.0296 | 0.030* | |
H19B | 0.8468 | 0.8632 | −0.0324 | 0.030* | |
N20 | 0.6692 (11) | 1.0658 (10) | −0.0336 (5) | 0.0249 (9) | |
H20A | 0.7245 | 1.1204 | −0.0313 | 0.030* | |
H20B | 0.5908 | 1.0827 | −0.0352 | 0.030* | |
O12 | 0.2333 (7) | 0.9439 (6) | 0.0356 (3) | 0.0181 (10) | |
H121 | 0.1877 | 0.8906 | 0.0399 | 0.022* | |
H122 | 0.2103 | 0.9712 | 0.0046 | 0.022* | |
O13 | 0.3967 (7) | 1.0792 (7) | −0.0483 (3) | 0.0181 (10) | |
H131 | 0.3797 | 1.0641 | −0.0819 | 0.022* | |
H132 | 0.3594 | 1.1377 | −0.0428 | 0.022* | |
O14 | 0.3135 (9) | 0.7928 (7) | −0.0567 (4) | 0.0181 (10) | |
H141 | 0.3186 | 0.8041 | −0.0898 | 0.022* | |
H142 | 0.2419 | 0.8054 | −0.0526 | 0.022* | |
S11 | 0.0446 (4) | 0.8135 (3) | 0.48584 (15) | 0.0170 (8) | |
O15 | 0.0669 (7) | 0.7164 (6) | 0.4470 (3) | 0.0171 (9) | |
O16 | 0.0752 (6) | 0.9236 (6) | 0.4635 (3) | 0.0171 (9) | |
O17 | −0.0875 (8) | 0.8114 (7) | 0.4923 (3) | 0.0171 (9) | |
O18 | 0.1206 (7) | 0.7914 (6) | 0.5408 (3) | 0.0171 (9) | |
S12 | 0.3433 (4) | 0.0625 (3) | 0.30619 (15) | 0.0167 (8) | |
O19 | 0.3147 (8) | −0.0269 (7) | 0.3431 (4) | 0.0285 (11) | |
O20 | 0.3087 (8) | 0.1721 (7) | 0.3313 (3) | 0.0285 (11) | |
O21 | 0.4753 (9) | 0.0635 (8) | 0.3028 (4) | 0.0285 (11) | |
O22 | 0.2695 (8) | 0.0525 (7) | 0.2497 (4) | 0.0285 (11) | |
S13 | 0.0318 (3) | 0.3167 (3) | 0.49290 (15) | 0.0148 (8) | |
O23 | 0.1037 (7) | 0.2637 (6) | 0.5428 (3) | 0.0135 (9) | |
O24 | −0.0988 (8) | 0.2973 (7) | 0.4912 (3) | 0.0135 (9) | |
O25 | 0.0799 (9) | 0.2921 (9) | 0.4416 (4) | 0.0135 (9) | 0.620 (9) |
O26 | 0.0505 (9) | 0.4439 (9) | 0.5051 (4) | 0.0135 (9) | 0.620 (9) |
O25' | 0.0618 (16) | 0.2170 (16) | 0.4489 (7) | 0.0135 (9) | 0.380 (9) |
O26' | 0.0622 (15) | 0.4256 (14) | 0.4727 (7) | 0.0135 (9) | 0.380 (9) |
S14 | 0.3566 (4) | 0.5588 (3) | 0.29742 (17) | 0.0209 (8) | |
O27 | 0.4891 (10) | 0.5403 (9) | 0.2982 (5) | 0.0376 (11) | |
O28 | 0.2885 (8) | 0.5043 (7) | 0.2466 (4) | 0.0376 (11) | |
O29 | 0.3164 (8) | 0.5118 (7) | 0.3478 (4) | 0.0376 (11) | |
O30 | 0.3337 (8) | 0.6840 (7) | 0.2958 (4) | 0.0376 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0161 (6) | 0.0184 (5) | 0.0178 (5) | −0.0019 (4) | 0.0017 (5) | 0.0003 (4) |
S1 | 0.0178 (19) | 0.0174 (16) | 0.027 (2) | −0.0038 (13) | 0.0040 (15) | −0.0045 (13) |
S2 | 0.0147 (13) | 0.0521 (18) | 0.0180 (13) | −0.0012 (13) | 0.0031 (11) | −0.0086 (13) |
C1 | 0.018 (4) | 0.024 (4) | 0.010 (3) | 0.004 (3) | 0.001 (3) | −0.006 (3) |
C2 | 0.018 (4) | 0.024 (4) | 0.010 (3) | 0.004 (3) | 0.001 (3) | −0.006 (3) |
N1 | 0.020 (3) | 0.035 (3) | 0.024 (3) | −0.005 (2) | 0.006 (2) | −0.004 (2) |
N2 | 0.020 (3) | 0.035 (3) | 0.024 (3) | −0.005 (2) | 0.006 (2) | −0.004 (2) |
N3 | 0.020 (3) | 0.035 (3) | 0.024 (3) | −0.005 (2) | 0.006 (2) | −0.004 (2) |
N4 | 0.020 (3) | 0.035 (3) | 0.024 (3) | −0.005 (2) | 0.006 (2) | −0.004 (2) |
O1 | 0.018 (2) | 0.024 (2) | 0.025 (2) | −0.0018 (17) | 0.0021 (17) | 0.0031 (17) |
O2 | 0.018 (2) | 0.024 (2) | 0.025 (2) | −0.0018 (17) | 0.0021 (17) | 0.0031 (17) |
O3 | 0.018 (2) | 0.024 (2) | 0.025 (2) | −0.0018 (17) | 0.0021 (17) | 0.0031 (17) |
O4 | 0.018 (2) | 0.024 (2) | 0.025 (2) | −0.0018 (17) | 0.0021 (17) | 0.0031 (17) |
Cd2 | 0.0125 (6) | 0.0234 (5) | 0.0170 (5) | −0.0011 (4) | 0.0046 (4) | −0.0009 (4) |
S3 | 0.0166 (14) | 0.0519 (19) | 0.0171 (13) | 0.0006 (13) | 0.0028 (11) | −0.0040 (13) |
S4 | 0.017 (2) | 0.0209 (16) | 0.0234 (18) | −0.0031 (14) | 0.0098 (15) | −0.0071 (13) |
C3 | 0.023 (6) | 0.027 (6) | 0.018 (5) | 0.000 (5) | −0.004 (4) | 0.006 (4) |
C4 | 0.014 (5) | 0.023 (5) | 0.007 (4) | −0.004 (4) | 0.002 (4) | 0.001 (4) |
N5 | 0.014 (3) | 0.031 (3) | 0.028 (3) | 0.000 (2) | 0.008 (2) | −0.004 (2) |
N6 | 0.014 (3) | 0.031 (3) | 0.028 (3) | 0.000 (2) | 0.008 (2) | −0.004 (2) |
N7 | 0.014 (3) | 0.031 (3) | 0.028 (3) | 0.000 (2) | 0.008 (2) | −0.004 (2) |
N8 | 0.014 (3) | 0.031 (3) | 0.028 (3) | 0.000 (2) | 0.008 (2) | −0.004 (2) |
O5 | 0.024 (2) | 0.032 (2) | 0.026 (2) | 0.0030 (18) | 0.0040 (18) | 0.0001 (18) |
O6 | 0.024 (2) | 0.032 (2) | 0.026 (2) | 0.0030 (18) | 0.0040 (18) | 0.0001 (18) |
O7 | 0.024 (2) | 0.032 (2) | 0.026 (2) | 0.0030 (18) | 0.0040 (18) | 0.0001 (18) |
O8 | 0.024 (2) | 0.032 (2) | 0.026 (2) | 0.0030 (18) | 0.0040 (18) | 0.0001 (18) |
Cd3 | 0.0166 (6) | 0.0212 (5) | 0.0174 (6) | 0.0002 (4) | 0.0027 (4) | −0.0015 (4) |
S5 | 0.0170 (19) | 0.0155 (15) | 0.0241 (18) | −0.0021 (13) | 0.0064 (14) | −0.0035 (12) |
S6 | 0.0256 (15) | 0.0354 (16) | 0.0195 (13) | −0.0119 (12) | 0.0079 (11) | −0.0114 (11) |
S7 | 0.0198 (14) | 0.0270 (14) | 0.0210 (13) | −0.0006 (11) | 0.0044 (11) | 0.0063 (11) |
C5 | 0.017 (3) | 0.025 (3) | 0.017 (3) | −0.004 (3) | 0.002 (3) | 0.002 (3) |
C6 | 0.017 (3) | 0.025 (3) | 0.017 (3) | −0.004 (3) | 0.002 (3) | 0.002 (3) |
C7 | 0.017 (3) | 0.025 (3) | 0.017 (3) | −0.004 (3) | 0.002 (3) | 0.002 (3) |
N9 | 0.023 (2) | 0.048 (3) | 0.022 (2) | −0.008 (2) | 0.0042 (17) | −0.0047 (18) |
N10 | 0.023 (2) | 0.048 (3) | 0.022 (2) | −0.008 (2) | 0.0042 (17) | −0.0047 (18) |
N11 | 0.023 (2) | 0.048 (3) | 0.022 (2) | −0.008 (2) | 0.0042 (17) | −0.0047 (18) |
N12 | 0.023 (2) | 0.048 (3) | 0.022 (2) | −0.008 (2) | 0.0042 (17) | −0.0047 (18) |
N13 | 0.023 (2) | 0.048 (3) | 0.022 (2) | −0.008 (2) | 0.0042 (17) | −0.0047 (18) |
N14 | 0.023 (2) | 0.048 (3) | 0.022 (2) | −0.008 (2) | 0.0042 (17) | −0.0047 (18) |
O9 | 0.015 (2) | 0.023 (2) | 0.021 (2) | −0.0054 (19) | −0.0016 (18) | −0.0028 (19) |
O10 | 0.015 (2) | 0.023 (2) | 0.021 (2) | −0.0054 (19) | −0.0016 (18) | −0.0028 (19) |
O11 | 0.015 (2) | 0.023 (2) | 0.021 (2) | −0.0054 (19) | −0.0016 (18) | −0.0028 (19) |
Cd4 | 0.0141 (6) | 0.0188 (5) | 0.0154 (5) | −0.0011 (4) | 0.0039 (4) | −0.0014 (4) |
S8 | 0.0228 (14) | 0.0256 (14) | 0.0175 (13) | 0.0002 (11) | 0.0012 (11) | 0.0043 (11) |
S9 | 0.0198 (14) | 0.0319 (15) | 0.0175 (12) | −0.0061 (11) | 0.0070 (10) | −0.0024 (11) |
S10 | 0.018 (2) | 0.0168 (16) | 0.0280 (19) | −0.0023 (13) | 0.0086 (15) | −0.0014 (13) |
C8 | 0.027 (4) | 0.013 (3) | 0.022 (3) | −0.002 (3) | 0.011 (3) | 0.002 (3) |
C9 | 0.027 (4) | 0.013 (3) | 0.022 (3) | −0.002 (3) | 0.011 (3) | 0.002 (3) |
C10 | 0.027 (4) | 0.013 (3) | 0.022 (3) | −0.002 (3) | 0.011 (3) | 0.002 (3) |
N15 | 0.024 (2) | 0.030 (2) | 0.022 (2) | −0.0051 (18) | 0.0038 (17) | 0.0013 (17) |
N16 | 0.024 (2) | 0.030 (2) | 0.022 (2) | −0.0051 (18) | 0.0038 (17) | 0.0013 (17) |
N17 | 0.024 (2) | 0.030 (2) | 0.022 (2) | −0.0051 (18) | 0.0038 (17) | 0.0013 (17) |
N18 | 0.024 (2) | 0.030 (2) | 0.022 (2) | −0.0051 (18) | 0.0038 (17) | 0.0013 (17) |
N19 | 0.024 (2) | 0.030 (2) | 0.022 (2) | −0.0051 (18) | 0.0038 (17) | 0.0013 (17) |
N20 | 0.024 (2) | 0.030 (2) | 0.022 (2) | −0.0051 (18) | 0.0038 (17) | 0.0013 (17) |
O12 | 0.019 (2) | 0.025 (2) | 0.011 (2) | 0.003 (2) | 0.0043 (18) | −0.0006 (18) |
O13 | 0.019 (2) | 0.025 (2) | 0.011 (2) | 0.003 (2) | 0.0043 (18) | −0.0006 (18) |
O14 | 0.019 (2) | 0.025 (2) | 0.011 (2) | 0.003 (2) | 0.0043 (18) | −0.0006 (18) |
S11 | 0.0145 (18) | 0.0192 (15) | 0.0169 (16) | 0.0014 (13) | 0.0007 (13) | −0.0014 (12) |
O15 | 0.016 (2) | 0.024 (2) | 0.0121 (17) | 0.0030 (16) | 0.0037 (15) | −0.0031 (15) |
O16 | 0.016 (2) | 0.024 (2) | 0.0121 (17) | 0.0030 (16) | 0.0037 (15) | −0.0031 (15) |
O17 | 0.016 (2) | 0.024 (2) | 0.0121 (17) | 0.0030 (16) | 0.0037 (15) | −0.0031 (15) |
O18 | 0.016 (2) | 0.024 (2) | 0.0121 (17) | 0.0030 (16) | 0.0037 (15) | −0.0031 (15) |
S12 | 0.0132 (17) | 0.0206 (15) | 0.0173 (17) | 0.0013 (13) | 0.0056 (13) | −0.0020 (13) |
O19 | 0.023 (2) | 0.032 (2) | 0.030 (2) | 0.0016 (18) | 0.0043 (18) | 0.0011 (19) |
O20 | 0.023 (2) | 0.032 (2) | 0.030 (2) | 0.0016 (18) | 0.0043 (18) | 0.0011 (19) |
O21 | 0.023 (2) | 0.032 (2) | 0.030 (2) | 0.0016 (18) | 0.0043 (18) | 0.0011 (19) |
O22 | 0.023 (2) | 0.032 (2) | 0.030 (2) | 0.0016 (18) | 0.0043 (18) | 0.0011 (19) |
S13 | 0.0094 (17) | 0.0220 (16) | 0.0132 (15) | 0.0023 (12) | 0.0022 (12) | −0.0002 (12) |
O23 | 0.011 (2) | 0.021 (2) | 0.0093 (19) | 0.0021 (17) | 0.0047 (16) | 0.0007 (16) |
O24 | 0.011 (2) | 0.021 (2) | 0.0093 (19) | 0.0021 (17) | 0.0047 (16) | 0.0007 (16) |
O25 | 0.011 (2) | 0.021 (2) | 0.0093 (19) | 0.0021 (17) | 0.0047 (16) | 0.0007 (16) |
O26 | 0.011 (2) | 0.021 (2) | 0.0093 (19) | 0.0021 (17) | 0.0047 (16) | 0.0007 (16) |
O25' | 0.011 (2) | 0.021 (2) | 0.0093 (19) | 0.0021 (17) | 0.0047 (16) | 0.0007 (16) |
O26' | 0.011 (2) | 0.021 (2) | 0.0093 (19) | 0.0021 (17) | 0.0047 (16) | 0.0007 (16) |
S14 | 0.0185 (19) | 0.0208 (16) | 0.0233 (18) | 0.0006 (14) | 0.0023 (14) | −0.0053 (13) |
O27 | 0.026 (3) | 0.042 (3) | 0.044 (3) | −0.003 (2) | 0.003 (2) | −0.007 (2) |
O28 | 0.026 (3) | 0.042 (3) | 0.044 (3) | −0.003 (2) | 0.003 (2) | −0.007 (2) |
O29 | 0.026 (3) | 0.042 (3) | 0.044 (3) | −0.003 (2) | 0.003 (2) | −0.007 (2) |
O30 | 0.026 (3) | 0.042 (3) | 0.044 (3) | −0.003 (2) | 0.003 (2) | −0.007 (2) |
Cd1—O2 | 2.323 (7) | C7—N14 | 1.334 (13) |
Cd1—O3 | 2.350 (7) | N9—H9A | 0.8800 |
Cd1—O4 | 2.367 (10) | N9—H9B | 0.8800 |
Cd1—O1 | 2.423 (9) | N10—H10A | 0.8800 |
Cd1—S1 | 2.580 (4) | N10—H10B | 0.8800 |
Cd1—S2 | 2.598 (4) | N11—H11A | 0.8800 |
S1—C1 | 1.743 (16) | N11—H11B | 0.8800 |
S2—C2 | 1.718 (9) | N12—H12A | 0.8800 |
C1—N2 | 1.312 (18) | N12—H12B | 0.8800 |
C1—N1 | 1.32 (2) | N13—H13A | 0.8800 |
C2—N4 | 1.314 (13) | N13—H13B | 0.8800 |
C2—N3 | 1.325 (12) | N14—H14A | 0.8800 |
N1—H1A | 0.8800 | N14—H14B | 0.8800 |
N1—H1B | 0.8800 | O9—H91 | 0.8206 |
N2—H2A | 0.8800 | O9—H92 | 0.8215 |
N2—H2B | 0.8800 | O10—H101 | 0.8138 |
N3—H3A | 0.8800 | O10—H102 | 0.8211 |
N3—H3B | 0.8800 | O11—H111 | 0.8227 |
N4—H4A | 0.8800 | O11—H112 | 0.8191 |
N4—H4B | 0.8800 | Cd4—O12 | 2.303 (7) |
O1—H11 | 0.8191 | Cd4—O14 | 2.422 (9) |
O1—H12 | 0.8237 | Cd4—O13 | 2.452 (9) |
O2—H21 | 0.8211 | Cd4—S10 | 2.566 (4) |
O2—H22 | 0.8219 | Cd4—S9 | 2.597 (3) |
O3—H31 | 0.8252 | Cd4—S8 | 2.705 (3) |
O3—H32 | 0.8223 | S8—C8 | 1.757 (10) |
O4—H41 | 0.8216 | S9—C9 | 1.752 (10) |
O4—H42 | 0.8133 | S10—C10 | 1.733 (15) |
Cd2—O8 | 2.355 (11) | C8—N15 | 1.293 (14) |
Cd2—O6 | 2.362 (8) | C8—N16 | 1.319 (14) |
Cd2—O7 | 2.364 (8) | C9—N18 | 1.301 (13) |
Cd2—O5 | 2.398 (10) | C9—N17 | 1.311 (13) |
Cd2—S4 | 2.580 (4) | C10—N20 | 1.322 (18) |
Cd2—S3 | 2.585 (4) | C10—N19 | 1.32 (2) |
S3—C3 | 1.731 (11) | N15—H15A | 0.8800 |
S4—C4 | 1.726 (15) | N15—H15B | 0.8800 |
C3—N5 | 1.314 (13) | N16—H16A | 0.8800 |
C3—N6 | 1.320 (13) | N16—H16B | 0.8800 |
C4—N8 | 1.312 (19) | N17—H17A | 0.8800 |
C4—N7 | 1.313 (18) | N17—H17B | 0.8800 |
N5—H5A | 0.8800 | N18—H18A | 0.8800 |
N5—H5B | 0.8800 | N18—H18B | 0.8800 |
N6—H6A | 0.8800 | N19—H19A | 0.8800 |
N6—H6B | 0.8800 | N19—H19B | 0.8800 |
N7—H7A | 0.8800 | N20—H20A | 0.8800 |
N7—H7B | 0.8800 | N20—H20B | 0.8800 |
N8—H8A | 0.8800 | O12—H121 | 0.8195 |
N8—H8B | 0.8800 | O12—H122 | 0.8146 |
O5—H51 | 0.8497 | O13—H131 | 0.8174 |
O5—H52 | 0.8208 | O13—H132 | 0.8223 |
O6—H61 | 0.8232 | O14—H141 | 0.8179 |
O6—H62 | 0.8253 | O14—H142 | 0.8213 |
O7—H71 | 0.8188 | S11—O16 | 1.461 (8) |
O7—H72 | 0.8210 | S11—O18 | 1.472 (8) |
O8—H81 | 0.8250 | S11—O17 | 1.484 (9) |
O8—H82 | 0.8146 | S11—O15 | 1.519 (8) |
Cd3—O9 | 2.340 (8) | S12—O19 | 1.441 (10) |
Cd3—O10 | 2.455 (9) | S12—O21 | 1.466 (11) |
Cd3—O11 | 2.480 (10) | S12—O22 | 1.474 (9) |
Cd3—S5 | 2.559 (4) | S12—O20 | 1.497 (9) |
Cd3—S6 | 2.579 (3) | S13—O26' | 1.427 (17) |
Cd3—S7 | 2.700 (3) | S13—O25 | 1.444 (10) |
S5—C5 | 1.719 (15) | S13—O24 | 1.448 (9) |
S6—C6 | 1.724 (10) | S13—O23 | 1.468 (8) |
S7—C7 | 1.709 (10) | S13—O26 | 1.532 (11) |
C5—N10 | 1.32 (2) | S13—O25' | 1.645 (18) |
C5—N9 | 1.32 (2) | S14—O29 | 1.459 (10) |
C6—N12 | 1.304 (13) | S14—O27 | 1.470 (11) |
C6—N11 | 1.321 (13) | S14—O28 | 1.476 (10) |
C7—N13 | 1.321 (14) | S14—O30 | 1.494 (9) |
O2—Cd1—O3 | 77.0 (3) | N11—C6—S6 | 122.1 (8) |
O2—Cd1—O4 | 94.3 (3) | N13—C7—N14 | 118.3 (9) |
O3—Cd1—O4 | 78.3 (3) | N13—C7—S7 | 122.2 (8) |
O2—Cd1—O1 | 81.0 (3) | N14—C7—S7 | 119.5 (8) |
O3—Cd1—O1 | 153.0 (3) | C5—N9—H9A | 120.0 |
O4—Cd1—O1 | 88.0 (3) | C5—N9—H9B | 120.0 |
O2—Cd1—S1 | 166.8 (2) | H9A—N9—H9B | 120.0 |
O3—Cd1—S1 | 114.2 (2) | C5—N10—H10A | 120.0 |
O4—Cd1—S1 | 82.0 (3) | C5—N10—H10B | 120.0 |
O1—Cd1—S1 | 86.2 (2) | H10A—N10—H10B | 120.0 |
O2—Cd1—S2 | 99.9 (2) | C6—N11—H11A | 120.0 |
O3—Cd1—S2 | 86.8 (2) | C6—N11—H11B | 120.0 |
O4—Cd1—S2 | 156.5 (2) | H11A—N11—H11B | 120.0 |
O1—Cd1—S2 | 112.5 (2) | C6—N12—H12A | 120.0 |
S1—Cd1—S2 | 87.92 (13) | C6—N12—H12B | 120.0 |
C1—S1—Cd1 | 104.8 (4) | H12A—N12—H12B | 120.0 |
C2—S2—Cd1 | 109.9 (4) | C7—N13—H13A | 120.0 |
N2—C1—N1 | 119.5 (14) | C7—N13—H13B | 120.0 |
N2—C1—S1 | 122.0 (11) | H13A—N13—H13B | 120.0 |
N1—C1—S1 | 118.6 (11) | C7—N14—H14A | 120.0 |
N4—C2—N3 | 119.6 (9) | C7—N14—H14B | 120.0 |
N4—C2—S2 | 121.2 (8) | H14A—N14—H14B | 120.0 |
N3—C2—S2 | 119.2 (8) | Cd3—O9—H91 | 110.3 |
C1—N1—H1A | 120.0 | Cd3—O9—H92 | 116.7 |
C1—N1—H1B | 120.0 | H91—O9—H92 | 106.9 |
H1A—N1—H1B | 120.0 | Cd3—O10—H102 | 112.4 |
C1—N2—H2A | 120.0 | H101—O10—H102 | 107.7 |
C1—N2—H2B | 120.0 | Cd3—O11—H111 | 123.3 |
H2A—N2—H2B | 120.0 | Cd3—O11—H112 | 124.5 |
C2—N3—H3A | 120.0 | H111—O11—H112 | 106.9 |
C2—N3—H3B | 120.0 | O12—Cd4—O14 | 81.1 (3) |
H3A—N3—H3B | 120.0 | O12—Cd4—O13 | 88.1 (3) |
C2—N4—H4A | 120.0 | O14—Cd4—O13 | 91.4 (3) |
C2—N4—H4B | 120.0 | O12—Cd4—S10 | 160.2 (2) |
H4A—N4—H4B | 120.0 | O14—Cd4—S10 | 79.3 (2) |
Cd1—O1—H11 | 112.7 | O13—Cd4—S10 | 89.3 (2) |
Cd1—O1—H12 | 127.8 | O12—Cd4—S9 | 97.88 (19) |
H11—O1—H12 | 106.9 | O14—Cd4—S9 | 174.9 (2) |
Cd1—O2—H21 | 99.3 | O13—Cd4—S9 | 83.6 (2) |
H21—O2—H22 | 106.9 | S10—Cd4—S9 | 101.34 (13) |
Cd1—O3—H31 | 104.9 | O12—Cd4—S8 | 88.72 (19) |
Cd1—O3—H32 | 137.0 | O14—Cd4—S8 | 86.5 (2) |
H31—O3—H32 | 106.4 | O13—Cd4—S8 | 176.4 (2) |
Cd1—O4—H41 | 118.2 | S10—Cd4—S8 | 93.18 (12) |
Cd1—O4—H42 | 97.6 | S9—Cd4—S8 | 98.55 (11) |
H41—O4—H42 | 107.7 | C8—S8—Cd4 | 113.7 (3) |
O8—Cd2—O6 | 95.5 (3) | C9—S9—Cd4 | 107.7 (4) |
O8—Cd2—O7 | 78.0 (3) | C10—S10—Cd4 | 105.5 (5) |
O6—Cd2—O7 | 75.3 (3) | N15—C8—N16 | 121.0 (9) |
O8—Cd2—O5 | 90.4 (3) | N15—C8—S8 | 119.7 (8) |
O6—Cd2—O5 | 79.3 (3) | N16—C8—S8 | 119.1 (8) |
O7—Cd2—O5 | 150.8 (3) | N18—C9—N17 | 121.7 (9) |
O8—Cd2—S4 | 82.8 (3) | N18—C9—S9 | 121.2 (8) |
O6—Cd2—S4 | 165.6 (2) | N17—C9—S9 | 117.1 (8) |
O7—Cd2—S4 | 118.0 (2) | N20—C10—N19 | 119.2 (14) |
O5—Cd2—S4 | 86.3 (2) | N20—C10—S10 | 122.7 (12) |
O8—Cd2—S3 | 154.4 (2) | N19—C10—S10 | 118.2 (11) |
O6—Cd2—S3 | 99.1 (2) | C8—N15—H15A | 120.0 |
O7—Cd2—S3 | 85.6 (2) | C8—N15—H15B | 120.0 |
O5—Cd2—S3 | 112.8 (2) | H15A—N15—H15B | 120.0 |
S4—Cd2—S3 | 87.91 (13) | C8—N16—H16A | 120.0 |
C3—S3—Cd2 | 111.0 (4) | C8—N16—H16B | 120.0 |
C4—S4—Cd2 | 105.0 (4) | H16A—N16—H16B | 120.0 |
N5—C3—N6 | 118.7 (10) | C9—N17—H17A | 120.0 |
N5—C3—S3 | 119.8 (8) | C9—N17—H17B | 120.0 |
N6—C3—S3 | 121.5 (8) | H17A—N17—H17B | 120.0 |
N8—C4—N7 | 120.6 (13) | C9—N18—H18A | 120.0 |
N8—C4—S4 | 118.3 (11) | C9—N18—H18B | 120.0 |
N7—C4—S4 | 121.1 (11) | H18A—N18—H18B | 120.0 |
C3—N5—H5A | 120.0 | C10—N19—H19A | 120.0 |
C3—N5—H5B | 120.0 | C10—N19—H19B | 120.0 |
H5A—N5—H5B | 120.0 | H19A—N19—H19B | 120.0 |
C3—N6—H6A | 120.0 | C10—N20—H20A | 120.0 |
C3—N6—H6B | 120.0 | C10—N20—H20B | 120.0 |
H6A—N6—H6B | 120.0 | H20A—N20—H20B | 120.0 |
C4—N7—H7A | 120.0 | Cd4—O12—H121 | 121.2 |
C4—N7—H7B | 120.0 | H121—O12—H122 | 107.9 |
H7A—N7—H7B | 120.0 | Cd4—O13—H131 | 115.0 |
C4—N8—H8A | 120.0 | Cd4—O13—H132 | 126.2 |
C4—N8—H8B | 120.0 | H131—O13—H132 | 107.3 |
H8A—N8—H8B | 120.0 | Cd4—O14—H141 | 119.0 |
Cd2—O5—H51 | 123.5 | Cd4—O14—H142 | 102.3 |
Cd2—O5—H52 | 129.5 | H141—O14—H142 | 107.3 |
H51—O5—H52 | 104.9 | O16—S11—O18 | 110.8 (5) |
Cd2—O6—H61 | 103.5 | O16—S11—O17 | 109.8 (5) |
Cd2—O6—H62 | 127.4 | O18—S11—O17 | 109.4 (5) |
H61—O6—H62 | 106.4 | O16—S11—O15 | 111.9 (4) |
Cd2—O7—H72 | 110.7 | O18—S11—O15 | 107.1 (4) |
H71—O7—H72 | 107.5 | O17—S11—O15 | 107.8 (5) |
Cd2—O8—H81 | 134.9 | O19—S12—O21 | 110.6 (6) |
H81—O8—H82 | 107.1 | O19—S12—O22 | 111.6 (5) |
O9—Cd3—O10 | 87.9 (3) | O21—S12—O22 | 110.9 (6) |
O9—Cd3—O11 | 79.7 (3) | O19—S12—O20 | 106.7 (5) |
O10—Cd3—O11 | 85.6 (3) | O21—S12—O20 | 109.3 (6) |
O9—Cd3—S5 | 158.8 (2) | O22—S12—O20 | 107.5 (5) |
O10—Cd3—S5 | 87.8 (2) | O26'—S13—O25 | 75.7 (8) |
O11—Cd3—S5 | 79.3 (3) | O26'—S13—O24 | 114.5 (8) |
O9—Cd3—S6 | 97.1 (2) | O25—S13—O24 | 116.0 (6) |
O10—Cd3—S6 | 85.1 (2) | O26'—S13—O23 | 122.2 (8) |
O11—Cd3—S6 | 170.2 (2) | O25—S13—O23 | 112.9 (5) |
S5—Cd3—S6 | 103.29 (13) | O24—S13—O23 | 111.3 (5) |
O9—Cd3—S7 | 88.8 (2) | O25—S13—O26 | 107.6 (6) |
O10—Cd3—S7 | 173.9 (2) | O24—S13—O26 | 105.2 (5) |
O11—Cd3—S7 | 88.7 (2) | O23—S13—O26 | 102.6 (5) |
S5—Cd3—S7 | 93.29 (12) | O26'—S13—O25' | 109.9 (9) |
S6—Cd3—S7 | 100.53 (12) | O24—S13—O25' | 99.6 (7) |
C5—S5—Cd3 | 105.9 (5) | O23—S13—O25' | 94.9 (7) |
C6—S6—Cd3 | 107.3 (4) | O26—S13—O25' | 141.6 (8) |
C7—S7—Cd3 | 113.8 (4) | O29—S14—O27 | 111.1 (6) |
N10—C5—N9 | 119.0 (14) | O29—S14—O28 | 109.9 (6) |
N10—C5—S5 | 122.0 (11) | O27—S14—O28 | 108.7 (6) |
N9—C5—S5 | 118.8 (11) | O29—S14—O30 | 108.8 (5) |
N12—C6—N11 | 119.1 (10) | O27—S14—O30 | 108.0 (6) |
N12—C6—S6 | 118.7 (8) | O28—S14—O30 | 110.2 (6) |
O2—Cd1—S1—C1 | 71.6 (11) | O9—Cd3—S6—C6 | −42.3 (4) |
O3—Cd1—S1—C1 | −140.9 (5) | O10—Cd3—S6—C6 | −129.6 (4) |
O4—Cd1—S1—C1 | 145.8 (6) | S5—Cd3—S6—C6 | 143.8 (4) |
O1—Cd1—S1—C1 | 57.3 (6) | S7—Cd3—S6—C6 | 47.9 (4) |
S2—Cd1—S1—C1 | −55.4 (5) | O9—Cd3—S7—C7 | 42.6 (4) |
O2—Cd1—S2—C2 | 20.4 (4) | O11—Cd3—S7—C7 | 122.3 (5) |
O3—Cd1—S2—C2 | −55.8 (4) | S5—Cd3—S7—C7 | −158.6 (4) |
O4—Cd1—S2—C2 | −106.0 (8) | S6—Cd3—S7—C7 | −54.4 (4) |
O1—Cd1—S2—C2 | 104.7 (5) | Cd3—S5—C5—N10 | 35.1 (12) |
S1—Cd1—S2—C2 | −170.2 (4) | Cd3—S5—C5—N9 | −148.8 (10) |
Cd1—S1—C1—N2 | −36.1 (12) | Cd3—S6—C6—N12 | −149.3 (8) |
Cd1—S1—C1—N1 | 144.1 (10) | Cd3—S6—C6—N11 | 34.3 (10) |
Cd1—S2—C2—N4 | 26.5 (10) | Cd3—S7—C7—N13 | −80.8 (9) |
Cd1—S2—C2—N3 | −156.1 (7) | Cd3—S7—C7—N14 | 102.4 (9) |
O8—Cd2—S3—C3 | 102.8 (8) | O12—Cd4—S8—C8 | −42.8 (5) |
O6—Cd2—S3—C3 | −21.4 (4) | O14—Cd4—S8—C8 | −124.0 (5) |
O7—Cd2—S3—C3 | 53.0 (4) | S10—Cd4—S8—C8 | 156.9 (4) |
O5—Cd2—S3—C3 | −103.6 (5) | S9—Cd4—S8—C8 | 55.0 (4) |
S4—Cd2—S3—C3 | 171.3 (4) | O12—Cd4—S9—C9 | 39.0 (4) |
O8—Cd2—S4—C4 | −150.5 (6) | O13—Cd4—S9—C9 | 126.1 (4) |
O6—Cd2—S4—C4 | −66.4 (11) | S10—Cd4—S9—C9 | −145.9 (4) |
O7—Cd2—S4—C4 | 137.2 (5) | S8—Cd4—S9—C9 | −50.9 (4) |
O5—Cd2—S4—C4 | −59.7 (5) | O12—Cd4—S10—C10 | 138.2 (8) |
S3—Cd2—S4—C4 | 53.3 (5) | O14—Cd4—S10—C10 | 147.4 (6) |
Cd2—S3—C3—N5 | 157.4 (8) | O13—Cd4—S10—C10 | 55.9 (6) |
Cd2—S3—C3—N6 | −21.8 (10) | S9—Cd4—S10—C10 | −27.4 (6) |
Cd2—S4—C4—N8 | −147.2 (10) | S8—Cd4—S10—C10 | −126.8 (6) |
Cd2—S4—C4—N7 | 35.7 (11) | Cd4—S8—C8—N15 | −103.8 (8) |
O9—Cd3—S5—C5 | −136.5 (7) | Cd4—S8—C8—N16 | 80.9 (8) |
O10—Cd3—S5—C5 | −57.8 (6) | Cd4—S9—C9—N18 | −32.9 (9) |
O11—Cd3—S5—C5 | −143.8 (6) | Cd4—S9—C9—N17 | 147.3 (7) |
S6—Cd3—S5—C5 | 26.6 (5) | Cd4—S10—C10—N20 | −32.0 (13) |
S7—Cd3—S5—C5 | 128.2 (5) | Cd4—S10—C10—N19 | 147.2 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O26i | 0.88 | 2.14 | 2.958 (16) | 154 |
N1—H1A···O26′i | 0.88 | 2.24 | 3.11 (2) | 168 |
N1—H1B···O17i | 0.88 | 2.10 | 2.927 (15) | 156 |
N1—H1B···O15i | 0.88 | 2.55 | 3.111 (14) | 122 |
N2—H2A···O24i | 0.88 | 2.08 | 2.934 (15) | 163 |
N2—H2B···O1 | 0.88 | 2.02 | 2.875 (14) | 165 |
N3—H3A···O27 | 0.88 | 2.14 | 3.014 (14) | 169 |
N4—H4A···O28 | 0.88 | 2.17 | 3.000 (13) | 157 |
N4—H4B···O3 | 0.88 | 2.21 | 3.028 (12) | 155 |
N4—H4B···O2 | 0.88 | 2.63 | 3.183 (12) | 121 |
O1—H11···O29ii | 0.82 | 1.96 | 2.743 (13) | 160 |
O1—H12···O14 | 0.82 | 1.97 | 2.770 (12) | 164 |
O2—H21···O26ii | 0.82 | 2.05 | 2.636 (12) | 128 |
O2—H21···O26′ii | 0.82 | 2.12 | 2.856 (18) | 150 |
O3—H32···O18ii | 0.82 | 1.91 | 2.679 (10) | 156 |
O4—H41···O15ii | 0.82 | 1.88 | 2.691 (13) | 172 |
O4—H42···O29ii | 0.81 | 2.16 | 2.973 (12) | 173 |
N5—H5A···O24i | 0.88 | 2.13 | 3.000 (11) | 171 |
N6—H6A···O23i | 0.88 | 2.14 | 2.986 (11) | 162 |
N6—H6B···O7 | 0.88 | 2.17 | 2.982 (12) | 153 |
N6—H6B···O6 | 0.88 | 2.59 | 3.157 (12) | 123 |
N7—H7A···O27 | 0.88 | 2.08 | 2.938 (17) | 165 |
N7—H7B···O5 | 0.88 | 2.06 | 2.915 (14) | 163 |
N8—H8A···O30 | 0.88 | 2.14 | 2.989 (15) | 162 |
N8—H8B···O21iii | 0.88 | 2.10 | 2.932 (15) | 159 |
N8—H8B···O19iii | 0.88 | 2.65 | 3.223 (14) | 124 |
O5—H52···O11 | 0.82 | 2.09 | 2.887 (13) | 164 |
O5—H51···N7 | 0.85 | 2.46 | 2.915 (14) | 114 |
O6—H62···O30iv | 0.83 | 1.84 | 2.641 (11) | 162 |
O7—H72···O22v | 0.82 | 1.95 | 2.718 (11) | 155 |
O8—H81···O16iv | 0.83 | 1.96 | 2.756 (12) | 162 |
O8—H82···O10iii | 0.81 | 2.18 | 2.922 (13) | 152 |
N9—H9A···O21 | 0.88 | 2.40 | 3.150 (17) | 143 |
N9—H9A···O20 | 0.88 | 2.50 | 3.320 (16) | 156 |
N9—H9B···O27 | 0.88 | 1.98 | 2.834 (17) | 164 |
N10—H10A···O21 | 0.88 | 2.26 | 3.040 (17) | 148 |
N10—H10B···O10 | 0.88 | 2.10 | 2.954 (15) | 163 |
N11—H11A···O18i | 0.88 | 1.98 | 2.855 (12) | 177 |
N11—H11B···O9 | 0.88 | 2.13 | 2.994 (12) | 167 |
N12—H12A···O17i | 0.88 | 1.93 | 2.797 (12) | 169 |
N13—H13A···O2iv | 0.88 | 2.36 | 3.193 (11) | 158 |
N13—H13B···O28iv | 0.88 | 1.98 | 2.848 (13) | 168 |
N14—H14A···O26i | 0.88 | 2.22 | 2.980 (13) | 145 |
O9—H91···O28iv | 0.82 | 2.03 | 2.810 (12) | 159 |
O9—H92···O20iv | 0.82 | 1.94 | 2.721 (11) | 159 |
O9—H92···O22iv | 0.82 | 2.54 | 3.189 (10) | 137 |
O10—H101···O9 | 0.81 | 2.67 | 3.331 (11) | 139 |
O10—H102···O25′iv | 0.82 | 1.77 | 2.57 (2) | 164 |
O10—H102···O25iv | 0.82 | 1.99 | 2.761 (13) | 156 |
O11—H111···O25iv | 0.82 | 2.15 | 2.851 (14) | 143 |
O11—H111···O26′iv | 0.82 | 2.18 | 2.972 (18) | 163 |
O11—H112···O29iv | 0.82 | 1.96 | 2.718 (13) | 153 |
N15—H15A···O30 | 0.88 | 2.44 | 3.222 (12) | 148 |
N15—H15A···N8 | 0.88 | 2.69 | 3.331 (15) | 131 |
N16—H16A···O6vi | 0.88 | 2.34 | 3.184 (11) | 161 |
N16—H16B···O23ii | 0.88 | 1.99 | 2.866 (11) | 172 |
N17—H17A···O21iii | 0.88 | 1.99 | 2.864 (13) | 176 |
N18—H18A···O22iii | 0.88 | 1.98 | 2.846 (12) | 169 |
N18—H18B···O12 | 0.88 | 2.15 | 2.998 (11) | 163 |
N19—H19A···O17vii | 0.88 | 2.42 | 3.174 (15) | 145 |
N19—H19A···O16vii | 0.88 | 2.43 | 3.258 (15) | 156 |
N19—H19B···O24i | 0.88 | 2.03 | 2.887 (15) | 163 |
N19—H19B···O25′i | 0.88 | 2.65 | 3.27 (2) | 129 |
N20—H20A···O17vii | 0.88 | 2.21 | 3.018 (16) | 153 |
N20—H20B···O13 | 0.88 | 2.11 | 2.966 (15) | 165 |
O12—H121···O23ii | 0.82 | 2.04 | 2.846 (10) | 167 |
O12—H122···O16viii | 0.81 | 2.06 | 2.740 (9) | 140 |
O13—H131···O19ii | 0.82 | 1.88 | 2.694 (12) | 171 |
O13—H132···O4iii | 0.82 | 2.23 | 2.981 (12) | 153 |
O14—H141···O20ii | 0.82 | 1.90 | 2.714 (11) | 173 |
O14—H142···O25ii | 0.82 | 2.10 | 2.750 (14) | 135 |
O14—H142···O25′ii | 0.82 | 2.00 | 2.79 (2) | 161 |
Symmetry codes: (i) x+1, −y+1, z−1/2; (ii) x, −y+1, z−1/2; (iii) x, y+1, z; (iv) x+1, y, z; (v) x+1, y+1, z; (vi) x−1, y, z; (vii) x+1, −y+2, z−1/2; (viii) x, −y+2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(CH4N2S)2(H2O)4][Cd(CH4N2S)3(H2O)3](SO4)2 |
Mr | 923.64 |
Crystal system, space group | Monoclinic, Pc |
Temperature (K) | 173 |
a, b, c (Å) | 10.9941 (3), 11.7602 (3), 24.0100 (5) |
β (°) | 98.9169 (12) |
V (Å3) | 3066.80 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.94 |
Crystal size (mm) | 0.07 × 0.06 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.876, 0.909 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16186, 9995, 8817 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.099, 1.08 |
No. of reflections | 9995 |
No. of parameters | 453 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0102P)2 + 30.5291P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.78, −0.64 |
Absolute structure | Flack, H. D. (1983). Acta Cryst. A39, 876–881 |
Absolute structure parameter | 0.15 (5) |
Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O26i | 0.88 | 2.14 | 2.958 (16) | 154 |
N1—H1A···O26'i | 0.88 | 2.24 | 3.11 (2) | 168 |
N1—H1B···O17i | 0.88 | 2.10 | 2.927 (15) | 156 |
N1—H1B···O15i | 0.88 | 2.55 | 3.111 (14) | 122 |
N2—H2A···O24i | 0.88 | 2.08 | 2.934 (15) | 163 |
N2—H2B···O1 | 0.88 | 2.02 | 2.875 (14) | 165 |
N3—H3A···O27 | 0.88 | 2.14 | 3.014 (14) | 169 |
N4—H4A···O28 | 0.88 | 2.17 | 3.000 (13) | 157 |
N4—H4B···O3 | 0.88 | 2.21 | 3.028 (12) | 155 |
N4—H4B···O2 | 0.88 | 2.63 | 3.183 (12) | 121 |
O1—H11···O29ii | 0.82 | 1.96 | 2.743 (13) | 160 |
O1—H12···O14 | 0.82 | 1.97 | 2.770 (12) | 164 |
O2—H21···O26ii | 0.82 | 2.05 | 2.636 (12) | 128 |
O2—H21···O26'ii | 0.82 | 2.12 | 2.856 (18) | 150 |
O3—H32···O18ii | 0.82 | 1.91 | 2.679 (10) | 156 |
O4—H41···O15ii | 0.82 | 1.88 | 2.691 (13) | 172 |
O4—H42···O29ii | 0.81 | 2.16 | 2.973 (12) | 173 |
N5—H5A···O24i | 0.88 | 2.13 | 3.000 (11) | 171 |
N6—H6A···O23i | 0.88 | 2.14 | 2.986 (11) | 162 |
N6—H6B···O7 | 0.88 | 2.17 | 2.982 (12) | 153 |
N6—H6B···O6 | 0.88 | 2.59 | 3.157 (12) | 123 |
N7—H7A···O27 | 0.88 | 2.08 | 2.938 (17) | 165 |
N7—H7B···O5 | 0.88 | 2.06 | 2.915 (14) | 163 |
N8—H8A···O30 | 0.88 | 2.14 | 2.989 (15) | 162 |
N8—H8B···O21iii | 0.88 | 2.10 | 2.932 (15) | 159 |
N8—H8B···O19iii | 0.88 | 2.65 | 3.223 (14) | 124 |
O5—H52···O11 | 0.82 | 2.09 | 2.887 (13) | 164 |
O5—H51···N7 | 0.85 | 2.46 | 2.915 (14) | 114 |
O6—H62···O30iv | 0.83 | 1.84 | 2.641 (11) | 162 |
O7—H72···O22v | 0.82 | 1.95 | 2.718 (11) | 155 |
O8—H81···O16iv | 0.83 | 1.96 | 2.756 (12) | 162 |
O8—H82···O10iii | 0.81 | 2.18 | 2.922 (13) | 152 |
N9—H9A···O21 | 0.88 | 2.40 | 3.150 (17) | 143 |
N9—H9A···O20 | 0.88 | 2.50 | 3.320 (16) | 156 |
N9—H9B···O27 | 0.88 | 1.98 | 2.834 (17) | 164 |
N10—H10A···O21 | 0.88 | 2.26 | 3.040 (17) | 148 |
N10—H10B···O10 | 0.88 | 2.10 | 2.954 (15) | 163 |
N11—H11A···O18i | 0.88 | 1.98 | 2.855 (12) | 177 |
N11—H11B···O9 | 0.88 | 2.13 | 2.994 (12) | 167 |
N12—H12A···O17i | 0.88 | 1.93 | 2.797 (12) | 169 |
N13—H13A···O2iv | 0.88 | 2.36 | 3.193 (11) | 158 |
N13—H13B···O28iv | 0.88 | 1.98 | 2.848 (13) | 168 |
N14—H14A···O26i | 0.88 | 2.22 | 2.980 (13) | 145 |
O9—H91···O28iv | 0.82 | 2.03 | 2.810 (12) | 159 |
O9—H92···O20iv | 0.82 | 1.94 | 2.721 (11) | 159 |
O9—H92···O22iv | 0.82 | 2.54 | 3.189 (10) | 137 |
O10—H101···O9 | 0.81 | 2.67 | 3.331 (11) | 139 |
O10—H102···O25'iv | 0.82 | 1.77 | 2.57 (2) | 164 |
O10—H102···O25iv | 0.82 | 1.99 | 2.761 (13) | 156 |
O11—H111···O25iv | 0.82 | 2.15 | 2.851 (14) | 143 |
O11—H111···O26'iv | 0.82 | 2.18 | 2.972 (18) | 163 |
O11—H112···O29iv | 0.82 | 1.96 | 2.718 (13) | 153 |
N15—H15A···O30 | 0.88 | 2.44 | 3.222 (12) | 148 |
N15—H15A···N8 | 0.88 | 2.69 | 3.331 (15) | 131 |
N16—H16A···O6vi | 0.88 | 2.34 | 3.184 (11) | 161 |
N16—H16B···O23ii | 0.88 | 1.99 | 2.866 (11) | 172 |
N17—H17A···O21iii | 0.88 | 1.99 | 2.864 (13) | 176 |
N18—H18A···O22iii | 0.88 | 1.98 | 2.846 (12) | 169 |
N18—H18B···O12 | 0.88 | 2.15 | 2.998 (11) | 163 |
N19—H19A···O17vii | 0.88 | 2.42 | 3.174 (15) | 145 |
N19—H19A···O16vii | 0.88 | 2.43 | 3.258 (15) | 156 |
N19—H19B···O24i | 0.88 | 2.03 | 2.887 (15) | 163 |
N19—H19B···O25'i | 0.88 | 2.65 | 3.27 (2) | 129 |
N20—H20A···O17vii | 0.88 | 2.21 | 3.018 (16) | 153 |
N20—H20B···O13 | 0.88 | 2.11 | 2.966 (15) | 165 |
O12—H121···O23ii | 0.82 | 2.04 | 2.846 (10) | 167 |
O12—H122···O16viii | 0.81 | 2.06 | 2.740 (9) | 140 |
O13—H131···O19ii | 0.82 | 1.88 | 2.694 (12) | 171 |
O13—H132···O4iii | 0.82 | 2.23 | 2.981 (12) | 153 |
O14—H141···O20ii | 0.82 | 1.90 | 2.714 (11) | 173 |
O14—H142···O25ii | 0.82 | 2.10 | 2.750 (14) | 135 |
O14—H142···O25'ii | 0.82 | 2.00 | 2.79 (2) | 161 |
Symmetry codes: (i) x+1, −y+1, z−1/2; (ii) x, −y+1, z−1/2; (iii) x, y+1, z; (iv) x+1, y, z; (v) x+1, y+1, z; (vi) x−1, y, z; (vii) x+1, −y+2, z−1/2; (viii) x, −y+2, z−1/2. |
Acknowledgements
This research was supported by the National Science and Engineering Research Council (NSERC) of Canada, the Canadian Foundation for Innovation (CFI) and the Province of Alberta (Department of Innovation and Science).
References
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A survey in the crystal structure database shows that mixing cadmium sulfate (CdSO4) with thiourea (TU) in the mole ratio 1:3 results in either monomeric [Cd(TU)3(SO4)] (Oussaid et al., 2000; Cavaica et al., 1970), (or dimeric [Cd(µ-TU)(TU)2(SO4)]2 complexes (Corao & Baggio, 1969) with the cadmium ion coordinating four (CdS3O) or five (CdS4O) ligand atoms, respectively.
With intention to prepare the mononuclear [Cd(TU)3(SO4)] complex for a solid state 113Cd NMR measurement (Jalilehvand et al., 2012), a solution was prepared of a mixture of CdSO4.8/3H2O and thiourea in 1:3.8 mole ratio in hot water, and slowly evaporated resulting in colorless crystals. Elemental analysis of a ground sample (i) used for the solid state 113Cd NMR spectroscopy showed that the bulk of the crystalline solid mainly consisted of the [Cd(TU)3(SO4)] complex (see Special details section). However, elemental analyses of two random samples of the colorless crystals (ii and iii) showed that the sample was inhomogeneous. An X-ray crystallographic structure determination of the colorless crystal, revealed that cis-[Cd(TU)2(H2O)4]2+ and fac-[Cd(TU)3(H2O)3]2+ complexes had co-crystallized in the crystal. To our knowledge, this is the first report on the structure of hydrated Cd(II) thiourea complexes.
The asymmetric unit of the title co-crystal contains two cadmium(II) complexes of each type together with four sulfate ions (Fig. 1). All Cd atoms exhibit distorted octahedral geometry. The Cd–S and Cd–O distances around Cd1 and Cd2 atoms in the bis(thiourea) complex, cis-[Cd(TU)2(H2O)4]2+, lie in the ranges 2.580 (4) - 2.599 (4) Å and 2.323 (8) - 2.421 (9) Å, respectively. In the tris(thiourea) complex, fac-[Cd(TU)3(H2O)3]2+, the corresponding bond lengths around Cd3 and Cd4 atoms are slightly longer and lie in the ranges 2.559 (4) - 2.706 (3) Å and 2.303 (7) - 2.480 (10) Å, respectively. The crystal structure is stabilized by strong hydrogen bonds (Tab. 1).