Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040808/ci6728sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040808/ci6728Isup2.hkl |
CCDC reference: 296717
Key indicators
- Single-crystal X-ray study
- T = 297 K
- Mean (C-C) = 0.004 Å
- R factor = 0.042
- wR factor = 0.098
- Data-to-parameter ratio = 15.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) ..... 10 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 10
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion
Compound (I) was prepared by the self-assembly synthesis method. Cadmium chloride (0.367 g, 2 mmol), maleic acid (0.464 g, 4 mmol) and thiosemicarbazide (0.182 g, 2 mmol) were mixed together in a methanol/water (1:1 v/v) solution (50 ml) with stirring. The pH of the mixture was maintained at 4.8–5.0. The solution was then filtered and evaporated slowly at room temperature in air. Colourless single crystals of (I) suitable for X-ray analysis were obtained from the reaction mother solution by the solvent-evaporation method after 7 d.
Water H atoms were located in a difference map and were refined isotropically. All other H atoms were positioned geometrically and allowed to ride on their parent atoms, with O—H = 0.82 Å, N—H = 0.86 or 0.90 Å and C—H = 0.93 Å, and with Uiso(H) = 1.2–1.5Ueq(carrier). The highest peak in the difference map is 1.35 Å from H3C and the deepest hole is ?? Å from ??.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).
[Cd(CH5N3S)2(H2O)2](C4H3O4)2·2H2O | F(000) = 604 |
Mr = 596.90 | Dx = 1.834 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2471 reflections |
a = 12.4444 (1) Å | θ = 1.7–27.5° |
b = 6.1239 (1) Å | µ = 1.27 mm−1 |
c = 14.9076 (3) Å | T = 297 K |
β = 107.9569 (10)° | Block, colourless |
V = 1080.74 (3) Å3 | 0.40 × 0.24 × 0.22 mm |
Z = 2 |
Siemens SMART CCD area-detector diffractometer | 2471 independent reflections |
Radiation source: fine-focus sealed tube | 2121 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.095 |
Detector resolution: 8.33 pixels mm-1 | θmax = 27.5°, θmin = 1.7° |
ω scans | h = −8→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −7→7 |
Tmin = 0.700, Tmax = 0.756 | l = −19→14 |
7169 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)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0234P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
2467 reflections | Δρmax = 1.07 e Å−3 |
159 parameters | Δρmin = −2.68 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0156 (16) |
[Cd(CH5N3S)2(H2O)2](C4H3O4)2·2H2O | V = 1080.74 (3) Å3 |
Mr = 596.90 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.4444 (1) Å | µ = 1.27 mm−1 |
b = 6.1239 (1) Å | T = 297 K |
c = 14.9076 (3) Å | 0.40 × 0.24 × 0.22 mm |
β = 107.9569 (10)° |
Siemens SMART CCD area-detector diffractometer | 2471 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2121 reflections with I > 2σ(I) |
Tmin = 0.700, Tmax = 0.756 | Rint = 0.095 |
7169 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 1.07 e Å−3 |
2467 reflections | Δρmin = −2.68 e Å−3 |
159 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.0000 | 0.0000 | 0.5000 | 0.01566 (14) | |
S1 | 0.09041 (6) | −0.32747 (10) | 0.59979 (5) | 0.0200 (2) | |
O1 | 0.60369 (19) | 0.7530 (4) | 0.70488 (17) | 0.0326 (6) | |
O2 | 0.51927 (19) | 0.4497 (4) | 0.63866 (17) | 0.0229 (5) | |
H1O2 | 0.4606 | 0.4152 | 0.5980 | 0.034* | |
O3 | 0.34931 (17) | 0.3541 (3) | 0.51436 (15) | 0.0204 (5) | |
O4 | 0.2110 (2) | 0.5226 (3) | 0.40642 (18) | 0.0249 (5) | |
N1 | 0.17525 (19) | 0.1442 (3) | 0.59001 (17) | 0.0158 (5) | |
H1N1 | 0.2167 | 0.1727 | 0.5514 | 0.019* | |
H2N1 | 0.1633 | 0.2717 | 0.6154 | 0.019* | |
N2 | 0.2376 (2) | 0.0058 (3) | 0.6628 (2) | 0.0167 (5) | |
H1N2 | 0.2972 | 0.0569 | 0.7036 | 0.020* | |
N3 | 0.2795 (2) | −0.3146 (4) | 0.74097 (18) | 0.0242 (6) | |
H1N3 | 0.3399 | −0.2540 | 0.7768 | 0.029* | |
H2N3 | 0.2651 | −0.4487 | 0.7499 | 0.029* | |
C1 | 0.2086 (2) | −0.2009 (4) | 0.67162 (19) | 0.0150 (6) | |
C2 | 0.5266 (2) | 0.6610 (5) | 0.6444 (2) | 0.0196 (6) | |
C3 | 0.4422 (2) | 0.8004 (4) | 0.5747 (2) | 0.0192 (6) | |
H3 | 0.4563 | 0.9496 | 0.5815 | 0.023* | |
C4 | 0.3507 (2) | 0.7468 (4) | 0.5051 (2) | 0.0175 (6) | |
H4 | 0.3116 | 0.8643 | 0.4705 | 0.021* | |
C5 | 0.3000 (3) | 0.5280 (4) | 0.4730 (2) | 0.0159 (6) | |
O1W | 0.05320 (19) | −0.1455 (4) | 0.36548 (15) | 0.0190 (4) | |
H1W1 | 0.079 (4) | −0.048 (7) | 0.341 (4) | 0.045 (13)* | |
H2W1 | 0.102 (3) | −0.233 (7) | 0.375 (3) | 0.037 (12)* | |
O2W | 0.13384 (19) | 0.1816 (3) | 0.28256 (16) | 0.0199 (5) | |
H1W2 | 0.076 (3) | 0.227 (6) | 0.248 (3) | 0.033 (11)* | |
H2W2 | 0.159 (3) | 0.281 (7) | 0.317 (3) | 0.042 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0165 (2) | 0.01311 (18) | 0.01522 (19) | 0.00239 (9) | 0.00165 (13) | 0.00377 (9) |
S1 | 0.0264 (4) | 0.0100 (3) | 0.0179 (4) | 0.0008 (3) | −0.0015 (3) | 0.0023 (2) |
O1 | 0.0280 (13) | 0.0275 (11) | 0.0313 (14) | 0.0013 (9) | −0.0070 (11) | −0.0068 (10) |
O2 | 0.0172 (12) | 0.0205 (9) | 0.0258 (12) | 0.0006 (9) | −0.0012 (9) | 0.0012 (9) |
O3 | 0.0194 (11) | 0.0135 (9) | 0.0265 (11) | −0.0020 (8) | 0.0045 (9) | 0.0020 (8) |
O4 | 0.0195 (12) | 0.0228 (11) | 0.0259 (13) | 0.0025 (8) | −0.0026 (10) | −0.0071 (8) |
N1 | 0.0169 (12) | 0.0113 (10) | 0.0198 (12) | 0.0011 (9) | 0.0063 (10) | 0.0033 (9) |
N2 | 0.0152 (14) | 0.0157 (12) | 0.0170 (13) | 0.0000 (8) | 0.0016 (10) | 0.0022 (8) |
N3 | 0.0270 (15) | 0.0188 (12) | 0.0209 (13) | 0.0034 (10) | −0.0012 (11) | 0.0047 (10) |
C1 | 0.0203 (15) | 0.0142 (12) | 0.0120 (13) | 0.0048 (10) | 0.0070 (11) | −0.0003 (10) |
C2 | 0.0179 (15) | 0.0212 (14) | 0.0208 (15) | 0.0017 (11) | 0.0073 (12) | −0.0027 (12) |
C3 | 0.0187 (15) | 0.0141 (12) | 0.0249 (16) | 0.0003 (10) | 0.0066 (12) | −0.0029 (11) |
C4 | 0.0181 (15) | 0.0134 (12) | 0.0220 (15) | 0.0015 (11) | 0.0074 (12) | 0.0008 (11) |
C5 | 0.0137 (15) | 0.0179 (13) | 0.0186 (15) | 0.0000 (10) | 0.0086 (12) | −0.0023 (10) |
O1W | 0.0224 (12) | 0.0172 (10) | 0.0187 (11) | 0.0048 (9) | 0.0083 (9) | 0.0040 (8) |
O2W | 0.0213 (12) | 0.0165 (10) | 0.0213 (11) | −0.0025 (9) | 0.0055 (9) | −0.0050 (9) |
Cd1—N1 | 2.352 (2) | N2—C1 | 1.334 (3) |
Cd1—N1i | 2.352 (2) | N2—H1N2 | 0.86 |
Cd1—O1W | 2.464 (2) | N3—C1 | 1.331 (3) |
Cd1—O1Wi | 2.464 (2) | N3—H1N3 | 0.86 |
Cd1—S1 | 2.5433 (7) | N3—H2N3 | 0.86 |
Cd1—S1i | 2.5433 (7) | C2—C3 | 1.496 (4) |
S1—C1 | 1.715 (3) | C3—C4 | 1.325 (4) |
O1—C2 | 1.232 (4) | C3—H3 | 0.93 |
O2—C2 | 1.298 (3) | C4—C5 | 1.496 (4) |
O2—H1O2 | 0.82 | C4—H4 | 0.93 |
O3—C5 | 1.287 (3) | O1W—H1W1 | 0.81 (5) |
O4—C5 | 1.239 (4) | O1W—H2W1 | 0.79 (4) |
N1—N2 | 1.407 (3) | O2W—H1W2 | 0.80 (4) |
N1—H1N1 | 0.90 | O2W—H2W2 | 0.80 (4) |
N1—H2N1 | 0.90 | ||
N1—Cd1—N1i | 179.999 (1) | C1—N2—H1N2 | 118.5 |
N1—Cd1—O1W | 99.53 (8) | N1—N2—H1N2 | 118.5 |
N1i—Cd1—O1W | 80.47 (8) | C1—N3—H1N3 | 120.0 |
N1—Cd1—O1Wi | 80.47 (8) | C1—N3—H2N3 | 120.0 |
N1i—Cd1—O1Wi | 99.53 (8) | H1N3—N3—H2N3 | 120.0 |
O1W—Cd1—O1Wi | 180.0 | N3—C1—N2 | 116.0 (3) |
N1—Cd1—S1 | 78.30 (5) | N3—C1—S1 | 119.0 (2) |
N1i—Cd1—S1 | 101.70 (5) | N2—C1—S1 | 125.0 (2) |
O1W—Cd1—S1 | 90.55 (6) | O1—C2—O2 | 121.8 (3) |
O1Wi—Cd1—S1 | 89.45 (6) | O1—C2—C3 | 117.9 (3) |
N1—Cd1—S1i | 101.70 (5) | O2—C2—C3 | 120.2 (3) |
N1i—Cd1—S1i | 78.30 (5) | C4—C3—C2 | 130.7 (3) |
O1W—Cd1—S1i | 89.45 (6) | C4—C3—H3 | 114.6 |
O1Wi—Cd1—S1i | 90.55 (6) | C2—C3—H3 | 114.6 |
S1—Cd1—S1i | 179.999 (1) | C3—C4—C5 | 130.5 (3) |
C1—S1—Cd1 | 98.54 (9) | C3—C4—H4 | 114.8 |
C2—O2—H1O2 | 109.5 | C5—C4—H4 | 114.8 |
N2—N1—Cd1 | 114.07 (16) | O4—C5—O3 | 122.6 (3) |
N2—N1—H1N1 | 108.7 | O4—C5—C4 | 117.7 (3) |
Cd1—N1—H1N1 | 108.7 | O3—C5—C4 | 119.7 (3) |
N2—N1—H2N1 | 108.7 | Cd1—O1W—H1W1 | 110 (3) |
Cd1—N1—H2N1 | 108.7 | Cd1—O1W—H2W1 | 119 (3) |
H1N1—N1—H2N1 | 107.6 | H1W1—O1W—H2W1 | 101 (4) |
C1—N2—N1 | 123.1 (2) | H1W2—O2W—H2W2 | 105 (4) |
N1—Cd1—S1—C1 | 6.61 (11) | N1—N2—C1—N3 | 176.3 (3) |
N1i—Cd1—S1—C1 | −173.39 (11) | N1—N2—C1—S1 | −2.3 (4) |
O1W—Cd1—S1—C1 | 106.22 (11) | Cd1—S1—C1—N3 | 176.2 (2) |
O1Wi—Cd1—S1—C1 | −73.78 (11) | Cd1—S1—C1—N2 | −5.2 (3) |
O1W—Cd1—N1—N2 | −97.65 (19) | O1—C2—C3—C4 | −177.9 (3) |
O1Wi—Cd1—N1—N2 | 82.35 (19) | O2—C2—C3—C4 | 3.8 (5) |
S1—Cd1—N1—N2 | −9.07 (18) | C2—C3—C4—C5 | 0.7 (6) |
S1i—Cd1—N1—N2 | 170.93 (18) | C3—C4—C5—O4 | 178.2 (3) |
Cd1—N1—N2—C1 | 9.6 (4) | C3—C4—C5—O3 | −2.0 (5) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O2···O3 | 0.82 | 1.60 | 2.415 (3) | 177 |
N1—H1N1···O3 | 0.90 | 2.20 | 3.020 (3) | 152 |
N1—H2N1···S1ii | 0.90 | 2.60 | 3.420 (2) | 152 |
N2—H1N2···O1iii | 0.86 | 1.95 | 2.772 (4) | 160 |
N3—H1N3···O2iii | 0.86 | 2.20 | 3.056 (4) | 171 |
N3—H2N3···O1iv | 0.86 | 2.40 | 3.009 (3) | 128 |
N3—H2N3···O2Wv | 0.86 | 2.33 | 3.068 (3) | 144 |
O1W—H1W1···O2W | 0.82 (5) | 1.89 (5) | 2.704 (3) | 178 (6) |
O1W—H2W1···O4vi | 0.79 (4) | 1.98 (4) | 2.761 (3) | 172 (4) |
O2W—H1W2···O1Wvii | 0.80 (4) | 2.09 (4) | 2.871 (3) | 166 (4) |
O2W—H2W2···O4 | 0.80 (4) | 1.96 (4) | 2.757 (3) | 175 (4) |
Symmetry codes: (ii) x, y+1, z; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, y−3/2, −z+3/2; (v) x, −y−1/2, z+1/2; (vi) x, y−1, z; (vii) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(CH5N3S)2(H2O)2](C4H3O4)2·2H2O |
Mr | 596.90 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 297 |
a, b, c (Å) | 12.4444 (1), 6.1239 (1), 14.9076 (3) |
β (°) | 107.9569 (10) |
V (Å3) | 1080.74 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.27 |
Crystal size (mm) | 0.40 × 0.24 × 0.22 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.700, 0.756 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7169, 2471, 2121 |
Rint | 0.095 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.098, 1.02 |
No. of reflections | 2467 |
No. of parameters | 159 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.07, −2.68 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 2003).
Cd1—N1 | 2.352 (2) | O4—C5 | 1.239 (4) |
Cd1—O1W | 2.464 (2) | N1—N2 | 1.407 (3) |
Cd1—S1 | 2.5433 (7) | N2—C1 | 1.334 (3) |
S1—C1 | 1.715 (3) | N3—C1 | 1.331 (3) |
O1—C2 | 1.232 (4) | C2—C3 | 1.496 (4) |
O2—C2 | 1.298 (3) | C3—C4 | 1.325 (4) |
O3—C5 | 1.287 (3) | C4—C5 | 1.496 (4) |
N1—Cd1—N1i | 179.999 (1) | O1W—Cd1—S1 | 90.55 (6) |
N1—Cd1—O1W | 99.53 (8) | N1—Cd1—S1i | 101.70 (5) |
N1i—Cd1—O1W | 80.47 (8) | O1W—Cd1—S1i | 89.45 (6) |
O1W—Cd1—O1Wi | 180.0 | S1—Cd1—S1i | 179.999 (1) |
N1—Cd1—S1 | 78.30 (5) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O2···O3 | 0.82 | 1.60 | 2.415 (3) | 177 |
N1—H1N1···O3 | 0.90 | 2.20 | 3.020 (3) | 152 |
N1—H2N1···S1ii | 0.90 | 2.60 | 3.420 (2) | 152 |
N2—H1N2···O1iii | 0.86 | 1.95 | 2.772 (4) | 160 |
N3—H1N3···O2iii | 0.86 | 2.20 | 3.056 (4) | 171 |
N3—H2N3···O1iv | 0.86 | 2.40 | 3.009 (3) | 128 |
N3—H2N3···O2Wv | 0.86 | 2.33 | 3.068 (3) | 144 |
O1W—H1W1···O2W | 0.82 (5) | 1.89 (5) | 2.704 (3) | 178 (6) |
O1W—H2W1···O4vi | 0.79 (4) | 1.98 (4) | 2.761 (3) | 172 (4) |
O2W—H1W2···O1Wvii | 0.80 (4) | 2.09 (4) | 2.871 (3) | 166 (4) |
O2W—H2W2···O4 | 0.80 (4) | 1.96 (4) | 2.757 (3) | 175 (4) |
Symmetry codes: (ii) x, y+1, z; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, y−3/2, −z+3/2; (v) x, −y−1/2, z+1/2; (vi) x, y−1, z; (vii) −x, y+1/2, −z+1/2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The assembly of complexes on the basis of adding building units and connecting them is the most efficient means for the construction of highly organized structures. This is achieved due to the advancement of crystallography and synthetic chemistry (Abrahams et al., 1999; Bowmaker et al., 1998). Being the most efficient means for construction of highly organized structures and rational design of functional materials, transition-metal-directed self-assembly has emerged as a new and major motif-forming mechanism in supramolecular architecture. The study of self-assembly processes and properties of supramolecular systems and/or molecular aggregates in natural and non-natural systems (organic and inorganic systems) has attracted much interest (Lawrence et al., 1995; Yaghi et al., 1998). Meanwhile, there is considerable current interest in crystal engineering based on the use of either coordinative bonds (Blake et al., 1999) or weaker intermolecular interactions. In the latter methodology, the hydrogen bond can influence the metal coordination geometry and adjust the structure of relative compounds because of the relative strength, directionality, flexibility and dynamic character of the bond (Allen et al., 1999; Russell et al., 1997). As part of our studies investigating the effective synthesis and the properties of complexes containing thiosemicarbazides, we report here the crystal structure of the title compound, (I), which is isomorphous to [Zn(CH5N3S)2(H2O)2]·2C4H3O4·2H2O (Li et al., 2005).
The asymmetric unit of (I) contains one-half of a [Cd(CH5N3S)2(H2O)2]2+ cation, the other half being inversion-related by (−x, −y, 1 − z), a maleate anion and a water molecule (Fig. 1). The CdII atom lies on a center of symmetry and is six-coordinated by two N, two S and two O atoms. Each of the two pairs of coordinated S and N atoms belongs to one of the two symmetry-related thiosemicarbazide ligands, in which the ligands serve as N,S-chelates, while the two coordinated O atoms belong to the symmetry-related water molecules. The CdN2S2O2 group forms a slightly distorted octahedral configuration. The linear O1W—Cd1—O1Wi group [symmetry code: (i) −x, −y, 1 − z] is almost perpendicular to the equatorial N1/S1/N1i/S1i plane, as evidenced by the angles subtended at atom Cd1 (Table 1). The coordination bond lengths (Cd—O, Cd—N and Cd—S) are normal (Allen et al., 1987), whereas the C1—N2 and C1—S2 bond distances in the thiosemicarbazide ligands are intermediate between the corresponding single- and double-bond lengths. These C—N and C—S bonds suggest, to some extent, the electronic delocalization effect on the chelate ligand upon complex formation.
The structure differs from that of related compounds (Zhang, Li, Chen et al., 2000; Zhang, Li, Nishiura et al., 2000; Burrows et al., 2000) in that the maleate group in (I) is not coordinated to the CdII atom but acts as an independent counter-ion, with mutual electrostatic interaction in the structure. This situation was also observed in our previous studies on the structures of trans-diaquabis(thiosemicarbazido-k2N,S)nickel(II) dimaleate dihydrate (Li, Usman, Razak, Fun et al., 2003), bis(thiosemicarbazido-k3N,S) nickel(II)–succinate–succinic acid (1/1/1) (Li, Usman, Razak, Rahman et al., 2003) and bis(thiosemicarbazide)zinc(II) bis(maleate) dihydrate (Li et al., 2005).
The thiosemicarbazide ligand is planar (r.m.s. deviation 0.017 Å) and the coordinated Cd1 atom is displaced from it by 0.242 (3) Å. The maleate anion is also planar (r.m.s. deviation 0.028 Å), with deviations of 0.046 (2) and 0.043 (2) Å in opposite directions for atoms O1 and O2, respectively.
The complex cation, the maleate anions and the uncoordinated water molecules are linked by O1W—H1W1···O2W, O2W—H2W2···O4 and N1—H1N1···O3 hydrogen bonds (Fig. 1), in which the maleate anions and the water molecules act as hydrogen-bond acceptors. In the crystal packing, the thiosemicarbazide ligands, maleate anions and water molecules serve as both hydrogen-bond donors and acceptors. The N1—H2N1···S1i, N2—H1N2···O1ii, N3—H1N3···O2ii and N3—H2N3···O1iii hydrogen bonds (see Table 2 for symmetry codes), together with the N1—H1N1···O3 hydrogen bond, link the complex cations and maleate anions into sheets parallel to the (102) plane (Fig. 2). The sheets are interconnected by N—H···O and O—H···O hydrogen bonds involving water molecules into a three-dimensional network.