Bis(thio­semicarbazide)zinc(II) bis­(maleate) dihydrate

In the title compound, [Zn(CH₅N₃S)₂(H₂O)₂](C₄H₃O₄)₂·2H₂O, the Zn^II ion lies on a centre of symmetry and is coordinated by two pairs of N and S atoms from two symmetry-related thio­semicarbazide ligands and two O atoms from two water mol­ecules in a distorted octa­hedral geometry. In the crystal structure, the components are effectively linked together by electrostatic inter­actions and hydrogen bonds of the O—H...O, N—H...O and N—H...S types into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.051
• wR factor = 0.128
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.06 Ratio
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Zn1    -   O1W     ..      23.36 su

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.44
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.21
PLAT417_ALERT_2_C Short Inter D-H..H-D       H1W1   ..  H1W2    ..       2.13 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         10

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   7 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
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

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).

Bis(thiosemicarbazide)zinc(II) bis(maleate) dihydrate

Crystal data

[Zn(CH5N3S)2(H2O)2](C4H3O4)2·2H2O	F(000) = 568
Mr = 549.88	Dx = 1.707 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6261 reflections
a = 13.0748 (2) Å	θ = 1.7–26.0°
b = 6.0256 (1) Å	µ = 1.41 mm^−1
c = 14.4306 (1) Å	T = 297 K
β = 109.790 (1)°	Block, colourless
V = 1069.75 (3) Å^3	0.50 × 0.28 × 0.20 mm
Z = 2

Data collection

Siemens SMART CCD area-detector diffractometer	2096 independent reflections
Radiation source: fine-focus sealed tube	1796 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
Detector resolution: 8.33 pixels mm^-1	θmax = 26.0°, θmin = 1.7°
ω scans	h = −16→14
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −7→7
Tmin = 0.628, Tmax = 0.754	l = −17→15
6261 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.128	w = 1/[σ^2(Fo^2) + (0.0721P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
2096 reflections	Δρmax = 0.55 e Å^−3
159 parameters	Δρmin = −1.29 e Å^−3
6 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.019 (4)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.0000	0.0000	0.5000	0.0365 (2)
S1	0.07396 (5)	−0.31344 (10)	0.60183 (5)	0.0312 (2)
O1	0.61679 (18)	0.7524 (4)	0.70980 (18)	0.0587 (7)
O2	0.52657 (19)	0.4468 (4)	0.65103 (19)	0.0508 (6)
H1O2	0.4679	0.4116	0.6104	0.076*
O3	0.35215 (17)	0.3493 (3)	0.52997 (17)	0.0456 (6)
O4	0.21197 (19)	0.5185 (3)	0.42588 (18)	0.0459 (6)
N1	0.15369 (17)	0.1477 (3)	0.57759 (15)	0.0270 (5)
H1N1	0.1869	0.1823	0.5341	0.032*
H2N1	0.1424	0.2750	0.6054	0.032*
N2	0.2233 (2)	0.0109 (3)	0.65152 (19)	0.0305 (5)
H1N2	0.2859	0.0611	0.6871	0.037*
N3	0.2678 (2)	−0.3064 (4)	0.73886 (18)	0.0401 (6)
H1N3	0.3293	−0.2471	0.7715	0.048*
H2N3	0.2533	−0.4394	0.7522	0.048*
C1	0.1951 (2)	−0.1926 (4)	0.66776 (17)	0.0243 (5)
C2	0.5365 (2)	0.6601 (4)	0.6525 (2)	0.0353 (6)
C3	0.4507 (2)	0.7993 (4)	0.5834 (2)	0.0364 (6)
H3	0.4656	0.9506	0.5885	0.044*
C4	0.3566 (2)	0.7462 (4)	0.5157 (2)	0.0328 (6)
H4	0.3175	0.8652	0.4797	0.039*
C5	0.3035 (2)	0.5249 (4)	0.4882 (2)	0.0310 (6)
O1W	0.05534 (17)	−0.1469 (3)	0.37421 (15)	0.0374 (5)
H1W1	0.073 (3)	−0.047 (5)	0.342 (3)	0.070 (13)*
H2W1	0.107 (3)	−0.237 (7)	0.396 (4)	0.13 (2)*
O2W	0.13298 (18)	0.1841 (3)	0.28682 (15)	0.0374 (5)
H1W2	0.0720 (18)	0.223 (6)	0.246 (2)	0.079 (15)*
H2W2	0.158 (3)	0.292 (4)	0.324 (2)	0.062 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0309 (3)	0.0226 (3)	0.0404 (3)	−0.00363 (15)	−0.0086 (2)	0.01220 (17)
S1	0.0342 (4)	0.0179 (4)	0.0318 (4)	−0.0005 (2)	−0.0015 (3)	0.0055 (2)
O1	0.0390 (13)	0.0471 (13)	0.0646 (16)	0.0011 (11)	−0.0156 (11)	−0.0079 (12)
O2	0.0353 (12)	0.0347 (11)	0.0653 (15)	0.0043 (9)	−0.0055 (11)	0.0053 (11)
O3	0.0379 (12)	0.0260 (10)	0.0616 (14)	−0.0023 (8)	0.0019 (10)	0.0036 (10)
O4	0.0305 (13)	0.0382 (12)	0.0569 (15)	0.0025 (8)	−0.0009 (11)	−0.0125 (9)
N1	0.0273 (11)	0.0189 (10)	0.0310 (11)	0.0025 (8)	0.0051 (8)	0.0043 (8)
N2	0.0229 (12)	0.0249 (12)	0.0370 (12)	−0.0003 (8)	0.0012 (9)	0.0038 (8)
N3	0.0342 (13)	0.0323 (12)	0.0403 (14)	0.0048 (10)	−0.0050 (10)	0.0097 (10)
C1	0.0274 (13)	0.0228 (11)	0.0222 (11)	0.0067 (9)	0.0077 (9)	0.0005 (9)
C2	0.0277 (14)	0.0324 (15)	0.0410 (15)	0.0013 (10)	0.0054 (12)	−0.0017 (12)
C3	0.0331 (15)	0.0241 (13)	0.0472 (16)	−0.0014 (10)	0.0072 (12)	0.0000 (11)
C4	0.0314 (15)	0.0238 (13)	0.0388 (14)	0.0044 (11)	0.0063 (11)	0.0031 (11)
C5	0.0275 (15)	0.0304 (14)	0.0361 (15)	0.0009 (10)	0.0121 (12)	−0.0040 (10)
O1W	0.0414 (12)	0.0309 (11)	0.0394 (11)	0.0068 (9)	0.0131 (9)	0.0082 (9)
O2W	0.0395 (13)	0.0333 (11)	0.0384 (12)	−0.0072 (9)	0.0118 (10)	−0.0087 (9)

Geometric parameters (Å, º)

Zn1—N1^i	2.136 (2)	N2—C1	1.324 (3)
Zn1—N1	2.136 (2)	N2—H1N2	0.86
Zn1—O1W	2.344 (2)	N3—C1	1.329 (3)
Zn1—O1W^i	2.344 (2)	N3—H1N3	0.86
Zn1—S1	2.3873 (6)	N3—H2N3	0.86
Zn1—S1^i	2.3873 (6)	C2—C3	1.482 (4)
S1—C1	1.710 (3)	C3—C4	1.327 (4)
O1—C2	1.228 (4)	C3—H3	0.93
O2—C2	1.291 (3)	C4—C5	1.493 (4)
O2—H1O2	0.82	C4—H4	0.93
O3—C5	1.276 (3)	O1W—H1W1	0.84 (4)
O4—C5	1.230 (4)	O1W—H2W1	0.84 (5)
N1—N2	1.410 (3)	O2W—H1W2	0.85 (3)
N1—H1N1	0.90	O2W—H2W2	0.84 (3)
N1—H2N1	0.90
N1^i—Zn1—N1	180	C1—N2—H1N2	119.1
N1^i—Zn1—O1W	85.35 (8)	N1—N2—H1N2	119.1
N1—Zn1—O1W	94.65 (8)	C1—N3—H1N3	120.0
N1^i—Zn1—O1W^i	94.65 (8)	C1—N3—H2N3	120.0
N1—Zn1—O1W^i	85.35 (8)	H1N3—N3—H2N3	120.0
O1W—Zn1—O1W^i	180	N2—C1—N3	116.5 (2)
N1^i—Zn1—S1	96.09 (5)	N2—C1—S1	123.8 (2)
N1—Zn1—S1	83.91 (5)	N3—C1—S1	119.7 (2)
O1W—Zn1—S1	90.63 (5)	O1—C2—O2	121.3 (3)
O1W^i—Zn1—S1	89.37 (5)	O1—C2—C3	118.4 (2)
N1^i—Zn1—S1^i	83.91 (5)	O2—C2—C3	120.2 (3)
N1—Zn1—S1^i	96.09 (5)	C4—C3—C2	131.4 (3)
O1W—Zn1—S1^i	89.37 (5)	C4—C3—H3	114.3
O1W^i—Zn1—S1^i	90.63 (5)	C2—C3—H3	114.3
S1—Zn1—S1^i	180	C3—C4—C5	130.0 (3)
C1—S1—Zn1	96.41 (8)	C3—C4—H4	115.0
C2—O2—H1O2	109.5	C5—C4—H4	115.0
N2—N1—Zn1	113.88 (14)	O4—C5—O3	121.7 (3)
N2—N1—H1N1	108.8	O4—C5—C4	118.2 (2)
Zn1—N1—H1N1	108.8	O3—C5—C4	120.1 (3)
N2—N1—H2N1	108.8	Zn1—O1W—H1W1	112 (3)
Zn1—N1—H2N1	108.8	Zn1—O1W—H2W1	112 (4)
H1N1—N1—H2N1	107.7	H1W1—O1W—H2W1	110 (2)
C1—N2—N1	121.9 (2)	H1W2—O2W—H2W2	108 (2)
N1^i—Zn1—S1—C1	−177.69 (9)	N1—N2—C1—N3	179.5 (2)
N1—Zn1—S1—C1	2.31 (9)	N1—N2—C1—S1	0.6 (4)
O1W—Zn1—S1—C1	96.92 (10)	Zn1—S1—C1—N2	−2.4 (2)
O1W^i—Zn1—S1—C1	−83.08 (10)	Zn1—S1—C1—N3	178.8 (2)
O1W—Zn1—N1—N2	−92.68 (17)	O1—C2—C3—C4	−179.1 (3)
O1W^i—Zn1—N1—N2	87.32 (17)	O2—C2—C3—C4	1.7 (5)
S1—Zn1—N1—N2	−2.54 (16)	C2—C3—C4—C5	2.0 (5)
S1^i—Zn1—N1—N2	177.45 (16)	C3—C4—C5—O4	176.0 (3)
Zn1—N1—N2—C1	1.9 (3)	C3—C4—C5—O3	−3.0 (5)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O3	0.82	1.61	2.429 (3)	179
N1—H1N1···O3	0.90	2.40	3.145 (3)	140
N1—H2N1···S1^ii	0.90	2.63	3.464 (2)	154
N2—H1N2···O1^iii	0.86	1.97	2.768 (3)	154
N3—H1N3···O2^iii	0.86	2.18	3.031 (4)	172
N3—H2N3···O1^iv	0.86	2.45	3.023 (3)	125
N3—H2N3···O2W^v	0.86	2.33	3.097 (3)	149
O1W—H1W1···O2W	0.84 (4)	1.90 (4)	2.732 (3)	171 (4)
O1W—H2W1···O4^vi	0.84 (5)	1.96 (4)	2.789 (3)	169 (5)
O2W—H1W2···O1W^vii	0.85 (3)	2.11 (3)	2.937 (3)	166 (3)
O2W—H2W2···O4	0.84 (3)	1.95 (3)	2.784 (3)	172 (3)

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.