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In the title compound, [Ni(CH5N3S)2(H2O)2](C4H3O4)2·2H2O, the Ni atom lies on a center of symmetry and is coordinated by N and S atoms from two thio­semicarbazide ligands and the O atoms of two water mol­ecules in a distorted octahedral geometry. In the asymmetric unit, the three components are linked together by one O-H...O and two N-H...O hydrogen bonds. The packing is built from molecular ribbons parallel to the b direction, stabilized by intramolecular hydrogen bonds, and by one N-H...S and two N-H...O intermolecular hydrogen bonds. The ribbons are further connected into columns by N-H...O interactions and then into a three-dimensional network by three O-H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103006425/ob1111sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103006425/ob1111Isup2.hkl
Contains datablock I

CCDC reference: 214146

Comment top

Self-assembly is the most efficient means for the construction of highly organized structure. The study of self-assembly processes and properties of supramolecular system and/or molecule aggregates in natural or non-natural systems, organic or inorganic systems, has attracted great interest (Lawrence et al., 1995; Yaghi, 1998). Meanwhile, there is currently considerable interest in crystal engineering based on the use of either coordinative bonds (Blake, 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 bond's relative strength, directionality, flexibility and dynamic character (Allen et al., 1999; Russell, 1997). The chemistry of metal complexes containing sulfur–nitrogen bidentate ligands has been studied widely because of their structural features and particular properties (Fun et al., 1996; West et al., 1993). Dicarboxylates constitute an important class of ligands in the formation of coordination polymers (Heinze et al., 1998; Groeneman et al., 1999). As part of our studies of the synthesis and characterization of potential non-linear optical materials, we report here the crystal structure of the title compound, (I).

The structure of (I) consists of three independent fragments (Fig. 1), namely the dicarboxylate anion (maleate) moiety, the coordinated nickel(II) cation moiety and water molecules for crystallization. The structure differs from that of? related compounds (Zhang et al., 2000; Burrows et al., 2000) in that the maleate moiety in (I) is not coordinated by the Ni atom but acts as an independent counterion with mutual electrostatic interaction in the structure. This situation was also observed in our previous study (Li et al., 2003) on the structure of bis[thiosemicarbazido-N,S]nickel(II) succinate succinic acid (1/1/1).

The asymmetric unit contains half of the complex molecule, and the other half is related by a center of symmetry at atom Ni1. Atom Ni1 is six-coordinated by N, S and 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 act as an N,S-chelate, while the two coordinated O atoms belong to the symmetry-related water molecules. The NiN2S2O2 group forms a distorted octahedral configuration. The linear O2W—Ni1—O2Wi bond is nearly perpendicular to the basal N1/S1/N1i/S1i plane, with angles subtended at atom Ni1 atom (Table 1). The coordinated bond lengths (Ni—O2W, Ni—N and Ni—S) are normal (Allen et al., 1987), whereas the C—N and C—S bond distances within the thiosemicarbazide ligands are intermediate between single and double bond. The C—N and C—S bonds? suggest to some extent the electronic delocalization effect on the ligand upon complex formation.

The thiosemicarbazide ligands are planar, with the coordinated Ni1 atom displaced by 0.054 (1) Å. The maleate anion moiety is also planar, with a maximum deviation of 0.028 (2) Å oppositely at atoms O2 and O3. Atoms O3 and O4 share one H atom. This is supported by the explicitly located H atom and the C2—O3 and C5—O4 bond lengths (Table 1), which are within the C—O single and double bond. This position of the H atom also maintains the planarity of the maleate anion.

In the asymmetric unit, the nickel cation, maleate anions and O1W water molecules are linked by N2—H2···O2, N3—H3A···O3 and O1W—H1W1···O2W hydrogen bonds (Fig. 1 and Table 2), in which the maleate anions and the water ligands act as hydrogen-bond acceptors. In the crystal packing, the thiosemicarbazide ligands and the two water molecules play an important role in the hydrogen bonds tailoring the molecules. The molecules are linked by three types of N—H···O, one N—H···S and three O—H···O hydrogen bonds (Table 2). The N1—H1A···O4i, N1—H1B···S1ii and N3—H3B···O1Wiii hydrogen bonds along with the intramolecular hydrogen bonds link the molecules into ribbons parallel to the b direction (Fig. 2). In this manner, a chain consists of three different hydrogen-bonded ring patterns (Bernstein et al., 1995), namely those linking the maleate anion to the thiosemicarbazide ligand [R22(8)], the maleate anion to two symmetry-related thiosemicarbazide ligands [R32(9)], and two symmetry-related thiosemicarbazide ligands [R22(8)]. The water molecules can be considered as bridges between the thiosemicarbazide ligand and the central Ni atom of the adjacent asymmteric unit. Two adjacent ribbons are symmetrically connected by N3—H3B···O2iii hydrogen bonds to form columns, and the columns are further connected into a three-dimensional network throughout the structure by O1W—H2W1···O5v, O2W—H1W2···O1Wvi and O2W—H2W2···O5vii hydrogen bonds.

Experimental top

Compound (I) was prepared by the self-assembly synthesis method. Solutions of nickel chloride hexahydrate, maleic acid and thiosemicarbazide in methanol/water (1:1 v/v) were mixed with stirring. The pH of the mixture was maintained at 4.8–5.0. The solution was filtrated and slowly evaporated at room temperature in air. Single crystals of (I) suitable for X-ray crystallographic measurement were obtained after one week.

Refinement top

All H atoms were located from difference Fourier maps and were refined isotropically. The Uiso values of atoms H1W2 and H34 were fixed, because their Uiso values became too large during refinement?. The C—H, O—H and N—H bond lengths are 0.93 (3)–0.96 (3), 0.86 (4)–1.10 (4) and 0.82 (3)–0.94 (3) Å, respectively. Atom H34 is shared between atoms O3 and O4 of the maleate anion, with an O3—H34 and O4—H34 distances of 1.10 (4) and 1.32 (4) Å, respectively. Owing to the poor quality of the crystal, Rint was obtained to be 0.084. The highest peak and deepest hole of the difference density are located at 0.93 and 0.77 Å from NI1, respectively.

Computing details top

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, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. A view of the structure of (I), showing displacement ellipsoids at the 50% probability level and the atom-numbering scheme.
[Figure 2] Fig. 2. Packing diagram of (I), showing the ribbon formations.
trans-Diaquabis(thiosemicarbazido-κ2N,S)nickel(II) dimaleate dihydrate top
Crystal data top
[Ni(CH5N3S)2(H2O)2](C4H3O4)2·2H2OF(000) = 564
Mr = 543.18Dx = 1.751 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.0487 (3) ÅCell parameters from 5224 reflections
b = 5.9574 (1) Åθ = 3.0–28.3°
c = 14.0254 (3) ŵ = 1.22 mm1
β = 109.078 (1)°T = 183 K
V = 1030.40 (4) Å3Wedge, blue
Z = 20.52 × 0.46 × 0.22 mm
Data collection top
Siemens SMART CCD area detector
diffractometer
2521 independent reflections
Radiation source: fine-focus sealed tube2162 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.084
Detector resolution: 8.33 pixels mm-1θmax = 28.3°, θmin = 3.0°
ω scansh = 917
Absorption correction: empirical (using intensity measurements)
SADABS (Sheldrick, 1996)
k = 77
Tmin = 0.570, Tmax = 0.776l = 1818
5956 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046All H-atom parameters refined
wR(F2) = 0.110 w = 1/[σ2(Fo2) + (0.0314P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
2521 reflectionsΔρmax = 0.77 e Å3
189 parametersΔρmin = 1.28 e Å3
0 restraintsExtinction correction: SHELXTL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.032 (3)
Crystal data top
[Ni(CH5N3S)2(H2O)2](C4H3O4)2·2H2OV = 1030.40 (4) Å3
Mr = 543.18Z = 2
Monoclinic, P21/cMo Kα radiation
a = 13.0487 (3) ŵ = 1.22 mm1
b = 5.9574 (1) ÅT = 183 K
c = 14.0254 (3) Å0.52 × 0.46 × 0.22 mm
β = 109.078 (1)°
Data collection top
Siemens SMART CCD area detector
diffractometer
2521 independent reflections
Absorption correction: empirical (using intensity measurements)
SADABS (Sheldrick, 1996)
2162 reflections with I > 2σ(I)
Tmin = 0.570, Tmax = 0.776Rint = 0.084
5956 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.110All H-atom parameters refined
S = 1.00Δρmax = 0.77 e Å3
2521 reflectionsΔρmin = 1.28 e Å3
189 parameters
Special details top

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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 (Å2) top
xyzUiso*/Ueq
Ni10.00000.50000.50000.00868 (15)
S10.07126 (4)0.81428 (8)0.60310 (4)0.01282 (17)
N10.14933 (15)0.3540 (3)0.57357 (14)0.0108 (4)
N20.22097 (17)0.4889 (3)0.64946 (17)0.0138 (4)
N30.26700 (18)0.8098 (3)0.73956 (16)0.0188 (4)
C10.19331 (17)0.6951 (3)0.66796 (16)0.0109 (4)
O2W0.05265 (13)0.3626 (3)0.61931 (12)0.0140 (3)
O1W0.13174 (15)0.1879 (3)0.78827 (14)0.0167 (4)
O20.38185 (15)0.2495 (3)0.78950 (15)0.0296 (5)
O30.47444 (15)0.5573 (3)0.84952 (15)0.0240 (4)
O40.64928 (14)0.6504 (3)0.97081 (15)0.0222 (4)
O50.79125 (15)0.4728 (3)1.07263 (15)0.0216 (4)
C20.46267 (19)0.3408 (4)0.84680 (18)0.0170 (5)
C30.5485 (2)0.1952 (4)0.91625 (19)0.0168 (5)
C40.64373 (19)0.2477 (4)0.98355 (18)0.0146 (4)
C50.69799 (19)0.4707 (4)1.01107 (19)0.0142 (5)
H20.277 (3)0.421 (5)0.692 (2)0.022 (7)*
H40.689 (2)0.129 (4)1.021 (2)0.019 (7)*
H30.525 (3)0.046 (5)0.907 (2)0.025 (8)*
H1A0.180 (2)0.317 (4)0.532 (2)0.018 (7)*
H1B0.130 (2)0.223 (5)0.600 (2)0.020 (7)*
H3B0.250 (3)0.951 (5)0.751 (2)0.025 (8)*
H3A0.328 (3)0.757 (6)0.767 (2)0.026 (8)*
H1W10.071 (2)0.231 (5)0.746 (2)0.025 (8)*
H2W10.159 (3)0.301 (6)0.826 (2)0.035 (9)*
H1W20.085 (3)0.475 (6)0.645 (3)0.050*
H2W20.100 (3)0.252 (6)0.601 (3)0.040 (9)*
H340.555 (3)0.595 (6)0.904 (3)0.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0080 (2)0.0049 (2)0.0101 (2)0.00045 (12)0.00116 (17)0.00128 (12)
S10.0125 (3)0.0063 (3)0.0147 (3)0.00030 (18)0.0023 (2)0.00273 (18)
N10.0096 (9)0.0061 (8)0.0144 (9)0.0003 (7)0.0007 (8)0.0027 (7)
N20.0081 (9)0.0107 (9)0.0167 (10)0.0003 (7)0.0039 (8)0.0018 (7)
N30.0118 (10)0.0157 (10)0.0219 (11)0.0025 (8)0.0042 (9)0.0056 (8)
C10.0104 (10)0.0116 (9)0.0101 (10)0.0029 (8)0.0026 (9)0.0012 (8)
O2W0.0146 (8)0.0102 (7)0.0164 (8)0.0024 (6)0.0039 (7)0.0018 (6)
O1W0.0161 (9)0.0152 (8)0.0176 (9)0.0021 (7)0.0041 (8)0.0037 (7)
O20.0187 (9)0.0212 (9)0.0350 (11)0.0000 (8)0.0100 (9)0.0027 (8)
O30.0154 (9)0.0134 (7)0.0336 (10)0.0014 (7)0.0051 (8)0.0022 (7)
O40.0169 (9)0.0105 (7)0.0328 (10)0.0006 (7)0.0005 (8)0.0014 (7)
O50.0129 (9)0.0176 (8)0.0278 (10)0.0015 (6)0.0022 (8)0.0055 (7)
C20.0128 (11)0.0148 (11)0.0204 (12)0.0019 (8)0.0013 (10)0.0005 (9)
C30.0158 (11)0.0095 (10)0.0222 (12)0.0003 (8)0.0024 (10)0.0009 (9)
C40.0147 (11)0.0092 (10)0.0179 (11)0.0025 (8)0.0026 (9)0.0011 (8)
C50.0131 (11)0.0131 (10)0.0171 (11)0.0005 (8)0.0060 (10)0.0015 (8)
Geometric parameters (Å, º) top
Ni1—N12.0747 (18)O2W—H1W20.92 (4)
Ni1—N1i2.0747 (18)O2W—H2W20.88 (4)
Ni1—O2Wi2.1666 (16)O1W—H1W10.86 (3)
Ni1—O2W2.1666 (16)O1W—H2W10.86 (4)
Ni1—S1i2.3627 (5)O2—C21.225 (3)
Ni1—S12.3627 (5)O3—C21.298 (3)
S1—C11.709 (2)O3—H341.10 (4)
N1—N21.415 (3)O4—C51.279 (3)
N1—H1A0.84 (3)O4—H341.32 (4)
N1—H1B0.94 (3)O5—C51.241 (3)
N2—C11.329 (3)C2—C31.497 (3)
N2—H20.87 (3)C3—C41.329 (3)
N3—C11.330 (3)C3—H30.93 (3)
N3—H3B0.90 (3)C4—C51.496 (3)
N3—H3A0.82 (3)C4—H40.96 (3)
N1—Ni1—N1i180.0C1—N3—H3B117 (2)
N1—Ni1—O2Wi93.39 (7)C1—N3—H3A120 (2)
N1i—Ni1—O2Wi86.61 (7)H3B—N3—H3A122 (3)
N1—Ni1—O2W86.61 (7)N2—C1—N3116.5 (2)
N1i—Ni1—O2W93.39 (7)N2—C1—S1123.03 (17)
O2Wi—Ni1—O2W180.0N3—C1—S1120.43 (17)
N1—Ni1—S1i95.15 (5)Ni1—O2W—H1W2109 (2)
N1i—Ni1—S1i84.85 (5)Ni1—O2W—H2W2116 (2)
O2Wi—Ni1—S1i89.28 (5)H1W2—O2W—H2W2107 (3)
O2W—Ni1—S1i90.72 (5)H1W1—O1W—H2W1107 (3)
N1—Ni1—S184.85 (5)C2—O3—H34107.4 (19)
N1i—Ni1—S195.15 (5)C5—O4—H34108.5 (16)
O2Wi—Ni1—S190.72 (5)O2—C2—O3121.9 (2)
O2W—Ni1—S189.28 (5)O2—C2—C3118.0 (2)
S1i—Ni1—S1180.0O3—C2—C3120.0 (2)
C1—S1—Ni196.23 (7)C4—C3—C2130.7 (2)
N2—N1—Ni1114.70 (13)C4—C3—H3120 (2)
N2—N1—H1A108.5 (19)C2—C3—H3109 (2)
Ni1—N1—H1A110.8 (19)C3—C4—C5130.2 (2)
N2—N1—H1B111.7 (17)C3—C4—H4118.8 (16)
Ni1—N1—H1B102.5 (17)C5—C4—H4110.9 (16)
H1A—N1—H1B108 (2)O5—C5—O4122.1 (2)
C1—N2—N1121.13 (19)O5—C5—C4117.5 (2)
C1—N2—H2121 (2)O4—C5—C4120.3 (2)
N1—N2—H2116 (2)
N1—Ni1—S1—C11.92 (9)N1—N2—C1—N3178.9 (2)
N1i—Ni1—S1—C1178.08 (9)N1—N2—C1—S10.1 (3)
O2Wi—Ni1—S1—C195.26 (8)Ni1—S1—C1—N21.71 (19)
O2W—Ni1—S1—C184.74 (8)Ni1—S1—C1—N3179.57 (17)
O2Wi—Ni1—N1—N292.73 (15)O2—C2—C3—C4178.4 (3)
O2W—Ni1—N1—N287.27 (15)O3—C2—C3—C42.6 (4)
S1i—Ni1—N1—N2177.69 (14)C2—C3—C4—C51.3 (4)
S1—Ni1—N1—N22.31 (14)C3—C4—C5—O5175.4 (3)
Ni1—N1—N2—C12.0 (3)C3—C4—C5—O43.7 (4)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H34···O41.10 (4)1.32 (4)2.423 (2)177 (2)
N1—H1A···O4ii0.84 (3)2.45 (3)3.137 (3)140 (2)
N1—H1B···S1iii0.94 (3)2.55 (3)3.438 (2)157 (2)
N2—H2···O20.87 (3)1.90 (3)2.756 (3)170 (4)
N3—H3A···O30.81 (4)2.23 (4)3.038 (3)169 (4)
N3—H3B···O1Wiv0.88 (3)2.30 (4)3.073 (3)148 (3)
N3—H3B···O2iv0.88 (3)2.41 (3)2.985 (3)123 (3)
O1W—H1W1···O2W0.86 (3)2.12 (3)2.959 (3)165 (3)
O1W—H2W1···O5v0.84 (3)1.93 (3)2.762 (3)169 (3)
O2W—H1W2···O1Wvi0.91 (4)1.81 (4)2.716 (3)172 (4)
O2W—H2W2···O5vii0.87 (4)1.91 (4)2.775 (3)174 (4)
Symmetry codes: (ii) x+1, y1/2, z+3/2; (iii) x, y1, z; (iv) x, y+1, z; (v) x+1, y+1, z+2; (vi) x, y+1/2, z+3/2; (vii) x1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula[Ni(CH5N3S)2(H2O)2](C4H3O4)2·2H2O
Mr543.18
Crystal system, space groupMonoclinic, P21/c
Temperature (K)183
a, b, c (Å)13.0487 (3), 5.9574 (1), 14.0254 (3)
β (°) 109.078 (1)
V3)1030.40 (4)
Z2
Radiation typeMo Kα
µ (mm1)1.22
Crystal size (mm)0.52 × 0.46 × 0.22
Data collection
DiffractometerSiemens SMART CCD area detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
SADABS (Sheldrick, 1996)
Tmin, Tmax0.570, 0.776
No. of measured, independent and
observed [I > 2σ(I)] reflections
5956, 2521, 2162
Rint0.084
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.110, 1.00
No. of reflections2521
No. of parameters189
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.77, 1.28

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
Ni1—N12.0747 (18)N2—C11.329 (3)
Ni1—O2W2.1666 (16)N3—C11.330 (3)
Ni1—S12.3627 (5)O3—C21.298 (3)
S1—C11.709 (2)O4—C51.279 (3)
N1—N21.415 (3)O5—C51.241 (3)
N1—Ni1—O2Wi93.39 (7)O2Wi—Ni1—S190.72 (5)
N1—Ni1—O2W86.61 (7)O2W—Ni1—S189.28 (5)
N1—Ni1—S184.85 (5)C1—S1—Ni196.23 (7)
N1i—Ni1—S195.15 (5)N2—N1—Ni1114.70 (13)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H34···O41.10 (4)1.32 (4)2.423 (2)177 (2)
N1—H1A···O4ii0.84 (3)2.45 (3)3.137 (3)140 (2)
N1—H1B···S1iii0.94 (3)2.55 (3)3.438 (2)157 (2)
N2—H2···O20.87 (3)1.90 (3)2.756 (3)170 (4)
N3—H3A···O30.81 (4)2.23 (4)3.038 (3)169 (4)
N3—H3B···O1Wiv0.88 (3)2.30 (4)3.073 (3)148 (3)
N3—H3B···O2iv0.88 (3)2.41 (3)2.985 (3)123 (3)
O1W—H1W1···O2W0.86 (3)2.12 (3)2.959 (3)165 (3)
O1W—H2W1···O5v0.84 (3)1.93 (3)2.762 (3)169 (3)
O2W—H1W2···O1Wvi0.91 (4)1.81 (4)2.716 (3)172 (4)
O2W—H2W2···O5vii0.87 (4)1.91 (4)2.775 (3)174 (4)
Symmetry codes: (ii) x+1, y1/2, z+3/2; (iii) x, y1, z; (iv) x, y+1, z; (v) x+1, y+1, z+2; (vi) x, y+1/2, z+3/2; (vii) x1, y+1/2, z1/2.
 

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