Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300641X/ob6227sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680300641X/ob6227Isup2.hkl |
CCDC reference: 209900
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.065
- wR factor = 0.174
- Data-to-parameter ratio = 10.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_213 Alert C Atom N2 has ADP max/min Ratio ........... 3.10 prolate
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Solutions of nickel chloride hexahydrate, maleic acid and thiosemicarbazide in methanol–water (volume ratio 1:1) were mixed together with stirring. The pH of the resulting solution was controlled at 4.8–5.0. The solution was then filtrated and slowly evaporated at room temperature in air. After one week, wedge-shaped blue single crystals of (I) suitable for X-ray diffraction analysis were obtained.
The H atoms attached to N and O atoms were located in difference Fourier maps and were refined isotropically, whereas those attached at C atoms were fixed geometrically and treated as riding atoms, with C—H distances = 0.97 Å and Uiso(H) = 1.2Ueq(C). The large maximum and minium main axis ADP ratio (3.10) for atom N2 may indicate unresolved disorder.
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, 2003).
[Ni(CH5N3S)2](C4H4O4)·C4H6O4 | Z = 1 |
Mr = 475.15 | F(000) = 246 |
Triclinic, P1 | Dx = 1.794 Mg m−3 |
a = 6.3886 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.4876 (3) Å | Cell parameters from 2847 reflections |
c = 8.9485 (3) Å | θ = 2.5–29.5° |
α = 102.688 (1)° | µ = 1.40 mm−1 |
β = 107.056 (1)° | T = 293 K |
γ = 98.926 (1)° | Block, brown |
V = 439.83 (3) Å3 | 0.50 × 0.40 × 0.30 mm |
Siemens SMART CCD area-detector diffractometer | 1521 independent reflections |
Radiation source: fine-focus sealed tube | 1350 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 2.5° |
ω scans | h = −6→7 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −10→9 |
Tmin = 0.525, Tmax = 0.658 | l = −10→10 |
2494 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)] = 0.065 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.174 | w = 1/[σ2(Fo2) + (0.1198P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
1521 reflections | Δρmax = 0.79 e Å−3 |
148 parameters | Δρmin = −1.74 e Å−3 |
4 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.055 (16) |
[Ni(CH5N3S)2](C4H4O4)·C4H6O4 | γ = 98.926 (1)° |
Mr = 475.15 | V = 439.83 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.3886 (3) Å | Mo Kα radiation |
b = 8.4876 (3) Å | µ = 1.40 mm−1 |
c = 8.9485 (3) Å | T = 293 K |
α = 102.688 (1)° | 0.50 × 0.40 × 0.30 mm |
β = 107.056 (1)° |
Siemens SMART CCD area-detector diffractometer | 1521 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1350 reflections with I > 2σ(I) |
Tmin = 0.525, Tmax = 0.658 | Rint = 0.064 |
2494 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 4 restraints |
wR(F2) = 0.174 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.79 e Å−3 |
1521 reflections | Δρmin = −1.74 e Å−3 |
148 parameters |
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 5 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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.5000 | 0.0000 | 0.5000 | 0.0133 (4) | |
S1 | 0.22033 (16) | 0.04027 (14) | 0.31535 (12) | 0.0229 (4) | |
N1 | 0.6822 (5) | 0.0406 (4) | 0.3709 (4) | 0.0160 (7) | |
N2 | 0.5869 (6) | 0.1083 (4) | 0.2407 (4) | 0.0188 (8) | |
N3 | 0.2731 (7) | 0.1672 (5) | 0.0804 (4) | 0.0236 (9) | |
C1 | 0.3721 (6) | 0.1104 (5) | 0.2029 (5) | 0.0154 (8) | |
H1A | 0.810 (4) | 0.101 (6) | 0.430 (5) | 0.039 (15)* | |
H1B | 0.711 (7) | −0.050 (3) | 0.333 (5) | 0.016 (11)* | |
H2A | 0.667 (7) | 0.122 (6) | 0.183 (5) | 0.035 (14)* | |
H3A | 0.339 (11) | 0.197 (8) | 0.013 (8) | 0.055 (18)* | |
H3B | 0.157 (10) | 0.197 (7) | 0.077 (7) | 0.044 (17)* | |
O1 | 1.4048 (6) | 0.4552 (4) | 0.7096 (4) | 0.0418 (10) | |
O2 | 1.0943 (5) | 0.2523 (3) | 0.6148 (3) | 0.0240 (7) | |
C2 | 1.1066 (7) | 0.4751 (5) | 0.4895 (5) | 0.0233 (10) | |
H2B | 1.0707 | 0.4050 | 0.3797 | 0.028* | |
H2C | 1.2191 | 0.5740 | 0.5055 | 0.028* | |
C3 | 1.2001 (7) | 0.3833 (5) | 0.6102 (5) | 0.0189 (9) | |
H1O | 1.457 (10) | 0.398 (6) | 0.778 (6) | 0.050* | |
O3 | 0.8412 (5) | 0.2489 (4) | 0.0805 (4) | 0.0231 (7) | |
O4 | 0.5431 (5) | 0.2944 (4) | −0.0915 (4) | 0.0246 (8) | |
C4 | 0.9086 (7) | 0.4377 (5) | −0.0716 (5) | 0.0272 (10) | |
H4A | 0.9778 | 0.3732 | −0.1387 | 0.033* | |
H4B | 0.8194 | 0.4967 | −0.1371 | 0.033* | |
C5 | 0.7538 (7) | 0.3200 (5) | −0.0231 (4) | 0.0161 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0109 (5) | 0.0200 (5) | 0.0119 (5) | 0.0039 (3) | 0.0041 (3) | 0.0094 (3) |
S1 | 0.0143 (6) | 0.0424 (8) | 0.0204 (6) | 0.0096 (5) | 0.0074 (5) | 0.0212 (5) |
N1 | 0.0131 (17) | 0.0196 (18) | 0.0194 (18) | 0.0080 (14) | 0.0045 (14) | 0.0121 (15) |
N2 | 0.0184 (18) | 0.0276 (19) | 0.0158 (17) | 0.0027 (14) | 0.0068 (14) | 0.0173 (15) |
N3 | 0.0200 (19) | 0.033 (2) | 0.0219 (19) | 0.0071 (16) | 0.0062 (16) | 0.0173 (16) |
C1 | 0.0146 (19) | 0.0166 (19) | 0.0134 (18) | 0.0023 (15) | 0.0028 (15) | 0.0043 (15) |
O1 | 0.0278 (18) | 0.0397 (19) | 0.043 (2) | −0.0096 (15) | −0.0138 (15) | 0.0291 (17) |
O2 | 0.0209 (15) | 0.0277 (16) | 0.0220 (15) | 0.0014 (12) | 0.0037 (12) | 0.0121 (13) |
C2 | 0.023 (2) | 0.029 (2) | 0.020 (2) | 0.0092 (18) | 0.0054 (17) | 0.0138 (18) |
C3 | 0.0181 (19) | 0.023 (2) | 0.0148 (19) | 0.0049 (16) | 0.0043 (16) | 0.0066 (17) |
O3 | 0.0199 (16) | 0.0302 (16) | 0.0247 (16) | 0.0051 (13) | 0.0061 (13) | 0.0210 (13) |
O4 | 0.0162 (16) | 0.0318 (17) | 0.0290 (18) | 0.0033 (13) | 0.0045 (14) | 0.0210 (14) |
C4 | 0.027 (2) | 0.033 (2) | 0.018 (2) | −0.0066 (19) | 0.0037 (18) | 0.0158 (19) |
C5 | 0.0187 (19) | 0.0171 (18) | 0.0116 (18) | 0.0013 (15) | 0.0043 (15) | 0.0052 (15) |
Ni1—N1 | 1.910 (3) | O1—C3 | 1.306 (5) |
Ni1—N1i | 1.910 (3) | O1—H1O | 0.88 (5) |
Ni1—S1 | 2.1784 (9) | O2—C3 | 1.223 (5) |
Ni1—S1i | 2.1784 (9) | C2—C3 | 1.506 (5) |
S1—C1 | 1.722 (4) | C2—C2ii | 1.536 (9) |
N1—N2 | 1.430 (4) | C2—H2B | 0.9700 |
N1—H1A | 0.84 (4) | C2—H2C | 0.9700 |
N1—H1B | 0.84 (4) | O3—C5 | 1.257 (5) |
N2—C1 | 1.318 (5) | O4—C5 | 1.266 (5) |
N2—H2A | 0.84 (5) | C4—C4iii | 1.506 (8) |
N3—C1 | 1.325 (5) | C4—C5 | 1.517 (5) |
N3—H3A | 0.88 (7) | C4—H4A | 0.9700 |
N3—H3B | 0.82 (6) | C4—H4B | 0.9700 |
N1—Ni1—N1i | 180.000 (1) | N3—C1—S1 | 119.9 (3) |
N1—Ni1—S1 | 87.92 (10) | C3—O1—H1O | 113 (4) |
N1i—Ni1—S1 | 92.08 (10) | C3—C2—C2ii | 110.6 (4) |
N1—Ni1—S1i | 92.08 (10) | C3—C2—H2B | 109.5 |
N1i—Ni1—S1i | 87.92 (10) | C2ii—C2—H2B | 109.5 |
S1—Ni1—S1i | 180.0 | C3—C2—H2C | 109.5 |
C1—S1—Ni1 | 97.37 (13) | C2ii—C2—H2C | 109.5 |
N2—N1—Ni1 | 115.8 (2) | H2B—C2—H2C | 108.1 |
N2—N1—H1A | 110 (4) | O2—C3—O1 | 122.8 (4) |
Ni1—N1—H1A | 111 (4) | O2—C3—C2 | 123.1 (4) |
N2—N1—H1B | 109 (3) | O1—C3—C2 | 114.2 (4) |
Ni1—N1—H1B | 107 (3) | C4iii—C4—C5 | 113.4 (4) |
H1A—N1—H1B | 103 (5) | C4iii—C4—H4A | 108.9 |
C1—N2—N1 | 117.9 (3) | C5—C4—H4A | 108.9 |
C1—N2—H2A | 126 (4) | C4iii—C4—H4B | 108.9 |
N1—N2—H2A | 115 (4) | C5—C4—H4B | 108.9 |
C1—N3—H3A | 124 (4) | H4A—C4—H4B | 107.7 |
C1—N3—H3B | 119 (4) | O3—C5—O4 | 123.0 (4) |
H3A—N3—H3B | 116 (6) | O3—C5—C4 | 118.4 (4) |
N2—C1—N3 | 120.6 (4) | O4—C5—C4 | 118.7 (3) |
N2—C1—S1 | 119.5 (3) | ||
N1—Ni1—S1—C1 | −8.69 (16) | Ni1—S1—C1—N2 | 5.7 (3) |
N1i—Ni1—S1—C1 | 171.31 (16) | Ni1—S1—C1—N3 | −173.7 (3) |
S1—Ni1—N1—N2 | 11.9 (3) | C2ii—C2—C3—O2 | 60.6 (6) |
S1i—Ni1—N1—N2 | −168.1 (3) | C2ii—C2—C3—O1 | −119.7 (5) |
Ni1—N1—N2—C1 | −11.3 (5) | C4iii—C4—C5—O3 | −49.0 (7) |
N1—N2—C1—N3 | −178.1 (3) | C4iii—C4—C5—O4 | 132.8 (5) |
N1—N2—C1—S1 | 2.5 (5) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.84 (4) | 2.06 (4) | 2.892 (4) | 168 (4) |
N1—H1B···O2iv | 0.84 (4) | 2.32 (4) | 3.061 (4) | 147 (4) |
N1—H1B···O4v | 0.84 (4) | 2.56 (4) | 3.147 (5) | 128 (4) |
O1—H1O···O4vi | 0.88 (5) | 1.63 (5) | 2.516 (5) | 177 (6) |
N2—H2A···O3 | 0.84 (5) | 1.98 (5) | 2.763 (5) | 156 (5) |
N3—H3A···O4 | 0.89 (7) | 1.99 (7) | 2.866 (5) | 167 (6) |
N3—H3B···O3vii | 0.81 (7) | 2.14 (7) | 2.948 (6) | 173 (6) |
C2—H2B···O3 | 0.97 | 2.57 | 3.496 (5) | 159 |
C4—H4A···O2viii | 0.97 | 2.58 | 3.514 (5) | 161 |
C4—H4B···O1ix | 0.97 | 2.53 | 3.285 (6) | 135 |
Symmetry codes: (iv) −x+2, −y, −z+1; (v) −x+1, −y, −z; (vi) x+1, y, z+1; (vii) x−1, y, z; (viii) x, y, z−1; (ix) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Ni(CH5N3S)2](C4H4O4)·C4H6O4 |
Mr | 475.15 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.3886 (3), 8.4876 (3), 8.9485 (3) |
α, β, γ (°) | 102.688 (1), 107.056 (1), 98.926 (1) |
V (Å3) | 439.83 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.40 |
Crystal size (mm) | 0.50 × 0.40 × 0.30 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.525, 0.658 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2494, 1521, 1350 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.174, 1.01 |
No. of reflections | 1521 |
No. of parameters | 148 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.79, −1.74 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
Ni1—N1 | 1.910 (3) | N3—C1 | 1.325 (5) |
Ni1—S1 | 2.1784 (9) | O1—C3 | 1.306 (5) |
S1—C1 | 1.722 (4) | O2—C3 | 1.223 (5) |
N1—N2 | 1.430 (4) | O3—C5 | 1.257 (5) |
N2—C1 | 1.318 (5) | O4—C5 | 1.266 (5) |
N1—Ni1—S1 | 87.92 (10) | N1i—Ni1—S1 | 92.08 (10) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.84 (4) | 2.06 (4) | 2.892 (4) | 168 (4) |
N1—H1B···O2ii | 0.84 (4) | 2.32 (4) | 3.061 (4) | 147 (4) |
N1—H1B···O4iii | 0.84 (4) | 2.56 (4) | 3.147 (5) | 128 (4) |
O1—H1O···O4iv | 0.88 (5) | 1.63 (5) | 2.516 (5) | 177 (6) |
N2—H2A···O3 | 0.84 (5) | 1.98 (5) | 2.763 (5) | 156 (5) |
N3—H3A···O4 | 0.89 (7) | 1.99 (7) | 2.866 (5) | 167 (6) |
N3—H3B···O3v | 0.81 (7) | 2.14 (7) | 2.948 (6) | 173 (6) |
C2—H2B···O3 | 0.97 | 2.57 | 3.496 (5) | 159 |
C4—H4A···O2vi | 0.97 | 2.58 | 3.514 (5) | 161 |
C4—H4B···O1vii | 0.97 | 2.53 | 3.285 (6) | 135 |
Symmetry codes: (ii) −x+2, −y, −z+1; (iii) −x+1, −y, −z; (iv) x+1, y, z+1; (v) x−1, y, z; (vi) x, y, z−1; (vii) x−1, y, z−1. |
Crystal engineering based on the use of either coordinative bonds or of weaker intermolecular interactions has attracted great interest, and in the latter methodology, hydrogen bonding can influence the metal coordination geometry due to its relative strength and directionality (Russell et al., 1997; Kawamoto et al., 1996). Meanwhile, self-assembly is the most efficient means for the construction of highly organized structures and transition-metal-directed self-assembly via coordination has emerged as a new and major motif in supramolecular architecture (Zhang, Li, Chen et al., 2000; Philp & Stoddart, 1996). Dicarboxylates constitute an important class of ligands in the formation of coordination polymers, and the chemistry of metal complexes containing S,N-bidentate ligands has been studied widely because of the structural features and particular properties of these compounds (Groeneman et al., 1999; Fun et al., 1996; West et al., 1993). We have synthesized a series of complexes containing thiosemicarbazide ligands and appropriate dicarboxylates in order to study their potential non-linear optical properties. In the present paper, we report the crystal structure of the title compound, (I).
The structure of (I) consists of three fragments, namely the thiocarbazide-coordinated nickel(II) dication, a succinate anion and a neutral succinic acid molecule, all of which are centrosymmetric (Fig. 1). In contrast to those of related compounds (Zhang, Li, Nishiura et al., 2000; Burrows et al., 2000), the succinate anion here does not coordinate to the Ni atom but acts as a counter-ion in the structure and mutual electrostatic interaction is expected.
The molecular structure of (I) shows that atom Ni1 is four-coordinated by N and S atoms from two symmetry-related bidentate thiosemicarbazide ligands, with two Ni—N and Ni—S bonds in a planar geometry. The Ni—S and Ni—N bond lengths are within normal ranges, and agree with those in (thiosemicarbazido-N,S)nickel(II) (Li et al., 2003). The chelate N1—N2—C1—S1—Ni1 ring is slightly out of planarity towards an envelope conformation, with atom Ni1 displaced by 0.273 (1) Å from the N1/N2/C1/S1 plane. The C1—S1 and C1—N2 bonds length are intermediate between single and double bonds. These results suggest that electronic delocalization acts to some extent on the ligand upon complex formation. Within the succinate anion, the C—O bond distances are between single- and double-bond values compared with the corresponding values in succinic acid, implying that the negative charge on this moiety is delocalized over the two C—O bonds.
In the asymmetric unit, the succinate anion and succinic acid molecule are linked together by a C2—H2B···O3 hydrogen bond (Fig. 1 and Table 2), and are interconnected to the coordinated thiosemicarbazide ligands by three N—H···O hydrogen bonds, viz. N1—H1A···O2, N2—H2A···O3 and N3—H3A···O4, in which the thiosemicarbazide ligands act as hydrogen-bond donors. The molecules are interconnected into columns parallel to the c direction by intermolecular N1—H1B···O4ii hydrogen bond (Table 2 and Fig. 2). The columns are further linked into a three-dimensional network by intermolecular N—H···O, O—H···O, and C—H···O hydrogen bonds (Fig. 3), viz. N1—H1B···O2i, O1—H1O···O4iii, N3—H3B···O3iv, C4—H4A···O2v and C4—H4B···O1vi (see Table 2 for details and symmetry codes).