Download citation
Download citation
link to html
The title ternary complex, [Ni(CH5N3S)2](C4H4O4)·C4H6O4, consists of a thio­semicarbazide-coordinated nickel cation, a succinate anion, and a neutral succinic acid mol­ecule, all of which are centrosymmetric. The Ni atom is four-coordinated in a planar geometry by N and S atoms from two symmetry-related thio­semicarbazide ligands. In the crystal structure, the three components are effectively linked together by mutual electrostatic interactions and hydrogen-bonding interactions of the N—H...O, C—H...O and O—H...O types.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300641X/ob6227sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680300641X/ob6227Isup2.hkl
Contains datablock I

CCDC reference: 209900

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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


Yellow Alert 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

Comment top

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).

Experimental top

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.

Refinement top

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.

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, 2003).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing ellipsoids at the 50% probability level and the atom-numbering scheme.
[Figure 2] Fig. 2. Packing diagram of the structure (I), showing the column formation parallel to the c direction.
[Figure 3] Fig. 3. Packing diagram of the structure (I), showing the hydrogen bonds between the molecular columns. H atoms not involved in hydrogen bonds have been omitted for clarity.
Bis(thiosemicarbazido-κ2N,S)nickel(II)–succinate–succinic acid (1/1/1) top
Crystal data top
[Ni(CH5N3S)2](C4H4O4)·C4H6O4Z = 1
Mr = 475.15F(000) = 246
Triclinic, P1Dx = 1.794 Mg m3
a = 6.3886 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.4876 (3) ÅCell parameters from 2847 reflections
c = 8.9485 (3) Åθ = 2.5–29.5°
α = 102.688 (1)°µ = 1.40 mm1
β = 107.056 (1)°T = 293 K
γ = 98.926 (1)°Block, brown
V = 439.83 (3) Å30.50 × 0.40 × 0.30 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
1521 independent reflections
Radiation source: fine-focus sealed tube1350 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.064
Detector resolution: 8.33 pixels mm-1θmax = 25.0°, θmin = 2.5°
ω scansh = 67
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 109
Tmin = 0.525, Tmax = 0.658l = 1010
2494 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)] = 0.065H 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 reflectionsΔρmax = 0.79 e Å3
148 parametersΔρmin = 1.74 e Å3
4 restraintsExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.055 (16)
Crystal data top
[Ni(CH5N3S)2](C4H4O4)·C4H6O4γ = 98.926 (1)°
Mr = 475.15V = 439.83 (3) Å3
Triclinic, P1Z = 1
a = 6.3886 (3) ÅMo Kα radiation
b = 8.4876 (3) ŵ = 1.40 mm1
c = 8.9485 (3) ÅT = 293 K
α = 102.688 (1)°0.50 × 0.40 × 0.30 mm
β = 107.056 (1)°
Data collection top
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 = 0.658Rint = 0.064
2494 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0654 restraints
wR(F2) = 0.174H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.79 e Å3
1521 reflectionsΔρmin = 1.74 e Å3
148 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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50000.00000.50000.0133 (4)
S10.22033 (16)0.04027 (14)0.31535 (12)0.0229 (4)
N10.6822 (5)0.0406 (4)0.3709 (4)0.0160 (7)
N20.5869 (6)0.1083 (4)0.2407 (4)0.0188 (8)
N30.2731 (7)0.1672 (5)0.0804 (4)0.0236 (9)
C10.3721 (6)0.1104 (5)0.2029 (5)0.0154 (8)
H1A0.810 (4)0.101 (6)0.430 (5)0.039 (15)*
H1B0.711 (7)0.050 (3)0.333 (5)0.016 (11)*
H2A0.667 (7)0.122 (6)0.183 (5)0.035 (14)*
H3A0.339 (11)0.197 (8)0.013 (8)0.055 (18)*
H3B0.157 (10)0.197 (7)0.077 (7)0.044 (17)*
O11.4048 (6)0.4552 (4)0.7096 (4)0.0418 (10)
O21.0943 (5)0.2523 (3)0.6148 (3)0.0240 (7)
C21.1066 (7)0.4751 (5)0.4895 (5)0.0233 (10)
H2B1.07070.40500.37970.028*
H2C1.21910.57400.50550.028*
C31.2001 (7)0.3833 (5)0.6102 (5)0.0189 (9)
H1O1.457 (10)0.398 (6)0.778 (6)0.050*
O30.8412 (5)0.2489 (4)0.0805 (4)0.0231 (7)
O40.5431 (5)0.2944 (4)0.0915 (4)0.0246 (8)
C40.9086 (7)0.4377 (5)0.0716 (5)0.0272 (10)
H4A0.97780.37320.13870.033*
H4B0.81940.49670.13710.033*
C50.7538 (7)0.3200 (5)0.0231 (4)0.0161 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0109 (5)0.0200 (5)0.0119 (5)0.0039 (3)0.0041 (3)0.0094 (3)
S10.0143 (6)0.0424 (8)0.0204 (6)0.0096 (5)0.0074 (5)0.0212 (5)
N10.0131 (17)0.0196 (18)0.0194 (18)0.0080 (14)0.0045 (14)0.0121 (15)
N20.0184 (18)0.0276 (19)0.0158 (17)0.0027 (14)0.0068 (14)0.0173 (15)
N30.0200 (19)0.033 (2)0.0219 (19)0.0071 (16)0.0062 (16)0.0173 (16)
C10.0146 (19)0.0166 (19)0.0134 (18)0.0023 (15)0.0028 (15)0.0043 (15)
O10.0278 (18)0.0397 (19)0.043 (2)0.0096 (15)0.0138 (15)0.0291 (17)
O20.0209 (15)0.0277 (16)0.0220 (15)0.0014 (12)0.0037 (12)0.0121 (13)
C20.023 (2)0.029 (2)0.020 (2)0.0092 (18)0.0054 (17)0.0138 (18)
C30.0181 (19)0.023 (2)0.0148 (19)0.0049 (16)0.0043 (16)0.0066 (17)
O30.0199 (16)0.0302 (16)0.0247 (16)0.0051 (13)0.0061 (13)0.0210 (13)
O40.0162 (16)0.0318 (17)0.0290 (18)0.0033 (13)0.0045 (14)0.0210 (14)
C40.027 (2)0.033 (2)0.018 (2)0.0066 (19)0.0037 (18)0.0158 (19)
C50.0187 (19)0.0171 (18)0.0116 (18)0.0013 (15)0.0043 (15)0.0052 (15)
Geometric parameters (Å, º) top
Ni1—N11.910 (3)O1—C31.306 (5)
Ni1—N1i1.910 (3)O1—H1O0.88 (5)
Ni1—S12.1784 (9)O2—C31.223 (5)
Ni1—S1i2.1784 (9)C2—C31.506 (5)
S1—C11.722 (4)C2—C2ii1.536 (9)
N1—N21.430 (4)C2—H2B0.9700
N1—H1A0.84 (4)C2—H2C0.9700
N1—H1B0.84 (4)O3—C51.257 (5)
N2—C11.318 (5)O4—C51.266 (5)
N2—H2A0.84 (5)C4—C4iii1.506 (8)
N3—C11.325 (5)C4—C51.517 (5)
N3—H3A0.88 (7)C4—H4A0.9700
N3—H3B0.82 (6)C4—H4B0.9700
N1—Ni1—N1i180.000 (1)N3—C1—S1119.9 (3)
N1—Ni1—S187.92 (10)C3—O1—H1O113 (4)
N1i—Ni1—S192.08 (10)C3—C2—C2ii110.6 (4)
N1—Ni1—S1i92.08 (10)C3—C2—H2B109.5
N1i—Ni1—S1i87.92 (10)C2ii—C2—H2B109.5
S1—Ni1—S1i180.0C3—C2—H2C109.5
C1—S1—Ni197.37 (13)C2ii—C2—H2C109.5
N2—N1—Ni1115.8 (2)H2B—C2—H2C108.1
N2—N1—H1A110 (4)O2—C3—O1122.8 (4)
Ni1—N1—H1A111 (4)O2—C3—C2123.1 (4)
N2—N1—H1B109 (3)O1—C3—C2114.2 (4)
Ni1—N1—H1B107 (3)C4iii—C4—C5113.4 (4)
H1A—N1—H1B103 (5)C4iii—C4—H4A108.9
C1—N2—N1117.9 (3)C5—C4—H4A108.9
C1—N2—H2A126 (4)C4iii—C4—H4B108.9
N1—N2—H2A115 (4)C5—C4—H4B108.9
C1—N3—H3A124 (4)H4A—C4—H4B107.7
C1—N3—H3B119 (4)O3—C5—O4123.0 (4)
H3A—N3—H3B116 (6)O3—C5—C4118.4 (4)
N2—C1—N3120.6 (4)O4—C5—C4118.7 (3)
N2—C1—S1119.5 (3)
N1—Ni1—S1—C18.69 (16)Ni1—S1—C1—N25.7 (3)
N1i—Ni1—S1—C1171.31 (16)Ni1—S1—C1—N3173.7 (3)
S1—Ni1—N1—N211.9 (3)C2ii—C2—C3—O260.6 (6)
S1i—Ni1—N1—N2168.1 (3)C2ii—C2—C3—O1119.7 (5)
Ni1—N1—N2—C111.3 (5)C4iii—C4—C5—O349.0 (7)
N1—N2—C1—N3178.1 (3)C4iii—C4—C5—O4132.8 (5)
N1—N2—C1—S12.5 (5)
Symmetry codes: (i) x+1, y, z+1; (ii) x+2, y+1, z+1; (iii) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.84 (4)2.06 (4)2.892 (4)168 (4)
N1—H1B···O2iv0.84 (4)2.32 (4)3.061 (4)147 (4)
N1—H1B···O4v0.84 (4)2.56 (4)3.147 (5)128 (4)
O1—H1O···O4vi0.88 (5)1.63 (5)2.516 (5)177 (6)
N2—H2A···O30.84 (5)1.98 (5)2.763 (5)156 (5)
N3—H3A···O40.89 (7)1.99 (7)2.866 (5)167 (6)
N3—H3B···O3vii0.81 (7)2.14 (7)2.948 (6)173 (6)
C2—H2B···O30.972.573.496 (5)159
C4—H4A···O2viii0.972.583.514 (5)161
C4—H4B···O1ix0.972.533.285 (6)135
Symmetry codes: (iv) x+2, y, z+1; (v) x+1, y, z; (vi) x+1, y, z+1; (vii) x1, y, z; (viii) x, y, z1; (ix) x1, y, z1.

Experimental details

Crystal data
Chemical formula[Ni(CH5N3S)2](C4H4O4)·C4H6O4
Mr475.15
Crystal system, space groupTriclinic, 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)
V3)439.83 (3)
Z1
Radiation typeMo Kα
µ (mm1)1.40
Crystal size (mm)0.50 × 0.40 × 0.30
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.525, 0.658
No. of measured, independent and
observed [I > 2σ(I)] reflections
2494, 1521, 1350
Rint0.064
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.174, 1.01
No. of reflections1521
No. of parameters148
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.79, 1.74

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
Ni1—N11.910 (3)N3—C11.325 (5)
Ni1—S12.1784 (9)O1—C31.306 (5)
S1—C11.722 (4)O2—C31.223 (5)
N1—N21.430 (4)O3—C51.257 (5)
N2—C11.318 (5)O4—C51.266 (5)
N1—Ni1—S187.92 (10)N1i—Ni1—S192.08 (10)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.84 (4)2.06 (4)2.892 (4)168 (4)
N1—H1B···O2ii0.84 (4)2.32 (4)3.061 (4)147 (4)
N1—H1B···O4iii0.84 (4)2.56 (4)3.147 (5)128 (4)
O1—H1O···O4iv0.88 (5)1.63 (5)2.516 (5)177 (6)
N2—H2A···O30.84 (5)1.98 (5)2.763 (5)156 (5)
N3—H3A···O40.89 (7)1.99 (7)2.866 (5)167 (6)
N3—H3B···O3v0.81 (7)2.14 (7)2.948 (6)173 (6)
C2—H2B···O30.972.573.496 (5)159
C4—H4A···O2vi0.972.583.514 (5)161
C4—H4B···O1vii0.972.533.285 (6)135
Symmetry codes: (ii) x+2, y, z+1; (iii) x+1, y, z; (iv) x+1, y, z+1; (v) x1, y, z; (vi) x, y, z1; (vii) x1, y, z1.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds