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Acta Cryst. (2008). E64, m824    [ doi:10.1107/S1600536808014293 ]

trans-Bis(1H-indole-3-carbaldehyde thiosemicarbazonato-[kappa]2N1,S)nickel(II)

M. R. Rizal, H. M. Ali and S. W. Ng

Abstract top

The Ni atom in the centrosymmetric title compound, [Ni(C10H9N4S)2], is N,S-chelated by the deprotonated Schiff bases in a square-planar geometry. The -CH=N-N=C(S)-NH2 frament is planar. Adjacent molecules are linked by hydrogen bonds between the indolyl -NH (donor) site and the double-bond =N- (acceptor) site of an adjacent molecule, forming a layer motif.

Comment top

A previous study reports the structure of 1H-indole-3-carboxaldehyde thiosemicarbazone (Rizal et al., 2008). The compound in its deprotonated form can function as a bidentate chelate, and this is confirmed in the present nickel(II) derivative (Scheme I, Fig. 1). The metal center lies on a center-of-inversion in a square planar coordination geometry. Adjacent molecules are linked by hydrogen bonds between the indolyl –NH (donor) site and the double-bond =N– (acceptor) site of an adjacent molecule to form a layer motif (Fig. 2).

Related literature top

For the structure of the neutral Schiff base, see: Rizal et al. (2008). For background literature on the medicinal activity of metal complexes of the Schiff base and related compounds, see: Husain et al. (2007); Wilson et al. (2005).

Experimental top

Nickel acetate tetrahydrate (0.06 g,0.22 mmol) and 1H-indole-3-carboxaldehyde thiosemicarbazone (0.10 g, 0.44 mmol), ethanol (4 ml) and water (10 ml) were sealed in a 15-ml, Teflon-lined, Parr bomb. The bomb was heated at 383 K for 2 days. The bomb when cooled to room temperature over a day to give orange plates.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The nitrogen-bound H-atoms were located in a difference Fourier map, and were refined with an N–H distance restraint of 0.88±0.01 Å; their temperature factors were freely refined.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001; Dolomanov et al., 2003); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of Ni(C10H9N4S)2 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The molecule lies on a center-of-inversion. Unlabeled atoms are related to the labeled ones by this symmetry element.
[Figure 2] Fig. 2. OLEX (Dolomanov et al., 2003) representation of the hydrogen-bonded layer motif.
trans-Bis(1H-indole-3-carbaldehyde thiosemicarbazonato-κ2N1,S)nickel(II) top
Crystal data top
[Ni(C10H9N4S)2]F000 = 508
Mr = 493.25Dx = 1.614 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1799 reflections
a = 10.4388 (3) Åθ = 2.6–24.7º
b = 5.2604 (1) ŵ = 1.19 mm−1
c = 19.1122 (5) ÅT = 100 (2) K
β = 104.803 (2)ºPlate, orange
V = 1014.66 (4) Å30.14 × 0.04 × 0.01 mm
Z = 2
Data collection top
Bruker SMART APEX
diffractometer		2326 independent reflections
Radiation source: fine-focus sealed tube1774 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.062
T = 100(2) Kθmax = 27.5º
φ and ω scansθmin = 2.0º
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		h = −12→13
Tmin = 0.851, Tmax = 0.988k = −6→6
12357 measured reflectionsl = −24→24
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)] = 0.034H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.081  w = 1/[σ2(Fo2) + (0.0362P)2 + 0.5143P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2326 reflectionsΔρmax = 0.43 e Å−3
154 parametersΔρmin = −0.30 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni(C10H9N4S)2]V = 1014.66 (4) Å3
Mr = 493.25Z = 2
Monoclinic, P21/cMo Kα
a = 10.4388 (3) ŵ = 1.19 mm−1
b = 5.2604 (1) ÅT = 100 (2) K
c = 19.1122 (5) Å0.14 × 0.04 × 0.01 mm
β = 104.803 (2)º
Data collection top
Bruker SMART APEX
diffractometer		2326 independent reflections
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		1774 reflections with I > 2σ(I)
Tmin = 0.851, Tmax = 0.988Rint = 0.062
12357 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0343 restraints
wR(F2) = 0.081H atoms treated by a mixture of
independent and constrained refinement
S = 1.02Δρmax = 0.43 e Å−3
2326 reflectionsΔρmin = −0.30 e Å−3
154 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50000.50000.50000.01261 (12)
S10.33444 (6)0.74950 (12)0.45463 (3)0.01747 (15)
N10.6654 (2)1.1528 (4)0.78929 (11)0.0171 (5)
H1N0.637 (3)1.262 (5)0.8165 (14)0.045 (10)*
N20.52205 (19)0.6972 (4)0.58664 (10)0.0143 (4)
N30.42554 (19)0.8723 (4)0.59419 (10)0.0153 (4)
N40.2345 (2)1.0700 (4)0.53342 (12)0.0205 (5)
H4N10.240 (3)1.177 (5)0.5691 (12)0.042 (10)*
H4N20.184 (3)1.121 (6)0.4919 (10)0.043 (10)*
C10.7786 (2)0.8186 (5)0.76257 (12)0.0154 (5)
C20.8845 (2)0.6471 (5)0.77478 (13)0.0182 (5)
H20.88690.51590.74100.022*
C30.9859 (2)0.6731 (5)0.83732 (13)0.0195 (5)
H31.05880.55900.84600.023*
C40.9830 (2)0.8646 (5)0.88809 (13)0.0190 (5)
H41.05380.87660.93060.023*
C50.8795 (2)1.0361 (5)0.87760 (12)0.0178 (5)
H50.87741.16590.91180.021*
C60.7782 (2)1.0092 (5)0.81421 (12)0.0159 (5)
C70.5945 (2)1.0621 (5)0.72458 (12)0.0166 (5)
H70.51321.13090.69690.020*
C80.6586 (2)0.8537 (5)0.70493 (12)0.0166 (5)
C90.6276 (2)0.6972 (5)0.64112 (12)0.0163 (5)
H90.69350.57610.63810.020*
C100.3354 (2)0.9073 (5)0.53374 (13)0.0159 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0129 (2)0.0143 (2)0.0104 (2)0.00022 (19)0.00260 (16)−0.00047 (18)
S10.0180 (3)0.0207 (3)0.0124 (3)0.0042 (3)0.0014 (2)−0.0010 (2)
N10.0177 (11)0.0189 (11)0.0140 (10)0.0007 (9)0.0029 (8)−0.0039 (9)
N20.0161 (10)0.0141 (10)0.0127 (9)0.0014 (8)0.0036 (8)−0.0004 (8)
N30.0155 (11)0.0171 (11)0.0137 (10)0.0021 (9)0.0047 (8)−0.0002 (8)
N40.0225 (12)0.0210 (12)0.0172 (11)0.0080 (9)0.0035 (9)−0.0025 (9)
C10.0156 (12)0.0156 (12)0.0151 (11)−0.0034 (10)0.0042 (10)0.0002 (9)
C20.0190 (13)0.0192 (13)0.0177 (12)−0.0019 (10)0.0068 (10)−0.0025 (10)
C30.0153 (13)0.0225 (14)0.0205 (12)0.0005 (11)0.0040 (10)0.0028 (11)
C40.0166 (13)0.0245 (14)0.0148 (11)−0.0037 (11)0.0018 (10)−0.0005 (10)
C50.0196 (13)0.0207 (14)0.0127 (11)−0.0040 (11)0.0034 (10)−0.0005 (10)
C60.0172 (12)0.0167 (12)0.0151 (11)−0.0011 (11)0.0063 (9)0.0013 (10)
C70.0166 (12)0.0190 (14)0.0137 (11)−0.0016 (10)0.0030 (10)−0.0003 (9)
C80.0191 (13)0.0177 (13)0.0135 (11)−0.0022 (10)0.0051 (10)0.0001 (10)
C90.0175 (12)0.0176 (13)0.0145 (11)0.0008 (10)0.0055 (10)0.0003 (10)
C100.0180 (13)0.0140 (12)0.0182 (12)−0.0033 (10)0.0092 (10)0.0007 (10)
Geometric parameters (Å, °) top
Ni1—N2i1.919 (2)C1—C61.408 (3)
Ni1—N21.918 (2)C1—C81.453 (3)
Ni1—S1i2.1669 (6)C2—C31.386 (3)
Ni1—S12.1669 (6)C2—H20.9500
S1—C101.723 (2)C3—C41.404 (4)
N1—C71.355 (3)C3—H30.9500
N1—C61.377 (3)C4—C51.382 (4)
N1—H1n0.88 (3)C4—H40.9500
N2—C91.309 (3)C5—C61.397 (3)
N2—N31.399 (3)C5—H50.9500
N3—C101.303 (3)C7—C81.385 (3)
N4—C101.355 (3)C7—H70.9500
N4—H4n10.88 (3)C8—C91.438 (3)
N4—H4n20.88 (3)C9—H90.9500
C1—C21.400 (3)
N2i—Ni1—N2180.000 (1)C2—C3—H3119.3
N2i—Ni1—S1i85.72 (6)C4—C3—H3119.3
N2—Ni1—S185.72 (6)C5—C4—C3121.5 (2)
N2—Ni1—S1i94.28 (6)C5—C4—H4119.3
N2i—Ni1—S194.28 (6)C3—C4—H4119.3
S1i—Ni1—S1180.0C4—C5—C6116.8 (2)
C10—S1—Ni196.63 (9)C4—C5—H5121.6
C7—N1—C6110.0 (2)C6—C5—H5121.6
C7—N1—H1N126 (2)N1—C6—C5129.5 (2)
C6—N1—H1N123 (2)N1—C6—C1107.7 (2)
C9—N2—N3113.60 (19)C5—C6—C1122.9 (2)
C9—N2—Ni1125.30 (17)N1—C7—C8109.7 (2)
N3—N2—Ni1120.96 (14)N1—C7—H7125.1
C10—N3—N2112.16 (19)C8—C7—H7125.1
C10—N4—H4N1121 (2)C7—C8—C9131.6 (2)
C10—N4—H4N2119 (2)C7—C8—C1106.1 (2)
H4N1—N4—H4N2114 (3)C9—C8—C1122.2 (2)
C2—C1—C6119.1 (2)N2—C9—C8129.5 (2)
C2—C1—C8134.4 (2)N2—C9—H9115.3
C6—C1—C8106.5 (2)C8—C9—H9115.3
C3—C2—C1118.5 (2)N3—C10—N4118.5 (2)
C3—C2—H2120.8N3—C10—S1123.44 (19)
C1—C2—H2120.8N4—C10—S1118.03 (18)
C2—C3—C4121.3 (2)
N2i—Ni1—S1—C10172.73 (10)C8—C1—C6—N1−0.4 (3)
N2—Ni1—S1—C10−7.27 (10)C2—C1—C6—C50.1 (4)
S1i—Ni1—N2—C915.3 (2)C8—C1—C6—C5−179.6 (2)
S1—Ni1—N2—C9−164.7 (2)C6—N1—C7—C80.3 (3)
S1i—Ni1—N2—N3−169.40 (16)N1—C7—C8—C9−177.4 (2)
S1—Ni1—N2—N310.60 (16)N1—C7—C8—C1−0.5 (3)
C9—N2—N3—C10166.4 (2)C2—C1—C8—C7−179.1 (3)
Ni1—N2—N3—C10−9.4 (3)C6—C1—C8—C70.6 (3)
C6—C1—C2—C3−0.5 (4)C2—C1—C8—C9−1.8 (4)
C8—C1—C2—C3179.2 (3)C6—C1—C8—C9177.8 (2)
C1—C2—C3—C40.6 (4)N3—N2—C9—C8−2.0 (4)
C2—C3—C4—C5−0.4 (4)Ni1—N2—C9—C8173.7 (2)
C3—C4—C5—C60.1 (4)C7—C8—C9—N2−7.0 (5)
C7—N1—C6—C5179.2 (2)C1—C8—C9—N2176.5 (2)
C7—N1—C6—C10.1 (3)N2—N3—C10—N4179.1 (2)
C4—C5—C6—N1−178.9 (2)N2—N3—C10—S11.4 (3)
C4—C5—C6—C10.1 (4)Ni1—S1—C10—N35.4 (2)
C2—C1—C6—N1179.3 (2)Ni1—S1—C10—N4−172.37 (19)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···N3ii0.88 (3)2.06 (2)2.876 (3)155 (3)
Symmetry codes: (ii) −x+1, y+1/2, −z+3/2.
Table 1
Selected geometric parameters (Å, °) top
Ni1—N21.918 (2)Ni1—S12.1669 (6)
N2—Ni1—S185.72 (6)N2—Ni1—S1i94.28 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···N3ii0.88 (3)2.06 (2)2.876 (3)155 (3)
Symmetry codes: (ii) −x+1, y+1/2, −z+3/2.
Acknowledgements top

We thank the Science Fund (12–02-03–2031) for supporting this study, and the University of Malaya for the purchase of the diffractometer.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Dolomanov, O. V., Blake, A. J., Champness, N. R. & Schröder, M. (2003). J. Appl. Cryst. 36, 1283–1284.

Husain, K., Abid, M. & Azam, A. (2007). Eur. J. Med. Chem. 42, 1300–1308.

Rizal, R. M., Ali, H. M. & Ng, S. W. (2008). Acta Cryst. E64, o919–o920.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2008). publCIF. In preparation.

Wilson, B. A., Venkatraman, R., Whitaker, C. & Tillison, Q. (2005). Int. J. Env. Res. Pub. Health, 2, 170–174.