trans-Bis(1H-indole-3-carbaldehyde thio­semicarbazonato-κ2N1,S)nickel(II)

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

doi:10.1107/S1600536808014293

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m824

doi:10.1107/S1600536808014293

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trans-Bis(1H-indole-3-carbaldehyde thiosemicarbazonato-κ²N¹,S)nickel(II)

Mohd. Razali Rizal,^a Hapipah M. Ali ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 24 April 2008; accepted 12 May 2008; online 17 May 2008)

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.

Related literature

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

Crystal data

[Ni(C₁₀H₉N₄S)₂]
M_r = 493.25
Monoclinic, P 2₁ /c
a = 10.4388 (3) Å
b = 5.2604 (1) Å
c = 19.1122 (5) Å
β = 104.803 (2)°
V = 1014.66 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.19 mm⁻¹
T = 100 (2) K
0.14 × 0.04 × 0.01 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.851, T_max = 0.988
12357 measured reflections
2326 independent reflections
1774 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.081
S = 1.02
2326 reflections
154 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ni1—N2	1.918 (2)
Ni1—S1	2.1669 (6)

N2—Ni1—S1	85.72 (6)
N2—Ni1—S1ⁱ	94.28 (6)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯N3ⁱⁱ	0.88 (3)	2.06 (2)	2.876 (3)	155 (3)
Symmetry code: (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014293/sg2241sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014293/sg2241Isup2.hkl

checkCIF report

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.

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

	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.
	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]	F(000) = 508
M_r = 493.25	D_x = 1.614 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1799 reflections
a = 10.4388 (3) Å	θ = 2.6–24.7°
b = 5.2604 (1) Å	µ = 1.19 mm⁻¹
c = 19.1122 (5) Å	T = 100 K
β = 104.803 (2)°	Plate, orange
V = 1014.66 (4) Å³	0.14 × 0.04 × 0.01 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	2326 independent reflections
Radiation source: fine-focus sealed tube	1774 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
T_min = 0.851, T_max = 0.988	k = −6→6
12357 measured reflections	l = −24→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0362P)² + 0.5143P] where P = (F_o² + 2F_c²)/3
2326 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.43 e Å⁻³
3 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Ni(C₁₀H₉N₄S)₂]	V = 1014.66 (4) Å³
M_r = 493.25	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.4388 (3) Å	µ = 1.19 mm⁻¹
b = 5.2604 (1) Å	T = 100 K
c = 19.1122 (5) Å	0.14 × 0.04 × 0.01 mm
β = 104.803 (2)°

Data collection top

Bruker SMART APEX diffractometer	2326 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1774 reflections with I > 2σ(I)
T_min = 0.851, T_max = 0.988	R_int = 0.062
12357 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	3 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.43 e Å⁻³
2326 reflections	Δρ_min = −0.30 e Å⁻³
154 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.5000	0.5000	0.01261 (12)
S1	0.33444 (6)	0.74950 (12)	0.45463 (3)	0.01747 (15)
N1	0.6654 (2)	1.1528 (4)	0.78929 (11)	0.0171 (5)
H1N	0.637 (3)	1.262 (5)	0.8165 (14)	0.045 (10)*
N2	0.52205 (19)	0.6972 (4)	0.58664 (10)	0.0143 (4)
N3	0.42554 (19)	0.8723 (4)	0.59419 (10)	0.0153 (4)
N4	0.2345 (2)	1.0700 (4)	0.53342 (12)	0.0205 (5)
H4N1	0.240 (3)	1.177 (5)	0.5691 (12)	0.042 (10)*
H4N2	0.184 (3)	1.121 (6)	0.4919 (10)	0.043 (10)*
C1	0.7786 (2)	0.8186 (5)	0.76257 (12)	0.0154 (5)
C2	0.8845 (2)	0.6471 (5)	0.77478 (13)	0.0182 (5)
H2	0.8869	0.5159	0.7410	0.022*
C3	0.9859 (2)	0.6731 (5)	0.83732 (13)	0.0195 (5)
H3	1.0588	0.5590	0.8460	0.023*
C4	0.9830 (2)	0.8646 (5)	0.88809 (13)	0.0190 (5)
H4	1.0538	0.8766	0.9306	0.023*
C5	0.8795 (2)	1.0361 (5)	0.87760 (12)	0.0178 (5)
H5	0.8774	1.1659	0.9118	0.021*
C6	0.7782 (2)	1.0092 (5)	0.81421 (12)	0.0159 (5)
C7	0.5945 (2)	1.0621 (5)	0.72458 (12)	0.0166 (5)
H7	0.5132	1.1309	0.6969	0.020*
C8	0.6586 (2)	0.8537 (5)	0.70493 (12)	0.0166 (5)
C9	0.6276 (2)	0.6972 (5)	0.64112 (12)	0.0163 (5)
H9	0.6935	0.5761	0.6381	0.020*
C10	0.3354 (2)	0.9073 (5)	0.53374 (13)	0.0159 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0129 (2)	0.0143 (2)	0.0104 (2)	0.00022 (19)	0.00260 (16)	−0.00047 (18)
S1	0.0180 (3)	0.0207 (3)	0.0124 (3)	0.0042 (3)	0.0014 (2)	−0.0010 (2)
N1	0.0177 (11)	0.0189 (11)	0.0140 (10)	0.0007 (9)	0.0029 (8)	−0.0039 (9)
N2	0.0161 (10)	0.0141 (10)	0.0127 (9)	0.0014 (8)	0.0036 (8)	−0.0004 (8)
N3	0.0155 (11)	0.0171 (11)	0.0137 (10)	0.0021 (9)	0.0047 (8)	−0.0002 (8)
N4	0.0225 (12)	0.0210 (12)	0.0172 (11)	0.0080 (9)	0.0035 (9)	−0.0025 (9)
C1	0.0156 (12)	0.0156 (12)	0.0151 (11)	−0.0034 (10)	0.0042 (10)	0.0002 (9)
C2	0.0190 (13)	0.0192 (13)	0.0177 (12)	−0.0019 (10)	0.0068 (10)	−0.0025 (10)
C3	0.0153 (13)	0.0225 (14)	0.0205 (12)	0.0005 (11)	0.0040 (10)	0.0028 (11)
C4	0.0166 (13)	0.0245 (14)	0.0148 (11)	−0.0037 (11)	0.0018 (10)	−0.0005 (10)
C5	0.0196 (13)	0.0207 (14)	0.0127 (11)	−0.0040 (11)	0.0034 (10)	−0.0005 (10)
C6	0.0172 (12)	0.0167 (12)	0.0151 (11)	−0.0011 (11)	0.0063 (9)	0.0013 (10)
C7	0.0166 (12)	0.0190 (14)	0.0137 (11)	−0.0016 (10)	0.0030 (10)	−0.0003 (9)
C8	0.0191 (13)	0.0177 (13)	0.0135 (11)	−0.0022 (10)	0.0051 (10)	0.0001 (10)
C9	0.0175 (12)	0.0176 (13)	0.0145 (11)	0.0008 (10)	0.0055 (10)	0.0003 (10)
C10	0.0180 (13)	0.0140 (12)	0.0182 (12)	−0.0033 (10)	0.0092 (10)	0.0007 (10)

Geometric parameters (Å, º) top

Ni1—N2ⁱ	1.919 (2)	C1—C6	1.408 (3)
Ni1—N2	1.918 (2)	C1—C8	1.453 (3)
Ni1—S1ⁱ	2.1669 (6)	C2—C3	1.386 (3)
Ni1—S1	2.1669 (6)	C2—H2	0.9500
S1—C10	1.723 (2)	C3—C4	1.404 (4)
N1—C7	1.355 (3)	C3—H3	0.9500
N1—C6	1.377 (3)	C4—C5	1.382 (4)
N1—H1n	0.88 (3)	C4—H4	0.9500
N2—C9	1.309 (3)	C5—C6	1.397 (3)
N2—N3	1.399 (3)	C5—H5	0.9500
N3—C10	1.303 (3)	C7—C8	1.385 (3)
N4—C10	1.355 (3)	C7—H7	0.9500
N4—H4n1	0.88 (3)	C8—C9	1.438 (3)
N4—H4n2	0.88 (3)	C9—H9	0.9500
C1—C2	1.400 (3)

N2ⁱ—Ni1—N2	180.000 (1)	C2—C3—H3	119.3
N2ⁱ—Ni1—S1ⁱ	85.72 (6)	C4—C3—H3	119.3
N2—Ni1—S1	85.72 (6)	C5—C4—C3	121.5 (2)
N2—Ni1—S1ⁱ	94.28 (6)	C5—C4—H4	119.3
N2ⁱ—Ni1—S1	94.28 (6)	C3—C4—H4	119.3
S1ⁱ—Ni1—S1	180.0	C4—C5—C6	116.8 (2)
C10—S1—Ni1	96.63 (9)	C4—C5—H5	121.6
C7—N1—C6	110.0 (2)	C6—C5—H5	121.6
C7—N1—H1N	126 (2)	N1—C6—C5	129.5 (2)
C6—N1—H1N	123 (2)	N1—C6—C1	107.7 (2)
C9—N2—N3	113.60 (19)	C5—C6—C1	122.9 (2)
C9—N2—Ni1	125.30 (17)	N1—C7—C8	109.7 (2)
N3—N2—Ni1	120.96 (14)	N1—C7—H7	125.1
C10—N3—N2	112.16 (19)	C8—C7—H7	125.1
C10—N4—H4N1	121 (2)	C7—C8—C9	131.6 (2)
C10—N4—H4N2	119 (2)	C7—C8—C1	106.1 (2)
H4N1—N4—H4N2	114 (3)	C9—C8—C1	122.2 (2)
C2—C1—C6	119.1 (2)	N2—C9—C8	129.5 (2)
C2—C1—C8	134.4 (2)	N2—C9—H9	115.3
C6—C1—C8	106.5 (2)	C8—C9—H9	115.3
C3—C2—C1	118.5 (2)	N3—C10—N4	118.5 (2)
C3—C2—H2	120.8	N3—C10—S1	123.44 (19)
C1—C2—H2	120.8	N4—C10—S1	118.03 (18)
C2—C3—C4	121.3 (2)

N2ⁱ—Ni1—S1—C10	172.73 (10)	C8—C1—C6—N1	−0.4 (3)
N2—Ni1—S1—C10	−7.27 (10)	C2—C1—C6—C5	0.1 (4)
S1ⁱ—Ni1—N2—C9	15.3 (2)	C8—C1—C6—C5	−179.6 (2)
S1—Ni1—N2—C9	−164.7 (2)	C6—N1—C7—C8	0.3 (3)
S1ⁱ—Ni1—N2—N3	−169.40 (16)	N1—C7—C8—C9	−177.4 (2)
S1—Ni1—N2—N3	10.60 (16)	N1—C7—C8—C1	−0.5 (3)
C9—N2—N3—C10	166.4 (2)	C2—C1—C8—C7	−179.1 (3)
Ni1—N2—N3—C10	−9.4 (3)	C6—C1—C8—C7	0.6 (3)
C6—C1—C2—C3	−0.5 (4)	C2—C1—C8—C9	−1.8 (4)
C8—C1—C2—C3	179.2 (3)	C6—C1—C8—C9	177.8 (2)
C1—C2—C3—C4	0.6 (4)	N3—N2—C9—C8	−2.0 (4)
C2—C3—C4—C5	−0.4 (4)	Ni1—N2—C9—C8	173.7 (2)
C3—C4—C5—C6	0.1 (4)	C7—C8—C9—N2	−7.0 (5)
C7—N1—C6—C5	179.2 (2)	C1—C8—C9—N2	176.5 (2)
C7—N1—C6—C1	0.1 (3)	N2—N3—C10—N4	179.1 (2)
C4—C5—C6—N1	−178.9 (2)	N2—N3—C10—S1	1.4 (3)
C4—C5—C6—C1	0.1 (4)	Ni1—S1—C10—N3	5.4 (2)
C2—C1—C6—N1	179.3 (2)	Ni1—S1—C10—N4	−172.37 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···N3ⁱⁱ	0.88 (3)	2.06 (2)	2.876 (3)	155 (3)

Symmetry code: (ii) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₀H₉N₄S)₂]
M_r	493.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.4388 (3), 5.2604 (1), 19.1122 (5)
β (°)	104.803 (2)
V (Å³)	1014.66 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.19
Crystal size (mm)	0.14 × 0.04 × 0.01

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.851, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	12357, 2326, 1774
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.081, 1.02
No. of reflections	2326
No. of parameters	154
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.30

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001; Dolomanov et al., 2003), publCIF (Westrip, 2008).

Selected geometric parameters (Å, º) top

Ni1—N2	1.918 (2)	Ni1—S1	2.1669 (6)

N2—Ni1—S1	85.72 (6)	N2—Ni1—S1ⁱ	94.28 (6)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···N3ⁱⁱ	0.88 (3)	2.06 (2)	2.876 (3)	155 (3)

Symmetry code: (ii) −x+1, y+1/2, −z+3/2.

Acknowledgements

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

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