trans-Bis(1H-indole-3-carbaldehyde thio­semicarbazonato-κ² N ¹,S)nickel(II)

Abstract

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,

• a = 10.4388 (3) Å

• b = 5.2604 (1) Å

• c = 19.1122 (5) Å

• β = 104.803 (2)°

• V = 1014.66 (4) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

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) .

supplementary crystallographic information

Comment

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).

Experimental

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

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.

Figures

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.

Crystal data

[Ni(C10H9N4S)2]	F000 = 508
Mr = 493.25	Dx = 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 = 2.6–24.7º
b = 5.2604 (1) Å	µ = 1.19 mm−1
c = 19.1122 (5) Å	T = 100 (2) K
β = 104.803 (2)º	Plate, orange
V = 1014.66 (4) Å3	0.14 × 0.04 × 0.01 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer	2326 independent reflections
Radiation source: fine-focus sealed tube	1774 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.062
T = 100(2) K	θmax = 27.5º
φ and ω scans	θmin = 2.0º
Absorption correction: Multi-scan(SADABS; Sheldrick, 1996)	h = −12→13
Tmin = 0.851, Tmax = 0.988	k = −6→6
12357 measured reflections	l = −24→24

Refinement

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)] = 0.034	H 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 reflections	Δρmax = 0.43 e Å−3
154 parameters	Δρmin = −0.30 e Å−3
3 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+1, −z+1.

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 codes: (ii) −x+1, y+1/2, −z+3/2.