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

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.081
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4N1   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4N2   ...          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels ..........          2

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C20 H18 N8 Ni1 S2
            Atom count from _chemical_formula_moiety:
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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).

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).

S2. 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.

S3. 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.

Computing details

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

	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)

Crystal data

[Ni(C10H9N4S)2]	F(000) = 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 = 2.6–24.7°
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) Å^3	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)
Graphite monochromator	Rint = 0.062
ϕ and ω scans	θmax = 27.5°, θmin = 2.0°
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 F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0362P)^2 + 0.5143P] where P = (Fo^2 + 2Fc^2)/3
2326 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.43 e Å^−3
3 restraints	Δρmin = −0.30 e Å^−3

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)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Ni1—N2^i	1.919 (2)	C1—C6	1.408 (3)
Ni1—N2	1.918 (2)	C1—C8	1.453 (3)
Ni1—S1^i	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)
N2^i—Ni1—N2	180.000 (1)	C2—C3—H3	119.3
N2^i—Ni1—S1^i	85.72 (6)	C4—C3—H3	119.3
N2—Ni1—S1	85.72 (6)	C5—C4—C3	121.5 (2)
N2—Ni1—S1^i	94.28 (6)	C5—C4—H4	119.3
N2^i—Ni1—S1	94.28 (6)	C3—C4—H4	119.3
S1^i—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)
N2^i—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)
S1^i—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)
S1^i—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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···N3^ii	0.88 (3)	2.06 (2)	2.876 (3)	155 (3)

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