Hydrogen-bonding and π–π stacking inter­actions in tris­(1,10-phenanthroline-κ2N,N′)nickel(II) bis­{[1-tert-butyl­imidazole-2(3H)-thione-κS]trichloridonickelate(II)} acetonitrile disolvate

Singh, U.P.; Aggarwal, V.

doi:10.1107/S1600536808018060

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m935-m936

doi:10.1107/S1600536808018060

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Hydrogen-bonding and π–π stacking interactions in tris(1,10-phenanthroline-κ²N,N′)nickel(II) bis{[1-tert-butylimidazole-2(3H)-thione-κS]trichloridonickelate(II)} acetonitrile disolvate

Udai P. Singh ^a ^* and Vaibhave Aggarwal ^a

^aDepartment of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, India
^*Correspondence e-mail: udaipfcy@iitr.ernet.in

(Received 1 April 2008; accepted 13 June 2008; online 19 June 2008)

The asymmetric unit of the title complex, [Ni(C₁₂H₈N₂)₃][NiCl₃(C₇H₁₂N₂S)]₂·2CH₃CN, consists of one anion, one-half of a cation and one acetonitrile molecule. The Ni^II atom in the [Ni(phen)₃]²⁺ cation (phen is 1,10-phenanthroline) lies on an inversion centre in an octahedral environment, whereas in the [NiCl₃(tm)]⁻ anion [tm is 1-tert-butylimidazole-2(3H)-thione], the geometry is distorted tetrahedral. In the crystal structure, intermolecular C—H⋯Cl hydrogen bonds and π–π stacking interactions (centroid–centroid distance = 3.52 Å) lead to the formation of a three-dimensional framework. One of the methyl groups of the tert-butyl group of N-tert-butyl-2-thioimidazole is disordered between two equally populated positions.

Related literature

For general background, see: Fatimi et al. (1994 ); Iradyan et al. (1987 ); Suescun et al. (1999 ); Yu et al. (2003 ); Fang & Dai (2006 ); Chen et al., (2007 ); Senda et al. (2006 ). For synthesis details, see: Kister et al. (1979 ).

Experimental

Crystal data

[Ni(C₁₂H₈N₂)₃][NiCl₃(C₇H₁₂N₂S)]₂·2C₂H₃N
M_r = 1324.04
Monoclinic, C 2/c
a = 22.8953 (15) Å
b = 15.2934 (10) Å
c = 19.9417 (19) Å
β = 123.543 (3)°
V = 5819.7 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.36 mm⁻¹
T = 298 (2) K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.737, T_max = 0.792
30921 measured reflections
5178 independent reflections
3346 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.157
S = 1.07
5178 reflections
370 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.24 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯Cl2	0.85 (6)	2.37 (7)	3.178 (6)	160 (6)
C2—H2⋯Cl3ⁱ	0.82 (7)	2.77 (7)	3.552 (8)	160 (4)
C5—H5C⋯S1	0.96	2.75	3.402 (9)	126
C7—H7A⋯S1	0.96	2.68	3.409 (8)	133
C10—H10⋯Cl3ⁱⁱ	0.93	2.72	3.557 (7)	151
C25—H25⋯N6ⁱⁱⁱ	0.93	2.60	3.502 (9)	162
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018060/su2050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018060/su2050Isup2.hkl

checkCIF report

Comment top

2-Thioimidazole (N,N,S donors) and its alkyl derivatives have antithyroid activity and platelet inhibitory effects. (Fatimi et al., 1994; Iradyan et al., 1987). The literature revealed the presence of various nickel(II) complexes with phenanthroline (Suescun et al., 1999; Yu et al. (2003); Fang & Dai, 2006; Chen et al., 2007) but none with N-tert-butyl-2-thioimidazole, except the one reported recently (Senda et al., 2006). The present work reports the first structure of a nickel(II) complex with N-tert-butyl-2-thioimidazole and 1,10 phenanthroline, containing a tetrahedral anion, [Ni(tm)(Cl)₃]^-, and an octahedral cation, [Ni(phen)₃]²⁺.

The title complex (I) is centrosymmetric, ionic in nature and comprises of one complex cation [Ni(phen)₃]²⁺ and two complex anions [Ni(tm)(Cl)₃]^- in the unit cell (Fig. 1). The metal centre in [Ni(phen)₃]²⁺ is in an octahedral environment, the equatorial plane of which is formed by four phen nitrogen atoms, and the axial positions are occupied by another two nitrogen atoms of phen, with Ni1—N bond distances in the range of 2.079 (4)–2.100 (4) Å. The dihedral angles between the meanplanes of the neighboring phen rings are 77.53°, 86.07° and 85.97°. The cis-angles in the octahedron deviate only slightly from 90° and the trans angle in the axial position is almost linear i.e. 170.54 (15)°. The nickel(II) atom in the [Ni(tm)(Cl)₃]^- anion is coordinated by three chlorine atoms and one sulfur atom of tm in a distorted tetrahedral geometry. The Ni—Cl bond distances are in the range of 2.251 (15) to 2.275 (15) Å. In the anion the two short bond distances (Ni2—Cl3 and Ni2—Cl1 of 2.2507 (15) and 2.253 (2) Å, respectively) and two long bond distances (Ni2—S1 and Ni2—Cl2 of 2.3054 (17) and 2.2753 (16) Å, respectively) make the geometry distorted tetrahedral.

Due to the presence of several intermolecular interactions between the three chloride ions bonded to atom Ni2 and the hydrogen atoms present on the phen rings, the complex cation is linked to six complex anions (Fig. 2 and Table 1), whereas the complex anions are linked to four complex cations through C—H···Cl hydrogen bonds (Fig. 3 and Table 1). In the crystal packing of complex (I) two layers are linked by hydrogen bonds in the bc plane. The [Ni(phen)₃]²⁺ cations and the [Ni(tm)(Cl)₃]^- anions interact with each other via hydrogen bonds formed by the terminally coordinated chloride ions of the complex anion (Cl1, Cl2 and Cl3) and the hydrogen atoms present on the phen ligands (Fig. 4). The two complex anions also interact with one another through π–π stacking, with a separation of ca. 3.52 Å, and intermolecular C—H···Cl and C—H···N interactions involving the hydrogen atom of the middle ring of phenanthroline and the nitrogen atom of the acetonitrile molecule present in the lattice (Table 1).

Related literature top

For general background, see: Fatimi et al. (1994); Iradyan et al. (1987); Suescun et al. (1999); Yu et al. (2003); Fang & Dai (2006); Chen et al., (2007); Senda et al. (2006). For synthesis details, see: Kister et al. (1979).

Experimental top

All the reagents were of commercial grade and were used as received. N-tert-butyl-thioimidazole (tm) was synthesized by a literature method (Kister et al., 1979). To a solution of NiCl₂.6H₂O (1.0 mmol) in 5 ml methanol, a methanolic solution of N-tert-butyl-2-thioimidazole (1.0 mmol) was added and the mixture stirred for 40 minutes. This mixture was then added to the solution obtained by mixing NiCl₂.6H₂O (1.0 mmol) in methanol with a methanolic solution of 1,10-phenanthroline (3.0 mmol). The whole reaction mixture was stirred for a further 30 minutes. The clear solution obtained was filtered and evaporated to dryness. The solid compound obtained was dissolved in acetonitrile and green single crystals, suitable for X-ray analysis, were obtained by slow evaporation at room temperature. Yield 62%. Analysis calculated for C₅₀H₄₈N₁₀S₂Cl₆Ni₃: C 48.30, H 3.86, N 11.27, S 5.15%; found: C 48.24, H 3.78, N 11.21, S 5.12%. Selected IR frequencies (KBr, ν, cm^-1): 725 (s), 849 (s), 1369 (w), 1575 (m), 1623 (w), 3060 (w), 3412 (s).

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: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the compound (I), shown with 30% probability displacement ellipsoids [H atoms have been omitted for clarity; Symmetry code: (i) -x, y, 0.5 - z.]
	Fig. 2. A view of the intermolecular C—H···Cl interactions involving the [Ni(phen)₃]⁺ cation.
	Fig. 3. A view of the intermolecular π–π stacking and C—H···Cl interactions involving the [Ni(tm)(Cl)₃]^- anion.
	Fig. 4. A view along the b axis of the crystal packing of complex (I), showing the interaction between two layers.

tris(1,10-phenanthroline-κ²N,N')nickel(II) bis{[1-tert-butylimidazole-2(3H)-thione-κS]trichloridonickelate(II)} acetonitrile disolvate top

Crystal data top

[Ni(C₁₂H₈N₂)₃][NiCl₃(C₇H₁₂N₂S)]₂·2C₂H₃N	F(000) = 2720
M_r = 1324.04	D_x = 1.511 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5736 reflections
a = 22.8953 (15) Å	θ = 1.7–25.1°
b = 15.2934 (10) Å	µ = 1.36 mm⁻¹
c = 19.9417 (19) Å	T = 298 K
β = 123.543 (3)°	Block, green
V = 5819.7 (8) Å³	0.24 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5178 independent reflections
Radiation source: fine-focus sealed tube	3346 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→26
T_min = 0.737, T_max = 0.792	k = −17→17
30921 measured reflections	l = −22→22

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0987P)² + 2.7947P] where P = (F_o² + 2F_c²)/3
5178 reflections	(Δ/σ)_max < 0.001
370 parameters	Δρ_max = 1.24 e Å⁻³
3 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Ni(C₁₂H₈N₂)₃][NiCl₃(C₇H₁₂N₂S)]₂·2C₂H₃N	V = 5819.7 (8) Å³
M_r = 1324.04	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.8953 (15) Å	µ = 1.36 mm⁻¹
b = 15.2934 (10) Å	T = 298 K
c = 19.9417 (19) Å	0.24 × 0.20 × 0.18 mm
β = 123.543 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5178 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3346 reflections with I > 2σ(I)
T_min = 0.737, T_max = 0.792	R_int = 0.076
30921 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	3 restraints
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 1.24 e Å⁻³
5178 reflections	Δρ_min = −0.55 e Å⁻³
370 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.00000	0.00042 (5)	0.25000	0.0324 (3)
N1	0.0571 (2)	0.1054 (2)	0.3259 (2)	0.0353 (12)
N2	0.0560 (2)	−0.0924 (2)	0.3397 (2)	0.0402 (12)
N3	0.0611 (2)	−0.0069 (3)	0.2013 (2)	0.0394 (12)
C8	0.1142 (3)	0.1047 (4)	0.3998 (3)	0.0432 (17)
C9	0.1465 (3)	0.1812 (4)	0.4422 (3)	0.0543 (19)
C10	0.1193 (3)	0.2601 (4)	0.4082 (4)	0.060 (2)
C11	0.0597 (3)	0.2640 (3)	0.3294 (3)	0.048 (2)
C12	0.0304 (2)	0.1842 (3)	0.2905 (3)	0.0359 (17)
C13	0.0280 (3)	0.3432 (4)	0.2882 (4)	0.065 (3)
C14	0.1128 (3)	−0.1368 (3)	0.3578 (3)	0.0534 (19)
C15	0.1476 (4)	−0.1940 (4)	0.4220 (4)	0.069 (2)
C16	0.1245 (4)	−0.2030 (4)	0.4708 (4)	0.071 (2)
C17	0.0649 (3)	−0.1584 (3)	0.4557 (3)	0.0542 (19)
C18	0.0313 (3)	−0.1036 (3)	0.3870 (3)	0.0424 (17)
C19	0.1208 (3)	0.0335 (4)	0.2245 (3)	0.0503 (17)
C20	0.1528 (3)	0.0259 (4)	0.1814 (4)	0.066 (3)
C21	0.1223 (4)	−0.0231 (5)	0.1145 (4)	0.068 (3)
C22	0.0604 (3)	−0.0683 (4)	0.0887 (4)	0.058 (2)
C23	0.0315 (3)	−0.0582 (3)	0.1348 (3)	0.0410 (17)
C24	0.0231 (4)	−0.1241 (5)	0.0183 (4)	0.072 (3)
C25	−0.0359 (4)	−0.1657 (4)	−0.0022 (4)	0.071 (3)
Ni2	0.29979 (3)	0.96924 (4)	0.47969 (4)	0.0434 (2)
Cl1	0.25801 (8)	0.97552 (11)	0.55872 (9)	0.0625 (6)
Cl2	0.27465 (7)	0.88260 (10)	0.37416 (8)	0.0583 (5)
Cl3	0.27772 (7)	1.10207 (9)	0.42193 (8)	0.0528 (5)
S1	0.41282 (7)	0.93790 (9)	0.58439 (8)	0.0452 (4)
N4	0.4404 (2)	0.8996 (3)	0.4710 (3)	0.0408 (16)
N5	0.5332 (2)	0.8910 (3)	0.5920 (2)	0.0381 (12)
C1	0.4636 (3)	0.9081 (3)	0.5493 (3)	0.0359 (17)
C2	0.5514 (3)	0.8728 (4)	0.5376 (3)	0.0479 (19)
C3	0.4945 (3)	0.8778 (4)	0.4641 (3)	0.0481 (17)
C4	0.5832 (3)	0.8870 (4)	0.6823 (3)	0.0452 (17)
C5	0.5869 (4)	0.9750 (4)	0.7181 (4)	0.089 (3)
C6	0.6584 (6)	0.8705 (16)	0.7056 (9)	0.093 (6)	0.75 (3)
C7	0.5581 (4)	0.8178 (5)	0.7141 (4)	0.077 (3)
C6A	0.643 (2)	0.830 (4)	0.695 (3)	0.093 (6)	0.25 (3)
N6	0.3858 (4)	0.7541 (4)	0.3045 (4)	0.091 (3)
C26	0.3366 (4)	0.7841 (4)	0.2533 (4)	0.066 (3)
C27	0.2734 (4)	0.8224 (5)	0.1875 (5)	0.093 (3)
H8	0.13350	0.05120	0.42420	0.0520*
H9	0.18670	0.17810	0.49400	0.0650*
H10	0.14000	0.31130	0.43680	0.0720*
H13	0.04640	0.39620	0.31450	0.0780*
H14	0.13000	−0.12900	0.32550	0.0640*
H15	0.18620	−0.22550	0.43130	0.0830*
H16	0.14870	−0.23950	0.51540	0.0860*
H19	0.14210	0.06790	0.27070	0.0600*
H20	0.19480	0.05460	0.19920	0.0790*
H21	0.14270	−0.02700	0.08520	0.0810*
H24	0.04090	−0.13130	−0.01350	0.0870*
H25	−0.05840	−0.20020	−0.04830	0.0850*
H2	0.593 (3)	0.867 (3)	0.555 (3)	0.036 (14)*
H3	0.486 (3)	0.868 (4)	0.409 (4)	0.061 (16)*
H5A	0.59570	1.01920	0.69050	0.1340*
H5B	0.62410	0.97510	0.77410	0.1340*
H4	0.397 (3)	0.897 (3)	0.435 (3)	0.039 (15)*
H6A	0.67440	0.92000	0.69040	0.1380*	0.75 (3)
H6B	0.65930	0.81930	0.67830	0.1380*	0.75 (3)
H6C	0.68860	0.86190	0.76270	0.1380*	0.75 (3)
H7A	0.50960	0.82750	0.69350	0.1160*
H7B	0.58520	0.82040	0.77180	0.1160*
H7C	0.56360	0.76130	0.69730	0.1160*
H5C	0.54330	0.98700	0.71250	0.1340*
H6A1	0.66990	0.86260	0.67940	0.1380*	0.25 (3)
H6A2	0.62430	0.77870	0.66220	0.1380*	0.25 (3)
H6A3	0.67260	0.81410	0.75030	0.1380*	0.25 (3)
H27A	0.24970	0.85310	0.20790	0.1400*
H27B	0.24340	0.77720	0.15140	0.1400*
H27C	0.28470	0.86250	0.15930	0.1400*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0334 (5)	0.0360 (5)	0.0257 (5)	0.0000	0.0151 (4)	0.0000
N1	0.035 (2)	0.042 (2)	0.028 (2)	0.0003 (18)	0.0168 (19)	−0.0034 (18)
N2	0.042 (2)	0.035 (2)	0.034 (2)	−0.0035 (19)	0.015 (2)	0.0018 (17)
N3	0.039 (2)	0.042 (2)	0.036 (2)	−0.0011 (19)	0.020 (2)	−0.0032 (18)
C8	0.035 (3)	0.060 (3)	0.030 (3)	−0.001 (2)	0.015 (2)	−0.005 (2)
C9	0.046 (3)	0.081 (4)	0.034 (3)	−0.016 (3)	0.021 (3)	−0.019 (3)
C10	0.077 (4)	0.062 (4)	0.055 (4)	−0.023 (3)	0.045 (4)	−0.029 (3)
C11	0.062 (4)	0.046 (3)	0.051 (4)	−0.010 (3)	0.041 (3)	−0.014 (3)
C12	0.043 (3)	0.040 (3)	0.035 (3)	−0.003 (2)	0.028 (2)	−0.004 (2)
C13	0.092 (5)	0.039 (3)	0.087 (5)	−0.016 (3)	0.064 (4)	−0.015 (3)
C14	0.042 (3)	0.043 (3)	0.057 (4)	0.007 (3)	0.016 (3)	−0.001 (3)
C15	0.062 (4)	0.050 (4)	0.063 (4)	0.008 (3)	0.014 (4)	0.007 (3)
C16	0.069 (4)	0.043 (3)	0.046 (4)	0.000 (3)	−0.003 (3)	0.014 (3)
C17	0.063 (4)	0.039 (3)	0.034 (3)	−0.014 (3)	0.010 (3)	0.005 (2)
C18	0.047 (3)	0.033 (3)	0.035 (3)	−0.009 (2)	0.015 (3)	−0.001 (2)
C19	0.044 (3)	0.057 (3)	0.051 (3)	−0.001 (3)	0.027 (3)	−0.002 (3)
C20	0.053 (4)	0.085 (5)	0.078 (5)	0.008 (3)	0.047 (4)	0.015 (4)
C21	0.074 (5)	0.091 (5)	0.064 (5)	0.021 (4)	0.054 (4)	0.018 (4)
C22	0.077 (4)	0.059 (3)	0.051 (4)	0.034 (3)	0.043 (3)	0.016 (3)
C23	0.049 (3)	0.040 (3)	0.034 (3)	0.014 (2)	0.023 (3)	0.005 (2)
C24	0.105 (6)	0.078 (4)	0.051 (4)	0.027 (4)	0.054 (4)	0.000 (3)
C25	0.104 (6)	0.059 (4)	0.041 (4)	0.022 (4)	0.035 (4)	−0.005 (3)
Ni2	0.0394 (4)	0.0561 (4)	0.0325 (4)	0.0045 (3)	0.0185 (3)	−0.0031 (3)
Cl1	0.0540 (9)	0.0980 (12)	0.0409 (8)	0.0098 (8)	0.0297 (7)	0.0020 (7)
Cl2	0.0496 (8)	0.0748 (10)	0.0400 (8)	0.0050 (7)	0.0181 (7)	−0.0152 (7)
Cl3	0.0476 (8)	0.0590 (8)	0.0495 (9)	−0.0008 (6)	0.0254 (7)	0.0015 (6)
S1	0.0413 (7)	0.0626 (8)	0.0318 (7)	0.0068 (6)	0.0203 (6)	−0.0018 (6)
N4	0.042 (3)	0.053 (3)	0.026 (2)	0.000 (2)	0.018 (2)	−0.0013 (19)
N5	0.039 (2)	0.051 (2)	0.026 (2)	0.0010 (19)	0.019 (2)	0.0021 (18)
C1	0.041 (3)	0.040 (3)	0.027 (3)	−0.001 (2)	0.019 (2)	0.002 (2)
C2	0.039 (3)	0.067 (4)	0.043 (3)	−0.004 (3)	0.026 (3)	−0.003 (3)
C3	0.051 (3)	0.061 (3)	0.040 (3)	−0.003 (3)	0.030 (3)	0.000 (3)
C4	0.040 (3)	0.065 (3)	0.029 (3)	0.004 (3)	0.018 (2)	0.006 (2)
C5	0.096 (6)	0.076 (5)	0.040 (4)	−0.009 (4)	0.003 (4)	−0.008 (3)
C6	0.036 (6)	0.183 (16)	0.043 (6)	0.002 (7)	0.012 (6)	0.004 (9)
C7	0.080 (5)	0.091 (5)	0.050 (4)	−0.001 (4)	0.029 (4)	0.023 (3)
C6A	0.036 (6)	0.183 (16)	0.043 (6)	0.002 (7)	0.012 (6)	0.004 (9)
N6	0.103 (5)	0.105 (5)	0.062 (4)	0.008 (4)	0.043 (4)	0.005 (4)
C26	0.088 (5)	0.066 (4)	0.054 (4)	−0.010 (4)	0.045 (4)	−0.002 (3)
C27	0.099 (6)	0.080 (5)	0.073 (5)	0.004 (4)	0.030 (5)	0.006 (4)

Geometric parameters (Å, º) top

Ni1—N1	2.095 (3)	C21—C22	1.395 (12)
Ni1—N2	2.079 (3)	C22—C24	1.450 (10)
Ni1—N3	2.101 (5)	C22—C23	1.407 (10)
Ni1—N1ⁱ	2.095 (3)	C24—C25	1.337 (13)
Ni1—N2ⁱ	2.079 (3)	C8—H8	0.9300
Ni1—N3ⁱ	2.101 (5)	C9—H9	0.9300
Ni2—Cl2	2.2753 (16)	C10—H10	0.9300
Ni2—Cl3	2.2507 (15)	C13—H13	0.9300
Ni2—S1	2.3054 (17)	C14—H14	0.9300
Ni2—Cl1	2.253 (2)	C15—H15	0.9300
S1—C1	1.717 (7)	C16—H16	0.9300
N1—C8	1.324 (7)	C19—H19	0.9300
N1—C12	1.359 (6)	C20—H20	0.9300
N2—C18	1.352 (8)	C21—H21	0.9300
N2—C14	1.328 (8)	C24—H24	0.9300
N3—C23	1.357 (6)	C25—H25	0.9300
N3—C19	1.329 (9)	C2—C3	1.320 (8)
N4—C1	1.349 (7)	C4—C5	1.504 (9)
N4—C3	1.361 (9)	C4—C6A	1.52 (6)
N5—C1	1.354 (8)	C4—C6	1.536 (19)
N5—C2	1.388 (8)	C4—C7	1.502 (11)
N5—C4	1.510 (6)	C2—H2	0.82 (7)
N4—H4	0.85 (6)	C3—H3	1.02 (7)
N6—C26	1.118 (11)	C5—H5A	0.9600
C8—C9	1.393 (8)	C5—H5B	0.9600
C9—C10	1.355 (9)	C5—H5C	0.9600
C10—C11	1.402 (9)	C6—H6A	0.9600
C11—C12	1.402 (7)	C6—H6B	0.9600
C11—C13	1.418 (8)	C6—H6C	0.9600
C12—C12ⁱ	1.436 (7)	C6A—H6A2	0.9600
C13—C13ⁱ	1.344 (10)	C6A—H6A3	0.9500
C14—C15	1.383 (8)	C6A—H6A1	0.9700
C15—C16	1.347 (13)	C7—H7B	0.9600
C16—C17	1.401 (12)	C7—H7C	0.9600
C17—C18	1.417 (7)	C7—H7A	0.9600
C17—C25ⁱ	1.412 (12)	C26—C27	1.435 (12)
C18—C23ⁱ	1.431 (10)	C27—H27A	0.9600
C19—C20	1.409 (10)	C27—H27B	0.9600
C20—C21	1.341 (10)	C27—H27C	0.9600

N1—Ni1—N2	93.42 (13)	C8—C9—H9	120.00
N1—Ni1—N3	93.77 (18)	C11—C10—H10	120.00
N1—Ni1—N1ⁱ	79.98 (13)	C9—C10—H10	120.00
N1—Ni1—N2ⁱ	170.55 (15)	C13ⁱ—C13—H13	119.00
N1—Ni1—N3ⁱ	90.91 (18)	C11—C13—H13	119.00
N2—Ni1—N3	96.30 (18)	N2—C14—H14	118.00
N1ⁱ—Ni1—N2	170.55 (15)	C15—C14—H14	118.00
N2—Ni1—N2ⁱ	93.90 (13)	C14—C15—H15	121.00
N2—Ni1—N3ⁱ	79.49 (18)	C16—C15—H15	121.00
N1ⁱ—Ni1—N3	90.91 (18)	C17—C16—H16	120.00
N2ⁱ—Ni1—N3	79.49 (18)	C15—C16—H16	119.00
N3—Ni1—N3ⁱ	173.89 (18)	N3—C19—H19	119.00
N1ⁱ—Ni1—N2ⁱ	93.42 (13)	C20—C19—H19	119.00
N1ⁱ—Ni1—N3ⁱ	93.77 (18)	C19—C20—H20	120.00
N2ⁱ—Ni1—N3ⁱ	96.30 (18)	C21—C20—H20	120.00
Cl1—Ni2—Cl2	133.14 (7)	C20—C21—H21	120.00
Cl1—Ni2—Cl3	104.92 (7)	C22—C21—H21	120.00
Cl1—Ni2—S1	94.21 (6)	C25—C24—H24	119.00
Cl2—Ni2—Cl3	100.47 (6)	C22—C24—H24	119.00
Cl2—Ni2—S1	107.47 (6)	C24—C25—H25	119.00
Cl3—Ni2—S1	118.25 (6)	C17ⁱ—C25—H25	119.00
Ni2—S1—C1	111.11 (19)	N4—C1—N5	106.5 (6)
Ni1—N1—C8	129.5 (3)	S1—C1—N5	128.4 (4)
Ni1—N1—C12	112.5 (3)	S1—C1—N4	125.1 (5)
C8—N1—C12	118.0 (4)	N5—C2—C3	108.5 (6)
C14—N2—C18	118.0 (4)	N4—C3—C2	107.3 (6)
Ni1—N2—C18	112.9 (4)	N5—C4—C6	110.6 (7)
Ni1—N2—C14	128.9 (4)	N5—C4—C5	109.7 (5)
Ni1—N3—C19	129.3 (4)	C5—C4—C6	104.1 (10)
C19—N3—C23	118.1 (5)	C5—C4—C7	111.4 (6)
Ni1—N3—C23	112.5 (4)	C5—C4—C6A	129 (2)
C1—N4—C3	110.0 (5)	C6—C4—C7	112.5 (10)
C2—N5—C4	124.5 (5)	C6A—C4—C7	93 (2)
C1—N5—C2	107.7 (4)	N5—C4—C7	108.5 (5)
C1—N5—C4	127.7 (5)	N5—C4—C6A	104.0 (19)
C1—N4—H4	121 (5)	N5—C2—H2	118 (4)
C3—N4—H4	128 (5)	C3—C2—H2	133 (4)
N1—C8—C9	122.4 (5)	N4—C3—H3	120 (4)
C8—C9—C10	120.1 (5)	C2—C3—H3	132 (4)
C9—C10—C11	119.5 (5)	C4—C5—H5A	109.00
C10—C11—C12	117.1 (5)	C4—C5—H5B	110.00
C12—C11—C13	119.2 (5)	C4—C5—H5C	110.00
C10—C11—C13	123.7 (5)	H5A—C5—H5B	109.00
N1—C12—C12ⁱ	117.6 (4)	H5A—C5—H5C	109.00
N1—C12—C11	123.0 (5)	H5B—C5—H5C	109.00
C11—C12—C12ⁱ	119.5 (4)	C4—C6—H6A	110.00
C11—C13—C13ⁱ	121.3 (6)	C4—C6—H6B	110.00
N2—C14—C15	123.5 (7)	C4—C6—H6C	109.00
C14—C15—C16	118.6 (8)	H6A—C6—H6B	109.00
C15—C16—C17	121.3 (6)	H6A—C6—H6C	109.00
C16—C17—C18	116.1 (6)	H6B—C6—H6C	109.00
C18—C17—C25ⁱ	118.7 (6)	C4—C6A—H6A2	110.00
C16—C17—C25ⁱ	125.2 (5)	C4—C6A—H6A3	110.00
N2—C18—C23ⁱ	117.6 (4)	H6A1—C6A—H6A2	109.00
N2—C18—C17	122.5 (6)	H6A1—C6A—H6A3	109.00
C17—C18—C23ⁱ	119.9 (6)	H6A2—C6A—H6A3	110.00
N3—C19—C20	122.1 (5)	C4—C6A—H6A1	109.00
C19—C20—C21	119.5 (7)	H7B—C7—H7C	109.00
C20—C21—C22	120.5 (8)	C4—C7—H7A	109.00
C21—C22—C23	117.0 (6)	C4—C7—H7B	109.00
C21—C22—C24	125.7 (8)	C4—C7—H7C	109.00
C23—C22—C24	117.3 (7)	H7A—C7—H7B	110.00
N3—C23—C18ⁱ	116.9 (6)	H7A—C7—H7C	110.00
C18ⁱ—C23—C22	120.3 (5)	N6—C26—C27	179.9 (12)
N3—C23—C22	122.8 (6)	C26—C27—H27A	109.00
C22—C24—C25	122.1 (8)	C26—C27—H27B	110.00
C17ⁱ—C25—C24	121.6 (6)	C26—C27—H27C	110.00
N1—C8—H8	119.00	H27A—C27—H27B	109.00
C9—C8—H8	119.00	H27A—C27—H27C	110.00
C10—C9—H9	120.00	H27B—C27—H27C	109.00

N2—Ni1—N1—C8	8.6 (6)	C1—N5—C2—C3	−0.6 (7)
N3—Ni1—N1—C8	−87.9 (6)	C4—N5—C2—C3	176.5 (5)
N1ⁱ—Ni1—N1—C8	−178.2 (6)	C2—N5—C1—N4	0.5 (6)
N3ⁱ—Ni1—N1—C8	88.2 (6)	C2—N5—C4—C7	−117.4 (7)
N2—Ni1—N1—C12	−173.1 (4)	C1—N5—C4—C7	59.2 (8)
N3—Ni1—N1—C12	90.3 (4)	C4—N5—C1—N4	−176.5 (5)
N1ⁱ—Ni1—N1—C12	0.1 (4)	C2—N5—C1—S1	−177.8 (4)
N3ⁱ—Ni1—N1—C12	−93.6 (4)	C2—N5—C4—C5	120.8 (7)
N1—Ni1—N2—C14	−92.3 (4)	C1—N5—C4—C6	−176.9 (11)
N3—Ni1—N2—C14	1.9 (4)	C2—N5—C4—C6	6.5 (12)
N2ⁱ—Ni1—N2—C14	81.7 (4)	N1—C8—C9—C10	0.5 (11)
N3ⁱ—Ni1—N2—C14	177.4 (4)	C8—C9—C10—C11	−1.8 (11)
N1—Ni1—N2—C18	84.0 (3)	C9—C10—C11—C12	1.4 (11)
N3—Ni1—N2—C18	178.2 (3)	C9—C10—C11—C13	−179.0 (7)
N2ⁱ—Ni1—N2—C18	−102.0 (3)	C12—C11—C13—C13ⁱ	−2.3 (11)
N3ⁱ—Ni1—N2—C18	−6.3 (3)	C10—C11—C12—N1	0.2 (10)
N1—Ni1—N3—C19	9.7 (5)	C13—C11—C12—C12ⁱ	0.9 (10)
N2—Ni1—N3—C19	−84.2 (5)	C10—C11—C12—C12ⁱ	−179.6 (6)
N1ⁱ—Ni1—N3—C19	89.7 (5)	C13—C11—C12—N1	−179.4 (6)
N2ⁱ—Ni1—N3—C19	−177.0 (5)	C10—C11—C13—C13ⁱ	178.1 (8)
N1—Ni1—N3—C23	−167.3 (3)	N1—C12—C12ⁱ—C11ⁱ	−180.0 (6)
N2—Ni1—N3—C23	98.9 (3)	C11—C12—C12ⁱ—N1ⁱ	−180.0 (6)
N1ⁱ—Ni1—N3—C23	−87.3 (3)	N1—C12—C12ⁱ—N1ⁱ	0.3 (8)
N2ⁱ—Ni1—N3—C23	6.1 (3)	C11—C12—C12ⁱ—C11ⁱ	−0.2 (9)
Cl3—Ni2—S1—C1	−81.0 (2)	C11—C13—C13ⁱ—C11ⁱ	3.1 (12)
Cl1—Ni2—S1—C1	169.56 (19)	N2—C14—C15—C16	−2.6 (9)
Cl2—Ni2—S1—C1	31.7 (2)	C14—C15—C16—C17	2.5 (10)
Ni2—S1—C1—N4	−3.1 (5)	C15—C16—C17—C25ⁱ	178.2 (6)
Ni2—S1—C1—N5	175.0 (4)	C15—C16—C17—C18	−0.4 (9)
Ni1—N1—C8—C9	179.3 (5)	C18—C17—C25ⁱ—C24ⁱ	1.8 (9)
C8—N1—C12—C12ⁱ	178.3 (6)	C16—C17—C25ⁱ—C24ⁱ	−176.8 (7)
Ni1—N1—C12—C11	−180.0 (5)	C16—C17—C18—C23ⁱ	177.6 (5)
C12—N1—C8—C9	1.1 (10)	C25ⁱ—C17—C18—N2	179.4 (5)
Ni1—N1—C12—C12ⁱ	−0.2 (6)	C25ⁱ—C17—C18—C23ⁱ	−1.1 (8)
C8—N1—C12—C11	−1.5 (9)	C16—C17—C18—N2	−1.9 (8)
Ni1—N2—C18—C23ⁱ	5.6 (5)	C17—C18—C23ⁱ—C22ⁱ	−0.5 (8)
C14—N2—C18—C17	2.0 (7)	N2—C18—C23ⁱ—N3ⁱ	−0.4 (7)
Ni1—N2—C18—C17	−174.8 (4)	C17—C18—C23ⁱ—N3ⁱ	−179.9 (5)
Ni1—N2—C14—C15	176.6 (4)	N2—C18—C23ⁱ—C22ⁱ	179.0 (5)
C14—N2—C18—C23ⁱ	−177.6 (4)	N3—C19—C20—C21	0.4 (10)
C18—N2—C14—C15	0.4 (7)	C19—C20—C21—C22	−1.8 (10)
Ni1—N3—C19—C20	−175.5 (4)	C20—C21—C22—C24	−179.1 (7)
C23—N3—C19—C20	1.3 (8)	C20—C21—C22—C23	1.4 (10)
C19—N3—C23—C22	−1.7 (8)	C24—C22—C23—C18ⁱ	1.5 (8)
Ni1—N3—C23—C18ⁱ	−5.0 (6)	C21—C22—C23—N3	0.4 (9)
C19—N3—C23—C18ⁱ	177.6 (5)	C24—C22—C23—N3	−179.2 (5)
Ni1—N3—C23—C22	175.6 (4)	C23—C22—C24—C25	−0.9 (10)
C3—N4—C1—N5	−0.3 (6)	C21—C22—C24—C25	179.6 (7)
C3—N4—C1—S1	178.2 (4)	C21—C22—C23—C18ⁱ	−179.0 (6)
C1—N4—C3—C2	−0.1 (7)	C22—C24—C25—C17ⁱ	−0.8 (11)
C4—N5—C1—S1	5.2 (8)	N5—C2—C3—N4	0.5 (7)
C1—N5—C4—C5	−62.7 (8)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···Cl2	0.85 (6)	2.37 (7)	3.178 (6)	160 (6)
C2—H2···Cl3ⁱⁱ	0.82 (7)	2.77 (7)	3.552 (8)	160 (4)
C5—H5C···S1	0.96	2.75	3.402 (9)	126
C7—H7A···S1	0.96	2.68	3.409 (8)	133
C10—H10···Cl3ⁱⁱⁱ	0.93	2.72	3.557 (7)	151
C25—H25···N6^iv	0.93	2.60	3.502 (9)	162

Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x+1/2, −y+3/2, −z+1; (iv) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₂H₈N₂)₃][NiCl₃(C₇H₁₂N₂S)]₂·2C₂H₃N
M_r	1324.04
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	22.8953 (15), 15.2934 (10), 19.9417 (19)
β (°)	123.543 (3)
V (Å³)	5819.7 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.36
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.737, 0.792
No. of measured, independent and observed [I > 2σ(I)] reflections	30921, 5178, 3346
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.157, 1.07
No. of reflections	5178
No. of parameters	370
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)	1.24, −0.55

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···Cl2	0.85 (6)	2.37 (7)	3.178 (6)	160 (6)
C2—H2···Cl3ⁱ	0.82 (7)	2.77 (7)	3.552 (8)	160 (4)
C5—H5C···S1	0.96	2.75	3.402 (9)	126
C7—H7A···S1	0.96	2.68	3.409 (8)	133
C10—H10···Cl3ⁱⁱ	0.93	2.72	3.557 (7)	151
C25—H25···N6ⁱⁱⁱ	0.93	2.60	3.502 (9)	162

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1/2, −y+3/2, −z+1; (iii) x−1/2, −y+1/2, z−1/2.

Acknowledgements

The authors thank the CSIR, New Delhi, for financial support.

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