trans-Diamminedichloridobis(1H-imidazole-κN3)nickel(II)

Kannan, P.S.; Ganeshraja, A.S.; Rajkumar, K.; Anbalagan, K.; SubbiahPandi, A.

doi:10.1107/S1600536813016747

metal-organic compounds

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Volume 69| Part 7| July 2013| Page m410

https://doi.org/10.1107/S1600536813016747

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trans-Diamminedichloridobis(1H-imidazole-κN³)nickel(II)

Piskala Subburaman Kannan,^a Ayyakannu Sundaram Ganeshraja,^b Kanniah Rajkumar,^b Krishnamoorthy Anbalagan ^b and Arunachalatheva SubbiahPandi ^c,^a ^*

^aDepartment of Physics, S.M.K. Fomra Institute of Technology, Thaiyur, Chennai 603 103, India, ^bDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India, and ^cDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India
^*Correspondence e-mail: a_sp59@yahoo.in

(Received 11 June 2013; accepted 16 June 2013; online 22 June 2013)

The whole molecule of the title compound, [NiCl₂(C₃H₄N₂)₂(NH₃)₂], is generated by inversion symmetry. The Ni^II ion, which is located on an inversion center, has a distorted octahedral coordination environment and is surrounded by two ammine N atoms and two Cl atoms in the equatorial plane, with two N atoms of two imidazole groups occupying the axial positions. The imidazole ring makes a dihedral angle of 81.78 (18)° with the Ni/N/Cl equatorial plane. In the crystal, molecules are linked via N—H⋯Cl hydrogen bonds and C—H⋯π interactions, forming a three-dimensional network.

Related literature

For applications of imidazole and its derivatives, see: Huang et al. (2008 , 2011 ). For the biological activity of imidazole derivatives, see: Gaonkar et al. (2009 ).

Experimental

Crystal data

[NiCl₂(C₃H₄N₂)₂(NH₃)₂]
M_r = 299.82
Orthorhombic, P b c a
a = 9.1349 (9) Å
b = 7.9451 (5) Å
c = 15.6121 (13) Å
V = 1133.09 (16) Å³
Z = 4
Mo Kα radiation
μ = 2.16 mm⁻¹
T = 293 K
0.5 × 0.4 × 0.4 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.369, T_max = 0.421
4464 measured reflections
1338 independent reflections
1137 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.129
S = 1.11
1338 reflections
71 parameters
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −1.00 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N3/C4/N5/C6/C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯Cl2ⁱ	0.86	2.53	3.268 (3)	144
N8—H8A⋯Cl2ⁱⁱ	0.89	2.32	3.180 (3)	162
N8—H8B⋯Cl2ⁱⁱⁱ	0.89	2.37	3.210 (3)	157
C4—H4⋯Cg1^iv	0.93	2.95	3.772 (5)	148
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iv) $[-x-{\script{1\over 2}}, y-{\script{3\over 2}}, z]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813016747/su2612sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813016747/su2612Isup2.hkl

checkCIF report

Comment top

Knowledge of the detailed coordination behaviour of imidazoles and their limitation in the possible use in complexes with specific catalytic activity is of great current importance. Because of their multiple coordination modes imidazole, namely 1,3-diazacyclopenta- 2,4-diene, and its derivatives have found a wide range of applications in coordination chemistry and for the construction of novel metal–organic frameworks (Huang et al., 2008; Huang et al., 2011).

The chemistry of imidazole occupies an extremely important position within the family of five-membered heterocyclic compounds. Synthesis of imidazole derivatives has attracted great interest in recent years due to their broad spectrum of biological activities (Gaonkar et al., 2009). Herein we report on the crystal structure of the title compound.

The molecular structure of the title compound as illustrated in Fig. 1. The nickel(II) ion is located on an inversion center and has a distorted NiN4Cl2 octahedral coordination environment. It is surrounded by four N atoms, two of which are in the equatorial plane with the Cl atoms, and the remaining two N atoms occupy the axial positions. The imidazole ring (N3/N5/C4/C6/C7) is planar with a maximum deviation of -0.005 (1)Å for atom C4. It makes a dihedral angle of 81.78 (18) ° with the equatorial plane of atoms Ni/Cl2/N3/Cl2a/N3a [symmetry code: (a) -x, -y, -z+1].

In the crystal, molecules are linked via N-H···Cl hydrogen bonds and C-H···π interactions forming a three-dimensional network (Table 1 and Fig. 2).

Related literature top

For applications of imidazole and its derivatives, see: Huang et al. (2008, 2011). For the biological activity of imidazole derivatives, see: Gaonkar et al. (2009).

Experimental top

A total of 10 mL of a 0.01 M aqueous solution of NiCl₂ was slowly mixed with 20 mL of a 0.02 M ammonia solution. After 1 h, 20 mL of a 0.02 M aqueous solution of imidazole was added drop wise. The mixture was slowly evaporated at room temperature, and deep-green block-like crystals of the title complex were obtained within 5 days. The crystals were filtered, washed with water, and dried in a desiccator over P₄O₁₀.

Structure description top

In the crystal, molecules are linked via N-H···Cl hydrogen bonds and C-H···π interactions forming a three-dimensional network (Table 1 and Fig. 2).

For applications of imidazole and its derivatives, see: Huang et al. (2008, 2011). For the biological activity of imidazole derivatives, see: Gaonkar et al. (2009).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the c axis. Dashed lines show the N—H···Cl hydrogen bonds [see Table 1 for details]

trans-Diamminedichloridobis(1H-imidazole-κN³)nickel(II) top

Crystal data top

[NiCl₂(C₃H₄N₂)₂(NH₃)₂]	F(000) = 616
M_r = 299.82	D_x = 1.758 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1338 reflections
a = 9.1349 (9) Å	θ = 5.2–29.1°
b = 7.9451 (5) Å	µ = 2.16 mm⁻¹
c = 15.6121 (13) Å	T = 293 K
V = 1133.09 (16) Å³	Block, green
Z = 4	0.5 × 0.4 × 0.4 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1338 independent reflections
Radiation source: fine-focus sealed tube	1137 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 15.9821 pixels mm^-1	θ_max = 29.1°, θ_min = 5.2°
ω and φ scan	h = −8→12
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −10→10
T_min = 0.369, T_max = 0.421	l = −21→15
4464 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0565P)² + 3.9561P] where P = (F_o² + 2F_c²)/3
1338 reflections	(Δ/σ)_max < 0.001
71 parameters	Δρ_max = 0.76 e Å⁻³
0 restraints	Δρ_min = −1.00 e Å⁻³

Crystal data top

[NiCl₂(C₃H₄N₂)₂(NH₃)₂]	V = 1133.09 (16) Å³
M_r = 299.82	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 9.1349 (9) Å	µ = 2.16 mm⁻¹
b = 7.9451 (5) Å	T = 293 K
c = 15.6121 (13) Å	0.5 × 0.4 × 0.4 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1338 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1137 reflections with I > 2σ(I)
T_min = 0.369, T_max = 0.421	R_int = 0.017
4464 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.11	Δρ_max = 0.76 e Å⁻³
1338 reflections	Δρ_min = −1.00 e Å⁻³
71 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C4	0.1725 (5)	0.0044 (5)	0.3343 (3)	0.0331 (9)
H4	0.2329	−0.0824	0.3530	0.040*
C6	0.0749 (5)	0.1968 (6)	0.2518 (3)	0.0369 (9)
H6	0.0539	0.2659	0.2053	0.044*
C7	0.0103 (4)	0.1991 (5)	0.3298 (2)	0.0288 (8)
H7	−0.0643	0.2720	0.3462	0.035*
Cl2	−0.25211 (9)	−0.00290 (10)	0.44598 (5)	0.0227 (2)
N3	0.0715 (3)	0.0774 (4)	0.38102 (17)	0.0209 (6)
N5	0.1766 (4)	0.0725 (5)	0.2555 (2)	0.0372 (8)
H5	0.2338	0.0425	0.2145	0.045*
N8	−0.0253 (3)	0.2503 (3)	0.53954 (16)	0.0128 (5)
H8A	−0.0989	0.2973	0.5109	0.015*
H8B	0.0568	0.3070	0.5292	0.015*
H8C	−0.0446	0.2530	0.5954	0.015*
Ni1	0.0000	0.0000	0.5000	0.0150 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C4	0.031 (2)	0.041 (2)	0.0275 (19)	0.0049 (16)	0.0083 (16)	0.0018 (15)
C6	0.040 (2)	0.050 (2)	0.0203 (16)	−0.0078 (19)	0.0006 (16)	0.0116 (18)
C7	0.0277 (19)	0.035 (2)	0.0233 (17)	0.0025 (15)	0.0011 (14)	0.0094 (15)
Cl2	0.0183 (4)	0.0255 (4)	0.0242 (4)	−0.0017 (3)	−0.0041 (3)	0.0038 (3)
N3	0.0209 (14)	0.0267 (14)	0.0152 (12)	−0.0010 (11)	0.0022 (11)	0.0021 (11)
N5	0.0391 (19)	0.052 (2)	0.0206 (14)	−0.0066 (17)	0.0140 (14)	−0.0034 (15)
N8	0.0144 (11)	0.0118 (10)	0.0123 (10)	0.0009 (9)	−0.0010 (9)	−0.0004 (9)
Ni1	0.0151 (3)	0.0177 (3)	0.0123 (3)	0.00026 (19)	−0.00016 (19)	0.00066 (19)

Geometric parameters (Å, º) top

C4—N3	1.312 (5)	N3—Ni1	2.063 (3)
C4—N5	1.345 (5)	N5—H5	0.8600
C4—H4	0.9300	N8—Ni1	2.095 (2)
C6—C7	1.353 (6)	N8—H8A	0.8900
C6—N5	1.357 (6)	N8—H8B	0.8900
C6—H6	0.9300	N8—H8C	0.8900
C7—N3	1.374 (5)	Ni1—N3ⁱ	2.063 (3)
C7—H7	0.9300	Ni1—N8ⁱ	2.095 (2)
Cl2—Ni1	2.4527 (9)	Ni1—Cl2ⁱ	2.4527 (9)

N3—C4—N5	110.5 (4)	Ni1—N8—H8C	109.5
N3—C4—H4	124.7	H8A—N8—H8C	109.5
N5—C4—H4	124.7	H8B—N8—H8C	109.5
C7—C6—N5	105.7 (3)	N3ⁱ—Ni1—N3	180.0
C7—C6—H6	127.1	N3ⁱ—Ni1—N8	89.00 (11)
N5—C6—H6	127.1	N3—Ni1—N8	91.00 (11)
C6—C7—N3	109.7 (4)	N3ⁱ—Ni1—N8ⁱ	91.00 (11)
C6—C7—H7	125.2	N3—Ni1—N8ⁱ	89.00 (11)
N3—C7—H7	125.2	N8—Ni1—N8ⁱ	180.0
C4—N3—C7	105.9 (3)	N3ⁱ—Ni1—Cl2ⁱ	89.45 (8)
C4—N3—Ni1	126.3 (3)	N3—Ni1—Cl2ⁱ	90.55 (8)
C7—N3—Ni1	127.2 (2)	N8—Ni1—Cl2ⁱ	89.62 (7)
C4—N5—C6	108.2 (3)	N8ⁱ—Ni1—Cl2ⁱ	90.38 (7)
C4—N5—H5	125.9	N3ⁱ—Ni1—Cl2	90.55 (8)
C6—N5—H5	125.9	N3—Ni1—Cl2	89.45 (8)
Ni1—N8—H8A	109.5	N8—Ni1—Cl2	90.38 (7)
Ni1—N8—H8B	109.5	N8ⁱ—Ni1—Cl2	89.62 (7)
H8A—N8—H8B	109.5	Cl2ⁱ—Ni1—Cl2	180.0

N5—C6—C7—N3	−0.1 (5)	C4—N3—Ni1—N8	143.9 (3)
N5—C4—N3—C7	−0.9 (5)	C7—N3—Ni1—N8	−46.1 (3)
N5—C4—N3—Ni1	170.8 (3)	C4—N3—Ni1—N8ⁱ	−36.1 (3)
C6—C7—N3—C4	0.6 (5)	C7—N3—Ni1—N8ⁱ	133.9 (3)
C6—C7—N3—Ni1	−171.1 (3)	C4—N3—Ni1—Cl2ⁱ	54.3 (3)
N3—C4—N5—C6	0.9 (5)	C7—N3—Ni1—Cl2ⁱ	−135.7 (3)
C7—C6—N5—C4	−0.5 (5)	C4—N3—Ni1—Cl2	−125.7 (3)
C4—N3—Ni1—N3ⁱ	126 (8)	C7—N3—Ni1—Cl2	44.3 (3)
C7—N3—Ni1—N3ⁱ	−64 (8)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N3/C4/N5/C6/C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···Cl2ⁱⁱ	0.86	2.53	3.268 (3)	144
N8—H8A···Cl2ⁱⁱⁱ	0.89	2.32	3.180 (3)	162
N8—H8B···Cl2^iv	0.89	2.37	3.210 (3)	157
C4—H4···Cg1^v	0.93	2.95	3.772 (5)	148

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

Experimental details

Crystal data
Chemical formula	[NiCl₂(C₃H₄N₂)₂(NH₃)₂]
M_r	299.82
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	9.1349 (9), 7.9451 (5), 15.6121 (13)
V (Å³)	1133.09 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.16
Crystal size (mm)	0.5 × 0.4 × 0.4

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.369, 0.421
No. of measured, independent and observed [I > 2σ(I)] reflections	4464, 1338, 1137
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.129, 1.11
No. of reflections	1338
No. of parameters	71
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.76, −1.00

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N3/C4/N5/C6/C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···Cl2ⁱ	0.86	2.53	3.268 (3)	144
N8—H8A···Cl2ⁱⁱ	0.89	2.32	3.180 (3)	162
N8—H8B···Cl2ⁱⁱⁱ	0.89	2.37	3.210 (3)	157
C4—H4···Cg1^iv	0.93	2.95	3.772 (5)	148

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

Acknowledgements

ASP and PSK are grateful to the Department of Chemistry, Pondicherry University, for the single-crystal XRD instrumentation facility. KA thanks the CSIR, New Delhi (Lr: No. 01 (2570)/12/EMR-II/3.4.2012) for financial support through a major research project.

References

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Gaonkar, S. L., Rai, K. M. L. & Shetty, N. S. (2009). Med. Chem. Res. 18, 221–230. Web of Science CrossRef CAS Google Scholar
Huang, X.-F., Fu, D.-W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 1795–1797. Web of Science CSD CrossRef CAS Google Scholar
Huang, Z.-J., Tang, J.-N., Luo, Z.-R., Wang, D.-Y. & Wei, H. (2011). Acta Cryst. E67, m408. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page m410

https://doi.org/10.1107/S1600536813016747

Open

access