metal-organic compounds
trans-Diamminedichloridobis(1H-imidazole-κN3)nickel(II)
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
The whole molecule of the title compound, [NiCl2(C3H4N2)2(NH3)2], is generated by inversion symmetry. The NiII 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
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Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell CrysAlis CCD; 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 and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536813016747/su2612sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813016747/su2612Isup2.hkl
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.
All the H atoms were fixed geometrically and allowed to ride on their parent N or C atoms: N-H = 0.86 and 0.89 Å for NH and NH3 H atoms, respectively, C—H = 0.93–0.97 Å; Uiso(H) = 1.5Ueq(C-methyl) and = 1.2Ueq(N,C) for other H atoms.
Knowledge of the detailed coordination behaviour of imidazoles and their limitation in the possible use in complexes with specific
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
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 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).
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).
Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell
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).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] |
[NiCl2(C3H4N2)2(NH3)2] | F(000) = 616 |
Mr = 299.82 | Dx = 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 |
Oxford Diffraction Xcalibur Eos diffractometer | 1338 independent reflections |
Radiation source: fine-focus sealed tube | 1137 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 15.9821 pixels mm-1 | θmax = 29.1°, θmin = 5.2° |
ω and φ scan | h = −8→12 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −10→10 |
Tmin = 0.369, Tmax = 0.421 | l = −21→15 |
4464 measured reflections |
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(Fo2) + (0.0565P)2 + 3.9561P] where P = (Fo2 + 2Fc2)/3 |
1338 reflections | (Δ/σ)max < 0.001 |
71 parameters | Δρmax = 0.76 e Å−3 |
0 restraints | Δρmin = −1.00 e Å−3 |
[NiCl2(C3H4N2)2(NH3)2] | V = 1133.09 (16) Å3 |
Mr = 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 |
Oxford Diffraction Xcalibur Eos diffractometer | 1338 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 1137 reflections with I > 2σ(I) |
Tmin = 0.369, Tmax = 0.421 | Rint = 0.017 |
4464 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.76 e Å−3 |
1338 reflections | Δρmin = −1.00 e Å−3 |
71 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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. |
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···Cl2iv | 0.89 | 2.37 | 3.210 (3) | 157 |
C4—H4···Cg1v | 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] |
Mr | 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) |
Tmin, Tmax | 0.369, 0.421 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4464, 1338, 1137 |
Rint | 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 |
Δρmax, Δρmin (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).
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···Cg1iv | 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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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).