cis-Bis[(4-nitro­phen­yl)cyanamido-κN 1]bis­(1,10-phenanthroline-κ2 N,N′)nickel(II) methanol monosolvate

Hossein Chiniforoshan; Mehdi Jazestani; Behrouz Notash

doi:10.1107/S1600536812009890

. 2012 Mar 14;68(Pt 4):m417–m418. doi: 10.1107/S1600536812009890

cis-Bis[(4-nitrophenyl)cyanamido-κN ¹]bis(1,10-phenanthroline-κ² N,N′)nickel(II) methanol monosolvate

Hossein Chiniforoshan ^a,^*, Mehdi Jazestani ^a, Behrouz Notash ^b

PMCID: PMC3343823 PMID: 22589797

Abstract

In the title compound, [Ni(C₇H₄N₃O₂)₂(C₁₂H₈N₂)₂]·CH₃OH, the Ni^II atom is six-coordinated in a distorted N₆ octahedral geometry and is chelated by two phenanthroline ligands and two phenylcyanamide groups which occupy cis positions. The (4-nitrophenyl)cyanamide anions act as monodentate ligands. There is one classical intermolecular O—H⋯N hydrogen bond and several C—H⋯O hydrogen bonds are also observed.

Related literature

For background to phenylcyanamide ligands and their complexes, see: Crutchley (2001 ▶). For mononuclear complexes of phenylcyanamide complexes, see: Letcher et al. (1993 ▶); Kim et al. (2002 ▶); Shen et al. (1999 ▶). For polynuclear complexes of phenylcyanamide ligands, see: Ainscough et al. (1991 ▶); Chiniforoshan et al. (2009 ▶, 2010 ▶, 2012 ▶); Escuer et al. (2004 ▶). For related structures, see: Wu et al. (2004 ▶); Cheng et al. (2002 ▶); Shen et al. (1999 ▶). For the preparation of 4-nitro-phenylcyanamide used in the synthesis of the title compound, see: Crutchley & Naklicki (1989 ▶).

Experimental

Crystal data

[Ni(C₇H₄N₃O₂)₂(C₁₂H₈N₂)₂]·CH₄O
M _r = 775.40
Triclinic,
a = 10.019 (2) Å
b = 11.307 (2) Å
c = 16.403 (3) Å
α = 103.54 (3)°
β = 92.96 (3)°
γ = 99.77 (3)°
V = 1772.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 298 K
0.25 × 0.20 × 0.10 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2005 ▶) T _min = 0.862, T _max = 0.938
19823 measured reflections
9512 independent reflections
6693 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.139
S = 1.06
9512 reflections
501 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812009890/bt5812sup1.cif

e-68-0m417-sup1.cif^{(31.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009890/bt5812Isup2.hkl

e-68-0m417-Isup2.hkl^{(465.2KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯N9ⁱ	0.91 (3)	1.98 (4)	2.883 (4)	174 (5)
C39—H39B⋯O4ⁱⁱ	0.96	2.55	3.435 (7)	153
C22—H22⋯O1ⁱⁱⁱ	0.93	2.57	3.469 (6)	162
C16—H16⋯O2^iv	0.93	2.45	3.312 (6)	154

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The authors acknowledge financial support from Isfahan University of Technology.

supplementary crystallographic information

Comment

Phenylcyanmide ligands (pcyd) can act as monodentate (Letcher et al., 1993; Kim et al., 2002; Shen et al., 1999) and also as bridging ligands (Crutchley, 2001). In the bridging mode, the cyanamido group (NCN) is coordinated in the end-to-end mode, forming polynuclear complexes (Chiniforoshan et al. 2009, 2010, 2012; Escuer et al., 2004; Ainscough et al., 1991).

Following our work with this family of ligands, we report here the synthesis and crystal structure of mononuclear [Ni(Phen)₂(4-NO₂-pcyd)₂].CH₃OH compound of (4-nitrophenyl)cyanamide ligand, Crutchley & Naklicki (1989). The asymmetric unit of the title compound is shown in Fig. 1. In the structure of the title compound, nickel(II) atom has a distorted octahedral geometry (Fig. 1). The coordination environment consist of four nitrogen atoms from two 1,10-phenanthroline ligand and two anionic 4-NO₂-phenylcyanamide ligands which occupy cis position. Bond lengths and angles are in the normal ranges reported for similar structures (Wu et al., 2004; Cheng et al., 2002; Shen et al., 1999). Crutchley (2001) has shown that the angle of a metal atom with the axial CN moiety ranges from 180° to 120°. These angles for the title compound are equal to 153.2 (2) and 150.6 (3)° for Ni(1)—N(5)—C(25) and Ni(1)—N(8)—C(32), respectively. There are several intermolecular O—H···N and C—H···O hydrogen bonds which play important role in the stabilization of crystal structure (Table 1 & Fig. 2).

Experimental

A solution of Ni(OAc)₂.4H₂O (0.24 gr, 0.1 mmol) in 25 ml of methanol was slowly added to methanolic solution (in 35 ml) of 4-nitrophenylcynamide (Crutchley & Naklicki, 1989) (0.32 gr, 0.2 mmol) and 1,10-phenanthroline (0.39 gr, 0.2 mmol). The mixture was stirred at ambient temperature and the yellow solid filtered after 5 h. The yellow crystals suitable for X-ray structure determination were obtained by dissolving this solid in DMF then diffused by methanol after 3 weeks.