Dichloridobis(phenanthridine-κN)zinc(II)

Zeinab Khoshtarkib; Amin Ebadi; Robabeh Alizadeh; Roya Ahmadi; Vahid Amani

doi:10.1107/S160053680901959X

. 2009 Jun 6;65(Pt 7):m739–m740. doi: 10.1107/S160053680901959X

Dichloridobis(phenanthridine-κN)zinc(II)

Zeinab Khoshtarkib ^a, Amin Ebadi ^b, Robabeh Alizadeh ^c,^*, Roya Ahmadi ^a, Vahid Amani ^a

PMCID: PMC2969295 PMID: 21582680

Abstract

In the molecule of the title compound, [ZnCl₂(C₁₃H₉N)₂], the Zn^II atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from two phenanthridine ligands and by two terminal Cl atoms. The dihedral angle between the planes of the phenanthridine ring systems is 69.92 (3)°. An intramolecular C—H⋯Cl interaction results in the formation of a planar five-membered ring, which is oriented at a dihedral angle of 8.32 (3)° with respect to the adjacent phenanthridine ring system. In the crystal structure, π–π contacts between the phenanthridine systems [centroid–centroid distances = 3.839 (2), 3.617 (1) and 3.682 (1) Å] may stabilize the structure. Two weak C—H⋯π interactions are also found.

Related literature

For related structures, see: Ahmadi et al. (2008 ▶); Çelik et al. (2004 ▶); Cui et al. (1998 ▶); Gruia et al. (2007 ▶); Khalighi et al. (2008 ▶); Khan & Tuck (1984 ▶); Khavasi et al. (2008 ▶); Kozhevnikov et al. (2006 ▶); Liu et al. (2004 ▶); Markowitz et al. (2006 ▶); Musie et al. (2004 ▶); Preston & Kennard (1969 ▶); Reimann et al. (1966 ▶); Shen et al. (2004 ▶); Steffen & Palenik (1977 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[ZnCl₂(C₁₃H₉N)₂]
M _r = 494.71
Monoclinic,
a = 16.193 (3) Å
b = 10.101 (2) Å
c = 14.491 (3) Å
β = 116.02 (3)°
V = 2130.0 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.42 mm⁻¹
T = 298 K
0.45 × 0.30 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.610, T _max = 0.740
16947 measured reflections
5732 independent reflections
4612 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.086
S = 1.09
5732 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901959X/hk2696sup1.cif

e-65-0m739-sup1.cif^{(22.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901959X/hk2696Isup2.hkl

e-65-0m739-Isup2.hkl^{(275KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cl1—Zn1	2.2234 (7)
Cl2—Zn1	2.2456 (7)
N1—Zn1	2.0785 (17)
N2—Zn1	2.0775 (17)

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N2—Zn1—N1	105.19 (7)
N2—Zn1—Cl1	108.18 (5)
N1—Zn1—Cl1	106.23 (5)
N2—Zn1—Cl2	113.54 (5)
N1—Zn1—Cl2	107.46 (6)
Cl1—Zn1—Cl2	115.49 (3)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl1	0.93	2.77	3.434 (3)	129
C17—H17⋯Cg6ⁱ	0.93	2.82	3.535 (3)	134
C24—H24⋯Cg5ⁱⁱ	0.93	2.81	3.508 (3)	132

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Symmetry codes: (i) Inline graphic ; (ii) . Cg5 and Cg6 are the centroids of the C15–C20 and C21–C26 rings, respectively.

Acknowledgments

We are grateful to Damghan University of Basic Sciences for financial support.

supplementary crystallographic information

Comment

There are several Zn^II complexes, with formula, [ZnCl₂(N)₂], such as [ZnCl₂(AMS)₂], (II) (Shen et al., 2004), [ZnCl₂(4-CNpy)₂], (III) (Steffen & Palenik, 1977), [ZnCl₂(pht)₂], (IV) (Çelik et al., 2004), [ZnCl₂(quin)₂], (V) (Cui et al., 1998), [ZnCl₂(quino)₂], (VI) (Markowitz et al., 2006) and [ZnCl₂(meim)₂], (VII) (Musie et al., 2004) [where AMS is 3-Amino-5-methylisoxazole, 4-CNpy is 4-cyanopyridine, pht is phthalazine, quin is quinoline, quino is quinoxaline and meim is 1-methylimidazole] have been synthesized and characterized by single-crystal X-ray diffraction methods.

There are also several Zn^II complexes, with formula, [ZnCl₂(N—N)], such as [ZnCl₂(bipy)], (VIII) (Khan & Tuck, 1984), [ZnCl₂(biim)], (IX) (Gruia et al., 2007), [ZnCl₂(phbipy)], (X) (Kozhevnikov et al., 2006), [ZnCl₂(phen)], (XI) (Reimann et al., 1966), [ZnCl₂(dmphen)], (XII) (Preston & Kennard, 1969), [ZnCl₂(dpdmbip)], (XIII) (Liu et al., 2004), [ZnCl₂(dm4bt)], (XIV) (Khavasi et al., 2008), [ZnCl₂(5,5'-dmbpy)], (XV) (Khalighi et al., 2008) and [ZnCl₂(6-mbipy)], (XVI) (Ahmadi et al., 2008) [where bipy is 2,2'-bipyridine, biim is 2,2'-biimidazole, phbipy is 5-phenyl-2,2'-bipyridine, phen is 1,10-phenanthroline, dmphen is 2,9-dimethyl-1,10-phenanthroline, dpdmbip is 4,4'-diphenyl-6,6'-dimethyl-2,2'-bipyrimidine, dm4bt is 2,2'-dimethyl-4,4'-bithiazole, 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine and 6-mbipy is 6-methyl-2,2'-bipyridine] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound, (I).

In the molecule of the title compound (Fig 1), Zn^II atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from two phenanthridine and two terminal Cl atoms (Table 1). The bond lengths (Allen et al., 1987) and angles are within normal ranges. Phenanthridine ring systems A (N1/C1-C13) and B (N2/C14-C26) are, of course, planar and the dihedral angle between them is A/B = 69.92 (3)°. Intramolecular C-H···Cl interaction (Table 2) results in the formation of a planar five-membered ring C (Zn1/Cl1/N1/C1/H1), which is oriented with respect to the adjacent phenanthridine ring system A at a dihedral angle of 8.32 (3)°.

In the crystal structure (Fig. 2), the π–π contacts between the phenanthridine rings, Cg2—Cg3ⁱ, Cg4—Cg6ⁱⁱ and Cg6—Cg6ⁱⁱ, [symmetry codes: (i) 1 - x, -y, -z, (ii) -x, -y, -z, where Cg2, Cg3, Cg4 and Cg6 are centroids of the rings (C2-C7), (C8-C13), (N2/C14/C15/C20/C21/C26) and (C21-C26), respectively] may stabilize the structure, with centroid-centroid distances of 3.839 (2), 3.617 (1) and 3.682 (1) Å, respectively. There also exist two weak C—H···π interactions (Table 2).

Experimental

For the preparation of the title compound, (I), a solution of phenanthridine (0.30 g, 1.66 mmol) in methanol (15 ml) was added to a solution of ZnCl₂ (0.11 g, 0.83 mmol) in acetonitrile (30 ml) and the resulting colorless solution was stirred for 30 min at 313 K, and then it was left to evaporate slowly at room temperature. After one week, colorless prismatic crystals of the title compound were isolated (yield; 0.31 g, 75.5%).