Dichlorido(5,5′-dimethyl-2,2′-bipyridine-κ2N,N′)zinc(II)

Khalighi, A.; Ahmadi, R.; Amani, V.; Khavasi, H.R.

doi:10.1107/S1600536808027104

Dichlorido(5,5′-dimethyl-2,2′-bipyridine-κ²N,N′)zinc(II)

A. Khalighi, R. Ahmadi, V. Amani and H. R. Khavasi

The asymmetric unit of the title compound, [ZnCl₂(C₁₂H₁₂N₂)], contains two independent molecules. The Zn^II atoms are four-coordinated in distorted tetrahedral configurations by two N atoms from 5,5′-dimethyl-2,2′-bipyridine and two terminal Cl atoms. In the crystal structure, intermolecular C—H

Cl hydrogen bonds link the molecules. There are C—H

π contacts between the methyl groups and the pyridine and five-membered rings containing Zn^II atoms; π–π contacts also exist between the pyridine rings [centroid–centroid distances = 3.665 (5) and 3.674 (5) Å].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808027104/hk2517sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808027104/hk2517Isup2.hkl Contains datablock I

CCDC reference: 702431

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.013 Å
R factor = 0.066
wR factor = 0.150
Data-to-parameter ratio = 23.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C20    --  C21     ..       5.36 su
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         13
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C12 H12 Cl2 N2 Zn
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C12 H12 Cl2 N2 Zn

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           29.30
           From the CIF: _reflns_number_total               7167
           Count of symmetry unique reflns         3846
           Completeness (_total/calc)            186.35%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      3321
           Fraction of Friedel pairs measured     0.863
           Are heavy atom types Z>Si present        yes
PLAT033_ALERT_4_G Flack Parameter Value Deviates from Zero .......       0.07

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

There are several Zn^II complexes, with formula, [ZnCl₂(N—N)], such as [ZnCl₂(bipy)], (II), (Khan & Tuck, 1984), [ZnCl₂(biim)], (III), (Gruia et al., 2007), [ZnCl₂(phbipy)], (IV), (Kozhevnikov et al., 2006), [ZnCl₂(phen)], (V), (Reimann et al., 1966), [ZnCl₂(dmphen)], (VI), (Preston & Kennard, 1969), [ZnCl₂(dpdmbip)], (VII), (Liu et al., 2004) and [ZnCl₂(dm4bt)], (VIII), (Khavasi et al., 2008) [where bipy is 2,2'-bipyridine, biim is 2,2'-biimidazole, phbipy is 5-phenyl-2,2'-bi- pyridine, phen is 1,10-phenanthroline, dmphen is 2,9-dimethyl-1,10-phenanthro- line, dpdmbip is 4,4'-diphenyl-6,6'-dimethyl-2,2'-bipyrimidine and dm4bt is 2,2'-dimethyl-4,4'-bithiazole] have been synthesized and characterized by single-crystal X-ray diffraction methods. There are also several Zn^II complexes, with formula, [ZnCl₂L₂], such as [ZnCl₂(py)₂], (IX), (Steffen & Palenik, 1976), [ZnCl₂(4-cypy)₂], (X), (Steffen & Palenik, 1977), [ZnCl₂(2-ampy)₂], (XI), (Qin et al., 1999) and [ZnCl₂(im)₂], (XII), (Lundberg, 1966), [where py is pyridine, 4-cypy is 4-cyanopyridine, 2-ampy is 2-aminopyridine and im is imidazole] 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).

The asymmetric unit of (I), (Fig. 1), contains two independent molecules. The Zn^II atoms are four-coordinated in distorted tetrahedral configurations (Table 1) by two N atoms from 5,5'-dimethyl-2,2'-bipyridine and two terminal Cl. The Zn-Cl and Zn-N bond lengths and angles (Table 1) are within normal ranges, as in (II), (V) and (VIII).

In the crystal structure, intermolecular C-H···Cl hydrogen bonds (Table 2) link the molecules, in which they may be effective in the stabilization of the structure. There also exist C—H···π contacts (Table 1) between the methyl groups and pyridine, (Zn1/N1/N2/C6/C7) and (Zn2/N3/N4/C18/C19) rings. The π—π contacts between the pyridine rings, Cg3···Cg6ⁱ and Cg4···Cg5ⁱⁱ [symmetry codes: (i) x, y, z; (ii) x, 1 + y, z, where Cg3, Cg4, Cg5 and Cg6 are centroids of the rings (N1/C1/C2/C4-C6), (N2/C7-C10/C12), (N3/C13/C14/C16-C18) and (N4/C19-C22/C24), respectively] further stabilize the structure, with centroid-centroid distances of 3.665 (5) and 3.674 (5) Å, respectively.

Related literature top

For related literature, see: Gruia et al. (2007); Khan & Tuck (1984); Khavasi et al. (2008); Kozhevnikov et al. (2006); Liu et al. (2004); Lundberg (1966); Preston & Kennard (1969); Qin et al. (1999); Reimann et al. (1966); Steffen & Palenik (1976, 1977).

Experimental top

For the preparation of the title compound, a solution of 5,5'-dimethyl-2,2' -bipyridine (0.25 g, 1.33 mmol) in methanol (100 ml) was added to a solution of ZnCl₂ (0.18 g, 1.33 mmol) in methanol (100 ml) and the resulting colorless solution was stirred for 5 min at room temperature, and then left to evaporate slowly at room temperature. After one week, colorless block crystals of the title compound were isolated (yield; 0.32 g, 73.4%, m.p. < 573 K).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A packing diagram of the title compound.

Dichlorido(5,5'-dimethyl-2,2'-bipyridine-κ²N,N')zinc(II) top

Crystal data top

[ZnCl₂(C₁₂H₁₂N₂)]	F(000) = 1296
M_r = 320.53	D_x = 1.569 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2610 reflections
a = 16.267 (2) Å	θ = 2.2–29.3°
b = 11.1704 (16) Å	µ = 2.18 mm⁻¹
c = 14.9328 (14) Å	T = 298 K
V = 2713.4 (6) Å³	Block, colorless
Z = 8	0.28 × 0.20 × 0.07 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	7167 independent reflections
Radiation source: fine-focus sealed tube	4463 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ϕ and ω scans	θ_max = 29.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −22→13
T_min = 0.612, T_max = 0.860	k = −13→15
14309 measured reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.066	H-atom parameters constrained
wR(F²) = 0.150	w = 1/[σ²(F_o²) + (0.0545P)² + 2.0209P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.045
7167 reflections	Δρ_max = 0.29 e Å⁻³
307 parameters	Δρ_min = −0.30 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 3320 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (3)

Crystal data top

[ZnCl₂(C₁₂H₁₂N₂)]	V = 2713.4 (6) Å³
M_r = 320.53	Z = 8
Orthorhombic, Pna2₁	Mo Kα radiation
a = 16.267 (2) Å	µ = 2.18 mm⁻¹
b = 11.1704 (16) Å	T = 298 K
c = 14.9328 (14) Å	0.28 × 0.20 × 0.07 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	7167 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	4463 reflections with I > 2σ(I)
T_min = 0.612, T_max = 0.860	R_int = 0.066
14309 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	H-atom parameters constrained
wR(F²) = 0.150	Δρ_max = 0.29 e Å⁻³
S = 1.08	Δρ_min = −0.30 e Å⁻³
7167 reflections	Absolute structure: Flack (1983), 3320 Friedel pairs
307 parameters	Absolute structure parameter: 0.07 (3)
1 restraint

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
Zn1	−0.27268 (5)	−0.87606 (8)	−0.43784 (5)	0.0530 (4)
Zn2	−0.77530 (5)	−1.11325 (7)	−0.47118 (5)	0.0521 (3)
Cl1	−0.33658 (15)	−0.9839 (2)	−0.33543 (19)	0.0872 (8)
Cl2	−0.35350 (12)	−0.7899 (2)	−0.53825 (16)	0.0671 (6)
Cl3	−0.84859 (13)	−1.0208 (2)	−0.36748 (16)	0.0644 (6)
Cl4	−0.84271 (14)	−1.2264 (2)	−0.56774 (19)	0.0823 (8)
N1	−0.1798 (4)	−0.7734 (5)	−0.3840 (4)	0.0508 (16)
N2	−0.1730 (4)	−0.9564 (5)	−0.4975 (4)	0.0508 (15)
N3	−0.6710 (4)	−1.1912 (5)	−0.4188 (4)	0.0521 (14)
N4	−0.6855 (4)	−1.0095 (6)	−0.5312 (5)	0.0503 (15)
C1	−0.1882 (5)	−0.6828 (7)	−0.3260 (5)	0.0541 (18)
H1	−0.2408	−0.6608	−0.3081	0.065*
C2	−0.1206 (6)	−0.6198 (7)	−0.2909 (6)	0.060 (2)
C3	−0.1361 (7)	−0.5168 (8)	−0.2285 (6)	0.089 (3)
H3A	−0.1689	−0.4576	−0.2584	0.107*
H3B	−0.0846	−0.4819	−0.2108	0.107*
H3C	−0.1648	−0.5449	−0.1764	0.107*
C4	−0.0441 (6)	−0.6540 (9)	−0.3175 (6)	0.071 (2)
H4	0.0018	−0.6146	−0.2949	0.085*
C5	−0.0340 (5)	−0.7457 (9)	−0.3773 (6)	0.062 (2)
H5	0.0183	−0.7674	−0.3963	0.075*
C6	−0.1031 (5)	−0.8063 (7)	−0.4095 (5)	0.0524 (19)
C7	−0.1007 (4)	−0.9082 (7)	−0.4741 (6)	0.0459 (17)
C8	−0.0275 (5)	−0.9510 (8)	−0.5090 (5)	0.061 (2)
H8	0.0226	−0.9168	−0.4930	0.073*
C9	−0.0309 (5)	−1.0467 (9)	−0.5686 (6)	0.069 (3)
H9	0.0177	−1.0773	−0.5921	0.082*
C10	−0.1045 (7)	−1.0967 (8)	−0.5934 (6)	0.062 (3)
C11	−0.1117 (7)	−1.1986 (8)	−0.6598 (6)	0.082 (3)
H11A	−0.1368	−1.2664	−0.6311	0.098*
H11B	−0.0579	−1.2202	−0.6807	0.098*
H11C	−0.1449	−1.1739	−0.7096	0.098*
C12	−0.1746 (5)	−1.0486 (7)	−0.5547 (6)	0.057 (2)
H12	−0.2252	−1.0820	−0.5694	0.068*
C13	−0.6682 (5)	−1.2826 (7)	−0.3606 (6)	0.059 (2)
H13	−0.7178	−1.3166	−0.3429	0.071*
C14	−0.5966 (6)	−1.3302 (9)	−0.3250 (6)	0.067 (2)
C15	−0.5985 (7)	−1.4306 (9)	−0.2602 (6)	0.089 (3)
H15A	−0.6285	−1.4068	−0.2078	0.107*
H15B	−0.5434	−1.4516	−0.2438	0.107*
H15C	−0.6251	−1.4985	−0.2871	0.107*
C16	−0.5243 (6)	−1.2783 (9)	−0.3560 (7)	0.074 (3)
H16	−0.4741	−1.3087	−0.3370	0.089*
C17	−0.5255 (5)	−1.1830 (9)	−0.4141 (6)	0.074 (2)
H17	−0.4765	−1.1473	−0.4322	0.089*
C18	−0.6005 (5)	−1.1398 (8)	−0.4458 (7)	0.0552 (19)
C19	−0.6087 (4)	−1.0390 (7)	−0.5074 (5)	0.0501 (17)
C20	−0.5433 (5)	−0.9743 (9)	−0.5441 (7)	0.072 (3)
H20	−0.4894	−0.9962	−0.5310	0.086*
C21	−0.5580 (6)	−0.8791 (8)	−0.5990 (5)	0.069 (2)
H21	−0.5140	−0.8339	−0.6199	0.083*
C22	−0.6369 (6)	−0.8486 (7)	−0.6240 (5)	0.0578 (19)
C23	−0.6548 (6)	−0.7477 (8)	−0.6847 (6)	0.080 (3)
H23A	−0.6848	−0.7765	−0.7357	0.096*
H23B	−0.6042	−0.7120	−0.7042	0.096*
H23C	−0.6871	−0.6891	−0.6536	0.096*
C24	−0.6992 (5)	−0.9174 (7)	−0.5874 (5)	0.0572 (18)
H24	−0.7533	−0.8990	−0.6023	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0310 (4)	0.0557 (5)	0.0721 (10)	−0.0013 (4)	0.0036 (4)	0.0035 (4)
Zn2	0.0336 (4)	0.0550 (5)	0.0678 (9)	0.0005 (4)	−0.0026 (4)	−0.0006 (4)
Cl1	0.0615 (14)	0.0871 (16)	0.113 (2)	0.0035 (12)	0.0292 (13)	0.0328 (14)
Cl2	0.0426 (10)	0.0783 (13)	0.0805 (15)	0.0030 (9)	−0.0096 (9)	0.0048 (11)
Cl3	0.0490 (11)	0.0682 (12)	0.0759 (14)	−0.0025 (9)	0.0060 (9)	−0.0081 (10)
Cl4	0.0550 (13)	0.0829 (15)	0.109 (2)	0.0089 (11)	−0.0215 (12)	−0.0355 (14)
N1	0.038 (3)	0.049 (3)	0.065 (4)	−0.002 (3)	−0.007 (3)	0.012 (3)
N2	0.037 (3)	0.047 (3)	0.069 (4)	−0.003 (3)	0.011 (3)	0.009 (3)
N3	0.041 (3)	0.057 (3)	0.058 (4)	−0.001 (3)	−0.001 (3)	−0.011 (3)
N4	0.034 (3)	0.063 (4)	0.055 (4)	−0.002 (3)	0.003 (3)	−0.008 (3)
C1	0.045 (4)	0.057 (4)	0.061 (4)	−0.002 (3)	−0.008 (3)	0.002 (3)
C2	0.065 (5)	0.062 (5)	0.053 (5)	−0.006 (4)	−0.016 (4)	0.013 (4)
C3	0.135 (10)	0.068 (6)	0.066 (6)	−0.018 (6)	−0.023 (6)	0.001 (4)
C4	0.067 (6)	0.080 (6)	0.066 (5)	−0.028 (5)	−0.016 (4)	0.006 (5)
C5	0.035 (4)	0.088 (6)	0.063 (5)	−0.004 (4)	−0.002 (3)	0.010 (5)
C6	0.046 (4)	0.058 (4)	0.054 (4)	−0.010 (3)	−0.005 (3)	0.021 (3)
C7	0.027 (3)	0.056 (4)	0.055 (5)	0.003 (3)	0.007 (3)	0.017 (4)
C8	0.046 (4)	0.073 (5)	0.065 (5)	0.012 (4)	0.008 (3)	0.014 (4)
C9	0.051 (5)	0.093 (7)	0.062 (5)	0.025 (5)	0.021 (4)	0.027 (5)
C10	0.081 (7)	0.057 (4)	0.048 (5)	0.023 (5)	0.013 (4)	0.022 (4)
C11	0.102 (8)	0.073 (6)	0.071 (6)	0.026 (5)	0.017 (5)	0.005 (5)
C12	0.041 (4)	0.059 (5)	0.071 (5)	−0.002 (3)	0.000 (3)	0.017 (4)
C13	0.058 (5)	0.056 (5)	0.064 (5)	0.001 (4)	−0.009 (4)	−0.008 (4)
C14	0.069 (6)	0.070 (5)	0.061 (5)	0.029 (5)	−0.013 (4)	−0.019 (4)
C15	0.112 (9)	0.082 (7)	0.073 (6)	0.028 (6)	−0.029 (6)	−0.006 (5)
C16	0.052 (5)	0.093 (7)	0.078 (6)	0.032 (5)	−0.014 (4)	−0.013 (5)
C17	0.037 (4)	0.098 (7)	0.089 (6)	0.006 (4)	−0.012 (4)	−0.016 (5)
C18	0.048 (4)	0.059 (4)	0.058 (5)	0.008 (4)	0.010 (4)	−0.020 (4)
C19	0.033 (3)	0.068 (4)	0.049 (4)	0.001 (3)	0.002 (3)	−0.018 (3)
C20	0.039 (4)	0.098 (7)	0.078 (6)	−0.011 (4)	0.005 (4)	−0.032 (5)
C21	0.078 (6)	0.076 (6)	0.053 (5)	−0.021 (5)	0.005 (4)	−0.006 (4)
C22	0.077 (6)	0.054 (4)	0.042 (4)	−0.005 (4)	0.008 (3)	−0.008 (3)
C23	0.093 (7)	0.076 (6)	0.071 (6)	−0.018 (5)	0.013 (5)	−0.007 (5)
C24	0.050 (4)	0.066 (5)	0.055 (4)	0.005 (4)	0.002 (3)	−0.002 (4)

Geometric parameters (Å, º) top

Zn1—Cl1	2.206 (2)	C11—H11B	0.9600
Zn1—Cl2	2.215 (2)	C11—H11C	0.9600
Zn2—Cl3	2.211 (2)	C12—N2	1.338 (10)
Zn2—Cl4	2.207 (3)	C12—H12	0.9300
Zn1—N1	2.058 (6)	C13—N3	1.341 (10)
Zn1—N2	2.057 (6)	C13—C14	1.386 (11)
Zn2—N3	2.063 (6)	C13—H13	0.9300
Zn2—N4	2.066 (6)	C14—C16	1.389 (13)
C1—N1	1.339 (10)	C14—C15	1.482 (13)
C1—C2	1.406 (12)	C15—H15A	0.9600
C1—H1	0.9300	C15—H15B	0.9600
C2—C4	1.362 (14)	C15—H15C	0.9600
C2—C3	1.502 (12)	C16—C17	1.374 (13)
C3—H3A	0.9600	C16—H16	0.9300
C3—H3B	0.9600	C17—C18	1.397 (11)
C3—H3C	0.9600	C17—H17	0.9300
C4—C5	1.369 (13)	C18—N3	1.343 (10)
C4—H4	0.9300	C18—C19	1.460 (12)
C5—C6	1.396 (11)	C19—N4	1.341 (9)
C5—H5	0.9300	C19—C20	1.397 (11)
C6—N1	1.357 (10)	C20—C21	1.364 (13)
C6—C7	1.491 (11)	C20—H20	0.9300
C7—N2	1.339 (9)	C21—C22	1.379 (14)
C7—C8	1.387 (10)	C21—H21	0.9300
C8—C9	1.392 (12)	C22—C24	1.384 (12)
C8—H8	0.9300	C22—C23	1.476 (12)
C9—C10	1.372 (14)	C23—H23A	0.9600
C9—H9	0.9300	C23—H23B	0.9600
C10—C12	1.386 (13)	C23—H23C	0.9600
C10—C11	1.514 (13)	C24—N4	1.348 (10)
C11—H11A	0.9600	C24—H24	0.9300

N1—Zn1—N2	80.5 (2)	N3—C13—C14	124.8 (8)
N1—Zn1—Cl1	112.2 (2)	N3—C13—H13	117.6
N1—Zn1—Cl2	117.23 (18)	C14—C13—H13	117.6
N2—Zn1—Cl1	115.64 (18)	C13—C14—C16	115.0 (9)
N2—Zn1—Cl2	111.4 (2)	C13—C14—C15	121.6 (9)
Cl1—Zn1—Cl2	115.28 (10)	C16—C14—C15	123.4 (9)
N3—Zn2—N4	79.7 (3)	C14—C15—H15A	109.4
N3—Zn2—Cl3	112.09 (18)	C14—C15—H15B	109.5
N3—Zn2—Cl4	114.47 (17)	H15A—C15—H15B	109.5
N4—Zn2—Cl4	112.8 (2)	C14—C15—H15C	109.5
N4—Zn2—Cl3	115.01 (18)	H15A—C15—H15C	109.5
Cl4—Zn2—Cl3	117.19 (9)	H15B—C15—H15C	109.5
N1—C1—C2	122.6 (8)	C17—C16—C14	121.4 (8)
N1—C1—H1	118.7	C17—C16—H16	119.3
C2—C1—H1	118.7	C14—C16—H16	119.3
C4—C2—C1	117.7 (8)	C16—C17—C18	119.6 (9)
C4—C2—C3	123.4 (9)	C16—C17—H17	120.2
C1—C2—C3	118.9 (9)	C18—C17—H17	120.2
C2—C3—H3A	109.5	N3—C18—C17	119.7 (9)
C2—C3—H3B	109.5	N3—C18—C19	116.2 (7)
H3A—C3—H3B	109.5	C17—C18—C19	124.1 (8)
C2—C3—H3C	109.5	N4—C19—C20	118.6 (8)
H3A—C3—H3C	109.5	N4—C19—C18	116.2 (7)
H3B—C3—H3C	109.5	C20—C19—C18	125.2 (8)
C2—C4—C5	120.8 (8)	C21—C20—C19	120.3 (9)
C2—C4—H4	119.6	C21—C20—H20	119.9
C5—C4—H4	119.6	C19—C20—H20	119.9
C4—C5—C6	119.4 (8)	C20—C21—C22	121.4 (9)
C4—C5—H5	120.3	C20—C21—H21	119.3
C6—C5—H5	120.3	C22—C21—H21	119.3
N1—C6—C5	120.8 (8)	C21—C22—C24	115.9 (8)
N1—C6—C7	114.4 (7)	C21—C22—C23	122.7 (9)
C5—C6—C7	124.8 (8)	C24—C22—C23	121.3 (9)
N2—C7—C8	121.1 (8)	C22—C23—H23A	109.5
N2—C7—C6	116.9 (7)	C22—C23—H23B	109.5
C8—C7—C6	122.0 (8)	H23A—C23—H23B	109.5
C7—C8—C9	118.2 (8)	C22—C23—H23C	109.5
C7—C8—H8	120.9	H23A—C23—H23C	109.5
C9—C8—H8	120.9	H23B—C23—H23C	109.5
C10—C9—C8	121.3 (8)	N4—C24—C22	123.2 (8)
C10—C9—H9	119.4	N4—C24—H24	118.4
C8—C9—H9	119.4	C22—C24—H24	118.4
C9—C10—C12	116.6 (9)	C1—N1—C6	118.8 (7)
C9—C10—C11	123.3 (9)	C1—N1—Zn1	126.7 (5)
C12—C10—C11	120.2 (10)	C6—N1—Zn1	114.5 (5)
C10—C11—H11A	109.4	C12—N2—C7	119.4 (7)
C10—C11—H11B	109.5	C12—N2—Zn1	126.8 (5)
H11A—C11—H11B	109.5	C7—N2—Zn1	113.8 (5)
C10—C11—H11C	109.5	C13—N3—C18	119.4 (7)
H11A—C11—H11C	109.5	C13—N3—Zn2	126.6 (5)
H11B—C11—H11C	109.5	C18—N3—Zn2	114.0 (6)
N2—C12—C10	123.4 (8)	C19—N4—C24	120.5 (7)
N2—C12—H12	118.3	C19—N4—Zn2	114.0 (5)
C10—C12—H12	118.3	C24—N4—Zn2	125.5 (5)

N1—C1—C2—C4	−0.3 (13)	N2—Zn1—N1—C1	−179.1 (6)
N1—C1—C2—C3	177.9 (7)	Cl1—Zn1—N1—C1	−65.2 (7)
C1—C2—C4—C5	0.8 (13)	Cl2—Zn1—N1—C1	71.6 (7)
C3—C2—C4—C5	−177.4 (9)	N2—Zn1—N1—C6	−1.4 (5)
C2—C4—C5—C6	−1.5 (14)	Cl1—Zn1—N1—C6	112.5 (5)
C4—C5—C6—N1	1.7 (12)	Cl2—Zn1—N1—C6	−110.7 (5)
C4—C5—C6—C7	−179.5 (8)	C10—C12—N2—C7	−1.2 (12)
N1—C6—C7—N2	−1.5 (9)	C10—C12—N2—Zn1	178.9 (6)
C5—C6—C7—N2	179.6 (8)	C8—C7—N2—C12	0.8 (12)
N1—C6—C7—C8	178.1 (7)	C6—C7—N2—C12	−179.6 (6)
C5—C6—C7—C8	−0.8 (11)	C8—C7—N2—Zn1	−179.3 (6)
N2—C7—C8—C9	−0.6 (12)	C6—C7—N2—Zn1	0.3 (9)
C6—C7—C8—C9	179.8 (7)	N1—Zn1—N2—C12	−179.6 (7)
C7—C8—C9—C10	0.8 (13)	Cl1—Zn1—N2—C12	70.3 (7)
C8—C9—C10—C12	−1.2 (12)	Cl2—Zn1—N2—C12	−64.0 (7)
C8—C9—C10—C11	178.3 (8)	N1—Zn1—N2—C7	0.5 (6)
C9—C10—C12—N2	1.4 (12)	Cl1—Zn1—N2—C7	−109.6 (5)
C11—C10—C12—N2	−178.1 (8)	Cl2—Zn1—N2—C7	116.2 (6)
N3—C13—C14—C16	−1.8 (12)	C14—C13—N3—C18	−0.1 (12)
N3—C13—C14—C15	179.3 (8)	C14—C13—N3—Zn2	−178.1 (6)
C13—C14—C16—C17	3.1 (13)	C17—C18—N3—C13	0.8 (13)
C15—C14—C16—C17	−178.1 (9)	C19—C18—N3—C13	−178.5 (7)
C14—C16—C17—C18	−2.6 (15)	C17—C18—N3—Zn2	179.0 (7)
C16—C17—C18—N3	0.5 (15)	C19—C18—N3—Zn2	−0.3 (10)
C16—C17—C18—C19	179.8 (8)	N4—Zn2—N3—C13	178.9 (7)
N3—C18—C19—N4	−0.8 (11)	Cl4—Zn2—N3—C13	−70.6 (7)
C17—C18—C19—N4	179.9 (8)	Cl3—Zn2—N3—C13	66.0 (6)
N3—C18—C19—C20	−179.3 (7)	N4—Zn2—N3—C18	0.8 (6)
C17—C18—C19—C20	1.4 (14)	Cl4—Zn2—N3—C18	111.3 (6)
N4—C19—C20—C21	3.6 (12)	Cl3—Zn2—N3—C18	−112.1 (6)
C18—C19—C20—C21	−178.0 (8)	C20—C19—N4—C24	−1.7 (10)
C19—C20—C21—C22	−4.0 (13)	C18—C19—N4—C24	179.7 (7)
C20—C21—C22—C24	2.4 (12)	C20—C19—N4—Zn2	−179.9 (6)
C20—C21—C22—C23	−178.8 (8)	C18—C19—N4—Zn2	1.5 (8)
C21—C22—C24—N4	−0.5 (11)	C22—C24—N4—C19	0.3 (11)
C23—C22—C24—N4	−179.4 (7)	C22—C24—N4—Zn2	178.3 (5)
C2—C1—N1—C6	0.5 (11)	N3—Zn2—N4—C19	−1.3 (5)
C2—C1—N1—Zn1	178.2 (6)	Cl4—Zn2—N4—C19	−113.6 (5)
C5—C6—N1—C1	−1.2 (10)	Cl3—Zn2—N4—C19	108.4 (5)
C7—C6—N1—C1	179.8 (6)	N3—Zn2—N4—C24	−179.4 (6)
C5—C6—N1—Zn1	−179.1 (6)	Cl4—Zn2—N4—C24	68.3 (6)
C7—C6—N1—Zn1	1.9 (7)	Cl3—Zn2—N4—C24	−69.7 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl3ⁱ	0.93	2.82	3.516 (8)	132
C16—H16···Cl3ⁱⁱ	0.93	2.83	3.638 (10)	146
C3—H3A···Cg5	0.96	3.10	3.719 (6)	124
C11—H11A···Cg2ⁱⁱⁱ	0.96	2.83	3.688 (5)	150
C15—H15C···Cg1^iv	0.96	2.84	3.704 (6)	150
C23—H23C···Cg4	0.96	3.11	3.690 (6)	120

Symmetry codes: (i) x+1/2, −y−3/2, z; (ii) x+1/2, −y−5/2, z; (iii) x, y+1, z; (iv) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₂H₁₂N₂)]
M_r	320.53
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	298
a, b, c (Å)	16.267 (2), 11.1704 (16), 14.9328 (14)
V (Å³)	2713.4 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.18
Crystal size (mm)	0.28 × 0.20 × 0.07

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.612, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	14309, 7167, 4463
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.689

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.150, 1.08
No. of reflections	7167
No. of parameters	307
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.30
Absolute structure	Flack (1983), 3320 Friedel pairs
Absolute structure parameter	0.07 (3)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Zn1—Cl1	2.206 (2)	Zn1—N1	2.058 (6)
Zn1—Cl2	2.215 (2)	Zn1—N2	2.057 (6)
Zn2—Cl3	2.211 (2)	Zn2—N3	2.063 (6)
Zn2—Cl4	2.207 (3)	Zn2—N4	2.066 (6)

N1—Zn1—N2	80.5 (2)	N3—Zn2—N4	79.7 (3)
N1—Zn1—Cl1	112.2 (2)	N3—Zn2—Cl3	112.09 (18)
N1—Zn1—Cl2	117.23 (18)	N3—Zn2—Cl4	114.47 (17)
N2—Zn1—Cl1	115.64 (18)	N4—Zn2—Cl4	112.8 (2)
N2—Zn1—Cl2	111.4 (2)	N4—Zn2—Cl3	115.01 (18)
Cl1—Zn1—Cl2	115.28 (10)	Cl4—Zn2—Cl3	117.19 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl3ⁱ	0.93	2.82	3.516 (8)	132.00
C16—H16···Cl3ⁱⁱ	0.93	2.83	3.638 (10)	146.00
C3—H3A···Cg5	0.96	3.10	3.719 (6)	123.79
C11—H11A···Cg2ⁱⁱⁱ	0.96	2.83	3.688 (5)	149.98
C15—H15C···Cg1^iv	0.96	2.84	3.704 (6)	150.43
C23—H23C···Cg4	0.96	3.11	3.690 (6)	120.16

Symmetry codes: (i) x+1/2, −y−3/2, z; (ii) x+1/2, −y−5/2, z; (iii) x, y+1, z; (iv) x, y−1, z.

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