Dichloridobis(3-chloro­pyridine-κN)zinc

Liu, Y.-H.; Xu, L.; Dai, D.-M.; Zou, J.-W.

doi:10.1107/S1600536811020447

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m915

doi:10.1107/S1600536811020447

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Dichloridobis(3-chloropyridine-κN)zinc

Yan-Hui Liu,^a Lin Xu,^b Dong-Mei Dai ^c and Jian-Wei Zou ^c ^*

^aDepartment of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang 310027, People's Republic of China, ^bDepartment of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China, and ^cNingbo Institute of Technology, Zhejiang University, Ningbo, Zhejiang 315100, People's Republic of China
^*Correspondence e-mail: jwzou@nit.zju.edu.cn

(Received 11 May 2011; accepted 28 May 2011; online 11 June 2011)

In the crystal structure of the title compound, [ZnCl₂(C₅H₄ClN)₂], discrete complex molecules are found in which the Zn^II cations are coordinated by two chloride anions and the N atoms of the two 3-chloropyridine ligands within a slightly distorted tetrahedron. Moreover, intermolecular C—Cl⋯Cl—C halogen interactions (Cl⋯Cl = 3.442 Å) are found between the building blocks.

Related literature

For the background of this work, see: Bertani et al. (2010 ); Metrangolo & Resnati (2001 ); Leininger et al. (2000 ); Lommerse et al. (1996 ). For related structures, see: Bhosekar et al. (2008 ); Wriedt et al. (2009 ).

Experimental

Crystal data

[ZnCl₂(C₅H₄ClN)₂]
M_r = 363.35
Triclinic, $[P \overline 1]$
a = 7.3429 (15) Å
b = 7.9220 (16) Å
c = 13.259 (3) Å
α = 95.17 (3)°
β = 91.14 (3)°
γ = 117.37 (3)°
V = 680.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.57 mm⁻¹
T = 298 K
0.44 × 0.42 × 0.19 mm

Data collection

Siemens CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.398, T_max = 0.641
5839 measured reflections
2640 independent reflections
2066 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.147
S = 1.16
2640 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −1.24 e Å⁻³

Data collection: XSCANS (Siemens, 1994 ); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020447/nc2231sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020447/nc2231Isup2.hkl

checkCIF report

Comment top

Halogen interactions as one weak noncovalent interaction, is of importance in e.g. crystal engineering and molecular recognition processes (Metrangolo & Resnati, 2001). Such interactions are widely found in various organometallic coordination compounds like e.g. in coordination compounds built up on multidentate ligands with pyridine groups which generate networks with a variety of special functions ( Leininger et al., 2000 and Bertani et al., 2010).

As a part of our project on halogen halogen interactions the tile compound was prepared and characterized by single crystal X-ray diffraction. In the crystal structure of the title compound discrete complexes are found in which each zinc(II) cation is coordinated by two 3-chloropyridine ligands and two chloride anions. The coordination environment around the Zn cations consists of slightly distorted tetrahedra, which is typical for such complexes ( Bhosekar et al., 2008; Wriedt et al., 2009). The crystal structure is characterized by intermolecular C—Cl···Cl—C interactions with Cl···Cl separations less than the sum of Van der Waals radii (Lommerse, et al., 1996).

Related literature top

For the background of this work, see: Bertani et al.(2010); Metrangolo & Resnati (2001); Leininger et al. (2000); Lommerse et al. (1996). For related structures, see: Bhosekar et al. (2008); Wriedt et al. (2009).

Experimental top

Zinc(II) chloride (1 mmol) dissolved in 10 mL of ethanol, was added dropwise to a stirred solution of 3-chloropyridine (1 mmol) in 10 mL of ethanol. Subsequently, the mixture was refluxed for 2 h, and the resulting solution was further concentrated by the rotary evaporation at 40 Celsius degree. Finally, the concentrated solution was left to slowly evaporate at room temperature until the crystal formed.

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS (Siemens, 1994); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Crystal structure of the title compound with labeling and displacement elliposids drawn at the 30% probability level.
	Fig. 2. Crystal structure of the title compound with view along the c-axis and C—Cl···Cl interactions shown as dashed lines.

Dichloridobis(3-chloropyridine-κN)zinc top

Crystal data top

[ZnCl₂(C₅H₄ClN)₂]	Z = 2
M_r = 363.35	F(000) = 360
Triclinic, P1	D_x = 1.773 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3429 (15) Å	Cell parameters from 2456 reflections
b = 7.9220 (16) Å	θ = 2.1–19.6°
c = 13.259 (3) Å	µ = 2.57 mm⁻¹
α = 95.17 (3)°	T = 298 K
β = 91.14 (3)°	Prism, colorless
γ = 117.37 (3)°	0.44 × 0.42 × 0.19 mm
V = 680.5 (2) Å³

Data collection top

Bruker P4 diffractometer	2640 independent reflections
Radiation source: fine-focus sealed tube	2066 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 26.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→9
T_min = 0.398, T_max = 0.641	k = −9→9
5839 measured reflections	l = −16→13

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.051P)² + 1.6856P] where P = (F_o² + 2F_c²)/3
2640 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −1.24 e Å⁻³

Crystal data top

[ZnCl₂(C₅H₄ClN)₂]	γ = 117.37 (3)°
M_r = 363.35	V = 680.5 (2) Å³
Triclinic, P1	Z = 2
a = 7.3429 (15) Å	Mo Kα radiation
b = 7.9220 (16) Å	µ = 2.57 mm⁻¹
c = 13.259 (3) Å	T = 298 K
α = 95.17 (3)°	0.44 × 0.42 × 0.19 mm
β = 91.14 (3)°

Data collection top

Bruker P4 diffractometer	2640 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2066 reflections with I > 2σ(I)
T_min = 0.398, T_max = 0.641	R_int = 0.044
5839 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.16	Δρ_max = 0.82 e Å⁻³
2640 reflections	Δρ_min = −1.24 e Å⁻³
154 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
Zn1	0.13903 (9)	0.76409 (9)	0.24334 (5)	0.0394 (2)
Cl4	0.9010 (2)	1.1496 (2)	0.46968 (12)	0.0522 (4)
Cl2	0.1747 (3)	0.5228 (2)	0.29582 (12)	0.0544 (4)
Cl3	0.6030 (3)	0.6881 (3)	−0.08020 (13)	0.0623 (5)
Cl1	−0.1516 (2)	0.7837 (3)	0.24273 (13)	0.0620 (5)
N1	0.2137 (7)	0.7713 (6)	0.0913 (3)	0.0399 (10)
N2	0.3755 (7)	1.0102 (6)	0.3193 (3)	0.0373 (10)
C7	0.6947 (7)	1.1654 (7)	0.4135 (4)	0.0357 (11)
C6	0.5425 (8)	1.0075 (8)	0.3607 (4)	0.0394 (12)
H6A	0.5536	0.8948	0.3529	0.047*
C2	0.4034 (9)	0.7317 (8)	−0.0417 (4)	0.0417 (12)
C1	0.3685 (8)	0.7401 (7)	0.0598 (4)	0.0404 (12)
H1A	0.4533	0.7241	0.1069	0.048*
C10	0.3626 (9)	1.1745 (8)	0.3302 (4)	0.0404 (12)
H10A	0.2466	1.1768	0.3024	0.049*
C8	0.6861 (9)	1.3362 (8)	0.4244 (5)	0.0483 (14)
H8A	0.7912	1.4458	0.4597	0.058*
C3	0.2782 (10)	0.7512 (9)	−0.1128 (4)	0.0530 (15)
H3A	0.2975	0.7388	−0.1817	0.064*
C5	0.0957 (9)	0.7987 (9)	0.0231 (4)	0.0488 (14)
H5A	−0.0088	0.8248	0.0457	0.059*
C9	0.5139 (10)	1.3371 (8)	0.3805 (5)	0.0510 (15)
H9A	0.5021	1.4495	0.3856	0.061*
C4	0.1231 (10)	0.7898 (11)	−0.0794 (5)	0.0623 (18)
H4A	0.0389	0.8094	−0.1251	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0408 (4)	0.0457 (4)	0.0344 (4)	0.0230 (3)	0.0014 (3)	0.0013 (3)
Cl4	0.0480 (8)	0.0630 (9)	0.0488 (9)	0.0289 (7)	−0.0058 (6)	0.0059 (7)
Cl2	0.0670 (10)	0.0490 (8)	0.0522 (9)	0.0309 (7)	−0.0005 (7)	0.0082 (6)
Cl3	0.0603 (10)	0.0855 (12)	0.0581 (10)	0.0463 (9)	0.0203 (8)	0.0154 (8)
Cl1	0.0484 (8)	0.0895 (12)	0.0586 (10)	0.0424 (9)	0.0047 (7)	−0.0018 (8)
N1	0.048 (3)	0.048 (2)	0.030 (2)	0.028 (2)	0.0003 (19)	0.0024 (18)
N2	0.043 (2)	0.039 (2)	0.028 (2)	0.018 (2)	0.0044 (18)	0.0022 (17)
C7	0.029 (2)	0.040 (3)	0.035 (3)	0.013 (2)	0.000 (2)	0.006 (2)
C6	0.047 (3)	0.049 (3)	0.032 (3)	0.029 (3)	0.006 (2)	0.008 (2)
C2	0.047 (3)	0.044 (3)	0.041 (3)	0.026 (3)	0.010 (2)	0.006 (2)
C1	0.046 (3)	0.044 (3)	0.039 (3)	0.029 (3)	−0.002 (2)	0.003 (2)
C10	0.047 (3)	0.050 (3)	0.035 (3)	0.031 (3)	0.006 (2)	0.007 (2)
C8	0.049 (3)	0.039 (3)	0.046 (3)	0.014 (3)	−0.004 (3)	−0.005 (2)
C3	0.053 (3)	0.072 (4)	0.029 (3)	0.025 (3)	0.005 (2)	0.005 (3)
C5	0.049 (3)	0.068 (4)	0.041 (3)	0.037 (3)	0.002 (3)	0.005 (3)
C9	0.060 (4)	0.043 (3)	0.055 (4)	0.029 (3)	−0.001 (3)	0.003 (3)
C4	0.060 (4)	0.101 (5)	0.037 (3)	0.046 (4)	−0.002 (3)	0.011 (3)

Geometric parameters (Å, º) top

Zn1—N2	2.072 (4)	C2—C3	1.372 (8)
Zn1—N1	2.098 (4)	C2—C1	1.376 (8)
Zn1—Cl1	2.2099 (17)	C1—H1A	0.9300
Zn1—Cl2	2.2130 (16)	C10—C9	1.356 (8)
Cl4—C7	1.736 (5)	C10—H10A	0.9300
Cl3—C2	1.730 (6)	C8—C9	1.385 (9)
N1—C1	1.336 (7)	C8—H8A	0.9300
N1—C5	1.340 (7)	C3—C4	1.379 (9)
N2—C10	1.342 (7)	C3—H3A	0.9300
N2—C6	1.344 (7)	C5—C4	1.378 (9)
C7—C6	1.352 (7)	C5—H5A	0.9300
C7—C8	1.378 (8)	C9—H9A	0.9300
C6—H6A	0.9300	C4—H4A	0.9300

N2—Zn1—N1	104.62 (18)	N1—C1—C2	120.5 (5)
N2—Zn1—Cl1	110.33 (14)	N1—C1—H1A	119.7
N1—Zn1—Cl1	104.81 (14)	C2—C1—H1A	119.7
N2—Zn1—Cl2	105.93 (14)	N2—C10—C9	121.9 (5)
N1—Zn1—Cl2	105.50 (13)	N2—C10—H10A	119.1
Cl1—Zn1—Cl2	124.03 (8)	C9—C10—H10A	119.1
C1—N1—C5	119.1 (5)	C7—C8—C9	117.0 (5)
C1—N1—Zn1	122.1 (4)	C7—C8—H8A	121.5
C5—N1—Zn1	118.7 (4)	C9—C8—H8A	121.5
C10—N2—C6	118.7 (5)	C2—C3—C4	118.2 (6)
C10—N2—Zn1	120.6 (4)	C2—C3—H3A	120.9
C6—N2—Zn1	120.7 (4)	C4—C3—H3A	120.9
C6—C7—C8	121.0 (5)	N1—C5—C4	122.5 (6)
C6—C7—Cl4	119.0 (4)	N1—C5—H5A	118.7
C8—C7—Cl4	120.0 (4)	C4—C5—H5A	118.7
N2—C6—C7	121.3 (5)	C10—C9—C8	120.1 (5)
N2—C6—H6A	119.4	C10—C9—H9A	120.0
C7—C6—H6A	119.4	C8—C9—H9A	120.0
C3—C2—C1	120.9 (5)	C5—C4—C3	118.6 (6)
C3—C2—Cl3	119.6 (5)	C5—C4—H4A	120.7
C1—C2—Cl3	119.4 (4)	C3—C4—H4A	120.7

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₅H₄ClN)₂]
M_r	363.35
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.3429 (15), 7.9220 (16), 13.259 (3)
α, β, γ (°)	95.17 (3), 91.14 (3), 117.37 (3)
V (Å³)	680.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.57
Crystal size (mm)	0.44 × 0.42 × 0.19

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.398, 0.641
No. of measured, independent and observed [I > 2σ(I)] reflections	5839, 2640, 2066
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.147, 1.16
No. of reflections	2640
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −1.24

Computer programs: XSCANS (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Acknowledgements

The authors are grateful to the Natural Science Foundation of Zhejiang Province (grant No. Y4110066) for financial support.

References

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