Dichlorido(6,6′-dimethyl-2,2′-bipyridine-κ2N,N′)zinc(II)

Alizadeh, R.; Kalateh, K.; Ebadi, A.; Ahmadi, R.; Amani, V.

doi:10.1107/S1600536809038215

metal-organic compounds

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Volume 65| Part 10| October 2009| Page m1250

doi:10.1107/S1600536809038215

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Dichlorido(6,6′-dimethyl-2,2′-bipyridine-κ²N,N′)zinc(II)

Robabeh Alizadeh,^a ^* Khadijeh Kalateh,^b Amin Ebadi,^c Roya Ahmadi ^b and Vahid Amani ^b

^aDamghan University of Basic Sciences, School of Chemistry, Damghan, Iran, ^bIslamic Azad University, Shahr-e-Rey Branch, Tehran, Iran, and ^cDepartment of Chemistry, Islamic Azad University, Kazerun Branch, Kazerun, Fars, Iran
^*Correspondence e-mail: robabeh_alizadeh@yahoo.com

(Received 17 September 2009; accepted 21 September 2009; online 26 September 2009)

In the title compound, [ZnCl₂(C₁₂H₁₂N₂)], the complete molecule is generated by crystallographic mirror symmetry, with the Zn atom and both chloride ions lying on the reflecting plane, yielding a distorted ZnN₂Cl₂ tetrahedral coordination for the metal ion. In the crystal, there are π–π contacts between the pyridine rings [centroid–centroid distance = 3.7857 (17) Å].

Related literature

For related structures containing Zn bonded to two chloride ions and a phenanthroline/bipyridine derivative, see: Ahmadi et al. (2008 , 2009a ,b ); Alizadeh et al. (2009 ); Gruia et al. (2007 ); Khalighi et al. (2008 ); Khan & Tuck (1984 ); Khavasi et al. (2008 ); Khoshtarkib et al. (2009 ); Kozhevnikov et al. (2006 ); Liu et al. (2004 ); Preston & Kennard (1969 ); Reimann et al. (1966 ).

Experimental

Crystal data

[ZnCl₂(C₁₂H₁₂N₂)]
M_r = 320.53
Monoclinic, P 2₁ /m
a = 7.6957 (15) Å
b = 11.266 (2) Å
c = 8.1431 (16) Å
β = 110.61 (3)°
V = 660.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.24 mm⁻¹
T = 298 K
0.40 × 0.33 × 0.30 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.421, T_max = 0.512
8852 measured reflections
2075 independent reflections
1972 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.101
S = 1.26
2075 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—N1	2.0569 (18)
Zn1—Cl1	2.2013 (11)
Zn1—Cl2	2.2035 (10)

N1ⁱ—Zn1—N1	80.71 (10)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z]$ .

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 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038215/hb5106sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809038215/hb5106Isup2.hkl

checkCIF report

Comment top

Recently, we reported the synthes and crystal structure of [ZnCl₂(phend)], (II), (Khoshtarkib et al., 2009), [HgBr₂(2,9-dmphen)], (III), (Alizadeh et al., 2009), [HgCl₂(2,9-dmPh2phen)].0.5 CH₃CN, (IV) (Ahmadi, et al., 2009a) and [Pb₄(NO₃)₈(6-mbpy)₄], (V), (Ahmadi, et al., 2009b) [where phend is phenanthridine, 2,9-dmphen is 2,9-dimethyl-1,10-phenanthroline, 2,9-dmPh2phen is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and 6-mbpy is 6-methyl-2,2'-bipyridine].

There are several Zn^II complexes, with formula, [ZnCl₂(N—N)], such as [ZnCl₂(bipy)], (VI), (Khan & Tuck, 1984), [ZnCl₂(biim)], (VII), (Gruia et al., 2007), [ZnCl₂(phbipy)], (IIX), (Kozhevnikov et al., 2006), [ZnCl₂(phen)], (IX), (Reimann et al., 1966), [ZnCl₂(dmphen)], (X), (Preston & Kennard, 1969), [ZnCl₂(dpdmbip)], (XI), (Liu et al., 2004), [ZnCl₂(dm4bt)], (XII), (Khavasi et al., 2008), [ZnCl₂(5,5'-dmbpy)], (XIII), (Khalighi et al., 2008) and [ZnCl₂(6-mbpy)], (XIV), (Ahmadi, Kalateh, Ebadi 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 and 5,5'-dmbpy 5,5'-dimethyl-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).

The asymmetric unit of the title compound, (I), (Fig. 1), contains half molecule. The Zn^II atom is four-coordinated in distorted tetrahedral configurations by two N atoms from one 6,6'-dimethyl-2,2'-bipyridine and two terminal Cl atoms. The Zn—Cl and Zn—N bond lengths and angles are collected in Table 1.

In the crystal structure, the π-π contacts between the rings A (N1/C2—C6) and rings A, Cg2···Cg2ⁱ [distance = 3.7857 (17) Å, symmetry cods: 1-X,2-Y,1-Z]. It seems this π-π stacking is effective in the stabilization of the crystal structure (Fig. 2).

Related literature top

For related structures containing Zn bonded to two chloride ions and a phenanthroline/bipyridine derivative, see: Ahmadi et al. (2008, 2009a,b); Alizadeh et al. (2009); Gruia et al. (2007); Khalighi et al. (2008); Khan & Tuck (1984); Khavasi et al. (2008); Khoshtarkib et al. (2009); Kozhevnikov et al. (2006); Liu et al. (2004); Preston & Kennard (1969); Reimann et al. (1966).

Experimental top

A solution of 6,6'-dimethyl-2,2'-bipyridine (0.20 g, 1.10 mmol) in methanol (10 ml) was added to a solution of ZnCl₂ (0.15 g, 0.88 mmol) in acetonitrile (10 ml) and the resulting colourless solution was stirred for 20 min at at 313 K. This solution was left to evaporate slowly at room temperature. After one week, colorless prisms of (I) were isolated (yield 0.26 g, 73.7%).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (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 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (a) x,-y + 3/2,z]
	Fig. 2. Tha unit-cell packing of (I).

Dichlorido(6,6'-dimethyl-2,2'-bipyridine-κ²N,N')zinc(II) top

Crystal data top

[ZnCl₂(C₁₂H₁₂N₂)]	F(000) = 324
M_r = 320.53	D_x = 1.611 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1170 reflections
a = 7.6957 (15) Å	θ = 2.8–30.6°
b = 11.266 (2) Å	µ = 2.24 mm⁻¹
c = 8.1431 (16) Å	T = 298 K
β = 110.61 (3)°	Prism, colourless
V = 660.8 (3) Å³	0.40 × 0.33 × 0.30 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	2075 independent reflections
Radiation source: fine-focus sealed tube	1972 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans	θ_max = 30.6°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −10→10
T_min = 0.421, T_max = 0.512	k = −16→16
8852 measured reflections	l = −11→10

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.26	w = 1/[σ²(F_o²) + (0.036P)² + 0.4143P] where P = (F_o² + 2F_c²)/3
2075 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[ZnCl₂(C₁₂H₁₂N₂)]	V = 660.8 (3) Å³
M_r = 320.53	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 7.6957 (15) Å	µ = 2.24 mm⁻¹
b = 11.266 (2) Å	T = 298 K
c = 8.1431 (16) Å	0.40 × 0.33 × 0.30 mm
β = 110.61 (3)°

Data collection top

Bruker SMART CCD diffractometer	2075 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	1972 reflections with I > 2σ(I)
T_min = 0.421, T_max = 0.512	R_int = 0.043
8852 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.26	Δρ_max = 0.70 e Å⁻³
2075 reflections	Δρ_min = −0.55 e Å⁻³
83 parameters

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
C1	0.9103 (5)	1.0397 (3)	0.7493 (4)	0.0605 (7)
H1A	0.8626	1.0161	0.8386	0.091*
H1B	0.9085	1.1247	0.7405	0.091*
H1C	1.0355	1.0117	0.7793	0.091*
C2	0.7921 (3)	0.9875 (2)	0.5768 (3)	0.0415 (5)
C3	0.6959 (4)	1.0566 (2)	0.4331 (4)	0.0525 (6)
H3	0.7041	1.1389	0.4413	0.063*
C4	0.5891 (4)	1.0046 (3)	0.2791 (4)	0.0524 (6)
H4	0.5246	1.0512	0.1825	0.063*
C5	0.5776 (3)	0.8820 (2)	0.2679 (3)	0.0424 (5)
H5	0.5053	0.8449	0.1644	0.051*
C6	0.6762 (3)	0.81599 (18)	0.4143 (3)	0.0317 (4)
N1	0.7813 (2)	0.86822 (16)	0.5661 (2)	0.0330 (3)
Cl1	1.20088 (11)	0.7500	0.88188 (13)	0.0521 (2)
Cl2	0.74082 (14)	0.7500	0.94980 (13)	0.0511 (2)
Zn1	0.89560 (5)	0.7500	0.76788 (4)	0.03392 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0688 (19)	0.0401 (13)	0.0625 (17)	−0.0094 (12)	0.0104 (15)	−0.0154 (12)
C2	0.0457 (12)	0.0306 (10)	0.0480 (12)	−0.0039 (8)	0.0162 (10)	−0.0032 (8)
C3	0.0694 (17)	0.0281 (10)	0.0616 (16)	0.0033 (10)	0.0249 (14)	0.0063 (10)
C4	0.0641 (16)	0.0434 (13)	0.0473 (13)	0.0122 (12)	0.0168 (12)	0.0161 (11)
C5	0.0453 (12)	0.0424 (12)	0.0342 (10)	0.0048 (9)	0.0074 (9)	0.0057 (9)
C6	0.0326 (9)	0.0308 (9)	0.0300 (8)	0.0014 (7)	0.0091 (7)	0.0016 (7)
N1	0.0341 (8)	0.0288 (8)	0.0328 (8)	−0.0010 (6)	0.0075 (6)	−0.0002 (6)
Cl1	0.0325 (4)	0.0642 (6)	0.0492 (5)	0.000	0.0014 (3)	0.000
Cl2	0.0548 (5)	0.0567 (5)	0.0479 (4)	0.000	0.0255 (4)	0.000
Zn1	0.03172 (18)	0.03621 (19)	0.02830 (18)	0.000	0.00368 (12)	0.000

Geometric parameters (Å, º) top

C1—C2	1.499 (4)	C4—H4	0.9300
C1—H1A	0.9600	C5—C6	1.383 (3)
C1—H1B	0.9600	C5—H5	0.9300
C1—H1C	0.9600	C6—N1	1.350 (3)
C2—N1	1.347 (3)	C6—C6ⁱ	1.487 (4)
C2—C3	1.384 (4)	Zn1—N1	2.0569 (18)
C3—C4	1.366 (4)	Zn1—Cl1	2.2013 (11)
C3—H3	0.9300	Zn1—Cl2	2.2035 (10)
C4—C5	1.386 (4)	Zn1—N1ⁱ	2.0569 (18)

C2—C1—H1A	109.5	C6—C5—C4	118.4 (2)
C2—C1—H1B	109.5	C6—C5—H5	120.8
H1A—C1—H1B	109.5	C4—C5—H5	120.8
C2—C1—H1C	109.5	N1—C6—C5	121.6 (2)
H1A—C1—H1C	109.5	N1—C6—C6ⁱ	115.83 (11)
H1B—C1—H1C	109.5	C5—C6—C6ⁱ	122.51 (14)
N1—C2—C3	120.3 (2)	C2—N1—C6	119.82 (19)
N1—C2—C1	117.1 (2)	C2—N1—Zn1	126.50 (16)
C3—C2—C1	122.6 (2)	C6—N1—Zn1	113.51 (13)
C4—C3—C2	120.3 (2)	N1ⁱ—Zn1—N1	80.71 (10)
C4—C3—H3	119.8	N1ⁱ—Zn1—Cl1	115.45 (6)
C2—C3—H3	119.8	N1—Zn1—Cl1	115.45 (6)
C3—C4—C5	119.5 (2)	N1ⁱ—Zn1—Cl2	110.90 (6)
C3—C4—H4	120.3	N1—Zn1—Cl2	110.90 (6)
C5—C4—H4	120.3	Cl1—Zn1—Cl2	117.76 (5)

N1—C2—C3—C4	0.0 (4)	C5—C6—N1—C2	−0.2 (3)
C1—C2—C3—C4	−179.6 (3)	C6ⁱ—C6—N1—C2	178.78 (16)
C2—C3—C4—C5	0.1 (5)	C5—C6—N1—Zn1	175.34 (17)
C3—C4—C5—C6	−0.2 (4)	C6ⁱ—C6—N1—Zn1	−5.7 (3)
C4—C5—C6—N1	0.3 (4)	C2—N1—Zn1—N1ⁱ	−178.10 (16)
C4—C5—C6—C6ⁱ	−178.63 (19)	C6—N1—Zn1—N1ⁱ	6.69 (17)
C3—C2—N1—C6	0.0 (4)	C2—N1—Zn1—Cl1	−64.2 (2)
C1—C2—N1—C6	179.7 (2)	C6—N1—Zn1—Cl1	120.55 (13)
C3—C2—N1—Zn1	−174.88 (19)	C2—N1—Zn1—Cl2	73.0 (2)
C1—C2—N1—Zn1	4.7 (3)	C6—N1—Zn1—Cl2	−102.24 (14)

Symmetry code: (i) x, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₂H₁₂N₂)]
M_r	320.53
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	298
a, b, c (Å)	7.6957 (15), 11.266 (2), 8.1431 (16)
β (°)	110.61 (3)
V (Å³)	660.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.24
Crystal size (mm)	0.40 × 0.33 × 0.30

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.421, 0.512
No. of measured, independent and observed [I > 2σ(I)] reflections	8852, 2075, 1972
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.101, 1.26
No. of reflections	2075
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.55

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

Selected geometric parameters (Å, º) top

Zn1—N1	2.0569 (18)	Zn1—Cl2	2.2035 (10)
Zn1—Cl1	2.2013 (11)

N1ⁱ—Zn1—N1	80.71 (10)

Symmetry code: (i) x, −y+3/2, z.

Acknowledgements

We are grateful to the Damghan University of Basic Sciences and Islamic Azad University, Shahr-e-Rey Branch, for financial support.

References

Ahmadi, R., Kalateh, K., Alizadeh, R., Khoshtarkib, Z. & Amani, V. (2009a). Acta Cryst. E65, m848–m849. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ahmadi, R., Kalateh, K., Alizadeh, R., Khoshtarkib, Z. & Amani, V. (2009b). Acta Cryst. E65, m1169–m1170. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ahmadi, R., Kalateh, K., Ebadi, A., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1266. Web of Science CSD CrossRef IUCr Journals Google Scholar
Alizadeh, R., Heidari, A., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m483–m484. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Gruia, L. M., Rochon, F. D. & Beauchamp, A. L. (2007). Inorg. Chim. Acta, 360, 1825–1840. Web of Science CSD CrossRef CAS Google Scholar
Khalighi, A., Ahmadi, R., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1211–m1212. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Khan, M. A. & Tuck, D. G. (1984). Acta Cryst. C40, 60–62. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Khavasi, H. R., Abedi, A., Amani, V., Notash, B. & Safari, N. (2008). Polyhedron, 27, 1848–1854. Web of Science CSD CrossRef CAS Google Scholar
Khoshtarkib, Z., Ebadi, A., Alizadeh, R., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m739–m740. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Kozhevnikov, D. N., Shabunina, O. V., Kopchuk, D. S., Slepukhin, P. A. & Kozhevnikov, V. N. (2006). Tetrahedron Lett. 47, 7025–7029. Web of Science CSD CrossRef CAS Google Scholar
Liu, Q. D., Wang, R. & Wang, S. (2004). Dalton Trans. pp. 2073-2079. Web of Science CSD CrossRef PubMed Google Scholar
Preston, H. S. & Kennard, C. H. L. (1969). J. Chem. Soc. A, pp. 1965–1968. Google Scholar
Reimann, C. W., Block, S. & Perloff, A. (1966). Inorg. Chem. 5, 1185–1189. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1998). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar