Dichlorido[2,2′-(oxydimethyl­ene)dipyridine]zinc(II)

Li, J.M.

doi:10.1107/S1600536808034600

metal-organic compounds

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Volume 64| Part 11| November 2008| Page m1468

doi:10.1107/S1600536808034600

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Dichlorido[2,2′-(oxydimethylene)dipyridine]zinc(II)

Jin Min Li ^a ^*

^aChemistry and Chemical Engineering College, Shanxi Datong University, Datong 037009, People's Republic of China
^*Correspondence e-mail: jinminli1957@yahoo.com.cn

(Received 11 October 2008; accepted 23 October 2008; online 31 October 2008)

In the title complex, [ZnCl₂(C₁₂H₁₂N₂O)], the Zn^II atom is coordinated in a distorted trigonal-bipyramidal geometry by two Cl atoms, and one O atom and two N atoms from the 2,2′-(oxydimethylene)dipyridine ligand. In the complex, the two pyridine rings make a dihedral angle of 15.44 (14)°. There is a weak intermolecular π–π stacking interaction between pyridine rings; the centroid–centroid distance is 3.8079 (17) Å.

Related literature

For the isotypic Cd and Cu analogs of the title compound, see: Li (2007 ) and Li (2008 ), respectively.

Experimental

Crystal data

[ZnCl₂(C₁₂H₁₂N₂O)]
M_r = 336.51
Monoclinic, P 2₁ /c
a = 8.0874 (12) Å
b = 12.5013 (18) Å
c = 15.6210 (16) Å
β = 121.180 (11)°
V = 1351.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.20 mm⁻¹
T = 298 (2) K
0.40 × 0.32 × 0.13 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.466, T_max = 0.751
5529 measured reflections
2388 independent reflections
2158 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.069
S = 1.05
2388 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected bond lengths (Å)

Cl1—Zn1	2.2803 (6)
Cl2—Zn1	2.2642 (7)
N1—Zn1	2.1178 (18)
N2—Zn1	2.1128 (18)
O1—Zn1	2.2252 (16)

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034600/is2347sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034600/is2347Isup2.hkl

checkCIF report

Comment top

2,2'-(oxydimethylene)dipyridine is an useful tridentate terminal ligand and the Cd^II complex with it as ligand has been published (Li, 2007). Herein the crystal structure of the title Zn complex, (I), with 2,2'-(oxydimethylene)dipyridine as ligand, is reported.

The molecular structure of (I) is shown in Fig. 1. In this mononuclear complex, atom Zn1 is in a distorted trigonal bipyramidal coordination environment (Table 1). In the crystal structure, there are a weak π-π stacking interaction between symmetry related pyridyl rings, with the relevant distances being Cg1···Cg1ⁱ = 3.8079 (17) Å and a perpendicular distance of 3.597 Å [symmetry code (i) 1-x, 2-y, -z; Cg1 is the centroid of the N1/C1—C5 ring]. The title compound is isostructural with the Cd^II complex (Li, 2007).

Related literature top

For the isotypic Cd and Cu analogs of the title compound, see: Li (2007) and Li (2008), respectively.

Experimental top

A methanol solution (5 ml) of 2,2'-(oxydimethylene)dipyridine (0.0345 g, 0.172 mmol) was added into 8 ml H₂O solution containing ZnCl₂ (0.0241 g, 0.177 mmol). The mixed solution was stirred for a few minutes. The colorless single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).

Figures top

Fig. 1. View of complex (I), showing the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level

Dichlorido[2,2'-(oxydimethylene)dipyridine]zinc(II) top

Crystal data top

[ZnCl₂(C₁₂H₁₂N₂O)]	F(000) = 680
M_r = 336.51	D_x = 1.654 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3915 reflections
a = 8.0874 (12) Å	θ = 2.9–28.1°
b = 12.5013 (18) Å	µ = 2.20 mm⁻¹
c = 15.6210 (16) Å	T = 298 K
β = 121.180 (11)°	Block, colorless
V = 1351.2 (3) Å³	0.40 × 0.32 × 0.13 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2388 independent reflections
Radiation source: fine-focus sealed tube	2158 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
T_min = 0.466, T_max = 0.751	k = −14→8
5529 measured reflections	l = −17→18

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0373P)² + 0.2883P] where P = (F_o² + 2F_c²)/3
2388 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[ZnCl₂(C₁₂H₁₂N₂O)]	V = 1351.2 (3) Å³
M_r = 336.51	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0874 (12) Å	µ = 2.20 mm⁻¹
b = 12.5013 (18) Å	T = 298 K
c = 15.6210 (16) Å	0.40 × 0.32 × 0.13 mm
β = 121.180 (11)°

Data collection top

Bruker SMART APEX CCD diffractometer	2388 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2158 reflections with I > 2σ(I)
T_min = 0.466, T_max = 0.751	R_int = 0.024
5529 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 1.05	Δρ_max = 0.51 e Å⁻³
2388 reflections	Δρ_min = −0.35 e Å⁻³
163 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	0.4107 (3)	0.83139 (18)	−0.04103 (18)	0.0431 (5)
C2	0.2717 (3)	0.9110 (2)	−0.0806 (2)	0.0609 (7)
H2	0.2077	0.9271	−0.1485	0.073*
C3	0.4597 (4)	0.8595 (2)	0.1155 (2)	0.0560 (6)
H3	0.5236	0.8417	0.1831	0.067*
C4	0.3238 (4)	0.9395 (2)	0.0809 (3)	0.0687 (8)
H4	0.2964	0.9752	0.1243	0.082*
C5	0.2299 (4)	0.9658 (2)	−0.0178 (3)	0.0698 (8)
H5	0.1384	1.0203	−0.0425	0.084*
C6	0.4609 (3)	0.7685 (2)	−0.10595 (18)	0.0503 (6)
H6A	0.3458	0.7537	−0.1702	0.060*
H6B	0.5515	0.8079	−0.1171	0.060*
C7	0.6087 (3)	0.59950 (19)	−0.09923 (16)	0.0460 (5)
H7A	0.6875	0.6357	−0.1205	0.055*
H7B	0.4990	0.5673	−0.1575	0.055*
C8	0.7246 (3)	0.51540 (18)	−0.02358 (16)	0.0397 (5)
C9	0.7807 (3)	0.4226 (2)	−0.05024 (19)	0.0495 (6)
H9	0.7444	0.4107	−0.1165	0.059*
C10	0.8902 (4)	0.3486 (2)	0.0219 (2)	0.0537 (6)
H10	0.9305	0.2863	0.0054	0.064*
C11	0.9394 (3)	0.36760 (19)	0.1189 (2)	0.0508 (6)
H11	1.0125	0.3182	0.1690	0.061*
C12	0.8788 (3)	0.46096 (18)	0.14068 (18)	0.0456 (5)
H12	0.9123	0.4736	0.2064	0.055*
Cl1	0.71768 (8)	0.63978 (5)	0.25220 (4)	0.04925 (16)
Cl2	0.98849 (8)	0.77735 (5)	0.14453 (5)	0.05218 (16)
N1	0.5035 (3)	0.80611 (14)	0.05554 (14)	0.0426 (4)
N2	0.7730 (2)	0.53478 (14)	0.07069 (13)	0.0386 (4)
O1	0.5448 (3)	0.67253 (13)	−0.05431 (12)	0.0539 (4)
Zn1	0.71979 (3)	0.686250 (19)	0.111610 (17)	0.03705 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0374 (11)	0.0391 (12)	0.0482 (14)	−0.0003 (9)	0.0189 (10)	0.0079 (10)
C2	0.0492 (14)	0.0550 (15)	0.0680 (17)	0.0116 (12)	0.0229 (13)	0.0196 (14)
C3	0.0644 (15)	0.0483 (14)	0.0592 (16)	0.0069 (12)	0.0346 (13)	−0.0003 (12)
C4	0.0747 (18)	0.0504 (16)	0.094 (2)	0.0070 (14)	0.0533 (18)	−0.0080 (16)
C5	0.0595 (16)	0.0487 (15)	0.104 (2)	0.0156 (13)	0.0439 (17)	0.0120 (16)
C6	0.0497 (13)	0.0538 (14)	0.0417 (13)	0.0048 (11)	0.0196 (10)	0.0125 (11)
C7	0.0496 (12)	0.0524 (14)	0.0371 (12)	−0.0020 (11)	0.0232 (10)	−0.0055 (11)
C8	0.0393 (11)	0.0425 (12)	0.0393 (12)	−0.0079 (9)	0.0217 (9)	−0.0068 (10)
C9	0.0547 (13)	0.0495 (14)	0.0519 (14)	−0.0101 (11)	0.0329 (12)	−0.0153 (12)
C10	0.0568 (14)	0.0395 (12)	0.0784 (19)	−0.0017 (11)	0.0444 (14)	−0.0067 (13)
C11	0.0491 (13)	0.0425 (13)	0.0603 (16)	0.0047 (10)	0.0281 (12)	0.0069 (11)
C12	0.0471 (12)	0.0437 (13)	0.0430 (13)	0.0021 (10)	0.0213 (10)	0.0012 (10)
Cl1	0.0624 (3)	0.0501 (3)	0.0403 (3)	−0.0039 (3)	0.0301 (3)	0.0019 (3)
Cl2	0.0507 (3)	0.0541 (3)	0.0561 (4)	−0.0081 (3)	0.0307 (3)	−0.0034 (3)
N1	0.0420 (10)	0.0387 (10)	0.0445 (11)	0.0025 (8)	0.0206 (9)	0.0011 (8)
N2	0.0419 (9)	0.0362 (9)	0.0380 (10)	−0.0004 (7)	0.0208 (8)	−0.0025 (8)
O1	0.0673 (10)	0.0512 (10)	0.0332 (9)	0.0166 (8)	0.0190 (8)	0.0023 (7)
Zn1	0.04082 (16)	0.03641 (17)	0.03043 (17)	0.00126 (10)	0.01599 (12)	−0.00073 (10)

Geometric parameters (Å, º) top

C1—N1	1.329 (3)	C7—H7B	0.9700
C1—C2	1.384 (3)	C8—N2	1.336 (3)
C1—C6	1.496 (3)	C8—C9	1.386 (3)
C2—C5	1.375 (4)	C9—C10	1.370 (4)
C2—H2	0.9300	C9—H9	0.9300
C3—N1	1.339 (3)	C10—C11	1.373 (4)
C3—C4	1.373 (4)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.375 (3)
C4—C5	1.360 (4)	C11—H11	0.9300
C4—H4	0.9300	C12—N2	1.346 (3)
C5—H5	0.9300	C12—H12	0.9300
C6—O1	1.409 (3)	Cl1—Zn1	2.2803 (6)
C6—H6A	0.9700	Cl2—Zn1	2.2642 (7)
C6—H6B	0.9700	N1—Zn1	2.1178 (18)
C7—O1	1.403 (3)	N2—Zn1	2.1128 (18)
C7—C8	1.494 (3)	O1—Zn1	2.2252 (16)
C7—H7A	0.9700

N1—C1—C2	121.9 (2)	C10—C9—H9	120.3
N1—C1—C6	116.90 (19)	C8—C9—H9	120.3
C2—C1—C6	121.2 (2)	C9—C10—C11	119.0 (2)
C5—C2—C1	118.8 (3)	C9—C10—H10	120.5
C5—C2—H2	120.6	C11—C10—H10	120.5
C1—C2—H2	120.6	C10—C11—C12	118.9 (2)
N1—C3—C4	122.4 (3)	C10—C11—H11	120.5
N1—C3—H3	118.8	C12—C11—H11	120.5
C4—C3—H3	118.8	N2—C12—C11	122.6 (2)
C5—C4—C3	119.1 (3)	N2—C12—H12	118.7
C5—C4—H4	120.5	C11—C12—H12	118.7
C3—C4—H4	120.5	C1—N1—C3	118.5 (2)
C4—C5—C2	119.3 (2)	C1—N1—Zn1	119.86 (15)
C4—C5—H5	120.4	C3—N1—Zn1	121.64 (17)
C2—C5—H5	120.4	C8—N2—C12	118.13 (19)
O1—C6—C1	106.18 (18)	C8—N2—Zn1	120.46 (14)
O1—C6—H6A	110.5	C12—N2—Zn1	120.81 (15)
C1—C6—H6A	110.5	C7—O1—C6	117.43 (18)
O1—C6—H6B	110.5	C7—O1—Zn1	117.11 (13)
C1—C6—H6B	110.5	C6—O1—Zn1	115.38 (14)
H6A—C6—H6B	108.7	N2—Zn1—N1	139.71 (7)
O1—C7—C8	107.76 (17)	N2—Zn1—O1	71.63 (6)
O1—C7—H7A	110.2	N1—Zn1—O1	71.44 (7)
C8—C7—H7A	110.2	N2—Zn1—Cl2	101.41 (5)
O1—C7—H7B	110.2	N1—Zn1—Cl2	103.18 (5)
C8—C7—H7B	110.2	O1—Zn1—Cl2	105.09 (5)
H7A—C7—H7B	108.5	N2—Zn1—Cl1	99.63 (5)
N2—C8—C9	121.9 (2)	N1—Zn1—Cl1	99.33 (6)
N2—C8—C7	116.73 (19)	O1—Zn1—Cl1	141.69 (5)
C9—C8—C7	121.4 (2)	Cl2—Zn1—Cl1	113.22 (3)
C10—C9—C8	119.4 (2)

N1—C1—C2—C5	0.5 (4)	C8—C7—O1—Zn1	25.3 (2)
C6—C1—C2—C5	179.5 (2)	C1—C6—O1—C7	−178.79 (18)
N1—C3—C4—C5	0.0 (4)	C1—C6—O1—Zn1	−34.2 (2)
C3—C4—C5—C2	0.7 (4)	C8—N2—Zn1—N1	40.8 (2)
C1—C2—C5—C4	−0.9 (4)	C12—N2—Zn1—N1	−148.24 (15)
N1—C1—C6—O1	20.9 (3)	C8—N2—Zn1—O1	16.36 (15)
C2—C1—C6—O1	−158.1 (2)	C12—N2—Zn1—O1	−172.68 (17)
O1—C7—C8—N2	−11.5 (3)	C8—N2—Zn1—Cl2	−85.92 (15)
O1—C7—C8—C9	169.19 (19)	C12—N2—Zn1—Cl2	85.04 (16)
N2—C8—C9—C10	−0.5 (3)	C8—N2—Zn1—Cl1	157.83 (14)
C7—C8—C9—C10	178.7 (2)	C12—N2—Zn1—Cl1	−31.21 (16)
C8—C9—C10—C11	0.9 (3)	C1—N1—Zn1—N2	−40.5 (2)
C9—C10—C11—C12	−0.6 (3)	C3—N1—Zn1—N2	140.93 (17)
C10—C11—C12—N2	−0.1 (4)	C1—N1—Zn1—O1	−16.06 (16)
C2—C1—N1—C3	0.2 (3)	C3—N1—Zn1—O1	165.40 (19)
C6—C1—N1—C3	−178.8 (2)	C1—N1—Zn1—Cl2	85.67 (16)
C2—C1—N1—Zn1	−178.39 (17)	C3—N1—Zn1—Cl2	−92.87 (18)
C6—C1—N1—Zn1	2.6 (3)	C1—N1—Zn1—Cl1	−157.66 (16)
C4—C3—N1—C1	−0.5 (4)	C3—N1—Zn1—Cl1	23.80 (18)
C4—C3—N1—Zn1	178.1 (2)	C7—O1—Zn1—N2	−23.24 (15)
C9—C8—N2—C12	−0.2 (3)	C6—O1—Zn1—N2	−167.91 (17)
C7—C8—N2—C12	−179.44 (19)	C7—O1—Zn1—N1	173.15 (17)
C9—C8—N2—Zn1	171.03 (15)	C6—O1—Zn1—N1	28.48 (15)
C7—C8—N2—Zn1	−8.2 (2)	C7—O1—Zn1—Cl2	74.03 (16)
C11—C12—N2—C8	0.5 (3)	C6—O1—Zn1—Cl2	−70.65 (16)
C11—C12—N2—Zn1	−170.71 (17)	C7—O1—Zn1—Cl1	−105.42 (16)
C8—C7—O1—C6	169.28 (19)	C6—O1—Zn1—Cl1	109.91 (15)

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₂H₁₂N₂O)]
M_r	336.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.0874 (12), 12.5013 (18), 15.6210 (16)
β (°)	121.180 (11)
V (Å³)	1351.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.20
Crystal size (mm)	0.40 × 0.32 × 0.13

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.466, 0.751
No. of measured, independent and observed [I > 2σ(I)] reflections	5529, 2388, 2158
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.069, 1.05
No. of reflections	2388
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.35

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cl1—Zn1	2.2803 (6)	N2—Zn1	2.1128 (18)
Cl2—Zn1	2.2642 (7)	O1—Zn1	2.2252 (16)
N1—Zn1	2.1178 (18)

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, J. M. (2007). Acta Cryst. E63, m2241. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, J. M. (2008). Acta Cryst. E64, m1467 Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). 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