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

Li, J.M.

doi:10.1107/S1600536808034612

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1467

doi:10.1107/S1600536808034612

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Dichlorido[2,2′-(oxydimethylene)dipyridine]copper(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, [CuCl₂(C₁₂H₁₂N₂O)], the Cu^II ion is coordinated in a distorted trigonal-bipyramidal environment. In the crystal structure, there is a weak π–π stacking interaction between symmetry-related pyridine rings, with a centroid-to-centroid distance of 3.8134 (17) Å. In addition, there is relatively close contact between the pyridine ring π-system and a symmetry-related Cu^II ion (Cu⋯centroid distance of 3.868 Å).

Related literature

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

Experimental

Crystal data

[CuCl₂(C₁₂H₁₂N₂O)]
M_r = 334.68
Monoclinic, P 2₁ /c
a = 8.1599 (10) Å
b = 12.5534 (15) Å
c = 15.3846 (14) Å
β = 123.574 (9)°
V = 1313.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.06 mm⁻¹
T = 298 (2) K
0.46 × 0.40 × 0.34 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.451, T_max = 0.541 (expected range = 0.414–0.497)
5381 measured reflections
2323 independent reflections
2152 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.066
S = 1.09
2323 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cl1—Cu1	2.4109 (6)
Cl2—Cu1	2.2538 (6)
Cu1—N2	2.0021 (17)
Cu1—N1	2.0092 (18)
Cu1—O1	2.0813 (14)

N2—Cu1—N1	155.06 (7)
N2—Cu1—O1	78.29 (6)
N1—Cu1—O1	77.99 (7)
N2—Cu1—Cl2	98.17 (5)
N1—Cu1—Cl2	97.71 (6)
O1—Cu1—Cl2	147.65 (4)
N2—Cu1—Cl1	93.36 (5)
N1—Cu1—Cl1	96.97 (6)
O1—Cu1—Cl1	96.81 (4)
Cl2—Cu1—Cl1	115.53 (2)

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034612/lh2712sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034612/lh2712Isup2.hkl

checkCIF report

Comment top

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

The molecular structure of (I) is shown in Fig. 1. The atom Cu1 is coordinated in a distorted trigonal-bipyramidal environment (Table 1). In the crystal structure, there is a weak π-π stacking interaction between symmetry related pyridyl rings, with the relevant distances being Cg1···Cg1ⁱ = 3.8134 (17) Å and a perpendicular distance of 3.556 Å [symmetry code (i) -x, 2 - y, -z; Cg1 is the centroid of the N1/C2—C6 ring]. In addition, there is close contact between a π-ring system and symmetry related Cu atom, with the relative distances being: Cg2···Cu1ⁱⁱ = 3.868 Å, Cg2_perp···Cu1ⁱⁱ = 3.635 Å [symmetry code: (ii) -x, 1 - y, -z; Cg2 is the centroid of the N2/C8—C12 ring; Cg2_perp···Cu1ⁱⁱ is the perpendicular distance from Cu1ⁱⁱ to N2/C8—C12 ring]. The title compound is isostructural with the Cadmium analog (Li, 2007) although the Cd analog was solved and refined in the non-standard P2₁/n setting of space group P2₁/c.

Related literature top

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

Experimental top

6 ml me thanol solution of 2,2'-[oxydi(methylene)]dipyridine (0.0418 g, 0.209 mmol) was added into 8 ml H₂O solution containing CuCl₂.2H₂O (0.0362 g, 0.212 mmol), and the mixed soulution was stirred for a few minutes. The green 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, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level

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

Crystal data top

[CuCl₂(C₁₂H₁₂N₂O)]	F(000) = 676
M_r = 334.68	D_x = 1.693 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4907 reflections
a = 8.1599 (10) Å	θ = 2.3–28.3°
b = 12.5534 (15) Å	µ = 2.06 mm⁻¹
c = 15.3846 (14) Å	T = 298 K
β = 123.574 (9)°	Block, green
V = 1313.0 (3) Å³	0.46 × 0.40 × 0.34 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2323 independent reflections
Radiation source: fine-focus sealed tube	2152 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.451, T_max = 0.541	k = −11→14
5381 measured reflections	l = −18→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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0361P)² + 0.5176P] where P = (F_o² + 2F_c²)/3
2323 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[CuCl₂(C₁₂H₁₂N₂O)]	V = 1313.0 (3) Å³
M_r = 334.68	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1599 (10) Å	µ = 2.06 mm⁻¹
b = 12.5534 (15) Å	T = 298 K
c = 15.3846 (14) Å	0.46 × 0.40 × 0.34 mm
β = 123.574 (9)°

Data collection top

Bruker SMART APEX CCD diffractometer	2323 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2152 reflections with I > 2σ(I)
T_min = 0.451, T_max = 0.541	R_int = 0.016
5381 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.09	Δρ_max = 0.33 e Å⁻³
2323 reflections	Δρ_min = −0.27 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	−0.0360 (3)	0.76246 (18)	−0.10853 (17)	0.0407 (5)
H1A	−0.1499	0.7554	−0.1795	0.049*
H1B	0.0687	0.7967	−0.1103	0.049*
C2	−0.0341 (4)	0.8555 (2)	0.1167 (2)	0.0481 (6)
H2	0.0297	0.8372	0.1868	0.058*
C3	−0.1666 (4)	0.9378 (2)	0.0794 (2)	0.0576 (7)
H3	−0.1909	0.9750	0.1235	0.069*
C4	−0.2628 (4)	0.9644 (2)	−0.0242 (2)	0.0604 (7)
H4	−0.3532	1.0200	−0.0516	0.072*
C5	−0.2232 (4)	0.9072 (2)	−0.0868 (2)	0.0507 (6)
H5	−0.2882	0.9231	−0.1574	0.061*
C6	−0.0864 (3)	0.82611 (17)	−0.04415 (17)	0.0357 (5)
C7	0.1210 (3)	0.59462 (18)	−0.09417 (16)	0.0369 (5)
H7A	0.2093	0.6368	−0.1039	0.044*
H7B	0.0243	0.5614	−0.1601	0.044*
C8	0.2343 (3)	0.51119 (17)	−0.01249 (15)	0.0320 (4)
C9	0.3812 (3)	0.46002 (18)	0.15917 (17)	0.0368 (5)
H9	0.4090	0.4735	0.2255	0.044*
C10	0.4063 (3)	0.34591 (18)	0.0442 (2)	0.0427 (5)
H10	0.4507	0.2836	0.0311	0.051*
C11	0.2964 (3)	0.41864 (18)	−0.03445 (18)	0.0405 (5)
H11	0.2645	0.4055	−0.1016	0.049*
C12	0.4491 (3)	0.36715 (19)	0.14218 (19)	0.0420 (5)
H12	0.5231	0.3193	0.1965	0.050*
Cl1	0.46540 (8)	0.76638 (5)	0.12142 (4)	0.04202 (15)
Cl2	0.20944 (9)	0.63873 (5)	0.25169 (4)	0.04202 (15)
Cu1	0.18810 (4)	0.673873 (19)	0.102078 (18)	0.03121 (10)
N1	0.0076 (3)	0.80023 (14)	0.05709 (14)	0.0359 (4)
N2	0.2764 (2)	0.53190 (13)	0.08332 (13)	0.0310 (4)
O1	0.0261 (2)	0.66050 (11)	−0.05971 (11)	0.0324 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0432 (12)	0.0411 (13)	0.0352 (11)	0.0067 (10)	0.0201 (10)	0.0108 (10)
C2	0.0580 (15)	0.0417 (13)	0.0490 (14)	0.0070 (12)	0.0323 (12)	−0.0021 (11)
C3	0.0632 (17)	0.0426 (14)	0.0748 (19)	0.0087 (13)	0.0430 (16)	−0.0074 (13)
C4	0.0536 (15)	0.0377 (14)	0.086 (2)	0.0142 (12)	0.0366 (15)	0.0069 (14)
C5	0.0452 (13)	0.0427 (14)	0.0552 (15)	0.0097 (11)	0.0221 (12)	0.0123 (12)
C6	0.0320 (11)	0.0316 (11)	0.0395 (12)	0.0005 (8)	0.0173 (10)	0.0059 (9)
C7	0.0425 (12)	0.0396 (12)	0.0326 (11)	−0.0007 (10)	0.0232 (10)	−0.0024 (9)
C8	0.0300 (10)	0.0321 (11)	0.0352 (10)	−0.0050 (8)	0.0189 (9)	−0.0044 (9)
C9	0.0341 (11)	0.0374 (12)	0.0345 (11)	0.0015 (9)	0.0162 (9)	0.0023 (9)
C10	0.0391 (12)	0.0308 (11)	0.0646 (16)	0.0000 (9)	0.0327 (12)	−0.0045 (11)
C11	0.0420 (12)	0.0394 (13)	0.0470 (13)	−0.0066 (10)	0.0290 (11)	−0.0112 (10)
C12	0.0355 (11)	0.0354 (12)	0.0523 (14)	0.0047 (10)	0.0225 (11)	0.0072 (10)
Cl1	0.0417 (3)	0.0411 (3)	0.0482 (3)	−0.0068 (2)	0.0279 (3)	−0.0045 (2)
Cl2	0.0550 (3)	0.0420 (3)	0.0353 (3)	−0.0009 (3)	0.0289 (3)	0.0015 (2)
Cu1	0.03650 (16)	0.02880 (16)	0.02902 (15)	0.00285 (10)	0.01855 (12)	0.00079 (9)
N1	0.0363 (10)	0.0307 (9)	0.0402 (10)	0.0028 (8)	0.0209 (8)	0.0014 (8)
N2	0.0314 (8)	0.0288 (9)	0.0325 (9)	−0.0017 (7)	0.0175 (7)	−0.0023 (7)
O1	0.0341 (8)	0.0336 (8)	0.0286 (7)	0.0023 (6)	0.0168 (6)	0.0025 (6)

Geometric parameters (Å, º) top

C1—O1	1.428 (3)	C7—H7B	0.9700
C1—C6	1.496 (3)	C8—N2	1.341 (3)
C1—H1A	0.9700	C8—C11	1.382 (3)
C1—H1B	0.9700	C9—N2	1.343 (3)
C2—N1	1.336 (3)	C9—C12	1.376 (3)
C2—C3	1.372 (4)	C9—H9	0.9300
C2—H2	0.9300	C10—C12	1.372 (4)
C3—C4	1.373 (4)	C10—C11	1.379 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.375 (4)	C11—H11	0.9300
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.379 (3)	Cl1—Cu1	2.4109 (6)
C5—H5	0.9300	Cl2—Cu1	2.2538 (6)
C6—N1	1.341 (3)	Cu1—N2	2.0021 (17)
C7—O1	1.421 (3)	Cu1—N1	2.0092 (18)
C7—C8	1.499 (3)	Cu1—O1	2.0813 (14)
C7—H7A	0.9700

O1—C1—C6	106.14 (17)	N2—C9—H9	118.9
O1—C1—H1A	110.5	C12—C9—H9	118.9
C6—C1—H1A	110.5	C12—C10—C11	118.8 (2)
O1—C1—H1B	110.5	C12—C10—H10	120.6
C6—C1—H1B	110.5	C11—C10—H10	120.6
H1A—C1—H1B	108.7	C10—C11—C8	119.4 (2)
N1—C2—C3	123.0 (2)	C10—C11—H11	120.3
N1—C2—H2	118.5	C8—C11—H11	120.3
C3—C2—H2	118.5	C10—C12—C9	119.3 (2)
C2—C3—C4	118.8 (3)	C10—C12—H12	120.4
C2—C3—H3	120.6	C9—C12—H12	120.4
C4—C3—H3	120.6	N2—Cu1—N1	155.06 (7)
C3—C4—C5	118.8 (2)	N2—Cu1—O1	78.29 (6)
C3—C4—H4	120.6	N1—Cu1—O1	77.99 (7)
C5—C4—H4	120.6	N2—Cu1—Cl2	98.17 (5)
C4—C5—C6	119.6 (2)	N1—Cu1—Cl2	97.71 (6)
C4—C5—H5	120.2	O1—Cu1—Cl2	147.65 (4)
C6—C5—H5	120.2	N2—Cu1—Cl1	93.36 (5)
N1—C6—C5	121.6 (2)	N1—Cu1—Cl1	96.97 (6)
N1—C6—C1	116.70 (18)	O1—Cu1—Cl1	96.81 (4)
C5—C6—C1	121.7 (2)	Cl2—Cu1—Cl1	115.53 (2)
O1—C7—C8	107.73 (16)	C2—N1—C6	118.2 (2)
O1—C7—H7A	110.2	C2—N1—Cu1	126.14 (16)
C8—C7—H7A	110.2	C6—N1—Cu1	115.53 (15)
O1—C7—H7B	110.2	C8—N2—C9	118.52 (18)
C8—C7—H7B	110.2	C8—N2—Cu1	115.92 (14)
H7A—C7—H7B	108.5	C9—N2—Cu1	125.45 (14)
N2—C8—C11	121.7 (2)	C7—O1—C1	115.70 (16)
N2—C8—C7	116.77 (18)	C7—O1—Cu1	112.11 (12)
C11—C8—C7	121.47 (19)	C1—O1—Cu1	111.27 (12)
N2—C9—C12	122.3 (2)

N1—C2—C3—C4	0.7 (4)	Cl1—Cu1—N1—C6	81.62 (15)
C2—C3—C4—C5	0.2 (4)	C11—C8—N2—C9	−0.2 (3)
C3—C4—C5—C6	−1.0 (4)	C7—C8—N2—C9	−178.63 (18)
C4—C5—C6—N1	1.0 (4)	C11—C8—N2—Cu1	176.38 (15)
C4—C5—C6—C1	−179.2 (2)	C7—C8—N2—Cu1	−2.1 (2)
O1—C1—C6—N1	27.4 (3)	C12—C9—N2—C8	1.0 (3)
O1—C1—C6—C5	−152.4 (2)	C12—C9—N2—Cu1	−175.19 (16)
O1—C7—C8—N2	−20.0 (2)	N1—Cu1—N2—C8	33.8 (2)
O1—C7—C8—C11	161.56 (18)	O1—Cu1—N2—C8	15.52 (14)
C12—C10—C11—C8	0.7 (3)	Cl2—Cu1—N2—C8	162.86 (13)
N2—C8—C11—C10	−0.7 (3)	Cl1—Cu1—N2—C8	−80.74 (14)
C7—C8—C11—C10	177.7 (2)	N1—Cu1—N2—C9	−149.93 (18)
C11—C10—C12—C9	0.1 (3)	O1—Cu1—N2—C9	−168.19 (18)
N2—C9—C12—C10	−1.0 (3)	Cl2—Cu1—N2—C9	−20.85 (17)
C3—C2—N1—C6	−0.7 (4)	Cl1—Cu1—N2—C9	95.55 (17)
C3—C2—N1—Cu1	−176.6 (2)	C8—C7—O1—C1	160.80 (17)
C5—C6—N1—C2	−0.1 (3)	C8—C7—O1—Cu1	31.76 (19)
C1—C6—N1—C2	−180.0 (2)	C6—C1—O1—C7	−166.95 (17)
C5—C6—N1—Cu1	176.21 (18)	C6—C1—O1—Cu1	−37.49 (19)
C1—C6—N1—Cu1	−3.6 (2)	N2—Cu1—O1—C7	−26.88 (13)
N2—Cu1—N1—C2	143.8 (2)	N1—Cu1—O1—C7	160.88 (14)
O1—Cu1—N1—C2	162.1 (2)	Cl2—Cu1—O1—C7	−113.67 (13)
Cl2—Cu1—N1—C2	14.7 (2)	Cl1—Cu1—O1—C7	65.17 (13)
Cl1—Cu1—N1—C2	−102.4 (2)	N2—Cu1—O1—C1	−158.20 (14)
N2—Cu1—N1—C6	−32.2 (3)	N1—Cu1—O1—C1	29.56 (14)
O1—Cu1—N1—C6	−13.90 (15)	Cl2—Cu1—O1—C1	115.01 (13)
Cl2—Cu1—N1—C6	−161.33 (15)	Cl1—Cu1—O1—C1	−66.16 (13)

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₂H₁₂N₂O)]
M_r	334.68
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.1599 (10), 12.5534 (15), 15.3846 (14)
β (°)	123.574 (9)
V (Å³)	1313.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.06
Crystal size (mm)	0.46 × 0.40 × 0.34

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.451, 0.541
No. of measured, independent and observed [I > 2σ(I)] reflections	5381, 2323, 2152
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.066, 1.09
No. of reflections	2323
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.27

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cl1—Cu1	2.4109 (6)	Cu1—N1	2.0092 (18)
Cl2—Cu1	2.2538 (6)	Cu1—O1	2.0813 (14)
Cu1—N2	2.0021 (17)

N2—Cu1—N1	155.06 (7)	O1—Cu1—Cl2	147.65 (4)
N2—Cu1—O1	78.29 (6)	N2—Cu1—Cl1	93.36 (5)
N1—Cu1—O1	77.99 (7)	N1—Cu1—Cl1	96.97 (6)
N2—Cu1—Cl2	98.17 (5)	O1—Cu1—Cl1	96.81 (4)
N1—Cu1—Cl2	97.71 (6)	Cl2—Cu1—Cl1	115.53 (2)

References

Bruker (2007). 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
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