catena-Poly[[dianilinedichloridocopper(II)]-μ2-2,5-bis­(4-pyrid­yl)-1,3,4-oxadiazole]

Meng, Q.; Wu, Y.; Zhang, C.

doi:10.1107/S1600536809054191

metal-organic compounds

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Volume 66| Part 1| January 2010| Page m97

doi:10.1107/S1600536809054191

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catena-Poly[[dianilinedichloridocopper(II)]-μ₂-2,5-bis(4-pyridyl)-1,3,4-oxadiazole]

Qinglong Meng,^a Yiming Wu ^a and Chi Zhang ^b ^*

^aSchool of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, Jiangsu, People's Republic of China, and ^bResearch Center for Advanced Molecular Materials, School of Chemistry and Chemical Engineering, Scientific Research Academy, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, Jiangsu, People's Republic of China
^*Correspondence e-mail: chizhang@ujs.edu.cn

(Received 2 December 2009; accepted 16 December 2009; online 24 December 2009)

In the title compound, [CuCl₂(C₆H₇N)₂(C₁₂H₈N₄O)]_n, the Cu atom, located on an inversion center, is coordinated by four N atoms from two aniline ligands and two 2,5-bis(4-pyridyl)-1,3,4-oxadiazole ligands. Two Cl atoms lying above and below the plane formed by these four N atoms interact weakly with the Cu atom [Cu—Cl = 2.7870 (7) Å]. The trans 2,5-bis(4-pyridyl)-1,3,4-oxadiazole ligands act as bridging ligands, linking adjacent Cu atoms and forming a one-dimensional coordination polymer. Two anilines coordinate with each Cu atom as terminal groups. The structure contains two classical N—H⋯Cl and two non-classical C—H⋯Cl hydrogen bonds.

Related literature

Unsymmetric organic bridging ligands can play different roles in the construction of metal-organic frameworks, see: Du et al. (2004 ); Dong et al. (2005 ). For Cu—Cl distances, see: Handley et al. (2001 ).

Experimental

Crystal data

[CuCl₂(C₆H₇N)₂(C₁₂H₈N₄O)]
M_r = 544.93
Monoclinic, C 2/c
a = 27.028 (5) Å
b = 12.618 (3) Å
c = 6.7904 (14) Å
β = 94.96 (3)°
V = 2307.1 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.21 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku CCD area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.329, T_max = 0.463
5331 measured reflections
2233 independent reflections
2106 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.085
S = 1.04
2233 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.90	2.53	3.406 (2)	165
N1—H1B⋯Cl1ⁱⁱ	0.90	2.56	3.393 (2)	154
C9—H9A⋯Cl1ⁱⁱⁱ	0.93	2.70	3.285 (2)	121
C2—H2C⋯Cl1	0.93	2.66	3.328 (2)	129
Symmetry codes: (i) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) $[-x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z-1]$ ; (iii) $[-x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536809054191/pv2245sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809054191/pv2245Isup2.hkl

checkCIF report

Comment top

The unsymmetric organic bridging ligands can play different roles in constructing metal-organic frameworks (Du et al., 2004; Dong et al., 2005). Recently, we have synthesized a new one-dimensional polymer with unsymmetric organic 2,5-bis(4-pyridyl)-1,3,4-oxadiazole as bridging ligand. In this paper, the crystal structure of the title compound, (I), is presented.

As illustrated in Fig. 1, each Cu coordinates with four N atoms from two anilines and two 2,5-bis(4-pyridyl)-1,3,4-oxadiazole ligands, and two Cl atoms lying above and below the plane formed by the N atoms around Cu interact with Cu atom to form an octahedral geometry. The Cu—Cl bonds (2.7870 (7) Å) are longer than normal value (Handley et al., 2001). 2,5-Bis(4-pyridyl)-1,3,4-oxadiazoles act as bridging ligands to connect adjacent two Cu atoms to construct a unique one-dimensional chain. The crystal structure shows a range of classical N—H···Cl and non-classical C—H···Cl hydrogen bonds (Table 1).

Related literature top

Unsymmetric organic bridging ligands can play different roles in the construction of metal-organic frameworks, see: Du et al. (2004); Dong et al. (2005). For normal Cu—Cl distances, see: Handley et al. (2001).

Experimental top

2,5-Bis(4-pyridyl)-1,3,4-oxadiazole (1 mmol) and copper chloride (1 mmol) were added into N,N'-dimethylformamide (5 ml) with thorough stirring for 5 minutes. The solution underwent an additional stir for one minute after aniline (2 ml) was added. After filtration, 10 ml i-PrOH was successively laid on the surface of above filtrate. Black block crystals were obtained after ten days.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 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).

Figures top

Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids; H atoms have been omitted for clarity. Symmetry code: (i) -x - 1/2, -y + 1/2, -z.

catena-Poly[[dianilinedichloridocopper(II)]-µ₂-2,5- bis(4-pyridyl)-1,3,4-oxadiazole] top

Crystal data top

[CuCl₂(C₆H₇N)₂(C₁₂H₈N₄O)]	F(000) = 1116
M_r = 544.93	D_x = 1.569 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4915 reflections
a = 27.028 (5) Å	θ = 3.0–28.9°
b = 12.618 (3) Å	µ = 1.21 mm⁻¹
c = 6.7904 (14) Å	T = 293 K
β = 94.96 (3)°	Prism, black
V = 2307.1 (8) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku CCD area-detector diffractometer	2233 independent reflections
Radiation source: fine-focus sealed tube	2106 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 28.5714 pixels mm^-1	θ_max = 26.0°, θ_min = 3.0°
phi and ω scans	h = −28→33
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −15→13
T_min = 0.329, T_max = 0.463	l = −8→8
5331 measured reflections

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0436P)² + 2.9828P] where P = (F_o² + 2F_c²)/3
2233 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[CuCl₂(C₆H₇N)₂(C₁₂H₈N₄O)]	V = 2307.1 (8) Å³
M_r = 544.93	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 27.028 (5) Å	µ = 1.21 mm⁻¹
b = 12.618 (3) Å	T = 293 K
c = 6.7904 (14) Å	0.20 × 0.20 × 0.20 mm
β = 94.96 (3)°

Data collection top

Rigaku CCD area-detector diffractometer	2233 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2106 reflections with I > 2σ(I)
T_min = 0.329, T_max = 0.463	R_int = 0.018
5331 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.04	Δρ_max = 0.33 e Å⁻³
2233 reflections	Δρ_min = −0.31 e Å⁻³
156 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
Cu1	−0.2500	0.2500	0.0000	0.03226 (14)
Cl1	−0.25356 (2)	0.38364 (4)	−0.32770 (8)	0.03830 (16)
O1	−0.5000	0.13053 (16)	−0.2500	0.0314 (4)
N1	−0.21455 (6)	0.14463 (14)	−0.1808 (3)	0.0307 (4)
H1A	−0.2260	0.0793	−0.1575	0.037*
H1B	−0.2248	0.1606	−0.3069	0.037*
N2	−0.47412 (6)	−0.03453 (15)	−0.2314 (3)	0.0439 (5)
N3	−0.31537 (6)	0.18313 (14)	−0.1116 (2)	0.0302 (4)
C1	−0.16136 (8)	0.13839 (16)	−0.1674 (3)	0.0297 (4)
C2	−0.35055 (8)	0.24122 (16)	−0.2121 (3)	0.0318 (5)
H2C	−0.3421	0.3077	−0.2578	0.038*
C3	−0.13423 (9)	0.21652 (19)	−0.2524 (3)	0.0384 (5)
H3A	−0.1504	0.2698	−0.3277	0.046*
C4	−0.37354 (7)	0.04244 (17)	−0.0989 (3)	0.0327 (5)
H4A	−0.3801	−0.0273	−0.0650	0.039*
C5	−0.41057 (7)	0.10551 (16)	−0.1900 (3)	0.0294 (4)
C6	−0.13728 (9)	0.05767 (19)	−0.0619 (3)	0.0393 (5)
H6A	−0.1554	0.0039	−0.0081	0.047*
C7	−0.46097 (7)	0.06337 (17)	−0.2226 (3)	0.0316 (4)
C8	−0.08592 (10)	0.0568 (2)	−0.0361 (4)	0.0526 (7)
H8A	−0.0696	0.0023	0.0355	0.063*
C9	−0.32679 (7)	0.08464 (17)	−0.0592 (3)	0.0315 (4)
H9A	−0.3022	0.0430	0.0065	0.038*
C10	−0.39873 (8)	0.20621 (17)	−0.2503 (3)	0.0324 (4)
H10A	−0.4227	0.2495	−0.3153	0.039*
C11	−0.05886 (9)	0.1359 (2)	−0.1157 (4)	0.0546 (7)
H11A	−0.0244	0.1357	−0.0958	0.066*
C12	−0.08290 (9)	0.2150 (2)	−0.2247 (4)	0.0489 (6)
H12A	−0.0646	0.2678	−0.2804	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0197 (2)	0.0341 (2)	0.0427 (2)	−0.00195 (14)	0.00072 (15)	−0.00980 (15)
Cl1	0.0389 (3)	0.0335 (3)	0.0414 (3)	−0.0028 (2)	−0.0027 (2)	0.0045 (2)
O1	0.0211 (9)	0.0319 (10)	0.0406 (11)	0.000	−0.0006 (8)	0.000
N1	0.0295 (9)	0.0312 (9)	0.0313 (9)	−0.0004 (7)	0.0024 (7)	0.0004 (7)
N2	0.0222 (9)	0.0345 (10)	0.0735 (14)	0.0003 (8)	−0.0040 (9)	0.0004 (9)
N3	0.0229 (8)	0.0341 (9)	0.0336 (9)	0.0001 (7)	0.0016 (7)	−0.0058 (7)
C1	0.0298 (10)	0.0310 (10)	0.0287 (10)	0.0015 (8)	0.0055 (8)	−0.0039 (8)
C2	0.0296 (11)	0.0328 (11)	0.0331 (11)	−0.0014 (8)	0.0034 (9)	0.0006 (8)
C3	0.0409 (13)	0.0385 (12)	0.0368 (12)	−0.0018 (10)	0.0094 (10)	0.0013 (9)
C4	0.0268 (10)	0.0313 (10)	0.0395 (11)	0.0012 (9)	0.0004 (8)	−0.0019 (9)
C5	0.0225 (10)	0.0345 (11)	0.0310 (10)	−0.0015 (8)	0.0010 (8)	−0.0046 (8)
C6	0.0396 (12)	0.0385 (12)	0.0405 (12)	0.0028 (10)	0.0072 (10)	0.0022 (10)
C7	0.0230 (9)	0.0337 (11)	0.0375 (11)	0.0034 (9)	−0.0005 (8)	−0.0008 (9)
C8	0.0423 (14)	0.0611 (17)	0.0538 (15)	0.0199 (13)	0.0007 (11)	0.0028 (13)
C9	0.0245 (10)	0.0323 (10)	0.0371 (11)	0.0027 (9)	−0.0009 (8)	−0.0031 (9)
C10	0.0261 (10)	0.0364 (11)	0.0341 (11)	0.0035 (9)	−0.0018 (8)	0.0016 (9)
C11	0.0289 (12)	0.0780 (19)	0.0577 (16)	0.0022 (13)	0.0085 (11)	−0.0111 (14)
C12	0.0421 (13)	0.0549 (15)	0.0522 (15)	−0.0115 (12)	0.0191 (12)	−0.0065 (12)

Geometric parameters (Å, º) top

Cu1—N3ⁱ	2.0436 (17)	C2—H2C	0.9300
Cu1—N3	2.0436 (17)	C3—C12	1.384 (3)
Cu1—N1ⁱ	2.0966 (17)	C3—H3A	0.9300
Cu1—N1	2.0966 (17)	C4—C9	1.376 (3)
Cu1—Cl1	2.7870 (7)	C4—C5	1.383 (3)
Cu1—Cl1ⁱ	2.7870 (7)	C4—H4A	0.9300
O1—C7	1.353 (2)	C5—C10	1.381 (3)
O1—C7ⁱⁱ	1.353 (2)	C5—C7	1.461 (3)
N1—C1	1.435 (3)	C6—C8	1.384 (3)
N1—H1A	0.9000	C6—H6A	0.9300
N1—H1B	0.9000	C8—C11	1.375 (4)
N2—C7	1.285 (3)	C8—H8A	0.9300
N2—N2ⁱⁱ	1.400 (3)	C9—H9A	0.9300
N3—C9	1.336 (3)	C10—H10A	0.9300
N3—C2	1.340 (3)	C11—C12	1.372 (4)
C1—C6	1.376 (3)	C11—H11A	0.9300
C1—C3	1.384 (3)	C12—H12A	0.9300
C2—C10	1.378 (3)

N3ⁱ—Cu1—N3	180.00	C10—C2—H2C	118.7
N3ⁱ—Cu1—N1ⁱ	86.87 (7)	C12—C3—C1	119.6 (2)
N3—Cu1—N1ⁱ	93.13 (7)	C12—C3—H3A	120.2
N3ⁱ—Cu1—N1	93.13 (7)	C1—C3—H3A	120.2
N3—Cu1—N1	86.87 (7)	C9—C4—C5	118.8 (2)
N1ⁱ—Cu1—N1	180.00	C9—C4—H4A	120.6
N3ⁱ—Cu1—Cl1	90.87 (6)	C5—C4—H4A	120.6
N3—Cu1—Cl1	89.13 (6)	C10—C5—C4	119.00 (19)
N1ⁱ—Cu1—Cl1	95.61 (5)	C10—C5—C7	121.81 (19)
N1—Cu1—Cl1	84.39 (5)	C4—C5—C7	119.19 (19)
N3ⁱ—Cu1—Cl1ⁱ	89.13 (6)	C1—C6—C8	119.7 (2)
N3—Cu1—Cl1ⁱ	90.87 (6)	C1—C6—H6A	120.1
N1ⁱ—Cu1—Cl1ⁱ	84.39 (5)	C8—C6—H6A	120.1
N1—Cu1—Cl1ⁱ	95.61 (5)	N2—C7—O1	112.73 (18)
Cl1—Cu1—Cl1ⁱ	180.00	N2—C7—C5	127.37 (19)
C7—O1—C7ⁱⁱ	102.5 (2)	O1—C7—C5	119.89 (18)
C1—N1—Cu1	120.26 (13)	C11—C8—C6	120.4 (2)
C1—N1—H1A	107.3	C11—C8—H8A	119.8
Cu1—N1—H1A	107.3	C6—C8—H8A	119.8
C1—N1—H1B	107.3	N3—C9—C4	122.48 (19)
Cu1—N1—H1B	107.3	N3—C9—H9A	118.8
H1A—N1—H1B	106.9	C4—C9—H9A	118.8
C7—N2—N2ⁱⁱ	106.03 (12)	C2—C10—C5	118.60 (19)
C9—N3—C2	118.33 (18)	C2—C10—H10A	120.7
C9—N3—Cu1	119.83 (14)	C5—C10—H10A	120.7
C2—N3—Cu1	121.05 (14)	C12—C11—C8	119.8 (2)
C6—C1—C3	120.0 (2)	C12—C11—H11A	120.1
C6—C1—N1	119.99 (19)	C8—C11—H11A	120.1
C3—C1—N1	119.90 (19)	C11—C12—C3	120.4 (2)
N3—C2—C10	122.5 (2)	C11—C12—H12A	119.8
N3—C2—H2C	118.7	C3—C12—H12A	119.8

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱⁱⁱ	0.90	2.53	3.406 (2)	165
N1—H1B···Cl1^iv	0.90	2.56	3.393 (2)	154
C9—H9A···Cl1ⁱ	0.93	2.70	3.285 (2)	121
C2—H2C···Cl1	0.93	2.66	3.328 (2)	129

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

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₆H₇N)₂(C₁₂H₈N₄O)]
M_r	544.93
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	27.028 (5), 12.618 (3), 6.7904 (14)
β (°)	94.96 (3)
V (Å³)	2307.1 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.21
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku CCD area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.329, 0.463
No. of measured, independent and observed [I > 2σ(I)] reflections	5331, 2233, 2106
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.085, 1.04
No. of reflections	2233
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.31

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.90	2.53	3.406 (2)	165
N1—H1B···Cl1ⁱⁱ	0.90	2.56	3.393 (2)	154
C9—H9A···Cl1ⁱⁱⁱ	0.93	2.70	3.285 (2)	121
C2—H2C···Cl1	0.93	2.66	3.328 (2)	129

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 50472048).

References

Dong, Y. B., Ma, J. P., Mark, D. S., Huang, R. Q., Tang, B., Chen, D. Z. & Loye, H. C. (2005). Solid State Sci. 4, 1313–1320. Web of Science CSD CrossRef Google Scholar
Du, M., Lam, C. K., Bu, X. H. & Mak, T. C. K. (2004). Inorg. Chem. Commun. 8, 315–318. Web of Science CSD CrossRef Google Scholar
Handley, D. A., Hitchcock, P. B., Lee, T. H. & Leigh, G. J. (2001). Inorg. Chim. Acta, 316, 59–64. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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