Poly[[μ2-1,2-bis­(4-pyrid­yl)ethene-κ2N:N′]-di-μ3-bromido-dicopper(I)]

Shen, F.M.; Lush, S.F.

doi:10.1107/S1600536810030734

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page m1071

https://doi.org/10.1107/S1600536810030734

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Poly[[μ₂-1,2-bis(4-pyridyl)ethene-κ²N:N′]-di-μ₃-bromido-dicopper(I)]

Fwu Ming Shen ^a and Shie Fu Lush ^b ^*

^aDepartment of Biotechnology, Yuanpei University, HsinChu 30015, Taiwan, and ^bGeneral Education Center, Yuanpei University, HsinChu 30015, Taiwan
^*Correspondence e-mail: lush@mail.ypu.edu.tw

(Received 30 July 2010; accepted 2 August 2010; online 11 August 2010)

In the title polymeric Cu^I compound, [Cu₂Br₂(C₁₂H₁₀N₂)]_n, the Cu cation is coordinated by an N atom from the 1,2-bis(4-pyridyl)ethene ligand and three Br⁻ anions in a distorted tetrahedral CuBr₃N coordination geometry. Each Br⁻ anion bridges three Cu cations related by inversion centers, forming a stair-like polymeric chain along the a axis, and the terminal N atoms of the 1,2-bis(4-pyridyl)ethene ligand, located across an inversion center, coordinate the Cu cations from neighboring chains, forming polymeric sheets.

Related literature

For related structures, see: Yang (2009 ); Wang (2008 ); Näther & Greve (2001 ). For stair-like structures, see: Healy et al. (1989 ); Jasinski et al. (1985 ).

Experimental

Crystal data

[Cu₂Br₂(C₁₂H₁₀N₂)]
M_r = 234.56
Monoclinic, P 2₁ /c
a = 3.9066 (3) Å
b = 15.1047 (13) Å
c = 11.1050 (9) Å
β = 95.149 (2)°
V = 652.64 (9) Å³
Z = 4
Mo Kα radiation
μ = 9.36 mm⁻¹
T = 294 K
0.40 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.487, T_max = 0.938
3454 measured reflections
1162 independent reflections
1083 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.096
S = 1.30
1162 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.91 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Br—Cu1	2.5645 (12)
Br—Cu1ⁱ	2.4723 (13)
Br—Cu1ⁱⁱ	2.5195 (13)
N1—Cu1	2.009 (5)

Br—Cu1—N1	105.79 (16)
Br—Cu1—Brⁱ	108.79 (4)
Br—Cu1—Brⁱⁱ	110.86 (4)
Brⁱ—Cu1—N1	119.11 (16)
Brⁱⁱ—Cu1—N1	109.30 (16)
Brⁱ—Cu1—Brⁱⁱ	102.99 (4)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+1.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810030734/xu5009sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030734/xu5009Isup2.hkl

checkCIF report

Comment top

In the structural investigations of compounds of Cu^I halide, such as bromide (Yang, 2009; Wang, 2008; Näther & Greve, 2001), has been found. A four coordination polymer, resulted from the hydrothermal treatment of CuBr with 1,2-bis(4-pyridyl)ethene.

As Fig. 1, the symmetric unit consists of one copper(I) ion, one bromide ligand and half 1,2-bis(4-pyridyl)ethene ligand, all on general positions. The Cu^I atom is tetrahedral and coordinated by three µ₃-bridging Br atoms and the each bromide bridges the other two Cu cations, while the N atoms of 1,2-bis(4-pyridyl)ethene ligand coordinate the other Cu cations, forming the three-dimensional polymeric architecture (Fig. 2).

The polymer frameworks has four-membered Cu—Br—Cu—Br units that form the step of a stair (Healy et al., 1989; Jasinski et al., 1985) and 1,2-bis(4-pyridyl)ethene ligand across those stairs, shown as Fig. 2. Cu···Cu distances are between 2.8852 (16)~2.9332 (16) Å and Cu—Br—Cu angles are 71.21 (4)~102.99 (4), respectively.

Related literature top

For related structures, see: Yang (2009); Wang (2008); Näther & Greve (2001). For stair-like structures, see: Healy et al. (1989); Jasinski et al. (1985).

Experimental top

CuBr (0.1097 g, 0.50 mmol) and 1,2-bis(4-pyridyl)ethene (0.0913 g, 0.50 mmol) were mixed in 10 ml deionized water. After being stirred for 30 min, the mixture was placed in a 25 ml Teflon liner reactor and heated at 423 K in an oven for 24 h. The resulting solution was slowly cooled to room temperature. The orange transparent single crystals of the title compound were obtained in 46.45% yield.

Structure description top

For related structures, see: Yang (2009); Wang (2008); Näther & Greve (2001). For stair-like structures, see: Healy et al. (1989); Jasinski et al. (1985).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The coordination environment around the Cu(I) cation with the atom numbering. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A diagram of the unit cell packing showing two-dimensional sheet structure.

Poly[[µ₂-1,2-bis(4-pyridyl)ethene-κ²N:N']-di-µ₃-bromido- dicopper(I)] top

Crystal data top

[Cu₂Br₂(C₁₂H₁₀N₂)]	F(000) = 448
M_r = 234.56	D_x = 2.387 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2187 reflections
a = 3.9066 (3) Å	θ = 2.5–25.0°
b = 15.1047 (13) Å	µ = 9.36 mm⁻¹
c = 11.1050 (9) Å	T = 294 K
β = 95.149 (2)°	Columnar, orange
V = 652.64 (9) Å³	0.40 × 0.10 × 0.05 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1162 independent reflections
Radiation source: fine-focus sealed tube	1083 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 9 pixels mm^-1	θ_max = 25.1°, θ_min = 2.3°
CCD rotation images, thick slices scans	h = −4→4
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −17→17
T_min = 0.487, T_max = 0.938	l = −9→13
3454 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.30	w = 1/[σ²(F_o²) + (0.022P)² + 3.3443P] where P = (F_o² + 2F_c²)/3
1162 reflections	(Δ/σ)_max = 0.010
82 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.91 e Å⁻³

Crystal data top

[Cu₂Br₂(C₁₂H₁₀N₂)]	V = 652.64 (9) Å³
M_r = 234.56	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.9066 (3) Å	µ = 9.36 mm⁻¹
b = 15.1047 (13) Å	T = 294 K
c = 11.1050 (9) Å	0.40 × 0.10 × 0.05 mm
β = 95.149 (2)°

Data collection top

Nonius KappaCCD diffractometer	1162 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	1083 reflections with I > 2σ(I)
T_min = 0.487, T_max = 0.938	R_int = 0.037
3454 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.30	Δρ_max = 0.61 e Å⁻³
1162 reflections	Δρ_min = −0.91 e Å⁻³
82 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
Br	0.19561 (17)	0.49650 (5)	0.33505 (6)	0.0347 (2)
Cu1	0.2671 (3)	0.56165 (6)	0.54908 (9)	0.0473 (3)
N1	0.3103 (14)	0.6931 (3)	0.5275 (5)	0.0343 (17)
C1	0.1767 (19)	0.7337 (4)	0.4255 (6)	0.039 (2)
C2	0.2046 (19)	0.8230 (5)	0.4055 (7)	0.041 (2)
C3	0.3818 (18)	0.8766 (4)	0.4912 (6)	0.034 (2)
C4	0.520 (2)	0.8355 (5)	0.5972 (6)	0.040 (2)
C5	0.4799 (18)	0.7450 (4)	0.6095 (6)	0.037 (2)
C6	0.4128 (19)	0.9711 (4)	0.4647 (7)	0.036 (2)
H1	0.05970	0.69940	0.36560	0.0470*
H2	0.10420	0.84770	0.33410	0.0490*
H4	0.63640	0.86840	0.65860	0.0480*
H5	0.57850	0.71860	0.67990	0.0440*
H6	0.30120	0.99200	0.39280	0.0440*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0345 (4)	0.0376 (4)	0.0312 (4)	−0.0036 (3)	−0.0006 (3)	0.0001 (3)
Cu1	0.0589 (6)	0.0302 (5)	0.0520 (6)	−0.0054 (4)	0.0000 (4)	0.0062 (4)
N1	0.041 (3)	0.023 (3)	0.039 (3)	−0.001 (2)	0.005 (3)	0.000 (2)
C1	0.048 (4)	0.029 (4)	0.038 (4)	0.002 (3)	−0.006 (3)	−0.002 (3)
C2	0.049 (4)	0.036 (4)	0.035 (4)	0.002 (3)	−0.006 (3)	0.007 (3)
C3	0.038 (4)	0.023 (3)	0.041 (4)	0.003 (3)	0.011 (3)	0.006 (3)
C4	0.050 (4)	0.035 (4)	0.035 (4)	−0.006 (3)	−0.001 (3)	−0.006 (3)
C5	0.043 (4)	0.029 (3)	0.037 (4)	−0.004 (3)	−0.003 (3)	0.001 (3)
C6	0.043 (4)	0.029 (4)	0.036 (4)	0.002 (3)	−0.001 (3)	0.000 (3)

Geometric parameters (Å, º) top

Br—Cu1	2.5645 (12)	C3—C6	1.465 (9)
Br—Cu1ⁱ	2.4723 (13)	C4—C5	1.384 (10)
Br—Cu1ⁱⁱ	2.5195 (13)	C6—C6ⁱⁱⁱ	1.321 (10)
N1—Cu1	2.009 (5)	C1—H1	0.9300
N1—C1	1.351 (8)	C2—H2	0.9300
N1—C5	1.332 (8)	C4—H4	0.9300
C1—C2	1.373 (10)	C5—H5	0.9300
C2—C3	1.386 (10)	C6—H6	0.9300
C3—C4	1.396 (10)

Br···C1	3.724 (6)	C4···H6ⁱⁱⁱ	2.7000
Br···H1	3.1300	C6···H4ⁱⁱⁱ	2.7800
Br···H2^iv	3.0900	H1···Br	3.1300
Br···H6^iv	3.0500	H2···H6	2.3800
C1···C5^v	3.551 (10)	H2···Br^ix	3.0900
C2···C3^v	3.527 (10)	H4···C6ⁱⁱⁱ	2.7800
C2···C4^v	3.570 (11)	H4···H6ⁱⁱⁱ	2.2000
C3···C2^vi	3.527 (10)	H5···C2^x	3.0800
C4···C2^vi	3.570 (11)	H6···H2	2.3800
C5···C1^vi	3.551 (10)	H6···Br^ix	3.0500
C6···C6^vii	3.498 (10)	H6···C4ⁱⁱⁱ	2.7000
C2···H5^viii	3.0800	H6···H4ⁱⁱⁱ	2.2000

Cu1—Br—Cu1ⁱ	71.21 (4)	C2—C3—C6	118.5 (6)
Cu1—Br—Cu1ⁱⁱ	69.15 (4)	C4—C3—C6	124.8 (6)
Cu1ⁱ—Br—Cu1ⁱⁱ	102.99 (4)	C3—C4—C5	118.9 (6)
Br—Cu1—N1	105.79 (16)	N1—C5—C4	124.6 (6)
Br—Cu1—Brⁱ	108.79 (4)	C3—C6—C6ⁱⁱⁱ	124.9 (7)
Br—Cu1—Brⁱⁱ	110.86 (4)	N1—C1—H1	118.00
Brⁱ—Cu1—N1	119.11 (16)	C2—C1—H1	118.00
Brⁱⁱ—Cu1—N1	109.30 (16)	C1—C2—H2	120.00
Brⁱ—Cu1—Brⁱⁱ	102.99 (4)	C3—C2—H2	120.00
Cu1—N1—C1	121.2 (4)	C3—C4—H4	121.00
Cu1—N1—C5	122.8 (4)	C5—C4—H4	121.00
C1—N1—C5	115.9 (5)	N1—C5—H5	118.00
N1—C1—C2	123.5 (6)	C4—C5—H5	118.00
C1—C2—C3	120.3 (7)	C3—C6—H6	118.00
C2—C3—C4	116.8 (6)	C6ⁱⁱⁱ—C6—H6	118.00

Cu1ⁱ—Br—Cu1—N1	−129.06 (17)	Brⁱ—Cu1—N1—C1	−97.7 (5)
Cu1ⁱⁱ—Br—Cu1—N1	118.37 (17)	Cu1—N1—C1—C2	−178.8 (6)
Cu1ⁱ—Br—Cu1—Brⁱ	0.00 (4)	C5—N1—C1—C2	−1.0 (10)
Cu1ⁱⁱ—Br—Cu1—Brⁱ	−112.57 (5)	Cu1—N1—C5—C4	179.0 (6)
Cu1ⁱ—Br—Cu1—Brⁱⁱ	112.57 (5)	C1—N1—C5—C4	1.2 (10)
Cu1ⁱⁱ—Br—Cu1—Brⁱⁱ	0.00 (4)	N1—C1—C2—C3	1.1 (11)
Cu1ⁱ—Brⁱ—Cu1—N1	121.22 (19)	C1—C2—C3—C4	−1.3 (11)
Cu1ⁱⁱ—Brⁱⁱ—Cu1—Br	0.00 (4)	C1—C2—C3—C6	178.4 (7)
Cu1ⁱⁱ—Brⁱⁱ—Cu1—N1	−116.22 (17)	C2—C3—C4—C5	1.4 (10)
Cu1ⁱ—Brⁱ—Cu1—Br	0.00 (5)	C6—C3—C4—C5	−178.3 (7)
Brⁱⁱ—Cu1—N1—C1	144.4 (5)	C2—C3—C6—C6ⁱⁱⁱ	−176.7 (7)
Brⁱⁱ—Cu1—N1—C5	−33.2 (6)	C4—C3—C6—C6ⁱⁱⁱ	3.0 (12)
Brⁱ—Cu1—N1—C5	84.7 (5)	C3—C4—C5—N1	−1.5 (11)
Br—Cu1—N1—C1	25.0 (5)	C3—C6—C6ⁱⁱⁱ—C3ⁱⁱⁱ	−180.0 (7)
Br—Cu1—N1—C5	−152.6 (5)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+2, −z+1; (iv) −x, y−1/2, −z+1/2; (v) x−1, y, z; (vi) x+1, y, z; (vii) −x, −y+2, −z+1; (viii) x, −y+3/2, z−1/2; (ix) −x, y+1/2, −z+1/2; (x) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu₂Br₂(C₁₂H₁₀N₂)]
M_r	234.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	3.9066 (3), 15.1047 (13), 11.1050 (9)
β (°)	95.149 (2)
V (Å³)	652.64 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	9.36
Crystal size (mm)	0.40 × 0.10 × 0.05

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.487, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	3454, 1162, 1083
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.096, 1.30
No. of reflections	1162
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.91

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

Br—Cu1	2.5645 (12)	Br—Cu1ⁱⁱ	2.5195 (13)
Br—Cu1ⁱ	2.4723 (13)	N1—Cu1	2.009 (5)

Br—Cu1—N1	105.79 (16)	Brⁱ—Cu1—N1	119.11 (16)
Br—Cu1—Brⁱ	108.79 (4)	Brⁱⁱ—Cu1—N1	109.30 (16)
Br—Cu1—Brⁱⁱ	110.86 (4)	Brⁱ—Cu1—Brⁱⁱ	102.99 (4)

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

Acknowledgements

This work was supported financially by Yuanpei University, Taiwan.

References

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