catena-Poly[[di-μ-bromido-dicopper(I)]bis­[μ-η2,σ1-4-(2-allyl-2H-tetra­zol-5-yl)pyridine]]

Wang, W.

doi:10.1107/S1600536808012439

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m902

doi:10.1107/S1600536808012439

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catena-Poly[[di-μ-bromido-dicopper(I)]bis[μ-η²,σ¹-4-(2-allyl-2H-tetrazol-5-yl)pyridine]]

Wei Wang ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: seu_ww@yahoo.com.cn

(Received 24 April 2008; accepted 29 April 2008; online 7 June 2008)

The title compound, [CuBr(C₉H₉N₅)]_n, prepared by the solvothermal treatment of CuBr with 4-(2-allyl-2H-tetrazol-5-yl)pyridine, is a new homometallic Cu^I–olefin coordination polymer in which dinuclear Cu₂Br₂ units are linked by the organic olefin ligand 4-(2-allyl-2H-tetrazol-5-yl)pyridine, which acts as a bidentate ligand connecting two neighbouring Cu₂Br₂ units through the pyridine N atom and the double bond of the allyl group. The coordination of Cu(I) is slightly distorted tetrahedral.

Related literature

For the solvothermal synthesis and related structures, see: Ye et al. (2005 , 2007 ).

Experimental

Crystal data

[CuBr(C₉H₉N₅)]
M_r = 330.66
Monoclinic, C 2/c
a = 17.502 (3) Å
b = 12.047 (2) Å
c = 13.664 (3) Å
β = 129.52 (3)°
V = 2222.4 (12) Å³
Z = 8
Mo Kα radiation
μ = 5.54 mm⁻¹
T = 293 (2) K
0.2 × 0.15 × 0.1 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.661, T_max = 1 (expected range = 0.380–0.575)
11222 measured reflections
2552 independent reflections
1962 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.088
S = 1.07
2552 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005); 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: ORTEPIII (Johnson & Burnett, 1997 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012439/dn2345sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012439/dn2345Isup2.hkl

checkCIF report

Comment top

Hydrothermal or solvothermal syntheses can offer some interesting reactions and compounds which can't be obtain through conventional solution techniques. In sealed tube, unstable copper (I) salt can exist under vacuums, and then interesting copper (I) organometallic compound can be prepared. The title compound is obtained through solvothermal treatment of CuBr and 4-(2-allyl-2H-tetrazol -5-yl) pyridine in methanol solvent at 75°C.

The copper(I) is coordinated to two organic ligands and two bridging Br atoms to fulfill its tetrahedral coordination environment (Fig 1).The organic ligand acts as a bidentate ligand connecting two neighbouring Cu₂Br₂ dinucler units through N atom from pyridine ring and double bond of the allyl group thus leading to an homometallic Cu^I olefin coordination polymer developing along the b axis. Unfortunately, the N atoms of the tetrazole ring fail to coordinate to Cu^I.

Related literature top

For the solvothermal synthesis and related structures, see: Ye et al. (2005, 2007).

Experimental top

A mixture of 4-(2-allyl-2H-tetrazol-5-yl) pyridine(20 mg, 0.2 mmol), CuBr (35 mg,0.4 mmol), and methanol (2 ml) sealed in a glass tube were maintained at 75 °C with yield 75%. Crystals suitable for X-ray analysis were obtained after 5 days

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Johnson & Burnett, 1997) and ORTEP-32 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The one-dimensional structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) 1 - x, y, 3/2 - z; (ii)x, y - 1, z; (C) x, y + 1, z; (iii) 1 - x, 1 + y, 3/2 - z.].

catena-Poly[[di-µ-bromido-dicopper(I)]bis[µ-η²,σ¹- 4-(2-allyl-2H-tetrazol-5-yl)pyridine]] top

Crystal data top

[CuBr(C₉H₉N₅)]	F(000) = 1296
M_r = 330.66	D_x = 1.977 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 10074 reflections
a = 17.502 (3) Å	θ = 3.0–28.8°
b = 12.047 (2) Å	µ = 5.54 mm⁻¹
c = 13.664 (3) Å	T = 293 K
β = 129.52 (3)°	Block, colorless
V = 2222.4 (12) Å³	0.2 × 0.15 × 0.1 mm
Z = 8

Data collection top

Rigaku Mercury2 diffractometer	2552 independent reflections
Radiation source: fine-focus sealed tube	1962 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −22→22
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.661, T_max = 1	l = −17→17
11222 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.03P)² + 4.1679P] where P = (F_o² + 2F_c²)/3
2552 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.77 e Å⁻³

Crystal data top

[CuBr(C₉H₉N₅)]	V = 2222.4 (12) Å³
M_r = 330.66	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 17.502 (3) Å	µ = 5.54 mm⁻¹
b = 12.047 (2) Å	T = 293 K
c = 13.664 (3) Å	0.2 × 0.15 × 0.1 mm
β = 129.52 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2552 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1962 reflections with I > 2σ(I)
T_min = 0.661, T_max = 1	R_int = 0.050
11222 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.07	Δρ_max = 0.40 e Å⁻³
2552 reflections	Δρ_min = −0.77 e Å⁻³
145 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.39530 (4)	−0.00789 (3)	0.59335 (4)	0.03898 (15)
Br1	0.41669 (3)	−0.00735 (3)	0.79367 (3)	0.03492 (12)
N1	0.4034 (2)	0.4106 (2)	0.5433 (3)	0.0379 (8)
N2	0.3650 (3)	0.4582 (3)	0.3597 (3)	0.0448 (8)
N3	0.3835 (3)	0.3508 (3)	0.3743 (3)	0.0475 (9)
N4	0.4055 (2)	0.3250 (2)	0.4833 (3)	0.0363 (7)
N5	0.3645 (2)	0.8317 (2)	0.5386 (3)	0.0319 (7)
C1	0.2905 (3)	0.0849 (3)	0.4367 (4)	0.0397 (9)
H1A	0.2909	0.0807	0.3661	0.048*
H1B	0.2243	0.0836	0.4105	0.048*
C2	0.3548 (3)	0.1574 (3)	0.5299 (4)	0.0376 (9)
H2	0.3295	0.2001	0.5648	0.045*
C3	0.4350 (3)	0.2120 (3)	0.5368 (4)	0.0449 (10)
H3A	0.4950	0.2157	0.6246	0.054*
H3B	0.4488	0.1681	0.4902	0.054*
C4	0.3456 (3)	0.6920 (3)	0.4013 (3)	0.0356 (9)
H4	0.3317	0.6742	0.3251	0.043*
C5	0.3673 (2)	0.6090 (3)	0.4859 (3)	0.0285 (7)
C6	0.3807 (3)	0.7513 (3)	0.6168 (3)	0.0338 (8)
H6	0.3909	0.7711	0.6901	0.041*
C7	0.3451 (3)	0.8007 (3)	0.4310 (3)	0.0366 (9)
H7	0.3304	0.8554	0.3732	0.044*
C8	0.3830 (3)	0.6403 (3)	0.5945 (3)	0.0338 (8)
H8	0.3951	0.5871	0.6522	0.041*
C9	0.3769 (3)	0.4926 (3)	0.4619 (3)	0.0315 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0551 (3)	0.0158 (2)	0.0379 (3)	0.0008 (2)	0.0258 (2)	−0.00052 (17)
Br1	0.0433 (2)	0.0305 (2)	0.0396 (2)	−0.00627 (16)	0.03041 (19)	−0.00676 (15)
N1	0.0484 (19)	0.0190 (15)	0.0431 (19)	0.0017 (14)	0.0276 (17)	0.0017 (13)
N2	0.062 (2)	0.0236 (16)	0.043 (2)	0.0066 (16)	0.0307 (18)	0.0007 (14)
N3	0.068 (2)	0.0244 (17)	0.048 (2)	0.0036 (16)	0.036 (2)	−0.0030 (14)
N4	0.0409 (18)	0.0135 (14)	0.050 (2)	0.0011 (13)	0.0271 (17)	−0.0007 (13)
N5	0.0372 (17)	0.0154 (14)	0.0352 (17)	0.0002 (12)	0.0193 (15)	−0.0010 (12)
C1	0.039 (2)	0.0268 (19)	0.048 (2)	0.0042 (16)	0.0248 (19)	0.0102 (17)
C2	0.057 (2)	0.0164 (17)	0.047 (2)	0.0117 (17)	0.037 (2)	0.0068 (15)
C3	0.044 (2)	0.0163 (18)	0.064 (3)	0.0055 (16)	0.029 (2)	0.0065 (17)
C4	0.051 (2)	0.0209 (17)	0.031 (2)	−0.0029 (16)	0.0243 (19)	−0.0024 (14)
C5	0.0269 (17)	0.0171 (16)	0.0332 (18)	−0.0031 (14)	0.0153 (16)	−0.0011 (13)
C6	0.045 (2)	0.0199 (17)	0.038 (2)	−0.0036 (15)	0.0272 (19)	−0.0026 (15)
C7	0.049 (2)	0.0185 (17)	0.037 (2)	0.0002 (16)	0.0248 (19)	0.0047 (15)
C8	0.042 (2)	0.0199 (17)	0.036 (2)	−0.0025 (15)	0.0236 (18)	0.0034 (14)
C9	0.0322 (17)	0.0168 (17)	0.0372 (19)	−0.0029 (14)	0.0182 (16)	0.0003 (14)

Geometric parameters (Å, º) top

Cu1—N5ⁱ	2.017 (3)	C1—H1A	0.9700
Cu1—C1	2.050 (4)	C1—H1B	0.9700
Cu1—C2	2.106 (3)	C2—C3	1.496 (6)
Cu1—Br1	2.5156 (9)	C2—H2	0.9800
Cu1—Br1ⁱⁱ	2.5973 (11)	C3—H3A	0.9700
Br1—Cu1ⁱⁱ	2.5973 (11)	C3—H3B	0.9700
N1—C9	1.330 (4)	C4—C7	1.373 (5)
N1—N4	1.332 (4)	C4—C5	1.386 (5)
N2—N3	1.317 (4)	C4—H4	0.9300
N2—C9	1.340 (5)	C5—C8	1.378 (5)
N3—N4	1.317 (5)	C5—C9	1.475 (4)
N4—C3	1.475 (4)	C6—C8	1.378 (5)
N5—C6	1.332 (4)	C6—H6	0.9300
N5—C7	1.334 (4)	C7—H7	0.9300
N5—Cu1ⁱⁱⁱ	2.017 (3)	C8—H8	0.9300
C1—C2	1.351 (5)

N5ⁱ—Cu1—C1	106.55 (13)	C3—C2—Cu1	109.5 (2)
N5ⁱ—Cu1—C2	144.30 (14)	C1—C2—H2	115.7
C1—Cu1—C2	37.93 (14)	C3—C2—H2	115.7
N5ⁱ—Cu1—Br1	103.04 (9)	Cu1—C2—H2	115.7
C1—Cu1—Br1	123.33 (12)	N4—C3—C2	110.9 (3)
C2—Cu1—Br1	102.94 (10)	N4—C3—H3A	109.5
N5ⁱ—Cu1—Br1ⁱⁱ	99.28 (9)	C2—C3—H3A	109.5
C1—Cu1—Br1ⁱⁱ	124.96 (11)	N4—C3—H3B	109.5
C2—Cu1—Br1ⁱⁱ	102.07 (11)	C2—C3—H3B	109.5
Br1—Cu1—Br1ⁱⁱ	95.64 (4)	H3A—C3—H3B	108.0
Cu1—Br1—Cu1ⁱⁱ	84.36 (4)	C7—C4—C5	119.4 (3)
C9—N1—N4	101.0 (3)	C7—C4—H4	120.3
N3—N2—C9	106.6 (3)	C5—C4—H4	120.3
N4—N3—N2	105.6 (3)	C8—C5—C4	117.6 (3)
N3—N4—N1	114.3 (3)	C8—C5—C9	121.8 (3)
N3—N4—C3	122.5 (3)	C4—C5—C9	120.6 (3)
N1—N4—C3	123.2 (3)	N5—C6—C8	123.3 (3)
C6—N5—C7	117.1 (3)	N5—C6—H6	118.3
C6—N5—Cu1ⁱⁱⁱ	121.9 (2)	C8—C6—H6	118.3
C7—N5—Cu1ⁱⁱⁱ	119.8 (2)	N5—C7—C4	123.2 (3)
C2—C1—Cu1	73.3 (2)	N5—C7—H7	118.4
C2—C1—H1A	116.2	C4—C7—H7	118.4
Cu1—C1—H1A	116.2	C6—C8—C5	119.3 (3)
C2—C1—H1B	116.2	C6—C8—H8	120.3
Cu1—C1—H1B	116.2	C5—C8—H8	120.3
H1A—C1—H1B	113.2	N1—C9—N2	112.5 (3)
C1—C2—C3	122.0 (4)	N1—C9—C5	123.2 (3)
C1—C2—Cu1	68.8 (2)	N2—C9—C5	124.2 (3)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y, −z+3/2; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[CuBr(C₉H₉N₅)]
M_r	330.66
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	17.502 (3), 12.047 (2), 13.664 (3)
β (°)	129.52 (3)
V (Å³)	2222.4 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	5.54
Crystal size (mm)	0.2 × 0.15 × 0.1

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.661, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	11222, 2552, 1962
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.088, 1.07
No. of reflections	2552
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.77

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Johnson & Burnett, 1997) and ORTEP-32 for Windows (Farrugia, 1997).

Acknowledgements

This work was supported by a Start-up Grant from SEU to Professor Ren-Gen Xiong.

References

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