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

Wang, W.

doi:10.1107/S1600536808017820

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m930

doi:10.1107/S1600536808017820

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catena-Poly[[di-μ-chlorido-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 7 April 2008; accepted 12 June 2008; online 19 June 2008)

The title polymer, [Cu₂Cl₂(C₉H₉N₅)₂]_n, has been prepared by the solvothermal treatment of CuCl with 4-(2-allyl-2H-tetrazol-5-yl)pyridine. The crystal structure shows that the title compound is a homometallic Cu^I–olefin coordination polymer, in which the Cu₂Cl₂ nodes are bridged by two olefin ligands. The asymmetric unit contains one-half of the monomer, the complete monomer having twofold rotation symmetry. The coordination environment of Cu^I is slightly distorted tetrahedral, with coordination sites being two μ₂-Cl atoms, one pyridine N atom of an organic ligand and one allylic double bond of a symmetry-related ligand. Each organic molecule behaves as a bidentate ligand, connecting two neighboring Cu₂Cl₂ dimers in the polymeric chain, which runs along [010].

Related literature

For the solvothermal synthesis and for related structures, see: Ye et al. (2005 , 2007 ). For related structures, see: Wang (2008a,b,c).

Experimental

Crystal data

[Cu₂Cl₂(C₉H₉N₅)₂]
M_r = 286.21
Monoclinic, C 2/c
a = 17.270 (3) Å
b = 12.040 (2) Å
c = 13.064 (3) Å
β = 127.94 (3)°
V = 2142.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 2.27 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 = 0.643, T_max = 0.800
10753 measured reflections
2451 independent reflections
1814 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.100
S = 1.06
2451 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.39 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: PLATON (Spek, 2003 ) and XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017820/bh2171sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017820/bh2171Isup2.hkl

checkCIF report

Comment top

Under hydrothermal or solvothermal conditions, some interesting reactions and compounds can be obtained, while these products could not be synthesized using conventional solution techniques. In sealed tubes, unstable Cu^I salts can exist under reduced pressure, and then interesting Cu^I coordination compounds can be obtained. The title compound is obtained through solvothermal treatment of CuCl and 4-(2-allyl-2H-tetrazol-5-yl)pyridine in methanol solvent at 348 K. Colourless block crystals suitable for X-ray diffractions have been isolated.

The Cu^I ion is coordinated to two olefin ligands and two bridging Cl atoms in a tetrahedral environment (Fig. 1). Two olefin ligands related by a twofold axis link the neighbouring Cu₂Cl₂ dimers to form an homometallic Cu^I olefin coordination polymer, developing along the [010] axis, with the Cu₂Cl₂ dimers acting as nodes. The allyl groups coordinate to Cu^I centers through N atoms of pyridine rings and double bonds of allyl groups. Unfortunately, the N atoms of tetrazole rings fail to coordinate Cu^I ions (Fig. 2).

Related literature top

For the solvothermal synthesis and for related structures, see: Ye et al. (2005, 2007). For related structures, see: Wang (2008a,b,c).

Experimental top

A mixture of 4-(2-allyl-2H-tetrazol-5-yl)pyridine (20 mg, 0.2 mmol), CuCl (36 mg, 0.4 mmol), and methanol (2 ml) sealed in a glass tube were maintained at 348 K. 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: PLATON (Spek, 2003) and XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of a part of the title polymer, with atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. Symmetry codes: (A) x, y - 1, z; (B) x, y + 1, z.
	Fig. 2. The one-dimensional chain structure of the title compound.

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

Crystal data top

[Cu₂Cl₂(C₉H₉N₅)₂]	F(000) = 1152
M_r = 286.21	D_x = 1.775 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9724 reflections
a = 17.270 (3) Å	θ = 3.2–28.8°
b = 12.040 (2) Å	µ = 2.27 mm⁻¹
c = 13.064 (3) Å	T = 293 K
β = 127.94 (3)°	Block, colourless
V = 2142.3 (7) Å³	0.2 × 0.15 × 0.1 mm
Z = 8

Data collection top

Rigaku Mercury2 diffractometer	2451 independent reflections
Radiation source: fine-focus sealed tube	1814 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
CCD_Profile_fitting scans	h = −22→22
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.643, T_max = 0.800	l = −16→16
10753 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0422P)² + 0.6044P] where P = (F_o² + 2F_c²)/3
2451 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Cu₂Cl₂(C₉H₉N₅)₂]	V = 2142.3 (7) Å³
M_r = 286.21	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 17.270 (3) Å	µ = 2.27 mm⁻¹
b = 12.040 (2) Å	T = 293 K
c = 13.064 (3) Å	0.2 × 0.15 × 0.1 mm
β = 127.94 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2451 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1814 reflections with I > 2σ(I)
T_min = 0.643, T_max = 0.800	R_int = 0.059
10753 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.06	Δρ_max = 0.33 e Å⁻³
2451 reflections	Δρ_min = −0.39 e Å⁻³
154 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.39314 (3)	0.49203 (3)	0.59806 (4)	0.03726 (16)
Cl1	0.57394 (6)	0.49142 (6)	0.69868 (8)	0.0343 (2)
N1	0.3855 (2)	0.8479 (2)	0.3785 (3)	0.0460 (7)
N2	0.40548 (19)	0.91092 (19)	0.5524 (3)	0.0362 (6)
N3	0.3659 (2)	0.9552 (2)	0.3613 (3)	0.0435 (7)
N4	0.40899 (19)	0.82409 (19)	0.4924 (3)	0.0345 (6)
N5	0.36588 (18)	0.33219 (19)	0.5431 (2)	0.0304 (6)
C1	0.2946 (2)	0.5831 (2)	0.4346 (3)	0.0388 (8)
H1A	0.2411	0.5472	0.4259	0.068 (12)*
H1C	0.3062	0.5683	0.3729	0.052 (11)*
C2	0.3534 (2)	0.6549 (2)	0.5330 (3)	0.0350 (7)
H2A	0.3419	0.6698	0.5948	0.089 (15)*
C3	0.4367 (2)	0.7121 (2)	0.5475 (3)	0.0402 (8)
H3A	0.4545	0.6695	0.5027	0.030 (8)*
H3B	0.4928	0.7163	0.6374	0.052 (11)*
C4	0.3685 (2)	0.1086 (2)	0.4905 (3)	0.0273 (6)
C5	0.3489 (2)	0.2998 (2)	0.4331 (3)	0.0345 (7)
H5A	0.3356	0.3559	0.3720	0.041 (9)*
C6	0.3829 (2)	0.1409 (2)	0.6025 (3)	0.0321 (7)
H6A	0.3937	0.0860	0.6633	0.047 (10)*
C7	0.3811 (2)	0.2523 (2)	0.6256 (3)	0.0317 (7)
H7A	0.3911	0.2741	0.7037	0.033 (8)*
C8	0.3495 (2)	0.1902 (2)	0.4032 (3)	0.0346 (7)
H8A	0.3371	0.1704	0.3231	0.054 (11)*
C9	0.3785 (2)	0.9917 (2)	0.4676 (3)	0.0301 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0528 (3)	0.0168 (2)	0.0349 (2)	−0.00049 (16)	0.0233 (2)	−0.00040 (15)
Cl1	0.0435 (4)	0.0304 (4)	0.0372 (4)	0.0055 (3)	0.0290 (4)	0.0058 (3)
N1	0.069 (2)	0.0269 (14)	0.0416 (16)	0.0058 (13)	0.0335 (16)	−0.0005 (12)
N2	0.0465 (15)	0.0205 (12)	0.0401 (15)	−0.0013 (11)	0.0259 (13)	0.0008 (11)
N3	0.067 (2)	0.0263 (14)	0.0390 (16)	0.0078 (13)	0.0332 (16)	0.0024 (12)
N4	0.0431 (16)	0.0165 (12)	0.0435 (16)	0.0016 (10)	0.0265 (14)	−0.0001 (11)
N5	0.0371 (14)	0.0179 (12)	0.0321 (13)	−0.0020 (10)	0.0191 (12)	−0.0013 (10)
C1	0.0421 (19)	0.0278 (16)	0.0394 (18)	0.0039 (14)	0.0215 (16)	0.0070 (14)
C2	0.052 (2)	0.0180 (14)	0.0432 (19)	0.0075 (13)	0.0337 (18)	0.0074 (13)
C3	0.043 (2)	0.0164 (14)	0.051 (2)	0.0045 (13)	0.0234 (18)	0.0053 (14)
C4	0.0293 (15)	0.0182 (14)	0.0291 (15)	−0.0021 (11)	0.0153 (13)	−0.0002 (11)
C5	0.0465 (19)	0.0197 (14)	0.0325 (18)	−0.0001 (13)	0.0218 (16)	0.0043 (12)
C6	0.0415 (18)	0.0191 (14)	0.0348 (17)	−0.0026 (12)	0.0229 (15)	0.0023 (13)
C7	0.0423 (18)	0.0228 (15)	0.0328 (17)	−0.0037 (12)	0.0245 (16)	−0.0014 (12)
C8	0.0468 (19)	0.0257 (15)	0.0319 (17)	−0.0024 (13)	0.0246 (15)	−0.0009 (13)
C9	0.0357 (16)	0.0170 (14)	0.0347 (16)	−0.0027 (12)	0.0202 (14)	−0.0002 (12)

Geometric parameters (Å, º) top

Cu1—N5	2.006 (2)	C1—H1C	0.9600
Cu1—C1	2.047 (3)	C2—C3	1.497 (4)
Cu1—C2	2.079 (3)	C2—H2A	0.9599
Cu1—Cl1ⁱ	2.3491 (11)	C3—H3A	0.9598
Cu1—Cl1	2.5358 (12)	C3—H3B	0.9599
Cl1—Cu1ⁱ	2.3491 (11)	C4—C8	1.384 (4)
N1—N4	1.310 (4)	C4—C6	1.381 (4)
N1—N3	1.319 (4)	C4—C9ⁱⁱ	1.471 (4)
N2—C9	1.325 (4)	C5—C8	1.378 (4)
N2—N4	1.330 (3)	C5—H5A	0.9600
N3—C9	1.341 (4)	C6—C7	1.379 (4)
N4—C3	1.464 (3)	C6—H6A	0.9599
N5—C5	1.336 (4)	C7—H7A	0.9600
N5—C7	1.345 (4)	C8—H8A	0.9600
C1—C2	1.351 (4)	C9—C4ⁱⁱⁱ	1.471 (4)
C1—H1A	0.9600

N5—Cu1—C1	106.18 (11)	C3—C2—Cu1	109.4 (2)
N5—Cu1—C2	144.35 (12)	C1—C2—H2A	119.7
C1—Cu1—C2	38.23 (12)	C3—C2—H2A	119.1
N5—Cu1—Cl1ⁱ	104.01 (8)	Cu1—C2—H2A	91.1
C1—Cu1—Cl1ⁱ	130.46 (11)	N4—C3—C2	111.3 (3)
C2—Cu1—Cl1ⁱ	104.77 (10)	N4—C3—H3A	108.8
N5—Cu1—Cl1	97.23 (8)	C2—C3—H3A	108.7
C1—Cu1—Cl1	120.78 (11)	N4—C3—H3B	109.4
C2—Cu1—Cl1	101.90 (10)	C2—C3—H3B	110.4
Cl1ⁱ—Cu1—Cl1	92.81 (5)	H3A—C3—H3B	108.2
Cu1ⁱ—Cl1—Cu1	87.19 (5)	C8—C4—C6	118.1 (3)
N4—N1—N3	106.1 (3)	C8—C4—C9ⁱⁱ	120.6 (3)
C9—N2—N4	101.8 (2)	C6—C4—C9ⁱⁱ	121.2 (3)
N1—N3—C9	106.4 (3)	N5—C5—C8	123.4 (3)
N1—N4—N2	113.7 (2)	N5—C5—H5A	118.0
N1—N4—C3	122.7 (3)	C8—C5—H5A	118.6
N2—N4—C3	123.6 (3)	C7—C6—C4	119.5 (3)
C5—N5—C7	117.3 (2)	C7—C6—H6A	120.5
C5—N5—Cu1	120.90 (19)	C4—C6—H6A	119.9
C7—N5—Cu1	120.8 (2)	N5—C7—C6	122.6 (3)
C2—C1—Cu1	72.17 (18)	N5—C7—H7A	118.4
C2—C1—H1A	120.4	C6—C7—H7A	119.0
Cu1—C1—H1A	90.3	C4—C8—C5	119.0 (3)
C2—C1—H1C	119.6	C4—C8—H8A	120.2
Cu1—C1—H1C	107.9	C5—C8—H8A	120.8
H1A—C1—H1C	120.0	N2—C9—N3	112.0 (3)
C1—C2—C3	121.1 (3)	N2—C9—C4ⁱⁱⁱ	123.9 (3)
C1—C2—Cu1	69.60 (17)	N3—C9—C4ⁱⁱⁱ	124.0 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cl1ⁱ	0.96	2.81	3.459 (3)	126

Symmetry code: (i) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Cu₂Cl₂(C₉H₉N₅)₂]
M_r	286.21
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	17.270 (3), 12.040 (2), 13.064 (3)
β (°)	127.94 (3)
V (Å³)	2142.3 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.27
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	0.643, 0.800
No. of measured, independent and observed [I > 2σ(I)] reflections	10753, 2451, 1814
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.100, 1.06
No. of reflections	2451
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.39

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003) and XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

References

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