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

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].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.042
• wR factor = 0.100
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level B
CELLV02_ALERT_1_B  The supplied cell volume s.u. differs from that
            calculated from the cell parameter s.u.'s by > 4
            Calculated cell volume su =      11.28
            Cell volume su given      =       7.00
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    --  Cl1     ..      32.53 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    --  Cl1_c   ..      15.26 su

Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.29
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

All H atoms were placed geometrically and treated as riding with C—H = 0.93 (aromatic), 0.97 (methylene) or 0.96 Å (methyl), with U_iso(H) = 1.2U_eq(Caromatic, Cmethylene) or U_iso(H) = 1.5U_eq(Cmethyl).

Computing details

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

	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]]

Crystal data

[Cu2Cl2(C9H9N5)2]	F(000) = 1152
Mr = 286.21	Dx = 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) Å^3	0.2 × 0.15 × 0.1 mm
Z = 8

Data collection

Rigaku Mercury2 diffractometer	2451 independent reflections
Radiation source: fine-focus sealed tube	1814 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scans	h = −22→22
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
Tmin = 0.643, Tmax = 0.800	l = −16→16
10753 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0422P)^2 + 0.6044P] where P = (Fo^2 + 2Fc^2)/3
2451 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—Cl1^i	2.3491 (11)	C3—H3A	0.9598
Cu1—Cl1	2.5358 (12)	C3—H3B	0.9599
Cl1—Cu1^i	2.3491 (11)	C4—C8	1.384 (4)
N1—N4	1.310 (4)	C4—C6	1.381 (4)
N1—N3	1.319 (4)	C4—C9^ii	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—C4^iii	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—Cl1^i	104.01 (8)	Cu1—C2—H2A	91.1
C1—Cu1—Cl1^i	130.46 (11)	N4—C3—C2	111.3 (3)
C2—Cu1—Cl1^i	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
Cl1^i—Cu1—Cl1	92.81 (5)	H3A—C3—H3B	108.2
Cu1^i—Cl1—Cu1	87.19 (5)	C8—C4—C6	118.1 (3)
N4—N1—N3	106.1 (3)	C8—C4—C9^ii	120.6 (3)
C9—N2—N4	101.8 (2)	C6—C4—C9^ii	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—C4^iii	123.9 (3)
C1—C2—Cu1	69.60 (17)	N3—C9—C4^iii	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)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cl1^i	0.96	2.81	3.459 (3)	126

Symmetry code: (i) −x+1, y, −z+3/2.