catena-Poly[[chloridocopper(I)]-μ-η²,σ¹-3-(2-allyl-2H-tetra­zol-5-yl)pyridine]

The title compound, [CuCl(C₉H₉N₅)]_n, prepared by solvo­thermal synthesis, is a new homometallic Cu^I–olefin coordination polymer in which the Cu^I atoms are linked by the 3-(2-allyl-2H-tetra­zol-5-yl)pyridine ligands and are each bonded to one terminal Cl atom. The organic ligand acts as a bidentate ligand bridging two neighboring Cu centers through the bonds to the N atom of the pyridine ring and the double bond of the allyl group. Weak Cu...Cl [3.136 (8) Å), C—H...Cl and C—H...N inter­actions connect the coordination polymers into a three-dimensional structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.045
• wR factor = 0.104
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.22
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C8     -   C9     ...       1.36 Ang.
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.80
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.797
            Tmax scaled      0.797 Tmin scaled      0.643
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT793_ALERT_4_G Check the Absolute Configuration of C8     .....          R

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 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 occur. Often new compounds can be obtained that cannot be synthesized using conventional solution techniques. In sealed tube, unstable copper(I) salt can exist under vacuum, and thus interesting copper(I) coordination compounds can be obtained (Ye et al., 2005, 2007). The title compound, as colorless block crystals suitable for X-ray analysis, was obtained through solvothermal treatment of CuCl and 3-(2-allyl-2H-tetrazol -5-yl)pyridine in methanol at 75°C. Isostructural product was obtained when CuBr was used for the reaction (Wang, 2008).

The 3-(2-allyl-2H-tetrazol-5-yl) pyridine ligands bind to the copper(I) centers through the N atom of pyridine and double bond of the allyl group (C8—C9 1.364 (5) Å). The copper atom is coordinated to two olefinic organic ligands and one terminal Cl atom in a trigonal environment (Fig 1, Table 1). The organic ligands link the neighboring Cu centers to form a homometallic Cu(I) coordination polymer developing along the c axis. Unfortunately, the N atoms of the tetrazole ring fail to coordinate to Cu(I)(Fig. 1).

Finally, weak Cu—Cl (3.136 Å), C–H···Cl and C–H···N interactions between the coordination polymers lead to the formation of the three-dimensional structure (Fig. 2).

Related literature

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

S2. Experimental

A mixture of 3-(2-allyl-2H-tetrazol-5-yl)pyridine(20 mg, 0.2 mmol), CuCl (17.9 mg, 0.2 mmol) were placed in a thick Pyrex tube (ca 20 cm in length). After addition of methanol, the tube was frozen with liquid nitrogen, evacuated under vaccum, sealed with a torch and kept at 348 K. Colorless block-shaped crystals suitable for X-ray analysis were obtained after 5 d (yield 61% based on the organic ligand).

S3. Refinement

All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic), 0.97 Å (methylene) and 0.96Å (methyl) with U_iso(H) = 1.2U_eq(Caromatic, Cmethylene) and 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 SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the title compound with displacement ellipsoids shown at the 30% probability level [symmetry codes: A: x, y - 1, z + 1; B: x, y + 1, z - 1; C: x, y + 2, z - 2.
	Fig. 2. Crystal packing of the title compound viewed along the b axis. Weak interactions are shown as dashed lines.

catena-Poly[[chloridocopper(I)]-µ-η²,σ¹-3-(2-allyl-2H- tetrazol-5-yl)pyridine]

Crystal data

[CuCl(C9H9N5)]	Z = 2
Mr = 286.21	F(000) = 288
Triclinic, P1	Dx = 1.776 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3005 (15) Å	Cell parameters from 5070 reflections
b = 7.6560 (15) Å	θ = 3.2–27.5°
c = 9.981 (2) Å	µ = 2.27 mm^−1
α = 80.51 (3)°	T = 293 K
β = 77.00 (3)°	Block, colorless
γ = 84.68 (3)°	0.2 × 0.15 × 0.1 mm
V = 535.23 (19) Å^3

Data collection

Rigaku Mercury2 diffractometer	2443 independent reflections
Radiation source: fine-focus sealed tube	1918 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.806, Tmax = 1	l = −12→12
5572 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0388P)^2] where P = (Fo^2 + 2Fc^2)/3
2443 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.15988 (6)	−0.16243 (6)	0.38989 (4)	0.03499 (17)
Cl3	−0.15148 (11)	−0.11291 (11)	0.40805 (10)	0.0362 (2)
N1	0.2905 (4)	0.0083 (4)	0.2319 (3)	0.0273 (6)
N2	0.0888 (4)	0.4924 (4)	−0.2268 (3)	0.0288 (6)
N3	0.2403 (4)	0.4402 (4)	−0.1738 (3)	0.0307 (7)
N4	−0.0077 (4)	0.2863 (4)	−0.0651 (3)	0.0365 (7)
N5	−0.0620 (4)	0.4030 (4)	−0.1640 (3)	0.0363 (7)
C1	0.4677 (5)	0.0501 (5)	0.2253 (3)	0.0345 (8)
H1A	0.5306	−0.0055	0.2974	0.039 (10)*
C2	0.5620 (5)	0.1711 (5)	0.1194 (4)	0.0375 (9)
H2A	0.6894	0.1957	0.1169	0.034 (10)*
C3	0.4697 (5)	0.2565 (5)	0.0182 (4)	0.0344 (8)
H3A	0.5327	0.3399	−0.0568	0.040 (10)*
C4	0.2031 (5)	0.0904 (4)	0.1323 (3)	0.0266 (7)
H4A	0.0779	0.0591	0.1349	0.029 (9)*
C5	0.2858 (4)	0.2174 (4)	0.0256 (3)	0.0256 (7)
C6	0.0802 (5)	0.6439 (4)	−0.3365 (3)	0.0307 (8)
H6A	0.1222	0.7458	−0.3100	0.030 (10)*
H6B	−0.0483	0.6696	−0.3450	0.037 (10)*
C7	0.1745 (5)	0.3120 (4)	−0.0734 (3)	0.0266 (7)
C8	0.1990 (5)	0.6128 (4)	−0.4751 (3)	0.0303 (8)
H8A	0.1838	0.5028	−0.5045	0.028 (9)*
C9	0.3666 (5)	0.6878 (5)	−0.5325 (4)	0.0414 (10)
H9A	0.4217	0.7393	−0.4705	0.075 (16)*
H9B	0.4567	0.6248	−0.5960	0.066 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0274 (3)	0.0380 (3)	0.0312 (3)	−0.00009 (18)	−0.00526 (18)	0.01645 (19)
Cl3	0.0272 (5)	0.0346 (5)	0.0449 (5)	−0.0015 (3)	−0.0117 (4)	0.0051 (4)
N1	0.0277 (15)	0.0261 (14)	0.0234 (13)	−0.0003 (11)	−0.0041 (12)	0.0069 (11)
N2	0.0307 (15)	0.0278 (15)	0.0243 (14)	−0.0005 (12)	−0.0062 (12)	0.0058 (12)
N3	0.0346 (16)	0.0295 (15)	0.0253 (14)	−0.0053 (12)	−0.0076 (13)	0.0070 (12)
N4	0.0345 (17)	0.0377 (17)	0.0304 (16)	−0.0084 (13)	−0.0051 (13)	0.0160 (14)
N5	0.0321 (17)	0.0388 (18)	0.0335 (16)	−0.0084 (13)	−0.0049 (13)	0.0086 (14)
C1	0.0304 (19)	0.045 (2)	0.0252 (17)	−0.0044 (16)	−0.0086 (15)	0.0090 (16)
C2	0.0280 (19)	0.042 (2)	0.043 (2)	−0.0100 (16)	−0.0110 (16)	0.0004 (18)
C3	0.037 (2)	0.033 (2)	0.0295 (18)	−0.0104 (16)	−0.0036 (16)	0.0069 (16)
C4	0.0246 (17)	0.0270 (17)	0.0235 (16)	−0.0051 (13)	−0.0012 (13)	0.0061 (13)
C5	0.0284 (17)	0.0243 (16)	0.0221 (15)	−0.0020 (13)	−0.0028 (14)	−0.0010 (13)
C6	0.037 (2)	0.0258 (18)	0.0246 (17)	0.0003 (15)	−0.0068 (15)	0.0069 (14)
C7	0.0304 (18)	0.0234 (17)	0.0223 (16)	−0.0028 (14)	−0.0014 (14)	0.0024 (13)
C8	0.036 (2)	0.0221 (17)	0.0275 (17)	0.0038 (14)	−0.0066 (15)	0.0073 (14)
C9	0.0293 (19)	0.041 (2)	0.046 (2)	0.0094 (16)	−0.0110 (18)	0.0140 (18)

Geometric parameters (Å, º)

Cu1—N1	1.995 (3)	C2—H2A	0.9600
Cu1—C9^i	2.026 (3)	C3—C5	1.386 (5)
Cu1—C8^i	2.044 (3)	C3—H3A	0.9600
Cu1—Cl3	2.2408 (10)	C4—C5	1.387 (4)
N1—C4	1.340 (4)	C4—H4A	0.9601
N1—C1	1.345 (4)	C5—C7	1.476 (4)
N2—N5	1.327 (4)	C6—C8	1.501 (5)
N2—N3	1.332 (4)	C6—H6A	0.9600
N2—C6	1.465 (4)	C6—H6B	0.9600
N3—C7	1.321 (4)	C8—C9	1.364 (5)
N4—N5	1.323 (4)	C8—Cu1^ii	2.044 (3)
N4—C7	1.344 (4)	C8—H8A	0.9600
C1—C2	1.384 (5)	C9—Cu1^ii	2.026 (3)
C1—H1A	0.9599	C9—H9A	0.9600
C2—C3	1.382 (5)	C9—H9B	0.9600
N1—Cu1—C9^i	105.86 (13)	C5—C4—H4A	118.6
N1—Cu1—C8^i	143.90 (13)	C3—C5—C4	118.7 (3)
C9^i—Cu1—C8^i	39.16 (14)	C3—C5—C7	121.7 (3)
N1—Cu1—Cl3	108.44 (9)	C4—C5—C7	119.6 (3)
C9^i—Cu1—Cl3	145.70 (11)	N2—C6—C8	113.1 (3)
C8^i—Cu1—Cl3	106.88 (10)	N2—C6—H6A	108.9
C4—N1—C1	117.8 (3)	C8—C6—H6A	108.7
C4—N1—Cu1	121.4 (2)	N2—C6—H6B	109.0
C1—N1—Cu1	120.7 (2)	C8—C6—H6B	109.1
N5—N2—N3	113.9 (3)	H6A—C6—H6B	107.9
N5—N2—C6	121.6 (3)	N3—C7—N4	112.9 (3)
N3—N2—C6	124.2 (3)	N3—C7—C5	123.1 (3)
C7—N3—N2	101.4 (3)	N4—C7—C5	123.8 (3)
N5—N4—C7	106.3 (3)	C9—C8—C6	123.7 (4)
N4—N5—N2	105.5 (3)	C9—C8—Cu1^ii	69.73 (19)
N1—C1—C2	122.6 (3)	C6—C8—Cu1^ii	105.9 (2)
N1—C1—H1A	118.6	C9—C8—H8A	115.7
C2—C1—H1A	118.8	C6—C8—H8A	115.7
C3—C2—C1	119.0 (3)	Cu1^ii—C8—H8A	116.0
C3—C2—H2A	120.6	C8—C9—Cu1^ii	71.11 (19)
C1—C2—H2A	120.4	C8—C9—H9A	115.8
C2—C3—C5	118.8 (3)	Cu1^ii—C9—H9A	116.3
C2—C3—H3A	120.5	C8—C9—H9B	117.2
C5—C3—H3A	120.7	Cu1^ii—C9—H9B	116.7
N1—C4—C5	123.0 (3)	H9A—C9—H9B	113.5
N1—C4—H4A	118.4

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl3^iii	0.96	2.79	3.675 (4)	154
C2—H2A···N4^iii	0.96	2.59	3.379 (5)	139
C4—H4A···N4	0.96	2.57	2.909 (4)	101
C6—H6A···Cl3^iv	0.96	2.83	3.607 (4)	139

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