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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.039
• wR factor = 0.088
• Data-to-parameter ratio = 17.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Br1    -   Cu1     ..      38.08 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Br1    -   Cu1_c   ..      61.43 su

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.57
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.55
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C1     -   C2     ...       1.35 Ang.

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      0.575
            Tmax scaled      0.575 Tmin scaled      0.380
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
   2 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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

S3. Refinement

All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic), 0.97 Å (methylene) or 0.98 Å (methine) with U_iso(H) = 1.2U_eq (C).

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: ORTEPIII (Johnson & Burnett, 1997) and ORTEP-32 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

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]]

Crystal data

[CuBr(C9H9N5)]	F(000) = 1296
Mr = 330.66	Dx = 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) Å^3	0.2 × 0.15 × 0.1 mm
Z = 8

Data collection

Rigaku Mercury2 diffractometer	2552 independent reflections
Radiation source: fine-focus sealed tube	1962 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
CCD_Profile_fitting scans	h = −22→22
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
Tmin = 0.661, Tmax = 1	l = −17→17
11222 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.03P)^2 + 4.1679P] where P = (Fo^2 + 2Fc^2)/3
2552 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.77 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

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

Cu1—N5^i	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—Br1^ii	2.5973 (11)	C3—H3A	0.9700
Br1—Cu1^ii	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—Cu1^iii	2.017 (3)	C8—H8	0.9300
C1—C2	1.351 (5)
N5^i—Cu1—C1	106.55 (13)	C3—C2—Cu1	109.5 (2)
N5^i—Cu1—C2	144.30 (14)	C1—C2—H2	115.7
C1—Cu1—C2	37.93 (14)	C3—C2—H2	115.7
N5^i—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
N5^i—Cu1—Br1^ii	99.28 (9)	C2—C3—H3A	109.5
C1—Cu1—Br1^ii	124.96 (11)	N4—C3—H3B	109.5
C2—Cu1—Br1^ii	102.07 (11)	C2—C3—H3B	109.5
Br1—Cu1—Br1^ii	95.64 (4)	H3A—C3—H3B	108.0
Cu1—Br1—Cu1^ii	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—Cu1^iii	121.9 (2)	C8—C6—H6	118.3
C7—N5—Cu1^iii	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.