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Two polymeric complexes, [CuCl2L2]n, where L is 2-propyltetrazole (C4H8N4) or 2-allyltetrazole (C4H6N4), are the first coordination polymers of 2-substituted tetrazoles in which only the tetrazole rings bridge neighbouring Cu atoms. In both complexes, the Cu atoms lie on inversion centres and are six-coordinated in tetragonally distorted octahedral geometries, CuCl2N4, with two N1 tetrazole ring atoms in the axial positions and two Cl atoms and two N4 tetrazole ring atoms in the equatorial sites. The Cl atoms do not participate in the polymeric layer formation.
Supporting information
CCDC references: 269003; 269004
2-Propyltetrazole and 2-allyltetrazole were prepared by the method described by Gaponik et al. (1980). For the synthesis of (I), 2-propyltetrazole (1.23 g, 0.011 mol) was added to a solution of CuCl2·2H2O (0.85 g, 0.005 mol) in methanol (10 ml). The mixture was stirred for 1 h at room temperature and then kept for about 20 d at room temperature in air. Green–blue crystals of (I) were obtained (yield 1.20 g, 67%). Analysis for (I), found: Cu 17.9, Cl 19.5%; C8H16Cl2CuN8 requires: Cu 17.7, Cl 19.8. For the synthesis of (II), CuCl2·2H2O (0.85 g, 0.005 mol) was added to a solution containing 2-allylterazole (1.21 g, 0.011 mol) in a methanol–diethyl ether mixture (50 ml, molar ratio 1:4). The resulting mixture was stirred for 1 h at room temperature. After removing about 35 ml of solvent by heating the mixture at 353 K (water bath) for 30 min in air, it was cooled to room temperature and filtered. From the filtrate, 10 d later, green–blue crystals of (II) were obtained (yield 0.91 g, 51%). Analysis for (II), found: Cu 17.6, Cl 19.5%; C8H12Cl2CuN8 requires: Cu 17.9, Cl 20.0%.
The H atoms were included in geometrically calculated positions, with C—H = 0.93–0.97 Å, and refined using a riding model, with Uiso(H) equal to 1.5Ueq(C) for the methyl group and 1.2Ueq(C) for other H atoms.
For both compounds, data collection: R3m Software (Nicolet, 1980); cell refinement: R3m Software; data reduction: R3m Software; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
(I) poly[[dichlorocopper(II)]-di-µ
2-2-propyl-2
H-tetrazole-
κ2N1:
N4]
top
Crystal data top
[CuCl2(C4H8N4)2] | F(000) = 732 |
Mr = 358.73 | Dx = 1.590 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 24 reflections |
a = 9.885 (3) Å | θ = 16.6–22.0° |
b = 8.867 (2) Å | µ = 1.81 mm−1 |
c = 17.092 (4) Å | T = 292 K |
V = 1498.1 (7) Å3 | Prism, green-blue |
Z = 4 | 0.58 × 0.54 × 0.40 mm |
Data collection top
Nicolet R3m four-circle diffractometer | 2024 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 30.1°, θmin = 2.4° |
ω/2θ scans | h = 0→13 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→12 |
Tmin = 0.379, Tmax = 0.483 | l = −24→2 |
2477 measured reflections | 3 standard reflections every 100 reflections |
2201 independent reflections | intensity decay: none |
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) = 0.124 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0762P)2 + 0.5691P] where P = (Fo2 + 2Fc2)/3 |
2201 reflections | (Δ/σ)max < 0.001 |
89 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.80 e Å−3 |
Crystal data top
[CuCl2(C4H8N4)2] | V = 1498.1 (7) Å3 |
Mr = 358.73 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.885 (3) Å | µ = 1.81 mm−1 |
b = 8.867 (2) Å | T = 292 K |
c = 17.092 (4) Å | 0.58 × 0.54 × 0.40 mm |
Data collection top
Nicolet R3m four-circle diffractometer | 2024 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.027 |
Tmin = 0.379, Tmax = 0.483 | 3 standard reflections every 100 reflections |
2477 measured reflections | intensity decay: none |
2201 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.67 e Å−3 |
2201 reflections | Δρmin = −0.80 e Å−3 |
89 parameters | |
Special details top
Experimental. Because of instability on the air, single-crystal was mounted in glass capillary. |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.03073 (14) | |
Cl1 | 0.60885 (5) | 0.47837 (6) | 0.61608 (3) | 0.03696 (15) | |
N1 | 0.15612 (18) | 0.2420 (2) | 0.54928 (10) | 0.0406 (4) | |
N2 | 0.19012 (16) | 0.30519 (19) | 0.61691 (9) | 0.0351 (3) | |
N3 | 0.29953 (17) | 0.3880 (2) | 0.61424 (9) | 0.0375 (4) | |
N4 | 0.34130 (16) | 0.37998 (18) | 0.54076 (9) | 0.0336 (3) | |
C5 | 0.2534 (2) | 0.2918 (3) | 0.50275 (11) | 0.0394 (4) | |
H5 | 0.2599 | 0.2683 | 0.4499 | 0.047* | |
C6 | 0.1067 (2) | 0.2940 (3) | 0.68746 (12) | 0.0448 (5) | |
H6A | 0.1588 | 0.3275 | 0.7323 | 0.054* | |
H6B | 0.0817 | 0.1895 | 0.6960 | 0.054* | |
C7 | −0.0195 (3) | 0.3884 (4) | 0.68043 (16) | 0.0552 (6) | |
H7A | −0.0790 | 0.3425 | 0.6421 | 0.066* | |
H7B | −0.0662 | 0.3880 | 0.7303 | 0.066* | |
C8 | 0.0068 (4) | 0.5486 (5) | 0.6569 (3) | 0.0806 (11) | |
H8A | 0.0745 | 0.5913 | 0.6905 | 0.121* | |
H8B | −0.0753 | 0.6059 | 0.6614 | 0.121* | |
H8C | 0.0380 | 0.5513 | 0.6037 | 0.121* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0298 (2) | 0.0310 (2) | 0.0315 (2) | −0.00562 (10) | 0.00078 (10) | 0.00283 (10) |
Cl1 | 0.0375 (3) | 0.0381 (3) | 0.0353 (2) | −0.00010 (17) | −0.00241 (16) | 0.00357 (16) |
N1 | 0.0444 (9) | 0.0355 (8) | 0.0417 (8) | −0.0127 (7) | 0.0074 (7) | −0.0051 (6) |
N2 | 0.0369 (8) | 0.0325 (7) | 0.0358 (7) | −0.0057 (6) | 0.0049 (6) | 0.0006 (6) |
N3 | 0.0370 (8) | 0.0415 (8) | 0.0339 (7) | −0.0089 (7) | 0.0036 (6) | 0.0004 (6) |
N4 | 0.0350 (7) | 0.0320 (7) | 0.0339 (7) | −0.0063 (6) | 0.0040 (6) | 0.0008 (6) |
C5 | 0.0445 (11) | 0.0360 (9) | 0.0377 (9) | −0.0121 (8) | 0.0071 (7) | −0.0052 (7) |
C6 | 0.0484 (11) | 0.0494 (11) | 0.0368 (9) | −0.0105 (9) | 0.0106 (8) | 0.0009 (8) |
C7 | 0.0423 (11) | 0.0690 (17) | 0.0543 (13) | −0.0038 (11) | 0.0093 (10) | −0.0136 (12) |
C8 | 0.096 (3) | 0.066 (2) | 0.079 (2) | 0.0259 (17) | 0.0224 (18) | −0.001 (2) |
Geometric parameters (Å, º) top
Cu1—N4 | 2.0196 (15) | N4—C5 | 1.337 (3) |
Cu1—N4i | 2.0197 (16) | C5—H5 | 0.9300 |
Cu1—Cl1 | 2.2652 (6) | C6—C7 | 1.507 (4) |
Cu1—Cl1i | 2.2652 (6) | C6—H6A | 0.9700 |
Cu1—N1ii | 2.7739 (17) | C6—H6B | 0.9700 |
Cu1—N1iii | 2.7739 (17) | C7—C8 | 1.499 (5) |
Cu1—Cu1iii | 6.6396 (13) | C7—H7A | 0.9700 |
N1—C5 | 1.324 (2) | C7—H7B | 0.9700 |
N1—N2 | 1.328 (2) | C8—H8A | 0.9600 |
N2—N3 | 1.308 (2) | C8—H8B | 0.9600 |
N2—C6 | 1.464 (2) | C8—H8C | 0.9600 |
N3—N4 | 1.324 (2) | | |
| | | |
N4—Cu1—N4i | 180.0 | N2—N3—N4 | 105.13 (15) |
N4—Cu1—Cl1 | 91.27 (5) | N3—N4—C5 | 106.84 (15) |
N4i—Cu1—Cl1 | 88.73 (5) | N3—N4—Cu1 | 122.77 (12) |
N4—Cu1—Cl1i | 88.73 (5) | C5—N4—Cu1 | 130.17 (12) |
N4i—Cu1—Cl1i | 91.27 (5) | N1—C5—N4 | 112.04 (16) |
Cl1—Cu1—Cl1i | 180.0 | N1—C5—H5 | 124.0 |
N4—Cu1—N1ii | 82.57 (6) | N4—C5—H5 | 124.0 |
N4i—Cu1—N1ii | 97.43 (6) | N2—C6—C7 | 111.27 (19) |
Cl1—Cu1—N1ii | 93.66 (4) | N2—C6—H6A | 109.4 |
Cl1i—Cu1—N1ii | 86.34 (4) | C7—C6—H6A | 109.4 |
N4—Cu1—N1iii | 97.43 (6) | N2—C6—H6B | 109.4 |
N4i—Cu1—N1iii | 82.57 (6) | C7—C6—H6B | 109.4 |
Cl1—Cu1—N1iii | 86.34 (4) | H6A—C6—H6B | 108.0 |
Cl1i—Cu1—N1iii | 93.66 (4) | C8—C7—C6 | 113.8 (2) |
N1ii—Cu1—N1iii | 180.00 (7) | C8—C7—H7A | 108.8 |
N4—Cu1—Cu1iii | 103.08 (5) | C6—C7—H7A | 108.8 |
N4i—Cu1—Cu1iii | 76.92 (5) | C8—C7—H7B | 108.8 |
Cl1—Cu1—Cu1iii | 65.788 (16) | C6—C7—H7B | 108.8 |
Cl1i—Cu1—Cu1iii | 114.212 (16) | H7A—C7—H7B | 107.7 |
N1ii—Cu1—Cu1iii | 158.53 (3) | C7—C8—H8A | 109.5 |
N1iii—Cu1—Cu1iii | 21.47 (3) | C7—C8—H8B | 109.5 |
C5—N1—N2 | 101.42 (16) | H8A—C8—H8B | 109.5 |
N3—N2—N1 | 114.57 (15) | C7—C8—H8C | 109.5 |
N3—N2—C6 | 122.16 (16) | H8A—C8—H8C | 109.5 |
N1—N2—C6 | 123.09 (16) | H8B—C8—H8C | 109.5 |
| | | |
C5—N1—N2—N3 | −0.1 (2) | Cl1—Cu1—N4—C5 | −151.34 (19) |
C5—N1—N2—C6 | 175.1 (2) | Cl1i—Cu1—N4—C5 | 28.66 (19) |
N1—N2—N3—N4 | 0.0 (2) | N1ii—Cu1—N4—C5 | 115.1 (2) |
C6—N2—N3—N4 | −175.24 (18) | N1iii—Cu1—N4—C5 | −64.9 (2) |
N2—N3—N4—C5 | 0.1 (2) | Cu1iii—Cu1—N4—C5 | −85.92 (19) |
N2—N3—N4—Cu1 | 175.18 (13) | N2—N1—C5—N4 | 0.2 (3) |
Cl1—Cu1—N4—N3 | 34.81 (15) | N3—N4—C5—N1 | −0.2 (3) |
Cl1i—Cu1—N4—N3 | −145.19 (15) | Cu1—N4—C5—N1 | −174.77 (15) |
N1ii—Cu1—N4—N3 | −58.71 (15) | N3—N2—C6—C7 | 102.9 (2) |
N1iii—Cu1—N4—N3 | 121.29 (15) | N1—N2—C6—C7 | −71.9 (3) |
Cu1iii—Cu1—N4—N3 | 100.23 (15) | N2—C6—C7—C8 | −51.6 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, z; (iii) x+1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···Cl1i | 0.93 | 2.83 | 3.183 (2) | 104 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
(II) poly[[dichlorocopper(II)]-di-µ
2-2-allyl-2
H-tetrazole-
κ2N1:
N4]
top
Crystal data top
[CuCl2(C4H6N4)2] | F(000) = 358 |
Mr = 354.70 | Dx = 1.688 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 8.524 (3) Å | θ = 17.9–23.6° |
b = 8.855 (3) Å | µ = 1.95 mm−1 |
c = 9.593 (2) Å | T = 292 K |
β = 105.51 (2)° | Prism, green-blue |
V = 697.7 (4) Å3 | 0.40 × 0.38 × 0.26 mm |
Z = 2 | |
Data collection top
Nicolet R3m four-circle diffractometer | 1824 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.062 |
Graphite monochromator | θmax = 29.6°, θmin = 2.5° |
ω/2θ scans | h = 0→11 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→12 |
Tmin = 0.484, Tmax = 0.600 | l = −13→12 |
2066 measured reflections | 3 standard reflections every 100 reflections |
1949 independent reflections | intensity decay: none |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0721P)2 + 0.3127P] where P = (Fo2 + 2Fc2)/3 |
1949 reflections | (Δ/σ)max < 0.001 |
88 parameters | Δρmax = 0.69 e Å−3 |
0 restraints | Δρmin = −0.95 e Å−3 |
Crystal data top
[CuCl2(C4H6N4)2] | V = 697.7 (4) Å3 |
Mr = 354.70 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.524 (3) Å | µ = 1.95 mm−1 |
b = 8.855 (3) Å | T = 292 K |
c = 9.593 (2) Å | 0.40 × 0.38 × 0.26 mm |
β = 105.51 (2)° | |
Data collection top
Nicolet R3m four-circle diffractometer | 1824 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.062 |
Tmin = 0.484, Tmax = 0.600 | 3 standard reflections every 100 reflections |
2066 measured reflections | intensity decay: none |
1949 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.69 e Å−3 |
1949 reflections | Δρmin = −0.95 e Å−3 |
88 parameters | |
Special details top
Experimental. Because of instability on the air, single-crystal was mounted in glass capillary. |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 1.0000 | 0.5000 | 0.5000 | 0.02679 (13) | |
Cl1 | 0.75801 (6) | 0.38044 (6) | 0.46359 (5) | 0.03523 (15) | |
N1 | 0.9006 (2) | 0.7743 (2) | 0.1272 (2) | 0.0371 (4) | |
N2 | 0.7622 (2) | 0.70125 (19) | 0.11737 (18) | 0.0300 (3) | |
N3 | 0.7682 (2) | 0.6046 (2) | 0.22137 (18) | 0.0333 (4) | |
N4 | 0.9182 (2) | 0.61315 (18) | 0.30631 (18) | 0.0296 (3) | |
C5 | 0.9958 (3) | 0.7167 (3) | 0.2467 (2) | 0.0371 (4) | |
H5 | 1.1040 | 0.7443 | 0.2853 | 0.044* | |
C6 | 0.6133 (3) | 0.7260 (3) | 0.0005 (2) | 0.0386 (4) | |
H6A | 0.6116 | 0.8297 | −0.0323 | 0.046* | |
H6B | 0.5196 | 0.7114 | 0.0383 | 0.046* | |
C7 | 0.5992 (3) | 0.6231 (3) | −0.1253 (3) | 0.0490 (6) | |
H7 | 0.5045 | 0.6314 | −0.2005 | 0.059* | |
C8 | 0.7047 (6) | 0.5230 (4) | −0.1416 (4) | 0.0665 (9) | |
H8A | 0.8015 | 0.5101 | −0.0697 | 0.080* | |
H8B | 0.6834 | 0.4645 | −0.2250 | 0.080* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.02700 (19) | 0.02710 (19) | 0.02549 (19) | −0.00584 (10) | 0.00565 (13) | 0.00328 (10) |
Cl1 | 0.0297 (2) | 0.0370 (3) | 0.0372 (3) | −0.00925 (17) | 0.00589 (18) | 0.00577 (18) |
N1 | 0.0320 (8) | 0.0404 (9) | 0.0387 (9) | −0.0012 (7) | 0.0091 (7) | 0.0138 (7) |
N2 | 0.0292 (7) | 0.0324 (8) | 0.0291 (7) | 0.0013 (6) | 0.0092 (6) | 0.0045 (6) |
N3 | 0.0328 (8) | 0.0357 (8) | 0.0302 (7) | −0.0032 (6) | 0.0062 (6) | 0.0071 (6) |
N4 | 0.0298 (7) | 0.0299 (7) | 0.0293 (7) | −0.0023 (6) | 0.0083 (6) | 0.0035 (6) |
C5 | 0.0323 (9) | 0.0409 (10) | 0.0366 (10) | −0.0039 (8) | 0.0068 (8) | 0.0123 (8) |
C6 | 0.0311 (9) | 0.0442 (11) | 0.0376 (10) | 0.0035 (8) | 0.0042 (8) | 0.0098 (9) |
C7 | 0.0528 (14) | 0.0496 (13) | 0.0377 (11) | −0.0132 (11) | 0.0002 (10) | 0.0052 (10) |
C8 | 0.094 (3) | 0.0516 (15) | 0.0532 (17) | −0.0029 (16) | 0.0182 (17) | −0.0106 (13) |
Geometric parameters (Å, º) top
Cu1—N4 | 2.0615 (16) | N3—N4 | 1.322 (2) |
Cu1—N4i | 2.0615 (16) | N4—C5 | 1.345 (3) |
Cu1—Cl1 | 2.2611 (8) | C5—H5 | 0.9300 |
Cu1—Cl1i | 2.2611 (8) | C6—C7 | 1.491 (4) |
Cu1—N1ii | 2.5987 (18) | C6—H6A | 0.9700 |
Cu1—Cu1ii | 6.5276 (13) | C6—H6B | 0.9700 |
N1—C5 | 1.318 (3) | C7—C8 | 1.302 (5) |
N1—N2 | 1.326 (2) | C7—H7 | 0.9300 |
N2—N3 | 1.305 (2) | C8—H8A | 0.9300 |
N2—C6 | 1.468 (3) | C8—H8B | 0.9300 |
| | | |
N4—Cu1—N4i | 180.00 (8) | N2—N3—N4 | 105.48 (16) |
N4—Cu1—Cl1 | 90.77 (5) | N3—N4—C5 | 106.39 (16) |
N4i—Cu1—Cl1 | 89.23 (5) | N3—N4—Cu1 | 124.47 (13) |
N4—Cu1—Cl1i | 89.23 (5) | C5—N4—Cu1 | 128.92 (14) |
N4i—Cu1—Cl1i | 90.77 (5) | N1—C5—N4 | 112.03 (19) |
Cl1—Cu1—Cl1i | 180.00 (3) | N1—C5—H5 | 124.0 |
N4—Cu1—N1ii | 91.42 (7) | N4—C5—H5 | 124.0 |
N4i—Cu1—N1ii | 88.58 (7) | N2—C6—C7 | 113.16 (19) |
Cl1—Cu1—N1ii | 88.06 (5) | N2—C6—H6A | 108.9 |
Cl1i—Cu1—N1ii | 91.94 (5) | C7—C6—H6A | 108.9 |
N4—Cu1—Cu1ii | 74.57 (5) | N2—C6—H6B | 108.9 |
N4i—Cu1—Cu1ii | 105.43 (5) | C7—C6—H6B | 108.9 |
Cl1—Cu1—Cu1ii | 75.41 (2) | H6A—C6—H6B | 107.8 |
Cl1i—Cu1—Cu1ii | 104.59 (2) | C8—C7—C6 | 127.2 (3) |
N1ii—Cu1—Cu1ii | 21.46 (4) | C8—C7—H7 | 116.4 |
C5—N1—N2 | 101.67 (16) | C6—C7—H7 | 116.4 |
N3—N2—N1 | 114.43 (16) | C7—C8—H8A | 120.0 |
N3—N2—C6 | 122.05 (17) | C7—C8—H8B | 120.0 |
N1—N2—C6 | 123.52 (17) | H8A—C8—H8B | 120.0 |
| | | |
C5—N1—N2—N3 | −0.2 (2) | Cl1—Cu1—N4—C5 | 178.28 (19) |
C5—N1—N2—C6 | 179.5 (2) | Cl1i—Cu1—N4—C5 | −1.72 (19) |
N1—N2—N3—N4 | 0.3 (2) | N1ii—Cu1—N4—C5 | −93.7 (2) |
C6—N2—N3—N4 | −179.45 (18) | Cu1ii—Cu1—N4—C5 | −107.09 (19) |
N2—N3—N4—C5 | −0.2 (2) | N2—N1—C5—N4 | 0.0 (3) |
N2—N3—N4—Cu1 | 174.81 (13) | N3—N4—C5—N1 | 0.1 (3) |
Cl1—Cu1—N4—N3 | 4.39 (16) | Cu1—N4—C5—N1 | −174.62 (15) |
Cl1i—Cu1—N4—N3 | −175.61 (16) | N3—N2—C6—C7 | −89.1 (3) |
N1ii—Cu1—N4—N3 | 92.47 (16) | N1—N2—C6—C7 | 91.2 (2) |
Cu1ii—Cu1—N4—N3 | 79.02 (16) | N2—C6—C7—C8 | −2.7 (4) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···Cl1i | 0.93 | 2.63 | 3.122 (2) | 114 |
C6—H6B···Cl1iii | 0.97 | 2.80 | 3.548 (2) | 135 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [CuCl2(C4H8N4)2] | [CuCl2(C4H6N4)2] |
Mr | 358.73 | 354.70 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21/c |
Temperature (K) | 292 | 292 |
a, b, c (Å) | 9.885 (3), 8.867 (2), 17.092 (4) | 8.524 (3), 8.855 (3), 9.593 (2) |
α, β, γ (°) | 90, 90, 90 | 90, 105.51 (2), 90 |
V (Å3) | 1498.1 (7) | 697.7 (4) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.81 | 1.95 |
Crystal size (mm) | 0.58 × 0.54 × 0.40 | 0.40 × 0.38 × 0.26 |
|
Data collection |
Diffractometer | Nicolet R3m four-circle diffractometer | Nicolet R3m four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.379, 0.483 | 0.484, 0.600 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2477, 2201, 2024 | 2066, 1949, 1824 |
Rint | 0.027 | 0.062 |
(sin θ/λ)max (Å−1) | 0.705 | 0.694 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.124, 1.13 | 0.037, 0.109, 1.07 |
No. of reflections | 2201 | 1949 |
No. of parameters | 89 | 88 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.80 | 0.69, −0.95 |
Selected bond lengths (Å) for (I) topCu1—N4 | 2.0196 (15) | N1—N2 | 1.328 (2) |
Cu1—Cl1 | 2.2652 (6) | N2—N3 | 1.308 (2) |
Cu1—N1i | 2.7739 (17) | N2—C6 | 1.464 (2) |
Cu1—Cu1ii | 6.6396 (13) | N3—N4 | 1.324 (2) |
N1—C5 | 1.324 (2) | N4—C5 | 1.337 (3) |
Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x+1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···Cl1iii | 0.93 | 2.83 | 3.183 (2) | 104 |
Symmetry code: (iii) −x+1, −y+1, −z+1. |
Selected bond lengths (Å) for (II) topCu1—N4 | 2.0615 (16) | N1—N2 | 1.326 (2) |
Cu1—Cl1 | 2.2611 (8) | N2—N3 | 1.305 (2) |
Cu1—N1i | 2.5987 (18) | N2—C6 | 1.468 (3) |
Cu1—Cu1i | 6.5276 (13) | N3—N4 | 1.322 (2) |
N1—C5 | 1.318 (3) | N4—C5 | 1.345 (3) |
Symmetry code: (i) −x+2, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···Cl1ii | 0.93 | 2.63 | 3.122 (2) | 114 |
C6—H6B···Cl1iii | 0.97 | 2.80 | 3.548 (2) | 135 |
Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2. |
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We have recently reported the crystal structures of a number of copper(II) chloride complexes with 2-substituted tetrazoles (Lyakhov et al., 2005, and references cited therein). Some of them present chain coordination polymers with only Cl atoms as bridges between the neighbouring Cu atoms (Lyakhov et al., 2003a; Lyakhov et al., 2005). In other compounds, either chain coordination polymers (Lyakhov, Gaponik, Degtyarik, Matulis et al., 2003) or layered ones (Lyakhov et al., 2003b), polymeric structures are formed through both Cl bridges and tetrazole ring coordination. Here, we report two complexes of copper(II) chloride with 2-substituted tetrazoles, which are coordination polymers due only to the bridging coordination of the tetrazole rings. They are of the composition [CuCl2L2], where L is 2-propyltetrazole in (I) (Fig. 1) and 2-allyltetrazole in (II) (Fig. 2).
The tetrazole rings of the ligand molecules of complexes (I) and (II) are essentially planar, with mean deviations of the tetrazole ring atoms from their least-squares plane being 0.0007 (14) and 0.0010 (14) Å for (I) and (II), respectively. The ring geometries (Tables 1 and 3) are similar to those found previously for complexes of 2-substituted tetrazoles. For both compounds, the shortest ring bond is the formal N2—N3 single bond of 1.308 (2) and 1.305 (2) Å for (I) and (II), respectively. The remaining ring bonds lie within the ranges 1.324 (2)–1.337 (3) Å for (I) and 1.318 (3)–1.345 (3) Å for (II).
In both compounds, the Cu1 atoms lie on inversion centres and have tetragonally distorted octahedral coordination (Tables 1 and 3). In both complexes, the equatorial positions of the octahedra are occupied by two N4 and two Cl1 atoms, while two N1 atoms lie in the axial sites. The Cu1—N4 distances are similar in (I) and (II), as are the Cu1—Cl1 bond lengths, while the Cu1—N1 bond in (I) is 0.175 (2) Å longer than that in (II).
Both compounds are layered coordination polymers, in which only the ligand molecules act as bridges between neighbouring Cu atoms, through tetrazole ring atoms N4 and N1. The Cl atoms do not participate in the formation of polymeric layers. Figs. 3 and 4 show that the atomic arrangement of the polymeric layers is similar in both compounds. There are also differences within the layers of (I) and (II) with respect to the tetrazole ring orientations. The Cl1—Cu1—N4—C5 dihedral angle is −151.34 (19)° for (I) and 178.28 (19)° for (II), so that in the latter the tetrazole ring lies almost in the equatorial plane of the Cu octahedron.
In 2-substituted tetrazoles, N1 ring atoms may be the preferred metal binding site compared with N3 atoms, based on the observed Cu—N1 bond lengths of 2.7739 (17) Å in (I), 2.5987 (18) Å in (II) and 2.851 (2) Å in the related complex [CuCl2L2], where L is 2-ethyltetrazole (Lyakhov et al., 2003b), and the Cu—N3 bond length of 2.926 (3) Å in the complex [Cu3L4Cl6], where L is 2-allyltetrazole (Lyakhov, Gaponik, Degtyarik, Matulis et al., 2003). Reliable conclusions about the electron-donating properties of the N1 and N3 tetrazole ring atoms requires further experimental study, as well as verification by quantum-chemical calculations.
In the structures of (I) and (II), there are weak C5—H5···Cl hydrogen bonds (Tables 2 and 4), implemented inside the polymeric layers. In complex (II), there are also interlayer hydrogen bonds between the methylene H atom of the allyl substituent and a Cl atom of a neighbouring layer (Table 4). Because the propyl and allyl substituents at the N2 tetrazole ring atom of the ligand molecules are similar in size, it was expected that complexes (I) and (II) would be isostructural. However, the obtained data show a similarity only in the atomic arrangement inside the polymeric layers.