Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041700/hg2284sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041700/hg2284Isup2.hkl |
CCDC reference: 660177
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.015 Å
- R factor = 0.065
- wR factor = 0.164
- Data-to-parameter ratio = 19.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N1 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 15
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 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu (2) 1.95 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 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 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
The title compound was prepared by the reaction of 1-vinylimidazole (0.47 g, 5 mmol) with CuBr2 (0.72 g, 5 mmol) by means of hydrothermal synthesis in a stainless-steel reactor with a Teflon liner at 383 K for 24 h. Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.
H atoms were positioned geometrically (C—H = 0.93 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2 times Ueq(C).
In the title compound,(I), The CuII cation is coordinated by four N atoms from four 1-vinylimidazole ligand and two trans coordinated Br- anions in a distorted octahedral geometry (Fig. 1). The equatorial planes are formed by four Cu—N(1-vinylimadazole) bonds [Cu—N2 = 2.007 (6) Å, Cu—N4 = 2.029 (6) Å] and the axial positions are occupied by two Br- ions [Cu—Br = 3.0340 (11) Å]. The Cu—N bond lengths agree well with those observed in [Cu(imidazole)Br2] (Parker & Breneman, 1995), but the Cu—Br bond length is shorter than that in [Cu(imidazole)Br2]. In the crystal, the intramolecular and intermolecular C—H···Br hydrogen bonds form three-dimensional hydrogen bond networks to stabilize the structure.
For related literature, see: Parker & Breneman (1995).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
[CuBr2(C5H6N2)4] | F(000) = 598 |
Mr = 599.82 | Dx = 1.614 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2268 reflections |
a = 7.7280 (15) Å | θ = 4–15° |
b = 15.144 (3) Å | µ = 4.15 mm−1 |
c = 11.039 (2) Å | T = 293 K |
β = 107.23 (3)° | Block, blue |
V = 1234.0 (5) Å3 | 0.40 × 0.10 × 0.10 mm |
Z = 2 |
Bruker SMART 1K CCD area-detector diffractometer | 2416 independent reflections |
Radiation source: fine-focus sealed tube | 1446 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
Thin–slice ω scans | θmax = 26.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −9→9 |
Tmin = 0.605, Tmax = 0.659 | k = 0→18 |
2568 measured reflections | l = 0→13 |
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.07P)2 + P] where P = (Fo2 + 2Fc2)/3 |
2416 reflections | (Δ/σ)max < 0.001 |
124 parameters | Δρmax = 0.82 e Å−3 |
2 restraints | Δρmin = −0.84 e Å−3 |
[CuBr2(C5H6N2)4] | V = 1234.0 (5) Å3 |
Mr = 599.82 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.7280 (15) Å | µ = 4.15 mm−1 |
b = 15.144 (3) Å | T = 293 K |
c = 11.039 (2) Å | 0.40 × 0.10 × 0.10 mm |
β = 107.23 (3)° |
Bruker SMART 1K CCD area-detector diffractometer | 2416 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1446 reflections with I > 2σ(I) |
Tmin = 0.605, Tmax = 0.659 | Rint = 0.013 |
2568 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 2 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.82 e Å−3 |
2416 reflections | Δρmin = −0.84 e Å−3 |
124 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br | 0.17188 (11) | 0.38082 (6) | 0.45787 (8) | 0.054 | |
Cu | 0.5000 | 0.5000 | 0.5000 | 0.0477 (4) | |
N1 | 0.3333 (10) | 0.5776 (5) | 0.8077 (7) | 0.0598 (19) | |
N2 | 0.4621 (8) | 0.5408 (4) | 0.6632 (6) | 0.0460 (16) | |
N3 | 0.0973 (9) | 0.6672 (4) | 0.2833 (7) | 0.0514 (17) | |
N4 | 0.3382 (8) | 0.5963 (4) | 0.3984 (6) | 0.0452 (16) | |
C1 | 0.1989 (17) | 0.6136 (7) | 0.9774 (11) | 0.100 | |
H1A | 0.3135 | 0.6120 | 1.0361 | 0.120* | |
H1B | 0.0980 | 0.6262 | 1.0039 | 0.120* | |
C2 | 0.1776 (18) | 0.5966 (8) | 0.8455 (11) | 0.104 | |
H2A | 0.0635 | 0.5981 | 0.7861 | 0.125* | |
C3 | 0.3085 (11) | 0.5535 (5) | 0.6875 (8) | 0.053 (2) | |
H3A | 0.1954 | 0.5466 | 0.6282 | 0.064* | |
C4 | 0.5950 (13) | 0.5582 (7) | 0.7757 (9) | 0.066 (3) | |
H4A | 0.7193 | 0.5556 | 0.7880 | 0.079* | |
C5 | 0.5153 (15) | 0.5795 (7) | 0.8639 (9) | 0.076 (3) | |
H5A | 0.5738 | 0.5931 | 0.9483 | 0.091* | |
C6 | −0.1584 (14) | 0.7383 (7) | 0.1260 (10) | 0.089 (3) | |
H6A | −0.0796 | 0.7619 | 0.0851 | 0.106* | |
H6B | −0.2820 | 0.7497 | 0.0952 | 0.106* | |
C7 | −0.0897 (13) | 0.6847 (6) | 0.2360 (8) | 0.072 (3) | |
H7A | −0.1687 | 0.6612 | 0.2767 | 0.086* | |
C8 | 0.2447 (13) | 0.7082 (6) | 0.2648 (8) | 0.060 (2) | |
H8A | 0.2434 | 0.7573 | 0.2140 | 0.072* | |
C9 | 0.3952 (12) | 0.6632 (6) | 0.3353 (8) | 0.059 (2) | |
H9A | 0.5147 | 0.6758 | 0.3396 | 0.071* | |
C10 | 0.1625 (11) | 0.6012 (5) | 0.3668 (8) | 0.052 (2) | |
H10A | 0.0902 | 0.5638 | 0.3980 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.054 | 0.054 | 0.054 | 0.000 | 0.016 | 0.000 |
Cu | 0.0553 (8) | 0.0510 (8) | 0.0381 (8) | 0.0152 (7) | 0.0157 (6) | 0.0062 (7) |
N1 | 0.071 (5) | 0.066 (5) | 0.050 (5) | 0.006 (4) | 0.029 (4) | −0.002 (4) |
N2 | 0.039 (3) | 0.052 (4) | 0.046 (4) | 0.009 (3) | 0.012 (3) | 0.003 (3) |
N3 | 0.060 (4) | 0.041 (4) | 0.052 (4) | 0.008 (3) | 0.014 (3) | 0.009 (3) |
N4 | 0.050 (4) | 0.047 (4) | 0.040 (4) | 0.007 (3) | 0.015 (3) | 0.010 (3) |
C1 | 0.100 | 0.100 | 0.100 | 0.000 | 0.030 | 0.000 |
C2 | 0.104 | 0.104 | 0.104 | 0.000 | 0.031 | 0.000 |
C3 | 0.056 (5) | 0.049 (5) | 0.056 (6) | 0.001 (4) | 0.018 (4) | −0.002 (4) |
C4 | 0.063 (6) | 0.086 (7) | 0.049 (6) | 0.007 (5) | 0.018 (5) | −0.010 (5) |
C5 | 0.093 (8) | 0.076 (7) | 0.048 (6) | 0.007 (6) | 0.007 (6) | −0.004 (5) |
C6 | 0.076 (7) | 0.085 (8) | 0.090 (8) | 0.018 (6) | 0.002 (6) | 0.024 (7) |
C7 | 0.068 (6) | 0.074 (7) | 0.065 (7) | 0.019 (5) | 0.008 (5) | 0.000 (5) |
C8 | 0.083 (6) | 0.043 (5) | 0.056 (6) | 0.016 (5) | 0.021 (5) | 0.011 (4) |
C9 | 0.063 (5) | 0.061 (6) | 0.060 (6) | 0.005 (5) | 0.027 (5) | 0.013 (5) |
C10 | 0.055 (5) | 0.036 (5) | 0.068 (6) | 0.007 (4) | 0.024 (4) | 0.008 (4) |
Cu—Br | 3.0340 (11) | C1—H1A | 0.9300 |
Cu—N2 | 2.007 (6) | C1—H1B | 0.9300 |
Cu—N2i | 2.007 (6) | C2—H2A | 0.9300 |
Cu—N4i | 2.029 (6) | C3—H3A | 0.9300 |
Cu—N4 | 2.029 (6) | C4—C5 | 1.336 (13) |
N1—C3 | 1.334 (10) | C4—H4A | 0.9300 |
N1—C5 | 1.359 (12) | C5—H5A | 0.9300 |
N1—C2 | 1.414 (13) | C6—C7 | 1.427 (8) |
N2—C3 | 1.306 (9) | C6—H6A | 0.9300 |
N2—C4 | 1.383 (11) | C6—H6B | 0.9300 |
N3—C10 | 1.351 (10) | C7—H7A | 0.9300 |
N3—C8 | 1.365 (11) | C8—C9 | 1.374 (12) |
N3—C7 | 1.408 (10) | C8—H8A | 0.9300 |
N4—C10 | 1.301 (10) | C9—H9A | 0.9300 |
N4—C9 | 1.373 (10) | C10—H10A | 0.9300 |
C1—C2 | 1.439 (9) | ||
N2—Cu—N2i | 180.000 (1) | N2—C3—N1 | 111.9 (8) |
N2—Cu—N4i | 87.4 (2) | N2—C3—H3A | 124.0 |
N2i—Cu—N4i | 92.6 (2) | N1—C3—H3A | 124.0 |
N2—Cu—N4 | 92.6 (2) | C5—C4—N2 | 108.6 (9) |
N2i—Cu—N4 | 87.4 (2) | C5—C4—H4A | 125.7 |
N4i—Cu—N4 | 180.000 (1) | N2—C4—H4A | 125.7 |
C3—N1—C5 | 106.5 (8) | C4—C5—N1 | 107.5 (9) |
C3—N1—C2 | 117.7 (9) | C4—C5—H5A | 126.2 |
C5—N1—C2 | 135.8 (9) | N1—C5—H5A | 126.2 |
C3—N2—C4 | 105.4 (7) | C7—C6—H6A | 120.0 |
C3—N2—Cu | 127.8 (6) | C7—C6—H6B | 120.0 |
C4—N2—Cu | 126.7 (5) | H6A—C6—H6B | 120.0 |
C10—N3—C8 | 106.2 (7) | N3—C7—C6 | 120.3 (9) |
C10—N3—C7 | 121.8 (7) | N3—C7—H7A | 119.8 |
C8—N3—C7 | 132.0 (7) | C6—C7—H7A | 119.8 |
C10—N4—C9 | 106.7 (7) | N3—C8—C9 | 107.1 (7) |
C10—N4—Cu | 127.8 (5) | N3—C8—H8A | 126.5 |
C9—N4—Cu | 124.9 (5) | C9—C8—H8A | 126.5 |
C2—C1—H1A | 120.0 | N4—C9—C8 | 108.0 (8) |
C2—C1—H1B | 120.0 | N4—C9—H9A | 126.0 |
H1A—C1—H1B | 120.0 | C8—C9—H9A | 126.0 |
N1—C2—C1 | 118.8 (11) | N4—C10—N3 | 112.0 (7) |
N1—C2—H2A | 120.6 | N4—C10—H10A | 124.0 |
C1—C2—H2A | 120.6 | N3—C10—H10A | 124.0 |
N4i—Cu—N2—C3 | −126.5 (7) | Cu—N2—C4—C5 | −176.9 (6) |
N4—Cu—N2—C3 | 53.5 (7) | N2—C4—C5—N1 | −1.3 (12) |
N4i—Cu—N2—C4 | 51.0 (7) | C3—N1—C5—C4 | 1.2 (11) |
N4—Cu—N2—C4 | −129.0 (7) | C2—N1—C5—C4 | −176.8 (11) |
N2—Cu—N4—C10 | −73.6 (7) | C10—N3—C7—C6 | −164.0 (9) |
N2i—Cu—N4—C10 | 106.4 (7) | C8—N3—C7—C6 | 18.7 (15) |
N2—Cu—N4—C9 | 115.8 (7) | C10—N3—C8—C9 | 2.0 (10) |
N2i—Cu—N4—C9 | −64.2 (7) | C7—N3—C8—C9 | 179.6 (9) |
C3—N1—C2—C1 | 173.5 (10) | C10—N4—C9—C8 | 0.0 (10) |
C5—N1—C2—C1 | −8.7 (19) | Cu—N4—C9—C8 | 172.3 (6) |
C4—N2—C3—N1 | −0.2 (10) | N3—C8—C9—N4 | −1.3 (10) |
Cu—N2—C3—N1 | 177.6 (5) | C9—N4—C10—N3 | 1.3 (10) |
C5—N1—C3—N2 | −0.6 (10) | Cu—N4—C10—N3 | −170.7 (5) |
C2—N1—C3—N2 | 177.8 (8) | C8—N3—C10—N4 | −2.1 (10) |
C3—N2—C4—C5 | 1.0 (11) | C7—N3—C10—N4 | −180.0 (7) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···Brii | 0.93 | 2.79 | 3.643 (12) | 154 |
C3—H3A···Brii | 0.93 | 2.93 | 3.717 (9) | 144 |
C8—H8A···Briii | 0.93 | 2.87 | 3.772 (9) | 163 |
C10—H10A···Br | 0.93 | 2.88 | 3.480 (8) | 124 |
Symmetry codes: (ii) −x, −y+1, −z+1; (iii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [CuBr2(C5H6N2)4] |
Mr | 599.82 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.7280 (15), 15.144 (3), 11.039 (2) |
β (°) | 107.23 (3) |
V (Å3) | 1234.0 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.15 |
Crystal size (mm) | 0.40 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.605, 0.659 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2568, 2416, 1446 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.164, 1.03 |
No. of reflections | 2416 |
No. of parameters | 124 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.82, −0.84 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···Bri | 0.93 | 2.79 | 3.643 (12) | 154 |
C3—H3A···Bri | 0.93 | 2.93 | 3.717 (9) | 144 |
C8—H8A···Brii | 0.93 | 2.87 | 3.772 (9) | 163 |
C10—H10A···Br | 0.93 | 2.88 | 3.480 (8) | 124 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+1/2. |
In the title compound,(I), The CuII cation is coordinated by four N atoms from four 1-vinylimidazole ligand and two trans coordinated Br- anions in a distorted octahedral geometry (Fig. 1). The equatorial planes are formed by four Cu—N(1-vinylimadazole) bonds [Cu—N2 = 2.007 (6) Å, Cu—N4 = 2.029 (6) Å] and the axial positions are occupied by two Br- ions [Cu—Br = 3.0340 (11) Å]. The Cu—N bond lengths agree well with those observed in [Cu(imidazole)Br2] (Parker & Breneman, 1995), but the Cu—Br bond length is shorter than that in [Cu(imidazole)Br2]. In the crystal, the intramolecular and intermolecular C—H···Br hydrogen bonds form three-dimensional hydrogen bond networks to stabilize the structure.