Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054888/bt2579sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054888/bt2579Isup2.hkl |
CCDC reference: 672605
Key indicators
- Single-crystal X-ray study
- T = 300 K
- Mean (C-C) = 0.013 Å
- R factor = 0.043
- wR factor = 0.132
- Data-to-parameter ratio = 12.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........ O2 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 13
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 26.96 From the CIF: _reflns_number_total 1936 Count of symmetry unique reflns 1280 Completeness (_total/calc) 151.25% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 656 Fraction of Friedel pairs measured 0.512 Are heavy atom types Z>Si present yes PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1 (2) 1.97 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Kamar et al. (2004); Xia et al. (2006); Xiao & Shreeve (2005).
2,2'-biimidazole was synthesized according to the literature procedure (Xiao & Shreeve, 2005). A mixture of Cd(CO3)2, 2,2'-biimidazole in 1:1 molar ratio with 10 ml water was sealed into a Teflon-lined pressure vessel and heated at 433 K for 72 h. After the mixture cooled to room temperature, yellow crystals were formed, coolected by filtration, washed in deionized water, and finally dried in air.
After having located them in a difference map, all H-atoms were fixed geometrically at ideal positions. They were allowed to ride on their parent atoms with C–H=0.93 Å and N–H=0.86 Å with Uiso(H)=1.2Ueq(C,N).
Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Cd(C6H6N4)3]CO3 | Dx = 1.699 Mg m−3 |
Mr = 574.85 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41 | Cell parameters from 3277 reflections |
Hall symbol: I 4bw | θ = 3.3–26.2° |
a = 12.3477 (8) Å | µ = 1.02 mm−1 |
c = 14.7379 (10) Å | T = 300 K |
V = 2247.0 (3) Å3 | Block, yellow |
Z = 4 | 0.30 × 0.20 × 0.20 mm |
F(000) = 1152 |
Bruker SMART CCD area-detector diffractometer | 1936 independent reflections |
Radiation source: fine-focus sealed tube | 1761 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
phi and ω scans | θmax = 27.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −15→15 |
Tmin = 0.749, Tmax = 0.822 | k = −15→15 |
6885 measured reflections | l = −18→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0486P)2 + 13.566P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max < 0.001 |
1936 reflections | Δρmax = 0.47 e Å−3 |
160 parameters | Δρmin = −0.45 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 654 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.15 (6) |
[Cd(C6H6N4)3]CO3 | Z = 4 |
Mr = 574.85 | Mo Kα radiation |
Tetragonal, I41 | µ = 1.02 mm−1 |
a = 12.3477 (8) Å | T = 300 K |
c = 14.7379 (10) Å | 0.30 × 0.20 × 0.20 mm |
V = 2247.0 (3) Å3 |
Bruker SMART CCD area-detector diffractometer | 1936 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1761 reflections with I > 2σ(I) |
Tmin = 0.749, Tmax = 0.822 | Rint = 0.071 |
6885 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0486P)2 + 13.566P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | Δρmax = 0.47 e Å−3 |
1936 reflections | Δρmin = −0.45 e Å−3 |
160 parameters | Absolute structure: Flack (1983), 654 Friedel pairs |
1 restraint | Absolute structure parameter: −0.15 (6) |
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 | ||
Cd1 | 0.5000 | 0.5000 | 0.62805 (5) | 0.0349 (2) | |
C1 | 0.2725 (6) | 0.5529 (6) | 0.7110 (6) | 0.0338 (16) | |
C2 | 0.1821 (8) | 0.6941 (7) | 0.6645 (7) | 0.048 (2) | |
H2 | 0.1273 | 0.7445 | 0.6548 | 0.058* | |
C3 | 0.2828 (6) | 0.6956 (7) | 0.6299 (8) | 0.051 (2) | |
H3 | 0.3099 | 0.7496 | 0.5923 | 0.061* | |
C4 | 0.3048 (5) | 0.4522 (6) | 0.7546 (5) | 0.0307 (15) | |
C5 | 0.3097 (8) | 0.3090 (8) | 0.8389 (8) | 0.050 (2) | |
H5 | 0.2936 | 0.2568 | 0.8824 | 0.060* | |
C6 | 0.3972 (8) | 0.3106 (7) | 0.7806 (7) | 0.045 (2) | |
H6 | 0.4508 | 0.2578 | 0.7779 | 0.054* | |
C7 | 0.5318 (8) | 0.7177 (7) | 0.4728 (7) | 0.052 (2) | |
H7 | 0.5419 | 0.7752 | 0.5126 | 0.062* | |
C8 | 0.5272 (7) | 0.7257 (6) | 0.3827 (8) | 0.047 (2) | |
H8 | 0.5331 | 0.7891 | 0.3491 | 0.057* | |
C9 | 0.5070 (6) | 0.5591 (6) | 0.4221 (6) | 0.0349 (17) | |
N1 | 0.1769 (5) | 0.6027 (5) | 0.7172 (5) | 0.0363 (15) | |
H1 | 0.1221 | 0.5814 | 0.7485 | 0.044* | |
N2 | 0.3394 (5) | 0.6073 (5) | 0.6574 (5) | 0.0402 (16) | |
N3 | 0.2529 (5) | 0.3988 (5) | 0.8194 (5) | 0.0376 (15) | |
H3A | 0.1932 | 0.4182 | 0.8446 | 0.045* | |
N4 | 0.3932 (5) | 0.4014 (5) | 0.7273 (5) | 0.0378 (15) | |
N5 | 0.5194 (6) | 0.6120 (6) | 0.4973 (5) | 0.0393 (16) | |
N6 | 0.5124 (6) | 0.6240 (6) | 0.3486 (5) | 0.0420 (16) | |
H6A | 0.5076 | 0.6054 | 0.2925 | 0.050* | |
C11 | 0.5000 | 0.5000 | 0.1353 (17) | 0.030 (3) | |
O1 | 0.4868 (5) | 0.4101 (4) | 0.1714 (4) | 0.0392 (12) | |
O2 | 0.5000 | 0.5000 | 0.0415 (6) | 0.047 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0302 (5) | 0.0455 (6) | 0.0290 (4) | −0.0016 (5) | 0.000 | 0.000 |
C1 | 0.027 (4) | 0.044 (4) | 0.030 (4) | −0.001 (3) | −0.001 (3) | −0.001 (3) |
C2 | 0.055 (5) | 0.045 (5) | 0.045 (5) | 0.007 (4) | −0.008 (4) | 0.013 (4) |
C3 | 0.041 (4) | 0.058 (5) | 0.054 (6) | 0.007 (4) | −0.004 (5) | 0.028 (5) |
C4 | 0.025 (3) | 0.037 (4) | 0.030 (4) | −0.004 (3) | 0.002 (3) | 0.001 (3) |
C5 | 0.050 (5) | 0.049 (5) | 0.051 (6) | 0.001 (4) | 0.000 (4) | 0.019 (4) |
C6 | 0.048 (5) | 0.039 (4) | 0.048 (6) | 0.011 (4) | −0.005 (4) | 0.009 (4) |
C7 | 0.067 (6) | 0.041 (5) | 0.048 (6) | −0.012 (4) | −0.006 (5) | −0.011 (4) |
C8 | 0.065 (5) | 0.026 (3) | 0.051 (6) | −0.004 (3) | 0.016 (5) | 0.004 (4) |
C9 | 0.034 (4) | 0.036 (4) | 0.035 (4) | −0.003 (3) | −0.005 (3) | 0.004 (3) |
N1 | 0.030 (3) | 0.046 (4) | 0.033 (4) | 0.004 (3) | 0.008 (3) | 0.005 (3) |
N2 | 0.043 (4) | 0.038 (3) | 0.040 (4) | 0.001 (3) | 0.008 (3) | 0.011 (3) |
N3 | 0.033 (3) | 0.040 (4) | 0.040 (4) | 0.004 (3) | 0.001 (3) | 0.011 (3) |
N4 | 0.026 (3) | 0.045 (4) | 0.043 (4) | 0.003 (3) | −0.004 (3) | 0.006 (3) |
N5 | 0.048 (4) | 0.042 (4) | 0.028 (4) | −0.007 (3) | 0.011 (3) | −0.005 (3) |
N6 | 0.053 (4) | 0.041 (4) | 0.031 (4) | −0.004 (3) | −0.002 (3) | 0.004 (3) |
C11 | 0.036 (6) | 0.038 (7) | 0.016 (8) | −0.002 (6) | 0.000 | 0.000 |
O1 | 0.052 (3) | 0.033 (3) | 0.033 (3) | −0.002 (2) | −0.002 (3) | 0.005 (2) |
O2 | 0.071 (6) | 0.032 (4) | 0.037 (5) | 0.009 (4) | 0.000 | 0.000 |
Cd1—N4 | 2.315 (7) | C5—H5 | 0.9300 |
Cd1—N4i | 2.315 (7) | C6—N4 | 1.370 (11) |
Cd1—N5i | 2.383 (7) | C6—H6 | 0.9300 |
Cd1—N5 | 2.383 (7) | C7—C8 | 1.333 (14) |
Cd1—N2 | 2.424 (7) | C7—N5 | 1.364 (11) |
Cd1—N2i | 2.424 (7) | C7—H7 | 0.9300 |
C1—N2 | 1.326 (10) | C8—N6 | 1.364 (11) |
C1—N1 | 1.334 (10) | C8—H8 | 0.9300 |
C1—C4 | 1.455 (11) | C9—N5 | 1.296 (11) |
C2—C3 | 1.344 (13) | C9—N6 | 1.349 (11) |
C2—N1 | 1.372 (11) | C9—C9i | 1.469 (16) |
C2—H2 | 0.9300 | N1—H1 | 0.8600 |
C3—N2 | 1.357 (10) | N3—H3A | 0.8600 |
C3—H3 | 0.9300 | N6—H6A | 0.8600 |
C4—N4 | 1.323 (10) | C11—O1i | 1.242 (12) |
C4—N3 | 1.326 (10) | C11—O1 | 1.242 (12) |
C5—N3 | 1.343 (11) | C11—O2 | 1.38 (3) |
C5—C6 | 1.380 (14) | ||
N4—Cd1—N4i | 101.6 (4) | C5—C6—H6 | 125.0 |
N4—Cd1—N5i | 98.5 (2) | C8—C7—N5 | 109.3 (8) |
N4i—Cd1—N5i | 150.8 (2) | C8—C7—H7 | 125.4 |
N4—Cd1—N5 | 150.8 (2) | N5—C7—H7 | 125.4 |
N4i—Cd1—N5 | 98.5 (2) | C7—C8—N6 | 107.7 (8) |
N5i—Cd1—N5 | 72.1 (3) | C7—C8—H8 | 126.1 |
N4—Cd1—N2 | 73.1 (2) | N6—C8—H8 | 126.1 |
N4i—Cd1—N2 | 93.8 (2) | N5—C9—N6 | 112.5 (7) |
N5i—Cd1—N2 | 112.3 (2) | N5—C9—C9i | 120.9 (5) |
N5—Cd1—N2 | 84.8 (2) | N6—C9—C9i | 126.6 (5) |
N4—Cd1—N2i | 93.8 (2) | C1—N1—C2 | 107.4 (7) |
N4i—Cd1—N2i | 73.1 (2) | C1—N1—H1 | 126.3 |
N5i—Cd1—N2i | 84.8 (2) | C2—N1—H1 | 126.3 |
N5—Cd1—N2i | 112.3 (2) | C1—N2—C3 | 105.3 (7) |
N2—Cd1—N2i | 159.5 (4) | C1—N2—Cd1 | 109.8 (5) |
N2—C1—N1 | 111.0 (7) | C3—N2—Cd1 | 143.8 (6) |
N2—C1—C4 | 121.7 (7) | C4—N3—C5 | 108.2 (7) |
N1—C1—C4 | 127.3 (7) | C4—N3—H3A | 125.9 |
C3—C2—N1 | 105.6 (8) | C5—N3—H3A | 125.9 |
C3—C2—H2 | 127.2 | C4—N4—C6 | 104.1 (7) |
N1—C2—H2 | 127.2 | C4—N4—Cd1 | 114.4 (5) |
C2—C3—N2 | 110.6 (8) | C6—N4—Cd1 | 140.6 (6) |
C2—C3—H3 | 124.7 | C9—N5—C7 | 105.6 (7) |
N2—C3—H3 | 124.7 | C9—N5—Cd1 | 112.8 (5) |
N4—C4—N3 | 112.4 (7) | C7—N5—Cd1 | 141.4 (6) |
N4—C4—C1 | 119.9 (7) | C9—N6—C8 | 104.9 (8) |
N3—C4—C1 | 127.6 (7) | C9—N6—H6A | 127.5 |
N3—C5—C6 | 105.3 (8) | C8—N6—H6A | 127.5 |
N3—C5—H5 | 127.3 | O1i—C11—O1 | 129 (2) |
C6—C5—H5 | 127.3 | O1i—C11—O2 | 115.4 (11) |
N4—C6—C5 | 109.9 (8) | O1—C11—O2 | 115.4 (11) |
N4—C6—H6 | 125.0 | ||
N1—C2—C3—N2 | 1.4 (12) | C1—C4—N4—Cd1 | 10.2 (9) |
N2—C1—C4—N4 | −13.9 (12) | C5—C6—N4—C4 | 0.3 (10) |
N1—C1—C4—N4 | 165.8 (8) | C5—C6—N4—Cd1 | 167.6 (8) |
N2—C1—C4—N3 | 169.1 (8) | N4i—Cd1—N4—C4 | 86.5 (6) |
N1—C1—C4—N3 | −11.2 (14) | N5i—Cd1—N4—C4 | −114.8 (6) |
N3—C5—C6—N4 | 0.6 (12) | N5—Cd1—N4—C4 | −46.3 (9) |
N5—C7—C8—N6 | −0.4 (11) | N2—Cd1—N4—C4 | −4.0 (6) |
N2—C1—N1—C2 | 0.3 (10) | N2i—Cd1—N4—C4 | 159.9 (6) |
C4—C1—N1—C2 | −179.5 (8) | N4i—Cd1—N4—C6 | −80.0 (10) |
C3—C2—N1—C1 | −1.0 (11) | N5i—Cd1—N4—C6 | 78.7 (10) |
N1—C1—N2—C3 | 0.6 (10) | N5—Cd1—N4—C6 | 147.2 (9) |
C4—C1—N2—C3 | −179.7 (8) | N2—Cd1—N4—C6 | −170.4 (10) |
N1—C1—N2—Cd1 | −170.7 (5) | N2i—Cd1—N4—C6 | −6.5 (10) |
C4—C1—N2—Cd1 | 9.1 (9) | N6—C9—N5—C7 | 1.0 (10) |
C2—C3—N2—C1 | −1.3 (11) | C9i—C9—N5—C7 | 179.0 (9) |
C2—C3—N2—Cd1 | 164.7 (8) | N6—C9—N5—Cd1 | 176.7 (5) |
N4—Cd1—N2—C1 | −2.7 (5) | C9i—C9—N5—Cd1 | −5.3 (11) |
N4i—Cd1—N2—C1 | −103.7 (6) | C8—C7—N5—C9 | −0.4 (11) |
N5i—Cd1—N2—C1 | 89.8 (6) | C8—C7—N5—Cd1 | −174.0 (7) |
N5—Cd1—N2—C1 | 158.0 (6) | N4—Cd1—N5—C9 | −73.2 (7) |
N2i—Cd1—N2—C1 | −54.7 (5) | N4i—Cd1—N5—C9 | 153.4 (5) |
N4—Cd1—N2—C3 | −168.3 (11) | N5i—Cd1—N5—C9 | 1.9 (4) |
N4i—Cd1—N2—C3 | 90.6 (11) | N2—Cd1—N5—C9 | −113.6 (6) |
N5i—Cd1—N2—C3 | −75.9 (11) | N2i—Cd1—N5—C9 | 78.3 (6) |
N5—Cd1—N2—C3 | −7.6 (11) | N4—Cd1—N5—C7 | 100.1 (10) |
N2i—Cd1—N2—C3 | 139.7 (11) | N4i—Cd1—N5—C7 | −33.2 (10) |
N4—C4—N3—C5 | 1.6 (10) | N5i—Cd1—N5—C7 | 175.2 (11) |
C1—C4—N3—C5 | 178.8 (8) | N2—Cd1—N5—C7 | 59.8 (10) |
C6—C5—N3—C4 | −1.3 (11) | N2i—Cd1—N5—C7 | −108.4 (10) |
N3—C4—N4—C6 | −1.2 (9) | N5—C9—N6—C8 | −1.3 (9) |
C1—C4—N4—C6 | −178.6 (7) | C9i—C9—N6—C8 | −179.1 (9) |
N3—C4—N4—Cd1 | −172.4 (5) | C7—C8—N6—C9 | 1.0 (10) |
Symmetry code: (i) −x+1, −y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1ii | 0.86 | 1.90 | 2.737 (9) | 163 |
N1—H1···O2iii | 0.86 | 1.92 | 2.753 (8) | 163 |
N6—H6A···O1i | 0.86 | 1.80 | 2.644 (9) | 169 |
Symmetry codes: (i) −x+1, −y+1, z; (ii) −y+1/2, x, z+3/4; (iii) y−1/2, −x+1, z+3/4. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C6H6N4)3]CO3 |
Mr | 574.85 |
Crystal system, space group | Tetragonal, I41 |
Temperature (K) | 300 |
a, c (Å) | 12.3477 (8), 14.7379 (10) |
V (Å3) | 2247.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.749, 0.822 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6885, 1936, 1761 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.638 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.132, 1.17 |
No. of reflections | 1936 |
No. of parameters | 160 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0486P)2 + 13.566P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.47, −0.45 |
Absolute structure | Flack (1983), 654 Friedel pairs |
Absolute structure parameter | −0.15 (6) |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1i | 0.86 | 1.90 | 2.737 (9) | 162.8 |
N1—H1···O2ii | 0.86 | 1.92 | 2.753 (8) | 162.7 |
N6—H6A···O1iii | 0.86 | 1.80 | 2.644 (9) | 168.7 |
Symmetry codes: (i) −y+1/2, x, z+3/4; (ii) y−1/2, −x+1, z+3/4; (iii) −x+1, −y+1, z. |
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There has been increasing interest in the recent years for the coordinating ability of 2,2'-biimidazole (H2biim) (Xia et al., 2006; Kamar et al., 2004). It is a bidentate chelating ligand with multiple proton-donor sites which can coordinate to a transition metal in its neutral (H2biim), singly-deprotonated (Hbiim-) and doubly-deprotonated (biim2-) forms. Furthermore, the uncoordinated N atoms, which may be protonated or not, can participate in various patterns of hydrogen bonds with other components of the structure, leading to a broad variety of crystalline structures.
Here, we report the synthesis and crystal structure of the title compound, consisting of [Cd(H2biim)3]2+ complex cations with CO32- acting as counter anions. The central CdII ion of the title compound exhibits a distorted octahedral geometry. It is coordinated to six N atoms from three 2,2'-biimidazole ligands.
The crystal packing is stabilized by N—H···O hydrogen bonds.