Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703067X/hb2453sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703067X/hb2453Isup2.hkl |
CCDC reference: 654832
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.018
- wR factor = 0.049
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.71 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 3 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C8 H4 O4
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 Cd1 (2) 2.13 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 4
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 1 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 1 ALERT type 5 Informative message, check
2,2'-Biimidazole was synthesized according to the literature method (Fieselmann et al., 1978). Benzene-1,4-dicarboxylic acid, 2,2'-biimidazole and cadmium acetate dihydrate were reacted in a molar ratio of 1:2:1. The mixture was stirred for 30 min, then the pH was adjusted to 6.5 with an aqueous solution of NaOH (0.1 M). The mixture with a total volume of 21 ml was heated at 433 K for 5 d in a sealed 25 ml Teflon-lined stainless steel vessel under autogenous pressure. After the reaction mixture was slowly cooled to room temperature at a rate of 5 K h-1, colourless blocks of (I) were obtained.
The water H atoms were located in a difference map and refined as riding in their as-found relative positions with free refinement for their Uiso values. The other H atoms were positioned geometrically (C—H = 0.93 Å, N—H = 0.86 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).
As part of the ongoing study of complexes containing 2,2'-biimidazole (H2biim) as a ligand (Ding et al.,2005), we now report the title compound, (I), which contains Cd2+-containing complex ions, charge balanced by benzene-1,4-dicarboxylate dianions.
The Cd atom (site symmetry 1) in (I) is coordinated by four N atoms of two H2biim ligands and two O atoms from two water molecules, in a octahedral geometry (Table 1, Fig. 1). The cation and anion interact by way of N—H···O and O—H···O hydrogen bonds (Table 2).
The plane-to-plane distance of 3.26 Å between the C1 imidazol ring and its symmetry equivalent partner at (3 - x, -y, 2 - z), in an offset fashion (slippage = 1.10 Å) indicates a strong π–π interaction (Fig. 2).
For a related structure, see: Ding et al. (2005). For the ligand synthesis, see: Fieselmann et al. (1978). For reference geometrical data, see: Allen et al. (1987).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97 and local programs.
[Cd(C6H6N4)2(H2O)2](C8H4O4) | F(000) = 584 |
Mr = 580.84 | Dx = 1.660 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 903 reflections |
a = 8.336 (2) Å | θ = 2.6–25.8° |
b = 11.009 (3) Å | µ = 0.99 mm−1 |
c = 12.688 (4) Å | T = 293 K |
β = 93.674 (3)° | Block, colourless |
V = 1161.9 (6) Å3 | 0.58 × 0.53 × 0.25 mm |
Z = 2 |
Bruker SMART CCD diffractometer | 2294 independent reflections |
Radiation source: fine-focus sealed tube | 2139 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
ω scans | θmax = 26.1°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) or Bruker (1997)? | h = −10→10 |
Tmin = 0.596, Tmax = 0.786 | k = −13→13 |
9682 measured reflections | l = −15→15 |
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)] = 0.018 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.049 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0258P)2 + 0.5043P] where P = (Fo2 + 2Fc2)/3 |
2294 reflections | (Δ/σ)max = 0.003 |
162 parameters | Δρmax = 0.30 e Å−3 |
4 restraints | Δρmin = −0.26 e Å−3 |
[Cd(C6H6N4)2(H2O)2](C8H4O4) | V = 1161.9 (6) Å3 |
Mr = 580.84 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.336 (2) Å | µ = 0.99 mm−1 |
b = 11.009 (3) Å | T = 293 K |
c = 12.688 (4) Å | 0.58 × 0.53 × 0.25 mm |
β = 93.674 (3)° |
Bruker SMART CCD diffractometer | 2294 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) or Bruker (1997)? | 2139 reflections with I > 2σ(I) |
Tmin = 0.596, Tmax = 0.786 | Rint = 0.014 |
9682 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 4 restraints |
wR(F2) = 0.049 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.30 e Å−3 |
2294 reflections | Δρmin = −0.26 e Å−3 |
162 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 | ||
Cd1 | 1.0000 | 0.0000 | 1.0000 | 0.02922 (7) | |
OW1 | 1.08556 (16) | 0.14916 (12) | 0.87749 (10) | 0.0465 (3) | |
HW1A | 1.1376 | 0.1233 | 0.8272 | 0.058 (7)* | |
HW1B | 1.1015 | 0.2283 | 0.8870 | 0.061 (7)* | |
O2 | 0.62681 (16) | 0.09753 (13) | 1.35814 (11) | 0.0526 (4) | |
O1 | 0.72382 (15) | −0.05438 (15) | 1.26778 (11) | 0.0510 (4) | |
N1 | 1.25379 (15) | −0.08664 (12) | 1.01642 (10) | 0.0272 (3) | |
N2 | 1.48489 (15) | −0.08867 (12) | 1.11125 (10) | 0.0289 (3) | |
H2A | 1.5591 | −0.0698 | 1.1587 | 0.035* | |
N3 | 1.34980 (16) | 0.12255 (13) | 1.23815 (11) | 0.0352 (3) | |
H3A | 1.4448 | 0.1088 | 1.2661 | 0.042* | |
N4 | 1.13014 (16) | 0.10607 (13) | 1.13365 (10) | 0.0321 (3) | |
C8 | 0.8710 (2) | 0.00788 (13) | 1.42460 (14) | 0.0297 (4) | |
C7 | 0.7303 (2) | 0.01824 (15) | 1.34368 (14) | 0.0340 (4) | |
C9 | 1.0192 (2) | −0.03370 (17) | 1.39653 (14) | 0.0342 (4) | |
H9 | 1.0326 | −0.0567 | 1.3271 | 0.041* | |
C3 | 1.33955 (18) | −0.03673 (14) | 1.09696 (12) | 0.0249 (3) | |
C1 | 1.3500 (2) | −0.17504 (15) | 0.97813 (13) | 0.0322 (3) | |
H1 | 1.3222 | −0.2257 | 0.9212 | 0.039* | |
C10 | 1.1479 (2) | −0.04125 (17) | 1.47141 (13) | 0.0340 (4) | |
H10 | 1.2471 | −0.0688 | 1.4518 | 0.041* | |
C4 | 1.27572 (18) | 0.06208 (14) | 1.15733 (12) | 0.0264 (3) | |
C2 | 1.4928 (2) | −0.17705 (15) | 1.03637 (14) | 0.0336 (4) | |
H2 | 1.5791 | −0.2286 | 1.0270 | 0.040* | |
C6 | 1.1112 (2) | 0.19951 (17) | 1.20294 (15) | 0.0414 (4) | |
H6 | 1.0202 | 0.2481 | 1.2052 | 0.050* | |
C5 | 1.2461 (2) | 0.20980 (19) | 1.26767 (15) | 0.0436 (4) | |
H5 | 1.2644 | 0.2658 | 1.3220 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.02300 (10) | 0.03417 (11) | 0.02907 (10) | 0.00073 (6) | −0.00917 (7) | −0.00343 (6) |
OW1 | 0.0536 (8) | 0.0415 (8) | 0.0455 (8) | 0.0030 (6) | 0.0117 (6) | 0.0052 (6) |
O2 | 0.0464 (8) | 0.0513 (8) | 0.0563 (8) | 0.0186 (7) | −0.0271 (7) | −0.0148 (7) |
O1 | 0.0353 (7) | 0.0740 (10) | 0.0412 (8) | 0.0118 (7) | −0.0167 (6) | −0.0207 (7) |
N1 | 0.0257 (6) | 0.0282 (7) | 0.0270 (6) | −0.0006 (5) | −0.0036 (5) | −0.0018 (5) |
N2 | 0.0227 (6) | 0.0315 (7) | 0.0316 (7) | 0.0014 (5) | −0.0058 (5) | 0.0000 (5) |
N3 | 0.0281 (7) | 0.0417 (8) | 0.0340 (7) | 0.0040 (6) | −0.0115 (6) | −0.0114 (6) |
N4 | 0.0261 (7) | 0.0364 (8) | 0.0326 (7) | 0.0045 (6) | −0.0061 (5) | −0.0080 (6) |
C8 | 0.0278 (8) | 0.0277 (8) | 0.0321 (9) | −0.0017 (6) | −0.0102 (7) | 0.0019 (6) |
C7 | 0.0297 (9) | 0.0391 (9) | 0.0317 (9) | −0.0003 (7) | −0.0104 (7) | 0.0007 (7) |
C9 | 0.0327 (9) | 0.0412 (9) | 0.0277 (8) | 0.0006 (7) | −0.0057 (7) | −0.0021 (7) |
C3 | 0.0231 (7) | 0.0254 (7) | 0.0258 (7) | −0.0006 (6) | −0.0023 (6) | 0.0019 (6) |
C1 | 0.0343 (8) | 0.0297 (8) | 0.0322 (8) | 0.0014 (7) | −0.0002 (7) | −0.0057 (6) |
C10 | 0.0265 (8) | 0.0398 (9) | 0.0346 (9) | 0.0031 (7) | −0.0052 (7) | −0.0013 (7) |
C4 | 0.0244 (7) | 0.0290 (8) | 0.0251 (7) | 0.0000 (6) | −0.0043 (6) | −0.0017 (6) |
C2 | 0.0315 (8) | 0.0297 (8) | 0.0397 (9) | 0.0055 (6) | 0.0023 (7) | −0.0025 (7) |
C6 | 0.0348 (9) | 0.0444 (10) | 0.0440 (10) | 0.0117 (8) | −0.0062 (8) | −0.0160 (8) |
C5 | 0.0415 (10) | 0.0463 (10) | 0.0412 (10) | 0.0083 (8) | −0.0100 (8) | −0.0216 (8) |
Cd1—N4 | 2.2759 (14) | N3—H3A | 0.8600 |
Cd1—N4i | 2.2759 (14) | N4—C4 | 1.323 (2) |
Cd1—N1i | 2.3178 (14) | N4—C6 | 1.369 (2) |
Cd1—N1 | 2.3178 (14) | C8—C9 | 1.385 (3) |
Cd1—OW1 | 2.4007 (14) | C8—C10ii | 1.388 (3) |
Cd1—OW1i | 2.4007 (14) | C8—C7 | 1.513 (2) |
OW1—HW1A | 0.8438 | C9—C10 | 1.389 (2) |
OW1—HW1B | 0.8879 | C9—H9 | 0.9300 |
O2—C7 | 1.249 (2) | C3—C4 | 1.451 (2) |
O1—C7 | 1.250 (2) | C1—C2 | 1.360 (2) |
N1—C3 | 1.328 (2) | C1—H1 | 0.9300 |
N1—C1 | 1.370 (2) | C10—C8ii | 1.388 (3) |
N2—C3 | 1.341 (2) | C10—H10 | 0.9300 |
N2—C2 | 1.364 (2) | C2—H2 | 0.9300 |
N2—H2A | 0.8600 | C6—C5 | 1.354 (2) |
N3—C4 | 1.340 (2) | C6—H6 | 0.9300 |
N3—C5 | 1.361 (2) | C5—H5 | 0.9300 |
N4—Cd1—N4i | 180.0 | C9—C8—C10ii | 119.26 (16) |
N4—Cd1—N1i | 104.16 (5) | C9—C8—C7 | 121.05 (16) |
N4i—Cd1—N1i | 75.84 (5) | C10ii—C8—C7 | 119.68 (16) |
N4—Cd1—N1 | 75.84 (5) | O2—C7—O1 | 124.34 (16) |
N4i—Cd1—N1 | 104.16 (5) | O2—C7—C8 | 117.75 (16) |
N1i—Cd1—N1 | 180.0 | O1—C7—C8 | 117.90 (16) |
N4—Cd1—OW1 | 89.10 (5) | C8—C9—C10 | 120.43 (17) |
N4i—Cd1—OW1 | 90.90 (5) | C8—C9—H9 | 119.8 |
N1i—Cd1—OW1 | 88.15 (5) | C10—C9—H9 | 119.8 |
N1—Cd1—OW1 | 91.85 (5) | N1—C3—N2 | 111.39 (14) |
N4—Cd1—OW1i | 90.90 (5) | N1—C3—C4 | 121.26 (13) |
N4i—Cd1—OW1i | 89.10 (5) | N2—C3—C4 | 127.35 (14) |
N1i—Cd1—OW1i | 91.85 (5) | C2—C1—N1 | 109.33 (14) |
N1—Cd1—OW1i | 88.15 (5) | C2—C1—H1 | 125.3 |
OW1—Cd1—OW1i | 180.0 | N1—C1—H1 | 125.3 |
Cd1—OW1—HW1A | 116.5 | C8ii—C10—C9 | 120.31 (17) |
Cd1—OW1—HW1B | 129.1 | C8ii—C10—H10 | 119.8 |
HW1A—OW1—HW1B | 110.8 | C9—C10—H10 | 119.8 |
C3—N1—C1 | 105.55 (13) | N4—C4—N3 | 111.29 (14) |
C3—N1—Cd1 | 110.01 (10) | N4—C4—C3 | 121.10 (13) |
C1—N1—Cd1 | 144.33 (11) | N3—C4—C3 | 127.58 (14) |
C3—N2—C2 | 107.07 (13) | C1—C2—N2 | 106.66 (14) |
C3—N2—H2A | 126.5 | C1—C2—H2 | 126.7 |
C2—N2—H2A | 126.5 | N2—C2—H2 | 126.7 |
C4—N3—C5 | 106.95 (14) | C5—C6—N4 | 109.06 (15) |
C4—N3—H3A | 126.5 | C5—C6—H6 | 125.5 |
C5—N3—H3A | 126.5 | N4—C6—H6 | 125.5 |
C4—N4—C6 | 105.74 (13) | C6—C5—N3 | 106.96 (15) |
C4—N4—Cd1 | 111.59 (10) | C6—C5—H5 | 126.5 |
C6—N4—Cd1 | 142.64 (11) | N3—C5—H5 | 126.5 |
N4—Cd1—N1—C3 | 3.63 (10) | C1—N1—C3—C4 | 179.68 (14) |
N4i—Cd1—N1—C3 | −176.37 (10) | Cd1—N1—C3—C4 | −3.15 (18) |
OW1—Cd1—N1—C3 | 92.23 (11) | C2—N2—C3—N1 | −0.33 (18) |
OW1i—Cd1—N1—C3 | −87.77 (11) | C2—N2—C3—C4 | −179.77 (16) |
N4—Cd1—N1—C1 | 178.95 (19) | C3—N1—C1—C2 | 0.00 (19) |
N4i—Cd1—N1—C1 | −1.05 (19) | Cd1—N1—C1—C2 | −175.44 (13) |
OW1—Cd1—N1—C1 | −92.45 (19) | C8—C9—C10—C8ii | 0.4 (3) |
OW1i—Cd1—N1—C1 | 87.55 (19) | C6—N4—C4—N3 | 0.15 (19) |
N1i—Cd1—N4—C4 | 176.15 (11) | Cd1—N4—C4—N3 | −178.11 (11) |
N1—Cd1—N4—C4 | −3.85 (11) | C6—N4—C4—C3 | −177.99 (15) |
OW1—Cd1—N4—C4 | −95.99 (11) | Cd1—N4—C4—C3 | 3.75 (19) |
OW1i—Cd1—N4—C4 | 84.01 (11) | C5—N3—C4—N4 | 0.0 (2) |
N1i—Cd1—N4—C6 | −1.1 (2) | C5—N3—C4—C3 | 177.98 (17) |
N1—Cd1—N4—C6 | 178.9 (2) | N1—C3—C4—N4 | −0.4 (2) |
OW1—Cd1—N4—C6 | 86.8 (2) | N2—C3—C4—N4 | 179.02 (15) |
OW1i—Cd1—N4—C6 | −93.2 (2) | N1—C3—C4—N3 | −178.18 (15) |
C9—C8—C7—O2 | −151.17 (18) | N2—C3—C4—N3 | 1.2 (3) |
C10ii—C8—C7—O2 | 28.4 (2) | N1—C1—C2—N2 | −0.2 (2) |
C9—C8—C7—O1 | 30.0 (3) | C3—N2—C2—C1 | 0.31 (18) |
C10ii—C8—C7—O1 | −150.43 (18) | C4—N4—C6—C5 | −0.2 (2) |
C10ii—C8—C9—C10 | −0.4 (3) | Cd1—N4—C6—C5 | 177.10 (16) |
C7—C8—C9—C10 | 179.16 (16) | N4—C6—C5—N3 | 0.2 (2) |
C1—N1—C3—N2 | 0.21 (18) | C4—N3—C5—C6 | −0.1 (2) |
Cd1—N1—C3—N2 | 177.38 (10) |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, −y, −z+3. |
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—HW1A···O1i | 0.84 | 1.88 | 2.718 (2) | 171 |
OW1—HW1B···O2iii | 0.89 | 1.97 | 2.822 (2) | 161 |
N2—H2A···O1iv | 0.86 | 1.89 | 2.7471 (18) | 171 |
N3—H3A···O2iv | 0.86 | 1.86 | 2.6972 (19) | 165 |
Symmetry codes: (i) −x+2, −y, −z+2; (iii) x+1/2, −y+1/2, z−1/2; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C6H6N4)2(H2O)2](C8H4O4) |
Mr | 580.84 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.336 (2), 11.009 (3), 12.688 (4) |
β (°) | 93.674 (3) |
V (Å3) | 1161.9 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.99 |
Crystal size (mm) | 0.58 × 0.53 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) or Bruker (1997)? |
Tmin, Tmax | 0.596, 0.786 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9682, 2294, 2139 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.049, 1.04 |
No. of reflections | 2294 |
No. of parameters | 162 |
No. of restraints | 4 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.26 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXL97 and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—HW1A···O1i | 0.84 | 1.88 | 2.718 (2) | 171 |
OW1—HW1B···O2ii | 0.89 | 1.97 | 2.822 (2) | 161 |
N2—H2A···O1iii | 0.86 | 1.89 | 2.7471 (18) | 171 |
N3—H3A···O2iii | 0.86 | 1.86 | 2.6972 (19) | 165 |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) x+1/2, −y+1/2, z−1/2; (iii) x+1, y, z. |
As part of the ongoing study of complexes containing 2,2'-biimidazole (H2biim) as a ligand (Ding et al.,2005), we now report the title compound, (I), which contains Cd2+-containing complex ions, charge balanced by benzene-1,4-dicarboxylate dianions.
The Cd atom (site symmetry 1) in (I) is coordinated by four N atoms of two H2biim ligands and two O atoms from two water molecules, in a octahedral geometry (Table 1, Fig. 1). The cation and anion interact by way of N—H···O and O—H···O hydrogen bonds (Table 2).
The plane-to-plane distance of 3.26 Å between the C1 imidazol ring and its symmetry equivalent partner at (3 - x, -y, 2 - z), in an offset fashion (slippage = 1.10 Å) indicates a strong π–π interaction (Fig. 2).