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The title compound, [Cd(C6H6N4)3]CO3, is composed of discrete cations and anions, which are each located on a twofold rotation axis. The central CdII ion exhibits a distorted octa­hedral geometry and is coordinated by six N atoms from three 2,2′-biimidazole mol­ecules. The crystal packing is stabilized by N—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054888/bt2579sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054888/bt2579Isup2.hkl
Contains datablock I

CCDC reference: 672605

Key indicators

  • Single-crystal X-ray study
  • T = 300 K
  • Mean [sigma](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

Comment top

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.

Related literature top

For related literature, see: Kamar et al. (2004); Xia et al. (2006); Xiao & Shreeve (2005).

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of the title compound, showing 50% probability displacement ellipsoids for the non-hydrogen atoms. [Symmetry codes:(a) 1 - x, 1 - y, z;(b) 1 - x, 1 - y, z]
[Figure 2] Fig. 2. Packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
Tris(2,2'-bi-1H-imidazole)cadmium(II) carbonate top
Crystal data top
[Cd(C6H6N4)3]CO3Dx = 1.699 Mg m3
Mr = 574.85Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41Cell parameters from 3277 reflections
Hall symbol: I 4bwθ = 3.3–26.2°
a = 12.3477 (8) ŵ = 1.02 mm1
c = 14.7379 (10) ÅT = 300 K
V = 2247.0 (3) Å3Block, yellow
Z = 40.30 × 0.20 × 0.20 mm
F(000) = 1152
Data collection top
Bruker SMART CCD area-detector
diffractometer
1936 independent reflections
Radiation source: fine-focus sealed tube1761 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.071
phi and ω scansθmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1515
Tmin = 0.749, Tmax = 0.822k = 1515
6885 measured reflectionsl = 1812
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-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 reflectionsΔρmax = 0.47 e Å3
160 parametersΔρmin = 0.45 e Å3
1 restraintAbsolute structure: Flack (1983), 654 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.15 (6)
Crystal data top
[Cd(C6H6N4)3]CO3Z = 4
Mr = 574.85Mo Kα radiation
Tetragonal, I41µ = 1.02 mm1
a = 12.3477 (8) ÅT = 300 K
c = 14.7379 (10) Å0.30 × 0.20 × 0.20 mm
V = 2247.0 (3) Å3
Data collection top
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 = 0.822Rint = 0.071
6885 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.132 w = 1/[σ2(Fo2) + (0.0486P)2 + 13.566P]
where P = (Fo2 + 2Fc2)/3
S = 1.17Δρmax = 0.47 e Å3
1936 reflectionsΔρmin = 0.45 e Å3
160 parametersAbsolute structure: Flack (1983), 654 Friedel pairs
1 restraintAbsolute structure parameter: 0.15 (6)
Special details top

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
xyzUiso*/Ueq
Cd10.50000.50000.62805 (5)0.0349 (2)
C10.2725 (6)0.5529 (6)0.7110 (6)0.0338 (16)
C20.1821 (8)0.6941 (7)0.6645 (7)0.048 (2)
H20.12730.74450.65480.058*
C30.2828 (6)0.6956 (7)0.6299 (8)0.051 (2)
H30.30990.74960.59230.061*
C40.3048 (5)0.4522 (6)0.7546 (5)0.0307 (15)
C50.3097 (8)0.3090 (8)0.8389 (8)0.050 (2)
H50.29360.25680.88240.060*
C60.3972 (8)0.3106 (7)0.7806 (7)0.045 (2)
H60.45080.25780.77790.054*
C70.5318 (8)0.7177 (7)0.4728 (7)0.052 (2)
H70.54190.77520.51260.062*
C80.5272 (7)0.7257 (6)0.3827 (8)0.047 (2)
H80.53310.78910.34910.057*
C90.5070 (6)0.5591 (6)0.4221 (6)0.0349 (17)
N10.1769 (5)0.6027 (5)0.7172 (5)0.0363 (15)
H10.12210.58140.74850.044*
N20.3394 (5)0.6073 (5)0.6574 (5)0.0402 (16)
N30.2529 (5)0.3988 (5)0.8194 (5)0.0376 (15)
H3A0.19320.41820.84460.045*
N40.3932 (5)0.4014 (5)0.7273 (5)0.0378 (15)
N50.5194 (6)0.6120 (6)0.4973 (5)0.0393 (16)
N60.5124 (6)0.6240 (6)0.3486 (5)0.0420 (16)
H6A0.50760.60540.29250.050*
C110.50000.50000.1353 (17)0.030 (3)
O10.4868 (5)0.4101 (4)0.1714 (4)0.0392 (12)
O20.50000.50000.0415 (6)0.047 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0302 (5)0.0455 (6)0.0290 (4)0.0016 (5)0.0000.000
C10.027 (4)0.044 (4)0.030 (4)0.001 (3)0.001 (3)0.001 (3)
C20.055 (5)0.045 (5)0.045 (5)0.007 (4)0.008 (4)0.013 (4)
C30.041 (4)0.058 (5)0.054 (6)0.007 (4)0.004 (5)0.028 (5)
C40.025 (3)0.037 (4)0.030 (4)0.004 (3)0.002 (3)0.001 (3)
C50.050 (5)0.049 (5)0.051 (6)0.001 (4)0.000 (4)0.019 (4)
C60.048 (5)0.039 (4)0.048 (6)0.011 (4)0.005 (4)0.009 (4)
C70.067 (6)0.041 (5)0.048 (6)0.012 (4)0.006 (5)0.011 (4)
C80.065 (5)0.026 (3)0.051 (6)0.004 (3)0.016 (5)0.004 (4)
C90.034 (4)0.036 (4)0.035 (4)0.003 (3)0.005 (3)0.004 (3)
N10.030 (3)0.046 (4)0.033 (4)0.004 (3)0.008 (3)0.005 (3)
N20.043 (4)0.038 (3)0.040 (4)0.001 (3)0.008 (3)0.011 (3)
N30.033 (3)0.040 (4)0.040 (4)0.004 (3)0.001 (3)0.011 (3)
N40.026 (3)0.045 (4)0.043 (4)0.003 (3)0.004 (3)0.006 (3)
N50.048 (4)0.042 (4)0.028 (4)0.007 (3)0.011 (3)0.005 (3)
N60.053 (4)0.041 (4)0.031 (4)0.004 (3)0.002 (3)0.004 (3)
C110.036 (6)0.038 (7)0.016 (8)0.002 (6)0.0000.000
O10.052 (3)0.033 (3)0.033 (3)0.002 (2)0.002 (3)0.005 (2)
O20.071 (6)0.032 (4)0.037 (5)0.009 (4)0.0000.000
Geometric parameters (Å, º) top
Cd1—N42.315 (7)C5—H50.9300
Cd1—N4i2.315 (7)C6—N41.370 (11)
Cd1—N5i2.383 (7)C6—H60.9300
Cd1—N52.383 (7)C7—C81.333 (14)
Cd1—N22.424 (7)C7—N51.364 (11)
Cd1—N2i2.424 (7)C7—H70.9300
C1—N21.326 (10)C8—N61.364 (11)
C1—N11.334 (10)C8—H80.9300
C1—C41.455 (11)C9—N51.296 (11)
C2—C31.344 (13)C9—N61.349 (11)
C2—N11.372 (11)C9—C9i1.469 (16)
C2—H20.9300N1—H10.8600
C3—N21.357 (10)N3—H3A0.8600
C3—H30.9300N6—H6A0.8600
C4—N41.323 (10)C11—O1i1.242 (12)
C4—N31.326 (10)C11—O11.242 (12)
C5—N31.343 (11)C11—O21.38 (3)
C5—C61.380 (14)
N4—Cd1—N4i101.6 (4)C5—C6—H6125.0
N4—Cd1—N5i98.5 (2)C8—C7—N5109.3 (8)
N4i—Cd1—N5i150.8 (2)C8—C7—H7125.4
N4—Cd1—N5150.8 (2)N5—C7—H7125.4
N4i—Cd1—N598.5 (2)C7—C8—N6107.7 (8)
N5i—Cd1—N572.1 (3)C7—C8—H8126.1
N4—Cd1—N273.1 (2)N6—C8—H8126.1
N4i—Cd1—N293.8 (2)N5—C9—N6112.5 (7)
N5i—Cd1—N2112.3 (2)N5—C9—C9i120.9 (5)
N5—Cd1—N284.8 (2)N6—C9—C9i126.6 (5)
N4—Cd1—N2i93.8 (2)C1—N1—C2107.4 (7)
N4i—Cd1—N2i73.1 (2)C1—N1—H1126.3
N5i—Cd1—N2i84.8 (2)C2—N1—H1126.3
N5—Cd1—N2i112.3 (2)C1—N2—C3105.3 (7)
N2—Cd1—N2i159.5 (4)C1—N2—Cd1109.8 (5)
N2—C1—N1111.0 (7)C3—N2—Cd1143.8 (6)
N2—C1—C4121.7 (7)C4—N3—C5108.2 (7)
N1—C1—C4127.3 (7)C4—N3—H3A125.9
C3—C2—N1105.6 (8)C5—N3—H3A125.9
C3—C2—H2127.2C4—N4—C6104.1 (7)
N1—C2—H2127.2C4—N4—Cd1114.4 (5)
C2—C3—N2110.6 (8)C6—N4—Cd1140.6 (6)
C2—C3—H3124.7C9—N5—C7105.6 (7)
N2—C3—H3124.7C9—N5—Cd1112.8 (5)
N4—C4—N3112.4 (7)C7—N5—Cd1141.4 (6)
N4—C4—C1119.9 (7)C9—N6—C8104.9 (8)
N3—C4—C1127.6 (7)C9—N6—H6A127.5
N3—C5—C6105.3 (8)C8—N6—H6A127.5
N3—C5—H5127.3O1i—C11—O1129 (2)
C6—C5—H5127.3O1i—C11—O2115.4 (11)
N4—C6—C5109.9 (8)O1—C11—O2115.4 (11)
N4—C6—H6125.0
N1—C2—C3—N21.4 (12)C1—C4—N4—Cd110.2 (9)
N2—C1—C4—N413.9 (12)C5—C6—N4—C40.3 (10)
N1—C1—C4—N4165.8 (8)C5—C6—N4—Cd1167.6 (8)
N2—C1—C4—N3169.1 (8)N4i—Cd1—N4—C486.5 (6)
N1—C1—C4—N311.2 (14)N5i—Cd1—N4—C4114.8 (6)
N3—C5—C6—N40.6 (12)N5—Cd1—N4—C446.3 (9)
N5—C7—C8—N60.4 (11)N2—Cd1—N4—C44.0 (6)
N2—C1—N1—C20.3 (10)N2i—Cd1—N4—C4159.9 (6)
C4—C1—N1—C2179.5 (8)N4i—Cd1—N4—C680.0 (10)
C3—C2—N1—C11.0 (11)N5i—Cd1—N4—C678.7 (10)
N1—C1—N2—C30.6 (10)N5—Cd1—N4—C6147.2 (9)
C4—C1—N2—C3179.7 (8)N2—Cd1—N4—C6170.4 (10)
N1—C1—N2—Cd1170.7 (5)N2i—Cd1—N4—C66.5 (10)
C4—C1—N2—Cd19.1 (9)N6—C9—N5—C71.0 (10)
C2—C3—N2—C11.3 (11)C9i—C9—N5—C7179.0 (9)
C2—C3—N2—Cd1164.7 (8)N6—C9—N5—Cd1176.7 (5)
N4—Cd1—N2—C12.7 (5)C9i—C9—N5—Cd15.3 (11)
N4i—Cd1—N2—C1103.7 (6)C8—C7—N5—C90.4 (11)
N5i—Cd1—N2—C189.8 (6)C8—C7—N5—Cd1174.0 (7)
N5—Cd1—N2—C1158.0 (6)N4—Cd1—N5—C973.2 (7)
N2i—Cd1—N2—C154.7 (5)N4i—Cd1—N5—C9153.4 (5)
N4—Cd1—N2—C3168.3 (11)N5i—Cd1—N5—C91.9 (4)
N4i—Cd1—N2—C390.6 (11)N2—Cd1—N5—C9113.6 (6)
N5i—Cd1—N2—C375.9 (11)N2i—Cd1—N5—C978.3 (6)
N5—Cd1—N2—C37.6 (11)N4—Cd1—N5—C7100.1 (10)
N2i—Cd1—N2—C3139.7 (11)N4i—Cd1—N5—C733.2 (10)
N4—C4—N3—C51.6 (10)N5i—Cd1—N5—C7175.2 (11)
C1—C4—N3—C5178.8 (8)N2—Cd1—N5—C759.8 (10)
C6—C5—N3—C41.3 (11)N2i—Cd1—N5—C7108.4 (10)
N3—C4—N4—C61.2 (9)N5—C9—N6—C81.3 (9)
C1—C4—N4—C6178.6 (7)C9i—C9—N6—C8179.1 (9)
N3—C4—N4—Cd1172.4 (5)C7—C8—N6—C91.0 (10)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O1ii0.861.902.737 (9)163
N1—H1···O2iii0.861.922.753 (8)163
N6—H6A···O1i0.861.802.644 (9)169
Symmetry codes: (i) x+1, y+1, z; (ii) y+1/2, x, z+3/4; (iii) y1/2, x+1, z+3/4.

Experimental details

Crystal data
Chemical formula[Cd(C6H6N4)3]CO3
Mr574.85
Crystal system, space groupTetragonal, I41
Temperature (K)300
a, c (Å)12.3477 (8), 14.7379 (10)
V3)2247.0 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.02
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.749, 0.822
No. of measured, independent and
observed [I > 2σ(I)] reflections
6885, 1936, 1761
Rint0.071
(sin θ/λ)max1)0.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.132, 1.17
No. of reflections1936
No. of parameters160
No. of restraints1
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0486P)2 + 13.566P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.47, 0.45
Absolute structureFlack (1983), 654 Friedel pairs
Absolute structure parameter0.15 (6)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O1i0.861.902.737 (9)162.8
N1—H1···O2ii0.861.922.753 (8)162.7
N6—H6A···O1iii0.861.802.644 (9)168.7
Symmetry codes: (i) y+1/2, x, z+3/4; (ii) y1/2, x+1, z+3/4; (iii) x+1, y+1, z.
 

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