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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): m1382.
Published online 2010 October 9. doi:  10.1107/S1600536810039000
PMCID: PMC3009373

Poly[[aqua­calcium(II)]-μ4-1H-imidazole-4,5-dicarboxyl­ato]

Abstract

In the title compound, [Ca(C5H2N2O4)(H2O)]n, the Ca2+ cations are eigthtfold coordinated by six O atoms and one N atom of four symmetry-related anions and one water mol­ecule within an irregular polyhedron. These CaO7N polyhedra are connected via the anions into a three-dimensional network. The anions are additionally linked by N—H(...)O and O—H(...)O hydrogen bonding.

Related literature

For general background to metal coordination polymers, see: Kitagawa et al. (2004 [triangle]). For related structures, see: Gao et al. (2004 [triangle]); Starosta & Leciejewicz (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1382-scheme1.jpg

Experimental

Crystal data

  • [Ca(C5H2N2O4)(H2O)]
  • M r = 212.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1382-efi7.jpg
  • a = 6.4752 (4) Å
  • b = 9.7627 (6) Å
  • c = 10.9079 (6) Å
  • β = 103.041 (2)°
  • V = 671.76 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.92 mm−1
  • T = 295 K
  • 0.45 × 0.20 × 0.15 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2008) [triangle] T min = 0.681, T max = 0.874
  • 6029 measured reflections
  • 1665 independent reflections
  • 1619 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.069
  • S = 1.08
  • 1665 reflections
  • 119 parameters
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2010 [triangle]); cell refinement: SAINT (Bruker, 2010 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810039000/nc2199sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039000/nc2199Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This research was supported by the National Science Council, Taiwan (NSC99–2113-M-033–005-MY2).

supplementary crystallographic information

Comment

The synthesis of metal coordination polymers has been a intense research due to their interesting topologies and potential applications (Kitagawa, et al., 2004). The imidazole-4,5-dicarboxylic acid (H3IDC) has been successively applied to construct two calcium complexes (Gao, et al., 2004; Starosta, et al., 2006). In our ongoing investigations in this field we report here the structure of a new Ca compound with the anionic imidazole-4,5-dicarboxylato ligand.

The asymmetric unit of the title compound conists of one Ca atom, one carboxylate ligand and one coordinated water molecule all of them located in general positions (Figure 1). The Ca center is eight-coordinated by six oxygen atoms and one nitrogen atom of four carboxylate ligands and one oxygen atom of a coordinated water molecule within an irregular polyhedron. The Ca—O distances range from 2.3197 (11) to 2.8777 (12) Å and the Ca—N distance amount to 2.4215 (10)Å. The CaO7N polyhedra are connected via the anions into a three-dimensional network and are further linked by N—H···O and O—H···O hydrogen bonding (Fig. 2 and Table 1).

Experimental

imidazole-4,5-dicarboxylic acid (C5H4N2O4, 0.0752 g, 0.45 mmol) and Ca(NO3)2.4H2O (0.2361 g, 1 mmol) were reacted in 10 mL of H2O in a Teflon-lined digestion bomb with an internal volume of 23 ml l. The reaction mixture was heated to 453 K for 5 d followed by slow cooling at 6 K/h to room temperature. The product consits of transparent colorless crystals.

Refinement

H atoms were constrained to ideal geometries, with C—H = 0.93 Å, O—H = 0.85 Å and N—H = 0.86 Å and refined with Uiso(H) = 1.2Ueq(1.5 for water H atoms) using a riding model.

Figures

Fig. 1.
Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) x + 1/2, -y + 1/2, z - 1/2; (ii) -x - 1/2, y + 1/2, -z + 1/2; (iii) -x, -y + 1, -z + 1.
Fig. 2.
Crystal structure of the title compound with view along the crystallographic b axis.

Crystal data

[Ca(C5H2N2O4)(H2O)]F(000) = 432
Mr = 212.18Dx = 2.098 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4091 reflections
a = 6.4752 (4) Åθ = 2.8–28.3°
b = 9.7627 (6) ŵ = 0.92 mm1
c = 10.9079 (6) ÅT = 295 K
β = 103.041 (2)°Columnar, colourless
V = 671.76 (7) Å30.45 × 0.20 × 0.15 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer1665 independent reflections
Radiation source: fine-focus sealed tube1619 reflections with I > 2σ(I)
graphiteRint = 0.024
Detector resolution: 8.3333 pixels mm-1θmax = 28.3°, θmin = 2.8°
[var phi] and ω scansh = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2008)k = −12→12
Tmin = 0.681, Tmax = 0.874l = −14→14
6029 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.069w = 1/[σ2(Fo2) + (0.0397P)2 + 0.2825P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1665 reflectionsΔρmax = 0.33 e Å3
119 parametersΔρmin = −0.35 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.092 (5)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
Ca10.08356 (4)0.55299 (2)0.17359 (2)0.01629 (12)
O1−0.22252 (16)0.39733 (10)0.20098 (8)0.0226 (2)
O2−0.25830 (16)0.22314 (10)0.70724 (8)0.0239 (2)
O3−0.40728 (15)0.13090 (9)0.52331 (8)0.0202 (2)
O4−0.30507 (15)0.19962 (9)0.28239 (8)0.0201 (2)
O50.38501 (16)0.60082 (11)0.08033 (10)0.0293 (2)
H5A0.51470.61140.11640.044*
H5B0.37630.58450.00280.044*
C1−0.26916 (17)0.32726 (12)0.28690 (10)0.0140 (2)
C2−0.27309 (17)0.39902 (11)0.40685 (10)0.0132 (2)
C3−0.31453 (17)0.22884 (12)0.58996 (11)0.0143 (2)
C4−0.23120 (19)0.57835 (12)0.53133 (11)0.0160 (2)
H4A−0.21280.66870.55860.019*
C5−0.27759 (17)0.35991 (11)0.52820 (10)0.0129 (2)
N1−0.24822 (16)0.47378 (10)0.60526 (9)0.0152 (2)
N2−0.24362 (16)0.53860 (10)0.41286 (10)0.0147 (2)
H2A−0.23470.59110.35100.018*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ca10.02062 (16)0.01716 (16)0.01057 (16)0.00256 (8)0.00247 (10)−0.00080 (8)
O10.0348 (5)0.0199 (5)0.0159 (4)−0.0034 (4)0.0118 (4)0.0003 (3)
O20.0332 (5)0.0246 (5)0.0121 (4)−0.0058 (4)0.0009 (4)0.0035 (3)
O30.0297 (5)0.0141 (4)0.0160 (4)−0.0067 (3)0.0032 (4)−0.0002 (3)
O40.0305 (5)0.0138 (4)0.0184 (4)−0.0033 (3)0.0103 (4)−0.0037 (3)
O50.0252 (5)0.0310 (6)0.0326 (5)−0.0034 (4)0.0082 (4)−0.0045 (4)
C10.0155 (5)0.0141 (5)0.0128 (5)0.0003 (4)0.0038 (4)−0.0012 (4)
C20.0151 (5)0.0111 (5)0.0133 (5)−0.0002 (4)0.0032 (4)−0.0001 (4)
C30.0159 (5)0.0141 (5)0.0130 (5)−0.0004 (4)0.0033 (4)0.0015 (4)
C40.0197 (5)0.0125 (5)0.0157 (5)−0.0007 (4)0.0041 (4)−0.0023 (4)
C50.0146 (5)0.0120 (5)0.0116 (5)−0.0011 (4)0.0020 (4)−0.0014 (4)
N10.0194 (5)0.0131 (4)0.0129 (5)−0.0015 (4)0.0030 (4)−0.0026 (4)
N20.0196 (5)0.0115 (5)0.0138 (5)−0.0003 (3)0.0054 (4)0.0009 (3)

Geometric parameters (Å, °)

Ca1—O3i2.3211 (9)O3—Ca1v2.4408 (9)
Ca1—N1ii2.4215 (10)O4—C11.2665 (14)
Ca1—O4i2.4336 (9)O4—Ca1vi2.4336 (9)
Ca1—O3iii2.4408 (9)O5—H5A0.8497
Ca1—O52.4411 (11)O5—H5B0.8496
Ca1—O12.5679 (10)C1—C21.4895 (15)
Ca1—O2ii2.6614 (10)C2—N21.3755 (14)
Ca1—O2iii2.8776 (10)C2—C51.3842 (15)
Ca1—C3iii3.0181 (12)C3—C51.4904 (16)
Ca1—Ca1iv3.8384 (5)C3—Ca1v3.0182 (12)
O1—C11.2511 (14)C4—N11.3209 (16)
O2—C31.2498 (14)C4—N21.3342 (15)
O2—Ca1ii2.6613 (10)C4—H4A0.9300
O2—Ca1v2.8777 (10)C5—N11.3806 (14)
O3—C31.2675 (14)N1—Ca1ii2.4215 (10)
O3—Ca1vi2.3212 (9)N2—H2A0.8600
O3i—Ca1—N1ii166.21 (3)O5—Ca1—Ca1iv73.40 (3)
O3i—Ca1—O4i76.01 (3)O1—Ca1—Ca1iv84.38 (2)
N1ii—Ca1—O4i92.65 (3)O2ii—Ca1—Ca1iv134.22 (2)
O3i—Ca1—O3iii72.60 (3)O2iii—Ca1—Ca1iv83.473 (19)
N1ii—Ca1—O3iii121.18 (3)C3iii—Ca1—Ca1iv59.22 (2)
O4i—Ca1—O3iii134.15 (3)C1—O1—Ca1137.21 (8)
O3i—Ca1—O579.88 (4)C3—O2—Ca1ii117.19 (8)
N1ii—Ca1—O5102.83 (4)C3—O2—Ca1v84.15 (7)
O4i—Ca1—O5131.87 (3)Ca1ii—O2—Ca1v158.66 (4)
O3iii—Ca1—O573.62 (3)C3—O3—Ca1vi148.04 (8)
O3i—Ca1—O194.03 (3)C3—O3—Ca1v104.46 (7)
N1ii—Ca1—O189.89 (3)Ca1vi—O3—Ca1v107.40 (3)
O4i—Ca1—O172.51 (3)C1—O4—Ca1vi135.14 (8)
O3iii—Ca1—O177.25 (3)Ca1—O5—H5A129.0
O5—Ca1—O1150.74 (3)Ca1—O5—H5B119.9
O3i—Ca1—O2ii104.41 (3)H5A—O5—H5B108.7
N1ii—Ca1—O2ii63.83 (3)O1—C1—O4125.60 (10)
O4i—Ca1—O2ii70.90 (3)O1—C1—C2117.11 (10)
O3iii—Ca1—O2ii149.31 (3)O4—C1—C2117.22 (10)
O5—Ca1—O2ii75.80 (3)N2—C2—C5105.09 (10)
O1—Ca1—O2ii133.11 (3)N2—C2—C1118.56 (10)
O3i—Ca1—O2iii120.77 (3)C5—C2—C1135.93 (10)
N1ii—Ca1—O2iii73.01 (3)O2—C3—O3122.99 (11)
O4i—Ca1—O2iii141.64 (3)O2—C3—C5117.48 (10)
O3iii—Ca1—O2iii48.30 (3)O3—C3—C5119.48 (10)
O5—Ca1—O2iii86.41 (3)O2—C3—Ca1v71.53 (7)
O1—Ca1—O2iii72.09 (3)O3—C3—Ca1v51.54 (6)
O2ii—Ca1—O2iii127.387 (11)C5—C3—Ca1v170.99 (8)
O3i—Ca1—C3iii96.57 (3)N1—C4—N2111.80 (11)
N1ii—Ca1—C3iii97.22 (3)N1—C4—H4A124.1
O4i—Ca1—C3iii144.90 (3)N2—C4—H4A124.1
O3iii—Ca1—C3iii23.99 (3)N1—C5—C2109.29 (10)
O5—Ca1—C3iii78.38 (3)N1—C5—C3115.48 (10)
O1—Ca1—C3iii73.91 (3)C2—C5—C3135.17 (10)
O2ii—Ca1—C3iii142.98 (3)C4—N1—C5105.64 (10)
O2iii—Ca1—C3iii24.33 (3)C4—N1—Ca1ii127.80 (8)
O3i—Ca1—Ca1iv37.36 (2)C5—N1—Ca1ii119.26 (7)
N1ii—Ca1—Ca1iv156.42 (3)C4—N2—C2108.16 (10)
O4i—Ca1—Ca1iv107.26 (2)C4—N2—H2A125.9
O3iii—Ca1—Ca1iv35.24 (2)C2—N2—H2A125.9

Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x+1/2, −y+1/2, z−1/2; (iv) −x, −y+1, −z; (v) x−1/2, −y+1/2, z+1/2; (vi) −x−1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O5—H5A···O4vii0.852.132.9552 (14)162
O5—H5B···O1iv0.852.233.0109 (14)153
N2—H2A···O4i0.861.862.7220 (13)176

Symmetry codes: (vii) −x+1/2, y+1/2, −z+1/2; (iv) −x, −y+1, −z; (i) −x−1/2, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2199).

References

  • Bruker (2008). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2010). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gao, S., Zhang, X.-F., Huo, L.-H. & Zhao, H. (2004). Acta Cryst. E60, m1790–m1792.
  • Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed.43, 2334–2375. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Starosta, W. & Leciejewicz, J. (2006). Acta Cryst. E62, m2648–m2650.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography