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

Chang, Y.-T.; Yeh, C.-T.; Kao, C.-C.; Lin, C.-H.

doi:10.1107/S1600536810039000

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page m1382

https://doi.org/10.1107/S1600536810039000

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

Ya-Ting Chang,^a Chun-Ting Yeh,^a Ching-Che Kao ^a and Chia-Her Lin ^a ^*

^aDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li 320, Taiwan
^*Correspondence e-mail: chiaher@cycu.edu.tw

(Received 27 September 2010; accepted 29 September 2010; online 9 October 2010)

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 ). For related structures, see: Gao et al. (2004 ); Starosta & Leciejewicz (2006 ).

Experimental

Crystal data

[Ca(C₅H₂N₂O₄)(H₂O)]
M_r = 212.18
Monoclinic, P 2₁ /n
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) 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[F² > 2σ(F²)] = 0.025
wR(F²) = 0.069
S = 1.08
1665 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O4ⁱ	0.85	2.13	2.9552 (14)	162
O5—H5B⋯O1ⁱⁱ	0.85	2.23	3.0109 (14)	153
N2—H2A⋯O4ⁱⁱⁱ	0.86	1.86	2.7220 (13)	176
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z; (iii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039000/nc2199Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

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

Figures top

	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.

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

Crystal data top

[Ca(C₅H₂N₂O₄)(H₂O)]	F(000) = 432
M_r = 212.18	D_x = 2.098 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4091 reflections
a = 6.4752 (4) Å	θ = 2.8–28.3°
b = 9.7627 (6) Å	µ = 0.92 mm⁻¹
c = 10.9079 (6) Å	T = 295 K
β = 103.041 (2)°	Columnar, colourless
V = 671.76 (7) Å³	0.45 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1665 independent reflections
Radiation source: fine-focus sealed tube	1619 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.3°, θ_min = 2.8°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −12→12
T_min = 0.681, T_max = 0.874	l = −14→14
6029 measured reflections

Refinement top

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)] = 0.025	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0397P)² + 0.2825P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1665 reflections	Δρ_max = 0.33 e Å⁻³
119 parameters	Δρ_min = −0.35 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.092 (5)

Crystal data top

[Ca(C₅H₂N₂O₄)(H₂O)]	V = 671.76 (7) Å³
M_r = 212.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.4752 (4) Å	µ = 0.92 mm⁻¹
b = 9.7627 (6) Å	T = 295 K
c = 10.9079 (6) Å	0.45 × 0.20 × 0.15 mm
β = 103.041 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1665 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1619 reflections with I > 2σ(I)
T_min = 0.681, T_max = 0.874	R_int = 0.024
6029 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 1.08	Δρ_max = 0.33 e Å⁻³
1665 reflections	Δρ_min = −0.35 e Å⁻³
119 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Ca1	0.08356 (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)
O5	0.38501 (16)	0.60082 (11)	0.08033 (10)	0.0293 (2)
H5A	0.5147	0.6114	0.1164	0.044*
H5B	0.3763	0.5845	0.0028	0.044*
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	−0.2128	0.6687	0.5586	0.019*
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	−0.2347	0.5911	0.3510	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.02062 (16)	0.01716 (16)	0.01057 (16)	0.00256 (8)	0.00247 (10)	−0.00080 (8)
O1	0.0348 (5)	0.0199 (5)	0.0159 (4)	−0.0034 (4)	0.0118 (4)	0.0003 (3)
O2	0.0332 (5)	0.0246 (5)	0.0121 (4)	−0.0058 (4)	0.0009 (4)	0.0035 (3)
O3	0.0297 (5)	0.0141 (4)	0.0160 (4)	−0.0067 (3)	0.0032 (4)	−0.0002 (3)
O4	0.0305 (5)	0.0138 (4)	0.0184 (4)	−0.0033 (3)	0.0103 (4)	−0.0037 (3)
O5	0.0252 (5)	0.0310 (6)	0.0326 (5)	−0.0034 (4)	0.0082 (4)	−0.0045 (4)
C1	0.0155 (5)	0.0141 (5)	0.0128 (5)	0.0003 (4)	0.0038 (4)	−0.0012 (4)
C2	0.0151 (5)	0.0111 (5)	0.0133 (5)	−0.0002 (4)	0.0032 (4)	−0.0001 (4)
C3	0.0159 (5)	0.0141 (5)	0.0130 (5)	−0.0004 (4)	0.0033 (4)	0.0015 (4)
C4	0.0197 (5)	0.0125 (5)	0.0157 (5)	−0.0007 (4)	0.0041 (4)	−0.0023 (4)
C5	0.0146 (5)	0.0120 (5)	0.0116 (5)	−0.0011 (4)	0.0020 (4)	−0.0014 (4)
N1	0.0194 (5)	0.0131 (4)	0.0129 (5)	−0.0015 (4)	0.0030 (4)	−0.0026 (4)
N2	0.0196 (5)	0.0115 (5)	0.0138 (5)	−0.0003 (3)	0.0054 (4)	0.0009 (3)

Geometric parameters (Å, º) top

Ca1—O3ⁱ	2.3211 (9)	O3—Ca1^v	2.4408 (9)
Ca1—N1ⁱⁱ	2.4215 (10)	O4—C1	1.2665 (14)
Ca1—O4ⁱ	2.4336 (9)	O4—Ca1^vi	2.4336 (9)
Ca1—O3ⁱⁱⁱ	2.4408 (9)	O5—H5A	0.8497
Ca1—O5	2.4411 (11)	O5—H5B	0.8496
Ca1—O1	2.5679 (10)	C1—C2	1.4895 (15)
Ca1—O2ⁱⁱ	2.6614 (10)	C2—N2	1.3755 (14)
Ca1—O2ⁱⁱⁱ	2.8776 (10)	C2—C5	1.3842 (15)
Ca1—C3ⁱⁱⁱ	3.0181 (12)	C3—C5	1.4904 (16)
Ca1—Ca1^iv	3.8384 (5)	C3—Ca1^v	3.0182 (12)
O1—C1	1.2511 (14)	C4—N1	1.3209 (16)
O2—C3	1.2498 (14)	C4—N2	1.3342 (15)
O2—Ca1ⁱⁱ	2.6613 (10)	C4—H4A	0.9300
O2—Ca1^v	2.8777 (10)	C5—N1	1.3806 (14)
O3—C3	1.2675 (14)	N1—Ca1ⁱⁱ	2.4215 (10)
O3—Ca1^vi	2.3212 (9)	N2—H2A	0.8600

O3ⁱ—Ca1—N1ⁱⁱ	166.21 (3)	O5—Ca1—Ca1^iv	73.40 (3)
O3ⁱ—Ca1—O4ⁱ	76.01 (3)	O1—Ca1—Ca1^iv	84.38 (2)
N1ⁱⁱ—Ca1—O4ⁱ	92.65 (3)	O2ⁱⁱ—Ca1—Ca1^iv	134.22 (2)
O3ⁱ—Ca1—O3ⁱⁱⁱ	72.60 (3)	O2ⁱⁱⁱ—Ca1—Ca1^iv	83.473 (19)
N1ⁱⁱ—Ca1—O3ⁱⁱⁱ	121.18 (3)	C3ⁱⁱⁱ—Ca1—Ca1^iv	59.22 (2)
O4ⁱ—Ca1—O3ⁱⁱⁱ	134.15 (3)	C1—O1—Ca1	137.21 (8)
O3ⁱ—Ca1—O5	79.88 (4)	C3—O2—Ca1ⁱⁱ	117.19 (8)
N1ⁱⁱ—Ca1—O5	102.83 (4)	C3—O2—Ca1^v	84.15 (7)
O4ⁱ—Ca1—O5	131.87 (3)	Ca1ⁱⁱ—O2—Ca1^v	158.66 (4)
O3ⁱⁱⁱ—Ca1—O5	73.62 (3)	C3—O3—Ca1^vi	148.04 (8)
O3ⁱ—Ca1—O1	94.03 (3)	C3—O3—Ca1^v	104.46 (7)
N1ⁱⁱ—Ca1—O1	89.89 (3)	Ca1^vi—O3—Ca1^v	107.40 (3)
O4ⁱ—Ca1—O1	72.51 (3)	C1—O4—Ca1^vi	135.14 (8)
O3ⁱⁱⁱ—Ca1—O1	77.25 (3)	Ca1—O5—H5A	129.0
O5—Ca1—O1	150.74 (3)	Ca1—O5—H5B	119.9
O3ⁱ—Ca1—O2ⁱⁱ	104.41 (3)	H5A—O5—H5B	108.7
N1ⁱⁱ—Ca1—O2ⁱⁱ	63.83 (3)	O1—C1—O4	125.60 (10)
O4ⁱ—Ca1—O2ⁱⁱ	70.90 (3)	O1—C1—C2	117.11 (10)
O3ⁱⁱⁱ—Ca1—O2ⁱⁱ	149.31 (3)	O4—C1—C2	117.22 (10)
O5—Ca1—O2ⁱⁱ	75.80 (3)	N2—C2—C5	105.09 (10)
O1—Ca1—O2ⁱⁱ	133.11 (3)	N2—C2—C1	118.56 (10)
O3ⁱ—Ca1—O2ⁱⁱⁱ	120.77 (3)	C5—C2—C1	135.93 (10)
N1ⁱⁱ—Ca1—O2ⁱⁱⁱ	73.01 (3)	O2—C3—O3	122.99 (11)
O4ⁱ—Ca1—O2ⁱⁱⁱ	141.64 (3)	O2—C3—C5	117.48 (10)
O3ⁱⁱⁱ—Ca1—O2ⁱⁱⁱ	48.30 (3)	O3—C3—C5	119.48 (10)
O5—Ca1—O2ⁱⁱⁱ	86.41 (3)	O2—C3—Ca1^v	71.53 (7)
O1—Ca1—O2ⁱⁱⁱ	72.09 (3)	O3—C3—Ca1^v	51.54 (6)
O2ⁱⁱ—Ca1—O2ⁱⁱⁱ	127.387 (11)	C5—C3—Ca1^v	170.99 (8)
O3ⁱ—Ca1—C3ⁱⁱⁱ	96.57 (3)	N1—C4—N2	111.80 (11)
N1ⁱⁱ—Ca1—C3ⁱⁱⁱ	97.22 (3)	N1—C4—H4A	124.1
O4ⁱ—Ca1—C3ⁱⁱⁱ	144.90 (3)	N2—C4—H4A	124.1
O3ⁱⁱⁱ—Ca1—C3ⁱⁱⁱ	23.99 (3)	N1—C5—C2	109.29 (10)
O5—Ca1—C3ⁱⁱⁱ	78.38 (3)	N1—C5—C3	115.48 (10)
O1—Ca1—C3ⁱⁱⁱ	73.91 (3)	C2—C5—C3	135.17 (10)
O2ⁱⁱ—Ca1—C3ⁱⁱⁱ	142.98 (3)	C4—N1—C5	105.64 (10)
O2ⁱⁱⁱ—Ca1—C3ⁱⁱⁱ	24.33 (3)	C4—N1—Ca1ⁱⁱ	127.80 (8)
O3ⁱ—Ca1—Ca1^iv	37.36 (2)	C5—N1—Ca1ⁱⁱ	119.26 (7)
N1ⁱⁱ—Ca1—Ca1^iv	156.42 (3)	C4—N2—C2	108.16 (10)
O4ⁱ—Ca1—Ca1^iv	107.26 (2)	C4—N2—H2A	125.9
O3ⁱⁱⁱ—Ca1—Ca1^iv	35.24 (2)	C2—N2—H2A	125.9

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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4^vii	0.85	2.13	2.9552 (14)	162
O5—H5B···O1^iv	0.85	2.23	3.0109 (14)	153
N2—H2A···O4ⁱ	0.86	1.86	2.7220 (13)	176

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

Experimental details

Crystal data
Chemical formula	[Ca(C₅H₂N₂O₄)(H₂O)]
M_r	212.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	6.4752 (4), 9.7627 (6), 10.9079 (6)
β (°)	103.041 (2)
V (Å³)	671.76 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.92
Crystal size (mm)	0.45 × 0.20 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.681, 0.874
No. of measured, independent and observed [I > 2σ(I)] reflections	6029, 1665, 1619
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.069, 1.08
No. of reflections	1665
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.35

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4ⁱ	0.85	2.13	2.9552 (14)	162.2
O5—H5B···O1ⁱⁱ	0.85	2.23	3.0109 (14)	153.2
N2—H2A···O4ⁱⁱⁱ	0.86	1.86	2.7220 (13)	175.6

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

Acknowledgements

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

References

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