Diaqua­bis­(5-carb­oxy-1H-imidazole-4-carboxyl­ato-κ2N3,O4)iron(II)

Du, C.-J.; Song, X.-H.; Wang, L.-S.; Du, C.-L.

doi:10.1107/S1600536811024779

metal-organic compounds

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Volume 67| Part 7| July 2011| Page m997

doi:10.1107/S1600536811024779

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Diaquabis(5-carboxy-1H-imidazole-4-carboxylato-κ²N³,O⁴)iron(II)

Chao-Jun Du,^a,^b ^* Xing-Hua Song,^a Li-Sheng Wang ^b and Chao-Ling Du ^c

^aDepartment of Chemical and Biochemical Engineering, Nanyang Institute of Technology, 473004 Nanyang, Henan, People's Republic of China, ^bSchool of Chemical Engineering and Environment, Beijing Institute of Technology, 100081 Beijing, People's Republic of China, and ^cCollege of Science, Nanjing University of Aeronautics and Astronautics, Nanjing 211100, People's Republic of China
^*Correspondence e-mail: chjdu@yahoo.com.cn

(Received 30 May 2011; accepted 23 June 2011; online 30 June 2011)

In the title compound, [Fe(C₅H₃N₂O₄)₂(H₂O)₂], the Fe^II ion lies on an inversion centre and is coordinated by two N and two O atoms from two 5-carboxy-1H-imidazole-4-carboxylate ligands and two water molecules in a distorted octahedral geometry. An intramolecular O—H⋯O hydrogen bond occurs. In the crystal, intermolecular N—H⋯O and O—H⋯O hydrogen bonds form a three-dimensional network, which consolidates the packing.

Related literature

For the diversity of coordination architectures of the metal atom in complexes with 4,5-dicarboxyimidazole, see: Shimizu et al. (2004 ); Fang & Zhang (2006 ). For the closely related crystal structures of the Zn, Mg and Cd complexes, see: Ma et al. (2003 ), Liu et al. (2004 ) and Zhang et al. (2004 ), respectively.

Experimental

Crystal data

[Fe(C₅H₃N₂O₄)₂(H₂O)₂]
M_r = 402.07
Monoclinic, P 2₁ /c
a = 5.0676 (9) Å
b = 22.769 (4) Å
c = 6.6725 (9) Å
β = 113.733 (10)°
V = 704.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.14 mm⁻¹
T = 298 K
0.32 × 0.28 × 0.25 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.712, T_max = 0.764
2872 measured reflections
1240 independent reflections
976 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.080
S = 1.05
1240 reflections
116 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3ⁱ	0.86	2.05	2.897 (3)	169
O3—H3⋯O2	0.82	1.74	2.525 (3)	160
O1W—H1W⋯O2ⁱⁱ	0.85	1.94	2.744 (3)	157
O1W—H2W⋯O1ⁱⁱⁱ	0.85	1.92	2.710 (3)	155
Symmetry codes: (i) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x+1, y, z+1; (iii) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811024779/cv5111sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024779/cv5111Isup2.hkl

checkCIF report

Comment top

In recent years, the construction of metal complexes based on 1H-imidazole-4,5-dicarboxylic acid ligand has been investigated in terms of their intriguing topologies. The diversity of coordination architecture of metal 4,5-dicarboxyimidazole has been described by Shimizu et al. (2004) and Fang et al. (2006). In order to search for new metal complexes based on 1H-imidazole-4,5-dicarboxylic acid ligand, the title complex (I) has been synthesized and its crystal determined.

The crystal structure of (I) is isostructural with the previously reported Zn (Ma et al., 2003), Mg (Zhang et al., 2004) and Cd (Liu et al., 2004) 4,5-dicarboxyimidazole complexes. In the four isostructural complexes, all metal ions lie on an inversion centre being coordinated by two N,O-bidentate 1H-imidazole-4,5-dicarboxylate monoanionic ligands and two water molecules in a distorted octahedral geometry.

In the crystal structure of (I), intermolecular N—H···O and O—H···O hydrogen bonds (Table 1) form three-dimensional hydrogen-bonding network, which consolidate the crystal packing.

Related literature top

For the diversity of coordination architectures of the metal atom in complexes with 4,5-dicarboxyimidazole, see: Shimizu et al. (2004); Fang & Zhang (2006). For the closely related crystal structures of the Zn, Mg and Cd complexes, see: Ma et al. (2003), Liu et al. (2004) and Zhang et al. (2004), respectively.

Experimental top

A mixture of FeSO₄^.7H₂O (0.10 mmol), 1H-imidazole-4,5-dicarboxylic acid (0.10 mmol), Et₃N (0.1 ml), EtOH (2 ml) and H₂O (2 ml) was sealed in a 10 ml Tefon-lined stainless-steel reactor and then heated to 393 K for 48 h under autogenous pressure, and then slowly cooled to room temperature at a rate of 5 K/h. Pale-yellow block crystals of the title complex were isolated, washed with distilled water, and dried in air (yield: 48%).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 40% probability level [symmetry code: (A) 2 - x, 2 - y, 1 - z].

Diaquabis(5-carboxy-1H-imidazole-4-carboxylato- κ²N³,O⁴)iron(II) top

Crystal data top

[Fe(C₅H₃N₂O₄)₂(H₂O)₂]	F(000) = 408
M_r = 402.07	D_x = 1.895 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1102 reflections
a = 5.0676 (9) Å	θ = 3.5–23.7°
b = 22.769 (4) Å	µ = 1.14 mm⁻¹
c = 6.6725 (9) Å	T = 298 K
β = 113.733 (10)°	Block, pale-yellow
V = 704.8 (2) Å³	0.32 × 0.28 × 0.25 mm
Z = 2

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1240 independent reflections
Radiation source: fine-focus sealed tube	976 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.2°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→5
T_min = 0.712, T_max = 0.764	k = −26→26
2872 measured reflections	l = −4→7

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0375P)² + 0.0621P] where P = (F_o² + 2F_c²)/3
1240 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Fe(C₅H₃N₂O₄)₂(H₂O)₂]	V = 704.8 (2) Å³
M_r = 402.07	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.0676 (9) Å	µ = 1.14 mm⁻¹
b = 22.769 (4) Å	T = 298 K
c = 6.6725 (9) Å	0.32 × 0.28 × 0.25 mm
β = 113.733 (10)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1240 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	976 reflections with I > 2σ(I)
T_min = 0.712, T_max = 0.764	R_int = 0.027
2872 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.05	Δρ_max = 0.25 e Å⁻³
1240 reflections	Δρ_min = −0.25 e Å⁻³
116 parameters

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

	x	y	z	U_iso*/U_eq
C1	1.2587 (6)	0.86826 (13)	0.4808 (4)	0.0322 (7)
H1	1.4476	0.8718	0.5837	0.039*
C2	0.8201 (6)	0.88774 (11)	0.2661 (4)	0.0265 (6)
C3	0.8639 (6)	0.82984 (12)	0.2373 (4)	0.0279 (6)
C4	0.5611 (5)	0.92523 (12)	0.1742 (4)	0.0268 (6)
C5	0.6789 (7)	0.78182 (14)	0.1066 (5)	0.0369 (7)
Fe1	1.0000	1.0000	0.5000	0.0278 (2)
N1	1.0693 (5)	0.91158 (10)	0.4203 (3)	0.0289 (6)
N2	1.1435 (5)	0.81868 (10)	0.3749 (4)	0.0335 (6)
H2	1.2302	0.7855	0.3906	0.040*
O1	0.5823 (4)	0.97682 (8)	0.2452 (3)	0.0313 (5)
O2	0.3337 (4)	0.90334 (9)	0.0295 (3)	0.0370 (5)
O3	0.4133 (4)	0.79590 (9)	−0.0221 (3)	0.0462 (6)
H3	0.3975	0.8318	−0.0301	0.069*
O4	0.7646 (5)	0.73195 (9)	0.1211 (4)	0.0515 (6)
O1W	0.8685 (4)	0.96305 (9)	0.7355 (3)	0.0392 (5)
H1W	1.0038	0.9508	0.8520	0.059*
H2W	0.7663	0.9851	0.7785	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0267 (15)	0.0259 (17)	0.0363 (16)	0.0013 (13)	0.0045 (12)	−0.0015 (13)
C2	0.0257 (15)	0.0223 (16)	0.0300 (14)	−0.0002 (12)	0.0098 (12)	0.0011 (12)
C3	0.0274 (16)	0.0224 (16)	0.0320 (15)	0.0013 (13)	0.0101 (12)	0.0011 (12)
C4	0.0259 (16)	0.0258 (18)	0.0268 (14)	0.0010 (12)	0.0088 (12)	0.0022 (12)
C5	0.0379 (18)	0.0283 (18)	0.0430 (18)	−0.0011 (15)	0.0144 (14)	−0.0057 (14)
Fe1	0.0267 (3)	0.0203 (3)	0.0314 (3)	0.0024 (3)	0.0067 (2)	−0.0026 (2)
N1	0.0271 (13)	0.0217 (13)	0.0331 (12)	0.0008 (11)	0.0073 (10)	−0.0030 (10)
N2	0.0316 (14)	0.0218 (14)	0.0432 (14)	0.0079 (11)	0.0110 (11)	0.0020 (11)
O1	0.0282 (11)	0.0220 (11)	0.0375 (11)	0.0047 (9)	0.0068 (9)	−0.0019 (9)
O2	0.0277 (11)	0.0317 (12)	0.0402 (11)	0.0007 (10)	0.0018 (9)	0.0000 (9)
O3	0.0367 (12)	0.0286 (13)	0.0570 (14)	−0.0070 (10)	0.0019 (10)	−0.0073 (11)
O4	0.0512 (15)	0.0258 (13)	0.0703 (16)	−0.0008 (11)	0.0169 (12)	−0.0131 (11)
O1W	0.0346 (12)	0.0437 (14)	0.0385 (11)	0.0168 (10)	0.0140 (9)	0.0092 (10)

Geometric parameters (Å, º) top

C1—N1	1.321 (3)	C5—O3	1.312 (3)
C1—N2	1.335 (3)	Fe1—O1Wⁱ	2.1128 (19)
C1—H1	0.9300	Fe1—O1W	2.1128 (19)
C2—C3	1.363 (4)	Fe1—N1	2.147 (2)
C2—N1	1.379 (3)	Fe1—N1ⁱ	2.147 (2)
C2—C4	1.476 (4)	Fe1—O1	2.1801 (18)
C3—N2	1.367 (3)	Fe1—O1ⁱ	2.1801 (18)
C3—C5	1.475 (4)	N2—H2	0.8600
C4—O1	1.255 (3)	O3—H3	0.8200
C4—O2	1.270 (3)	O1W—H1W	0.8498
C5—O4	1.206 (3)	O1W—H2W	0.8499

N1—C1—N2	111.1 (2)	O1Wⁱ—Fe1—O1	90.82 (7)
N1—C1—H1	124.4	O1W—Fe1—O1	89.18 (7)
N2—C1—H1	124.4	N1—Fe1—O1	77.53 (8)
C3—C2—N1	109.5 (2)	N1ⁱ—Fe1—O1	102.47 (8)
C3—C2—C4	132.0 (2)	O1Wⁱ—Fe1—O1ⁱ	89.18 (7)
N1—C2—C4	118.4 (2)	O1W—Fe1—O1ⁱ	90.82 (7)
C2—C3—N2	105.6 (2)	N1—Fe1—O1ⁱ	102.47 (8)
C2—C3—C5	134.4 (2)	N1ⁱ—Fe1—O1ⁱ	77.53 (7)
N2—C3—C5	120.0 (2)	O1—Fe1—O1ⁱ	179.999 (1)
O1—C4—O2	124.6 (2)	C1—N1—C2	105.6 (2)
O1—C4—C2	117.2 (2)	C1—N1—Fe1	142.71 (18)
O2—C4—C2	118.2 (2)	C2—N1—Fe1	111.22 (17)
O4—C5—O3	121.6 (3)	C1—N2—C3	108.2 (2)
O4—C5—C3	121.9 (3)	C1—N2—H2	125.9
O3—C5—C3	116.5 (3)	C3—N2—H2	125.9
O1Wⁱ—Fe1—O1W	179.998 (1)	C4—O1—Fe1	115.45 (16)
O1Wⁱ—Fe1—N1	93.27 (8)	C5—O3—H3	109.5
O1W—Fe1—N1	86.73 (8)	Fe1—O1W—H1W	115.5
O1Wⁱ—Fe1—N1ⁱ	86.73 (8)	Fe1—O1W—H2W	115.7
O1W—Fe1—N1ⁱ	93.27 (8)	H1W—O1W—H2W	105.2
N1—Fe1—N1ⁱ	179.999 (1)

N1—C2—C3—N2	−0.4 (3)	O1Wⁱ—Fe1—N1—C1	96.8 (3)
C4—C2—C3—N2	−176.4 (3)	O1W—Fe1—N1—C1	−83.2 (3)
N1—C2—C3—C5	176.3 (3)	O1—Fe1—N1—C1	−173.1 (3)
C4—C2—C3—C5	0.3 (5)	O1ⁱ—Fe1—N1—C1	6.9 (3)
C3—C2—C4—O1	174.6 (3)	O1Wⁱ—Fe1—N1—C2	−93.03 (18)
N1—C2—C4—O1	−1.1 (4)	O1W—Fe1—N1—C2	86.97 (18)
C3—C2—C4—O2	−5.5 (4)	O1—Fe1—N1—C2	−2.91 (16)
N1—C2—C4—O2	178.8 (2)	O1ⁱ—Fe1—N1—C2	177.09 (16)
C2—C3—C5—O4	−174.3 (3)	N1—C1—N2—C3	0.1 (3)
N2—C3—C5—O4	1.9 (5)	C2—C3—N2—C1	0.2 (3)
C2—C3—C5—O3	3.9 (5)	C5—C3—N2—C1	−177.1 (3)
N2—C3—C5—O3	−179.8 (3)	O2—C4—O1—Fe1	178.5 (2)
N2—C1—N1—C2	−0.3 (3)	C2—C4—O1—Fe1	−1.6 (3)
N2—C1—N1—Fe1	170.2 (2)	O1Wⁱ—Fe1—O1—C4	95.72 (19)
C3—C2—N1—C1	0.4 (3)	O1W—Fe1—O1—C4	−84.28 (19)
C4—C2—N1—C1	177.0 (2)	N1—Fe1—O1—C4	2.55 (18)
C3—C2—N1—Fe1	−173.45 (18)	N1ⁱ—Fe1—O1—C4	−177.45 (18)
C4—C2—N1—Fe1	3.2 (3)

Symmetry code: (i) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱⁱ	0.86	2.05	2.897 (3)	169
O3—H3···O2	0.82	1.74	2.525 (3)	160
O1W—H1W···O2ⁱⁱⁱ	0.85	1.94	2.744 (3)	157
O1W—H2W···O1^iv	0.85	1.92	2.710 (3)	155

Symmetry codes: (ii) x+1, −y+3/2, z+1/2; (iii) x+1, y, z+1; (iv) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₃N₂O₄)₂(H₂O)₂]
M_r	402.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	5.0676 (9), 22.769 (4), 6.6725 (9)
β (°)	113.733 (10)
V (Å³)	704.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.14
Crystal size (mm)	0.32 × 0.28 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.712, 0.764
No. of measured, independent and observed [I > 2σ(I)] reflections	2872, 1240, 976
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.080, 1.05
No. of reflections	1240
No. of parameters	116
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.25

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.86	2.05	2.897 (3)	169
O3—H3···O2	0.82	1.74	2.525 (3)	160
O1W—H1W···O2ⁱⁱ	0.85	1.94	2.744 (3)	157
O1W—H2W···O1ⁱⁱⁱ	0.85	1.92	2.710 (3)	155

Symmetry codes: (i) x+1, −y+3/2, z+1/2; (ii) x+1, y, z+1; (iii) −x+1, −y+2, −z+1.

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Liu, J.-W., Gao, S., Huo, L.-H., Gu, C.-S., Zhao, H. & Zhao, J.-G. (2004). Acta Cryst. E60, m1697–m1699. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, C.-B., Chen, F., Chen, C.-N. & Liu, Q.-T. (2003). Acta Cryst. C59, m516–m518. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shimizu, E., Kondo, M., Fuwa, Y., Sarker, R. P., Miyazawa, M., Ueno, M., Naito, T., Maeda, K. & Uchida, F. (2004). Inorg. Chem. Commun. 7, 1191–1194. Web of Science CSD CrossRef CAS Google Scholar
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doi:10.1107/S1600536811024779

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