catena-Poly[[[diaqua­iron(II)]-μ-pyrazine-2,3-dicarboxyl­ato] dihydrate]

Xu, H.; Ma, H.; Xu, M.; Zhao, W.; Guo, B.

doi:10.1107/S1600536807064501

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m104

https://doi.org/10.1107/S1600536807064501

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catena-Poly[[[diaquairon(II)]-μ-pyrazine-2,3-dicarboxylato] dihydrate]

Haiyun Xu,^a ^* Huailing Ma,^a Maotian Xu,^a Wenxian Zhao ^a and Baoguo Guo ^a

^aDepartment of Chemistry, Shangqiu Normal College, 476000 Shangqiu, Henan, People's Republic of China
^*Correspondence e-mail: xuhyun1970@sohu.com

(Received 19 November 2007; accepted 29 November 2007; online 6 December 2007)

The crystal structure of the title compound, {[Fe(C₆H₂N₂O₄)(H₂O)₂]·2H₂O}_n, was synthesized by a diffusion method. It has a one-dimensional polymeric chain structure and the chains are further connected into a three-dimensional structure by hydrogen bonds. The Fe^II ion has a distorted octahedral coordination environment, with two N and two O atoms from the pyrazine-2,3-dicarboxylate ligands in the equatorial plane and with two water molecules in axial positions. The Fe atom lies on a crystallographic centre of symmetry and a twofold rotation axis passes through the pyrazine ring.

Related literature

For related literature, see: Kondo et al. (1999 ); Kitaura et al. (2002 ); Zheng et al. (2002 ); Mao et al. (1996 ); Castillo et al. (2003 ); Konar et al. (2004 ); Muranishi & Okabe (2003 ); Richard et al. (1973 ); Xiang et al. (2004 ); Zou et al. (1999 ).

Experimental

Crystal data

[Fe(C₆H₂N₂O₄)(H₂O)₂]·2H₂O
M_r = 294.01
Monoclinic, C 2/c
a = 12.5650 (2) Å
b = 7.5158 (1) Å
c = 11.8314 (2) Å
β = 110.759 (1)°
V = 1044.77 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 298 (2) K
0.23 × 0.20 × 0.18 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.727, T_max = 0.777
5477 measured reflections
1291 independent reflections
1219 reflections with I > 2σ'(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.088
S = 1.03
1291 reflections
80 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O1ⁱ	0.85	2.17	2.890 (3)	142
O4—H4A⋯O2ⁱ	0.85	2.59	3.227 (3)	133
O4—H4B⋯O1ⁱⁱ	0.85	2.20	3.045 (3)	174
O3—H3A⋯O4ⁱⁱⁱ	0.85	2.41	3.210 (3)	156
O3—H3B⋯O2^iv	0.85	1.98	2.720 (2)	145
C3—H3⋯O2^v	0.93	2.51	3.232 (3)	135
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) x, y+1, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807064501/br2063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064501/br2063Isup2.hkl

checkCIF report

Comment top

Recently, the effective combination of coordination bond and hydrogen bond has been applied in the engineering study of inorganic-organic hybrid material and the construction of metal-organic coordination supramolecular complexes. The suitable organic ligand makes the complex not only to possess novel structure but also produces unique optical, electric and magnetic properties. Pyrazine-2,3-dicarboxylic acid (pzdcH2) has proved to be well suited for the construction of multidimensional frameworks, due to the presence of two adjacent carboxylate groups (O donor atoms) as substituents on the N-heterocyclic pyrazine ring (N donor atoms). A series of one-dimensional, two-dimensional and three-dimensional metal-organic coordination supramolecular complexes have been synthesized and characterized. Now, we report the crystal structure of the title compound (I), and the crystal structure is similar to the structures reported by Mao et al. (1996). In compound 1, the iron atom is hexacoordinate where the sphere about any iron atom includes the N1, N1A, O1, O1A, O3 and O3A atoms. The Fe atom lies on a crystallographic center of symmetry and that the ligand lies on a crystallographic twofold axis. Two coordinated water molecules are on the axis. The coordination distances for the Fe—O1 2.054 (1) Å are similar with the usual carboxyl oxygen to iron distance of 2.091 Å. The pzdc dianion ligands bridge Fe ions to form extended linear chains. In this structure, the pzdc dianion ligand coordinates to two metal centers via chelate interactions involving each nitrogen N(1) and oxygen O(1) from the adjacent carboxylate substituent (Fig. 1). As shown in Fig. 2, the chains are linked in a 3-D surpramolecular network by O—H···O hydrogen-bonding interactions.

Related literature top

For related literature, see: Kondo et al. (1999); Kitaura et al. (2002); Zheng et al. (2002); Mao et al. (1996); Castillo et al. (2003); Konar et al. (2004); Muranishi & Okabe (2003); Richard et al. (1973); Xiang et al. (2004); Zou et al. (1999).

Experimental top

The title compound was obtained by a diffusion method. In one arm of U-tube was placed (C₆H₂N₂O₄)Na₂ (42 mg, 0.2 mmol) in water/ethanol (1:1; 10 ml) and in the other H₁₂Cl₂O₁₄Fe (73 mg, 0.2 mmol) in water/ethanol (1:1; 10 ml). The red crystals were collected by filtration, washed with distilled water, followed by ethanol and dried under reduced pressure for 2 h.

Analysis found: C 24.39, H 3.41, N 9.26%; C₆H₁₀N₂O₈Fe requires: C 24.51, H 3.43, N 9.53%.

Structure description top

For related literature, see: Kondo et al. (1999); Kitaura et al. (2002); Zheng et al. (2002); Mao et al. (1996); Castillo et al. (2003); Konar et al. (2004); Muranishi & Okabe (2003); Richard et al. (1973); Xiang et al. (2004); Zou et al. (1999).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

	Fig. 1. The structure of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme. The H atoms are omitted for clarity.
	Fig. 2. three-dimensional supramolecular network of (I). O—H···O hydrogen bonds interactions shown.

catena-Poly[[[diaquairon(II)]-µ-pyrazine-2,3-dicarboxylato] dihydrate] top

Crystal data top

[Fe(C₆H₂N₂O₄)(H₂O)₂]·2H₂O	F(000) = 600
M_r = 294.01	D_x = 1.869 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3554 reflections
a = 12.5650 (2) Å	θ = 3.3–28.2°
b = 7.5158 (1) Å	µ = 1.48 mm⁻¹
c = 11.8314 (2) Å	T = 298 K
β = 110.759 (1)°	Block, red
V = 1044.77 (3) Å³	0.23 × 0.20 × 0.18 mm
Z = 4

Data collection top

CCD area-detector diffractometer	1291 independent reflections
Radiation source: fine-focus sealed tube	1219 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 28.3°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→16
T_min = 0.727, T_max = 0.777	k = −10→10
5477 measured reflections	l = −15→15

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)] = 0.029	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0523P)² + 1.9364P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1291 reflections	Δρ_max = 0.59 e Å⁻³
80 parameters	Δρ_min = −0.70 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.028 (2)

Crystal data top

[Fe(C₆H₂N₂O₄)(H₂O)₂]·2H₂O	V = 1044.77 (3) Å³
M_r = 294.01	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.5650 (2) Å	µ = 1.48 mm⁻¹
b = 7.5158 (1) Å	T = 298 K
c = 11.8314 (2) Å	0.23 × 0.20 × 0.18 mm
β = 110.759 (1)°

Data collection top

CCD area-detector diffractometer	1291 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1219 reflections with I > 2σ(I)
T_min = 0.727, T_max = 0.777	R_int = 0.019
5477 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	Δρ_max = 0.59 e Å⁻³
1291 reflections	Δρ_min = −0.70 e Å⁻³
80 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
Fe1	0.2500	0.2500	0.5000	0.01865 (18)
C1	0.08321 (16)	−0.0176 (3)	0.38935 (17)	0.0225 (4)
C2	0.04250 (15)	0.1436 (3)	0.30732 (16)	0.0202 (4)
C3	0.04814 (18)	0.4486 (3)	0.30161 (19)	0.0289 (5)
H3	0.0840	0.5557	0.3320	0.035*
N1	0.09020 (14)	0.2975 (2)	0.35810 (15)	0.0228 (3)
O1	0.18127 (13)	−0.0012 (2)	0.47077 (14)	0.0283 (3)
O2	0.01979 (14)	−0.1458 (2)	0.37732 (17)	0.0378 (4)
O3	0.32048 (15)	0.2010 (3)	0.36718 (16)	0.0387 (4)
H3A	0.3336	0.0941	0.3525	0.046*
H3B	0.3619	0.2805	0.3524	0.046*
O4	0.1817 (2)	0.2742 (3)	0.14299 (19)	0.0509 (6)
H4A	0.1531	0.1832	0.1004	0.061*
H4B	0.2226	0.3406	0.1168	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0141 (2)	0.0209 (3)	0.0166 (2)	−0.00144 (12)	0.00016 (15)	−0.00229 (12)
C1	0.0209 (8)	0.0219 (9)	0.0224 (8)	0.0007 (7)	0.0047 (7)	0.0014 (7)
C2	0.0158 (8)	0.0194 (9)	0.0222 (9)	−0.0005 (6)	0.0030 (7)	0.0004 (7)
C3	0.0279 (10)	0.0193 (9)	0.0318 (11)	−0.0031 (8)	0.0010 (9)	−0.0023 (8)
N1	0.0181 (7)	0.0223 (8)	0.0226 (8)	−0.0007 (6)	0.0005 (5)	−0.0013 (6)
O1	0.0244 (7)	0.0240 (6)	0.0276 (7)	−0.0012 (5)	−0.0018 (6)	0.0040 (5)
O2	0.0301 (8)	0.0273 (8)	0.0484 (10)	−0.0073 (6)	0.0047 (7)	0.0081 (7)
O3	0.0317 (9)	0.0544 (11)	0.0337 (9)	−0.0109 (8)	0.0160 (7)	−0.0108 (8)
O4	0.0651 (14)	0.0589 (13)	0.0310 (9)	−0.0257 (10)	0.0200 (10)	−0.0104 (8)

Geometric parameters (Å, º) top

Fe1—O1ⁱ	2.0539 (15)	C2—N1	1.343 (3)
Fe1—O1	2.0539 (15)	C2—C2ⁱⁱ	1.398 (3)
Fe1—O3	2.0919 (17)	C3—N1	1.329 (3)
Fe1—O3ⁱ	2.0919 (17)	C3—C3ⁱⁱ	1.381 (4)
Fe1—N1ⁱ	2.1420 (17)	C3—H3	0.9300
Fe1—N1	2.1420 (17)	O3—H3A	0.8500
C1—O2	1.226 (3)	O3—H3B	0.8500
C1—O1	1.273 (2)	O4—H4A	0.8500
C1—C2	1.523 (3)	O4—H4B	0.8501

O1ⁱ—Fe1—O1	180.0	O2—C1—C2	119.56 (17)
O1ⁱ—Fe1—O3	91.35 (7)	O1—C1—C2	114.93 (16)
O1—Fe1—O3	88.65 (7)	N1—C2—C2ⁱⁱ	120.03 (11)
O1ⁱ—Fe1—O3ⁱ	88.65 (7)	N1—C2—C1	113.86 (16)
O1—Fe1—O3ⁱ	91.35 (7)	C2ⁱⁱ—C2—C1	125.94 (10)
O3—Fe1—O3ⁱ	180.000 (1)	N1—C3—C3ⁱⁱ	120.82 (11)
O1ⁱ—Fe1—N1ⁱ	78.46 (6)	N1—C3—H3	119.6
O1—Fe1—N1ⁱ	101.54 (6)	C3ⁱⁱ—C3—H3	119.6
O3—Fe1—N1ⁱ	91.76 (7)	C3—N1—C2	118.46 (17)
O3ⁱ—Fe1—N1ⁱ	88.24 (7)	C3—N1—Fe1	129.20 (14)
O1ⁱ—Fe1—N1	101.54 (6)	C2—N1—Fe1	110.65 (13)
O1—Fe1—N1	78.46 (6)	C1—O1—Fe1	116.94 (13)
O3—Fe1—N1	88.24 (7)	Fe1—O3—H3A	118.9
O3ⁱ—Fe1—N1	91.76 (7)	Fe1—O3—H3B	118.9
N1ⁱ—Fe1—N1	180.0	H3A—O3—H3B	116.4
O2—C1—O1	125.39 (19)	H4A—O4—H4B	116.0

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1ⁱⁱⁱ	0.85	2.17	2.890 (3)	142
O4—H4A···O2ⁱⁱⁱ	0.85	2.59	3.227 (3)	133
O4—H4B···O1^iv	0.85	2.20	3.045 (3)	174
O3—H3A···O4^v	0.85	2.41	3.210 (3)	156
O3—H3B···O2^vi	0.85	1.98	2.720 (2)	145
C3—H3···O2^vii	0.93	2.51	3.232 (3)	135

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

Experimental details

Crystal data
Chemical formula	[Fe(C₆H₂N₂O₄)(H₂O)₂]·2H₂O
M_r	294.01
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	12.5650 (2), 7.5158 (1), 11.8314 (2)
β (°)	110.759 (1)
V (Å³)	1044.77 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.23 × 0.20 × 0.18

Data collection
Diffractometer	CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.727, 0.777
No. of measured, independent and observed [I > 2σ(I)] reflections	5477, 1291, 1219
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.088, 1.04
No. of reflections	1291
No. of parameters	80
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.70

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1ⁱ	0.85	2.17	2.890 (3)	141.7
O4—H4A···O2ⁱ	0.85	2.59	3.227 (3)	132.5
O4—H4B···O1ⁱⁱ	0.85	2.20	3.045 (3)	173.6
O3—H3A···O4ⁱⁱⁱ	0.85	2.41	3.210 (3)	156.1
O3—H3B···O2^iv	0.85	1.98	2.720 (2)	145.2
C3—H3···O2^v	0.93	2.51	3.232 (3)	135.2

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

Acknowledgements

The authors thank the Natural Science Foundation of Henan Province (grant No. 0511020300) for financial support.

References

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