Diaqua­(5-methyl­pyrazine-2-carboxyl­ato-κ2N1,O)iron(II)

Fan, G.; Sun, J.-J.; Zhang, J.-C.; Ma, Z.-Y.; Gao, S.-L.

doi:10.1107/S1600536808042529

metal-organic compounds

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Volume 65| Part 1| January 2009| Page m107

doi:10.1107/S1600536808042529

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Diaqua(5-methylpyrazine-2-carboxylato-κ²N¹,O)iron(II)

Guang Fan,^a Jia-Juan Sun,^a Jun-Cai Zhang,^a Zhan-Ying Ma ^a and Sheng-Li Gao ^b ^*

^aDepartment of Chemistry, Xianyang Normal University, Xianyang 712000, Shaanxi, People's Republic of China, and ^bDepartment of Chemistry, Northwest University, Xi'an 710069, Shaanxi, People's Republic of China
^*Correspondence e-mail: fanguang2004@163.com

(Received 13 December 2008; accepted 13 December 2008; online 20 December 2008)

In the neutral title complex, [Fe(C₆H₅N₂O₂)₂(H₂O)₂], the coordination geometry aound the Fe^II atom, which lies on an inversion centre, is distorted octahedral comprising two N atoms and two O atoms from two 5-methylpyrazine-2-carboxylate ligands, and two water molecules. The crystal structure is stabilized by a network of O—H⋯O hydrogen bonds, resulting in a two-dimensional supramolecular structure.

Related literature

For background to this study, see: Fan et al. (2007 ).

Experimental

Crystal data

[Fe(C₆H₅N₂O₂)₂(H₂O)₂]
M_r = 366.12
Triclinic, $[P \overline 1]$
a = 5.068 (1) Å
b = 6.401 (1) Å
c = 12.381 (1) Å
α = 103.851 (2)°
β = 91.790(10)°
γ = 108.340 (2)°
V = 368.22 (10) Å³
Z = 1
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 298 (2) K
0.18 × 0.09 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.832, T_max = 0.949
1916 measured reflections
1260 independent reflections
1061 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.095
S = 1.00
1260 reflections
107 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O1ⁱ	0.85	1.93	2.720 (3)	155
O3—H3B⋯O2ⁱⁱ	0.85	1.86	2.673 (3)	159
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+2, -z+1.

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); 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: 10.1107/S1600536808042529/ng2527sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042529/ng2527Isup2.hkl

checkCIF report

Comment top

The background to this study is set out in the preceding paper (Fan et al., 2007). Here we report the crystal structure of a mononuclear Fe^II (Fig. 1).

The asymmetric unit consists of a Fe^II atom, which lies on an inversion centre, one 2mpac ligand and two water molecules. A ring nitrogen atom and an oxygen atom of the carboxylate group from 2mpac ligand with Fe1—O1 = 2.103 (2) Å and Fe1—N1 = 2.167 (3) Å are involved in coordination to the Fe^II atom; these form a square. The coordination of the two water molecules with Fe1—O3 = 2.114 (2) Å occupied the axial sites results in the formation of a distorted octahedral geometry.

In the crystal structure, hydrogen bonding interactions are observed between the hydrogen atoms of the coordinated water molecules and the oxygen atoms of the carboxyl groups of a neighbouring unit, affording a two-dimensional supramolecular structure (Figure 2).

Related literature top

For background to this study, see: Fan et al. (2007).

Experimental top

The title compound was obtained from the mixture of ferrous ammonium sulfate hexahydrate(0.10 g, 0.25 mmol), 5-methylpyrazine-2-carboxylic acid (0.70 g, 0.5 mmol) and distilled water (20 ml), which was placed at room temperature for two weeks and red single crystals were obtained finally.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. A view of the molecular structure of title complex with the atom-labling scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code for A: 1-X, 1-Y, 1-Z.
	Fig. 2. Two-dimensional supramolecular structure of the title complex.

Diaqua(5-methylpyrazine-2-carboxylato-k²N¹,O)iron(II) top

Crystal data top

[Fe(C₆H₅N₂O₂)₂(H₂O)₂]	Z = 1
M_r = 366.12	F(000) = 188
Triclinic, P1	D_x = 1.651 Mg m⁻³
a = 5.068 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.401 (1) Å	Cell parameters from 715 reflections
c = 12.3810 (12) Å	θ = 3.4–26.8°
α = 103.851 (2)°	µ = 1.06 mm⁻¹
β = 91.079 (1)°	T = 298 K
γ = 108.340 (2)°	Block, red
V = 368.22 (10) Å³	0.18 × 0.09 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1260 independent reflections
Radiation source: fine-focus sealed tube	1061 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→6
T_min = 0.832, T_max = 0.949	k = −7→7
1916 measured reflections	l = −14→12

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0456P)²] where P = (F_o² + 2F_c²)/3
1260 reflections	(Δ/σ)_max < 0.001
107 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Fe(C₆H₅N₂O₂)₂(H₂O)₂]	γ = 108.340 (2)°
M_r = 366.12	V = 368.22 (10) Å³
Triclinic, P1	Z = 1
a = 5.068 (1) Å	Mo Kα radiation
b = 6.401 (1) Å	µ = 1.06 mm⁻¹
c = 12.3810 (12) Å	T = 298 K
α = 103.851 (2)°	0.18 × 0.09 × 0.05 mm
β = 91.079 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1260 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1061 reflections with I > 2σ(I)
T_min = 0.832, T_max = 0.949	R_int = 0.025
1916 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	Δρ_max = 0.33 e Å⁻³
1260 reflections	Δρ_min = −0.28 e Å⁻³
107 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	0.5000	0.5000	0.5000	0.0326 (3)
N1	0.5923 (6)	0.4742 (4)	0.3281 (2)	0.0323 (7)
N2	0.6791 (7)	0.4921 (6)	0.1096 (2)	0.0508 (8)
O1	0.3162 (5)	0.7203 (4)	0.45178 (18)	0.0359 (6)
O2	0.2550 (5)	0.8729 (4)	0.3133 (2)	0.0472 (7)
O3	0.8721 (5)	0.7772 (4)	0.56033 (19)	0.0423 (6)
H3A	1.0121	0.7975	0.5226	0.051*
H3B	0.8701	0.9077	0.5961	0.051*
C1	0.3463 (7)	0.7489 (5)	0.3543 (3)	0.0330 (8)
C2	0.5049 (7)	0.6138 (5)	0.2826 (3)	0.0313 (8)
C3	0.5494 (8)	0.6191 (7)	0.1744 (3)	0.0482 (10)
H3	0.4856	0.7167	0.1445	0.058*
C4	0.7211 (7)	0.3461 (6)	0.2642 (3)	0.0360 (8)
H4	0.7855	0.2487	0.2940	0.043*
C5	0.7624 (7)	0.3530 (6)	0.1548 (3)	0.0394 (8)
C6	0.9003 (9)	0.2011 (7)	0.0829 (3)	0.0582 (11)
H6A	0.7600	0.0722	0.0347	0.087*
H6B	1.0059	0.1495	0.1297	0.087*
H6C	1.0232	0.2847	0.0384	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0405 (5)	0.0352 (4)	0.0282 (4)	0.0197 (3)	0.0122 (3)	0.0092 (3)
N1	0.0366 (16)	0.0321 (16)	0.0329 (15)	0.0170 (13)	0.0109 (12)	0.0089 (13)
N2	0.064 (2)	0.068 (2)	0.0329 (17)	0.0347 (19)	0.0192 (15)	0.0171 (17)
O1	0.0419 (14)	0.0395 (14)	0.0356 (14)	0.0238 (11)	0.0170 (10)	0.0118 (11)
O2	0.0649 (18)	0.0445 (16)	0.0469 (15)	0.0355 (14)	0.0114 (12)	0.0151 (13)
O3	0.0427 (15)	0.0346 (14)	0.0527 (16)	0.0186 (12)	0.0178 (11)	0.0082 (12)
C1	0.0330 (19)	0.0275 (18)	0.037 (2)	0.0099 (15)	0.0054 (14)	0.0044 (15)
C2	0.0337 (19)	0.0296 (18)	0.0322 (19)	0.0137 (15)	0.0061 (14)	0.0066 (15)
C3	0.063 (3)	0.059 (3)	0.038 (2)	0.035 (2)	0.0160 (18)	0.020 (2)
C4	0.039 (2)	0.037 (2)	0.039 (2)	0.0206 (16)	0.0122 (16)	0.0104 (16)
C5	0.038 (2)	0.047 (2)	0.0333 (19)	0.0198 (17)	0.0102 (15)	0.0036 (17)
C6	0.065 (3)	0.063 (3)	0.047 (2)	0.030 (2)	0.019 (2)	−0.001 (2)

Geometric parameters (Å, º) top

Fe1—O1ⁱ	2.103 (2)	O3—H3A	0.8500
Fe1—O1	2.103 (2)	O3—H3B	0.8499
Fe1—O3ⁱ	2.114 (2)	C1—C2	1.510 (5)
Fe1—O3	2.114 (2)	C2—C3	1.369 (5)
Fe1—N1ⁱ	2.167 (3)	C3—H3	0.9300
Fe1—N1	2.167 (3)	C4—C5	1.384 (5)
N1—C4	1.331 (4)	C4—H4	0.9300
N1—C2	1.339 (4)	C5—C6	1.505 (5)
N2—C5	1.323 (4)	C6—H6A	0.9600
N2—C3	1.335 (5)	C6—H6B	0.9600
O1—C1	1.268 (4)	C6—H6C	0.9600
O2—C1	1.232 (4)

O1ⁱ—Fe1—O1	180.00 (11)	H3A—O3—H3B	107.6
O1ⁱ—Fe1—O3ⁱ	89.75 (9)	O2—C1—O1	126.0 (3)
O1—Fe1—O3ⁱ	90.25 (9)	O2—C1—C2	117.9 (3)
O1ⁱ—Fe1—O3	90.25 (9)	O1—C1—C2	116.0 (3)
O1—Fe1—O3	89.75 (9)	N1—C2—C3	119.7 (3)
O3ⁱ—Fe1—O3	180.00 (10)	N1—C2—C1	116.5 (3)
O1ⁱ—Fe1—N1ⁱ	77.21 (9)	C3—C2—C1	123.7 (3)
O1—Fe1—N1ⁱ	102.79 (9)	N2—C3—C2	123.6 (3)
O3ⁱ—Fe1—N1ⁱ	92.02 (9)	N2—C3—H3	118.2
O3—Fe1—N1ⁱ	87.98 (9)	C2—C3—H3	118.2
O1ⁱ—Fe1—N1	102.79 (9)	N1—C4—C5	122.1 (3)
O1—Fe1—N1	77.21 (9)	N1—C4—H4	118.9
O3ⁱ—Fe1—N1	87.98 (9)	C5—C4—H4	118.9
O3—Fe1—N1	92.02 (9)	N2—C5—C4	121.0 (3)
N1ⁱ—Fe1—N1	180.000 (1)	N2—C5—C6	117.8 (3)
C4—N1—C2	117.2 (3)	C4—C5—C6	121.2 (3)
C4—N1—Fe1	130.3 (2)	C5—C6—H6A	109.5
C2—N1—Fe1	112.5 (2)	C5—C6—H6B	109.5
C5—N2—C3	116.3 (3)	H6A—C6—H6B	109.5
C1—O1—Fe1	117.6 (2)	C5—C6—H6C	109.5
Fe1—O3—H3A	121.1	H6A—C6—H6C	109.5
Fe1—O3—H3B	121.9	H6B—C6—H6C	109.5

O1ⁱ—Fe1—N1—C4	2.7 (3)	C4—N1—C2—C3	0.2 (5)
O1—Fe1—N1—C4	−177.3 (3)	Fe1—N1—C2—C3	179.5 (3)
O3ⁱ—Fe1—N1—C4	−86.6 (3)	C4—N1—C2—C1	177.0 (3)
O3—Fe1—N1—C4	93.4 (3)	Fe1—N1—C2—C1	−3.7 (3)
N1ⁱ—Fe1—N1—C4	131 (100)	O2—C1—C2—N1	−177.5 (3)
O1ⁱ—Fe1—N1—C2	−176.5 (2)	O1—C1—C2—N1	1.4 (4)
O1—Fe1—N1—C2	3.5 (2)	O2—C1—C2—C3	−0.9 (5)
O3ⁱ—Fe1—N1—C2	94.2 (2)	O1—C1—C2—C3	178.0 (3)
O3—Fe1—N1—C2	−85.8 (2)	C5—N2—C3—C2	1.1 (6)
N1ⁱ—Fe1—N1—C2	−48 (100)	N1—C2—C3—N2	−0.5 (6)
O1ⁱ—Fe1—O1—C1	29 (100)	C1—C2—C3—N2	−177.0 (3)
O3ⁱ—Fe1—O1—C1	−90.8 (2)	C2—N1—C4—C5	−0.6 (5)
O3—Fe1—O1—C1	89.2 (2)	Fe1—N1—C4—C5	−179.8 (2)
N1ⁱ—Fe1—O1—C1	177.1 (2)	C3—N2—C5—C4	−1.5 (5)
N1—Fe1—O1—C1	−2.9 (2)	C3—N2—C5—C6	177.9 (3)
Fe1—O1—C1—O2	−179.3 (3)	N1—C4—C5—N2	1.3 (5)
Fe1—O1—C1—C2	1.9 (4)	N1—C4—C5—C6	−178.0 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1ⁱⁱ	0.85	1.93	2.720 (3)	155
O3—H3B···O2ⁱⁱⁱ	0.85	1.86	2.673 (3)	159

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

Experimental details

Crystal data
Chemical formula	[Fe(C₆H₅N₂O₂)₂(H₂O)₂]
M_r	366.12
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.068 (1), 6.401 (1), 12.3810 (12)
α, β, γ (°)	103.851 (2), 91.079 (1), 108.340 (2)
V (Å³)	368.22 (10)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.06
Crystal size (mm)	0.18 × 0.09 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.832, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	1916, 1260, 1061
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.095, 1.00
No. of reflections	1260
No. of parameters	107
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.28

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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
O3—H3A···O1ⁱ	0.85	1.93	2.720 (3)	155.0
O3—H3B···O2ⁱⁱ	0.85	1.86	2.673 (3)	159.3

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

Acknowledgements

We gratefully acknowledge the Special Research Fund of Xianyang Normal University for Talent Introduction (08XSYK305) and the Financial Support Fund from the Education Department of Shaanxi Province (No. 07JK424).

References

Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fan, G., Chen, S.-P. & Gao, S.-L. (2007). Acta Cryst. E63, m772–m773. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar