catena-Poly[[(pyrimidine-2-carb­oxy­lic acid)iron(II)]-μ-oxalato]

Zhao, J.-P.; Liu, F.-C.

doi:10.1107/S1600536810030023

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page m1059

https://doi.org/10.1107/S1600536810030023

Open

access

catena-Poly[[(pyrimidine-2-carboxylic acid)iron(II)]-μ-oxalato]

Jiong-Peng Zhao ^a and Fu-Chen Liu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300191, People's Republic of China
^*Correspondence e-mail: fuchenliutj@yahoo.com

(Received 12 June 2010; accepted 28 July 2010; online 4 August 2010)

In the title complex, [Fe(C₂O₄)(C₅H₄N₂O₄)]_n, the Fe^II ion is coordinated by two oxalate anions and a pyrimidine-2-carboxylic acid ligand in a slightly distorted octahedral geometry. Each oxalate anion chelates to two Fe^II ions, forming chains along the a axis. The chains are further connected by O—H⋯O and C—H⋯O hydrogen bonds, stabilizing the structure. An intramolecular O—H⋯N interaction results in a five-membered ring.

Related literature

For related structures, see: Zhang et al. (2008 ).

Experimental

Crystal data

[Fe(C₂O₄)(C₅H₄N₂O₄)]
M_r = 267.97
Orthorhombic, P n a 2₁
a = 9.0524 (18) Å
b = 9.1578 (18) Å
c = 11.329 (2) Å
V = 939.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.62 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.16 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.780, T_max = 1
7603 measured reflections
1658 independent reflections
1503 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.083
S = 1.11
1658 reflections
145 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ), 783 Friedel pairs
Flack parameter: 0.05 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O3ⁱ	0.93	2.48	3.279 (6)	145
O6—H6⋯O1ⁱⁱ	0.85	2.17	2.988 (5)	161
O6—H6⋯N2	0.85	2.40	2.743 (6)	105
Symmetry codes: (i) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006 ); cell refinement: PROCESS-AUTO (Rigaku, 1998 ); data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810030023/pv2297sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030023/pv2297Isup2.hkl

checkCIF report

Comment top

Pyrimidine-2-carboxylic acid (HL) and oxalate anion have similar coordination mode, acting as bidentate ligands, and some Cd complexes have been reported containing both ligands (Zhang et al., 2008). Here we report the synthesis and crystal structure of a new iron complex with pyrimidine-2-carboxylic acid and oxalate as co-ligands.

In the title complex, the Fe^II ions are coordinated by one HL ligand and two oxalate anions in a slightly distorted octahedral geometry (Fig. 1). Each oxalate anion chelates to two Fe^II ions resulting a chain along the a-axis. There is an intramolecular interaction O6—H6···N2 resulting in a five membererd ring. The O—H···O and C—H···O type hydrogen bonds between the oxalate and HL ligands impart stability to the structure (Fig. 2).

Related literature top

For related structures, see: Zhang et al. (2008).

Experimental top

A mixture of Fe(III) chloride (2 mmol), oxalate acid (2 mmol)and pyrimidine-2-carbonitrile (1 mmol), in 10 ml dimethyl formamate (DMF) solvent was sealed in a Teflon-lined stainless-steel Parr bomb was heated at 413 K for 48 h. Red crystals of the title complex were collected after the bomb was allowed to cool to room temperature; yield 20%.

Structure description top

For related structures, see: Zhang et al. (2008).

Computing details top

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The coordinated mode and linkage of the complex. Ellipsoids are drawn at the 30% probability level. Symmetry codes: i = x+1/2,-y-1/2,z ii= x-1/2,-y-1/2,z
	Fig. 2. A partial packing diagram of the unit cell viewed down the c-axis.

catena-Poly[[(pyrimidine-2-carboxylic acid)iron(II)]-µ-oxalato] top

Crystal data top

[Fe(C₂O₄)(C₅H₄N₂O₄)]	F(000) = 536
M_r = 267.97	D_x = 1.895 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 8691 reflections
a = 9.0524 (18) Å	θ = 3.2–27.5°
b = 9.1578 (18) Å	µ = 1.62 mm⁻¹
c = 11.329 (2) Å	T = 293 K
V = 939.2 (3) Å³	Block, red
Z = 4	0.2 × 0.18 × 0.16 mm

Data collection top

Rigaku SCXmini diffractometer	1658 independent reflections
Radiation source: fine-focus sealed tube	1503 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.074
ω scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.780, T_max = 1	k = −10→10
7603 measured reflections	l = −13→13

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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0339P)² + 0.7762P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
1658 reflections	Δρ_max = 0.46 e Å⁻³
145 parameters	Δρ_min = −0.30 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 783 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (3)

Crystal data top

[Fe(C₂O₄)(C₅H₄N₂O₄)]	V = 939.2 (3) Å³
M_r = 267.97	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 9.0524 (18) Å	µ = 1.62 mm⁻¹
b = 9.1578 (18) Å	T = 293 K
c = 11.329 (2) Å	0.2 × 0.18 × 0.16 mm

Data collection top

Rigaku SCXmini diffractometer	1658 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1503 reflections with I > 2σ(I)
T_min = 0.780, T_max = 1	R_int = 0.074
7603 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.083	Δρ_max = 0.46 e Å⁻³
S = 1.11	Δρ_min = −0.30 e Å⁻³
1658 reflections	Absolute structure: Flack (1983), 783 Friedel pairs
145 parameters	Absolute structure parameter: 0.05 (3)
1 restraint

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
Fe1	0.13566 (6)	−0.08170 (6)	0.71653 (7)	0.02969 (18)
C4	0.1749 (5)	0.2409 (5)	0.7015 (4)	0.0263 (10)
O5	0.2520 (4)	0.0586 (3)	0.8376 (3)	0.0397 (9)
O1	−0.0702 (3)	−0.0924 (3)	0.8009 (3)	0.0293 (7)
N1	0.0989 (4)	0.1349 (4)	0.6452 (4)	0.0307 (9)
O6	0.3406 (5)	0.2878 (5)	0.8630 (4)	0.0624 (12)
H6	0.3456	0.3746	0.8369	0.075*
C3	0.2601 (5)	0.1886 (5)	0.8074 (4)	0.0325 (11)
O3	−0.2731 (3)	−0.2329 (4)	0.8046 (3)	0.0353 (8)
O2	0.0098 (4)	−0.2138 (4)	0.5963 (3)	0.0343 (8)
C7	0.0149 (5)	0.1768 (6)	0.5565 (4)	0.0349 (12)
H7A	−0.0405	0.1072	0.5163	0.042*
O4	−0.1781 (4)	−0.3696 (4)	0.6089 (3)	0.0368 (9)
C5	0.0923 (6)	0.4168 (6)	0.5831 (5)	0.0438 (13)
H5A	0.0916	0.5141	0.5597	0.053*
C6	0.0066 (6)	0.3211 (6)	0.5216 (5)	0.0408 (13)
H6A	−0.0539	0.3511	0.4598	0.049*
N2	0.1764 (5)	0.3806 (4)	0.6738 (4)	0.0350 (11)
C2	−0.1034 (5)	−0.2649 (5)	0.6452 (4)	0.0263 (11)
C1	−0.1539 (5)	−0.1906 (5)	0.7602 (4)	0.0256 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0248 (3)	0.0246 (3)	0.0396 (4)	−0.0008 (3)	0.0015 (4)	0.0021 (4)
C4	0.028 (2)	0.028 (2)	0.023 (3)	0.0011 (17)	0.002 (2)	−0.002 (2)
O5	0.053 (2)	0.0245 (19)	0.042 (2)	−0.0094 (17)	−0.0203 (18)	0.0093 (15)
O1	0.0252 (17)	0.0282 (17)	0.0344 (19)	0.0003 (15)	0.0030 (15)	−0.0040 (15)
N1	0.030 (2)	0.034 (2)	0.029 (2)	0.0011 (18)	0.0004 (18)	0.0003 (18)
O6	0.076 (3)	0.049 (3)	0.062 (3)	−0.010 (2)	−0.010 (2)	0.007 (2)
C3	0.033 (3)	0.035 (3)	0.029 (3)	−0.007 (2)	−0.006 (2)	−0.001 (2)
O3	0.0304 (19)	0.0338 (19)	0.042 (2)	−0.0084 (16)	0.0102 (17)	−0.0078 (17)
O2	0.0298 (18)	0.0426 (19)	0.0304 (18)	−0.0060 (16)	0.0071 (16)	−0.0054 (17)
C7	0.033 (3)	0.042 (3)	0.030 (3)	−0.002 (2)	−0.007 (2)	−0.003 (2)
O4	0.0292 (18)	0.041 (2)	0.040 (2)	−0.0042 (16)	0.0069 (17)	−0.0142 (17)
C5	0.053 (3)	0.033 (3)	0.045 (3)	0.010 (3)	−0.001 (3)	0.008 (3)
C6	0.043 (3)	0.043 (3)	0.037 (3)	0.010 (3)	−0.008 (3)	0.002 (2)
N2	0.041 (3)	0.024 (2)	0.039 (3)	−0.0041 (17)	−0.0069 (19)	0.0036 (16)
C2	0.023 (2)	0.030 (3)	0.026 (3)	0.007 (2)	−0.001 (2)	−0.001 (2)
C1	0.021 (2)	0.024 (2)	0.032 (2)	0.003 (2)	0.0027 (19)	0.0036 (18)

Geometric parameters (Å, º) top

Fe1—O1	2.097 (3)	O6—H6	0.8500
Fe1—O4ⁱ	2.128 (3)	O3—C1	1.252 (5)
Fe1—O3ⁱ	2.136 (3)	O3—Fe1ⁱⁱ	2.136 (3)
Fe1—O2	2.148 (3)	O2—C2	1.255 (6)
Fe1—O5	2.154 (3)	C7—C6	1.382 (7)
Fe1—N1	2.168 (4)	C7—H7A	0.9300
C4—N2	1.318 (6)	O4—C2	1.243 (6)
C4—N1	1.350 (6)	O4—Fe1ⁱⁱ	2.128 (3)
C4—C3	1.504 (7)	C5—N2	1.321 (7)
O5—C3	1.240 (6)	C5—C6	1.362 (8)
O1—C1	1.263 (6)	C5—H5A	0.9300
N1—C7	1.317 (6)	C6—H6A	0.9300
O6—C3	1.325 (6)	C2—C1	1.540 (6)

O1—Fe1—O4ⁱ	162.87 (14)	C3—O6—H6	120.4
O1—Fe1—O3ⁱ	95.38 (13)	O5—C3—O6	124.0 (4)
O4ⁱ—Fe1—O3ⁱ	78.16 (13)	O5—C3—C4	119.7 (4)
O1—Fe1—O2	77.96 (12)	O6—C3—C4	116.3 (4)
O4ⁱ—Fe1—O2	86.49 (14)	C1—O3—Fe1ⁱⁱ	113.1 (3)
O3ⁱ—Fe1—O2	93.08 (14)	C2—O2—Fe1	111.3 (3)
O1—Fe1—O5	99.90 (14)	N1—C7—C6	121.9 (5)
O4ⁱ—Fe1—O5	95.90 (15)	N1—C7—H7A	119.1
O3ⁱ—Fe1—O5	89.29 (13)	C6—C7—H7A	119.1
O2—Fe1—O5	176.94 (13)	C2—O4—Fe1ⁱⁱ	113.7 (3)
O1—Fe1—N1	94.37 (14)	N2—C5—C6	124.4 (5)
O4ⁱ—Fe1—N1	95.72 (14)	N2—C5—H5A	117.8
O3ⁱ—Fe1—N1	163.96 (15)	C6—C5—H5A	117.8
O2—Fe1—N1	101.40 (14)	C5—C6—C7	115.9 (5)
O5—Fe1—N1	76.50 (14)	C5—C6—H6A	122.0
N2—C4—N1	126.2 (5)	C7—C6—H6A	122.0
N2—C4—C3	119.6 (4)	C4—N2—C5	115.0 (4)
N1—C4—C3	114.2 (4)	O4—C2—O2	125.8 (5)
C3—O5—Fe1	115.2 (3)	O4—C2—C1	117.4 (4)
C1—O1—Fe1	113.6 (3)	O2—C2—C1	116.8 (4)
C7—N1—C4	116.5 (4)	O3—C1—O1	126.2 (4)
C7—N1—Fe1	129.7 (4)	O3—C1—C2	117.3 (4)
C4—N1—Fe1	113.8 (3)	O1—C1—C2	116.5 (4)

O1—Fe1—O5—C3	−99.7 (4)	N1—C4—C3—O5	−2.3 (6)
O4ⁱ—Fe1—O5—C3	86.9 (4)	N2—C4—C3—O6	−4.2 (7)
O3ⁱ—Fe1—O5—C3	165.0 (4)	N1—C4—C3—O6	177.7 (4)
N1—Fe1—O5—C3	−7.5 (4)	O1—Fe1—O2—C2	−17.7 (3)
O4ⁱ—Fe1—O1—C1	−10.5 (6)	O4ⁱ—Fe1—O2—C2	155.1 (3)
O3ⁱ—Fe1—O1—C1	−77.3 (3)	O3ⁱ—Fe1—O2—C2	77.2 (3)
O2—Fe1—O1—C1	14.7 (3)	N1—Fe1—O2—C2	−109.8 (3)
O5—Fe1—O1—C1	−167.5 (3)	C4—N1—C7—C6	1.0 (7)
N1—Fe1—O1—C1	115.5 (3)	Fe1—N1—C7—C6	−178.9 (4)
N2—C4—N1—C7	−2.3 (7)	N2—C5—C6—C7	−2.2 (9)
C3—C4—N1—C7	175.7 (4)	N1—C7—C6—C5	1.0 (8)
N2—C4—N1—Fe1	177.7 (4)	N1—C4—N2—C5	1.2 (7)
C3—C4—N1—Fe1	−4.3 (5)	C3—C4—N2—C5	−176.7 (4)
O1—Fe1—N1—C7	−74.8 (4)	C6—C5—N2—C4	1.2 (8)
O4ⁱ—Fe1—N1—C7	91.3 (4)	Fe1ⁱⁱ—O4—C2—O2	−178.8 (4)
O3ⁱ—Fe1—N1—C7	157.9 (5)	Fe1ⁱⁱ—O4—C2—C1	1.0 (5)
O2—Fe1—N1—C7	3.8 (4)	Fe1—O2—C2—O4	−162.4 (4)
O5—Fe1—N1—C7	−174.0 (4)	Fe1—O2—C2—C1	17.8 (5)
O1—Fe1—N1—C4	105.3 (3)	Fe1ⁱⁱ—O3—C1—O1	−173.3 (4)
O4ⁱ—Fe1—N1—C4	−88.6 (3)	Fe1ⁱⁱ—O3—C1—C2	6.6 (5)
O3ⁱ—Fe1—N1—C4	−22.1 (7)	Fe1—O1—C1—O3	169.6 (4)
O2—Fe1—N1—C4	−176.2 (3)	Fe1—O1—C1—C2	−10.3 (5)
O5—Fe1—N1—C4	6.1 (3)	O4—C2—C1—O3	−5.4 (6)
Fe1—O5—C3—O6	−172.2 (4)	O2—C2—C1—O3	174.4 (4)
Fe1—O5—C3—C4	7.8 (6)	O4—C2—C1—O1	174.4 (4)
N2—C4—C3—O5	175.8 (5)	O2—C2—C1—O1	−5.7 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O3ⁱⁱⁱ	0.93	2.48	3.279 (6)	145
O6—H6···O1^iv	0.85	2.17	2.988 (5)	161
O6—H6···N2	0.85	2.40	2.743 (6)	105

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

Experimental details

Crystal data
Chemical formula	[Fe(C₂O₄)(C₅H₄N₂O₄)]
M_r	267.97
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	9.0524 (18), 9.1578 (18), 11.329 (2)
V (Å³)	939.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.62
Crystal size (mm)	0.2 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.780, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	7603, 1658, 1503
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.083, 1.11
No. of reflections	1658
No. of parameters	145
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.30
Absolute structure	Flack (1983), 783 Friedel pairs
Absolute structure parameter	0.05 (3)

Computer programs: SCXmini Benchtop Crystallography System Software (Rigaku, 2006), PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O3ⁱ	0.93	2.48	3.279 (6)	145
O6—H6···O1ⁱⁱ	0.85	2.17	2.988 (5)	161
O6—H6···N2	0.85	2.40	2.743 (6)	105

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

Acknowledgements

The authors acknowledge financial support from Tianjin Municipal Education Commission, Tianjin, People's Republic of China (grant No. 20060503).

References

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2006). SCXmini Benchtop Crystallography System Software. Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, J.-Y., Yue, Q., Jia, Q.-X., Cheng, A.-L. & Gao, E.-Q. (2008). CrystEngComm, 10 1443–1449. Web of Science CSD CrossRef CAS Google Scholar