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Acta Cryst. (2007). E63, m2534    [ doi:10.1107/S1600536807044091 ]

Poly[([mu]2-N,N-dimethylformamide-[kappa]2O:O)([mu]4-terephthalato-[kappa]4O:O':O'':O''')iron(II)]

H. Lu, Y.-L. Fu, Y. Zhang and S. W. Ng

Abstract top

In the crystal structure of the title compound, [Fe(C8H4O4)(C3H7NO)]n, the FeII atom and the terephthalate group occupy special positions of 2/m site symmetry. The FeII atom is octahedrally coordinated: two O atoms of two dimethylformamide molecules occupy the axial positions, and the equatorial sites are occupied by the carboxylate O atoms of four different terephthalate groups. The compound adopts a polymeric three-dimensional framework structure. The C and N atoms of the dimethylformamide ligand are disordered equally over two sites each, with further disorder of the H atoms.

Comment top

This study continues with the study on [(C8H4O4)(C3H7NO)Co]n (Fu et al., 2004; the present Fe(II) analog is isostructural with the Co(II) analog (Fu et al., 2004).

Related literature top

This FeII compound has the same structure as the CoII analogue (Fu et al., 2004).

Experimental top

Ferrous chloride tetrahydrate (0.198 g, 1 mmol), terephthalic acid (0.166 g, 1 mmol) and N,N-dimethylformamide (10 ml) were sealed in a 15-ml, Teflon-lined, stainless-steel bomb, which was heated at 433 K for 2 days. Red crystals were obtained when the bomb was cooled slowly to room temperature; yield 30% based on Fe.

Refinement top

The DMF molecule (comprising the O2, N1, C4, C5 and C6 atoms) lies on the Wyckoff 4 e site (of mm2 symmetry) and is disordered over two positions with respect to its carbon atoms only. As the disorder refined to almost 1/2, the occupancies of these carbon atoms was fixed as 1/4. The three N—C distances were restrained to within ±0.01 Å.

Hydrogen atoms were placed at calculated positions (C—H = 0.93 Å for the sp2 hybridized parent C atoms and 0.96 Å for the methyl C atoms) and were included in the refinements in the riding model approximation, with U(H) = 1.2Ueq for the aromatic H atoms and 1.5Ueq for the methyl H atoms. The two methyl groups were rotated so as to fit the electron density.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: Atomic coordinates taken from Fu et al. (2004); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) plot of a portion of [Fe(C8H4O4)(C3H7NO)]n. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are drawn as spheres of arbitrary radii. The disorder in the DMF molecules is not shown.
Poly[(µ2-N,N-dimethylformamide-κ2O:O) (µ4-terephthalato-κ4O:O':O'':O''')iron(II)] top
Crystal data top
[Fe(C8H4O4)(C3H7NO)]F000 = 600
Mr = 293.06Dx = 1.558 Mg m−3
Orthorhombic, ImmaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -I 2b 2Cell parameters from 2096 reflections
a = 19.3652 (15) Åθ = 2.5–28.5º
b = 7.2856 (6) ŵ = 1.22 mm−1
c = 8.8571 (7) ÅT = 295 (2) K
V = 1249.62 (17) Å3Block, red
Z = 40.25 × 0.19 × 0.08 mm
Data collection top
Bruker APEX area-detector
diffractometer		791 independent reflections
Radiation source: fine-focus sealed tube730 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 295(2) Kθmax = 27.5º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −25→24
Tmin = 0.357, Tmax = 0.909k = −9→7
3421 measured reflectionsl = −8→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.113  w = 1/[σ2(Fo2) + (0.0721P)2 + 1.8869P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
791 reflectionsΔρmax = 0.73 e Å−3
63 parametersΔρmin = −0.66 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Fe(C8H4O4)(C3H7NO)]V = 1249.62 (17) Å3
Mr = 293.06Z = 4
Orthorhombic, ImmaMo Kα
a = 19.3652 (15) ŵ = 1.22 mm−1
b = 7.2856 (6) ÅT = 295 (2) K
c = 8.8571 (7) Å0.25 × 0.19 × 0.08 mm
Data collection top
Bruker APEX area-detector
diffractometer		791 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		730 reflections with I > 2σ(I)
Tmin = 0.357, Tmax = 0.909Rint = 0.021
3421 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0403 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.08Δρmax = 0.73 e Å−3
791 reflectionsΔρmin = −0.66 e Å−3
63 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Fe10.50000.50000.50000.0209 (3)
O10.42136 (10)0.5968 (3)0.3639 (3)0.0461 (6)
O20.50000.75000.6390 (4)0.0333 (8)
N10.50000.75000.8974 (5)0.0533 (15)
C10.39343 (19)0.75000.3459 (5)0.0360 (8)
C20.31894 (19)0.75000.2960 (5)0.0390 (9)
C30.28393 (15)0.5876 (4)0.2733 (5)0.0630 (11)
H30.30640.47660.28960.076*
C40.5267 (4)0.75000.7594 (8)0.0380 (16)0.50
H40.57470.75000.75670.046*0.50
C50.5296 (7)0.75001.0396 (10)0.078 (4)0.50
H5A0.57760.78141.03150.117*0.25
H5B0.52520.63021.08370.117*0.25
H5C0.50660.83841.10220.117*0.25
C60.4266 (5)0.75000.9021 (13)0.088 (4)0.50
H6A0.41130.70100.99700.133*0.25
H6B0.40900.67560.82130.133*0.25
H6C0.40990.87340.89100.133*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0135 (4)0.0240 (4)0.0250 (4)0.0000.0000.0017 (2)
O10.0312 (9)0.0361 (11)0.0709 (13)0.0036 (8)−0.0270 (9)0.0003 (9)
O20.044 (2)0.0279 (17)0.0279 (17)0.0000.0000.000
N10.084 (4)0.046 (3)0.029 (2)0.0000.0000.000
C10.0266 (17)0.0360 (19)0.045 (2)0.000−0.0180 (15)0.000
C20.0261 (17)0.0346 (18)0.056 (2)0.000−0.0204 (16)0.000
C30.0374 (17)0.0293 (14)0.122 (3)0.0040 (11)−0.0381 (19)0.0023 (17)
C40.052 (4)0.029 (3)0.033 (3)0.000−0.006 (3)0.000
C50.136 (13)0.068 (7)0.030 (4)0.000−0.010 (6)0.000
C60.125 (12)0.094 (9)0.047 (6)0.0000.026 (7)0.000
Geometric parameters (Å, °) top
Fe1—O1i2.0663 (17)N1—C6iv1.422 (9)
Fe1—O1ii2.0663 (17)C1—O1v1.250 (2)
Fe1—O12.0663 (17)C1—C21.509 (5)
Fe1—O1iii2.0663 (17)C2—C31.378 (3)
Fe1—O22.199 (2)C2—C3v1.378 (3)
Fe1—O2i2.199 (2)C3—C3vi1.377 (5)
O1—C11.250 (2)C3—H30.9300
O2—C41.185 (8)C4—H40.9300
O2—C4iv1.185 (8)C5—H5A0.9600
O2—Fe1iv2.1987 (19)C5—H5B0.9600
N1—C4iv1.327 (7)C5—H5C0.9600
N1—C41.327 (7)C6—H6A0.9600
N1—C51.384 (8)C6—H6B0.9600
N1—C5iv1.384 (8)C6—H6C0.9600
N1—C61.422 (9)
O1i—Fe1—O1ii85.05 (13)C4iv—N1—C668.7 (6)
O1i—Fe1—O1180.0C4—N1—C6114.6 (7)
O1ii—Fe1—O194.95 (13)C5—N1—C6112.8 (8)
O1i—Fe1—O1iii94.95 (13)C5iv—N1—C663.9 (8)
O1ii—Fe1—O1iii180.00 (7)C4iv—N1—C6iv114.6 (7)
O1—Fe1—O1iii85.05 (13)C4—N1—C6iv68.7 (6)
O1i—Fe1—O287.49 (7)C5—N1—C6iv63.9 (8)
O1ii—Fe1—O292.51 (7)C5iv—N1—C6iv112.8 (8)
O1—Fe1—O292.51 (7)C6—N1—C6iv176.7 (10)
O1iii—Fe1—O287.49 (7)O1v—C1—O1126.4 (3)
O1i—Fe1—O2i92.51 (7)O1v—C1—C2116.81 (16)
O1ii—Fe1—O2i87.49 (7)O1—C1—C2116.81 (16)
O1—Fe1—O2i87.49 (7)C3—C2—C3v118.3 (3)
O1iii—Fe1—O2i92.51 (7)C3—C2—C1120.87 (17)
O2—Fe1—O2i180.0C3v—C2—C1120.87 (17)
C1—O1—Fe1134.27 (19)C3vi—C3—C2120.86 (17)
C4—O2—C4iv51.8 (8)C3vi—C3—H3119.6
C4—O2—Fe1120.26 (12)C2—C3—H3119.6
C4iv—O2—Fe1120.26 (12)O2—C4—N1131.1 (7)
C4—O2—Fe1iv120.26 (12)O2—C4—H4114.4
C4iv—O2—Fe1iv120.26 (12)N1—C4—H4114.4
Fe1—O2—Fe1iv111.87 (15)N1—C5—H5A109.5
C4iv—N1—C445.9 (7)N1—C5—H5B109.5
C4iv—N1—C5178.5 (7)N1—C5—H5C109.5
C4—N1—C5132.6 (6)N1—C6—H6A109.5
C4iv—N1—C5iv132.6 (6)N1—C6—H6B109.5
C4—N1—C5iv178.5 (7)N1—C6—H6C109.5
C5—N1—C5iv49.0 (12)
O1ii—Fe1—O1—C1−80.3 (4)Fe1—O1—C1—O1v29.3 (7)
O1iii—Fe1—O1—C199.7 (4)Fe1—O1—C1—C2−151.3 (3)
O2—Fe1—O1—C112.5 (3)O1v—C1—C2—C3180.0 (4)
O2i—Fe1—O1—C1−167.5 (3)O1—C1—C2—C30.6 (6)
O1i—Fe1—O2—C4−17.2 (4)O1v—C1—C2—C3v−0.6 (6)
O1ii—Fe1—O2—C4−102.1 (4)O1—C1—C2—C3v180.0 (4)
O1—Fe1—O2—C4162.8 (4)C3v—C2—C3—C3vi1.0 (10)
O1iii—Fe1—O2—C477.9 (4)C1—C2—C3—C3vi−179.6 (5)
O1i—Fe1—O2—C4iv−77.9 (5)C4iv—O2—C4—N10.0
O1ii—Fe1—O2—C4iv−162.8 (4)Fe1—O2—C4—N1−106.5 (2)
O1—Fe1—O2—C4iv102.1 (5)Fe1iv—O2—C4—N1106.5 (2)
O1iii—Fe1—O2—C4iv17.2 (4)C4iv—N1—C4—O20.0
O1i—Fe1—O2—Fe1iv132.46 (6)C5iv—N1—C4—O20.00 (5)
O1ii—Fe1—O2—Fe1iv47.54 (6)C6—N1—C4—O20.000 (2)
O1—Fe1—O2—Fe1iv−47.54 (6)C6iv—N1—C4—O2180.000 (2)
O1iii—Fe1—O2—Fe1iv−132.46 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, z; (iii) x, −y+1, −z+1; (iv) −x+1, −y+3/2, z; (v) x, −y+3/2, z; (vi) −x+1/2, y, −z+1/2.
Acknowledgements top

The authors thank the Natural Scientific Foundation Committee of Shanxi Province (grant No. 20041031) and the University of Malaya for generously supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2002). SAINT (Version 6.36A) and SMART (Version ?). Bruker AXS Inc., Madison, Winsonsin, USA. [These programs do not have concurrent version numbers. Please give the correct values]

Fu, Y.-L., Ren, J.-L. & Ng, S. W. (2004). Acta Cryst. E60, m1507–m1509.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.