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Acta Cryst. (2008). E64, m728    [ doi:10.1107/S1600536808011045 ]

Poly[([mu]3-nicotinato-[kappa]3O:O':N)([mu]2-nicotinato-[kappa]3O,O':N)iron(II)]

S. W. Ng

Abstract top

In the crystal structure of the title compound, [Fe(C6H4NO2)2]n, one nicotinate group O,O'-chelates one Fe atom and binds through the N atom to the other Fe atom; the second nicotinate group bridges three Fe atoms through the N and two O atoms. The [mu]2- and [mu]3-bridging modes of the two nicotinate groups result in a polymeric three-dimensional network structure. The Fe atom shows octahedral coordination geometry but one of the Fe-O bonds is somewhat long [2.522 (2) Å].

Comment top

The crystal structures of a large number of divalent metal dinicotinates are known; the compounds exists as water-coordinated compounds in which the nicotinate ion binds through the aromatic N atom and not through the carboxyl group, as exemplified by tetraaquadinicotinatoiron(II). The report on this compound lists the crystal structures of tetraaquametal dinicotinates (Liang et al., 2005). Tetraaquadinicotinatoiron is synthesized by reaction of the metal salt with nicotinic acid under aqueous conditions; under hydrothermal conditions, the synthesis has yielded the anhydrous compound (I). Iron dinicotinate (Fig. 1) has the nicotinate group engaged into two types of bridging interactions; one group O,O'-chelate to one Fe atom and binds through the N atom to the other Fe atom; the second nicotinate group bridges three Fe atoms through the N and two O atoms. The µ2 and µ3 bridging modes of the two nicotinate groups result in a polymeric three-dimensional network structure (Fig. 2). The Fe atom shows the common octahedral coordination geometry but one of the Fe–O bonds is somewhat long (Table 1).

Related literature top

For zwitterionc tetraaquadi(nicotinato-κN)iron(II), see: Liang et al. (2005).

Experimental top

Iron powder (0.056 g, 1 mmol), nicotinic acid (0.218 g 2 mmol) and water (10 ml) heated in a 23-ml, Teflon-lined, Parr bomb at 423 K for 3 days. The bomb was cooled to room temperature at a rate of 10 K per min to give yellow block-shaped crystals (in 10% yield based on nicotinic acid rate of 10 oC.h-1. The yellow block crystals of iron dinicoinate were obtained (yield 8.2% based on nicotinic acid).

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001) and OLEX (Dolomanov et al., 2003); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. 50% Probability thermal ellipsoid plot illustrating the octahedral geometry at iron.
[Figure 2] Fig. 2. OLEX (Dolomanov et al., 2003) illustration of the three-dimensional network motif.
Poly[(µ3-nicotinato-κ3O:O':N)(µ2-nicotinato- κ3O,O':N)iron(II)] top
Crystal data top
[Fe(C6H4NO2)2]F000 = 608
Mr = 300.05Dx = 1.612 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6064 reflections
a = 10.8771 (7) Åθ = 2.1–27.5º
b = 9.6066 (6) ŵ = 1.23 mm−1
c = 12.7284 (8) ÅT = 295 (2) K
β = 111.619 (1)ºBlock, yellow
V = 1236.5 (1) Å30.41 × 0.34 × 0.25 mm
Z = 4
Data collection top
Bruker APEX
diffractometer		2762 independent reflections
Radiation source: fine-focus sealed tube2428 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
T = 295(2) Kθmax = 27.5º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→14
Tmin = 0.564, Tmax = 0.749k = −10→12
7255 measured reflectionsl = −13→16
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)] = 0.028H-atom parameters constrained
wR(F2) = 0.078  w = 1/[σ2(Fo2) + (0.0475P)2 + 0.2265P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2762 reflectionsΔρmax = 0.24 e Å−3
172 parametersΔρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Fe(C6H4NO2)2]V = 1236.5 (1) Å3
Mr = 300.05Z = 4
Monoclinic, P21/nMo Kα
a = 10.8771 (7) ŵ = 1.23 mm−1
b = 9.6066 (6) ÅT = 295 (2) K
c = 12.7284 (8) Å0.41 × 0.34 × 0.25 mm
β = 111.619 (1)º
Data collection top
Bruker APEX
diffractometer		2762 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2428 reflections with I > 2σ(I)
Tmin = 0.564, Tmax = 0.749Rint = 0.018
7255 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028172 parameters
wR(F2) = 0.078H-atom parameters constrained
S = 1.02Δρmax = 0.24 e Å−3
2762 reflectionsΔρmin = −0.27 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.40603 (2)0.37707 (2)0.580119 (18)0.02707 (10)
O10.28044 (15)0.19952 (16)0.64714 (12)0.0540 (4)
O20.43525 (13)0.34442 (14)0.74858 (11)0.0398 (3)
O30.32118 (11)0.33429 (14)0.41409 (10)0.0345 (3)
O40.45693 (13)0.46511 (14)0.36328 (12)0.0477 (3)
N10.25364 (13)0.02956 (15)0.94060 (12)0.0335 (3)
N20.06748 (13)0.27149 (15)0.09200 (12)0.0335 (3)
C10.35420 (18)0.24585 (18)0.73955 (15)0.0371 (4)
C20.35386 (17)0.18565 (18)0.84835 (14)0.0336 (4)
C30.25803 (17)0.09027 (18)0.84724 (15)0.0344 (4)
H30.19320.06710.77800.041*
C40.34759 (18)0.0657 (2)1.03903 (15)0.0396 (4)
H40.34620.02461.10470.048*
C50.4460 (2)0.1601 (2)1.04838 (16)0.0450 (5)
H50.50900.18241.11870.054*
C60.44980 (18)0.2211 (2)0.95150 (16)0.0415 (4)
H60.51560.28490.95540.050*
C70.35595 (15)0.39427 (16)0.34127 (14)0.0283 (3)
C80.26579 (15)0.37708 (15)0.22048 (14)0.0281 (3)
C90.15745 (16)0.29047 (17)0.19585 (13)0.0314 (3)
H90.14640.24240.25520.038*
C100.08654 (19)0.3417 (2)0.00799 (15)0.0400 (4)
H100.02510.3306−0.06510.048*
C110.19213 (19)0.4291 (2)0.02432 (15)0.0432 (4)
H110.20130.4753−0.03660.052*
C120.28458 (18)0.44749 (18)0.13239 (15)0.0368 (4)
H120.35720.50540.14560.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.02436 (14)0.03310 (15)0.01968 (14)−0.00138 (8)0.00333 (10)−0.00096 (8)
O10.0695 (10)0.0593 (9)0.0300 (7)−0.0046 (8)0.0145 (7)0.0019 (6)
O20.0405 (7)0.0448 (7)0.0379 (7)0.0017 (6)0.0188 (6)0.0113 (5)
O30.0304 (6)0.0479 (7)0.0207 (6)−0.0014 (5)0.0042 (5)−0.0011 (5)
O40.0393 (7)0.0507 (8)0.0417 (8)−0.0193 (6)0.0014 (6)−0.0023 (6)
N10.0301 (7)0.0397 (8)0.0282 (7)−0.0009 (6)0.0080 (6)0.0040 (6)
N20.0311 (7)0.0408 (8)0.0225 (7)−0.0059 (6)0.0027 (6)0.0003 (6)
C10.0419 (9)0.0396 (9)0.0332 (9)0.0092 (8)0.0176 (8)0.0055 (7)
C20.0358 (9)0.0359 (9)0.0311 (9)0.0018 (7)0.0146 (7)0.0027 (7)
C30.0331 (8)0.0396 (9)0.0267 (8)0.0007 (7)0.0065 (7)0.0021 (7)
C40.0389 (9)0.0504 (11)0.0267 (9)−0.0055 (8)0.0089 (7)0.0053 (8)
C50.0426 (10)0.0566 (12)0.0285 (9)−0.0122 (9)0.0045 (8)0.0005 (8)
C60.0403 (9)0.0462 (10)0.0368 (10)−0.0110 (8)0.0127 (8)0.0018 (8)
C70.0255 (8)0.0286 (8)0.0262 (8)0.0026 (6)0.0044 (6)−0.0032 (6)
C80.0270 (8)0.0311 (8)0.0240 (8)−0.0006 (6)0.0066 (6)−0.0023 (6)
C90.0305 (8)0.0383 (9)0.0224 (8)−0.0044 (7)0.0061 (6)0.0015 (6)
C100.0433 (10)0.0458 (10)0.0222 (8)−0.0046 (8)0.0017 (7)0.0014 (7)
C110.0519 (11)0.0481 (10)0.0274 (9)−0.0099 (9)0.0121 (8)0.0059 (8)
C120.0378 (9)0.0398 (9)0.0313 (9)−0.0093 (7)0.0109 (7)0.0003 (7)
Geometric parameters (Å, °) top
Fe1—O12.522 (2)C2—C31.384 (2)
Fe1—O22.072 (1)C2—C61.385 (3)
Fe1—O32.012 (1)C3—H30.9300
Fe1—O4i2.061 (1)C4—C51.375 (3)
Fe1—N1ii2.212 (1)C4—H40.9300
Fe1—N2iii2.224 (1)C5—C61.379 (3)
O1—C11.237 (2)C5—H50.9300
O2—C11.270 (2)C6—H60.9300
O3—C71.262 (2)C7—C81.497 (2)
O4—C71.233 (2)C8—C91.381 (2)
O4—Fe1i2.0611 (12)C8—C121.388 (2)
N1—C41.338 (2)C9—H90.9300
N1—C31.340 (2)C10—C111.375 (3)
N1—Fe1iv2.2124 (14)C10—H100.9300
N2—C91.336 (2)C11—C121.384 (2)
N2—C101.343 (2)C11—H110.9300
N2—Fe1v2.2243 (14)C12—H120.9300
C1—C21.502 (2)
O1—Fe1—O256.18 (5)N1—C3—C2123.49 (16)
O1—Fe1—O396.95 (5)N1—C3—H3118.3
O1—Fe1—O4i142.30 (5)C2—C3—H3118.3
O1—Fe1—N1ii89.36 (5)N1—C4—C5123.64 (17)
O1—Fe1—N2iii93.18 (5)N1—C4—H4118.2
O2—Fe1—O3153.10 (6)C5—C4—H4118.2
O2—Fe1—O4i86.23 (5)C4—C5—C6118.78 (18)
O2—Fe1—N1ii92.17 (5)C4—C5—H5120.6
O2—Fe1—N2iii90.93 (5)C6—C5—H5120.6
O3—Fe1—O4i120.67 (6)C5—C6—C2118.87 (17)
O3—Fe1—N1ii88.50 (5)C5—C6—H6120.6
O3—Fe1—N2iii89.17 (5)C2—C6—H6120.6
O4i—Fe1—N1ii89.39 (6)O4—C7—O3124.60 (16)
O4i—Fe1—N2iii89.83 (6)O4—C7—C8119.06 (15)
N1ii—Fe1—N2iii176.74 (5)O3—C7—C8116.33 (14)
C1—O1—Fe180.56 (11)C9—C8—C12118.53 (15)
C1—O2—Fe1100.52 (11)C9—C8—C7118.75 (15)
C7—O3—Fe1122.17 (11)C12—C8—C7122.70 (15)
C7—O4—Fe1i162.57 (13)N2—C9—C8124.03 (15)
C4—N1—C3116.93 (15)N2—C9—H9118.0
C4—N1—Fe1iv125.34 (12)C8—C9—H9118.0
C3—N1—Fe1iv117.73 (11)N2—C10—C11123.46 (16)
C9—N2—C10116.58 (14)N2—C10—H10118.3
C9—N2—Fe1v115.27 (11)C11—C10—H10118.3
C10—N2—Fe1v128.13 (12)C10—C11—C12119.27 (17)
O1—C1—O2122.67 (17)C10—C11—H11120.4
O1—C1—C2121.14 (17)C12—C11—H11120.4
O2—C1—C2116.18 (16)C11—C12—C8118.12 (16)
C3—C2—C6118.28 (16)C11—C12—H12120.9
C3—C2—C1120.21 (16)C8—C12—H12120.9
C6—C2—C1121.49 (16)
O3—Fe1—O1—C1177.00 (11)C1—C2—C3—N1178.18 (15)
O4i—Fe1—O1—C1−6.40 (16)C3—N1—C4—C50.0 (3)
O2—Fe1—O1—C1−1.54 (10)Fe1iv—N1—C4—C5179.39 (16)
N1ii—Fe1—O1—C1−94.59 (11)N1—C4—C5—C6−0.4 (3)
N2iii—Fe1—O1—C187.45 (11)C4—C5—C6—C20.4 (3)
O3—Fe1—O2—C1−1.69 (18)C3—C2—C6—C50.1 (3)
O4i—Fe1—O2—C1178.53 (11)C1—C2—C6—C5−178.59 (17)
N1ii—Fe1—O2—C189.28 (11)Fe1i—O4—C7—O3−68.9 (5)
N2iii—Fe1—O2—C1−91.70 (11)Fe1i—O4—C7—C8110.7 (4)
O1—Fe1—O2—C11.51 (10)Fe1—O3—C7—O412.9 (2)
O4i—Fe1—O3—C75.56 (14)Fe1—O3—C7—C8−166.66 (10)
O2—Fe1—O3—C7−174.18 (11)O4—C7—C8—C9175.90 (15)
N1ii—Fe1—O3—C793.97 (13)O3—C7—C8—C9−4.5 (2)
N2iii—Fe1—O3—C7−83.75 (13)O4—C7—C8—C12−5.9 (2)
O1—Fe1—O3—C7−176.85 (12)O3—C7—C8—C12173.73 (15)
Fe1—O1—C1—O22.49 (16)C10—N2—C9—C80.4 (3)
Fe1—O1—C1—C2−176.46 (16)Fe1v—N2—C9—C8179.22 (13)
Fe1—O2—C1—O1−3.0 (2)C12—C8—C9—N2−1.1 (3)
Fe1—O2—C1—C2175.95 (12)C7—C8—C9—N2177.20 (15)
O1—C1—C2—C3−9.1 (3)C9—N2—C10—C110.3 (3)
O2—C1—C2—C3171.91 (16)Fe1v—N2—C10—C11−178.38 (15)
O1—C1—C2—C6169.55 (18)N2—C10—C11—C12−0.2 (3)
O2—C1—C2—C6−9.5 (2)C10—C11—C12—C8−0.5 (3)
C4—N1—C3—C20.4 (3)C9—C8—C12—C111.1 (3)
Fe1iv—N1—C3—C2−178.97 (13)C7—C8—C12—C11−177.12 (16)
C6—C2—C3—N1−0.5 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+1/2, y−1/2, −z+3/2; (v) x−1/2, −y+1/2, z−1/2.
Table 1
Selected geometric parameters (Å, °) top
Fe1—O12.522 (2)Fe1—O4i2.061 (1)
Fe1—O22.072 (1)Fe1—N1ii2.212 (1)
Fe1—O32.012 (1)Fe1—N2iii2.224 (1)
O1—Fe1—O256.18 (5)O2—Fe1—N2iii90.93 (5)
O1—Fe1—O396.95 (5)O3—Fe1—O4i120.67 (6)
O1—Fe1—O4i142.30 (5)O3—Fe1—N1ii88.50 (5)
O1—Fe1—N1ii89.36 (5)O3—Fe1—N2iii89.17 (5)
O1—Fe1—N2iii93.18 (5)O4i—Fe1—N1ii89.39 (6)
O2—Fe1—O3153.10 (6)O4i—Fe1—N2iii89.83 (6)
O2—Fe1—O4i86.23 (5)N1ii—Fe1—N2iii176.74 (5)
O2—Fe1—N1ii92.17 (5)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x+1/2, −y+1/2, z+1/2.
Acknowledgements top

I thank Mr Yan-Zhen Zheng of Sun Yat-Sen University for synthesizing the compound and measuring the crystal and the University of Malaya for supporting this study.

references
References top

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Westrip, S. P. (2008). publCIF. In preparation.