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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): m817–m818.
Published online 2008 May 17. doi:  10.1107/S1600536808014207
PMCID: PMC2961397

μ-Aqua-bis­(μ-4-methyl­benzoato-κ2 O:O′)bis­[(4-methyl­benzoato-κO)(1,10-phenanthroline-κ2 N,N′)iron(II)]

Abstract

In the title binuclear complex, [Fe2(C8H7O2)4(C12H8N2)2(H2O)], the FeII ion is six-coordinated by three carboxylate O atoms from three 4-methyl­benzoate ligands, two N atoms from two 1,10-phenanthroline ligands and one bridging aqua ligand in a distorted octa­hedral geometry. The coordinated water mol­ecule acting as the bridging ligand is located on a twofold axes and the complex mol­ecule displays C 2 mol­ecular symmetry. The Fe(...)Fe separation in the binuclear complex is 3.490 (3) Å. The crystal structure is stabilized by hydrogen bonding and π–π stacking inter­actions [the centroid–centroid distance between adjacent 1,10-phenanthroline ring systems is 3.653 (2) Å, and that between the 1,10-phenanthroline ring system and the phenyl ring of the 4-methyl­benzoate unit of a neighbouring complex is 3.622 (3) Å].

Related literature

For related literature, see: Song et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m817-scheme1.jpg

Experimental

Crystal data

  • [Fe2(C8H7O2)4(C12H8N2)2(H2O)]
  • M r = 1030.67
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m817-efi2.jpg
  • a = 23.1987 (6) Å
  • b = 15.7222 (4) Å
  • c = 15.6464 (4) Å
  • β = 121.017 (1)°
  • V = 4890.8 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.66 mm−1
  • T = 296 (2) K
  • 0.20 × 0.19 × 0.16 mm

Data collection

  • Bruker APEXII area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.880, T max = 0.902
  • 31900 measured reflections
  • 5066 independent reflections
  • 3725 reflections with I > 2σ(I)
  • R int = 0.053

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.133
  • S = 1.05
  • 5066 reflections
  • 326 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014207/kp2167sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014207/kp2167Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The author acknowledges South China Normal University for supporting this work.

supplementary crystallographic information

Comment

In the structural investigation of 4-methylbenzoate complexes, it has been found that the 4-methylbenzoic acid functions as a multidentate ligand [Song et al. (2007)] with versatile binding and coordination modes. In this report, an iron(II) complex, (I) (Fig. 1) was obtained by the reaction of 4-methylbenzoic acid, 1,10-phenanthroline and ferrous chloride in alkaline aqueous solution.

A half of the binuclear complex is an asymmetric unit where FeII ion is in the distorted octahedral geometry with the six coordinating atoms: three carboxyl O atoms from two µ2-bridging 4-methylbenzoate ligands and one 4-methylbenzoate ligand, two N atoms from one chelating 1,10-phenanthroline ligands, and one µ2-bridging aqua ligand. The Fe···Fe separation is 3.490 (3) Å. The crystal packing is via O—H···O hydrogen bond (Table 1) and via two π-π stacking interactions (Fig. 2). The centroid to centroid distance between adjacent 1,10-phenanthroline rings (x, –y,-1/2 + z) is 3.653 (2) Å, whereas the centroid to centroid distance between 1,10-phenanthroline ring and phenyl ring of 4-methylbenzoate of neighbouring complexes (1/2 - x, 1/2 - y, 1 - z) is 3.622 (3) Å.

Experimental

A mixture of ferrous chloride (1 mmol), 4-methylbenzate (1 mmol), 1,10-phenanthroline (1 mmol), NaOH (1.5 mmol) and H2O (12 mL) was placed in a 23 mL Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h-1. The crystals obtained were washed with water and dryed in air.

Refinement

Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2 Ueq(C). Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.82 Å, and with Uiso(H) = 1.5 Ueq(O).

Figures

Fig. 1.
The structure of (I) showing the atomic numbering scheme. Non-H atoms are shown with the 30% probability displacement ellipsoids. Unlabelled atoms are related to the labelled atoms by the symmetry code (-x, y, 1/2 - z).
Fig. 2.
A packing view of the title compound.

Crystal data

[Fe2(C8H7O2)4(C12H8N2)2(H2O)]F000 = 2136
Mr = 1030.67Dx = 1.400 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5300 reflections
a = 23.1987 (6) Åθ = 1.3–28.0º
b = 15.7222 (4) ŵ = 0.66 mm1
c = 15.6464 (4) ÅT = 296 (2) K
β = 121.0170 (10)ºBlock, colourless
V = 4890.8 (2) Å30.20 × 0.19 × 0.16 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer5066 independent reflections
Radiation source: fine-focus sealed tube3725 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.053
T = 296(2) Kθmax = 26.5º
[var phi] and ω scansθmin = 1.7º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −29→29
Tmin = 0.880, Tmax = 0.902k = −19→19
31900 measured reflectionsl = −19→19

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.133  w = 1/[σ2(Fo2) + (0.0679P)2 + 3.2244P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
5066 reflectionsΔρmax = 0.30 e Å3
326 parametersΔρmin = −0.42 e Å3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/Ueq
Fe10.041139 (18)0.35596 (2)0.37994 (3)0.03908 (15)
C10.10393 (16)0.51103 (18)0.5379 (2)0.0495 (7)
H10.06240.53650.49660.059*
C20.15332 (18)0.5574 (2)0.6182 (2)0.0612 (9)
H20.14470.61260.63020.073*
C30.21397 (18)0.5211 (2)0.6784 (2)0.0664 (10)
H30.24740.55150.73210.080*
C40.22666 (15)0.4382 (2)0.6603 (2)0.0545 (8)
C50.28939 (16)0.3946 (3)0.7205 (2)0.0717 (11)
H50.32500.42290.77380.086*
C60.29761 (16)0.3135 (3)0.7014 (2)0.0691 (10)
H60.33890.28710.74170.083*
C70.24490 (14)0.2671 (2)0.6211 (2)0.0543 (8)
C80.25042 (16)0.1818 (2)0.5991 (3)0.0636 (9)
H80.29050.15240.63800.076*
C90.19760 (17)0.1427 (2)0.5217 (3)0.0624 (9)
H90.20030.08550.50860.075*
C100.13890 (15)0.18871 (19)0.4614 (2)0.0523 (7)
H100.10340.16160.40680.063*
C110.18322 (13)0.30873 (18)0.55822 (19)0.0432 (6)
C120.17422 (13)0.39593 (18)0.57830 (19)0.0414 (6)
C130.07480 (12)0.46759 (16)0.25133 (19)0.0360 (6)
C140.11705 (13)0.54627 (16)0.28046 (19)0.0384 (6)
C150.17772 (14)0.54973 (19)0.3703 (2)0.0507 (7)
H150.19110.50410.41430.061*
C160.21825 (16)0.6204 (2)0.3949 (3)0.0636 (9)
H160.25940.62090.45450.076*
C170.19931 (19)0.6901 (2)0.3334 (3)0.0633 (9)
C180.13827 (19)0.68755 (19)0.2446 (3)0.0609 (9)
H180.12450.73440.20230.073*
C190.09739 (15)0.61659 (17)0.2176 (2)0.0462 (6)
H190.05670.61580.15720.055*
C200.2436 (2)0.7685 (3)0.3605 (4)0.1012 (16)
H20A0.28910.75380.40970.152*
H20B0.22760.81140.38690.152*
H20C0.24220.79000.30200.152*
C21−0.03260 (13)0.21381 (18)0.4188 (2)0.0419 (6)
C22−0.04954 (13)0.17394 (19)0.4901 (2)0.0441 (6)
C23−0.05669 (16)0.2209 (2)0.5580 (2)0.0582 (8)
H23−0.05040.27950.56080.070*
C24−0.07324 (18)0.1821 (3)0.6230 (3)0.0715 (10)
H24−0.07910.21520.66720.086*
C25−0.08085 (18)0.0948 (3)0.6218 (3)0.0680 (9)
C26−0.07224 (18)0.0482 (2)0.5554 (3)0.0677 (9)
H26−0.0761−0.01070.55500.081*
C27−0.05788 (15)0.08647 (19)0.4887 (2)0.0545 (8)
H27−0.05380.05340.44280.065*
C28−0.0974 (2)0.0524 (3)0.6938 (3)0.1022 (15)
H28A−0.08680.09040.74800.153*
H28B−0.07140.00120.71940.153*
H28C−0.14440.03870.65960.153*
N10.11349 (11)0.43230 (14)0.51775 (15)0.0415 (5)
N20.13141 (10)0.26953 (14)0.47845 (16)0.0411 (5)
O10.09509 (9)0.40711 (12)0.31245 (14)0.0455 (5)
O20.02203 (9)0.46592 (11)0.16733 (14)0.0449 (5)
O3−0.01572 (10)0.29140 (12)0.43251 (15)0.0517 (5)
O4−0.03673 (11)0.16889 (14)0.35009 (15)0.0555 (5)
O1W0.00000.26095 (16)0.25000.0398 (6)
H1W0.0291 (12)0.2479 (17)0.227 (2)0.060*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Fe10.0366 (2)0.0383 (2)0.0366 (2)0.00068 (15)0.01482 (18)0.00227 (16)
C10.0582 (18)0.0447 (16)0.0424 (15)−0.0101 (14)0.0236 (14)−0.0025 (13)
C20.082 (2)0.0510 (19)0.0527 (18)−0.0247 (17)0.0359 (19)−0.0115 (15)
C30.068 (2)0.077 (2)0.0430 (17)−0.0399 (19)0.0213 (17)−0.0120 (17)
C40.0486 (17)0.071 (2)0.0358 (15)−0.0213 (15)0.0159 (14)0.0032 (14)
C50.0423 (18)0.105 (3)0.0417 (18)−0.0271 (19)0.0026 (15)0.0093 (19)
C60.0330 (16)0.102 (3)0.0511 (19)−0.0008 (18)0.0061 (15)0.023 (2)
C70.0357 (15)0.076 (2)0.0480 (17)0.0066 (14)0.0190 (14)0.0223 (15)
C80.0464 (18)0.080 (2)0.066 (2)0.0248 (17)0.0302 (18)0.0348 (19)
C90.056 (2)0.057 (2)0.074 (2)0.0179 (16)0.0329 (19)0.0174 (17)
C100.0472 (17)0.0490 (17)0.0554 (18)0.0086 (13)0.0226 (15)0.0087 (14)
C110.0321 (13)0.0574 (18)0.0361 (14)0.0012 (12)0.0147 (12)0.0144 (12)
C120.0354 (14)0.0525 (16)0.0314 (13)−0.0105 (12)0.0137 (12)0.0046 (12)
C130.0333 (13)0.0368 (14)0.0404 (14)−0.0016 (11)0.0208 (12)−0.0015 (11)
C140.0386 (14)0.0401 (14)0.0368 (14)−0.0034 (11)0.0197 (12)−0.0051 (11)
C150.0429 (16)0.0550 (18)0.0469 (16)−0.0032 (13)0.0180 (14)−0.0038 (14)
C160.0505 (19)0.072 (2)0.061 (2)−0.0193 (17)0.0235 (16)−0.0280 (18)
C170.075 (2)0.057 (2)0.074 (2)−0.0326 (17)0.050 (2)−0.0351 (18)
C180.093 (3)0.0361 (16)0.075 (2)−0.0073 (16)0.058 (2)−0.0052 (15)
C190.0534 (17)0.0385 (14)0.0468 (16)−0.0029 (13)0.0259 (14)−0.0041 (12)
C200.131 (4)0.081 (3)0.124 (4)−0.067 (3)0.089 (3)−0.058 (3)
C210.0306 (13)0.0470 (16)0.0458 (15)0.0021 (11)0.0180 (12)0.0079 (13)
C220.0338 (14)0.0513 (16)0.0443 (15)−0.0009 (12)0.0181 (13)0.0071 (13)
C230.065 (2)0.0578 (19)0.0601 (19)−0.0069 (16)0.0380 (17)0.0005 (16)
C240.079 (2)0.087 (3)0.066 (2)−0.008 (2)0.049 (2)−0.0042 (19)
C250.065 (2)0.085 (3)0.061 (2)−0.0109 (19)0.0369 (18)0.0139 (19)
C260.075 (2)0.057 (2)0.074 (2)−0.0110 (17)0.041 (2)0.0135 (18)
C270.0579 (19)0.0508 (18)0.0568 (18)−0.0047 (14)0.0311 (16)0.0045 (14)
C280.109 (3)0.126 (4)0.093 (3)−0.022 (3)0.068 (3)0.025 (3)
N10.0429 (13)0.0426 (13)0.0329 (11)−0.0052 (10)0.0152 (10)0.0019 (10)
N20.0356 (12)0.0418 (12)0.0402 (12)0.0033 (10)0.0155 (10)0.0072 (10)
O10.0432 (11)0.0407 (11)0.0543 (12)0.0012 (8)0.0263 (9)0.0097 (9)
O20.0400 (10)0.0427 (11)0.0442 (11)−0.0085 (8)0.0162 (9)−0.0041 (8)
O30.0583 (12)0.0442 (11)0.0649 (13)−0.0038 (9)0.0406 (11)0.0047 (9)
O40.0634 (13)0.0565 (12)0.0519 (12)−0.0118 (10)0.0334 (11)−0.0035 (10)
O1W0.0425 (15)0.0403 (14)0.0374 (14)0.0000.0211 (12)0.000

Geometric parameters (Å, °)

Fe1—O32.1365 (18)C14—C191.391 (4)
Fe1—O2i2.1369 (18)C15—C161.376 (4)
Fe1—O12.1657 (18)C15—H150.9300
Fe1—N12.275 (2)C16—C171.373 (5)
Fe1—O1W2.2970 (17)C16—H160.9300
Fe1—N22.298 (2)C17—C181.382 (5)
C1—N11.324 (4)C17—C201.519 (4)
C1—C21.393 (4)C18—C191.382 (4)
C1—H10.9300C18—H180.9300
C2—C31.352 (5)C19—H190.9300
C2—H20.9300C20—H20A0.9600
C3—C41.398 (5)C20—H20B0.9600
C3—H30.9300C20—H20C0.9600
C4—C121.400 (4)C21—O41.248 (3)
C4—C51.436 (5)C21—O31.265 (3)
C5—C61.346 (5)C21—C221.499 (4)
C5—H50.9300C22—C231.372 (4)
C6—C71.422 (5)C22—C271.387 (4)
C6—H60.9300C23—C241.398 (4)
C7—C81.406 (5)C23—H230.9300
C7—C111.412 (4)C24—C251.383 (5)
C8—C91.349 (5)C24—H240.9300
C8—H80.9300C25—C261.367 (5)
C9—C101.395 (4)C25—C281.519 (5)
C9—H90.9300C26—C271.387 (4)
C10—N21.328 (4)C26—H260.9300
C10—H100.9300C27—H270.9300
C11—N21.355 (3)C28—H28A0.9600
C11—C121.446 (4)C28—H28B0.9600
C12—N11.354 (3)C28—H28C0.9600
C13—O21.252 (3)O2—Fe1i2.1369 (18)
C13—O11.256 (3)O1W—Fe1i2.2970 (17)
C13—C141.496 (3)O1W—H1W0.938 (8)
C14—C151.386 (4)
O3—Fe1—O2i93.91 (7)C14—C15—H15119.8
O3—Fe1—O1172.16 (8)C17—C16—C15121.6 (3)
O2i—Fe1—O189.79 (7)C17—C16—H16119.2
O3—Fe1—N1100.73 (8)C15—C16—H16119.2
O2i—Fe1—N186.60 (8)C16—C17—C18118.3 (3)
O1—Fe1—N186.37 (7)C16—C17—C20121.8 (4)
O3—Fe1—O1W88.54 (6)C18—C17—C20120.0 (4)
O2i—Fe1—O1W108.77 (7)C19—C18—C17121.2 (3)
O1—Fe1—O1W83.73 (6)C19—C18—H18119.4
N1—Fe1—O1W161.62 (6)C17—C18—H18119.4
O3—Fe1—N289.48 (8)C18—C19—C14120.1 (3)
O2i—Fe1—N2159.38 (8)C18—C19—H19119.9
O1—Fe1—N289.47 (7)C14—C19—H19119.9
N1—Fe1—N272.79 (8)C17—C20—H20A109.5
O1W—Fe1—N291.64 (7)C17—C20—H20B109.5
N1—C1—C2122.9 (3)H20A—C20—H20B109.5
N1—C1—H1118.5C17—C20—H20C109.5
C2—C1—H1118.5H20A—C20—H20C109.5
C3—C2—C1119.0 (3)H20B—C20—H20C109.5
C3—C2—H2120.5O4—C21—O3124.9 (3)
C1—C2—H2120.5O4—C21—C22118.1 (3)
C2—C3—C4120.3 (3)O3—C21—C22117.0 (3)
C2—C3—H3119.8C23—C22—C27118.4 (3)
C4—C3—H3119.8C23—C22—C21122.3 (3)
C3—C4—C12117.0 (3)C27—C22—C21119.4 (3)
C3—C4—C5124.1 (3)C22—C23—C24121.0 (3)
C12—C4—C5118.9 (3)C22—C23—H23119.5
C6—C5—C4121.2 (3)C24—C23—H23119.5
C6—C5—H5119.4C25—C24—C23120.3 (3)
C4—C5—H5119.4C25—C24—H24119.8
C5—C6—C7121.8 (3)C23—C24—H24119.8
C5—C6—H6119.1C26—C25—C24118.3 (3)
C7—C6—H6119.1C26—C25—C28121.3 (4)
C8—C7—C11117.3 (3)C24—C25—C28120.4 (4)
C8—C7—C6124.0 (3)C25—C26—C27121.7 (3)
C11—C7—C6118.6 (3)C25—C26—H26119.2
C9—C8—C7120.0 (3)C27—C26—H26119.2
C9—C8—H8120.0C26—C27—C22120.2 (3)
C7—C8—H8120.0C26—C27—H27119.9
C8—C9—C10119.3 (3)C22—C27—H27119.9
C8—C9—H9120.4C25—C28—H28A109.5
C10—C9—H9120.4C25—C28—H28B109.5
N2—C10—C9123.0 (3)H28A—C28—H28B109.5
N2—C10—H10118.5C25—C28—H28C109.5
C9—C10—H10118.5H28A—C28—H28C109.5
N2—C11—C7122.0 (3)H28B—C28—H28C109.5
N2—C11—C12118.2 (2)C1—N1—C12118.0 (2)
C7—C11—C12119.8 (3)C1—N1—Fe1125.91 (19)
N1—C12—C4122.7 (3)C12—N1—Fe1115.70 (18)
N1—C12—C11117.6 (2)C10—N2—C11118.3 (2)
C4—C12—C11119.6 (3)C10—N2—Fe1126.82 (19)
O2—C13—O1124.3 (2)C11—N2—Fe1114.71 (17)
O2—C13—C14118.0 (2)C13—O1—Fe1124.66 (16)
O1—C13—C14117.7 (2)C13—O2—Fe1i120.36 (16)
C15—C14—C19118.5 (3)C21—O3—Fe1126.24 (18)
C15—C14—C13120.3 (2)Fe1—O1W—Fe1i98.87 (10)
C19—C14—C13121.1 (2)Fe1—O1W—H1W115.5 (18)
C16—C15—C14120.3 (3)Fe1i—O1W—H1W81.6 (18)
C16—C15—H15119.8

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1W···O4i0.938 (8)1.80 (2)2.578 (2)138 (2)

Symmetry codes: (i) −x, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KP2167).

References

  • Bruker (2004). APEX2 and SMART Bruker AXS Inc, Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Song, W.-D., Gu, C.-S., Hao, X.-M. & Liu, J.-W. (2007). Acta Cryst. E63, m1023–m1024.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography