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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m877.
Published online 2009 July 8. doi:  10.1107/S1600536809025628
PMCID: PMC2977407

1,4-Diazo­niabicyclo­[2.2.2]octane diaqua­dichlorido­(oxalato-κ2 O,O′)iron(III) chloride

Abstract

In the title compound, (C6H14N2)[Fe(C2O4)Cl2(H2O)2]Cl, all ions are situated on twofold rotational axes. The FeIII ion is coordinated by two O atoms from a chelating oxalate ligand, two water mol­ecules and two chloride anions in a distorted octa­hedral geometry. Inter­molecular N—H(...)O, O—H(...)O and O—H(...)Cl hydrogen bonds form an extensive three-dimensional network which consolidates the crystal packing.

Related literature

For the crystal structures of related compounds, see: Fu et al. (2002 [triangle]); Keene et al. (2004 [triangle]); Sukhendu & Srinivasan (2007 [triangle]); Zhao & Xu (2008 [triangle]); Lee & Wang (1999 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m877-scheme1.jpg

Experimental

Crystal data

  • (C6H14N2)[Fe(C2O4)Cl2(H2O)2]Cl
  • M r = 400.44
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m877-efi1.jpg
  • a = 9.872 (2) Å
  • b = 9.6636 (19) Å
  • c = 8.4268 (17) Å
  • β = 109.57 (3)°
  • V = 757.4 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.55 mm−1
  • T = 293 K
  • 0.30 × 0.30 × 0.20 mm

Data collection

  • Rigaku Mercury CCD diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.638, T max = 0.734
  • 3954 measured reflections
  • 1729 independent reflections
  • 1684 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.020
  • wR(F 2) = 0.049
  • S = 1.08
  • 1729 reflections
  • 101 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.15 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 802 Friedel pairs
  • Flack parameter: 0.016 (13)

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025628/cv2580sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025628/cv2580Isup2.hkl

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

supplementary crystallographic information

Comment

Oxalic acid is often used as bridging ligand, which can adopt different coordination modes according to the different geometric requirements of metal centers when forming metal complexes (Sukhendu & Srinivasan, 2007; Zhao & Xu, 2008). We report here the crystal structure of the title compound, (1).

The stucture of (1) is shown in Fig. 1. This yellow ionic compound crystallizes in the monoclinic space group C2. It contains [Fe(ox)(H2O)2Cl2]- (ox is oxalate, C2O4) units, in which the FeIII ion is coordinated by two O atoms from a chelating oxalato ion, two O atoms from coordinated water molecules and two Cl anions, forming a distorted octahedron coordination geometry. The crystal packing is stabilized by N—H···O, O—H···O and O—H···Cl hydrogen bonds (Table 1, Fig. 2).

Experimental

A mixture of oxalic acid (0.01 mol 0.9 g) and iron(III) chloride (0.01 mol 1.62 g) and the 1,4-diaza-bicyclo[2.2.2]octane (dabco) (0.01 mol 1.12 g) in H2O (20 ml) was stirred until clear. Adjust the pH value of the solution to 4 with 10% HCl solution. After slow evaporation, yellow plate crystals of the title compand suitable for X-ray analysis were obtained with about 65% yield (based on Fe).

Refinement

H atoms bound to C and N atoms were positioned geometrically and refined as riding, with C—H = 0.97 and N—H = 0.91 Å, and with Uiso(H) = 1.2Ueq(parent atom). H atoms bound to O atoms were located in difference maps, but their O—H distances and H—O—H angles were restrained to the literature values.

Figures

Fig. 1.
A view of (1) with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. Symmetry codes: (A) -x, y, -z + 2; (B) -x + 1, y, -z + 1.
Fig. 2.
The crystal packing viewed along the a axis. Hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.

Crystal data

(C6H14N2)[Fe(C2O4)Cl2(H2O)2]ClF(000) = 410
Mr = 400.44Dx = 1.756 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 3950 reflections
a = 9.872 (2) Åθ = 3.0–27.5°
b = 9.6636 (19) ŵ = 1.55 mm1
c = 8.4268 (17) ÅT = 293 K
β = 109.57 (3)°Plate, yellow
V = 757.4 (3) Å30.30 × 0.30 × 0.20 mm
Z = 2

Data collection

Rigaku Mercury CCD diffractometer1729 independent reflections
Radiation source: fine-focus sealed tube1684 reflections with I > 2σ(I)
graphiteRint = 0.025
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)h = −12→12
Tmin = 0.638, Tmax = 0.734k = −12→12
3954 measured reflectionsl = −10→10

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.020w = 1/[σ2(Fo2) + (0.017P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.049(Δ/σ)max < 0.001
S = 1.08Δρmax = 0.17 e Å3
1729 reflectionsΔρmin = −0.15 e Å3
101 parametersExtinction correction: SHELXL97 (Sheldrick, 2008)
1 restraintExtinction coefficient: 0.0476 (15)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 802 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.016 (13)

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
Fe10.00001.02078 (3)1.00000.02213 (11)
Cl10.16532 (6)1.17560 (5)1.16036 (7)0.03727 (16)
Cl20.00000.85379 (10)0.50000.0462 (2)
N10.37619 (17)0.90236 (18)0.3965 (2)0.0285 (4)
H10.28530.90210.32070.034*
C10.07314 (19)0.7358 (2)1.0751 (2)0.0242 (4)
C20.3777 (2)0.9825 (2)0.5494 (2)0.0377 (5)
H2A0.30470.94700.59220.045*
H2B0.35721.07920.52070.045*
C30.4750 (2)0.9679 (3)0.3179 (3)0.0393 (5)
H3A0.43861.05820.27350.047*
H3B0.48120.91110.22570.047*
C40.4218 (3)0.7572 (2)0.4454 (3)0.0464 (6)
H4A0.40880.70170.34540.056*
H4B0.36380.71760.50670.056*
O10.11725 (13)0.85657 (14)1.13039 (16)0.0273 (3)
O20.11176 (16)1.00290 (19)0.83598 (18)0.0354 (4)
O30.13212 (14)0.62670 (16)1.1287 (2)0.0375 (4)
H2WA0.199 (3)1.033 (3)0.859 (3)0.046 (7)*
H2WB0.075 (3)0.971 (4)0.741 (4)0.075 (10)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Fe10.01824 (19)0.0248 (2)0.01995 (18)0.0000.00185 (14)0.000
Cl10.0293 (3)0.0348 (3)0.0404 (3)−0.0041 (2)0.0021 (2)−0.0136 (2)
Cl20.0591 (5)0.0447 (5)0.0256 (4)0.0000.0019 (3)0.000
N10.0172 (8)0.0399 (10)0.0226 (8)−0.0024 (7)−0.0010 (7)0.0007 (7)
C10.0175 (9)0.0296 (10)0.0273 (9)0.0010 (7)0.0099 (8)0.0025 (7)
C20.0249 (10)0.0499 (15)0.0397 (11)0.0031 (9)0.0125 (9)−0.0086 (10)
C30.0269 (10)0.0608 (14)0.0304 (10)0.0065 (9)0.0098 (9)0.0190 (10)
C40.0521 (15)0.0290 (13)0.0477 (15)−0.0115 (11)0.0030 (13)−0.0061 (11)
O10.0207 (7)0.0276 (7)0.0262 (7)0.0018 (6)−0.0019 (5)0.0003 (6)
O20.0291 (8)0.0488 (10)0.0300 (7)−0.0128 (7)0.0122 (6)−0.0117 (8)
O30.0294 (7)0.0313 (8)0.0520 (10)0.0096 (6)0.0139 (7)0.0145 (7)

Geometric parameters (Å, °)

Fe1—O2i2.0443 (14)C1—C1i1.569 (4)
Fe1—O22.0443 (14)C2—C3ii1.515 (3)
Fe1—O1i2.0526 (14)C2—H2A0.9700
Fe1—O12.0526 (14)C2—H2B0.9700
Fe1—Cl12.2913 (8)C3—C2ii1.515 (3)
Fe1—Cl1i2.2913 (8)C3—H3A0.9700
N1—C41.489 (2)C3—H3B0.9700
N1—C31.491 (3)C4—C4ii1.509 (5)
N1—C21.499 (2)C4—H4A0.9700
N1—H10.9100C4—H4B0.9700
C1—O31.216 (2)O2—H2WA0.87 (3)
C1—O11.278 (2)O2—H2WB0.82 (3)
O2i—Fe1—O2170.30 (10)O1—C1—C1i113.78 (10)
O2i—Fe1—O1i87.78 (6)N1—C2—C3ii108.47 (16)
O2—Fe1—O1i84.72 (6)N1—C2—H2A110.0
O2i—Fe1—O184.72 (6)C3ii—C2—H2A110.0
O2—Fe1—O187.78 (6)N1—C2—H2B110.0
O1i—Fe1—O178.73 (8)C3ii—C2—H2B110.0
O2i—Fe1—Cl195.48 (5)H2A—C2—H2B108.4
O2—Fe1—Cl190.85 (5)N1—C3—C2ii108.72 (15)
O1i—Fe1—Cl1169.42 (4)N1—C3—H3A109.9
O1—Fe1—Cl191.53 (5)C2ii—C3—H3A109.9
O2i—Fe1—Cl1i90.85 (5)N1—C3—H3B109.9
O2—Fe1—Cl1i95.48 (5)C2ii—C3—H3B109.9
O1i—Fe1—Cl1i91.53 (5)H3A—C3—H3B108.3
O1—Fe1—Cl1i169.42 (4)N1—C4—C4ii108.77 (11)
Cl1—Fe1—Cl1i98.47 (4)N1—C4—H4A109.9
C4—N1—C3109.93 (18)C4ii—C4—H4A109.9
C4—N1—C2109.49 (17)N1—C4—H4B109.9
C3—N1—C2110.04 (18)C4ii—C4—H4B109.9
C4—N1—H1109.1H4A—C4—H4B108.3
C3—N1—H1109.1C1—O1—Fe1116.67 (12)
C2—N1—H1109.1Fe1—O2—H2WA122.9 (15)
O3—C1—O1126.47 (18)Fe1—O2—H2WB122 (2)
O3—C1—C1i119.75 (12)H2WA—O2—H2WB115 (3)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1iii0.911.932.814 (2)162
O2—H2WA···O3iv0.87 (3)1.86 (3)2.722 (2)168 (2)
O2—H2WB···Cl20.82 (3)2.23 (3)3.0359 (17)170 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2580).

References

  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Fu, Y. L., Liu, Y. L., Shi, Z., Li, B. Z. & Pang, W. Q. (2002). J. Solid State Chem.163, 427–435.
  • Keene, T. D., Hursthouse, M. B. & Price, D. J. (2004). Acta Cryst. E60, m378–m380.
  • Lee, M. Y. & Wang, S. L. (1999). Chem. Mater.11, 3588–3594.
  • Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sukhendu, M. & Srinivasan, N. (2007). Chem. Eur. J.13, 968–977. [PubMed]
  • Zhao, J. & Xu, L. (2008). Inorg. Chim. Acta, 361, 2385–2395.

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