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1,4-Diazo­niabi­cyclo­[2.2.2]octane di­aqua­di­chlorido­(oxalato-κ2O,O′)iron(III) chloride

aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: cyik@163.com

(Received 24 June 2009; accepted 2 July 2009; online 8 July 2009)

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[Fu, Y. L., Liu, Y. L., Shi, Z., Li, B. Z. & Pang, W. Q. (2002). J. Solid State Chem. 163, 427-435.]); Keene et al. (2004[Keene, T. D., Hursthouse, M. B. & Price, D. J. (2004). Acta Cryst. E60, m378-m380.]); Sukhendu & Srinivasan (2007[Sukhendu, M. & Srinivasan, N. (2007). Chem. Eur. J. 13, 968-977.]); Zhao & Xu (2008[Zhao, J. & Xu, L. (2008). Inorg. Chim. Acta, 361, 2385-2395.]); Lee & Wang (1999[Lee, M. Y. & Wang, S. L. (1999). Chem. Mater. 11, 3588-3594.]).

[Scheme 1]

Experimental

Crystal data
  • (C6H14N2)[Fe(C2O4)Cl2(H2O)2]Cl

  • Mr = 400.44

  • Monoclinic, C 2

  • 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.638, Tmax = 0.734

  • 3954 measured reflections

  • 1729 independent reflections

  • 1684 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.020

  • wR(F2) = 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[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 802 Friedel pairs

  • Flack parameter: 0.016 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.91 1.93 2.814 (2) 162
O2—H2WA⋯O3ii 0.87 (3) 1.86 (3) 2.722 (2) 168 (2)
O2—H2WB⋯Cl2 0.82 (3) 2.23 (3) 3.0359 (17) 170 (3)
Symmetry codes: (i) x, y, z-1; (ii) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+2].

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL/PC (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] 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.
[Figure 2] Fig. 2. The crystal packing viewed along the a axis. Hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.
1,4-Diazoniabicyclo[2.2.2]octane diaquadichlorido(oxalato-κ2O,O')iron(III) chloride top
Crystal data top
(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 top
Rigaku Mercury CCD
diffractometer
1729 independent reflections
Radiation source: fine-focus sealed tube1684 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
h = 1212
Tmin = 0.638, Tmax = 0.734k = 1212
3954 measured reflectionsl = 1010
Refinement top
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)] = 0.020 w = 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 mapAbsolute structure parameter: 0.016 (13)
Crystal data top
(C6H14N2)[Fe(C2O4)Cl2(H2O)2]ClV = 757.4 (3) Å3
Mr = 400.44Z = 2
Monoclinic, C2Mo Kα radiation
a = 9.872 (2) ŵ = 1.55 mm1
b = 9.6636 (19) ÅT = 293 K
c = 8.4268 (17) Å0.30 × 0.30 × 0.20 mm
β = 109.57 (3)°
Data collection top
Rigaku Mercury CCD
diffractometer
1729 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
1684 reflections with I > 2σ(I)
Tmin = 0.638, Tmax = 0.734Rint = 0.025
3954 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.020H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.049Δρmax = 0.17 e Å3
S = 1.08Δρmin = 0.15 e Å3
1729 reflectionsAbsolute structure: Flack (1983), 802 Friedel pairs
101 parametersAbsolute structure parameter: 0.016 (13)
1 restraint
Special details top

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) top
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) top
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, º) top
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, º) top
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, z1; (iv) x+1/2, y+1/2, z+2.

Experimental details

Crystal data
Chemical formula(C6H14N2)[Fe(C2O4)Cl2(H2O)2]Cl
Mr400.44
Crystal system, space groupMonoclinic, C2
Temperature (K)293
a, b, c (Å)9.872 (2), 9.6636 (19), 8.4268 (17)
β (°) 109.57 (3)
V3)757.4 (3)
Z2
Radiation typeMo Kα
µ (mm1)1.55
Crystal size (mm)0.30 × 0.30 × 0.20
Data collection
DiffractometerRigaku Mercury CCD
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.638, 0.734
No. of measured, independent and
observed [I > 2σ(I)] reflections
3954, 1729, 1684
Rint0.025
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.049, 1.08
No. of reflections1729
No. of parameters101
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.15
Absolute structureFlack (1983), 802 Friedel pairs
Absolute structure parameter0.016 (13)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.911.932.814 (2)162.3
O2—H2WA···O3ii0.87 (3)1.86 (3)2.722 (2)168 (2)
O2—H2WB···Cl20.82 (3)2.23 (3)3.0359 (17)170 (3)
Symmetry codes: (i) x, y, z1; (ii) x+1/2, y+1/2, z+2.
 

References

First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationFu, Y. L., Liu, Y. L., Shi, Z., Li, B. Z. & Pang, W. Q. (2002). J. Solid State Chem. 163, 427–435.  Web of Science CSD CrossRef CAS Google Scholar
First citationKeene, T. D., Hursthouse, M. B. & Price, D. J. (2004). Acta Cryst. E60, m378–m380.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLee, M. Y. & Wang, S. L. (1999). Chem. Mater. 11, 3588–3594.  Web of Science CSD CrossRef CAS Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSukhendu, M. & Srinivasan, N. (2007). Chem. Eur. J. 13, 968–977.  PubMed Google Scholar
First citationZhao, J. & Xu, L. (2008). Inorg. Chim. Acta, 361, 2385–2395.  Web of Science CSD CrossRef CAS Google Scholar

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