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

Cai, Y.

doi:10.1107/S1600536809025628

metal-organic compounds

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Volume 65| Part 8| August 2009| Page m877

doi:10.1107/S1600536809025628

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

Ying Cai ^a ^*

^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 Fe^III 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 ); Keene et al. (2004 ); Sukhendu & Srinivasan (2007 ); Zhao & Xu (2008 ); Lee & Wang (1999 ).

Experimental

Crystal data

(C₆H₁₄N₂)[Fe(C₂O₄)Cl₂(H₂O)₂]Cl
M_r = 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 ) 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[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
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ), 802 Friedel pairs
Flack parameter: 0.016 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

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

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

checkCIF report

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 Fe^III 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).

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

	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.

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

Crystal data top

(C₆H₁₄N₂)[Fe(C₂O₄)Cl₂(H₂O)₂]Cl	F(000) = 410
M_r = 400.44	D_x = 1.756 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 3950 reflections
a = 9.872 (2) Å	θ = 3.0–27.5°
b = 9.6636 (19) Å	µ = 1.55 mm⁻¹
c = 8.4268 (17) Å	T = 293 K
β = 109.57 (3)°	Plate, yellow
V = 757.4 (3) Å³	0.30 × 0.30 × 0.20 mm
Z = 2

Data collection top

Rigaku Mercury CCD diffractometer	1729 independent reflections
Radiation source: fine-focus sealed tube	1684 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −12→12
T_min = 0.638, T_max = 0.734	k = −12→12
3954 measured reflections	l = −10→10

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.020	w = 1/[σ²(F_o²) + (0.017P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.049	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.17 e Å⁻³
1729 reflections	Δρ_min = −0.15 e Å⁻³
101 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
1 restraint	Extinction coefficient: 0.0476 (15)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 802 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.016 (13)

Crystal data top

(C₆H₁₄N₂)[Fe(C₂O₄)Cl₂(H₂O)₂]Cl	V = 757.4 (3) Å³
M_r = 400.44	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 9.872 (2) Å	µ = 1.55 mm⁻¹
b = 9.6636 (19) Å	T = 293 K
c = 8.4268 (17) Å	0.30 × 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)
T_min = 0.638, T_max = 0.734	R_int = 0.025
3954 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.049	Δρ_max = 0.17 e Å⁻³
S = 1.08	Δρ_min = −0.15 e Å⁻³
1729 reflections	Absolute structure: Flack (1983), 802 Friedel pairs
101 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
Fe1	0.0000	1.02078 (3)	1.0000	0.02213 (11)
Cl1	0.16532 (6)	1.17560 (5)	1.16036 (7)	0.03727 (16)
Cl2	0.0000	0.85379 (10)	0.5000	0.0462 (2)
N1	0.37619 (17)	0.90236 (18)	0.3965 (2)	0.0285 (4)
H1	0.2853	0.9021	0.3207	0.034*
C1	0.07314 (19)	0.7358 (2)	1.0751 (2)	0.0242 (4)
C2	0.3777 (2)	0.9825 (2)	0.5494 (2)	0.0377 (5)
H2A	0.3047	0.9470	0.5922	0.045*
H2B	0.3572	1.0792	0.5207	0.045*
C3	0.4750 (2)	0.9679 (3)	0.3179 (3)	0.0393 (5)
H3A	0.4386	1.0582	0.2735	0.047*
H3B	0.4812	0.9111	0.2257	0.047*
C4	0.4218 (3)	0.7572 (2)	0.4454 (3)	0.0464 (6)
H4A	0.4088	0.7017	0.3454	0.056*
H4B	0.3638	0.7176	0.5067	0.056*
O1	0.11725 (13)	0.85657 (14)	1.13039 (16)	0.0273 (3)
O2	0.11176 (16)	1.00290 (19)	0.83598 (18)	0.0354 (4)
O3	0.13212 (14)	0.62670 (16)	1.1287 (2)	0.0375 (4)
H2WA	0.199 (3)	1.033 (3)	0.859 (3)	0.046 (7)*
H2WB	0.075 (3)	0.971 (4)	0.741 (4)	0.075 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01824 (19)	0.0248 (2)	0.01995 (18)	0.000	0.00185 (14)	0.000
Cl1	0.0293 (3)	0.0348 (3)	0.0404 (3)	−0.0041 (2)	0.0021 (2)	−0.0136 (2)
Cl2	0.0591 (5)	0.0447 (5)	0.0256 (4)	0.000	0.0019 (3)	0.000
N1	0.0172 (8)	0.0399 (10)	0.0226 (8)	−0.0024 (7)	−0.0010 (7)	0.0007 (7)
C1	0.0175 (9)	0.0296 (10)	0.0273 (9)	0.0010 (7)	0.0099 (8)	0.0025 (7)
C2	0.0249 (10)	0.0499 (15)	0.0397 (11)	0.0031 (9)	0.0125 (9)	−0.0086 (10)
C3	0.0269 (10)	0.0608 (14)	0.0304 (10)	0.0065 (9)	0.0098 (9)	0.0190 (10)
C4	0.0521 (15)	0.0290 (13)	0.0477 (15)	−0.0115 (11)	0.0030 (13)	−0.0061 (11)
O1	0.0207 (7)	0.0276 (7)	0.0262 (7)	0.0018 (6)	−0.0019 (5)	0.0003 (6)
O2	0.0291 (8)	0.0488 (10)	0.0300 (7)	−0.0128 (7)	0.0122 (6)	−0.0117 (8)
O3	0.0294 (7)	0.0313 (8)	0.0520 (10)	0.0096 (6)	0.0139 (7)	0.0145 (7)

Geometric parameters (Å, º) top

Fe1—O2ⁱ	2.0443 (14)	C1—C1ⁱ	1.569 (4)
Fe1—O2	2.0443 (14)	C2—C3ⁱⁱ	1.515 (3)
Fe1—O1ⁱ	2.0526 (14)	C2—H2A	0.9700
Fe1—O1	2.0526 (14)	C2—H2B	0.9700
Fe1—Cl1	2.2913 (8)	C3—C2ⁱⁱ	1.515 (3)
Fe1—Cl1ⁱ	2.2913 (8)	C3—H3A	0.9700
N1—C4	1.489 (2)	C3—H3B	0.9700
N1—C3	1.491 (3)	C4—C4ⁱⁱ	1.509 (5)
N1—C2	1.499 (2)	C4—H4A	0.9700
N1—H1	0.9100	C4—H4B	0.9700
C1—O3	1.216 (2)	O2—H2WA	0.87 (3)
C1—O1	1.278 (2)	O2—H2WB	0.82 (3)

O2ⁱ—Fe1—O2	170.30 (10)	O1—C1—C1ⁱ	113.78 (10)
O2ⁱ—Fe1—O1ⁱ	87.78 (6)	N1—C2—C3ⁱⁱ	108.47 (16)
O2—Fe1—O1ⁱ	84.72 (6)	N1—C2—H2A	110.0
O2ⁱ—Fe1—O1	84.72 (6)	C3ⁱⁱ—C2—H2A	110.0
O2—Fe1—O1	87.78 (6)	N1—C2—H2B	110.0
O1ⁱ—Fe1—O1	78.73 (8)	C3ⁱⁱ—C2—H2B	110.0
O2ⁱ—Fe1—Cl1	95.48 (5)	H2A—C2—H2B	108.4
O2—Fe1—Cl1	90.85 (5)	N1—C3—C2ⁱⁱ	108.72 (15)
O1ⁱ—Fe1—Cl1	169.42 (4)	N1—C3—H3A	109.9
O1—Fe1—Cl1	91.53 (5)	C2ⁱⁱ—C3—H3A	109.9
O2ⁱ—Fe1—Cl1ⁱ	90.85 (5)	N1—C3—H3B	109.9
O2—Fe1—Cl1ⁱ	95.48 (5)	C2ⁱⁱ—C3—H3B	109.9
O1ⁱ—Fe1—Cl1ⁱ	91.53 (5)	H3A—C3—H3B	108.3
O1—Fe1—Cl1ⁱ	169.42 (4)	N1—C4—C4ⁱⁱ	108.77 (11)
Cl1—Fe1—Cl1ⁱ	98.47 (4)	N1—C4—H4A	109.9
C4—N1—C3	109.93 (18)	C4ⁱⁱ—C4—H4A	109.9
C4—N1—C2	109.49 (17)	N1—C4—H4B	109.9
C3—N1—C2	110.04 (18)	C4ⁱⁱ—C4—H4B	109.9
C4—N1—H1	109.1	H4A—C4—H4B	108.3
C3—N1—H1	109.1	C1—O1—Fe1	116.67 (12)
C2—N1—H1	109.1	Fe1—O2—H2WA	122.9 (15)
O3—C1—O1	126.47 (18)	Fe1—O2—H2WB	122 (2)
O3—C1—C1ⁱ	119.75 (12)	H2WA—O2—H2WB	115 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱⁱ	0.91	1.93	2.814 (2)	162
O2—H2WA···O3^iv	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: (iii) x, y, z−1; (iv) −x+1/2, y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	(C₆H₁₄N₂)[Fe(C₂O₄)Cl₂(H₂O)₂]Cl
M_r	400.44
Crystal system, space group	Monoclinic, C2
Temperature (K)	293
a, b, c (Å)	9.872 (2), 9.6636 (19), 8.4268 (17)
β (°)	109.57 (3)
V (Å³)	757.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.55
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.638, 0.734
No. of measured, independent and observed [I > 2σ(I)] reflections	3954, 1729, 1684
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.049, 1.08
No. of reflections	1729
No. of parameters	101
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15
Absolute structure	Flack (1983), 802 Friedel pairs
Absolute structure parameter	0.016 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.91	1.93	2.814 (2)	162.3
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+1/2, y+1/2, −z+2.

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fu, 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
Keene, T. D., Hursthouse, M. B. & Price, D. J. (2004). Acta Cryst. E60, m378–m380. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sukhendu, M. & Srinivasan, N. (2007). Chem. Eur. J. 13, 968–977. PubMed Google Scholar
Zhao, J. & Xu, L. (2008). Inorg. Chim. Acta, 361, 2385–2395. Web of Science CSD CrossRef CAS Google Scholar

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