Diammonium diaqua­bis(malonato-κ2O,O′)cobaltate(II) dihydrate

Xu, H.; Wang, F.

doi:10.1107/S1600536808004625

metal-organic compounds

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Volume 64| Part 3| March 2008| Page m493

doi:10.1107/S1600536808004625

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Diammonium diaquabis(malonato-κ²O,O′)cobaltate(II) dihydrate

Haiyun Xu ^a ^* and Fengwu Wang ^a

^aDepartment of Chemistry, Huainan Normal College, 232001 Huainan, Anhui, People's Republic of China
^*Correspondence e-mail: xuhyun1970@sohu.com

(Received 18 January 2008; accepted 16 February 2008; online 22 February 2008)

The title complex, (NH₄)₂[Co(C₃H₃O₄)₂(H₂O)₂]·2H₂O, features a six-coordinate Co atom located on a center of symmetry. The octahedral O₆ coordination geometry is defined by two bidentate malonate ligands and two water molecules, with the latter in a trans configuration. The molecules are linked through O—H⋯O and N—H⋯O hydrogen-bonding interactions, forming a three-dimensional supramolecular network.

Related literature

For related literature, see: Delgado et al. (2006 ); Saadeh et al. (1993 ); Wang et al. (2005 ); Wuest (2005 ); Yolanda et al. (2002 ).

Experimental

Crystal data

(NH₄)₂[Co(C₃H₃O₄)₂(H₂O)₂]·2H₂O
M_r = 371.17
Triclinic, $[P \overline 1]$
a = 6.950 (2) Å
b = 7.075 (2) Å
c = 7.433 (2) Å
α = 89.032 (5)°
β = 73.076 (5)°
γ = 88.062 (5)°
V = 349.45 (17) Å³
Z = 1
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 298 (2) K
0.24 × 0.21 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.747, T_max = 0.801
1817 measured reflections
1285 independent reflections
1246 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.107
S = 1.09
1285 reflections
97 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O6ⁱ	0.85	1.90	2.723 (3)	164
O5—H5B⋯O4ⁱ	0.85	1.82	2.663 (3)	172
O6—H6A⋯O1ⁱⁱ	0.84	2.57	3.336 (3)	153
O6—H6A⋯O2ⁱⁱ	0.84	1.95	2.704 (3)	149
O6—H6B⋯O3ⁱⁱⁱ	0.85	2.57	3.063 (3)	118
O6—H6B⋯O5ⁱⁱⁱ	0.85	2.17	2.879 (3)	141
N1—H1A⋯O6^iv	0.85	2.16	2.950 (3)	155
N1—H1B⋯O3^v	0.85	1.97	2.805 (3)	165
N1—H1C⋯O4^vi	0.85	2.33	2.988 (3)	135
N1—H1D⋯O2	0.85	2.06	2.857 (4)	155
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y, -z; (v) -x, -y+1, -z+1; (vi) x, y, z-1.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808004625/tk2245sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808004625/tk2245Isup2.hkl

checkCIF report

Comment top

In the design of supramolecular complexes, a well known and effective strategy is the matching of suitable hydrogen bond donors and acceptors (Wuest, 2005). Metal aqua-ions may act as excellent, readily available hydrogen bond donors with limited acceptor properties. Several novel complexes with metal aqua-ions have been reported (Delgado et al., 2006; Saadeh et al., 1993; Wang et al., 2005; Yolanda et al., 2002.) We report here the crystal structure of the title complex, (I), [NH₄]₂[Co(C₃H₃O₄)₂(OH₂)₂].2H₂O, Fig. 1, in which the asymmetric comprises half a complex dianion, [Co(C₃H₃O₄)₂(OH₂)₂], situated on a center of inversion, an ammonium cation and a water molecule of crystallization.

The coordination polyhedron of the Co atom is that of an elongated octahedron defined by an O₆ donor set. Four carboxylate O atoms, derived from two bidentate malonate ligands, build the equatorial plane, whereas two water molecules occupy the axial sites. As expected the Co—O_axial distance [2.1020 (19) Å] is longer than the Co—O_equatorial distances [2.0502 (18) and 2.0592 (17) Å]. The bond angles around the cobalt atom are close to that expected for an ideal octahedron. The molecules are linked through O—H···O and N—H···O hydrogen-bonding interactions and form a 3-D supramolecular network, Fig. 2 and Table 2.

Related literature top

For related literature, see: Delgado et al. (2006); Saadeh et al. (1993); Wang et al. (2005); Wuest (2005); Yolanda et al. (2002).

Experimental top

Crystals of (I) were obtained by a diffusion method. In one arm of an U-tube was placed [NH₄]₂[C₃H₂O₄] (30 mg, 0.2 mmol) in water/ethanol (1:1; 10 ml) and in the other [Co(ClO₄)₂].6H₂O (37 mg, 0.1 mmol) in water/ethanol (1:1; 10 ml). The purple crystals were collected by filtration, washed with distilled water, followed by ethanol and dried under reduced pressure for 2 h. Analysis found: C 19.24, H 5.27, N 7.32; C₆H₂₀CoN₂O₁₂ requires: C 19.42, H 5.43, N 7.55.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of (I) expanded to show the coordination geometry of the Co atom which sits on a center of inversion; the unlabelled atoms are related by the symmetry operation -x, 2 - y, 1 - z. The figure shows 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The 3-D superamolecular structure of (I). Hydrogen bond interactions are shown as dashed lines.

Diammonium diaquabis(malonato-κ²O,O')cobalt(II) dihydrate top

Crystal data top

(NH₄)₂[Co(C₃H₃O₄)₂(H₂O)₂]·2H₂O	Z = 1
M_r = 371.17	F(000) = 193
Triclinic, P1	D_x = 1.764 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.950 (2) Å	Cell parameters from 1285 reflections
b = 7.075 (2) Å	θ = 2.9–25.5°
c = 7.433 (2) Å	µ = 1.29 mm⁻¹
α = 89.032 (5)°	T = 298 K
β = 73.076 (5)°	Block, purple
γ = 88.062 (5)°	0.24 × 0.21 × 0.18 mm
V = 349.45 (17) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	1285 independent reflections
Radiation source: fine-focus sealed tube	1246 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.747, T_max = 0.801	k = −7→8
1817 measured reflections	l = −6→8

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0668P)² + 0.0816P] where P = (F_o² + 2F_c²)/3
1285 reflections	(Δ/σ)_max < 0.001
97 parameters	Δρ_max = 0.39 e Å⁻³
4 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

(NH₄)₂[Co(C₃H₃O₄)₂(H₂O)₂]·2H₂O	γ = 88.062 (5)°
M_r = 371.17	V = 349.45 (17) Å³
Triclinic, P1	Z = 1
a = 6.950 (2) Å	Mo Kα radiation
b = 7.075 (2) Å	µ = 1.29 mm⁻¹
c = 7.433 (2) Å	T = 298 K
α = 89.032 (5)°	0.24 × 0.21 × 0.18 mm
β = 73.076 (5)°

Data collection top

Bruker SMART APEX CCD diffractometer	1285 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1246 reflections with I > 2σ(I)
T_min = 0.747, T_max = 0.801	R_int = 0.057
1817 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	4 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.09	Δρ_max = 0.39 e Å⁻³
1285 reflections	Δρ_min = −0.76 e Å⁻³
97 parameters

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
Co1	0.0000	1.0000	0.5000	0.0246 (2)
C1	0.2349 (4)	0.7294 (4)	0.2083 (4)	0.0302 (6)
C2	0.3182 (4)	0.6385 (4)	0.3572 (4)	0.0371 (7)
H2A	0.3696	0.5128	0.3143	0.045*
H2B	0.4320	0.7108	0.3638	0.045*
C3	0.1802 (4)	0.6198 (3)	0.5553 (3)	0.0265 (5)
N1	0.1772 (4)	0.2806 (4)	0.0011 (3)	0.0438 (6)
H1B	0.0825	0.2715	0.1031	0.053*
H1A	0.2558	0.1845	−0.0309	0.053*
H1C	0.1082	0.3123	−0.0726	0.053*
H1D	0.2470	0.3754	0.0071	0.053*
O1	0.1213 (3)	0.8738 (3)	0.2439 (2)	0.0322 (4)
O2	0.2920 (4)	0.6563 (3)	0.0484 (3)	0.0501 (6)
O3	0.0789 (3)	0.7649 (2)	0.6328 (2)	0.0315 (4)
O4	0.1752 (3)	0.4670 (2)	0.6380 (3)	0.0371 (5)
O5	0.2733 (3)	1.1242 (3)	0.4906 (3)	0.0347 (5)
H5A	0.3694	1.1179	0.3893	0.042*
H5B	0.2513	1.2374	0.5296	0.042*
O6	0.6141 (3)	0.0563 (3)	0.2034 (3)	0.0391 (5)
H6B	0.7011	0.0079	0.2521	0.047*
H6A	0.6729	0.1133	0.1038	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0283 (3)	0.0183 (3)	0.0245 (3)	0.00435 (19)	−0.0037 (2)	−0.00096 (19)
C1	0.0355 (14)	0.0214 (13)	0.0272 (13)	−0.0012 (11)	0.0012 (11)	−0.0005 (10)
C2	0.0345 (15)	0.0327 (15)	0.0364 (15)	0.0115 (12)	0.0003 (12)	0.0024 (12)
C3	0.0301 (13)	0.0227 (13)	0.0276 (13)	0.0007 (10)	−0.0103 (11)	−0.0007 (10)
N1	0.0573 (17)	0.0370 (14)	0.0322 (13)	0.0090 (12)	−0.0063 (12)	−0.0035 (10)
O1	0.0394 (11)	0.0270 (10)	0.0266 (9)	0.0088 (8)	−0.0047 (8)	−0.0021 (7)
O2	0.0817 (18)	0.0295 (11)	0.0280 (11)	0.0148 (11)	−0.0001 (11)	−0.0061 (8)
O3	0.0435 (11)	0.0218 (9)	0.0250 (9)	0.0067 (8)	−0.0040 (8)	0.0008 (7)
O4	0.0534 (13)	0.0203 (10)	0.0353 (11)	0.0045 (9)	−0.0099 (9)	0.0013 (8)
O5	0.0310 (10)	0.0241 (10)	0.0430 (11)	0.0009 (8)	−0.0012 (8)	−0.0054 (8)
O6	0.0400 (11)	0.0414 (12)	0.0322 (11)	−0.0001 (9)	−0.0054 (9)	0.0059 (9)

Geometric parameters (Å, º) top

Co1—O1	2.0502 (18)	C2—H2B	0.9699
Co1—O1ⁱ	2.0502 (18)	C3—O4	1.231 (3)
Co1—O3ⁱ	2.0592 (17)	C3—O3	1.272 (3)
Co1—O3	2.0592 (17)	N1—H1B	0.8500
Co1—O5ⁱ	2.1020 (19)	N1—H1A	0.8500
Co1—O5	2.1020 (19)	N1—H1C	0.8500
C1—O2	1.252 (3)	N1—H1D	0.8500
C1—O1	1.253 (3)	O5—H5A	0.8498
C1—C2	1.516 (4)	O5—H5B	0.8498
C2—C3	1.512 (4)	O6—H6B	0.8500
C2—H2A	0.9699	O6—H6A	0.8378

O1—Co1—O1ⁱ	180	C1—C2—H2A	107.8
O1—Co1—O3ⁱ	89.76 (7)	C3—C2—H2B	107.3
O1ⁱ—Co1—O3ⁱ	90.24 (7)	C1—C2—H2B	107.8
O1—Co1—O3	90.24 (7)	H2A—C2—H2B	107.1
O1ⁱ—Co1—O3	89.76 (7)	O4—C3—O3	122.4 (2)
O3ⁱ—Co1—O3	180	O4—C3—C2	119.0 (2)
O1—Co1—O5ⁱ	87.61 (8)	O3—C3—C2	118.6 (2)
O1ⁱ—Co1—O5ⁱ	92.39 (8)	H1B—N1—H1A	116.6
O3ⁱ—Co1—O5ⁱ	90.37 (8)	H1B—N1—H1C	99.2
O3—Co1—O5ⁱ	89.63 (8)	H1A—N1—H1C	116.0
O1—Co1—O5	92.39 (8)	H1B—N1—H1D	109.3
O1ⁱ—Co1—O5	87.61 (8)	H1A—N1—H1D	108.6
O3ⁱ—Co1—O5	89.63 (8)	H1C—N1—H1D	106.4
O3—Co1—O5	90.37 (8)	C1—O1—Co1	127.52 (17)
O5ⁱ—Co1—O5	180	C3—O3—Co1	127.00 (16)
O2—C1—O1	122.7 (3)	Co1—O5—H5A	118.7
O2—C1—C2	116.3 (2)	Co1—O5—H5B	109.9
O1—C1—C2	121.0 (2)	H5A—O5—H5B	111.0
C3—C2—C1	118.6 (2)	H6B—O6—H6A	109.3
C3—C2—H2A	107.7

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6ⁱⁱ	0.85	1.90	2.723 (3)	164
O5—H5B···O4ⁱⁱ	0.85	1.82	2.663 (3)	172
O6—H6A···O1ⁱⁱⁱ	0.84	2.57	3.336 (3)	153
O6—H6A···O2ⁱⁱⁱ	0.84	1.95	2.704 (3)	149
O6—H6B···O3^iv	0.85	2.57	3.063 (3)	118
O6—H6B···O5^iv	0.85	2.17	2.879 (3)	141
N1—H1A···O6^v	0.85	2.16	2.950 (3)	155
N1—H1B···O3^vi	0.85	1.97	2.805 (3)	165
N1—H1C···O4^vii	0.85	2.33	2.988 (3)	135
N1—H1D···O2	0.85	2.06	2.857 (4)	155

Symmetry codes: (ii) x, y+1, z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z; (vi) −x, −y+1, −z+1; (vii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	(NH₄)₂[Co(C₃H₃O₄)₂(H₂O)₂]·2H₂O
M_r	371.17
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.950 (2), 7.075 (2), 7.433 (2)
α, β, γ (°)	89.032 (5), 73.076 (5), 88.062 (5)
V (Å³)	349.45 (17)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.24 × 0.21 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.747, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections	1817, 1285, 1246
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.107, 1.09
No. of reflections	1285
No. of parameters	97
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.76

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6ⁱ	0.85	1.90	2.723 (3)	164
O5—H5B···O4ⁱ	0.85	1.82	2.663 (3)	172
O6—H6A···O1ⁱⁱ	0.84	2.57	3.336 (3)	153
O6—H6A···O2ⁱⁱ	0.84	1.95	2.704 (3)	149
O6—H6B···O3ⁱⁱⁱ	0.85	2.57	3.063 (3)	118
O6—H6B···O5ⁱⁱⁱ	0.85	2.17	2.879 (3)	141
N1—H1A···O6^iv	0.85	2.16	2.950 (3)	155
N1—H1B···O3^v	0.85	1.97	2.805 (3)	165
N1—H1C···O4^vi	0.85	2.33	2.988 (3)	135
N1—H1D···O2	0.85	2.06	2.857 (4)	155

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y, −z; (v) −x, −y+1, −z+1; (vi) x, y, z−1.

Acknowledgements

The authors thank the Natural Science Foundation of Anhui Province (No. KJ2007B093) for financial support.

References

Delgado, F. S., Ruiz-Përez, C., Sanchiz, J., Lloret, F. & Julve, M. (2006). CrystEngComm, 8, 530–544. Web of Science CSD CrossRef CAS Google Scholar
Saadeh, S. M., Trojan, K. L., Kampf, J. W., Hatfield, W. E. & Pecoraro, V. L. (1993). Inorg. Chem. 32, 3034–3040. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Wang, Z.-L., Wei, L.-H. & Niu, J.-Y. (2005). Acta Cryst. E61, m1907–m1908. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wuest, J. D. (2005). Chem. Commun. pp. 5830–5837. Web of Science CrossRef Google Scholar
Yolanda, R. M., Joaquín, S., Catalina, R. P., Francesc, L. & Miguel, J. (2002). CrystEngComm, 4, 631–637. Google Scholar