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Acta Cryst. (2008). E64, m493    [ doi:10.1107/S1600536808004625 ]

Diammonium diaquabis(malonato-[kappa]2O,O')cobaltate(II) dihydrate

H. Xu and F. Wang

Abstract top

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.

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—Oaxial distance [2.1020 (19) Å] is longer than the Co—Oequatorial 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.

Refinement top

All H atoms were placed geometrically with C—H, N—H and O—H distances of 0.97, 0.85 and 0.85 Å, respectively, and with Uiso(H) = 1.2Ueq(C, N, O). Hydroxyl-H atoms were allowed to rotate to best fit the experimental electron density.

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
[Figure 1] 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.
[Figure 2] 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]·2H2OZ = 1
Mr = 371.17F000 = 193
Triclinic, P1Dx = 1.764 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 6.950 (2) ÅCell parameters from 1285 reflections
b = 7.075 (2) Åθ = 2.9–25.5º
c = 7.433 (2) ŵ = 1.29 mm−1
α = 89.032 (5)ºT = 298 (2) K
β = 73.076 (5)ºBlock, purple
γ = 88.062 (5)º0.24 × 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 tube1246 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.057
T = 298(2) Kθmax = 25.5º
φ and ω scansθmin = 2.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.747, Tmax = 0.801k = −7→8
1817 measured reflectionsl = −6→8
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.0668P)2 + 0.0816P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
1285 reflectionsΔρmax = 0.39 e Å−3
97 parametersΔρmin = −0.76 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(NH4)2[Co(C3H3O4)2(H2O)2]·2H2Oγ = 88.062 (5)º
Mr = 371.17V = 349.45 (17) Å3
Triclinic, P1Z = 1
a = 6.950 (2) ÅMo Kα
b = 7.075 (2) ŵ = 1.29 mm−1
c = 7.433 (2) ÅT = 298 (2) K
α = 89.032 (5)º0.24 × 0.21 × 0.18 mm
β = 73.076 (5)º
Data collection top
Bruker SMART APEX CCD
diffractometer		1285 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1246 reflections with I > 2σ(I)
Tmin = 0.747, Tmax = 0.801Rint = 0.057
1817 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0414 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.09Δρmax = 0.39 e Å−3
1285 reflectionsΔρmin = −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
xyzUiso*/Ueq
Co10.00001.00000.50000.0246 (2)
C10.2349 (4)0.7294 (4)0.2083 (4)0.0302 (6)
C20.3182 (4)0.6385 (4)0.3572 (4)0.0371 (7)
H2A0.36960.51280.31430.045*
H2B0.43200.71080.36380.045*
C30.1802 (4)0.6198 (3)0.5553 (3)0.0265 (5)
N10.1772 (4)0.2806 (4)0.0011 (3)0.0438 (6)
H1B0.08250.27150.10310.053*
H1A0.25580.1845−0.03090.053*
H1C0.10820.3123−0.07260.053*
H1D0.24700.37540.00710.053*
O10.1213 (3)0.8738 (3)0.2439 (2)0.0322 (4)
O20.2920 (4)0.6563 (3)0.0484 (3)0.0501 (6)
O30.0789 (3)0.7649 (2)0.6328 (2)0.0315 (4)
O40.1752 (3)0.4670 (2)0.6380 (3)0.0371 (5)
O50.2733 (3)1.1242 (3)0.4906 (3)0.0347 (5)
H5A0.36941.11790.38930.042*
H5B0.25131.23740.52960.042*
O60.6141 (3)0.0563 (3)0.2034 (3)0.0391 (5)
H6B0.70110.00790.25210.047*
H6A0.67290.11330.10380.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0283 (3)0.0183 (3)0.0245 (3)0.00435 (19)−0.0037 (2)−0.00096 (19)
C10.0355 (14)0.0214 (13)0.0272 (13)−0.0012 (11)0.0012 (11)−0.0005 (10)
C20.0345 (15)0.0327 (15)0.0364 (15)0.0115 (12)0.0003 (12)0.0024 (12)
C30.0301 (13)0.0227 (13)0.0276 (13)0.0007 (10)−0.0103 (11)−0.0007 (10)
N10.0573 (17)0.0370 (14)0.0322 (13)0.0090 (12)−0.0063 (12)−0.0035 (10)
O10.0394 (11)0.0270 (10)0.0266 (9)0.0088 (8)−0.0047 (8)−0.0021 (7)
O20.0817 (18)0.0295 (11)0.0280 (11)0.0148 (11)−0.0001 (11)−0.0061 (8)
O30.0435 (11)0.0218 (9)0.0250 (9)0.0067 (8)−0.0040 (8)0.0008 (7)
O40.0534 (13)0.0203 (10)0.0353 (11)0.0045 (9)−0.0099 (9)0.0013 (8)
O50.0310 (10)0.0241 (10)0.0430 (11)0.0009 (8)−0.0012 (8)−0.0054 (8)
O60.0400 (11)0.0414 (12)0.0322 (11)−0.0001 (9)−0.0054 (9)0.0059 (9)
Geometric parameters (Å, °) top
Co1—O12.0502 (18)C2—H2B0.9699
Co1—O1i2.0502 (18)C3—O41.231 (3)
Co1—O3i2.0592 (17)C3—O31.272 (3)
Co1—O32.0592 (17)N1—H1B0.8500
Co1—O5i2.1020 (19)N1—H1A0.8500
Co1—O52.1020 (19)N1—H1C0.8500
C1—O21.252 (3)N1—H1D0.8500
C1—O11.253 (3)O5—H5A0.8498
C1—C21.516 (4)O5—H5B0.8498
C2—C31.512 (4)O6—H6B0.8500
C2—H2A0.9699O6—H6A0.8378
O1—Co1—O1i180C1—C2—H2A107.8
O1—Co1—O3i89.76 (7)C3—C2—H2B107.3
O1i—Co1—O3i90.24 (7)C1—C2—H2B107.8
O1—Co1—O390.24 (7)H2A—C2—H2B107.1
O1i—Co1—O389.76 (7)O4—C3—O3122.4 (2)
O3i—Co1—O3180O4—C3—C2119.0 (2)
O1—Co1—O5i87.61 (8)O3—C3—C2118.6 (2)
O1i—Co1—O5i92.39 (8)H1B—N1—H1A116.6
O3i—Co1—O5i90.37 (8)H1B—N1—H1C99.2
O3—Co1—O5i89.63 (8)H1A—N1—H1C116.0
O1—Co1—O592.39 (8)H1B—N1—H1D109.3
O1i—Co1—O587.61 (8)H1A—N1—H1D108.6
O3i—Co1—O589.63 (8)H1C—N1—H1D106.4
O3—Co1—O590.37 (8)C1—O1—Co1127.52 (17)
O5i—Co1—O5180C3—O3—Co1127.00 (16)
O2—C1—O1122.7 (3)Co1—O5—H5A118.7
O2—C1—C2116.3 (2)Co1—O5—H5B109.9
O1—C1—C2121.0 (2)H5A—O5—H5B111.0
C3—C2—C1118.6 (2)H6B—O6—H6A109.3
C3—C2—H2A107.7
Symmetry codes: (i) −x, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O6ii0.851.902.723 (3)164
O5—H5B···O4ii0.851.822.663 (3)172
O6—H6A···O1iii0.842.573.336 (3)153
O6—H6A···O2iii0.841.952.704 (3)149
O6—H6B···O3iv0.852.573.063 (3)118
O6—H6B···O5iv0.852.172.879 (3)141
N1—H1A···O6v0.852.162.950 (3)155
N1—H1B···O3vi0.851.972.805 (3)165
N1—H1C···O4vii0.852.332.988 (3)135
N1—H1D···O20.852.062.857 (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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O6i0.851.902.723 (3)164
O5—H5B···O4i0.851.822.663 (3)172
O6—H6A···O1ii0.842.573.336 (3)153
O6—H6A···O2ii0.841.952.704 (3)149
O6—H6B···O3iii0.852.573.063 (3)118
O6—H6B···O5iii0.852.172.879 (3)141
N1—H1A···O6iv0.852.162.950 (3)155
N1—H1B···O3v0.851.972.805 (3)165
N1—H1C···O4vi0.852.332.988 (3)135
N1—H1D···O20.852.062.857 (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 top

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

references
References top

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