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Poly[triaqua-μ4-fumarato-cobalt(II)], [Co(C4H2O4)(H2O)3]n, (I), contains two symmetry-independent octa­hedrally coordinated Co2+ ions, both on inversion centers. One Co2+ ion is coordinated by two water mol­ecules and four fumarate dianions, whereas the other Co2+ ion is surrounded by four water mol­ecules and two fumarate dianions. Each fumarate dianion is bonded to three Co2+ ions, leading to a two-dimensional structure. The fumarate dianions are nonplanar; the angle between the planes of the two carboxyl­ate groups is 54.9 (2)°. The cobalt(II) fumarate layers are connected by hydrogen bonding into a three-dimensional network. Compound (I) is not isostructural with calcium(II) fumarate trihydrate [Gupta et al. (1972). Acta Cryst. B28, 135–139]. In poly[μ4-fumarato-dimethano­lcobalt(II)], [Co(C4H2O4)(CH4O)2]n, (II), the Co2+ ions are octa­hedrally coordinated by four fumarate dianions and two methanol mol­ecules, leading to a three-dimensional structure. The fumarate group is planar. The Co2+ ions and the fumarate dianions both lie on inversion centers. Additionally, the one-dimensional structure of catena-poly[[[tetra­aqua­cobalt(II)]-μ2-fumarato] monohydrate], {[Co(C4H2O4)(H2O)4]·H2O}n, (III), was redetermined at a higher resolution, and the space group C2/c was confirmed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109030510/fg3108sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030510/fg3108Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030510/fg3108IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030510/fg3108IIIsup4.hkl
Contains datablock III

CCDC references: 749689; 749690; 749691

Comment top

Octahedral coordination of Co2+ ions was first observed by Werner (1893). To date, only two cobalt(II) fumarate complexes containing water molecules are known: cobalt(II) fumarate tetrahydrate [which is actually a tetraaquacobalt(II) fumarate (Konar et al., 2003; Zheng & Xie, 2004; Padmanabhan et al., 2008)] and cobalt(II) fumarate pentahydrate [which is actually a tetraaquacobalt(II) fumarate monohydrate (Gupta & Sinha, 1978; Konar et al., 2003; Marsh & Spek, 2001; Porollo et al., 1997)]. Compounds in which Co2+ ions [and other bivalent metal(II) ions] are bonded to saturated or unsaturated dicarboxylic acids, such as fumaric, maleic and succinic acid, have also been reported (e.g. Rao et al., 2004; Yaghi et al., 2003). In recent years, investigations of cobalt(II) fumarate phases containing additional organic ligands have been carried out (e.g. Chen et al., 2007; Konar et al., 2004; Liu et al., 2003; Ma et al., 2003; Manna et al., 2007; Zhang et al., 2004, 2005). Ligands included benzimidazole, o-phenanthroline, pyrazine, and pyridine and its derivatives. These compounds form chain structures, layers or three-dimensional frameworks. Saturated dicarboxylic acids tend to form coordination polymers with open three-dimensional frameworks. In contrast unsaturated dicarboxylic acids lead to metal(II) hydrate complexes with predominantly chain structures.

The cobalt(II) fumarate tetra- and pentahydrates built from the Co2+ ion and the fumarate dianion crystallize in one-dimensional polymeric chain structures (Gupta & Sinha, 1978; Konar et al., 2003; Marsh & Spek, 2001; Padmanabhan et al., 2008; Porollo et al., 1997; Zheng & Xie, 2004). These chains are connected into a three-dimensional network by hydrogen bonds between water molecules and carboxylate groups.

We have prepared a novel cobalt(II) fumarate trihydrate and a cobalt(II) fumarate methanol disolvate and have redetermined additionally the structure of cobalt(II) fumarate pentahydrate.

The trihydrate, (I), forms two-dimensional layers parallel to the 111 plane, as shown in Fig. 1. There are two symmetrically independent Co2+ ions, both on inversion centers. Atom Co1 is coordinated by two water molecules [Co1—O5 = 2.147 (2) Å] and four fumarate dianions [Co1—O1 = 2.0686 (18) Å and Co1—O4 = 2.1132 (18) Å], whereas atom Co2 is surrounded by four water molecules [Co2—O6 = 2.042 (2) Å and Co2—O7 = 2.183 (2) Å] and two fumarate dianions [Co2—O2 = 2.0755 (18) Å]. Both Co2+ ions are coordinated with a distorted octahedral geometry. Hence cobalt(II) fumarate trihydrate is actually a mixture of a tetracobalt(II) fumarate and a diaquacobalt(II) fumarate. The fumarate group has a trans conformation, with a C1—C2—C3—C4 torsion angle of 175.6 (2)°. The carboxylate groups are rotated out of the plane; the angles between the plane of the central butene group and the planes of the two carboxylate groups are 32.0 (2) and 23.0 (1)°. The fumarate dianions act as bridging ligands, linking the two symmetrically independant Co2+ ions to form layers parallel to the [111] plane. The layer is characterized by two different ring systems. There is a 14-membered ring, consisting of two Co1 atoms and two fumarate dianions, and a 22-membered ring, consisting of two Co1 atoms, two Co2 atoms and four fumarate dianions. The three independent water molecules act as donors for six different O—H···O hydrogen bonds (Table 1). Four of them connect the layers through an extensive hydrogen-bonding network to form a three-dimensional framework, as shown in Fig. 2. Within the layers the O6/H6B group is involved in a rather weak bifurcated hydrogen bond, while the O5/H5B group is involved in a rather strong hydrogen bond, as shown in Fig. 1. There is only one other report of the crystal structure of a metal(II) fumarate trihydrate, calcium(II) fumarate trihydrate (Gupta et al., 1972). Its coordination geometry, however, is not similar to that of (I). Its structure consists of an eightfold-coordinated Ca2+ ion surrounded by two independant and two symmetry-related water molecules and three symmetry-related fumarate dianions.

Cobalt(II) fumarate methanol disolvate, (II), belongs to the group of cobalt(II) fumarates containing an additional organic ligand. The octahedrally coordinated Co2+ ion is located on a crystallographic inversion center. Each Co2+ ion is bonded to O atoms of four symmetry-related fumarate groups [Co1—O1 = 2.1060 (10) Å and Co1—O2 = 2.1205 (9) Å] and two O atoms of two symmetry-related methanol groups [Co1—O3 = 2.0657 (10) Å], as shown in Fig. 3. The methanol OH group donates an intramolecular hydrogen bond to carboxylate atom O2 (Table 2). The fumarate group is planar (the mean deviation from the plane is only 0.002 Å) and has a crystallographic inversion center at the midpoint of the CC double bond. The Co2+ ions and fumarate dianions form a three-dimensional framework, as shown in Fig. 4. The structure is characterized by a system of 14-membered rings, consisting of two Co2+ ions and two fumarate dianions. Larger 22-membered rings consisting of four Co2+ ions and four fumarate dianions result in channels along the c-axis direction. The methanol ligands are located in these channels. The structure of (II) is clearly different from the structures of many two-dimensional coordination polymers that have been reported in the past few decades. Thus the incorporation of a methanol ligand into cobalt(II) fumarate phases offers an interesting method for structural modification and the synthesis of further novel metal–organic framework structures.

There has been some confusion about the correct space group of the pentahydrate, (III). The structure was originally determined by Gupta & Sinha (1978) in space group C2/c. It was redetermined by Porollo et al. (1997) and refined in the noncentrosymmetric space group C2. Marsh & Spek (2001) showed that the coordinates of this structure could be transformed to C2/c. Two years later the structure of (III) was redetermined by Konar et al. (2003) and refined in the noncentrosymmetric space group Cc. The present redetermination of the compound confirms the space group C2/c. The low R value (0.018) for the refinement in C2/c shows that space groups C2 and Cc can be excluded. The Co2+ ion is located on a twofold axis and has an octahedral coordination. Two cis positions are occupied by two fumarate groups and the other positions are occupied by four water molecules. The Co2+ ions and fumarate dianions form one-dimensional zigzag chains along the c direction, as shown in Fig. 5. These chains are connected by O—H···O hydrogen bonds (Table 3) into a three-dimensional network, as shown in Fig. 6. There is a crystallographic inversion center at the midpoint of the CC double bond of the fumarate group. The angle between the plane of the central butene group and the planes of the two carboxylate groups is 25.9 (1)°. A one-dimensional structure has also been observed in the crystal structure of cobalt(II) fumarate tetrahydrate (Konar et al., 2003). There the fumarate groups are in trans positions with respect to the Co2+ ions, resulting in almost linear chains.

The site symmetries of the cobalt and fumarate ions for all four compounds are given in Table 4. The compounds reported demonstrate all three of the types of framework (one-, two- and three-dimensional), that are possible for these structures.

Related literature top

For related literature, see: Chen et al. (2007); Gupta & Sinha (1978); Gupta et al. (1972); Konar et al. (2003, 2004); Liu et al. (2003); Ma et al. (2003); Manna et al. (2007); Marsh & Spek (2001); Padmanabhan et al. (2008); Porollo et al. (1997); Rao et al. (2004); Werner (1893); Yaghi et al. (2003); Zhang et al. (2004); Zheng & Xie (2004).

Experimental top

A methanol solution (50 ml) containing fumaric acid (0.93 g, 8 mmol) was heated at 333 K for 1 h with stirring and then left to cool to room temperature. After the addition of a methanol solution (50 ml) containing Co(CH3COO)2.4H2O (1 g, 4 mmol), a magenta-coloured powder precipitated. The precipitate was filtered off, washed with methanol and dried for 3 h at 323 K. The powder pattern of the precipitate and the calculated powder pattern from the single-crystal structure of cobalt(II) fumarate methanol disolvate were compared and proved to be congruent. Red crystals of the compounds reported here were prepared by vapour diffusion, using water as solvent in all three cases and acetone for (I), methanol for (II) and ethanol for (III) as antisolvent. Crystals of (I) formed after four days, crystals of compound (II) and (III) after one week.

Refinement top

The H atoms of the methyl group of (II) were constrained [C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C)]. All other H atoms in (I), (II) and (III) were located in difference Fourier syntheses and were freely refined [C—H = 0.93 (3) and 1.00 (3), 0.91 (2), and 0.928 (14) Å, respectively]. The crystal of (I) was twinned. The twin relations were htwin = h, ktwin = -0.115h - k and ltwin = -0.870h - l. The twin fraction refined to 0.241 (4).

Computing details top

For all compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART (Siemens, 1995); data reduction: SAINT (Siemens, 1995); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A layer of (I), parallel to the (111) plane, showing the two symmetrically independant Co2+ ions and their coordination geometry. Hydrogen bonds are represented by dotted lines. [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) x - 1, y, z - 1; (iii) -x + 1, -y + 2, -z + 1; (iv) -x + 1, -y + 1, -z + 2; (v) x + 1, y, z + 1.]
[Figure 2] Fig. 2. A packing diagram of (I) along the ab diagonal, showing the layers connected via hydrogen bonds, leading to a three-dimensional structure. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. A section of (II), showing the coordination geometry of the Co2+ ion. [Symmetry codes: (i) -x + 1/2, -y + 1/2, -z + 1; (ii) -x + 1, -y, -z + 2; (iii) x, -y, z - 1/2; (iv) -x + 1/2, y + 1/2, -z + 3/2.]
[Figure 4] Fig. 4. A packing diagram of (II) along the c axis, showing the three-dimensional structure.
[Figure 5] Fig. 5. The chain stucture of (III), showing the coordination geometry of the Co2+ ion. Hydrogen bonds are represented by dotted lines. [Symmetry codes: (i) -x + 1, y, -z + 1/2; (ii) -x + 3/2, -y + 1/2, -z + 1.]
[Figure 6] Fig. 6. A packing diagram of (III) along the a axis, showing the three-dimensional hydrogen-bonding system.
(I) Poly[triaqua-µ4-fumarato-cobalt(II)] top
Crystal data top
[Co(C4H2O4)(H2O)3]Z = 2
Mr = 227.03F(000) = 230
Triclinic, P1Dx = 1.985 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.8793 (17) ÅCell parameters from 58 reflections
b = 7.644 (2) Åθ = 3–23°
c = 8.026 (3) ŵ = 2.26 mm1
α = 101.51 (2)°T = 167 K
β = 112.03 (2)°Rod, red
γ = 92.82 (3)°0.52 × 0.20 × 0.14 mm
V = 379.8 (2) Å3
Data collection top
Siemens SMART 1K CCD
diffractometer
2411 independent reflections
Radiation source: normal-focus sealed tube1660 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
ω scansθmax = 31.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 910
Tmin = 0.575, Tmax = 0.729k = 1111
6668 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: difference Fourier map
wR(F2) = 0.091All H-atom parameters refined
S = 1.00 w = 1/[σ^2^(Fo^2^) + (0.04P)^2^]
where P = (Fo^2^ + 2Fc^2^)/3
2411 reflections(Δ/σ)max = 0.003
145 parametersΔρmax = 1.07 e Å3
0 restraintsΔρmin = 0.94 e Å3
Crystal data top
[Co(C4H2O4)(H2O)3]γ = 92.82 (3)°
Mr = 227.03V = 379.8 (2) Å3
Triclinic, P1Z = 2
a = 6.8793 (17) ÅMo Kα radiation
b = 7.644 (2) ŵ = 2.26 mm1
c = 8.026 (3) ÅT = 167 K
α = 101.51 (2)°0.52 × 0.20 × 0.14 mm
β = 112.03 (2)°
Data collection top
Siemens SMART 1K CCD
diffractometer
2411 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
1660 reflections with I > 2σ(I)
Tmin = 0.575, Tmax = 0.729Rint = 0.044
6668 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.091All H-atom parameters refined
S = 1.00Δρmax = 1.07 e Å3
2411 reflectionsΔρmin = 0.94 e Å3
145 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
Co10.00000.50000.50000.00918 (13)
Co20.50001.00000.50000.01026 (14)
O10.2944 (3)0.6128 (3)0.5305 (2)0.0136 (4)
O20.5960 (3)0.7970 (3)0.6380 (2)0.0124 (4)
O30.7892 (3)0.3575 (3)1.0426 (2)0.0159 (4)
O40.8770 (3)0.6109 (3)1.2664 (2)0.0127 (4)
O50.0018 (3)0.2402 (3)0.3366 (3)0.0143 (4)
O60.2449 (3)0.8438 (3)0.2860 (3)0.0165 (4)
O70.2892 (4)1.0519 (3)0.6454 (3)0.0202 (5)
C10.4824 (4)0.6640 (4)0.6432 (3)0.0100 (5)
C20.5795 (4)0.5610 (4)0.7870 (4)0.0117 (5)
C30.7224 (4)0.6340 (4)0.9549 (4)0.0133 (5)
C40.8021 (4)0.5255 (4)1.0966 (3)0.0118 (5)
H2A0.524 (5)0.430 (5)0.736 (4)0.019 (8)*
H3A0.766 (4)0.758 (4)0.991 (4)0.017 (8)*
H5A0.109 (8)0.228 (6)0.330 (6)0.059 (15)*
H5B0.063 (6)0.259 (5)0.242 (5)0.029 (10)*
H6A0.242 (6)0.780 (6)0.182 (6)0.053 (13)*
H6B0.195 (7)0.767 (6)0.316 (6)0.059 (15)*
H7A0.253 (5)1.142 (6)0.669 (5)0.028 (11)*
H7B0.209 (6)0.977 (6)0.652 (5)0.045 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0093 (3)0.0093 (3)0.0084 (2)0.0004 (2)0.00223 (19)0.0033 (2)
Co20.0116 (3)0.0084 (3)0.0096 (2)0.0014 (2)0.00254 (19)0.0028 (2)
O10.0072 (9)0.0178 (10)0.0151 (9)0.0005 (8)0.0029 (7)0.0056 (8)
O20.0118 (9)0.0103 (10)0.0143 (9)0.0003 (7)0.0032 (7)0.0051 (8)
O30.0213 (10)0.0124 (10)0.0115 (9)0.0036 (8)0.0036 (8)0.0031 (8)
O40.0143 (9)0.0117 (10)0.0096 (9)0.0013 (8)0.0024 (7)0.0021 (8)
O50.0143 (10)0.0166 (11)0.0128 (10)0.0048 (8)0.0046 (8)0.0058 (8)
O60.0196 (10)0.0155 (11)0.0134 (10)0.0033 (8)0.0064 (8)0.0024 (9)
O70.0244 (12)0.0162 (12)0.0269 (12)0.0067 (10)0.0162 (10)0.0071 (10)
C10.0120 (12)0.0102 (13)0.0079 (11)0.0030 (10)0.0047 (10)0.0003 (10)
C20.0118 (12)0.0105 (13)0.0145 (12)0.0031 (10)0.0062 (10)0.0043 (11)
C30.0159 (13)0.0108 (13)0.0141 (13)0.0024 (11)0.0063 (11)0.0040 (11)
C40.0076 (11)0.0155 (14)0.0124 (12)0.0007 (10)0.0038 (9)0.0036 (11)
Geometric parameters (Å, º) top
Co1—O12.0686 (18)O5—H5B0.76 (4)
Co1—O4i2.1133 (18)O6—H6A0.87 (5)
Co1—O52.147 (2)O6—H6B0.79 (5)
Co2—O62.042 (2)O7—H7A0.76 (4)
Co2—O22.0755 (18)O7—H7B0.80 (4)
Co2—O72.183 (2)C1—C21.495 (4)
O1—C11.255 (3)C2—C31.321 (4)
O2—C11.269 (3)C2—H2A1.00 (3)
O3—C41.258 (3)C3—C41.495 (4)
O4—C41.278 (3)C3—H3A0.93 (3)
O5—H5A0.79 (5)
O1—Co1—O4i93.85 (7)Co2—O7—H7A125 (3)
O1—Co1—O596.99 (8)Co2—O7—H7B125 (3)
O4i—Co1—O586.93 (8)H7A—O7—H7B107 (4)
O6—Co2—O295.65 (8)O1—C1—O2122.9 (2)
O6—Co2—O786.61 (9)O1—C1—C2118.8 (2)
O2—Co2—O787.69 (8)O2—C1—C2118.3 (2)
C1—O1—Co1144.11 (17)C3—C2—C1124.3 (3)
C1—O2—Co2128.33 (16)C3—C2—H2A125.5 (17)
C4—O4—Co1ii126.91 (17)C1—C2—H2A110.2 (17)
Co1—O5—H5A112 (3)C2—C3—C4121.5 (3)
Co1—O5—H5B97 (3)C2—C3—H3A119.9 (17)
H5A—O5—H5B100 (4)C4—C3—H3A118.3 (18)
Co2—O6—H6A127 (3)O3—C4—O4124.3 (2)
Co2—O6—H6B112 (3)O3—C4—C3118.6 (2)
H6A—O6—H6B98 (4)O4—C4—C3117.1 (2)
O4iii—Co1—O1—C1159.3 (3)Co2—O2—C1—O116.3 (4)
O4i—Co1—O1—C120.7 (3)Co2—O2—C1—C2165.40 (16)
O5—Co1—O1—C1108.0 (3)O1—C1—C2—C3147.4 (3)
O5iv—Co1—O1—C172.0 (3)O2—C1—C2—C334.3 (4)
O6—Co2—O2—C131.5 (2)C1—C2—C3—C4175.6 (2)
O6v—Co2—O2—C1148.5 (2)Co1ii—O4—C4—O30.5 (4)
O7—Co2—O2—C154.9 (2)Co1ii—O4—C4—C3179.58 (15)
O7v—Co2—O2—C1125.1 (2)C2—C3—C4—O323.3 (4)
Co1—O1—C1—O2146.5 (2)C2—C3—C4—O4155.8 (3)
Co1—O1—C1—C235.2 (4)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1, y, z+1; (iii) x1, y, z1; (iv) x, y+1, z+1; (v) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O2vi0.79 (6)1.97 (6)2.755 (3)170 (4)
O5—H5B···O3iii0.76 (4)1.87 (4)2.620 (3)167 (4)
O6—H6A···O3vi0.87 (4)1.83 (4)2.694 (3)175 (4)
O6—H6B···O10.79 (5)2.20 (5)2.833 (3)138 (4)
O6—H6B···O4iii0.79 (5)2.30 (5)2.957 (3)142 (4)
O7—H7A···O4vii0.76 (4)2.18 (4)2.936 (4)175 (4)
O7—H7B···O5iv0.80 (5)2.17 (5)2.971 (4)176 (4)
Symmetry codes: (iii) x1, y, z1; (iv) x, y+1, z+1; (vi) x+1, y+1, z+1; (vii) x+1, y+2, z+2.
(II) poly[µ4-fumarato-dimethanolcobalt(II)] top
Crystal data top
[Co(C4H2O4)(CH4O)2]F(000) = 484
Mr = 237.07Dx = 1.947 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 80 reflections
a = 15.547 (4) Åθ = 3–23°
b = 7.020 (2) ŵ = 2.12 mm1
c = 8.2270 (13) ÅT = 165 K
β = 115.73 (2)°Prism, red
V = 808.9 (4) Å30.40 × 0.26 × 0.24 mm
Z = 4
Data collection top
Siemens SMART 1K CCD
diffractometer
1611 independent reflections
Radiation source: normal-focus sealed tube1402 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 34.2°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 2323
Tmin = 0.530, Tmax = 0.602k = 1011
7132 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ^2^(Fo^2^) + (0.03P)^2^ + 1.1P]
where P = (Fo^2^ + 2Fc^2^)/3
1611 reflections(Δ/σ)max < 0.001
70 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.64 e Å3
Crystal data top
[Co(C4H2O4)(CH4O)2]V = 808.9 (4) Å3
Mr = 237.07Z = 4
Monoclinic, C2/cMo Kα radiation
a = 15.547 (4) ŵ = 2.12 mm1
b = 7.020 (2) ÅT = 165 K
c = 8.2270 (13) Å0.40 × 0.26 × 0.24 mm
β = 115.73 (2)°
Data collection top
Siemens SMART 1K CCD
diffractometer
1611 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
1402 reflections with I > 2σ(I)
Tmin = 0.530, Tmax = 0.602Rint = 0.025
7132 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.48 e Å3
1611 reflectionsΔρmin = 0.64 e Å3
70 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
Co10.25000.25000.50000.00897 (6)
O10.36063 (6)0.15407 (13)0.74360 (11)0.01288 (16)
O20.29011 (6)0.06569 (13)0.84046 (12)0.01423 (17)
O30.16082 (6)0.04138 (14)0.51795 (12)0.01573 (17)
C10.36385 (7)0.02119 (16)0.84867 (14)0.01062 (18)
C20.45934 (8)0.04100 (17)0.99018 (15)0.01236 (19)
C30.11717 (17)0.1002 (3)0.3861 (2)0.0453 (5)
H3B0.08900.04140.26620.068*
H3C0.06710.16350.40820.068*
H3D0.16510.19420.39230.068*
H2A0.4577 (13)0.141 (3)1.059 (3)0.021 (4)*
H3A0.1913 (15)0.014 (3)0.617 (3)0.037 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.00782 (9)0.00962 (10)0.00845 (10)0.00060 (7)0.00259 (7)0.00051 (7)
O10.0098 (3)0.0146 (4)0.0123 (3)0.0009 (3)0.0030 (3)0.0048 (3)
O20.0095 (3)0.0177 (4)0.0137 (4)0.0027 (3)0.0034 (3)0.0040 (3)
O30.0154 (4)0.0167 (4)0.0128 (4)0.0018 (3)0.0040 (3)0.0029 (3)
C10.0093 (4)0.0118 (5)0.0101 (4)0.0008 (3)0.0035 (3)0.0005 (4)
C20.0095 (4)0.0136 (5)0.0125 (4)0.0016 (4)0.0035 (3)0.0042 (4)
C30.0638 (13)0.0432 (10)0.0247 (8)0.0354 (10)0.0153 (8)0.0086 (7)
Geometric parameters (Å, º) top
Co1—O32.0656 (10)O3—C31.409 (2)
Co1—O3i2.0657 (10)O3—H3A0.84 (2)
Co1—O1i2.1060 (10)C1—C21.4998 (16)
Co1—O12.1060 (10)C2—C2v1.334 (2)
Co1—O2ii2.1204 (9)C2—H2A0.91 (2)
Co1—O2iii2.1205 (9)C3—H3B0.9800
O1—C11.2579 (14)C3—H3C0.9800
O2—C11.2742 (13)C3—H3D0.9800
O2—Co1iv2.1204 (9)
O3—Co1—O3i180.00 (5)C1—O2—Co1iv139.36 (8)
O3—Co1—O1i89.91 (4)C3—O3—Co1123.99 (10)
O3i—Co1—O1i90.09 (4)C3—O3—H3A107.4 (16)
O3—Co1—O190.09 (4)Co1—O3—H3A106.6 (15)
O3i—Co1—O189.91 (4)O1—C1—O2123.51 (10)
O1i—Co1—O1180.00 (5)O1—C1—C2118.68 (10)
O3—Co1—O2ii90.08 (4)O2—C1—C2117.80 (10)
O3i—Co1—O2ii89.92 (4)C2v—C2—C1122.37 (13)
O1i—Co1—O2ii93.20 (4)C2v—C2—H2A122.7 (11)
O1—Co1—O2ii86.80 (4)C1—C2—H2A114.9 (11)
O3—Co1—O2iii89.92 (4)O3—C3—H3B109.5
O3i—Co1—O2iii90.08 (4)O3—C3—H3C109.5
O1i—Co1—O2iii86.80 (4)H3B—C3—H3C109.5
O1—Co1—O2iii93.20 (4)O3—C3—H3D109.5
O2ii—Co1—O2iii180.0H3B—C3—H3D109.5
C1—O1—Co1131.57 (7)H3C—C3—H3D109.5
O3—Co1—O1—C10.17 (11)O2iii—Co1—O3—C327.84 (15)
O3i—Co1—O1—C1179.83 (11)Co1—O1—C1—O212.96 (18)
O2ii—Co1—O1—C189.91 (11)Co1—O1—C1—C2166.26 (8)
O2iii—Co1—O1—C190.09 (11)Co1iv—O2—C1—O1164.89 (9)
O1i—Co1—O3—C358.97 (15)Co1iv—O2—C1—C215.89 (18)
O1—Co1—O3—C3121.03 (15)O1—C1—C2—C2v0.8 (2)
O2ii—Co1—O3—C3152.16 (15)O2—C1—C2—C2v179.93 (15)
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1/2, y+1/2, z+3/2; (iii) x, y, z1/2; (iv) x+1/2, y1/2, z+3/2; (v) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O20.84 (2)1.85 (2)2.6485 (15)159 (2)
C2—H2A···O1vi0.91 (2)2.57 (2)3.1796 (18)125.4 (17)
Symmetry code: (vi) x, y, z+1/2.
(III) catena-poly[[[tetraaquacobalt(II)]-µ2-fumarato] monohydrate] top
Crystal data top
[Co(C4H2O4)(H2O)4]·H2OF(000) = 540
Mr = 263.07Dx = 1.906 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 121 reflections
a = 5.2561 (11) Åθ = 3–23°
b = 13.145 (2) ŵ = 1.90 mm1
c = 13.321 (3) ÅT = 166 K
β = 95.188 (16)°Block, red
V = 916.6 (3) Å30.60 × 0.55 × 0.50 mm
Z = 4
Data collection top
Siemens SMART 1K CCD
diffractometer
1815 independent reflections
Radiation source: normal-focus sealed tube1771 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 34.2°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 88
Tmin = 0.301, Tmax = 0.386k = 2019
8327 measured reflectionsl = 2020
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.018All H-atom parameters refined
wR(F2) = 0.049 w = 1/[σ^2^(Fo^2^) + (0.02P)^2^ + 0.6P]
where P = (Fo^2^ + 2Fc^2^)/3
S = 1.04(Δ/σ)max = 0.002
1815 reflectionsΔρmax = 0.56 e Å3
90 parametersΔρmin = 0.30 e Å3
0 restraintsExtinction correction: SHELXL97, Fc^*^=kFc[1+0.001xFc^2^λ^3^/sin(2θ)]^-1/4^
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0653 (17)
Crystal data top
[Co(C4H2O4)(H2O)4]·H2OV = 916.6 (3) Å3
Mr = 263.07Z = 4
Monoclinic, C2/cMo Kα radiation
a = 5.2561 (11) ŵ = 1.90 mm1
b = 13.145 (2) ÅT = 166 K
c = 13.321 (3) Å0.60 × 0.55 × 0.50 mm
β = 95.188 (16)°
Data collection top
Siemens SMART 1K CCD
diffractometer
1815 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
1771 reflections with I > 2σ(I)
Tmin = 0.301, Tmax = 0.386Rint = 0.025
8327 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0180 restraints
wR(F2) = 0.049All H-atom parameters refined
S = 1.04Δρmax = 0.56 e Å3
1815 reflectionsΔρmin = 0.30 e Å3
90 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
Co10.50000.521354 (11)0.25000.00894 (6)
O10.66720 (12)0.41061 (5)0.34838 (5)0.01388 (12)
O20.38818 (12)0.37949 (5)0.46236 (5)0.01486 (12)
O30.79528 (13)0.52833 (5)0.15710 (5)0.01689 (13)
O40.29066 (12)0.63086 (5)0.15840 (5)0.01271 (11)
O51.00000.29869 (7)0.25000.01504 (16)
C10.59750 (15)0.36517 (6)0.42601 (6)0.01087 (13)
C20.78514 (15)0.28956 (6)0.47320 (6)0.01180 (13)
H2A0.957 (3)0.3007 (11)0.4652 (10)0.016 (3)*
H3A0.931 (3)0.5574 (13)0.1571 (13)0.030 (4)*
H3B0.789 (4)0.4818 (14)0.1186 (16)0.037 (5)*
H4A0.328 (3)0.6854 (14)0.1814 (13)0.032 (4)*
H4B0.344 (3)0.6293 (14)0.1005 (14)0.032 (4)*
H5A0.918 (3)0.3344 (12)0.2784 (12)0.022 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.00957 (8)0.00820 (8)0.00915 (8)0.0000.00146 (5)0.000
O10.0155 (3)0.0131 (3)0.0138 (3)0.0038 (2)0.0057 (2)0.00536 (19)
O20.0125 (3)0.0185 (3)0.0142 (3)0.0035 (2)0.0042 (2)0.0051 (2)
O30.0134 (3)0.0202 (3)0.0180 (3)0.0057 (2)0.0063 (2)0.0072 (2)
O40.0150 (3)0.0117 (3)0.0116 (3)0.0000 (2)0.0022 (2)0.00047 (19)
O50.0194 (4)0.0104 (4)0.0165 (4)0.0000.0080 (3)0.000
C10.0121 (3)0.0094 (3)0.0111 (3)0.0001 (2)0.0012 (2)0.0011 (2)
C20.0115 (3)0.0117 (3)0.0123 (3)0.0013 (2)0.0014 (2)0.0025 (2)
Geometric parameters (Å, º) top
Co1—O32.0727 (8)O3—H3A0.810 (18)
Co1—O3i2.0727 (8)O3—H3B0.797 (19)
Co1—O12.0978 (7)O4—H4A0.797 (18)
Co1—O1i2.0978 (7)O4—H4B0.844 (18)
Co1—O42.1281 (7)O5—H5A0.761 (15)
Co1—O4i2.1281 (7)C1—C21.4978 (11)
O1—C11.2763 (10)C2—C2ii1.3326 (15)
O2—C11.2557 (10)C2—H2A0.928 (14)
O3—Co1—O3i174.93 (4)O4—Co1—O4i94.87 (4)
O3—Co1—O196.30 (3)C1—O1—Co1134.13 (5)
O3i—Co1—O187.23 (3)Co1—O3—H3A136.8 (12)
O3—Co1—O1i87.23 (3)Co1—O3—H3B111.2 (15)
O3i—Co1—O1i96.30 (3)H3A—O3—H3B110 (2)
O1—Co1—O1i92.12 (4)Co1—O4—H4A106.8 (13)
O3—Co1—O490.23 (3)Co1—O4—H4B108.1 (12)
O3i—Co1—O486.34 (3)H4A—O4—H4B106.4 (17)
O1—Co1—O4173.34 (2)O2—C1—O1124.61 (7)
O1i—Co1—O486.88 (3)O2—C1—C2120.28 (7)
O3—Co1—O4i86.34 (3)O1—C1—C2115.11 (7)
O3i—Co1—O4i90.23 (3)C2ii—C2—C1122.61 (9)
O1—Co1—O4i86.87 (3)C2ii—C2—H2A120.2 (9)
O1i—Co1—O4i173.34 (2)C1—C2—H2A117.2 (9)
O3—Co1—O1—C1179.12 (8)Co1—O1—C1—O20.60 (13)
O3i—Co1—O1—C14.53 (8)Co1—O1—C1—C2179.95 (5)
O1i—Co1—O1—C191.67 (8)O2—C1—C2—C2ii25.56 (14)
O4i—Co1—O1—C194.91 (8)O1—C1—C2—C2ii153.82 (10)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+3/2, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O4iii0.809 (16)2.121 (16)2.9306 (11)178.8 (17)
O3—H3B···O2i0.80 (2)1.91 (2)2.6481 (11)153 (2)
O4—H4A···O5iv0.797 (18)1.929 (18)2.7062 (12)164.8 (17)
O4—H4B···O2v0.844 (18)1.879 (18)2.7098 (11)167.6 (16)
O5—H5A···O10.761 (16)1.958 (16)2.7122 (10)171.4 (17)
C2—H2A···O2iii0.931 (16)2.495 (16)3.3982 (13)163.6 (12)
Symmetry codes: (i) x+1, y, z+1/2; (iii) x+1, y, z; (iv) x1/2, y+1/2, z; (v) x, y+1, z1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formula[Co(C4H2O4)(H2O)3][Co(C4H2O4)(CH4O)2][Co(C4H2O4)(H2O)4]·H2O
Mr227.03237.07263.07
Crystal system, space groupTriclinic, P1Monoclinic, C2/cMonoclinic, C2/c
Temperature (K)167165166
a, b, c (Å)6.8793 (17), 7.644 (2), 8.026 (3)15.547 (4), 7.020 (2), 8.2270 (13)5.2561 (11), 13.145 (2), 13.321 (3)
α, β, γ (°)101.51 (2), 112.03 (2), 92.82 (3)90, 115.73 (2), 9090, 95.188 (16), 90
V3)379.8 (2)808.9 (4)916.6 (3)
Z244
Radiation typeMo KαMo KαMo Kα
µ (mm1)2.262.121.90
Crystal size (mm)0.52 × 0.20 × 0.140.40 × 0.26 × 0.240.60 × 0.55 × 0.50
Data collection
DiffractometerSiemens SMART 1K CCD
diffractometer
Siemens SMART 1K CCD
diffractometer
Siemens SMART 1K CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Multi-scan
(SADABS; Sheldrick, 2000)
Multi-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax0.575, 0.7290.530, 0.6020.301, 0.386
No. of measured, independent and
observed [I > 2σ(I)] reflections
6668, 2411, 1660 7132, 1611, 1402 8327, 1815, 1771
Rint0.0440.0250.025
(sin θ/λ)max1)0.7350.7900.790
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.091, 1.00 0.023, 0.061, 1.01 0.018, 0.049, 1.04
No. of reflections241116111815
No. of parameters1457090
H-atom treatmentAll H-atom parameters refinedH atoms treated by a mixture of independent and constrained refinementAll H-atom parameters refined
Δρmax, Δρmin (e Å3)1.07, 0.940.48, 0.640.56, 0.30

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O2i0.79 (6)1.97 (6)2.755 (3)170 (4)
O5—H5B···O3ii0.76 (4)1.87 (4)2.620 (3)167 (4)
O6—H6A···O3i0.87 (4)1.83 (4)2.694 (3)175 (4)
O6—H6B···O10.79 (5)2.20 (5)2.833 (3)138 (4)
O6—H6B···O4ii0.79 (5)2.30 (5)2.957 (3)142 (4)
O7—H7A···O4iii0.76 (4)2.18 (4)2.936 (4)175 (4)
O7—H7B···O5iv0.80 (5)2.17 (5)2.971 (4)176 (4)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y, z1; (iii) x+1, y+2, z+2; (iv) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O20.84 (2)1.85 (2)2.6485 (15)159 (2)
C2—H2A···O1i0.91 (2)2.57 (2)3.1796 (18)125.4 (17)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O4i0.809 (16)2.121 (16)2.9306 (11)178.8 (17)
O3—H3B···O2ii0.80 (2)1.91 (2)2.6481 (11)153 (2)
O4—H4A···O5iii0.797 (18)1.929 (18)2.7062 (12)164.8 (17)
O4—H4B···O2iv0.844 (18)1.879 (18)2.7098 (11)167.6 (16)
O5—H5A···O10.761 (16)1.958 (16)2.7122 (10)171.4 (17)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z+1/2; (iii) x1/2, y+1/2, z; (iv) x, y+1, z1/2.
Site symmetries for cobalt(II) fumarate trihydrate, methanol disolvate, pentahydrate and tetrahydrate top
trihydratemethanol disolvatepentahydratetetrahydrate
space groupP1C2/cC2/cP21/c
Z2444
Co2+1, 1(a)121
fumarate1111
cobalt(II) fumarate-topology2D3D1D1D
(a) two symmetry independant Co2+ ions
 

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