Hexaaqua­cobalt(II) 4,4′-(1,2-dihy­droxy­ethane-1,2-di­yl)dibenzoate monohydrate

Abstract

The title compound, [Co(H₂O)₆](C₁₆H₁₂O₆)·H₂O, is composed of one 4,4′-(1,2-dihy­droxy­ethane-1,2-di­yl)dibenzoate anion lying on an inversion center, one [Co(H₂O)₆]²⁺ dicationic complex and a solvent water mol­ecule located on mirror planes. In the crystal, a chain is constructed via O—H⋯O hydrogen bonds involving the carboxyl­ate and hydroxyl groups of the organic anion; the chains are further connected into a three-dimensional framework by additional O—H⋯O hydrogen bonds between the [Co(H₂O)₆]²⁺ cations, solvent water mol­ecules and the anions.

Related literature

For background to metal-organic structures and their potential applications as functional materials, see: Liang et al. (2000 ▶); Kondo et al. (2004 ▶); Lin et al. (2004 ▶); Fan & Hanson (2005 ▶); Laborda et al. (2004 ▶); Fei et al. (2005 ▶); Zhang et al. (2006 ▶).

Experimental

Crystal data

• [Co(H₂O)₆](C₁₆H₁₂O₆)·H₂O

• M _r = 485.30

• Monoclinic,

• a = 6.0430 (6) Å

• b = 20.487 (2) Å

• c = 8.6341 (9) Å

• β = 104.115 (1)°

• V = 1036.66 (18) ų

• Z = 2

• Mo Kα radiation

• μ = 0.89 mm⁻¹

• T = 298 K

• 0.38 × 0.20 × 0.18 mm

Data collection

• Bruker SMART 1000 CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.728, T _max = 0.856

• 5184 measured reflections

• 1867 independent reflections

• 1675 reflections with I > 2σ(I)

• R _int = 0.039

Refinement

• R[F ² > 2σ(F ²)] = 0.075

• wR(F ²) = 0.177

• S = 1.25

• 1867 reflections

• 144 parameters

• 11 restraints

• H-atom parameters constrained

• Δρ_max = 0.58 e Å⁻³

• Δρ_min = −0.46 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1i	0.82	2.00	2.811 (8)	168
O1W—H1W⋯O1ii	0.85	1.96	2.814 (9)	180
O1W—H2W⋯O2iii	0.85	1.81	2.665 (8)	179
O2W—H3W⋯O3iv	0.85	2.00	2.847 (8)	180
O2W—H4W⋯O5Wv	0.85	2.19	3.035 (11)	179
O3W—H5W⋯O4Wvi	0.85	1.93	2.778 (11)	172
O3W—H6W⋯O5W	0.85	1.91	2.756 (13)	171
O5W—H9W⋯O2	0.85	1.93	2.767 (10)	169
O4W—H7W⋯O1vii	0.84	1.88	2.695 (7)	163
O4W—H7W⋯O2vii	0.84	2.70	3.296 (9)	130

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

supplementary crystallographic information

Comment

Metal-organic coordination polymers have been greatly developed in recent years due to their captivating structure (Kondo et al., 2004; Fan et al., 2005) and potential applications as functional materials in electronic (Lin et al., 2004), magnetic (Laborda et al., 2004; Liang et al., 2000; Fei et al., 2005) and optical (Zhang et al., 2006) fields. Thus, we choose the ligand 4,4'- (1,2-dihydroxyethane-1,2-diyl)dibenzoate and Co(NO3)₂ under hydrothermal conditions to obtain new metal-organic complex, We report here the synthesis and structure of the title compound.

As shown in Figure 1, the title compound [Co(H₂O)₆][C₁₆H₁₂O₆].H₂O is composed of one 4,4'-(1,2-dihydroxyethane-1,2-diyl)dibenzoate anion lying on inversion center, one [Co6H₂O]²⁺ dicationic complex and a solvent water molecule locating on mirror planes. The Co^II ion is coordinated by six water molecules in an octahedral geometry. The hydroxyl groups of the 4,4'-(1,2-dihydroxyethane-1,2-diyl)dibenzoate anion are oriented such the the H atoms are directed away from the plane of the benzene ring. In the crystal, a one-dimensional chain is constructed via O—H···O hydrogen bonds interactions involving the carboxylate and hydroxyl groups of the organic anion, which was further connected into a three-dimensional framework by additional O—H···O hydrogen bonds formed by [Co(H₂O)₆]²⁺ cations, solvent water molecules and the anions.

Experimental

A mixture of 4,4'-(1,2-dihydroxyethane-1,2-diyl)dibenzoate(0.5 mol, 0.15 g) and Co(NO₃)₂ (0.5 mol, 0.14 g) in 30 ml of absolute ethanol was heated under reflux for 6 h in the presence of 1-2 drops of NaOH. The reaction mixture was cooled to room temperature for 2 h. The light-red crystal was filtered off and washed several times using absolute ethanol.

Refinement

H atoms bound to C atoms were placed at calculated positions and were treated as riding on the parent atoms, with C—H = 0.93 Å(aromatic) and 0.98 Å(CH) and with U_iso(H) = 1.2 U_eq(C) H atoms of hydroxyl group and water molecules were located in a difference Fourier map and refined as riding, with O—H = 0.85 Å and U_iso(H) = 1.5 U_eq(O) for water O atoms and 1.2 U_eq(O) for hydroxyl O atoms.

Figures

Fig. 1.

The title compound, with the atom-numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids (H atoms are omitted for clarity). [Symmetry codes: (i) 2-x, -y, 1-z; (ii) x, 0.5-y, z.]

Fig. 2.

The packing and hydrogen bonding of the title compound down the a axis (H atoms is not shown in the picture for clarity).

Crystal data

[Co(H2O)6](C16H12O6)·H2O	F(000) = 506
Mr = 485.30	Dx = 1.555 Mg m−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 2215 reflections
a = 6.0430 (6) Å	θ = 2.5–24.0°
b = 20.487 (2) Å	µ = 0.89 mm−1
c = 8.6341 (9) Å	T = 298 K
β = 104.115 (1)°	Block, red
V = 1036.66 (18) Å3	0.38 × 0.20 × 0.18 mm
Z = 2

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	1867 independent reflections
Radiation source: fine-focus sealed tube	1675 reflections with I > 2σ(I)
graphite	Rint = 0.039
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −6→7
Tmin = 0.728, Tmax = 0.856	k = −24→24
5184 measured reflections	l = −8→10

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.075	H-atom parameters constrained
wR(F2) = 0.177	w = 1/[σ2(Fo2) + (0.P)2 + 7.8675P] where P = (Fo2 + 2Fc2)/3
S = 1.25	(Δ/σ)max < 0.001
1867 reflections	Δρmax = 0.58 e Å−3
144 parameters	Δρmin = −0.46 e Å−3
11 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0093 (18)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.8509 (2)	0.2500	0.54019 (15)	0.0234 (4)
O1	0.4205 (10)	0.1418 (3)	−0.2097 (7)	0.0505 (16)
O2	0.1731 (10)	0.1522 (3)	−0.0588 (8)	0.0616 (19)
O3	0.8284 (10)	−0.0725 (3)	0.4766 (7)	0.0536 (17)
H3	0.7734	−0.0959	0.3999	0.080*
O1W	0.8192 (10)	0.1750 (3)	0.6947 (7)	0.062 (2)
H1W	0.6984	0.1651	0.7232	0.093*
H2W	0.9330	0.1678	0.7727	0.093*
O2W	0.9112 (10)	0.1813 (3)	0.3752 (7)	0.0540 (16)
H3W	0.9892	0.1489	0.4198	0.081*
H4W	0.9848	0.2002	0.3158	0.081*
O3W	0.5046 (14)	0.2500	0.4420 (9)	0.061 (3)
H5W	0.4269	0.2500	0.5118	0.091*
H6W	0.4125	0.2500	0.3502	0.091*
O4W	1.2136 (12)	0.2500	0.6463 (9)	0.0351 (17)
H7W	1.2522	0.2875	0.6825	0.053*
O5W	0.1686 (19)	0.2500	0.1613 (12)	0.099 (4)
H9W	0.1690	0.2164	0.1036	0.148*
C1	0.3585 (14)	0.1323 (4)	−0.0814 (10)	0.044 (2)
C2	0.5138 (13)	0.0948 (4)	0.0530 (10)	0.041 (2)
C3	0.7192 (14)	0.0687 (4)	0.0317 (10)	0.045 (2)
H3A	0.7632	0.0762	−0.0627	0.054*
C4	0.8566 (15)	0.0316 (4)	0.1527 (10)	0.047 (2)
H4	0.9921	0.0142	0.1380	0.056*
C5	0.7956 (14)	0.0202 (4)	0.2936 (10)	0.043 (2)
C6	0.5928 (15)	0.0463 (4)	0.3163 (10)	0.048 (2)
H6	0.5508	0.0393	0.4117	0.058*
C7	0.4528 (14)	0.0831 (4)	0.1944 (10)	0.047 (2)
H7A	0.3163	0.0999	0.2089	0.056*
C8	0.9495 (15)	−0.0203 (4)	0.4267 (10)	0.046 (2)
H8A	1.0745	−0.0386	0.3863	0.055*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co1	0.0209 (7)	0.0289 (7)	0.0194 (7)	0.000	0.0032 (5)	0.000
O1	0.041 (3)	0.049 (4)	0.053 (4)	0.002 (3)	−0.005 (3)	0.010 (3)
O2	0.039 (4)	0.075 (5)	0.062 (4)	0.016 (3)	−0.005 (3)	0.024 (4)
O3	0.058 (4)	0.037 (3)	0.054 (4)	−0.004 (3)	−0.010 (3)	0.004 (3)
O1W	0.035 (3)	0.086 (5)	0.058 (4)	−0.008 (3)	−0.002 (3)	0.033 (4)
O2W	0.056 (4)	0.053 (4)	0.050 (4)	0.000 (3)	0.006 (3)	−0.010 (3)
O3W	0.037 (5)	0.118 (8)	0.024 (4)	0.000	−0.001 (4)	0.000
O4W	0.033 (4)	0.031 (4)	0.039 (4)	0.000	0.006 (3)	0.000
O5W	0.068 (7)	0.184 (14)	0.046 (6)	0.000	0.017 (5)	0.000
C1	0.039 (5)	0.038 (5)	0.047 (5)	−0.006 (4)	−0.009 (4)	0.008 (4)
C2	0.036 (4)	0.030 (4)	0.045 (5)	−0.001 (3)	−0.011 (4)	0.004 (4)
C3	0.045 (5)	0.039 (5)	0.044 (5)	0.001 (4)	−0.003 (4)	0.007 (4)
C4	0.042 (5)	0.041 (5)	0.047 (5)	0.011 (4)	−0.008 (4)	0.004 (4)
C5	0.040 (5)	0.029 (4)	0.047 (5)	−0.001 (3)	−0.014 (4)	0.002 (4)
C6	0.044 (5)	0.050 (5)	0.041 (5)	−0.001 (4)	−0.007 (4)	0.008 (4)
C7	0.034 (4)	0.045 (5)	0.054 (5)	0.002 (4)	−0.003 (4)	0.009 (4)
C8	0.044 (5)	0.032 (4)	0.048 (5)	0.000 (4)	−0.013 (4)	0.006 (4)

Geometric parameters (Å, °)

Co1—O3W	2.058 (8)	O4W—H7W	0.8413
Co1—O1Wi	2.074 (6)	O5W—H9W	0.8500
Co1—O1W	2.074 (6)	C1—C2	1.511 (10)
Co1—O2W	2.097 (6)	C2—C7	1.380 (12)
Co1—O2Wi	2.097 (6)	C2—C3	1.404 (12)
Co1—O4W	2.159 (7)	C3—C4	1.392 (11)
O1—C1	1.268 (10)	C3—H3A	0.9300
O2—C1	1.251 (11)	C4—C5	1.374 (12)
O3—C8	1.420 (10)	C4—H4	0.9300
O3—H3	0.8200	C5—C6	1.394 (12)
O1W—H1W	0.8500	C5—C8	1.534 (10)
O1W—H2W	0.8500	C6—C7	1.399 (11)
O2W—H3W	0.8500	C6—H6	0.9300
O2W—H4W	0.8500	C7—H7A	0.9300
O3W—H5W	0.8501	C8—C8ii	1.513 (16)
O3W—H6W	0.8500	C8—H8A	0.9800
O3W—Co1—O1Wi	91.2 (2)	O2—C1—C2	117.2 (8)
O3W—Co1—O1W	91.2 (2)	O1—C1—C2	119.3 (8)
O1Wi—Co1—O1W	95.6 (4)	C7—C2—C3	119.0 (7)
O3W—Co1—O2W	92.7 (2)	C7—C2—C1	121.2 (8)
O1Wi—Co1—O2W	173.2 (3)	C3—C2—C1	119.7 (8)
O1W—Co1—O2W	89.9 (3)	C4—C3—C2	119.6 (8)
O3W—Co1—O2Wi	92.7 (2)	C4—C3—H3A	120.2
O1Wi—Co1—O2Wi	89.9 (3)	C2—C3—H3A	120.2
O1W—Co1—O2Wi	173.2 (3)	C5—C4—C3	121.2 (8)
O2W—Co1—O2Wi	84.3 (4)	C5—C4—H4	119.4
O3W—Co1—O4W	179.3 (3)	C3—C4—H4	119.4
O1Wi—Co1—O4W	88.3 (2)	C4—C5—C6	119.6 (7)
O1W—Co1—O4W	88.3 (2)	C4—C5—C8	120.7 (8)
O2W—Co1—O4W	87.8 (2)	C6—C5—C8	119.7 (8)
O2Wi—Co1—O4W	87.8 (2)	C5—C6—C7	119.5 (8)
C8—O3—H3	109.5	C5—C6—H6	120.3
Co1—O1W—H1W	125.7	C7—C6—H6	120.3
Co1—O1W—H2W	117.0	C2—C7—C6	121.1 (8)
H1W—O1W—H2W	108.4	C2—C7—H7A	119.4
Co1—O2W—H3W	112.7	C6—C7—H7A	119.4
Co1—O2W—H4W	107.9	O3—C8—C8ii	107.0 (9)
H3W—O2W—H4W	108.4	O3—C8—C5	111.8 (7)
Co1—O3W—H5W	112.9	C8ii—C8—C5	112.1 (8)
Co1—O3W—H6W	138.9	O3—C8—H8A	108.6
H5W—O3W—H6W	108.2	C8ii—C8—H8A	108.6
Co1—O4W—H7W	108.6	C5—C8—H8A	108.6
O2—C1—O1	123.5 (8)
O2—C1—C2—C7	0.1 (12)	C4—C5—C6—C7	0.7 (12)
O1—C1—C2—C7	−179.7 (8)	C8—C5—C6—C7	−179.9 (7)
O2—C1—C2—C3	177.1 (8)	C3—C2—C7—C6	0.6 (13)
O1—C1—C2—C3	−2.8 (12)	C1—C2—C7—C6	177.5 (7)
C7—C2—C3—C4	0.1 (12)	C5—C6—C7—C2	−1.0 (13)
C1—C2—C3—C4	−176.9 (7)	C4—C5—C8—O3	−126.6 (9)
C2—C3—C4—C5	−0.4 (13)	C6—C5—C8—O3	54.0 (10)
C3—C4—C5—C6	0.0 (13)	C4—C5—C8—C8ii	113.3 (11)
C3—C4—C5—C8	−179.4 (7)	C6—C5—C8—C8ii	−66.1 (12)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1iii	0.82	2.00	2.811 (8)	168
O1W—H1W···O1iv	0.85	1.96	2.814 (9)	180
O1W—H2W···O2v	0.85	1.81	2.665 (8)	179
O2W—H3W···O3ii	0.85	2.00	2.847 (8)	180
O2W—H4W···O5Wvi	0.85	2.19	3.035 (11)	179
O3W—H5W···O4Wvii	0.85	1.93	2.778 (11)	172
O3W—H6W···O5W	0.85	1.91	2.756 (13)	171
O5W—H9W···O2	0.85	1.93	2.767 (10)	169
O4W—H7W···O1viii	0.84	1.88	2.695 (7)	163
O4W—H7W···O2viii	0.84	2.70	3.296 (9)	130

Symmetry codes: (iii) −x+1, −y, −z; (iv) x, y, z+1; (v) x+1, y, z+1; (ii) −x+2, −y, −z+1; (vi) x+1, y, z; (vii) x−1, y, z; (viii) x+1, −y+1/2, z+1.