Hexaaqua­cobalt(II) 3,3′-dicarb­oxy­biphenyl-4,4′-dicarboxyl­ate

Abstract

In the crystal structure of the title compound, [Co(H₂O)₆](C₁₆H₈O₈), both the cation and anion are centrosymmetric. The Co cation displays a CoO₆ octa­hedral geometry formed by six water mol­ecules. In the anion, the two carboxyl groups are oriented at dihedral angles of 4.8 (5) and 10.4 (7)° with respect to the benzene ring. Very strong O—H⋯O hydrogen bonds between the protonated and deprotonated carboxylate groups occur. Neighbouring cations and anions are connected through O—H⋯O hydrogen bonds into a three-dimensional supra­molecular structure.

Related literature

For related metal complexes with the biphenyl-3,3′,4,4′-tetra­carboxyl­ate ligand, see: Sun et al. (2009 ▶); Wang et al. (2005 ▶, 2006 ▶). For the structures containing the 4,4′-dicarb­oxy­biphenyl-3,3′-dicarboxyl­ate ligand, see: Kang et al. (2009a ▶,b ▶); Zhu et al. (2008 ▶).

Experimental

Crystal data

• [Co(H₂O)₆](C₁₆H₈O₈)

• M _r = 495.25

• Triclinic,

• a = 6.5197 (14) Å

• b = 7.9514 (17) Å

• c = 9.664 (2) Å

• α = 76.339 (2)°

• β = 87.656 (2)°

• γ = 86.221 (2)°

• V = 485.57 (18) ų

• Z = 1

• Mo Kα radiation

• μ = 0.96 mm⁻¹

• T = 293 K

• 0.23 × 0.19 × 0.12 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.804, T _max = 0.895

• 2871 measured reflections

• 1590 independent reflections

• 1305 reflections with I > 2σ(I)

• R _int = 0.028

Refinement

• R[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 0.169

• S = 1.00

• 1590 reflections

• 146 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.47 e Å⁻³

• Δρ_min = −0.43 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Co1—O5	2.054 (3)
Co1—O6	2.027 (3)
Co1—O7	2.082 (3)

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4	0.85 (2)	1.55 (2)	2.391 (5)	173 (8)
O5—H5B⋯O4i	0.96	2.17	2.820 (5)	124
O5—H5C⋯O2ii	0.96	1.97	2.789 (4)	142
O6—H6A⋯O3iii	0.96	1.84	2.676 (4)	144
O6—H6C⋯O1ii	0.96	1.79	2.708 (4)	159
O7—H7A⋯O1iv	0.96	1.83	2.749 (5)	159
O7—H7C⋯O3	0.96	1.99	2.822 (5)	144

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

Biphenyl–3,3',4,4'–tetracarboxylic acid have been used to construct high–dimensional supramolecular networks due to their versatile coordination modes and potential covalent or hydrogen bonding interactions with related parts in the assembly process (Sun et al. 2009; Wang et al. 2005) such as one-dimensional covalent zigzag chain coexist with one-dimensional hydrogen-bonded ladder (Wang et al. 2006). Here we reported a mononuclear complex, containing two ionic components of complex [Co(H₂O)₆](C₁₆H₁₈O₈) (I) in which the two parts are connected via O—H···O hydrogen bonds forming a three-dimensional framework. The structure of the compound (I) consists of discrete ionic entities. A labeled diagram of the crystal [Co(H₂O)₆](C₁₆H₁₈O₁₈) is shown in Fig. 1. In the cations, the metal atom is surrounded by six aqua ligands, exhibiting a slightly distorted octahedral stereochemistry. The cis/trans O—Co—O angles are nearly 90 °. The average Co—O distance for compound (I) is 2.077 Å. The anion 3,3',4,4'–biphenyltetralate contain inversion center. The mean plane was calculated throughout the six atoms of the benzene ring. Because of symmetric reason, the two benzene rings of the biphenyl ligand are coplanar. The carboxylate groups are almost coplanar with the benzene ring with the largest deviation of -0.205 (6) Å for O4. As expected, there are considerable hydrogen bonds in the structure. The bond distances and angles are listed in Table 2. A three–dimensional structure was formed via three kinds of hydrogen bonds between the coordinated water molecules and carboxyl groups which also help to consolide the crystal packing (Fig. 2).

Experimental

A mixture of biphenyl-3,3',4,4'-tetracarboxylic acid (0.2 mmol) and Co(NO₃)₂.6H₂O (0.4 mmol) in 12 ml methanol/water (8:3) sealed in a 25 ml Telflon-lined stainless steel autoclave was kept at 393 K for three days. Single crystals suitable for the X-ray experiment were obtained.

Refinement

The carboxyl H atom was located in a difference map and refined isotropically. The H atoms of aromatic ring and water molecules were generated geometrically and were included in the refinement in the riding model approximation with C—H = 0.93 Å, U_iso(H)= 1.2 U_eq(C) and O—H = 0.96 Å, U_iso(H)= 1.5U_eq(O).

Figures

Fig. 1.

The molecular structure of the title complex with the atom-numbering diagram. Ellipsoids were drawn at the 30% probability level.

Fig. 2.

The packing diagram of (I). Hydrogen bonds are marked by dashed line.

Crystal data

[Co(H2O)6](C16H8O8)	Z = 1
Mr = 495.25	F(000) = 255
Triclinic, P1	Dx = 1.694 Mg m−3
a = 6.5197 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9514 (17) Å	Cell parameters from 774 reflections
c = 9.664 (2) Å	θ = 2.2–25.0°
α = 76.339 (2)°	µ = 0.96 mm−1
β = 87.656 (2)°	T = 293 K
γ = 86.221 (2)°	Block, pink
V = 485.57 (18) Å3	0.23 × 0.19 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1590 independent reflections
Radiation source: fine-focus sealed tube	1305 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→7
Tmin = 0.804, Tmax = 0.895	k = −9→9
2871 measured reflections	l = −11→10

Refinement

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.1263P)2] where P = (Fo2 + 2Fc2)/3
1590 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.47 e Å−3
1 restraint	Δρmin = −0.43 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	1.0000	0.0000	0.5000	0.0281 (3)
O1	0.5091 (5)	0.1808 (4)	1.2457 (3)	0.0408 (8)
O2	0.3077 (5)	0.1278 (4)	1.0880 (4)	0.0396 (8)
O3	0.4682 (5)	0.2634 (5)	0.6417 (4)	0.0494 (10)
O4	0.2791 (5)	0.1755 (4)	0.8356 (3)	0.0417 (8)
O5	1.0135 (5)	−0.0174 (5)	0.2911 (3)	0.0434 (9)
H5B	0.9751	−0.1302	0.2858	0.065*
H5C	1.1512	−0.0002	0.2537	0.065*
O6	1.2248 (5)	0.1707 (5)	0.4594 (4)	0.0444 (9)
H6A	1.3079	0.1541	0.5419	0.067*
H6C	1.3089	0.1508	0.3803	0.067*
O7	0.7843 (5)	0.2081 (4)	0.4461 (4)	0.0441 (9)
H7A	0.6763	0.1760	0.3946	0.066*
H7C	0.7277	0.2372	0.5314	0.066*
C1	0.6112 (6)	0.2899 (5)	1.0027 (4)	0.0255 (9)
C2	0.7719 (6)	0.3637 (5)	1.0551 (5)	0.0257 (9)
H2B	0.7823	0.3463	1.1532	0.031*
C3	0.9157 (6)	0.4613 (5)	0.9679 (5)	0.0267 (9)
C4	0.8945 (7)	0.4888 (6)	0.8216 (5)	0.0336 (10)
H4B	0.9850	0.5580	0.7599	0.040*
C5	0.7413 (7)	0.4147 (6)	0.7674 (5)	0.0358 (11)
H5A	0.7335	0.4324	0.6691	0.043*
C6	0.5974 (6)	0.3144 (5)	0.8535 (5)	0.0279 (9)
C7	0.4682 (6)	0.1923 (5)	1.1202 (5)	0.0288 (10)
C8	0.4405 (7)	0.2462 (6)	0.7705 (5)	0.0311 (10)
H2	0.293 (12)	0.152 (9)	0.999 (2)	0.10 (3)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co1	0.0215 (5)	0.0511 (6)	0.0143 (5)	−0.0164 (3)	0.0002 (3)	−0.0092 (4)
O1	0.0359 (17)	0.070 (2)	0.0193 (19)	−0.0237 (16)	0.0020 (14)	−0.0103 (15)
O2	0.0344 (17)	0.062 (2)	0.025 (2)	−0.0271 (15)	0.0024 (15)	−0.0103 (16)
O3	0.046 (2)	0.087 (3)	0.024 (2)	−0.0326 (19)	0.0002 (16)	−0.0224 (17)
O4	0.0316 (17)	0.066 (2)	0.032 (2)	−0.0238 (15)	0.0005 (14)	−0.0133 (16)
O5	0.0368 (18)	0.077 (2)	0.0222 (18)	−0.0290 (16)	0.0048 (14)	−0.0167 (16)
O6	0.0373 (18)	0.074 (2)	0.028 (2)	−0.0310 (16)	0.0045 (15)	−0.0191 (16)
O7	0.0361 (18)	0.070 (2)	0.0301 (19)	−0.0101 (16)	−0.0049 (15)	−0.0162 (16)
C1	0.025 (2)	0.032 (2)	0.022 (2)	−0.0069 (16)	0.0007 (17)	−0.0092 (17)
C2	0.026 (2)	0.034 (2)	0.018 (2)	−0.0103 (17)	−0.0028 (17)	−0.0074 (17)
C3	0.024 (2)	0.033 (2)	0.024 (2)	−0.0054 (17)	−0.0038 (18)	−0.0064 (17)
C4	0.038 (2)	0.045 (2)	0.022 (2)	−0.023 (2)	−0.0027 (19)	−0.0090 (19)
C5	0.042 (3)	0.045 (3)	0.024 (3)	−0.019 (2)	−0.002 (2)	−0.0117 (19)
C6	0.024 (2)	0.034 (2)	0.029 (3)	−0.0078 (17)	−0.0020 (18)	−0.0103 (18)
C7	0.028 (2)	0.037 (2)	0.026 (3)	−0.0109 (18)	0.0014 (19)	−0.0126 (18)
C8	0.029 (2)	0.040 (2)	0.029 (3)	−0.0118 (19)	−0.0047 (19)	−0.0137 (19)

Geometric parameters (Å, °)

Co1—O5	2.054 (3)	O7—H7A	0.9600
Co1—O5i	2.054 (3)	O7—H7C	0.9600
Co1—O6	2.027 (3)	C1—C2	1.401 (6)
Co1—O6i	2.027 (3)	C1—C6	1.415 (6)
Co1—O7	2.082 (3)	C1—C7	1.534 (6)
Co1—O7i	2.082 (3)	C2—C3	1.383 (6)
O1—C7	1.233 (5)	C2—H2B	0.9300
O2—C7	1.276 (5)	C3—C4	1.390 (6)
O2—H2	0.85 (2)	C3—C3ii	1.516 (8)
O3—C8	1.226 (6)	C4—C5	1.374 (6)
O4—C8	1.295 (5)	C4—H4B	0.9300
O5—H5B	0.9600	C5—C6	1.389 (6)
O5—H5C	0.9601	C5—H5A	0.9300
O6—H6A	0.9600	C6—C8	1.526 (6)
O6—H6C	0.9600
O6—Co1—O6i	180.0	C2—C1—C6	118.3 (4)
O6—Co1—O5	90.40 (13)	C2—C1—C7	113.4 (4)
O6i—Co1—O5	89.60 (13)	C6—C1—C7	128.3 (4)
O6—Co1—O5i	89.60 (13)	C3—C2—C1	123.2 (4)
O6i—Co1—O5i	90.40 (13)	C3—C2—H2B	118.4
O5—Co1—O5i	180.0	C1—C2—H2B	118.4
O6—Co1—O7	88.72 (14)	C2—C3—C4	117.5 (4)
O6i—Co1—O7	91.28 (14)	C2—C3—C3ii	120.3 (5)
O5—Co1—O7	89.16 (14)	C4—C3—C3ii	122.2 (5)
O5i—Co1—O7	90.84 (14)	C5—C4—C3	120.6 (4)
O6—Co1—O7i	91.28 (14)	C5—C4—H4B	119.7
O6i—Co1—O7i	88.72 (14)	C3—C4—H4B	119.7
O5—Co1—O7i	90.83 (14)	C4—C5—C6	122.6 (4)
O5i—Co1—O7i	89.17 (14)	C4—C5—H5A	118.7
O7—Co1—O7i	180.000 (1)	C6—C5—H5A	118.7
C7—O2—H2	111 (5)	C5—C6—C1	117.8 (4)
Co1—O5—H5B	109.3	C5—C6—C8	113.7 (4)
Co1—O5—H5C	109.4	C1—C6—C8	128.5 (4)
H5B—O5—H5C	109.5	O1—C7—O2	120.9 (4)
Co1—O6—H6A	109.3	O1—C7—C1	118.8 (4)
Co1—O6—H6C	109.1	O2—C7—C1	120.3 (4)
H6A—O6—H6C	109.5	O3—C8—O4	121.2 (4)
Co1—O7—H7A	109.1	O3—C8—C6	118.9 (4)
Co1—O7—H7C	109.5	O4—C8—C6	119.9 (4)
H7A—O7—H7C	109.5
C6—C1—C2—C3	0.9 (6)	C2—C1—C6—C8	179.1 (4)
C7—C1—C2—C3	−178.3 (4)	C7—C1—C6—C8	−1.9 (7)
C1—C2—C3—C4	1.4 (6)	C2—C1—C7—O1	−2.9 (6)
C1—C2—C3—C3ii	179.4 (4)	C6—C1—C7—O1	178.0 (4)
C2—C3—C4—C5	−2.8 (7)	C2—C1—C7—O2	175.6 (4)
C3ii—C3—C4—C5	179.2 (5)	C6—C1—C7—O2	−3.5 (7)
C3—C4—C5—C6	2.0 (7)	C5—C6—C8—O3	9.6 (6)
C4—C5—C6—C1	0.3 (7)	C1—C6—C8—O3	−171.2 (4)
C4—C5—C6—C8	179.6 (4)	C5—C6—C8—O4	−168.7 (4)
C2—C1—C6—C5	−1.8 (6)	C1—C6—C8—O4	10.4 (7)
C7—C1—C6—C5	177.3 (4)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4	0.85 (2)	1.55 (2)	2.391 (5)	173 (8)
O5—H5B···O4iii	0.96	2.17	2.820 (5)	124
O5—H5C···O2iv	0.96	1.97	2.789 (4)	142
O6—H6A···O3v	0.96	1.84	2.676 (4)	144
O6—H6C···O1iv	0.96	1.79	2.708 (4)	159
O7—H7A···O1vi	0.96	1.83	2.749 (5)	159
O7—H7C···O3	0.96	1.99	2.822 (5)	144

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