Triaqua-(1,10-phenanthroline-2,9-dicarboxyl-ato)cobalt(II) dihydrate.

The title compound, [Co(C(14)H(6)N(2)O(4))(H(2)O)(3)]·2H(2)O, has two-fold crystallographic symmetry. The Co(II) atom is in a distorted penta-gonal-bipyramidal coordination environment with two N atoms and two O atoms from a tetradentate 1,10-phenanthroline-2,9-dicarboxyl-ate ligand and one O atom from a water mol-ecule forming the penta-gonal plane, and two O atoms from two water mol-ecules occupying axial positions. In the crystal, adjacent mol-ecules are linked by O-H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For the structures and properties of coordination compounds, see: Zhao et al. (2008 ▶); Poulsen et al. (2005 ▶). For the use of multi-carboxyl­ate and heterocyclic carboxylic acids in coordination chemistry, see: Luo et al. (2009 ▶); Han et al. (2009 ▶) and for the dicarboxyl­ate ligand H2PDA (H2PDA is 1,10-phenanthroline-2,9-dicarboxylic acid), see: Xie et al. (2005 ▶). For the isotypic structure [Mg(PDA)(H2O)3]·2H2O, see: Park et al. (2001 ▶). For the high affinity of the CoII ion to water mol­ecules, see: (Zhang & Chen (2009 ▶). For bond distances and angles in other seven-coordinated CoII complexes, see: Newkome et al. (1984 ▶); Rajput & Biradha (2007 ▶). For the synthesis of 1,10-phenanthroline-2,9-dicarboxylic acid, see: De Cian et al. (2007 ▶).

Experimental

Crystal data

[Co(C14H6N2O4)(H2O)3]·2H2O

M = 415.22

Orthorhombic,

a = 7.4093 (5) Å

b = 18.9267 (17) Å

c = 46.609 (4) Å

V = 6536.1 (9) Å3

Z = 16

Mo Kα radiation

μ = 1.11 mm−1

T = 296 K

0.20 × 0.19 × 0.17 mm

Data collection

Bruker SMART CCD diffractometer

9724 measured reflections

1877 independent reflections

1520 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.098

S = 1.06

1877 reflections

132 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.96 e Å−3

Δρmin = −0.46 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810007567/hg2639sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007567/hg2639Isup2.hkl

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

[Co(C14H6N2O4)(H2O)3]·2H2O	F(000) = 3408
Mr = 415.22	Dx = 1.688 Mg m−3
Orthorhombic, Fddd	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -F 2uv 2vw	Cell parameters from 2624 reflections
a = 7.4093 (5) Å	θ = 3.0–25.2°
b = 18.9267 (17) Å	µ = 1.11 mm−1
c = 46.609 (4) Å	T = 296 K
V = 6536.1 (9) Å3	Block, yellow
Z = 16	0.20 × 0.19 × 0.17 mm

Bruker APEXII CCD diffractometer	1520 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
graphite	θmax = 27.5°, θmin = 1.8°
φ and ω scans	h = −9→9
9724 measured reflections	k = −24→23
1877 independent reflections	l = −45→60

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0494P)2 + 16.2882P] where P = (Fo2 + 2Fc2)/3
1877 reflections	(Δ/σ)max = 0.001
132 parameters	Δρmax = 0.96 e Å−3
2 restraints	Δρmin = −0.46 e Å−3

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 > 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.8750	0.8750	0.575281 (8)	0.02703 (15)
C1	0.5006 (3)	0.79758 (12)	0.56914 (5)	0.0303 (5)
C2	0.5619 (3)	0.81188 (11)	0.53888 (5)	0.0286 (5)
C3	0.4668 (3)	0.79146 (13)	0.51428 (5)	0.0369 (5)
H3	0.3573	0.7678	0.5160	0.044*
C4	0.5356 (4)	0.80639 (13)	0.48763 (5)	0.0403 (6)
H4	0.4723	0.7936	0.4712	0.048*
C5	0.7025 (3)	0.84111 (12)	0.48536 (5)	0.0336 (5)
C6	0.7884 (3)	0.85853 (11)	0.51113 (4)	0.0283 (5)
C7	0.7938 (4)	0.85890 (13)	0.45911 (5)	0.0426 (6)
H7	0.7394	0.8479	0.4417	0.051*
H3A	0.953 (3)	0.8937 (8)	0.6302 (4)	0.063 (10)*
H5A	0.8692	0.7242	0.6386	0.075*
H5B	0.8592	0.6518	0.6227	0.075*	0.50
H5B'	0.7138	0.7061	0.6221	0.075*	0.50
H4A	1.088 (5)	0.7728 (17)	0.5770 (7)	0.049 (10)*
H4B	0.955 (5)	0.7546 (18)	0.5909 (8)	0.060 (11)*
N6	0.7184 (2)	0.84503 (10)	0.53724 (4)	0.0274 (4)
O1	0.6029 (2)	0.82142 (9)	0.58824 (4)	0.0380 (4)
O2	0.3589 (2)	0.76361 (11)	0.57280 (4)	0.0446 (5)
O3	0.8750	0.8750	0.61974 (5)	0.0459 (7)
O4	0.9892 (3)	0.77204 (10)	0.57658 (4)	0.0359 (4)
O5	0.8336 (4)	0.69890 (11)	0.62306 (5)	0.0670 (7)

	U11	U22	U33	U12	U13	U23
Co1	0.0278 (3)	0.0337 (3)	0.0196 (2)	−0.00067 (18)	0.000	0.000
C1	0.0231 (11)	0.0333 (12)	0.0344 (12)	0.0020 (9)	0.0013 (9)	−0.0046 (9)
C2	0.0256 (11)	0.0298 (11)	0.0305 (11)	0.0043 (9)	−0.0041 (9)	−0.0060 (8)
C3	0.0325 (13)	0.0401 (13)	0.0382 (13)	−0.0006 (10)	−0.0095 (10)	−0.0084 (10)
C4	0.0463 (15)	0.0418 (14)	0.0328 (13)	0.0055 (11)	−0.0153 (11)	−0.0087 (10)
C5	0.0438 (14)	0.0321 (12)	0.0248 (11)	0.0101 (11)	−0.0069 (9)	−0.0048 (9)
C6	0.0313 (12)	0.0296 (11)	0.0239 (10)	0.0057 (9)	−0.0010 (9)	−0.0015 (8)
C7	0.0637 (17)	0.0412 (14)	0.0228 (11)	0.0069 (12)	−0.0065 (11)	−0.0037 (9)
N6	0.0261 (9)	0.0320 (9)	0.0241 (9)	0.0013 (8)	−0.0014 (7)	−0.0023 (7)
O1	0.0327 (9)	0.0544 (10)	0.0268 (8)	−0.0075 (8)	0.0024 (7)	−0.0060 (7)
O2	0.0304 (10)	0.0550 (11)	0.0483 (11)	−0.0086 (8)	0.0052 (8)	−0.0053 (8)
O3	0.0490 (16)	0.0680 (17)	0.0206 (11)	−0.0285 (14)	0.000	0.000
O4	0.0312 (11)	0.0403 (10)	0.0363 (10)	0.0012 (8)	−0.0012 (8)	0.0004 (8)
O5	0.1009 (19)	0.0418 (11)	0.0582 (13)	−0.0027 (12)	0.0008 (13)	−0.0004 (10)

Co1—O3	2.072 (2)	C4—C5	1.404 (4)
Co1—O4	2.1254 (19)	C4—H4	0.9300
Co1—O4i	2.1254 (19)	C5—C6	1.399 (3)
Co1—N6i	2.1936 (18)	C5—C7	1.438 (3)
Co1—N6	2.1936 (18)	C6—N6	1.348 (3)
Co1—O1	2.3364 (16)	C6—C6i	1.426 (5)
Co1—O1i	2.3364 (16)	C7—C7i	1.349 (6)
C1—O2	1.243 (3)	C7—H7	0.9300
C1—O1	1.253 (3)	O3—H3A	0.837 (17)
C1—C2	1.506 (3)	O4—H4A	0.74 (4)
C2—N6	1.320 (3)	O4—H4B	0.79 (4)
C2—C3	1.400 (3)	O5—H5A	0.9066
C3—C4	1.372 (4)	O5—H5B	0.9119
C3—H3	0.9300	O5—H5B'	0.8988
O3—Co1—O4	88.37 (5)	C4—C3—C2	119.8 (2)
O3—Co1—O4i	88.37 (5)	C4—C3—H3	120.1
O4—Co1—O4i	176.75 (11)	C2—C3—H3	120.1
O3—Co1—N6i	143.92 (5)	C3—C4—C5	119.5 (2)
O4—Co1—N6i	92.83 (8)	C3—C4—H4	120.3
O4i—Co1—N6i	89.80 (7)	C5—C4—H4	120.3
O3—Co1—N6	143.92 (5)	C6—C5—C4	116.5 (2)
O4—Co1—N6	89.80 (7)	C6—C5—C7	117.5 (2)
O4i—Co1—N6	92.83 (8)	C4—C5—C7	126.0 (2)
N6i—Co1—N6	72.16 (10)	N6—C6—C5	123.7 (2)
O3—Co1—O1	75.02 (4)	N6—C6—C6i	115.43 (12)
O4—Co1—O1	86.46 (8)	C5—C6—C6i	120.83 (14)
O4i—Co1—O1	92.69 (7)	C7i—C7—C5	121.69 (15)
N6i—Co1—O1	141.06 (6)	C7i—C7—H7	119.2
N6—Co1—O1	68.91 (6)	C5—C7—H7	119.2
O3—Co1—O1i	75.02 (4)	C2—N6—C6	118.72 (18)
O4—Co1—O1i	92.69 (7)	C2—N6—Co1	122.73 (14)
O4i—Co1—O1i	86.46 (8)	C6—N6—Co1	118.50 (15)
N6i—Co1—O1i	68.91 (6)	C1—O1—Co1	119.62 (15)
N6—Co1—O1i	141.06 (6)	Co1—O3—H3A	125.6 (15)
O1—Co1—O1i	150.03 (8)	Co1—O4—H4A	112 (3)
O2—C1—O1	126.8 (2)	Co1—O4—H4B	106 (2)
O2—C1—C2	118.4 (2)	H4A—O4—H4B	108 (3)
O1—C1—C2	114.7 (2)	H5A—O5—H5B	118.1
N6—C2—C3	121.7 (2)	H5A—O5—H5B'	104.2
N6—C2—C1	113.83 (18)	H5B—O5—H5B'	110.7
C3—C2—C1	124.5 (2)
O2—C1—C2—N6	−176.6 (2)	C6i—C6—N6—Co1	0.2 (3)
O1—C1—C2—N6	2.6 (3)	O3—Co1—N6—C2	−2.8 (2)
O2—C1—C2—C3	2.2 (3)	O4—Co1—N6—C2	84.14 (17)
O1—C1—C2—C3	−178.6 (2)	O4i—Co1—N6—C2	−93.94 (17)
N6—C2—C3—C4	−0.5 (4)	N6i—Co1—N6—C2	177.2 (2)
C1—C2—C3—C4	−179.2 (2)	O1—Co1—N6—C2	−2.14 (16)
C2—C3—C4—C5	1.0 (4)	O1i—Co1—N6—C2	178.19 (14)
C3—C4—C5—C6	−0.1 (3)	O3—Co1—N6—C6	179.93 (11)
C3—C4—C5—C7	178.5 (2)	O4—Co1—N6—C6	−93.11 (16)
C4—C5—C6—N6	−1.3 (3)	O4i—Co1—N6—C6	88.81 (16)
C7—C5—C6—N6	179.9 (2)	N6i—Co1—N6—C6	−0.07 (11)
C4—C5—C6—C6i	177.6 (2)	O1—Co1—N6—C6	−179.40 (17)
C7—C5—C6—C6i	−1.2 (4)	O1i—Co1—N6—C6	0.9 (2)
C6—C5—C7—C7i	0.1 (4)	O2—C1—O1—Co1	174.59 (19)
C4—C5—C7—C7i	−178.6 (3)	C2—C1—O1—Co1	−4.5 (3)
C3—C2—N6—C6	−0.9 (3)	O3—Co1—O1—C1	−176.70 (18)
C1—C2—N6—C6	178.00 (18)	O4—Co1—O1—C1	−87.44 (18)
C3—C2—N6—Co1	−178.11 (16)	O4i—Co1—O1—C1	95.71 (18)
C1—C2—N6—Co1	0.7 (3)	N6i—Co1—O1—C1	2.7 (2)
C5—C6—N6—C2	1.8 (3)	N6—Co1—O1—C1	3.71 (16)
C6i—C6—N6—C2	−177.2 (2)	O1i—Co1—O1—C1	−176.70 (18)
C5—C6—N6—Co1	179.17 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1ii	0.837 (17)	1.957 (16)	2.778 (2)	167 (2)
O5—H5A···O2iii	0.91	1.95	2.837 (3)	164
O5—H5B···O5iv	0.91	1.93	2.803 (4)	161
O5—H5B'···O5iii	0.90	2.22	3.096 (6)	165
O4—H4A···O2v	0.74 (4)	2.02 (4)	2.750 (3)	171 (4)
O4—H4B···O5	0.79 (4)	2.04 (4)	2.818 (3)	169 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O1i	0.837 (17)	1.957 (16)	2.778 (2)	167 (2)
O5—H5A⋯O2ii	0.91	1.95	2.837 (3)	164
O5—H5B⋯O5iii	0.91	1.93	2.803 (4)	161
O5—H5B′⋯O5ii	0.90	2.22	3.096 (6)	165
O4—H4A⋯O2iv	0.74 (4)	2.02 (4)	2.750 (3)	171 (4)
O4—H4B⋯O5	0.79 (4)	2.04 (4)	2.818 (3)	169 (3)

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