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Acta Cryst. (2007). E63, m3009    [ doi:10.1107/S1600536807057509 ]

Diaqua(2,9-dimethyl-1,10-phenanthroline-[kappa]2N,N')(3-hydroxybenzoato-[kappa]2O,O')cobalt(II) nitrate

X. Xuan and P. Zhao

Abstract top

In the symmetric unit of the title compound, [Co(C7H5O3)(C14H12N2)(H2O)2]NO3, the Co2+ cation is coordinated by a bidentate 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand, a bidentate 3-hydroxybenzoate anion and two water molecules in a distorted octahedral environment. The 3-hydroxybenzoate ligand, Co atom and nitrate anion are situated on a crystallographic twofold rotation axis. The OH group of the benzoate anion is disordered over two symmetry-related positions with site-occupancy factors of 0.5. An extensive series of O-H...O hydrogen bonds, involving water molecules and 3-hydroxybenzoate and nitrate anions, and weak C-H...O hydrogen bonds lead to a supramolecular network structure.

Comment top

We have recently reported the structure of diaqua(3-hydroxy-benzoato-κ2O,O')(2,9-dimethyl-1,10-phenanthroline-κ2N,N')nickel(II) nitrate (Xuan et al. 2007). We report herein the isomorphous cobalt analogue,Co(C7H5O3)(C14H12N2)(H2O)2]·NO3, (I).

The asymmetric unit of the title compound is composed of one half of the CoII complex cation and one half of the non-coordinated nitrate anion: a twofold rotation axis passes through the central CoII atom, N atom and one O atom of the nitrate anion. The metal is in a distorted octahedral environment, being six-coordinated by two N atoms from the dmphen ligand and two O atoms from the carboxyl group of the 3-hydroxy-benzoate anion, defining the equatorial plane, and two O atoms from two water molecules in the apical position (Table 1). The OH group on the 3-hydroxybenzoate ligand is disordered over two symmetry-related positions with equal site occupancy.

The crystal structure is stabilized by a network of O—H···O and C—H···O hydrogen bonds (Table 2 and Figure 2). The former interactions link molecules into two-dimensional networks parallel to (010) while the latter ones join them along the [010] direction generating a three-dimensional framework.

Related literature top

The structure of a closely related Ni complex has been reported by Xuan & Zhao (2007).

Experimental top

To a solution of 2,9-dimethyl-1,10-phenanthroline (C14H12N2.0.5H2O, 0.1096 g, 0.5 mmol), 3-hydroxy-benzoate (0.1382 g, 1 mmol) and sodium hydroxide (0.03820 g, 1 mmol) in ethanol/water (v:v=1:1, 20 ml) was added a solution of Co(NO3)2·6H2O (0.1458 g, 0.5 mmol) in distilled water (10 ml). The resulting solution was stirred for 5 h at 323 K and then a pink precipitate was filtered. Brown single crystals of (I) were obtained by slow evaporation of the filtrate over two weeks.

Refinement top

The OH group of the benzoate anion is disordered over two symmetry-related positions with equal occupancy. The carbon-bound H atoms were placed in calculated positions and were included in the refinement in the riding model approximation, with d(C—H) = 0.93 Å, Uiso=1.2Ueq(C) for aromatic and 0.96 Å, Uiso = 1.5Ueq(C) for CH3 atoms. The hydroxyl H atoms were placed in calculated positions (O—H =0.82 Å) and refined with free torsion angles to fit the electron density; water H atoms were found in a difference Fourier and allowed to ride. For all O—H's, Uiso(H) = 1.5 Ueq(O).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. Symmetry code: (A) 1 − x, y, 3/2 − z for the cation; 1 − x, y, 1/2 − z for the anion.
[Figure 2] Fig. 2. Packing diagram of (I), viewed down [001], showing hydrogen bonds as dashed lines.
Diaqua(2,9-dimethyl-1,10-phenanthroline-κ2N,N')(3-hydroxybenzoato- κ2O,O')cobalt(II) nitrate top
Crystal data top
[Co(C7H5O3)(C14H12N2)(H2O)2]NO3F000 = 1032
Mr = 501.33Dx = 1.518 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5273 reflections
a = 10.9405 (14) Åθ = 2.3–28.0º
b = 28.750 (4) ŵ = 0.84 mm−1
c = 7.9670 (10) ÅT = 298 (2) K
β = 119.142 (1)ºBlock, brown
V = 2188.7 (5) Å30.49 × 0.40 × 0.37 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2040 independent reflections
Radiation source: fine-focus sealed tube1878 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 298(2) Kθmax = 25.5º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −13→13
Tmin = 0.67, Tmax = 0.73k = −34→34
8035 measured reflectionsl = −9→9
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)] = 0.032H-atom parameters constrained
wR(F2) = 0.102  w = 1/[σ2(Fo2) + (0.0659P)2 + 2.1796P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2040 reflectionsΔρmax = 0.50 e Å−3
159 parametersΔρmin = −0.39 e Å−3
33 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Co(C7H5O3)(C14H12N2)(H2O)2]NO3V = 2188.7 (5) Å3
Mr = 501.33Z = 4
Monoclinic, C2/cMo Kα
a = 10.9405 (14) ŵ = 0.84 mm−1
b = 28.750 (4) ÅT = 298 (2) K
c = 7.9670 (10) Å0.49 × 0.40 × 0.37 mm
β = 119.142 (1)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2040 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		1878 reflections with I > 2σ(I)
Tmin = 0.67, Tmax = 0.73Rint = 0.023
8035 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03233 restraints
wR(F2) = 0.102H-atom parameters constrained
S = 1.02Δρmax = 0.50 e Å−3
2040 reflectionsΔρmin = −0.39 e Å−3
159 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*/UeqOcc. (<1)
Co10.50000.294272 (13)0.75000.03386 (17)
O10.39631 (16)0.22788 (5)0.7385 (2)0.0405 (4)
O20.3140 (5)0.05502 (14)0.7959 (10)0.0861 (17)0.50
H20.27600.07050.84420.129*0.50
O30.38785 (18)0.29149 (5)0.4529 (2)0.0451 (4)
H1W0.30410.28930.41800.068*
H2W0.40250.30830.37950.068*
O40.4231 (3)0.39849 (12)0.2935 (4)0.1120 (11)
O50.50000.33543 (12)0.25000.0923 (12)
N10.6166 (2)0.35148 (7)0.7293 (3)0.0416 (4)
N20.50000.37833 (10)0.25000.0461 (6)
C10.7857 (3)0.30542 (11)0.6842 (6)0.0720 (9)
H1A0.85860.29530.80740.108*
H1B0.82280.30890.59780.108*
H1C0.71190.28280.63370.108*
C20.7295 (3)0.35093 (10)0.7058 (4)0.0528 (6)
C30.7935 (3)0.39298 (12)0.6971 (5)0.0717 (9)
H3A0.87240.39200.68170.086*
C40.7413 (4)0.43432 (12)0.7110 (5)0.0786 (10)
H40.78460.46170.70620.094*
C50.6219 (4)0.43603 (10)0.7327 (4)0.0647 (8)
C60.5623 (3)0.39312 (8)0.7410 (3)0.0465 (6)
C70.5582 (5)0.47851 (10)0.7418 (6)0.0882 (12)
H70.59790.50670.73620.106*
C80.50000.20572 (10)0.75000.0358 (7)
C90.50000.15334 (11)0.75000.0415 (7)
C100.3986 (3)0.12923 (9)0.7701 (4)0.0521 (6)
H100.33040.14540.78400.063*
C110.3985 (3)0.08081 (10)0.7696 (5)0.0672 (8)
C120.50000.05691 (14)0.75000.0799 (15)
H120.50000.02460.75000.096*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0271 (2)0.0265 (2)0.0455 (3)0.0000.01572 (19)0.000
O10.0319 (8)0.0312 (8)0.0581 (10)0.0011 (6)0.0218 (7)0.0000 (7)
O20.080 (3)0.036 (2)0.176 (6)−0.006 (2)0.088 (4)0.004 (3)
O30.0371 (9)0.0482 (10)0.0452 (9)−0.0074 (7)0.0162 (7)0.0025 (7)
O40.105 (2)0.146 (3)0.0908 (18)0.065 (2)0.0517 (16)0.0036 (17)
O50.167 (4)0.0530 (17)0.086 (2)0.0000.084 (2)0.000
N10.0362 (10)0.0363 (10)0.0437 (10)−0.0056 (8)0.0127 (8)0.0036 (8)
N20.0463 (15)0.0445 (15)0.0519 (16)0.0000.0273 (13)0.000
C10.0526 (17)0.0655 (18)0.114 (3)0.0096 (14)0.0531 (19)0.0277 (18)
C20.0387 (13)0.0547 (15)0.0579 (15)−0.0092 (11)0.0180 (11)0.0106 (12)
C30.0554 (17)0.073 (2)0.083 (2)−0.0241 (15)0.0304 (16)0.0104 (16)
C40.087 (2)0.0552 (19)0.088 (2)−0.0352 (17)0.039 (2)−0.0023 (16)
C50.088 (2)0.0371 (14)0.0630 (17)−0.0181 (14)0.0315 (16)−0.0035 (12)
C60.0547 (14)0.0333 (12)0.0405 (12)−0.0067 (10)0.0146 (11)0.0000 (9)
C70.137 (4)0.0310 (14)0.101 (3)−0.0160 (16)0.061 (3)−0.0025 (15)
C80.0318 (16)0.0290 (15)0.0423 (16)0.0000.0147 (13)0.000
C90.0371 (16)0.0296 (16)0.0519 (18)0.0000.0171 (14)0.000
C100.0468 (14)0.0344 (12)0.0782 (18)0.0014 (10)0.0328 (13)0.0044 (11)
C110.0629 (18)0.0359 (14)0.110 (2)−0.0060 (12)0.0478 (18)0.0052 (14)
C120.083 (3)0.0279 (18)0.140 (5)0.0000.063 (3)0.000
Geometric parameters (Å, °) top
Co1—O32.0706 (17)C1—H1C0.9600
Co1—O3i2.0706 (17)C2—C31.415 (4)
Co1—N1i2.1361 (19)C3—C41.346 (5)
Co1—N12.1363 (19)C3—H3A0.9300
Co1—O12.1993 (16)C4—C51.400 (5)
Co1—O1i2.1993 (16)C4—H40.9300
O1—C81.265 (2)C5—C61.412 (4)
O2—C111.280 (5)C5—C71.425 (5)
O2—H20.8200C6—C6i1.439 (6)
O3—H1W0.8200C7—C7i1.341 (9)
O3—H2W0.8313C7—H70.9300
O4—N21.204 (3)C8—C91.506 (4)
O5—N21.233 (4)C9—C10i1.382 (3)
N1—C21.337 (3)C9—C101.382 (3)
N1—C61.360 (3)C10—C111.392 (4)
C1—C21.490 (4)C10—H100.9300
C1—H1A0.9600C11—C121.378 (4)
C1—H1B0.9600C12—H120.9300
O3—Co1—O3i175.57 (9)N1—C2—C1119.2 (2)
O3—Co1—N1i94.26 (7)C3—C2—C1120.2 (3)
O3i—Co1—N1i89.15 (7)C4—C3—C2120.7 (3)
O3—Co1—N189.15 (7)C4—C3—H3A119.6
O3i—Co1—N194.27 (7)C2—C3—H3A119.6
N1i—Co1—N179.32 (11)C3—C4—C5120.0 (3)
O3—Co1—O184.97 (6)C3—C4—H4120.0
O3i—Co1—O191.18 (6)C5—C4—H4120.0
N1i—Co1—O1110.87 (7)C4—C5—C6117.1 (3)
N1—Co1—O1168.55 (7)C4—C5—C7123.1 (3)
O3—Co1—O1i91.18 (6)C6—C5—C7119.9 (3)
O3i—Co1—O1i84.96 (6)N1—C6—C5122.6 (3)
N1i—Co1—O1i168.55 (7)N1—C6—C6i118.26 (14)
N1—Co1—O1i110.87 (7)C5—C6—C6i119.10 (19)
O1—Co1—O1i59.57 (8)C7i—C7—C5121.0 (2)
C8—O1—Co190.46 (14)C7i—C7—H7119.5
C11—O2—H2109.5C5—C7—H7119.5
Co1—O3—H1W109.4O1i—C8—O1119.5 (3)
Co1—O3—H2W124.9O1i—C8—C9120.25 (13)
H1W—O3—H2W111.9O1—C8—C9120.25 (13)
C2—N1—C6119.0 (2)C10i—C9—C10119.8 (3)
C2—N1—Co1128.97 (18)C10i—C9—C8120.10 (16)
C6—N1—Co1112.06 (16)C10—C9—C8120.10 (16)
O4—N2—O4ii122.4 (5)C9—C10—C11120.1 (3)
O4—N2—O5118.8 (2)C9—C10—H10120.0
O4ii—N2—O5118.8 (2)C11—C10—H10120.0
C2—C1—H1A109.5O2—C11—C12114.6 (3)
C2—C1—H1B109.5O2—C11—C10125.4 (3)
H1A—C1—H1B109.5C12—C11—C10119.9 (3)
C2—C1—H1C109.5C11i—C12—C11120.2 (4)
H1A—C1—H1C109.5C11i—C12—H12119.9
H1B—C1—H1C109.5C11—C12—H12119.9
N1—C2—C3120.6 (3)
O3—Co1—O1—C894.35 (9)C3—C4—C5—C7−177.8 (3)
O3i—Co1—O1—C8−83.46 (9)C2—N1—C6—C5−1.1 (4)
N1i—Co1—O1—C8−173.00 (8)Co1—N1—C6—C5179.4 (2)
N1—Co1—O1—C835.0 (4)C2—N1—C6—C6i177.7 (3)
O1i—Co1—O1—C80.0Co1—N1—C6—C6i−1.8 (3)
O3—Co1—N1—C2−84.2 (2)C4—C5—C6—N10.2 (4)
O3i—Co1—N1—C292.9 (2)C7—C5—C6—N1178.7 (3)
N1i—Co1—N1—C2−178.7 (3)C4—C5—C6—C6i−178.6 (3)
O1—Co1—N1—C2−25.3 (4)C7—C5—C6—C6i−0.1 (5)
O1i—Co1—N1—C26.7 (2)C4—C5—C7—C7i178.4 (5)
O3—Co1—N1—C695.12 (16)C6—C5—C7—C7i0.0 (7)
O3i—Co1—N1—C6−87.70 (16)Co1—O1—C8—O1i0.0
N1i—Co1—N1—C60.62 (12)Co1—O1—C8—C9180.0
O1—Co1—N1—C6154.1 (3)O1i—C8—C9—C10i−10.93 (16)
O1i—Co1—N1—C6−173.93 (15)O1—C8—C9—C10i169.07 (16)
C6—N1—C2—C31.3 (4)O1i—C8—C9—C10169.07 (16)
Co1—N1—C2—C3−179.4 (2)O1—C8—C9—C10−10.93 (16)
C6—N1—C2—C1−177.4 (3)C10i—C9—C10—C11−0.2 (2)
Co1—N1—C2—C12.0 (4)C8—C9—C10—C11179.8 (2)
N1—C2—C3—C4−0.5 (5)C9—C10—C11—O2176.6 (5)
C1—C2—C3—C4178.1 (3)C9—C10—C11—C120.3 (5)
C2—C3—C4—C5−0.5 (5)O2—C11—C12—C11i−176.8 (5)
C3—C4—C5—C60.7 (5)C10—C11—C12—C11i−0.2 (2)
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H1W···O1iii0.821.992.772 (3)160
O2—H2···O4iii0.822.102.688 (7)128
O3—H2W···O50.831.972.765 (2)159
C1—H1C···O1i0.962.473.242 (4)137
C7—H7···O2iv0.932.583.418 (8)150
Symmetry codes: (iii) −x+1/2, −y+1/2, −z+1; (i) −x+1, y, −z+3/2; (iv) x+1/2, y+1/2, z.
Table 1
Selected geometric parameters (Å) top
Co1—O32.0706 (17)Co1—O12.1993 (16)
Co1—N12.1363 (19)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H1W···O1i0.821.992.772 (3)160
O2—H2···O4i0.822.102.688 (7)128
O3—H2W···O50.831.972.765 (2)159
C1—H1C···O1ii0.962.473.242 (4)137
C7—H7···O2iii0.932.583.418 (8)150
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, y, −z+3/2; (iii) x+1/2, y+1/2, z.
Acknowledgements top

Financial support from the Science Fund of Henan Province for Distinguished Young Scholars (grant No. 07410051005) is gratefully acknowledged.

references
References top

Bruker (1997). SMART, SAINT, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Xuan, X. & Zhao, P. (2007). Acta Cryst. E63, m2856–?.