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Acta Cryst. (2007). E63, m2975-m2976    [ doi:10.1107/S160053680705605X ]

Reinvestigation of bis(2,2'-bipyridine)(nitrato-[kappa]2O,O')cobalt(III) hydroxide nitrate tetrahydrate

A. Wojciechowska and M. Daszkiewicz

Abstract top

Single crystals of the title compound, [Co(NO3)(C10H8N2)2](OH)(NO3)·4H2O, were obtained from a Co2+-2,2'-bipyridine-CrO42- mixture as the second crystalline product. The present single-crystal study confirms a previous refinement [Reimann, Zocchi, Mighell & Santoro (1971). Acta Cryst. B27, 2211-2218], and also includes all H-atom positions, which were identified from a difference map. The structure displays an O-H...O hydrogen-bonding network between the non-coordinated nitrate group, the hydroxide anion and the water molecules, forming a framework around the distorted octahedral Co complex. A twofold rotation axis passes through Co and the nitrato ligand.

Comment top

Bis(2,2'-bipyridine)(nitrato-O,O')cobalt(III) hydroxide nitrate tetrahydrate (I) was unintentionally obtained from a [Co2+–2,2'-bipyridine–CrO42-] mixture as the second product. The first product was identified as [Co(bpy)3](CrO4)0.5.NO3.7H2O (Wojciechowska et al., 2003). The present single-crystal study confirms the previous refinement (Reimann et al., 1971), but with all hydrogen atoms, which were visible in the difference maps, included in the refinement (Fig. 1). Two organic ligands and one nitrate ion form a distorted octahedral coordination sphere around the Co(III) ion. The differences between the Co—Onitrate bond lengths, and the Co—O—N and Co—N—Oterminal angles are 0 Å, 0° and 180° respectively, which correlate exactly with the bidentate mode of the nitrate group (Kleywegt et al., 1985; Dowling et al., 1996). The nitrate groups, hydroxide ions and water molecules form a rich hydrogen bonding network, which surrounds the [Co(bpy)2(NO3-O,O')]+ cation and links to it via an Owater—H···Onitrate hydrogen bond (Fig. 2).

Related literature top

For an earlier structure refinement of the title compound, see: Reimann et al. (1971). For the crystal structure of [Co(bpy)3](CrO4)0.5NO3.7H2O, see: Wojciechowska et al. (2003). For geometrical studies of the coordination mode of the nitrate anion, see: Kleywegt et al. (1985); Dowling et al. (1996).

Experimental top

15 cm3 of a 0.50 M methanolic solution of 2,2'-bipyridine was added to 20 cm3 of an aqueous solution of K2CrO4 (0.25 M). After 15 min of mixing, 10 cm3 of an 0.25 M aqueous solution of cobalt nitrate was added dropwise. This mixture of [Co2+–2,2'-bipyridine–CrO42-] reagents in a 1:3:2 molar ratio was slowly evaporated at room temperature. After 14 days orange crystals of [Co(bpy)3](CrO4)0.5.NO3.7H2O were obtained. The crystals were filtered off and the filtrate was left to stand. After 30 days pink prismatic crystals of the title compound were isolated.

Refinement top

All the hydrogen atoms were visible on difference maps and were refined with isotropic displacement parameters correlated with the anisotropic displacement parameters of the atoms to which they were bonded [C—H 0.93 (2) Å and Uiso(H) = 1.2Ueq(C)]. The positions of hydrogen atoms in the hydroxide ion and water molecules were determined from difference maps and were not refined [Uiso(H) = 1.5Ueq(O)].

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. A view of [Co(bpy)2(NO3-O,O')]+ cation, showing the atom numbering scheme of the asymmetric unit. Displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. The hydrogen bonding network of (I) viewed along the c axis. Hydrogen bonds are indicated by dashed lines.
bis(2,2'-bipyridine)(nitrato-κ2O,O')cobalt(III) hydroxide nitrate tetrahydrate top
Crystal data top
[Co(NO3)(C10H8N2)2](OH)(NO3)·4H2OF(000) = 1208
Mr = 584.39Dx = 1.562 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2212 reflections
a = 10.949 (2) Åθ = 2.9–26.4°
b = 16.047 (3) ŵ = 0.76 mm−1
c = 14.456 (3) ÅT = 298 K
β = 101.92 (3)°Prism, pink
V = 2485.1 (9) Å30.38 × 0.25 × 0.21 mm
Z = 4
Data collection top
KUMA KM-4 with CCD area detector
diffractometer		2529 independent reflections
Radiation source: fine-focus sealed tube2212 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm-1θmax = 26.4°, θmin = 2.9°
ω–scanh = −13→13
Absorption correction: numerical
(CrysAlis RED; Oxford Diffraction, 2007)		k = −19→20
Tmin = 0.847, Tmax = 0.930l = −18→16
13043 measured reflections
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0763P)2 + 1.6632P]
where P = (Fo2 + 2Fc2)/3
2529 reflections(Δ/σ)max < 0.001
175 parametersΔρmax = 0.34 e Å−3
0 restraintsΔρmin = −0.54 e Å−3
Crystal data top
[Co(NO3)(C10H8N2)2](OH)(NO3)·4H2OV = 2485.1 (9) Å3
Mr = 584.39Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.949 (2) ŵ = 0.76 mm−1
b = 16.047 (3) ÅT = 298 K
c = 14.456 (3) Å0.38 × 0.25 × 0.21 mm
β = 101.92 (3)°
Data collection top
KUMA KM-4 with CCD area detector
diffractometer		2529 independent reflections
Absorption correction: numerical
(CrysAlis RED; Oxford Diffraction, 2007)		2212 reflections with I > 2σ(I)
Tmin = 0.847, Tmax = 0.930Rint = 0.035
13043 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.123Δρmax = 0.34 e Å−3
S = 1.06Δρmin = −0.54 e Å−3
2529 reflectionsAbsolute structure: ?
175 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/Ueq
Co10.50000.50622 (2)0.25000.03378 (17)
N110.50000.6494 (2)0.25000.0744 (11)
O110.50000.72623 (19)0.25000.1021 (13)
O120.55680 (17)0.60295 (11)0.19693 (12)0.0486 (4)
N210.50000.1667 (3)0.25000.0739 (10)
O210.50000.2402 (3)0.25000.177 (3)
O220.5834 (4)0.1293 (3)0.3002 (3)0.1659 (18)
N10.56282 (17)0.42330 (12)0.17425 (12)0.0374 (4)
N20.35747 (19)0.50549 (11)0.14648 (13)0.0361 (4)
C10.6699 (2)0.38072 (17)0.19718 (18)0.0497 (6)
H10.72320.39130.25490.060*
C20.7033 (3)0.3220 (2)0.1382 (2)0.0639 (8)
H20.77840.29340.15570.077*
C30.6250 (3)0.30562 (19)0.0530 (2)0.0629 (7)
H30.64590.26520.01280.075*
C40.5152 (2)0.34973 (17)0.02769 (18)0.0508 (6)
H40.46150.3400−0.03010.061*
C50.2822 (2)0.45824 (17)−0.01124 (16)0.0495 (6)
H50.29270.4256−0.06220.059*
C60.1773 (3)0.50778 (17)−0.0174 (2)0.0571 (7)
H60.11690.5093−0.07300.068*
C70.1630 (2)0.55457 (18)0.0591 (2)0.0572 (7)
H70.09240.58740.05620.069*
C80.2546 (2)0.55237 (16)0.14060 (18)0.0486 (6)
H80.24480.58400.19250.058*
C90.4859 (2)0.40857 (14)0.08920 (14)0.0380 (5)
C100.3712 (2)0.45814 (14)0.07220 (14)0.0382 (5)
O10.2572 (3)0.2652 (2)0.0904 (3)0.1321 (12)
H110.30830.23200.13420.198*
H120.18740.28020.11260.198*
O20.0487 (4)0.33863 (18)0.1216 (2)0.1137 (10)
H210.05040.28730.14850.171*
H220.05880.38950.15200.171*
O30.00000.4538 (3)0.25000.1300 (18)
H310.00000.51720.25000.195*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0356 (3)0.0405 (3)0.0229 (2)0.0000.00068 (16)0.000
N110.080 (3)0.055 (2)0.075 (2)0.000−0.014 (2)0.000
O110.129 (3)0.0345 (16)0.133 (3)0.0000.004 (3)0.000
O120.0555 (10)0.0477 (9)0.0398 (9)−0.0063 (8)0.0033 (7)0.0071 (7)
N210.086 (3)0.063 (2)0.075 (3)0.0000.022 (2)0.000
O210.257 (9)0.067 (3)0.218 (7)0.0000.078 (7)0.000
O220.161 (4)0.161 (4)0.147 (4)0.060 (3)−0.033 (3)0.016 (3)
N10.0374 (9)0.0447 (10)0.0286 (8)−0.0001 (7)0.0031 (7)−0.0012 (7)
N20.0364 (10)0.0425 (10)0.0274 (9)0.0009 (7)0.0020 (8)0.0033 (7)
C10.0428 (13)0.0601 (15)0.0439 (13)0.0087 (11)0.0033 (10)−0.0034 (11)
C20.0544 (16)0.0712 (19)0.0656 (18)0.0173 (14)0.0112 (13)−0.0103 (14)
C30.0657 (18)0.0674 (18)0.0578 (16)0.0080 (14)0.0179 (14)−0.0198 (14)
C40.0560 (15)0.0588 (15)0.0371 (11)−0.0078 (11)0.0089 (10)−0.0112 (11)
C50.0537 (15)0.0549 (15)0.0333 (12)−0.0088 (11)−0.0064 (10)0.0003 (10)
C60.0502 (16)0.0656 (17)0.0439 (15)−0.0060 (12)−0.0168 (12)0.0080 (11)
C70.0414 (13)0.0614 (16)0.0617 (16)0.0056 (11)−0.0054 (12)0.0104 (13)
C80.0435 (13)0.0547 (14)0.0452 (13)0.0056 (11)0.0035 (10)0.0020 (11)
C90.0422 (12)0.0436 (12)0.0272 (10)−0.0063 (9)0.0051 (9)0.0002 (8)
C100.0438 (12)0.0398 (12)0.0278 (10)−0.0068 (9)0.0003 (9)0.0033 (8)
O10.101 (2)0.135 (3)0.147 (3)0.003 (2)−0.004 (2)0.015 (2)
O20.139 (3)0.094 (2)0.105 (2)0.0196 (19)0.017 (2)0.0046 (16)
O30.191 (5)0.076 (3)0.106 (3)0.000−0.008 (3)0.000
Geometric parameters (Å, º) top
Co1—O12i1.8924 (17)C2—H20.9300
Co1—O121.8924 (17)C3—C41.378 (4)
Co1—N2i1.926 (2)C3—H30.9300
Co1—N21.926 (2)C4—C91.379 (3)
Co1—N1i1.9374 (19)C4—H40.9300
Co1—N11.9374 (19)C5—C61.384 (4)
Co1—N112.297 (4)C5—C101.385 (3)
N11—O111.233 (4)C5—H50.9300
N11—O121.314 (3)C6—C71.372 (4)
N11—O12i1.314 (3)C6—H60.9300
N21—O211.180 (6)C7—C81.380 (4)
N21—O22i1.202 (4)C7—H70.9300
N21—O221.202 (4)C8—H80.9300
N1—C11.338 (3)C9—C101.464 (3)
N1—C91.360 (3)O1—H110.9218
N2—C81.342 (3)O1—H120.9194
N2—C101.349 (3)O2—H210.9100
C1—C21.371 (4)O2—H220.9225
C1—H10.9300O3—H311.0180
C2—C31.372 (4)
O12i—Co1—O1269.80 (12)C8—N2—Co1125.47 (17)
O12i—Co1—N2i88.36 (7)C10—N2—Co1114.60 (15)
O12—Co1—N2i92.21 (8)N1—C1—C2122.0 (2)
O12—Co1—N288.36 (7)N1—C1—H1119.0
O12i—Co1—N292.21 (7)C2—C1—H1119.0
O12—Co1—N1i167.72 (8)C1—C2—C3119.5 (3)
O12—Co1—N198.59 (8)C1—C2—H2120.3
N2—Co1—N183.22 (8)C3—C2—H2120.3
N2—Co1—N1i96.30 (8)C2—C3—C4119.3 (2)
N2i—Co1—N2179.30 (10)C2—C3—H3120.4
O12i—Co1—N1i98.59 (8)C4—C3—H3120.4
N2i—Co1—N1i83.22 (8)C3—C4—C9119.1 (2)
O12i—Co1—N1167.72 (8)C3—C4—H4120.4
N2i—Co1—N196.30 (8)C9—C4—H4120.4
N1i—Co1—N193.25 (11)C6—C5—C10118.8 (2)
O12i—Co1—N1134.90 (6)C6—C5—H5120.6
O12—Co1—N1134.90 (6)C10—C5—H5120.6
N2i—Co1—N1190.35 (5)C7—C6—C5119.6 (2)
N2—Co1—N1190.35 (5)C7—C6—H6120.2
N1i—Co1—N11133.38 (6)C5—C6—H6120.2
N1—Co1—N11133.38 (6)C6—C7—C8119.3 (3)
O11—N11—O12124.54 (15)C6—C7—H7120.3
O11—N11—O12i124.54 (15)C8—C7—H7120.3
O12—N11—O12i110.9 (3)N2—C8—C7121.4 (2)
O11—N11—Co1180.0N2—C8—H8119.3
O12—N11—Co155.46 (15)C7—C8—H8119.3
O12i—N11—Co155.46 (15)N1—C9—C4121.3 (2)
N11—O12—Co189.64 (17)N1—C9—C10114.01 (19)
O21—N21—O22i119.9 (3)C4—C9—C10124.7 (2)
O21—N21—O22119.9 (3)N2—C10—C5121.2 (2)
O22i—N21—O22120.2 (6)N2—C10—C9113.90 (18)
C1—N1—C9118.8 (2)C5—C10—C9124.9 (2)
C1—N1—Co1127.28 (16)H11—O1—H12110.0
C9—N1—Co1113.87 (15)H21—O2—H22127.5
C8—N2—C10119.7 (2)
O12i—Co1—N11—O12180.0N11—Co1—N2—C8−46.18 (19)
N2i—Co1—N11—O1293.37 (11)O12i—Co1—N2—C10162.94 (16)
N2—Co1—N11—O12−86.63 (11)O12—Co1—N2—C1093.23 (16)
N1i—Co1—N11—O12174.35 (11)N1i—Co1—N2—C10−98.16 (16)
N1—Co1—N11—O12−5.65 (11)N1—Co1—N2—C10−5.62 (15)
O12—Co1—N11—O12i180.000 (1)N11—Co1—N2—C10128.08 (15)
N2i—Co1—N11—O12i−86.63 (11)C9—N1—C1—C2−1.0 (4)
N2—Co1—N11—O12i93.37 (11)Co1—N1—C1—C2178.6 (2)
N1i—Co1—N11—O12i−5.65 (11)N1—C1—C2—C3−0.3 (5)
N1—Co1—N11—O12i174.35 (11)C1—C2—C3—C41.1 (5)
O11—N11—O12—Co1180.0C2—C3—C4—C9−0.8 (4)
O12i—N11—O12—Co10.0C10—C5—C6—C7−0.8 (4)
O12i—Co1—O12—N110.0C5—C6—C7—C81.0 (4)
N2i—Co1—O12—N11−87.44 (9)C10—N2—C8—C7−1.3 (4)
N2—Co1—O12—N1192.96 (9)Co1—N2—C8—C7172.68 (19)
N1i—Co1—O12—N11−19.6 (4)C6—C7—C8—N20.1 (4)
N1—Co1—O12—N11175.85 (8)C1—N1—C9—C41.3 (3)
O12i—Co1—N1—C1114.8 (3)Co1—N1—C9—C4−178.29 (18)
O12—Co1—N1—C196.2 (2)C1—N1—C9—C10179.5 (2)
N2i—Co1—N1—C12.9 (2)Co1—N1—C9—C10−0.1 (2)
N2—Co1—N1—C1−176.5 (2)C3—C4—C9—N1−0.5 (4)
N1i—Co1—N1—C1−80.6 (2)C3—C4—C9—C10−178.4 (2)
N11—Co1—N1—C199.4 (2)C8—N2—C10—C51.4 (3)
O12i—Co1—N1—C9−65.6 (4)Co1—N2—C10—C5−173.18 (17)
O12—Co1—N1—C9−84.26 (16)C8—N2—C10—C9−178.4 (2)
N2i—Co1—N1—C9−177.47 (15)Co1—N2—C10—C97.0 (2)
N2—Co1—N1—C93.04 (15)C6—C5—C10—N2−0.4 (4)
N1i—Co1—N1—C999.00 (16)C6—C5—C10—C9179.5 (2)
N11—Co1—N1—C9−81.00 (16)N1—C9—C10—N2−4.4 (3)
O12i—Co1—N2—C8−11.3 (2)C4—C9—C10—N2173.6 (2)
O12—Co1—N2—C8−81.0 (2)N1—C9—C10—C5175.7 (2)
N1i—Co1—N2—C887.6 (2)C4—C9—C10—C5−6.2 (4)
N1—Co1—N2—C8−179.9 (2)
Symmetry code: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···O22i0.922.143.027 (6)162.4
O1—H11···O210.922.403.165 (4)139.9
O1—H12···O20.921.812.689 (5)158.4
O2—H21···O11ii0.911.942.718 (4)142.9
O2—H22···O30.921.972.748 (4)141.5
O3—H31···O22iii1.022.083.004 (6)150
O3—H31···O22iv1.022.083.004 (6)150
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x−1/2, y−1/2, z; (iii) x−1/2, y+1/2, z; (iv) −x+1/2, y+1/2, −z+1/2.
Selected geometric parameters (Å, º) top
Co1—O121.8924 (17)Co1—N11.9374 (19)
Co1—N21.926 (2)Co1—N112.297 (4)
O12i—Co1—O1269.80 (12)N2—Co1—N183.22 (8)
O12—Co1—N288.36 (7)N2—Co1—N1i96.30 (8)
O12i—Co1—N292.21 (7)N2i—Co1—N2179.30 (10)
O12—Co1—N1i167.72 (8)N1i—Co1—N193.25 (11)
O12—Co1—N198.59 (8)
Symmetry code: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···O22i0.922.143.027 (6)162.4
O1—H11···O210.922.403.165 (4)139.9
O1—H12···O20.921.812.689 (5)158.4
O2—H21···O11ii0.911.942.718 (4)142.9
O2—H22···O30.921.972.748 (4)141.5
O3—H31···O22iii1.022.083.004 (6)149.9
O3—H31···O22iv1.022.083.004 (6)149.9
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x−1/2, y−1/2, z; (iii) x−1/2, y+1/2, z; (iv) −x+1/2, y+1/2, −z+1/2.
references
References top

Brandenburg, K. (2005). DIAMOND. Release 3.0e. Crystal Impact GbR, Bonn, Germany.

Dowling, C., Murphy, V. J. & Parkin, G. (1996). Inorg. Chem. 35, 2415–2420.

Kleywegt, G. J., Wiesmeijer, W. G. R., Van Driel, G. J., Driessen, W. L., Reedijk, J. & Noordik, J. H. (1985). J. Chem. Soc. Dalton Trans. pp. 2177–2184.

Oxford Diffraction (2007). CrysAlis RED and CrysAlis CCD. Versions 1.171.31.8. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Reimann, C. W., Zocchi, M., Mighell, A. D. & Santoro, A. (1971). Acta Cryst. B27, 2211–2218.

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

Westrip (2007). publCIF. in preparation.

Wojciechowska, A., Staszak, Z., Bronowska, W., Pietraszko, A. & Cieslak-Golonka, M. (2003). J. Mol. Struct. 654, 197–204.