Tris­(pyridine 2 carboxyl­ato κ2O,N)­cobalt(III) monohydrate

metal-organic papers

Acta Cryst.(2005). E61, m481–m482 doi:10.1107/S160053680500317X Fu and Wang _[Co(C

6H4NO2)3]H2O

m481

Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

Tris(pyridine-2-carboxylato-

j

O

,

N

)cobalt(III)

monohydrate

Ai-Yun Fua,b* and Da-Qi Wangb

a_{Department of Chemistry, Dezhou University,}

Shandong Dezhou 253023, People’s Republic of China, andb_{Department of Chemistry,}

Liaocheng University, Shandong Liaocheng 252059, People’s Republic of China

Correspondence e-mail: aiyunfu@yahoo.com.cn

Key indicators

Single-crystal X-ray study

T= 298 K

Mean(C–C) = 0.006 A˚

Rfactor = 0.050

wRfactor = 0.066

Data-to-parameter ratio = 11.4

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

In the title complex, [Co(C6H4O2N)3]H2O, the cobalt(III) ion

shows a distorted octahedral coordination, comprising three N-atom donors and three O-atom donors from three bidentate pyridine-2-carboxylate ligands. The uncoordinated water molecule interacts with nearby carboxyl groups of the pyridine-2-carboxylate ligands by way of O—H O hydrogen bonds.

Comment

In the title compound, (I), the cobalt(III) atom shows a distorted octahedral coordination, comprising three N-atom donors and three O-atom donors from three bidenate pyri-dine-2-carboxylato ligands, as shown in Fig. 1. If the coordi-nating atoms are considered in isolation, this represents a meridional CoO3N3geometric isomer. Thecisbond angles in

the Co1 octahedron span the range 80.27 (11)–99.48 (11)_.

The mean Co—O bond length of 1.876 (2) A˚ is shorter than the mean Co—N bond length of 1.911 (3) A˚ (Table 1). In (I), each pyridine-2-carboxylate ligand coordinates to the CoIII atom via an O atom and an N atom, thus forming five-membered chelate rings, denoted R1, R2 andR3, containing atoms N1, N2 and N3, respectively. The pyridine rings, denoted py1, py2 and py3 containing atoms N1, N2, and N3, respectively, are approximately parallel to their respective chelate-ring planes [dihedral angles = 1.51 (18), 2.13 (16) and 1.60 (4) _{for R1/py1, R2/py2 and R3/py3, respectively]. The}

dihedral angles between pairs of pyridine rings are 80.54 (10), 85.27 (12) and 85.04 (13) _{for py1/py2, py1/py3, and py2/py3,}

respectively.

The uncoordinated water molecule in (I) forms O—H O hydrogen bonds (Table 2) to nearby carboxyl O atoms, resulting in an infinite chain along theadirection.

Experimental

CoCl26H2O (0.5 mmol) was dissolved in distilled water (10 ml), to which an aqueous mixture (20 ml) of pyridine-2-carboxylic acid (1.5 mmol) and NaOH (1.5 mmol) was added dropwise at 333 K. The

mixture was stirred for 6 h and part of the solvent was removed using a rotary vacuum evaporator. The resulting solution was filtered and left in air for 20 d, during which time dark-red prisms of (I) formed. Elemental analysis found: C 48.59, H 3.07, N 9.33; calculated for C18H14CoN3O7: C 48.78, H 3.18, N 9.48%.

Crystal data

[Co(C6H4NO2)3]H2O

Mr= 443.25 Monoclinic,C2=c a= 29.654 (18) A˚ b= 8.530 (5) A˚ c= 13.801 (8) A˚

= 95.829 (10)

V= 3473 (4) A˚3

Dx= 1.696 Mg m

3

MoKradiation Cell parameters from 1193

reflections

= 2.5–20.3 = 1.04 mm1

T= 298 (2) K Prism, dark red

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Bruker, 1997) Tmin= 0.760,Tmax= 0.835

9671 measured reflections

3589 independent reflections 2020 reflections withI> 2(I) Rint= 0.059

max= 26.5

h=25!37 k=10!10 l=14!17

Refinement

Refinement onF2

R[F2_{> 2(F}2_{)] = 0.050}

wR(F2_{) = 0.066}

S= 0.95 3589 reflections 315 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2_(F

o2)]

whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001

max= 0.75 e A˚

3 min=0.49 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

Co1—O1 1.873 (2)

Co1—O5 1.877 (2)

Co1—O3 1.881 (2)

Co1—N3 1.900 (3)

Co1—N2 1.914 (3)

Co1—N1 1.917 (3)

O1—Co1—O5 178.85 (11)

O1—Co1—O3 88.14 (10)

O5—Co1—O3 91.99 (10)

O1—Co1—N3 96.90 (13)

O5—Co1—N3 84.25 (13)

O3—Co1—N3 88.04 (10)

O1—Co1—N2 88.59 (12)

O5—Co1—N2 90.28 (12)

O3—Co1—N2 84.91 (11)

N3—Co1—N2 170.93 (11)

O1—Co1—N1 84.86 (11)

O5—Co1—N1 95.01 (11)

O3—Co1—N1 172.98 (12)

N3—Co1—N1 92.28 (11)

N2—Co1—N1 95.41 (11)

Table 2

Hydrogen-bonding geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O7—H14 O5i 0.886 (10) 2.012 (15) 2.864 (4) 161 (3)

O7—H13 O4 0.887 (10) 1.966 (12) 2.845 (4) 171 (3)

Symmetry code: (i)x;y;z1 2.

After the H atoms were located in a difference map, the water O— H distances were restrained to 0.88 (1) A˚ and theirUiso(H) values were allowed to refine freely. All the other H atoms, except H12 (positioned geometrically), were located in difference maps and restrained in their as-found relative positions 0.01 A˚ and their

Uiso(H) values were allowed to refine freely.

Data collection:SMART(Bruker, 1997); cell refinement and data reduction:SAINT(Bruker, 1997); program(s) used to solve structure:

SHELXS97(Sheldrick, 1997a); program(s) used to refine structure:

SHELXL97(Sheldrick, 1997a); molecular graphics and preparation of publication material:SHELXTL(Sheldrick, 1997b).

The authors thank the Science and Technology Office of Dezhou City, Shandong Province, People’s Republic of China, for research grant No. 030701.

References

Bruker (1997).SMART,SAINTandSADABS.Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Sheldrick, G. M. (1997b).SHELXTL.Version 5.1. Bruker AXS Inc., Madison, Figure 1

View of (I), showing 50% probability displacement ellipsoids and arbitrary spheres for H atoms.

Figure 2

supporting information

sup-1 Acta Cryst. (2005). E61, m481–m482

supporting information

Acta Cryst. (2005). E61, m481–m482 [https://doi.org/10.1107/S160053680500317X]

Tris(pyridine-2-carboxylato-

κ

O

,

N

)cobalt(III) monohydrate

Ai-Yun Fu and Da-Qi Wang

Tris(pyridine-2-carboxylato-κ2_{0,N)cobalt(III) monohydrate}

Crystal data

[Co(C6H4NO2)3]·H2O

Mr = 443.25

Monoclinic, C2/c Hall symbol: -C 2yc a = 29.654 (18) Å b = 8.530 (5) Å c = 13.801 (8) Å β = 95.829 (10)° V = 3473 (4) Å3

Z = 8

F(000) = 1808 Dx = 1.696 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1193 reflections θ = 2.5–20.3°

µ = 1.04 mm−1

T = 298 K Prism, dark red 0.28 × 0.25 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Bruker, 1997) Tmin = 0.760, Tmax = 0.835

9671 measured reflections 3589 independent reflections 2020 reflections with I > 2σ(I) Rint = 0.059

θmax = 26.5°, θmin = 1.4°

h = −25→37 k = −10→10 l = −14→17

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.050}

wR(F2_{) = 0.066}

S = 0.95 3589 reflections 315 parameters 3 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F o2)]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.75 e Å−3

Δρmin = −0.49 e Å−3

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

supporting information

sup-3 Acta Cryst. (2005). E61, m481–m482

H12 0.4244 (11) 0.536 (4) 0.881 (2) 0.050* H13 0.3733 (9) 0.239 (3) 0.4941 (17) 0.050* H14 0.4062 (10) 0.170 (2) 0.437 (2) 0.050*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Co1 0.0297 (3) 0.0420 (3) 0.0324 (3) −0.0001 (3) 0.0031 (2) −0.0001 (2) N1 0.0227 (17) 0.040 (2) 0.0297 (17) −0.0024 (15) 0.0000 (14) 0.0025 (14) N2 0.0283 (19) 0.0422 (19) 0.0282 (18) −0.0012 (16) 0.0035 (15) 0.0036 (14) N3 0.040 (2) 0.0359 (19) 0.0252 (16) −0.0055 (17) 0.0005 (14) −0.0001 (13) O1 0.0356 (16) 0.0473 (16) 0.0327 (15) 0.0046 (13) 0.0036 (12) 0.0017 (12) O2 0.0481 (19) 0.069 (2) 0.0633 (18) 0.0272 (17) 0.0013 (15) −0.0047 (15) O3 0.0334 (15) 0.0545 (17) 0.0345 (14) −0.0113 (14) 0.0080 (12) −0.0031 (12) O4 0.067 (2) 0.090 (2) 0.0303 (15) −0.0214 (17) 0.0028 (15) −0.0026 (14) O5 0.0312 (16) 0.0424 (16) 0.0472 (16) 0.0010 (14) 0.0045 (13) −0.0016 (12) O6 0.0414 (19) 0.0473 (18) 0.086 (2) 0.0145 (16) 0.0085 (16) −0.0046 (15) O7 0.087 (3) 0.060 (2) 0.093 (2) 0.0067 (19) 0.0449 (19) 0.0142 (18) C1 0.030 (2) 0.044 (3) 0.051 (3) 0.003 (2) −0.001 (2) −0.002 (2) C2 0.028 (2) 0.044 (2) 0.031 (2) 0.002 (2) 0.0024 (18) 0.0004 (18) C3 0.038 (3) 0.054 (3) 0.055 (3) 0.008 (2) 0.006 (2) −0.013 (2) C4 0.057 (3) 0.075 (3) 0.029 (3) −0.012 (3) 0.004 (2) −0.006 (2) C5 0.054 (3) 0.053 (3) 0.034 (3) −0.009 (2) −0.002 (2) 0.003 (2) C6 0.034 (3) 0.042 (3) 0.043 (3) 0.000 (2) −0.001 (2) 0.003 (2) C7 0.040 (3) 0.043 (3) 0.037 (2) 0.004 (2) 0.010 (2) −0.0032 (19) C8 0.027 (2) 0.035 (2) 0.038 (2) 0.0005 (19) −0.0003 (19) −0.0043 (18) C9 0.048 (3) 0.065 (3) 0.040 (3) −0.007 (3) 0.000 (3) −0.007 (2) C10 0.038 (3) 0.069 (3) 0.073 (4) −0.024 (3) 0.003 (3) −0.014 (3) C11 0.044 (3) 0.064 (3) 0.058 (3) −0.015 (3) 0.012 (3) 0.003 (2) C12 0.035 (3) 0.055 (3) 0.041 (3) −0.001 (2) 0.005 (2) 0.004 (2) C13 0.040 (3) 0.042 (3) 0.034 (2) 0.003 (2) 0.005 (2) −0.0012 (18) C14 0.027 (2) 0.048 (3) 0.029 (2) −0.001 (2) 0.0010 (17) −0.0040 (18) C15 0.039 (3) 0.051 (3) 0.044 (2) 0.006 (3) 0.006 (2) −0.001 (2) C16 0.036 (3) 0.067 (4) 0.047 (3) −0.017 (3) 0.007 (2) −0.003 (2) C17 0.053 (3) 0.051 (3) 0.037 (2) −0.015 (3) 0.003 (2) 0.000 (2) C18 0.047 (3) 0.048 (3) 0.037 (2) 0.003 (2) 0.003 (2) 0.000 (2)

Geometric parameters (Å, º)

Co1—O1 1.873 (2) C4—C5 1.355 (5)

Co1—O5 1.877 (2) C4—H2 0.95 (3)

Co1—O3 1.881 (2) C5—C6 1.381 (5)

Co1—N3 1.900 (3) C5—H3 0.98 (3)

Co1—N2 1.914 (3) C6—H4 0.97 (3)

Co1—N1 1.917 (3) C7—C8 1.491 (5)

N1—C6 1.328 (4) C8—C9 1.345 (5)

N1—C2 1.339 (4) C9—C10 1.354 (5)

N2—C8 1.345 (4) C10—C11 1.367 (5)

N3—C18 1.330 (4) C10—H6 0.92 (3)

N3—C14 1.351 (4) C11—C12 1.365 (5)

O1—C1 1.301 (4) C11—H7 1.02 (3)

O2—C1 1.204 (4) C12—H8 0.97 (3)

O3—C7 1.271 (4) C13—C14 1.478 (5)

O4—C7 1.231 (4) C14—C15 1.362 (5)

O5—C13 1.287 (4) C15—C16 1.358 (5)

O6—C13 1.217 (4) C15—H9 0.89 (3)

O7—H13 0.887 (10) C16—C17 1.369 (5)

O7—H14 0.886 (10) C16—H10 0.91 (3)

C1—C2 1.494 (5) C17—C18 1.373 (5)

C2—C3 1.381 (5) C17—H11 0.91 (3)

C3—C4 1.362 (5) C18—H12 0.90 (3)

C3—H1 0.85 (3)

supporting information

sup-5 Acta Cryst. (2005). E61, m481–m482

N1—C2—C1 114.6 (3) C15—C16—C17 119.5 (4) C3—C2—C1 124.6 (4) C15—C16—H10 118 (2) C4—C3—C2 119.5 (4) C17—C16—H10 122 (2) C4—C3—H1 123 (2) C16—C17—C18 118.6 (4) C2—C3—H1 118 (2) C16—C17—H11 128 (2) C5—C4—C3 119.2 (4) C18—C17—H11 114 (2) C5—C4—H2 122.1 (19) N3—C18—C17 122.0 (4) C3—C4—H2 118.7 (19) N3—C18—H12 111 (2) C4—C5—C6 119.6 (4) C17—C18—H12 127 (2)

C8—N2—N3—C14 −91.7 (3) O1—Co1—O3—C7 −77.9 (3) O5—Co1—N1—C2 −173.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O7—H14···O5i _{0.89 (1) 2.01 (2) 2.864 (4) 161 (3)}

O7—H13···O4 0.89 (1) 1.97 (1) 2.845 (4) 171 (3)