Cobalt(II) formate hydroxide

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metal-organic papers

Acta Cryst.(2005). E61, m2395–m2396 doi:10.1107/S1600536805033817 Fuet al. _[Co(CHO

2)(OH)]

m2395

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

Cobalt(II) formate hydroxide

Yun-Long Fu,aJia-Lin Ren,a Zhi-Wei Xuaand Seik Weng Ngb*

a

School of Chemistry and Materials Science, Shanxi Normal University, Linfen 041004, People’s Republic of China, andb_{Department of}

Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 295 K

Mean(O–C) = 0.005 A˚

Rfactor = 0.031

wRfactor = 0.077

Data-to-parameter ratio = 12.9

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

The title compound, poly[3-formato-3-hydroxo-cobalt(II)], [Co(CHO2)(OH)]n, adopts a polymeric three-dimensional network structure arising from the3-bridging mode of both the formate and the hydroxide. The Co atom lies in a fac octahedron of six O atoms, three of which belong to three different formates and the other three to different hydroxides.

Comment

The structure of cobalt(II) diformate has been reported recently; the compound was synthesized hydrothermally from cobaltous nitrate and formic acid in dimethylformamide (DMF). It crystallizes with DMF (Fuet al., 2005). With citric acid in place of formic acid, a similar synthesis affords cobalt(II) formate hydroxide, (I) (Fig. 1), the source of formic acid probably resulting from the decomposition of the citric acid. The compound adopts a three-dimensional network structure in which both the formate and hydroxide function in a 3-bridging mode; the Co

II

exists in a fac-octahedral arrangement; three of the O atoms belong to different formates and the other three to different hydroxides. The formate displays delocalized C—O bonds; one C—O bond is somewhat longer than the other. The O atom involved in the longer bond interacts with two Co atoms whereas the O atom involved in the shorter bond interacts with only one Co atom.

Experimental

A mixture of cobaltous nitrate hexahydrate (0.23 g, 0.5 mmol), citric acid (0.22 g, 1 mmol) and DMF (8 ml) was heated in a 15 ml Teflon-lined steel bomb at 400 K for 50 d. Red block-shaped crystals were obtained in about 40% yield (based on Co).

Crystal data

[Co(CHO2)(OH)] Mr= 120.96

Trigonal,R3

a= 11.698 (1) A˚

c= 11.661 (1) A˚

V= 1381.9 (2) A˚3 Z= 18

Dx= 2.616 Mg m

3

MoKradiation Cell parameters from 1480

reflections

= 2.7–28.0

= 5.37 mm1 T= 295 (2) K Block, red

0.160.110.09 mm

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Data collection

Bruker APEX area-detector diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.501,Tmax= 0.644

2498 measured reflections

698 independent reflections 667 reflections withI> 2(I)

Rint= 0.024 max= 27.5

h=15!7

k=15!14

l=13!14

Refinement

Refinement onF2 R[F2_{> 2}₍_F2_{)] = 0.031} wR(F2_{) = 0.077} S= 1.07 698 reflections 54 parameters

All H-atom parameters refined

w= 1/[2₍_F

o2) + (0.0393P)2

+ 11.747P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.62 e A˚

3

min=0.50 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

Co1—O1 2.122 (2) Co1—O1 2.156 (2) Co1—O2i

2.149 (2)

Co1—O3 2.047 (2) Co1—O3ii 2.042 (2) Co1—O3iii

2.114 (2) O1—Co1—O1 79.5 (1)

O1—Co1—O2i

84.2 (1) O1—Co1—O3 92.9 (1) O1—Co1—O3ii 102.6 (1) O1—Co1—O3iii 172.5 (1) O1—Co1—O2i 83.9 (1) O1—Co1—O3 86.9 (1) O1—Co1—O3ii

171.8 (1)

O1—Co1—O3iii 93.3 (1) O2i

—Co1—O3 170.8 (1) O2i —Co1—O3ii 88.4 (1) O2i —Co1—O3iii 97.0 (1) O3—Co1—O3ii 100.8 (1) O3—Co1—O3iii 84.8 (1) O3ii —Co1—O3iii 84.9 (1)

Symmetry codes: (i) xþyþ4 3;xþ

2 3;z

1

3; (ii) yþ1;xy;z; (iii)

xyþ1 3;x

1 3;zþ

2 3.

H atoms were located in a difference Fourier map and were refined with distance restraints of O—H = 0.85 (1) A˚ and C—H = 0.95 (1) A˚; their displacement parameters were freely refined.

Data collection:SMART(Bruker, 2002); cell refinement:SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication:SHELXL97.

The authors thank the Natural Scientific Foundation Committee of Shanxi Province (No. 20041031) and the University of Malaya for generously supporting this study.

References

Bruker (2002).SADABS,SAINTandSMART. Bruker AXS Inc., Madison, Winsonsin, USA.

Fu, Y.-L., Ji, M., Shen, X.-L. & Ng, S. W. (2005).Acta Cryst.E61, m688–m690. Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National

Laboratory, Tennessee, USA.

[image:2.610.311.564.72.317.2]

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

Figure 1

ORTEPII(Johnson, 1976) plot, illustrating the coordination geometry of Co and the 3-bridging modes of the —HCO2 and —OH groups.

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supporting information

sup-1 Acta Cryst. (2005). E61, m2395–m2396

supporting information

Acta Cryst. (2005). E61, m2395–m2396 [https://doi.org/10.1107/S1600536805033817]

Cobalt(II) formate hydroxide

Yun-Long Fu, Jia-Lin Ren, Zhi-Wei Xu and Seik Weng Ng

poly[µ3-formato-µ3-hydroxo-cobalt(II)]

Crystal data

[Co(CHO2)(OH)]

Mr = 120.96

Trigonal, R3 Hall symbol: -R 3 a = 11.698 (1) Å c = 11.661 (1) Å V = 1381.9 (2) Å3 Z = 18

F(000) = 1062

Dx = 2.616 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1480 reflections θ = 2.7–28.0°

µ = 5.37 mm−1 T = 295 K Block, red

0.16 × 0.11 × 0.09 mm

Data collection

Bruker APEX area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.501, Tmax = 0.644

2498 measured reflections 698 independent reflections 667 reflections with I > 2σ(I) Rint = 0.024

θmax = 27.5°, θmin = 2.7°

h = −15→7

k = −15→14

l = −13→14

Refinement

Refinement on F2 Least-squares matrix: full R[F2_{> 2}_σ₍_F2_{)] = 0.031} wR(F2_{) = 0.077} S = 1.07 698 reflections 54 parameters 2 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

All H-atom parameters refined w = 1/[σ2₍_F

o2) + (0.0393P)2 + 11.747P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001 Δρmax = 0.62 e Å−3 Δρmin = −0.50 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

Co1 0.60832 (4) 0.12202 (4) 0.41991 (3) 0.0130 (2)

O1 0.5722 (2) 0.0647 (2) 0.5948 (2) 0.0185 (5)

O2 0.6642 (3) 0.0312 (2) 0.7497 (2) 0.0236 (6)

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C1 0.6590 (4) 0.1012 (4) 0.6725 (3) 0.0225 (7)

H1 0.720 (4) 0.194 (1) 0.676 (5) 0.05 (2)*

H3 0.433 (4) 0.163 (4) 0.473 (3) 0.04 (2)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Co1 0.0126 (2) 0.0129 (3) 0.0130 (3) 0.0061 (2) 0.0006 (2) 0.0022 (2)

O1 0.018 (1) 0.019 (1) 0.016 (1) 0.007 (1) 0.000 (1) 0.005 (1)

O2 0.023 (1) 0.020 (1) 0.025 (1) 0.008 (1) −0.009 (1) 0.002 (1)

O3 0.014 (1) 0.014 (1) 0.013 (1) 0.008 (1) 0.003 (1) 0.001 (1)

C1 0.022 (2) 0.016 (2) 0.026 (2) 0.007 (1) −0.003 (1) 0.000 (1)

Geometric parameters (Å, º)

Co1—O1 2.122 (2) Co1—Co1v _{2.9942 (6)}

Co1—O1i _{2.156 (2)} _Co1—Co1iv _{2.9943 (6)}

Co1—O2ii _{2.149 (2)} _O1—C1 _{1.264 (4)}

Co1—O3 2.047 (2) O2—C1 1.240 (4)

Co1—O3iii _{2.042 (2)} _O3—H3 _{0.85 (1)}

Co1—O3iv _{2.114 (2)} _C1—H1 _{0.95 (1)}

O1—Co1—O1i _{79.5 (1)} _O3iii_—Co1—O3iv _{84.9 (1)}

O1—Co1—O2ii _{84.2 (1)} _{C1—O1—Co1} _{125.6 (2)}

O1—Co1—O3 92.9 (1) C1—O1—Co1i _{127.8 (2)}

O1—Co1—O3iii _{102.6 (1)} _{Co1—O1—Co1}i _{100.5 (1)}

O1—Co1—O3iv _{172.5 (1)} _{C1—O2—Co1}vi _{123.8 (2)}

O1i_—Co1—O2ii _{83.9 (1)} _Co1vii_—O3—Co1 _{139.0 (1)}

O1i_—Co1—O3 _{86.9 (1)} _Co1vii_—O3—Co1v _{92.2 (1)}

O1i_—Co1—O3iii _{171.8 (1)} _{Co1—O3—Co1}v _{92.0 (1)}

O1i_—Co1—O3iv _{93.3 (1)} _O2—C1—O1 _{126.4 (3)}

O2ii_—Co1—O3 _{170.8 (1)} _Co1vii_—O3—H3 _{107 (3)}

O2ii_—Co1—O3iii _{88.4 (1)} _{Co1—O3—H3} _{105 (3)}

O2ii_—Co1—O3iv _{97.0 (1)} _Co1v_—O3—H3 _{121 (4)}

O3—Co1—O3iii _{100.8 (1)} _O2—C1—H1 _{118 (3)}

O3—Co1—O3iv _{84.8 (1)} _O1—C1—H1 _{115 (3)}

O3iii_{—Co1—O1—C1} _{−17.7 (3)} _{O1—Co1—O3—Co1}vii _{109.8 (2)}

O3—Co1—O1—C1 −119.5 (3) O1i_{—Co1—O3—Co1}vii _{−171.0 (2)}

O2ii_{—Co1—O1—C1} _{69.3 (3)} _O3iii_{—Co1—O3—Co1}v _{102.0 (1)}

O1i_{—Co1—O1—C1} _{154.2 (3)} _O3iv_{—Co1—O3—Co1}v _{18.3 (1)}

O3iii_{—Co1—O1—Co1}i _{−171.9 (1)} _{O1—Co1—O3—Co1}v _{−154.6 (1)}

O3—Co1—O1—Co1i _{86.3 (1)} _O1i_{—Co1—O3—Co1}v _{−75.3 (1)}

O2ii_{—Co1—O1—Co1}i _{−84.9 (1)} _Co1vi_{—O2—C1—O1} _{11.4 (5)}

O3iii_{—Co1—O3—Co1}vii _{6.4 (2)} _{Co1—O1—C1—O2} _{−138.9 (3)}

O3iv_{—Co1—O3—Co1}vii _{−77.4 (2)} _Co1i_{—O1—C1—O2} _{8.2 (6)}

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supporting information

sup-3 Acta Cryst. (2005). E61, m2395–m2396

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O3—H3···O1i _{0.85 (1)} _{2.76 (5)} _{2.892 (3)} _{91 (4)}