Poly[dimethyl­ammonium [tris­(μ2-formato-κ2O:O′)cadmate(II)]]

Gao, S.; Ng, S.W.

doi:10.1107/S1600536810046830

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1599

https://doi.org/10.1107/S1600536810046830

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Poly[dimethylammonium [tris(μ₂-formato-κ²O:O′)cadmate(II)]]

Shan Gao ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 9 November 2010; accepted 12 November 2010; online 20 November 2010)

In the coordination polymer, {(C₂H₈N)[Cd(CHO₂)₃]}_n, the Cd^II atom lies on a special position of $[\overline{3}]$ site symmetry in an octahedron of O atoms. The formate unit bridges the metal atoms, generating a three-dimensional polyanionic framework. The disordered cations occupy the cavities within the framework, and are N—H⋯O hydrogen-bonded to the framework.

Related literature

For the tris(formato)zincate cation, see; Fortier & Creber (1985 ); Marsh (1986 ). Tris(formato)cadmate is not isotypic to the aforementioned Zn structures.

Experimental

Crystal data

(C₂H₈N)[Cd(CHO₂)₃]
M_r = 293.55
Trigonal, $[R \overline 3c ]$
a = 8.5121 (4) Å
c = 23.0022 (9) Å
V = 1443.36 (9) Å³
Z = 6
Mo Kα radiation
μ = 2.27 mm⁻¹
T = 293 K
0.22 × 0.19 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.635, T_max = 0.727
4250 measured reflections
370 independent reflections
352 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.055
S = 1.09
370 reflections
33 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.88	1.99	2.84 (7)	163

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810046830/hg2747sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046830/hg2747Isup2.hkl

checkCIF report

Comment top

For some hydrothermal syntheses involving carboxylic acids, the N,N-dimethylformamide that is used as solvent is partially converted to the dimethylammonium cation, whose charge is balanced by the carboxylate ion. In the present study, the attempt to synthesize a coordination compound of a cadmium carboxylate yielded the tris(formato)cadmate anion (Scheme I). In the salt (Fig. 1), the cadmium atom lies on a special position of 3 site symmetry in an octahedron of O atoms. The formate unit bridges the metal atoms to generate a three-dimensional polyanionic framework, whose cavities are occupied by disordered cations.

A similar tris(formato)zincate(II) has been reported; the compound was synthesized directly from a zinc salt and formic acid in DMF medium (Fortier & Creber, 1985; Marsh, 1986). The later study has assumed the cation to be the formamidine cation, (NH₂)CH(NH₂)⁺. Possibly, the cation is the dimethylammonium cation.

Related literature top

For the tris(formato)zincate cation, see; Fortier & Creber (1985); Marsh (1986). Tris(formato)cadmate is not isotypic.

Experimental top

N,N-Dimethylformamide (10 ml), water (1 ml), ethanol (1 ml), formic acid (0.1 ml), cadmium nitrate (5 mmol), 1,10-phenanthroline (5 mmol) and benzoic acid (5 mmol) were heated in a 23-ml Teflon-lined autoclave at 383 K for 3 days. After slow cooling the autoclave to room temperature, colorless crystals were obtained.

Structure description top

For the tris(formato)zincate cation, see; Fortier & Creber (1985); Marsh (1986). Tris(formato)cadmate is not isotypic.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of a portion of poly[dimethylammonium tris(formato)cadmate] at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Poly[dimethylammonium [tris(µ₂-formato-κ²O:O')cadmate(II)]] top

Crystal data top

(C₂H₈N)[Cd(CHO₂)₃]	D_x = 2.026 Mg m⁻³
M_r = 293.55	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 3921 reflections
Hall symbol: -R 3 2" c	θ = 3.3–37.5°
a = 8.5121 (4) Å	µ = 2.27 mm⁻¹
c = 23.0022 (9) Å	T = 293 K
V = 1443.36 (9) Å³	Prism, colorless
Z = 6	0.22 × 0.19 × 0.15 mm
F(000) = 864

Data collection top

Rigaku R-AXIS RAPID diffractometer	370 independent reflections
Radiation source: fine-focus sealed tube	352 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→9
T_min = 0.635, T_max = 0.727	l = −29→29
4250 measured reflections

Refinement top

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.055	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0419P)² + 0.5666P] where P = (F_o² + 2F_c²)/3
370 reflections	(Δ/σ)_max = 0.001
33 parameters	Δρ_max = 0.73 e Å⁻³
9 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

(C₂H₈N)[Cd(CHO₂)₃]	Z = 6
M_r = 293.55	Mo Kα radiation
Trigonal, R3c	µ = 2.27 mm⁻¹
a = 8.5121 (4) Å	T = 293 K
c = 23.0022 (9) Å	0.22 × 0.19 × 0.15 mm
V = 1443.36 (9) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	370 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	352 reflections with I > 2σ(I)
T_min = 0.635, T_max = 0.727	R_int = 0.024
4250 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	9 restraints
wR(F²) = 0.055	H-atom parameters constrained
S = 1.09	Δρ_max = 0.73 e Å⁻³
370 reflections	Δρ_min = −0.36 e Å⁻³
33 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cd1	0.0000	0.0000	0.0000	0.02669 (17)
O1	0.23112 (15)	0.21016 (15)	0.05612 (5)	0.0452 (3)
C1	0.2265 (2)	0.3333	0.0833	0.0328 (4)
H1A	0.1173	0.3333	0.0833	0.039*
N1	0.578 (6)	0.252 (5)	0.0797 (17)	0.040 (4)	0.167
H1B	0.5788	0.1489	0.0798	0.048*	0.167
H1	0.4646	0.2277	0.0792	0.048*	0.167
C2	0.680 (5)	0.365 (4)	0.0282 (14)	0.041 (4)*	0.167
H2A	0.6061	0.3181	−0.0061	0.062*	0.167
H2B	0.7899	0.3619	0.0232	0.062*	0.167
H2C	0.7079	0.4881	0.0344	0.062*	0.167
C3	0.676 (7)	0.364 (4)	0.1320 (15)	0.041 (4)*	0.167
H3A	0.6210	0.2961	0.1667	0.062*	0.167
H3B	0.6687	0.4732	0.1322	0.062*	0.167
H3C	0.8010	0.3952	0.1306	0.062*	0.167

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02630 (19)	0.02630 (19)	0.0275 (2)	0.01315 (10)	0.000	0.000
O1	0.0397 (6)	0.0420 (6)	0.0554 (7)	0.0215 (5)	−0.0121 (5)	−0.0206 (5)
C1	0.0301 (8)	0.0326 (11)	0.0367 (10)	0.0163 (5)	−0.0006 (4)	−0.0011 (8)
N1	0.040 (8)	0.028 (6)	0.055 (8)	0.019 (4)	−0.006 (7)	0.002 (7)

Geometric parameters (Å, º) top

Cd1—O1ⁱ	2.2841 (10)	N1—C3	1.505 (10)
Cd1—O1	2.2841 (10)	N1—H1B	0.8800
Cd1—O1ⁱⁱ	2.2841 (10)	N1—H1	0.8800
Cd1—O1ⁱⁱⁱ	2.2841 (10)	C2—H2A	0.9600
Cd1—O1^iv	2.2841 (10)	C2—H2B	0.9600
Cd1—O1^v	2.2841 (10)	C2—H2C	0.9600
O1—C1	1.2384 (14)	C3—H3A	0.9600
C1—O1^vi	1.2383 (14)	C3—H3B	0.9600
C1—H1A	0.9300	C3—H3C	0.9600
N1—C2	1.499 (10)

O1ⁱ—Cd1—O1	180.00 (5)	C2—N1—C3	105.3 (8)
O1ⁱ—Cd1—O1ⁱⁱ	91.20 (4)	C2—N1—H1B	110.7
O1—Cd1—O1ⁱⁱ	88.80 (4)	C3—N1—H1B	110.7
O1ⁱ—Cd1—O1ⁱⁱⁱ	91.20 (4)	C2—N1—H1	110.7
O1—Cd1—O1ⁱⁱⁱ	88.80 (4)	C3—N1—H1	110.7
O1ⁱⁱ—Cd1—O1ⁱⁱⁱ	91.20 (4)	H1B—N1—H1	108.8
O1ⁱ—Cd1—O1^iv	88.80 (4)	N1—C2—H2A	109.5
O1—Cd1—O1^iv	91.20 (4)	N1—C2—H2B	109.5
O1ⁱⁱ—Cd1—O1^iv	88.80 (4)	H2A—C2—H2B	109.5
O1ⁱⁱⁱ—Cd1—O1^iv	180.00 (7)	N1—C2—H2C	109.5
O1ⁱ—Cd1—O1^v	88.80 (4)	H2A—C2—H2C	109.5
O1—Cd1—O1^v	91.20 (4)	H2B—C2—H2C	109.5
O1ⁱⁱ—Cd1—O1^v	180.00 (5)	N1—C3—H3A	109.5
O1ⁱⁱⁱ—Cd1—O1^v	88.80 (4)	N1—C3—H3B	109.5
O1^iv—Cd1—O1^v	91.20 (4)	H3A—C3—H3B	109.5
C1—O1—Cd1	124.71 (11)	N1—C3—H3C	109.5
O1^vi—C1—O1	125.90 (19)	H3A—C3—H3C	109.5
O1^vi—C1—H1A	117.1	H3B—C3—H3C	109.5
O1—C1—H1A	117.1

O1ⁱⁱ—Cd1—O1—C1	151.34 (11)	O1^v—Cd1—O1—C1	−28.66 (11)
O1ⁱⁱⁱ—Cd1—O1—C1	60.11 (7)	Cd1—O1—C1—O1^vi	−174.40 (11)
O1^iv—Cd1—O1—C1	−119.89 (7)

Symmetry codes: (i) −x, −y, −z; (ii) y, −x+y, −z; (iii) x−y, x, −z; (iv) −x+y, −x, z; (v) −y, x−y, z; (vi) x−y+1/3, −y+2/3, −z+1/6.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88	1.99	2.84 (7)	163

Experimental details

Crystal data
Chemical formula	(C₂H₈N)[Cd(CHO₂)₃]
M_r	293.55
Crystal system, space group	Trigonal, R3c
Temperature (K)	293
a, c (Å)	8.5121 (4), 23.0022 (9)
V (Å³)	1443.36 (9)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	2.27
Crystal size (mm)	0.22 × 0.19 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.635, 0.727
No. of measured, independent and observed [I > 2σ(I)] reflections	4250, 370, 352
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.055, 1.09
No. of reflections	370
No. of parameters	33
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.36

Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO (Rigaku, 1998, CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88	1.99	2.84 (7)	163.3

Acknowledgements

We thank the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903) and the Innovation Team of the Education Bureau of Heilongjiang Province (No. 2010 t d03), Heilongjiang University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Fortier, S. & Creber, K. A. M. (1985). Acta Cryst. C41, 1763–1765. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Program for Absorption Correction, Tokyo, Japan. Google Scholar
Marsh, R. E. (1986). Acta Cryst. C42, 1327–1328. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar