Tetra­aqua­bis(3-carboxyl­atopyridine N-oxide-κO3)cadmium(II)

Zhang, C.-Y.; Gao, Q.; Cui, Y.; Xie, Y.-B.

doi:10.1107/S1600536809022430

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page m785

doi:10.1107/S1600536809022430

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Tetraaquabis(3-carboxylatopyridine N-oxide-κO³)cadmium(II)

Chao-Yan Zhang,^a Qian Gao,^a Yue Cui ^a and Ya-Bo Xie ^a ^*

^aCollege of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100022, People's Republic of China
^*Correspondence e-mail: xieyabo@bjut.edu.cn

(Received 5 June 2009; accepted 12 June 2009; online 17 June 2009)

In the title complex, [Cd(C₆H₄NO₃)₂(H₂O)₄], the Cd^II atom is situated on a crystallographic centre of inversion. The Cd^II atom shows a slightly distorted octahedral geometry and is coordinated by four O atoms from water molecules and two O atoms from deprotonated carboxyl groups of nicotinic acid N-oxide ligands. The mononuclear complex molecules are linked by O—H⋯O hydrogen bonds, forming a three-dimensional network structure.

Related literature

For a related stucture, see: Hilkka et al. (1983 ).

Experimental

Crystal data

[Cd(C₆H₄NO₃)₂(H₂O)₄]
M_r = 460.67
Monoclinic, P 2₁ /c
a = 8.896 (2) Å
b = 13.284 (3) Å
c = 6.902 (1) Å
β = 106.95 (3)°
V = 780.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.46 mm⁻¹
T = 293 K
0.24 × 0.24 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.705, T_max = 0.712
3886 measured reflections
1371 independent reflections
1216 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.047
S = 1.11
1371 reflections
115 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O2ⁱ	0.85	1.90	2.678 (2)	151
O1W—H1WB⋯O3ⁱⁱ	0.85	1.86	2.697 (2)	165
O2W—H2WA⋯O3ⁱⁱⁱ	0.86	1.86	2.716 (2)	175
O2W—H2WB⋯O2ⁱⁱ	0.86	1.93	2.787 (2)	173
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022430/im2121sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022430/im2121Isup2.hkl

checkCIF report

Comment top

The behaviour of nicotinic acid N-oxide ligand towards transition metals has been studied (Hilkka et al., 1983). Herein, we prepared a new complex with the similar structure.

The title complex (Fig. 1) is made up of tetraaquametal cations and nicotinate N-oxide anion. The Cd^II centre shows a slightly distorted octahedral geometry and is six-coordinated by four O atoms from water molecules and two O atoms from deprotonated carboxylic groups of nicotinic acid N-oxide ligands. The O atoms of the N-oxide function bridge two water ligands of adjacent complex molecules via O—H···O hydrogen bonds, forming infinite chains along c axis (Fig. 2). Otherwise, the chains are linked by additional O—H···O hydrogen bonds observed between carboxyl O atoms and H atoms of coordinated water molecules. In conclusion, the mononucear complexes are linked by O—H···O hydrogen bonds, forming a three-dimensional network structure.

Related literature top

For a related stucture, see: Hilkka et al. (1983).

Experimental top

A solution containing a 1 : 1 : 2 molar ratio of nicotinic acid N-oxide, LiOH × H₂O and Cd(NO₃)₂ × 4 H₂O in water was sealed in a 25 ml teflon reactor and kept at 140° for 3 days. The mixture was stepwise cooled to 40° with a rate of 10° per hour and was then allowed to cool to room temperature naturally. Colorless block-shaped crystals suitable for X-ray investagation were collected from the final mixture.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-hydrogen atoms. Symmetry related atoms labelled A have the symmetry code A = -x + 1, -y + 1, -z.
	Fig. 2. Supramolecular structure of the title compound realized by O—H···O hydrogen bond.

Tetraaquabis(3-carboxylatopyridine N-oxide-κO³)cadmium(II) top

Crystal data top

[Cd(C₆H₄NO₃)₂(H₂O)₄]	F(000) = 460
M_r = 460.67	D_x = 1.961 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2694 reflections
a = 8.896 (2) Å	θ = 2.4–30.8°
b = 13.284 (3) Å	µ = 1.46 mm⁻¹
c = 6.902 (1) Å	T = 293 K
β = 106.95 (3)°	Block, colorless
V = 780.2 (3) Å³	0.24 × 0.24 × 0.24 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1371 independent reflections
Radiation source: fine-focus sealed tube	1216 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→9
T_min = 0.705, T_max = 0.712	k = −15→13
3886 measured reflections	l = −8→8

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)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.047	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0239P)² + 0.3039P] where P = (F_o² + 2F_c²)/3
1371 reflections	(Δ/σ)_max = 0.001
115 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Cd(C₆H₄NO₃)₂(H₂O)₄]	V = 780.2 (3) Å³
M_r = 460.67	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.896 (2) Å	µ = 1.46 mm⁻¹
b = 13.284 (3) Å	T = 293 K
c = 6.902 (1) Å	0.24 × 0.24 × 0.24 mm
β = 106.95 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1371 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1216 reflections with I > 2σ(I)
T_min = 0.705, T_max = 0.712	R_int = 0.013
3886 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	0 restraints
wR(F²) = 0.047	H-atom parameters constrained
S = 1.11	Δρ_max = 0.26 e Å⁻³
1371 reflections	Δρ_min = −0.27 e Å⁻³
115 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

	x	y	z	U_iso*/U_eq
Cd1	0.5000	0.5000	0.0000	0.02694 (9)
O1	0.69494 (17)	0.61434 (10)	0.0646 (2)	0.0322 (3)
O2	0.54243 (17)	0.73900 (11)	−0.1003 (2)	0.0356 (4)
O3	0.84106 (18)	1.04656 (11)	0.1475 (2)	0.0351 (4)
C5	0.7630 (2)	0.88034 (15)	0.0896 (3)	0.0258 (4)
H5A	0.6623	0.9017	0.0195	0.031*
C1	0.7954 (2)	0.77885 (14)	0.1108 (3)	0.0234 (4)
O1W	0.6079 (2)	0.42109 (12)	0.3026 (2)	0.0475 (5)
C6	0.6669 (2)	0.70560 (15)	0.0175 (3)	0.0257 (4)
C4	1.0221 (2)	0.92024 (16)	0.2703 (3)	0.0323 (5)
H4A	1.0988	0.9685	0.3232	0.039*
O2W	0.37122 (19)	0.60651 (11)	0.1620 (2)	0.0387 (4)
N1	0.8750 (2)	0.94858 (13)	0.1691 (3)	0.0263 (4)
C2	0.9455 (3)	0.74878 (15)	0.2168 (3)	0.0293 (5)
H2A	0.9699	0.6807	0.2349	0.035*
C3	1.0585 (2)	0.82017 (17)	0.2953 (3)	0.0349 (5)
H3A	1.1600	0.8004	0.3656	0.042*
H1WA	0.5831	0.3597	0.2735	0.042*
H1WB	0.6909	0.4234	0.4033	0.042*
H2WA	0.3009	0.5861	0.2151	0.042*
H2WB	0.4182	0.6543	0.2406	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02508 (13)	0.02246 (14)	0.02930 (14)	−0.00329 (8)	0.00169 (9)	−0.00103 (8)
O1	0.0296 (8)	0.0189 (7)	0.0431 (9)	−0.0038 (6)	0.0024 (7)	0.0023 (6)
O2	0.0315 (8)	0.0226 (8)	0.0428 (9)	−0.0029 (6)	−0.0046 (7)	0.0027 (7)
O3	0.0339 (8)	0.0176 (7)	0.0483 (9)	−0.0020 (6)	0.0034 (7)	−0.0013 (7)
C5	0.0213 (10)	0.0232 (10)	0.0301 (11)	−0.0017 (8)	0.0031 (8)	−0.0001 (8)
C1	0.0270 (10)	0.0196 (10)	0.0235 (10)	−0.0022 (8)	0.0072 (8)	−0.0001 (8)
O1W	0.0593 (11)	0.0263 (8)	0.0391 (9)	−0.0105 (8)	−0.0133 (8)	0.0035 (7)
C6	0.0279 (11)	0.0219 (11)	0.0269 (10)	−0.0035 (8)	0.0073 (9)	−0.0012 (8)
C4	0.0241 (11)	0.0301 (12)	0.0378 (12)	−0.0073 (9)	0.0015 (9)	−0.0026 (9)
O2W	0.0365 (9)	0.0331 (8)	0.0477 (10)	−0.0077 (7)	0.0143 (7)	−0.0101 (7)
N1	0.0269 (9)	0.0200 (9)	0.0300 (9)	−0.0021 (7)	0.0052 (7)	−0.0007 (7)
C2	0.0314 (11)	0.0217 (11)	0.0326 (12)	0.0014 (8)	0.0061 (9)	0.0013 (9)
C3	0.0239 (11)	0.0328 (12)	0.0420 (13)	0.0008 (9)	0.0006 (9)	0.0025 (10)

Geometric parameters (Å, º) top

Cd1—O1ⁱ	2.2499 (14)	C1—C2	1.382 (3)
Cd1—O1	2.2499 (14)	C1—C6	1.496 (3)
Cd1—O1Wⁱ	2.2836 (16)	O1W—H1WA	0.8537
Cd1—O1W	2.2836 (16)	O1W—H1WB	0.8538
Cd1—O2W	2.3045 (16)	C4—N1	1.345 (3)
Cd1—O2Wⁱ	2.3045 (16)	C4—C3	1.367 (3)
O1—C6	1.261 (2)	C4—H4A	0.9300
O2—C6	1.248 (2)	O2W—H2WA	0.8559
O3—N1	1.335 (2)	O2W—H2WB	0.8603
C5—N1	1.340 (3)	C2—C3	1.373 (3)
C5—C1	1.377 (3)	C2—H2A	0.9300
C5—H5A	0.9300	C3—H3A	0.9300

O1ⁱ—Cd1—O1	180.0	Cd1—O1W—H1WA	102.3
O1ⁱ—Cd1—O1Wⁱ	91.98 (6)	Cd1—O1W—H1WB	139.5
O1—Cd1—O1Wⁱ	88.02 (6)	H1WA—O1W—H1WB	109.2
O1ⁱ—Cd1—O1W	88.02 (6)	O2—C6—O1	125.51 (19)
O1—Cd1—O1W	91.98 (6)	O2—C6—C1	118.05 (17)
O1Wⁱ—Cd1—O1W	180.00 (7)	O1—C6—C1	116.44 (18)
O1ⁱ—Cd1—O2W	92.70 (6)	N1—C4—C3	119.74 (19)
O1—Cd1—O2W	87.30 (6)	N1—C4—H4A	120.1
O1Wⁱ—Cd1—O2W	91.49 (7)	C3—C4—H4A	120.1
O1W—Cd1—O2W	88.51 (7)	Cd1—O2W—H2WA	122.8
O1ⁱ—Cd1—O2Wⁱ	87.30 (6)	Cd1—O2W—H2WB	122.7
O1—Cd1—O2Wⁱ	92.70 (6)	H2WA—O2W—H2WB	104.2
O1Wⁱ—Cd1—O2Wⁱ	88.51 (7)	O3—N1—C5	119.82 (16)
O1W—Cd1—O2Wⁱ	91.49 (7)	O3—N1—C4	119.00 (16)
O2W—Cd1—O2Wⁱ	180.0	C5—N1—C4	121.18 (18)
C6—O1—Cd1	120.98 (13)	C3—C2—C1	119.49 (19)
N1—C5—C1	120.73 (18)	C3—C2—H2A	120.3
N1—C5—H5A	119.6	C1—C2—H2A	120.3
C1—C5—H5A	119.6	C4—C3—C2	120.2 (2)
C5—C1—C2	118.64 (18)	C4—C3—H3A	119.9
C5—C1—C6	118.74 (18)	C2—C3—H3A	119.9
C2—C1—C6	122.62 (18)

O1ⁱ—Cd1—O1—C6	178 (100)	C5—C1—C6—O1	−170.21 (19)
O1Wⁱ—Cd1—O1—C6	39.82 (16)	C2—C1—C6—O1	10.0 (3)
O1W—Cd1—O1—C6	−140.18 (16)	C1—C5—N1—O3	−179.78 (18)
O2W—Cd1—O1—C6	−51.77 (16)	C1—C5—N1—C4	0.4 (3)
O2Wⁱ—Cd1—O1—C6	128.23 (16)	C3—C4—N1—O3	179.46 (19)
N1—C5—C1—C2	0.4 (3)	C3—C4—N1—C5	−0.7 (3)
N1—C5—C1—C6	−179.34 (18)	C5—C1—C2—C3	−1.0 (3)
Cd1—O1—C6—O2	−15.1 (3)	C6—C1—C2—C3	178.8 (2)
Cd1—O1—C6—C1	165.45 (13)	N1—C4—C3—C2	0.2 (4)
C5—C1—C6—O2	10.3 (3)	C1—C2—C3—C4	0.7 (3)
C2—C1—C6—O2	−169.5 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2ⁱ	0.85	1.90	2.678 (2)	151
O1W—H1WB···O3ⁱⁱ	0.85	1.86	2.697 (2)	165
O2W—H2WA···O3ⁱⁱⁱ	0.86	1.86	2.716 (2)	175
O2W—H2WB···O2ⁱⁱ	0.86	1.93	2.787 (2)	173

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

Experimental details

Crystal data
Chemical formula	[Cd(C₆H₄NO₃)₂(H₂O)₄]
M_r	460.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.896 (2), 13.284 (3), 6.902 (1)
β (°)	106.95 (3)
V (Å³)	780.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.46
Crystal size (mm)	0.24 × 0.24 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.705, 0.712
No. of measured, independent and observed [I > 2σ(I)] reflections	3886, 1371, 1216
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.047, 1.11
No. of reflections	1371
No. of parameters	115
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.27

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2ⁱ	0.85	1.90	2.678 (2)	150.6
O1W—H1WB···O3ⁱⁱ	0.85	1.86	2.697 (2)	164.8
O2W—H2WA···O3ⁱⁱⁱ	0.86	1.86	2.716 (2)	174.9
O2W—H2WB···O2ⁱⁱ	0.86	1.93	2.787 (2)	173.1

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

Acknowledgements

This work was supported Beijing Municipal Natural Science Foundation (grant No. 2082004).

References

Bruker (1998). SMART, SAINT and SADABS . Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hilkka, K., Univ, D. C. & Finland, J. J. (1983). Acta Chem. Scand. Ser. A, 37, 697–702. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar