Tetra­aqua­bis(5-hydroxy­nicotinato-κN)cadmium(II)

Jiang, M.-X.; Feng, Y.-L.

doi:10.1107/S1600536808035903

metal-organic compounds

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Volume 64| Part 12| December 2008| Page m1517

doi:10.1107/S1600536808035903

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Tetraaquabis(5-hydroxynicotinato-κN)cadmium(II)

Mei-Xiang Jiang ^a and Yun-Long Feng ^a ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
^*Correspondence e-mail: sky37@zjnu.edu.cn

(Received 22 October 2008; accepted 1 November 2008; online 8 November 2008)

The title compound, [Cd(C₆H₄NO₃)₂(H₂O)₄], was obtained by the reaction of cadmium chloride with 5-hydroxynicotinic acid. The Cd^II atom is located on an inversion centre and is coordinated by two N atoms from two 5-hydroxynicotinic acid ligands and four water molecules in a distorted octahedral geometry. The structure is stabilized by intermolecular O—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For cadmium componds and their photoluminescent properties, see: He et al. (2008 ); Kang et al. (2007 ); Zhang et al. (2006 ); Zora et al. (2006 ).

Experimental

Crystal data

[Cd(C₆H₄NO₃)₂(H₂O)₄]
M_r = 460.68
Triclinic, $[P \overline 1]$
a = 7.2190 (1) Å
b = 7.2510 (1) Å
c = 8.9260 (1) Å
α = 70.377 (1)°
β = 68.154 (1)°
γ = 65.7170 (10)°
V = 385.97 (1) Å³
Z = 1
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 296 (2) K
0.27 × 0.17 × 0.07 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.667, T_max = 0.903
6067 measured reflections
1759 independent reflections
1754 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.042
S = 1.09
1759 reflections
131 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O2ⁱ	0.81 (2)	1.94 (2)	2.742 (2)	171 (3)
O1W—H1WB⋯O3ⁱⁱ	0.79 (2)	2.20 (2)	2.973 (2)	164 (3)
O2W—H2WA⋯O1ⁱⁱⁱ	0.82 (2)	1.87 (2)	2.656 (2)	160 (3)
O2W—H2WB⋯O2^iv	0.82 (2)	1.93 (2)	2.735 (2)	165 (3)
O3—H3⋯O1^v	0.83 (2)	1.88 (2)	2.664 (2)	157 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+2; (iii) -x+2, -y+1, -z+1; (iv) x, y-1, z+1; (v) x-1, y, z.

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: XPREP (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808035903/at2660sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035903/at2660Isup2.hkl

checkCIF report

Comment top

There is intense research on the synthesis of the cadmium metal compounds for their interesting photoluminescent properties. A large number of these compounds have been synthesized (He et al., 2008; Zora et al., 2006; Kang et al.,2007; Zhang et al., 2006).

As illustrated in Fig. 1, the Cd(II) atom is coordinated by two nitrogen atoms from two 5-hydroxynicotinic acid ligands and four water molecules. Four coordinated atoms of O1W, O2W, O1WA and O2WA constitute the base of the octahedral, whereas N1 and N1A atoms occupy the apical position. The intermolecular hydrogen bonds play an important role in the formation of the three-dimensional network. As shown in Fig. 2, the intermolecular O—H···O hydrogen bonds link the neighboring molecules to a three-dimensional network.

Related literature top

For cadmium componds and their photoluminescent properties, see: He et al. (2008); Kang et al. (2007); Zhang et al. (2006); Zora et al. (2006).

Experimental top

A mixture of 0.5 mmol 5-hydroxynicotinic acid and 0.5 mmol of cadmium chloride in 10 ml distilled water was stirred for 30 min at 323 K, then the reaction mixture was filtered and well shaped colourless crystals of the title compound was obtained from the mother liquor by slow evaporation at room temperature for several days.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: XPREP (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme, displacement ellipsoids are shown at the 30% probability level. [Symmetry code: (A) -x + 1, -y + 1, -z + 2].
	Fig. 2. A view of the three dimensional framework of the title compound. The O—H···O interactions are depicted by dashed lines.

Tetraaquabis(5-hydroxynicotinato-κN)cadmium(II) top

Crystal data top

[Cd(C₆H₄NO₃)₂(H₂O)₄]	Z = 1
M_r = 460.68	F(000) = 230
Triclinic, P1	D_x = 1.982 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2190 (1) Å	Cell parameters from 5615 reflections
b = 7.2510 (1) Å	θ = 2.5–27.5°
c = 8.9260 (1) Å	µ = 1.48 mm⁻¹
α = 70.377 (1)°	T = 296 K
β = 68.154 (1)°	Sheet, colourless
γ = 65.717 (1)°	0.27 × 0.17 × 0.07 mm
V = 385.97 (1) Å³

Data collection top

Bruker APEXII diffractometer	1759 independent reflections
Radiation source: fine-focus sealed tube	1754 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.667, T_max = 0.903	k = −9→9
6067 measured reflections	l = −11→11

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)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.042	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0249P)² + 0.1253P] where P = (F_o² + 2F_c²)/3
1759 reflections	(Δ/σ)_max < 0.001
131 parameters	Δρ_max = 0.36 e Å⁻³
7 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Cd(C₆H₄NO₃)₂(H₂O)₄]	γ = 65.717 (1)°
M_r = 460.68	V = 385.97 (1) Å³
Triclinic, P1	Z = 1
a = 7.2190 (1) Å	Mo Kα radiation
b = 7.2510 (1) Å	µ = 1.48 mm⁻¹
c = 8.9260 (1) Å	T = 296 K
α = 70.377 (1)°	0.27 × 0.17 × 0.07 mm
β = 68.154 (1)°

Data collection top

Bruker APEXII diffractometer	1759 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1754 reflections with I > 2σ(I)
T_min = 0.667, T_max = 0.903	R_int = 0.017
6067 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	7 restraints
wR(F²) = 0.042	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.36 e Å⁻³
1759 reflections	Δρ_min = −0.34 e Å⁻³
131 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	1.0000	0.02626 (6)
O1	0.8938 (2)	0.7990 (2)	0.32463 (16)	0.0427 (3)
O1W	0.2684 (3)	0.3168 (3)	1.07212 (17)	0.0482 (4)
H1WA	0.287 (5)	0.249 (4)	1.009 (3)	0.072*
H1WB	0.209 (5)	0.270 (4)	1.163 (2)	0.072*
O2	0.6901 (2)	0.8709 (2)	0.16430 (15)	0.0429 (3)
O2W	0.7595 (2)	0.2074 (2)	0.92481 (18)	0.0478 (4)
H2WA	0.881 (3)	0.189 (4)	0.865 (3)	0.072*
H2WB	0.762 (5)	0.098 (3)	0.994 (3)	0.072*
O3	0.0066 (2)	0.7675 (2)	0.58671 (17)	0.0400 (3)
H3	0.002 (4)	0.785 (4)	0.491 (2)	0.053 (7)*
N1	0.4459 (2)	0.6297 (2)	0.74305 (16)	0.0264 (3)
C1	0.5945 (2)	0.6740 (2)	0.60554 (19)	0.0267 (3)
H1A	0.7280	0.6483	0.6138	0.032*
C2	0.5560 (2)	0.7568 (2)	0.45137 (18)	0.0245 (3)
C3	0.3595 (3)	0.7885 (2)	0.43778 (19)	0.0263 (3)
H3A	0.3310	0.8402	0.3354	0.032*
C4	0.2061 (2)	0.7415 (2)	0.5802 (2)	0.0270 (3)
C5	0.2549 (2)	0.6655 (3)	0.73035 (19)	0.0276 (3)
H5A	0.1507	0.6383	0.8260	0.033*
C6	0.7273 (3)	0.8123 (2)	0.30121 (19)	0.0288 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02499 (9)	0.03841 (10)	0.01604 (8)	−0.01493 (7)	−0.00552 (6)	−0.00099 (6)
O1	0.0313 (6)	0.0688 (9)	0.0266 (6)	−0.0259 (6)	−0.0010 (5)	−0.0044 (6)
O1W	0.0589 (9)	0.0749 (10)	0.0276 (6)	−0.0484 (8)	−0.0017 (6)	−0.0091 (7)
O2	0.0587 (8)	0.0592 (8)	0.0199 (6)	−0.0385 (7)	−0.0088 (5)	0.0028 (5)
O2W	0.0368 (7)	0.0424 (7)	0.0347 (7)	−0.0075 (6)	0.0072 (6)	0.0013 (6)
O3	0.0285 (6)	0.0620 (8)	0.0326 (7)	−0.0220 (6)	−0.0135 (5)	0.0007 (6)
N1	0.0258 (6)	0.0362 (7)	0.0187 (6)	−0.0141 (5)	−0.0068 (5)	−0.0018 (5)
C1	0.0252 (7)	0.0376 (8)	0.0208 (7)	−0.0155 (6)	−0.0064 (6)	−0.0037 (6)
C2	0.0278 (7)	0.0271 (7)	0.0195 (7)	−0.0128 (6)	−0.0046 (6)	−0.0033 (5)
C3	0.0312 (7)	0.0288 (7)	0.0207 (7)	−0.0120 (6)	−0.0109 (6)	−0.0005 (5)
C4	0.0249 (7)	0.0305 (7)	0.0281 (7)	−0.0112 (6)	−0.0107 (6)	−0.0026 (6)
C5	0.0254 (7)	0.0358 (8)	0.0219 (7)	−0.0143 (6)	−0.0053 (6)	−0.0023 (6)
C6	0.0340 (8)	0.0319 (8)	0.0206 (7)	−0.0166 (6)	−0.0025 (6)	−0.0038 (6)

Geometric parameters (Å, º) top

Cd1—O2W	2.2830 (14)	O3—C4	1.3543 (19)
Cd1—O2Wⁱ	2.2830 (14)	O3—H3	0.830 (17)
Cd1—N1ⁱ	2.2831 (13)	N1—C5	1.335 (2)
Cd1—N1	2.2831 (13)	N1—C1	1.3411 (19)
Cd1—O1W	2.3291 (13)	C1—C2	1.387 (2)
Cd1—O1Wⁱ	2.3291 (13)	C1—H1A	0.9300
O1—C6	1.255 (2)	C2—C3	1.385 (2)
O1W—H1WA	0.809 (17)	C2—C6	1.517 (2)
O1W—H1WB	0.794 (17)	C3—C4	1.389 (2)
O2—C6	1.244 (2)	C3—H3A	0.9300
O2W—H2WA	0.823 (17)	C4—C5	1.386 (2)
O2W—H2WB	0.822 (17)	C5—H5A	0.9300

O2W—Cd1—O2Wⁱ	180.0	C5—N1—C1	118.64 (13)
O2W—Cd1—N1ⁱ	87.79 (5)	C5—N1—Cd1	117.86 (10)
O2Wⁱ—Cd1—N1ⁱ	92.21 (5)	C1—N1—Cd1	123.49 (10)
O2W—Cd1—N1	92.21 (5)	N1—C1—C2	122.29 (14)
O2Wⁱ—Cd1—N1	87.79 (5)	N1—C1—H1A	118.9
N1ⁱ—Cd1—N1	180.000 (1)	C2—C1—H1A	118.9
O2W—Cd1—O1W	85.72 (6)	C3—C2—C1	118.97 (14)
O2Wⁱ—Cd1—O1W	94.28 (6)	C3—C2—C6	121.06 (14)
N1ⁱ—Cd1—O1W	90.57 (5)	C1—C2—C6	119.96 (14)
N1—Cd1—O1W	89.43 (5)	C2—C3—C4	118.68 (14)
O2W—Cd1—O1Wⁱ	94.28 (6)	C2—C3—H3A	120.7
O2Wⁱ—Cd1—O1Wⁱ	85.72 (6)	C4—C3—H3A	120.7
N1ⁱ—Cd1—O1Wⁱ	89.43 (5)	O3—C4—C5	115.78 (14)
N1—Cd1—O1Wⁱ	90.57 (5)	O3—C4—C3	125.40 (14)
O1W—Cd1—O1Wⁱ	180.0	C5—C4—C3	118.81 (14)
Cd1—O1W—H1WA	117 (2)	N1—C5—C4	122.55 (14)
Cd1—O1W—H1WB	127 (2)	N1—C5—H5A	118.7
H1WA—O1W—H1WB	110 (2)	C4—C5—H5A	118.7
Cd1—O2W—H2WA	131 (2)	O2—C6—O1	125.02 (15)
Cd1—O2W—H2WB	117 (2)	O2—C6—C2	117.26 (15)
H2WA—O2W—H2WB	105 (2)	O1—C6—C2	117.71 (14)
C4—O3—H3	108.2 (19)

O2W—Cd1—N1—C5	119.15 (12)	C1—C2—C3—C4	1.8 (2)
O2Wⁱ—Cd1—N1—C5	−60.85 (12)	C6—C2—C3—C4	−177.83 (14)
O1W—Cd1—N1—C5	33.45 (13)	C2—C3—C4—O3	178.81 (15)
O1Wⁱ—Cd1—N1—C5	−146.55 (13)	C2—C3—C4—C5	0.2 (2)
O2W—Cd1—N1—C1	−61.78 (13)	C1—N1—C5—C4	1.7 (2)
O2Wⁱ—Cd1—N1—C1	118.22 (13)	Cd1—N1—C5—C4	−179.16 (12)
O1W—Cd1—N1—C1	−147.47 (13)	O3—C4—C5—N1	179.22 (15)
O1Wⁱ—Cd1—N1—C1	32.53 (13)	C3—C4—C5—N1	−2.1 (2)
C5—N1—C1—C2	0.5 (2)	C3—C2—C6—O2	−5.8 (2)
Cd1—N1—C1—C2	−178.62 (11)	C1—C2—C6—O2	174.61 (15)
N1—C1—C2—C3	−2.2 (2)	C3—C2—C6—O1	173.06 (16)
N1—C1—C2—C6	177.42 (14)	C1—C2—C6—O1	−6.6 (2)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2ⁱⁱ	0.81 (2)	1.94 (2)	2.742 (2)	171 (3)
O1W—H1WB···O3ⁱⁱⁱ	0.79 (2)	2.20 (2)	2.9728 (19)	164 (3)
O2W—H2WA···O1^iv	0.82 (2)	1.87 (2)	2.6556 (18)	160 (3)
O2W—H2WB···O2^v	0.82 (2)	1.93 (2)	2.7349 (19)	165 (3)
O3—H3···O1^vi	0.83 (2)	1.88 (2)	2.6637 (19)	157 (3)

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

Experimental details

Crystal data
Chemical formula	[Cd(C₆H₄NO₃)₂(H₂O)₄]
M_r	460.68
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.2190 (1), 7.2510 (1), 8.9260 (1)
α, β, γ (°)	70.377 (1), 68.154 (1), 65.717 (1)
V (Å³)	385.97 (1)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.27 × 0.17 × 0.07

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.667, 0.903
No. of measured, independent and observed [I > 2σ(I)] reflections	6067, 1759, 1754
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.042, 1.09
No. of reflections	1759
No. of parameters	131
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.34

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), XPREP (Bruker, 2004), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2ⁱ	0.809 (17)	1.941 (17)	2.742 (2)	171 (3)
O1W—H1WB···O3ⁱⁱ	0.794 (17)	2.201 (18)	2.9728 (19)	164 (3)
O2W—H2WA···O1ⁱⁱⁱ	0.823 (17)	1.867 (18)	2.6556 (18)	160 (3)
O2W—H2WB···O2^iv	0.822 (17)	1.933 (17)	2.7349 (19)	165 (3)
O3—H3···O1^v	0.830 (17)	1.878 (19)	2.6637 (19)	157 (3)

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

References

Bruker (2004). SAINT, SMART and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
He, Y. H., Feng, Y. L., Lan, Y. Z. & Wen, Y. H. (2008). Cryst. Growth Des. 8, 3586–3594. Web of Science CSD CrossRef CAS Google Scholar
Kang, Y., Zhang, J., Qin, Y. Y., Li, Z. J. & Yao, Y. G. (2007). J. Mol. Struct. 784, 98–108. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, L. Y., Zhang, J. P., Lin, Y. Y. & Chen, X. M. (2006). Cryst. Growth Des. 6, 1684–1689. Web of Science CSD CrossRef CAS Google Scholar
Zora, P., Gordana, P., Marijana, V. & Drazen, V. T. (2006). Polyhedron, 25, 2353–2362. Google Scholar

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doi:10.1107/S1600536808035903

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