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

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.016

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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⋯O2iv	0.82 (2)	1.93 (2)	2.735 (2)	165 (3)
O3—H3⋯O1v	0.83 (2)	1.88 (2)	2.664 (2)	157 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The H atoms bonded to C atoms were positioned geometrically [aromatic C—H = 0.93 Å and aliphatic C—H = 0.97 Å, U_iso(H) = 1.2U_eq(C)]. The H atoms bonded to O atoms were located in a difference Fourier maps and refined with O—H distance restraints of 0.85 and U_iso(H) = 1.5U_eq(O).

Figures

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.

Crystal data

[Cd(C6H4NO3)2(H2O)4]	Z = 1
Mr = 460.68	F000 = 230
Triclinic, P1	Dx = 1.982 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 7.21900 (10) Å	Cell parameters from 5615 reflections
b = 7.25100 (10) Å	θ = 2.5–27.5º
c = 8.92600 (10) Å	µ = 1.48 mm−1
α = 70.3770 (10)º	T = 296 (2) K
β = 68.1540 (10)º	Sheet, colourless
γ = 65.7170 (10)º	0.27 × 0.17 × 0.07 mm
V = 385.972 (9) Å3

Data collection

Bruker APEXII diffractometer	1759 independent reflections
Radiation source: fine-focus sealed tube	1754 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.017
T = 296(2) K	θmax = 27.5º
ω scans	θmin = 2.5º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.667, Tmax = 0.903	k = −9→9
6067 measured reflections	l = −11→11

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.016	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.042	w = 1/[σ2(Fo2) + (0.0249P)2 + 0.1253P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
1759 reflections	Δρmax = 0.36 e Å−3
131 parameters	Δρmin = −0.33 e Å−3
7 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2ii	0.809 (17)	1.941 (17)	2.742 (2)	171 (3)
O1W—H1WB···O3iii	0.794 (17)	2.201 (18)	2.9728 (19)	164 (3)
O2W—H2WA···O1iv	0.823 (17)	1.867 (18)	2.6556 (18)	160 (3)
O2W—H2WB···O2v	0.822 (17)	1.933 (17)	2.7349 (19)	165 (3)
O3—H3···O1vi	0.830 (17)	1.878 (19)	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.