Diaquabis­{4-[(6-chloro­pyridin-3-yl)­methoxy]­benzoato}cadmium(II)

The title compound, [Cd(C₁₃H₉ClNO₃)₂(H₂O)₂], is a mononuclear complex in which the Cd^II atom, located on a twofold axis, shows an octa­hedral coordination geometry. It is surrounded by four carboxyl­ate O atoms from two 4-[(6-chloro­pyridin-3-yl)meth­oxy]benzoate acid ligands and two water mol­ecules. O—H...O hydrogen bonds link these complexes to generate a two-dimensional supra­molecular network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.038
• wR factor = 0.107
• Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.60

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1         (2)       2.07

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The synthesis and characterization of coordination compounds with infinite two- and three-dimensional networks have been an area of rapid growth in recent years because of the potential of these polymers in various applications, such as catalysis, electrical conductivity, host–guest chemistry and magnetism (Ermer, 1991; Fujita et al.,1994; Inoue et al.,1996; Kitazawa et al.,1994). In this paper, we report a new coordination compound, (I).

The asymmetric part of the unit cell contains one 4-((6-chloropyridin-3-yl)methoxy)benzoic acid (hereafter L) molecule, one water molecule and half Cd (II) atom located on a two fold axis (Fig. 1). Cd(II) atom is octahedrally surrounded by four carboxylate O atoms from L ligands and two water molecules. Each complex is linked to four adjacent molecules through O—H···O hydrogen bonds building a two-dimensional supramolecular structure (Table 1, Fig. 2).

Related literature

For related literature, see: Fujita et al. (1994); Inoue et al. (1996); Kitazawa et al. (1994).

For related literature, see: Ermer (1991).

S2. Experimental

A mixture of L (0.39 g, 1.50 mmol), Cd(OAc)₂·2H₂O (0.20 g, 0.75 mmol), NaOH (0.08 g, 2.00 mmol) and H₂O (10 ml) was stirred for 1 h and then sealed in a 25 ml Teflonlined stainless steel container. The container was heated to 150 °C and held at that temperature for 72 h, then cooled to 100 °C at a rate of 5 °C.h^-1, and held for 8 h, followed by further cooling to 30 °C at a rate of 3 °C.h^-1. Colorless crystals of I were collected in 72.9% yield based on Cd(OAc)₂·2H₂O.

S3. Refinement

All H atoms attached to C atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene) with U_iso(H) = 1.2U_eq(C). H atoms of water molecule were located in difference Fourier maps and included in the subsequent refinement using restraints (O—H= 0.85 (1) Å and H···H= 1.39 (2) Å) with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. Molecular view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. [Symmetry code: (i) -x, y, -z + 1/2]
	Fig. 2. Ball-stick representation of the two-dimensional supramolecular structure of (I). H atoms not involved in hydrogen bondings have been omitted for clarity.

diaquabis{4-[(6-chloropyridin-3-yl)methoxy]benzoato}cadmium(II)

Crystal data

[Cd(C13H9ClNO3)2(H2O)2]	Z = 4
Mr = 673.76	F(000) = 1352
Monoclinic, C2/c	Dx = 1.705 Mg m^−3
Hall symbol: -C2yc	Mo Kα radiation, λ = 0.71069 Å
a = 42.179 (8) Å	θ = 1.0–28.5°
b = 5.355 (1) Å	µ = 1.09 mm^−1
c = 12.068 (2) Å	T = 293 K
β = 105.688 (3)°	Block, colorless
V = 2624.2 (8) Å^3	0.35 × 0.32 × 0.28 mm

Data collection

Bruker APEX CCD area-detector diffractometer	3053 independent reflections
Radiation source: fine-focus sealed tube	2705 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 28.5°, θmin = 1.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −47→56
Tmin = 0.668, Tmax = 0.742	k = −5→7
7350 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0673P)^2] where P = (Fo^2 + 2Fc^2)/3
3053 reflections	(Δ/σ)max < 0.001
177 parameters	Δρmax = 1.11 e Å^−3
0 restraints	Δρmin = −1.32 e Å^−3

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	0.0000	0.10193 (5)	0.2500	0.03122 (12)
Cl1	0.22388 (3)	2.0232 (2)	0.93684 (10)	0.0703 (3)
O3	0.02898 (5)	0.2671 (4)	0.43946 (15)	0.0407 (5)
O1	0.13219 (6)	1.1274 (4)	0.64750 (19)	0.0482 (6)
O2	0.04099 (5)	0.3902 (3)	0.28184 (16)	0.0338 (4)
O1W	0.01884 (6)	−0.1942 (4)	0.15699 (17)	0.0491 (6)
H1A	0.0218	−0.2068	0.0906	0.074*
H1B	0.0231	−0.3320	0.1916	0.074*
C1	0.04501 (7)	0.4065 (5)	0.3902 (2)	0.0305 (6)
C2	0.06863 (7)	0.5953 (5)	0.4555 (2)	0.0331 (6)
C5	0.11184 (7)	0.9573 (6)	0.5787 (2)	0.0377 (7)
N1	0.18116 (8)	1.6700 (7)	0.8646 (3)	0.0625 (9)
C4	0.09167 (9)	0.8246 (7)	0.6313 (3)	0.0514 (9)
H4	0.0925	0.8554	0.7078	0.062*
C10	0.17138 (7)	1.4579 (6)	0.6830 (3)	0.0380 (6)
C6	0.11068 (8)	0.9102 (5)	0.4640 (3)	0.0395 (7)
H6	0.1243	0.9969	0.4283	0.047*
C13	0.20380 (8)	1.7999 (7)	0.8364 (3)	0.0453 (7)
C7	0.08877 (7)	0.7310 (6)	0.4039 (2)	0.0362 (6)
H7	0.0876	0.7014	0.3270	0.043*
C3	0.07039 (9)	0.6467 (7)	0.5699 (3)	0.0503 (9)
H3	0.0569	0.5592	0.6058	0.060*
C12	0.21300 (9)	1.7701 (8)	0.7365 (3)	0.0567 (9)
H12	0.2300	1.8642	0.7218	0.068*
C8	0.15233 (7)	1.2737 (6)	0.5960 (3)	0.0420 (7)
H8A	0.1388	1.3619	0.5298	0.050*
H8B	0.1674	1.1667	0.5699	0.050*
C11	0.16489 (9)	1.5008 (9)	0.7877 (3)	0.0593 (10)
H11	0.1484	1.4076	0.8059	0.071*
C9	0.19618 (9)	1.5959 (6)	0.6588 (3)	0.0522 (9)
H9	0.2016	1.5715	0.5898	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0474 (2)	0.02401 (17)	0.02261 (16)	0.000	0.01016 (12)	0.000
Cl1	0.0774 (6)	0.0702 (7)	0.0622 (6)	−0.0228 (5)	0.0169 (5)	−0.0343 (6)
O3	0.0606 (13)	0.0427 (12)	0.0210 (9)	−0.0154 (9)	0.0149 (8)	−0.0019 (9)
O1	0.0626 (14)	0.0560 (15)	0.0288 (11)	−0.0288 (10)	0.0171 (10)	−0.0100 (9)
O2	0.0513 (12)	0.0329 (11)	0.0198 (9)	−0.0038 (8)	0.0139 (8)	−0.0023 (7)
O1W	0.0920 (17)	0.0349 (11)	0.0275 (10)	0.0200 (11)	0.0284 (10)	0.0051 (9)
C1	0.0443 (15)	0.0275 (13)	0.0211 (12)	0.0015 (10)	0.0115 (11)	0.0002 (10)
C2	0.0458 (16)	0.0332 (15)	0.0223 (13)	−0.0051 (10)	0.0124 (12)	−0.0037 (10)
C5	0.0494 (17)	0.0384 (16)	0.0257 (14)	−0.0108 (12)	0.0106 (12)	−0.0059 (12)
N1	0.076 (2)	0.077 (2)	0.0399 (15)	−0.0291 (17)	0.0250 (15)	−0.0222 (16)
C4	0.076 (2)	0.060 (2)	0.0243 (14)	−0.0297 (18)	0.0239 (15)	−0.0139 (15)
C10	0.0435 (15)	0.0398 (16)	0.0303 (14)	−0.0042 (12)	0.0093 (12)	−0.0014 (12)
C6	0.0505 (17)	0.0443 (18)	0.0273 (14)	−0.0112 (12)	0.0168 (13)	0.0001 (12)
C13	0.0524 (18)	0.0437 (18)	0.0391 (16)	−0.0091 (14)	0.0109 (14)	−0.0116 (15)
C7	0.0473 (15)	0.0453 (17)	0.0185 (11)	−0.0047 (12)	0.0131 (11)	−0.0014 (12)
C3	0.073 (2)	0.059 (2)	0.0262 (15)	−0.0309 (16)	0.0254 (15)	−0.0115 (14)
C12	0.059 (2)	0.065 (2)	0.052 (2)	−0.0275 (17)	0.0250 (16)	−0.0152 (19)
C8	0.0496 (17)	0.0472 (18)	0.0304 (14)	−0.0138 (13)	0.0129 (12)	−0.0020 (13)
C11	0.071 (2)	0.072 (2)	0.0427 (19)	−0.032 (2)	0.0281 (18)	−0.0167 (19)
C9	0.062 (2)	0.065 (2)	0.0365 (17)	−0.0242 (16)	0.0244 (15)	−0.0140 (15)

Geometric parameters (Å, º)

Cd1—O1W	2.211 (2)	C5—C6	1.394 (4)
Cd1—O1W^i	2.211 (2)	N1—C13	1.299 (4)
Cd1—O2	2.2714 (19)	N1—C11	1.345 (5)
Cd1—O2^i	2.2714 (19)	C4—C3	1.379 (4)
Cd1—O3	2.4480 (19)	C4—H4	0.9300
Cd1—O3^i	2.4480 (19)	C10—C9	1.375 (4)
Cd1—C1	2.718 (3)	C10—C11	1.382 (4)
Cd1—C1^i	2.718 (3)	C10—C8	1.505 (4)
Cl1—C13	1.750 (3)	C6—C7	1.393 (4)
O3—C1	1.259 (3)	C6—H6	0.9300
O1—C5	1.368 (3)	C13—C12	1.372 (5)
O1—C8	1.417 (3)	C7—H7	0.9300
O2—C1	1.276 (3)	C3—H3	0.9300
O1W—H1A	0.8464	C12—C9	1.376 (5)
O1W—H1B	0.8432	C12—H12	0.9300
C1—C2	1.487 (4)	C8—H8A	0.9700
C2—C7	1.386 (4)	C8—H8B	0.9700
C2—C3	1.390 (4)	C11—H11	0.9300
C5—C4	1.387 (4)	C9—H9	0.9300
O1W—Cd1—O1W^i	88.35 (12)	C7—C2—C3	117.8 (3)
O1W—Cd1—O2	102.22 (8)	C7—C2—C1	121.5 (2)
O1W^i—Cd1—O2	139.74 (7)	C3—C2—C1	120.6 (2)
O1W—Cd1—O2^i	139.74 (7)	O1—C5—C4	115.2 (3)
O1W^i—Cd1—O2^i	102.22 (8)	O1—C5—C6	124.8 (3)
O2—Cd1—O2^i	94.39 (10)	C4—C5—C6	120.0 (3)
O1W—Cd1—O3	125.17 (8)	C13—N1—C11	117.0 (3)
O1W^i—Cd1—O3	86.69 (7)	C3—C4—C5	119.9 (3)
O2—Cd1—O3	55.35 (6)	C3—C4—H4	120.0
O2^i—Cd1—O3	94.44 (7)	C5—C4—H4	120.0
O1W—Cd1—O3^i	86.69 (7)	C9—C10—C11	117.1 (3)
O1W^i—Cd1—O3^i	125.17 (8)	C9—C10—C8	119.8 (3)
O2—Cd1—O3^i	94.44 (7)	C11—C10—C8	123.1 (3)
O2^i—Cd1—O3^i	55.36 (6)	C7—C6—C5	118.8 (3)
O3—Cd1—O3^i	137.64 (10)	C7—C6—H6	120.6
O1W—Cd1—C1	117.38 (9)	C5—C6—H6	120.6
O1W^i—Cd1—C1	113.62 (8)	N1—C13—C12	124.8 (3)
O2—Cd1—C1	27.82 (7)	N1—C13—Cl1	115.9 (2)
O2^i—Cd1—C1	93.96 (8)	C12—C13—Cl1	119.3 (3)
O3—Cd1—C1	27.57 (7)	C2—C7—C6	121.9 (2)
O3^i—Cd1—C1	116.93 (8)	C2—C7—H7	119.0
O1W—Cd1—C1^i	113.62 (8)	C6—C7—H7	119.0
O1W^i—Cd1—C1^i	117.38 (9)	C4—C3—C2	121.5 (3)
O2—Cd1—C1^i	93.96 (8)	C4—C3—H3	119.2
O2^i—Cd1—C1^i	27.82 (7)	C2—C3—H3	119.2
O3—Cd1—C1^i	116.93 (8)	C13—C12—C9	117.5 (3)
O3^i—Cd1—C1^i	27.57 (7)	C13—C12—H12	121.3
C1—Cd1—C1^i	106.27 (11)	C9—C12—H12	121.3
C1—O3—Cd1	88.26 (16)	O1—C8—C10	109.0 (2)
C5—O1—C8	117.0 (2)	O1—C8—H8A	109.9
C1—O2—Cd1	95.98 (16)	C10—C8—H8A	109.9
Cd1—O1W—H1A	134.7	O1—C8—H8B	109.9
Cd1—O1W—H1B	115.7	C10—C8—H8B	109.9
H1A—O1W—H1B	109.5	H8A—C8—H8B	108.3
O3—C1—O2	120.3 (3)	N1—C11—C10	123.5 (3)
O3—C1—C2	121.5 (2)	N1—C11—H11	118.2
O2—C1—C2	118.3 (2)	C10—C11—H11	118.2
O3—C1—Cd1	64.17 (14)	C10—C9—C12	120.1 (3)
O2—C1—Cd1	56.20 (14)	C10—C9—H9	120.0
C2—C1—Cd1	173.11 (19)	C12—C9—H9	120.0

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1B···O2^ii	0.84	1.88	2.708 (3)	169
O1W—H1A···O3^iii	0.85	1.95	2.799 (3)	175

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