catena-Poly[[(triaqua­cadmium)-μ-1,4-phenyl­enediacetato-κ⁴ O,O′:O′′,O′′′] dihydrate]

Abstract

In the title compound, {[Cd(C₁₀H₈O₄)(H₂O)₃]·2H₂O}_n, penta­gonal–bipyramidally coordinated Cd^II ions on a twofold rotation axis are linked by tethering 1,4-phenyl­enediacetate (1,4-phda) ligands into [Cd(1,4-phda)(H₂O)₃]_n coordination polymer chains. The chain motifs are oriented parallel to the c-axis direction. Individual chains are connected into a supra­molecular network via O—H⋯O hydrogen bonding involving the aqua ligands.

Related literature

For other cadmium coordination polymers containing 1,4-phda ligands, see: Wang & LaDuca (2010 ▶); Farnum et al. (2011 ▶).

Experimental

Crystal data

• [Cd(C₁₀H₈O₄)(H₂O)₃]·2H₂O

• M _r = 394.64

• Monoclinic,

• a = 7.6878 (7) Å

• b = 8.2295 (8) Å

• c = 22.735 (2) Å

• β = 95.752 (1)°

• V = 1431.1 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 1.57 mm⁻¹

• T = 173 K

• 0.34 × 0.32 × 0.29 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.621, T _max = 0.659

• 11122 measured reflections

• 1307 independent reflections

• 1296 reflections with I > 2σ(I)

• R _int = 0.025

Refinement

• R[F ² > 2σ(F ²)] = 0.013

• wR(F ²) = 0.031

• S = 1.19

• 1307 reflections

• 107 parameters

• 9 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Crystal Maker (Palmer, 2007 ▶); software used to prepare material for publication: SHELXL97.

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
O1—H1⋯O4i	0.84 (1)	1.96 (1)	2.8029 (15)	178 (2)
O1W—H1WA⋯O2	0.84 (2)	1.86 (2)	2.6934 (17)	172 (2)
O4—H4A⋯O1Wii	0.83 (1)	1.89 (2)	2.7004 (17)	167 (2)
O4—H4B⋯O3i	0.84 (1)	1.84 (2)	2.6706 (16)	175 (2)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Recently we have been investigating conformationally flexible phenylenediacetate ligands, especially 1,4-phenylenediacetate (1,4-phda), towards the construction of cadmium coordination polymers in tandem with dipodal nitrogen-base ligands (Wang & LaDuca, 2010; Farnum, et al., 2011). The title compound was obtained upon an attempt to prepare a cadmium 1,4-phda coordination polymer incorporating 4,4'-trimethylenedipiperidine.

The asymmetric unit of the title compound contains a Cd^II ion and an aqua ligand on a 2-fold crystallographic rotation axis, an additional aqua ligand, half of a 1,4-phda ligand whose centroid lies on a crystallographic inversion center, and one water molecule of crystallization. The Cd^II ion is pentagonal bipyramidally coordinated, with its apical positions occupied by aqua ligands. Its equatorial positions contain a third aqua ligand and two chelating carboxylate groups from two 1,4-phda ligands (Fig. 1).

[Cd(H₂O)₃]²⁺ fragments are connected by exobidentate 1,4-phda ligands via a bis(chelating) binding mode, generating one-dimensional [Cd(1,4-phda)(H₂O)₃]_n coordination polymer chains (Fig. 2). Within the chain, the Cd···Cd contact distances measure 11.889 (6) Å. The chain motifs are all oriented parallel to the c crystal direction. Each individual [Cd(1,4-phda)(H₂O)₃]_n chain is anchored to four others via O—H···O hydrogen bonding mechanisms between aqua ligands in neighboring chains, and between aqua ligands and ligated 1,4-phda carboxylate oxygen atoms. In this manner, the supramolecular crystal structure of the title compound is constructed (Fig. 3).Water molecules of crystallization are held between coordination polymer chains through additional O—H···O hydrogen bonding interactions.

Experimental

All starting materials were obtained commercially. A mixture of cadmium nitrate tetrahydrate (88 mg, 0.29 mmol), 1,4-phenylenediacetic acid (52 mg, 0.27 mmol), 4,4'-trimethylenedipiperidine (58 mg, 0.28 mmol) and 10.0 g water (550 mmol) was placed into a 23 ml Teflon-lined Parr acid digestion bomb, which was then heated under autogenous pressure at 393 K for 48 h. Colourless blocks of the title compound (57 mg, 0.14 mmol, 53% yield) were isolated after washing with distilled water and acetone, and drying in air.

Refinement

All H atoms bound to C atoms were placed in calculated positions, with C—H = 0.95 Å, and refined in riding mode with U_iso = 1.2U_eq(C). The H atoms bound to the aqua ligand O atom were found in a difference Fourier map, restrained with with O—H = 0.85 Å and refined with U_iso = 1.2U_eq(O).

Figures

Fig. 1.

The coordination environment of the title compound, showing 50% probability ellipsoids and partial atom numbering scheme. Hydrogen atom positions are shown as grey sticks. Color codes: violet Cd, red bound O, orange unligated O, black C. Symmetry codes: (i) -x, y, -z + 1/2; (ii) -x, -y, -z.

Fig. 2.

A single [Cd(1,4-phda)(H2O)3]n chain coordination polymer chain.

Fig. 3.

Supramolecular aggregation of [Cd(1,4-phda)(H2O)3]n chains. O—H···O hydrogen bonding is shown as dashed lines.

Crystal data

[Cd(C10H8O4)(H2O)3]·2H2O	F(000) = 792
Mr = 394.64	Dx = 1.832 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9928 reflections
a = 7.6878 (7) Å	θ = 2.7–25.3°
b = 8.2295 (8) Å	µ = 1.57 mm−1
c = 22.735 (2) Å	T = 173 K
β = 95.752 (1)°	Block, colourless
V = 1431.1 (2) Å3	0.34 × 0.32 × 0.29 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	1307 independent reflections
Radiation source: fine-focus sealed tube	1296 reflections with I > 2σ(I)
graphite	Rint = 0.025
ω–φ scans	θmax = 25.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.621, Tmax = 0.659	k = −9→9
11122 measured reflections	l = −27→27

Refinement

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)] = 0.013	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.031	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	w = 1/[σ2(Fo2) + (0.0098P)2 + 1.4668P] where P = (Fo2 + 2Fc2)/3
1307 reflections	(Δ/σ)max < 0.001
107 parameters	Δρmax = 0.27 e Å−3
9 restraints	Δρmin = −0.20 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	0.211515 (18)	0.2500	0.01614 (6)
O1	0.0000	0.4900 (2)	0.2500	0.0296 (4)
H1	0.070 (2)	0.552 (2)	0.2346 (8)	0.036*
O1W	0.21682 (17)	0.51653 (15)	0.09931 (5)	0.0252 (3)
H1WA	0.199 (3)	0.430 (2)	0.1171 (8)	0.030*
H1WB	0.307 (2)	0.506 (2)	0.0844 (8)	0.030*
O2	0.14213 (18)	0.25529 (14)	0.16357 (5)	0.0290 (3)
O3	0.09896 (14)	0.00183 (13)	0.18665 (5)	0.0208 (2)
O4	0.27315 (15)	0.20049 (14)	0.30205 (5)	0.0200 (2)
H4A	0.273 (2)	0.158 (2)	0.3350 (7)	0.024*
H4B	0.318 (2)	0.2927 (18)	0.3066 (8)	0.024*
C1	0.1256 (2)	0.0255 (2)	0.04864 (6)	0.0195 (3)
C2	0.2569 (2)	0.0525 (2)	0.10213 (7)	0.0215 (3)
H2A	0.3421	0.1368	0.0931	0.026*
H2B	0.3217	−0.0494	0.1121	0.026*
C3	0.0777 (2)	−0.1308 (2)	0.03026 (7)	0.0216 (3)
H3	0.1305	−0.2215	0.0508	0.026*
C4	−0.0466 (2)	−0.1567 (2)	−0.01772 (7)	0.0217 (3)
H4	−0.0777	−0.2644	−0.0295	0.026*
C5	0.1617 (2)	0.10626 (19)	0.15438 (6)	0.0177 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cd1	0.01982 (9)	0.01563 (9)	0.01342 (9)	0.000	0.00393 (6)	0.000
O1	0.0287 (10)	0.0159 (8)	0.0478 (11)	0.000	0.0214 (8)	0.000
O1W	0.0298 (7)	0.0207 (6)	0.0263 (6)	−0.0005 (5)	0.0085 (5)	0.0015 (5)
O2	0.0469 (8)	0.0178 (6)	0.0247 (6)	0.0008 (5)	0.0153 (6)	−0.0004 (5)
O3	0.0239 (6)	0.0196 (6)	0.0198 (6)	0.0015 (5)	0.0075 (5)	0.0010 (4)
O4	0.0242 (6)	0.0161 (6)	0.0199 (6)	−0.0012 (5)	0.0025 (5)	0.0003 (5)
C1	0.0212 (8)	0.0247 (8)	0.0139 (7)	0.0016 (7)	0.0080 (6)	−0.0005 (6)
C2	0.0205 (8)	0.0273 (9)	0.0174 (8)	0.0022 (7)	0.0055 (6)	−0.0010 (6)
C3	0.0275 (9)	0.0207 (8)	0.0173 (8)	0.0051 (7)	0.0059 (7)	0.0032 (6)
C4	0.0284 (9)	0.0188 (8)	0.0188 (8)	0.0002 (7)	0.0074 (7)	−0.0019 (6)
C5	0.0184 (8)	0.0216 (8)	0.0127 (7)	0.0015 (6)	−0.0012 (6)	−0.0005 (6)

Geometric parameters (Å, °)

Cd1—O1	2.2917 (17)	O4—H4A	0.827 (14)
Cd1—O4	2.3066 (12)	O4—H4B	0.836 (14)
Cd1—O4i	2.3066 (12)	C1—C3	1.391 (2)
Cd1—O2	2.3695 (12)	C1—C4ii	1.394 (2)
Cd1—O2i	2.3695 (12)	C1—C2	1.517 (2)
Cd1—O3	2.4187 (11)	C2—C5	1.522 (2)
Cd1—O3i	2.4187 (11)	C2—H2A	0.9900
O1—H1	0.842 (11)	C2—H2B	0.9900
O1W—H1WA	0.835 (15)	C3—C4	1.392 (2)
O1W—H1WB	0.810 (15)	C3—H3	0.9500
O2—C5	1.256 (2)	C4—C1ii	1.394 (2)
O3—C5	1.2571 (19)	C4—H4	0.9500
O1—Cd1—O4	92.25 (3)	Cd1—O4—H4A	113.4 (13)
O1—Cd1—O4i	92.25 (3)	Cd1—O4—H4B	111.8 (13)
O4—Cd1—O4i	175.49 (6)	H4A—O4—H4B	108.1 (18)
O1—Cd1—O2	81.25 (3)	C3—C1—C4ii	118.40 (15)
O4—Cd1—O2	87.69 (4)	C3—C1—C2	120.78 (15)
O4i—Cd1—O2	93.00 (4)	C4ii—C1—C2	120.79 (15)
O1—Cd1—O2i	81.25 (3)	C1—C2—C5	109.59 (13)
O4—Cd1—O2i	93.00 (4)	C1—C2—H2A	109.8
O4i—Cd1—O2i	87.69 (4)	C5—C2—H2A	109.8
O2—Cd1—O2i	162.51 (6)	C1—C2—H2B	109.8
O1—Cd1—O3	135.51 (3)	C5—C2—H2B	109.8
O4—Cd1—O3	87.30 (4)	H2A—C2—H2B	108.2
O4i—Cd1—O3	89.48 (4)	C1—C3—C4	121.14 (15)
O2—Cd1—O3	54.27 (4)	C1—C3—H3	119.4
O2i—Cd1—O3	143.22 (4)	C4—C3—H3	119.4
O1—Cd1—O3i	135.51 (3)	C3—C4—C1ii	120.47 (16)
O4—Cd1—O3i	89.48 (4)	C3—C4—H4	119.8
O4i—Cd1—O3i	87.30 (4)	C1ii—C4—H4	119.8
O2—Cd1—O3i	143.22 (4)	O2—C5—O3	120.75 (14)
O2i—Cd1—O3i	54.27 (4)	O2—C5—C2	119.26 (14)
O3—Cd1—O3i	88.97 (5)	O3—C5—C2	119.96 (14)
Cd1—O1—H1	127.1 (12)	O2—C5—Cd1	59.31 (8)
H1WA—O1W—H1WB	107.7 (19)	O3—C5—Cd1	61.56 (8)
C5—O2—Cd1	93.58 (9)	C2—C5—Cd1	177.81 (11)
C5—O3—Cd1	91.25 (9)
O1—Cd1—O2—C5	178.70 (10)	Cd1—O2—C5—O3	4.15 (16)
O4—Cd1—O2—C5	86.06 (10)	Cd1—O2—C5—C2	−178.08 (12)
O4i—Cd1—O2—C5	−89.48 (10)	Cd1—O3—C5—O2	−4.05 (15)
O2i—Cd1—O2—C5	178.70 (10)	Cd1—O3—C5—C2	178.19 (12)
O3—Cd1—O2—C5	−2.28 (9)	C1—C2—C5—O2	−92.22 (18)
O3i—Cd1—O2—C5	0.02 (14)	C1—C2—C5—O3	85.57 (18)
O1—Cd1—O3—C5	3.65 (11)	O1—Cd1—C5—O2	−1.36 (10)
O4—Cd1—O3—C5	−86.82 (9)	O4—Cd1—C5—O2	−92.46 (10)
O4i—Cd1—O3—C5	96.34 (9)	O4i—Cd1—C5—O2	91.83 (10)
O2—Cd1—O3—C5	2.27 (9)	O3—Cd1—C5—O2	175.95 (15)
O2i—Cd1—O3—C5	−178.22 (9)	O3i—Cd1—C5—O2	−179.99 (9)
O3i—Cd1—O3—C5	−176.35 (11)	C5i—Cd1—C5—O2	178.64 (10)
C5i—Cd1—O3—C5	−178.21 (5)	O1—Cd1—C5—O3	−177.31 (8)
C3—C1—C2—C5	−104.15 (17)	O4—Cd1—C5—O3	91.60 (9)
C4ii—C1—C2—C5	74.03 (18)	O4i—Cd1—C5—O3	−84.12 (9)
C4ii—C1—C3—C4	−0.2 (3)	O2—Cd1—C5—O3	−175.95 (15)
C2—C1—C3—C4	178.06 (14)	O3i—Cd1—C5—O3	4.07 (12)
C1—C3—C4—C1ii	0.2 (3)	C5i—Cd1—C5—O3	2.70 (8)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4iii	0.84 (1)	1.96 (1)	2.8029 (15)	178 (2)
O1W—H1WA···O2	0.84 (2)	1.86 (2)	2.6934 (17)	172.(2)
O4—H4A···O1Wiv	0.83 (1)	1.89 (2)	2.7004 (17)	167.(2)
O4—H4B···O3iii	0.84 (1)	1.84 (2)	2.6706 (16)	175 (2)

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