Aqua­bis(4-nitro­benzoato)-κ2O,O′;κO-(piperidinium-4-carboxyl­ato-κ2O,O′)cadmium(II)

Zhang, R.-W.; Wang, L.-L.; Zhao, X.-J.

doi:10.1107/S160053680901811X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages m664-m665

doi:10.1107/S160053680901811X

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Aquabis(4-nitrobenzoato)-κ²O,O′;κO-(piperidinium-4-carboxylato-κ²O,O′)cadmium(II)

Run-Wen Zhang,^a Li-Li Wang ^a and Xiao-Jun Zhao ^a ^*

^aCollege of Chemistry and Life Science, Tianjin Key Laboratory of Structure and Performance for Functional Molecule, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: xiaojun_zhao15@yahoo.com.cn

(Received 14 April 2009; accepted 13 May 2009; online 20 May 2009)

In the mixed ligand title compound, [Cd(C₆H₁₁NO₂)(C₇H₄NO₄)₂(H₂O)], which exhibits a discrete mononuclear structure, the Cd^IIatom is in a distorted octahedral geometry, surrounded by five carboxylate O atoms and one coordinated water molecule. The piperdinium ring adopts a chair conformation and the two 4-nitrobenzoate rings are oriented at a dihedral angle of 75.8 (1)°. Intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the mononuclear entities into a three-dimensional supramolecular network.

Related literature

For the framework topologies and potential applications of coordination complexes with mixed ligands, see: Muthu et al. (2002 ); Fujita et al. (1994 ); Zheng et al. (2004 ); Rosi et al. (2003 ). For 4-piperidinecarboxylic acid as a zwitterion in aqueous solution, see: Mora et al. (2002 ); and for its ability to act selectively as a bridging or terminal ligand, see: Inomata et al. (2002 ). For related structures, see: Adams et al. (2006a ,b ); Podesta & Orpen (2002 ); Delgado et al. (2001 ). For Cd—O bond lengths, see: Inomata et al. (2004 ); Wang et al. (2008 ).

Experimental

Crystal data

[Cd(C₆H₁₁NO₂)(C₇H₄NO₄)₂(H₂O)]
M_r = 591.80
Monoclinic, P 2₁ /c
a = 22.7135 (7) Å
b = 6.6294 (2) Å
c = 14.9658 (5) Å
β = 91.3400 (10)°
V = 2252.89 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 296 K
0.32 × 0.28 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.733, T_max = 0.804
10944 measured reflections
3950 independent reflections
3615 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.056
S = 1.05
3950 reflections
316 parameters
18 restraints
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cd1—O5	2.1917 (18)
Cd1—O11	2.3061 (19)
Cd1—O2	2.3229 (17)
Cd1—O9	2.3327 (17)
Cd1—O10	2.3534 (18)
Cd1—O1	2.3684 (19)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11A⋯O3ⁱ	0.85	2.26	3.019 (3)	149
O11—H11B⋯O10ⁱⁱ	0.85	1.91	2.754 (3)	172
N3—H3A⋯O9ⁱⁱⁱ	0.90	2.04	2.887 (3)	156
N3—H3B⋯O6^iv	0.90	1.89	2.762 (3)	163
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) x, y+1, z; (iv) $[x, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2001 ); 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) and DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901811X/bq2139sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901811X/bq2139Isup2.hkl

checkCIF report

Comment top

Recently, the rational design and skillful construction of the coordination complexes with mixed ligands have aroused great interest due to their intriguing framework topologies and potential applications in ino-exchange (Muthu et al., 2002), catalysis (Fujita et al., 1994), luminescence (Zheng et al., 2004), and gas storage (Rosi et al., 2003). Bearing two potential binding sites (–NH– and –COOH) capable of coordination with transition metal atoms, 4-piperidinecarboxylic acid exists as a zwitterion with the amino group protonated and the carboxylic group deprotonated in aqueous solution (Mora et al., 2002). Thus, by carefully control the degree of the protonation/deprotonation of carboxylic and/or amino groups, it can selectively act as a bridge ligand linking different metal atoms into an infinite high-dimensional framework or as a terminal ligand forming a discrete complex (Inomata et al., 2002). However, to the best of our knowledge, only a few examples involved in 4-piperidinecarboxylic acid have been reported by far (Adams et al., 2006a,b; Podesta et al., 2002). Thus, to continue to explore the coordination behavior of 4-piperidinecarboxylic acid, herein, we report the crystal structure of a Cd^II complex with 4-piperidinecarboxylate and 4-nitrobenzoxylate anion.

As shown in Fig. 1, the mononuclear structure of the title complex, (I), consists of one crystallographic independent Cd^II atom, two separate 4-nitrobenzoxylate anions, one zwitterionic 4-piperidinecarboxylate molecule, and one coordinated water molecule. The sole Cd^IIcenter is six-coordinated by one coordinated water molecule (O11), and five carboxylate O atoms from two independent 4-nitrobenzoxylate (O1, O2 and O5) and one 4-piperidinecarboxylate molecule (O9 and O10), exhibiting a distorted octahedral geometry (Table 1.). The Cd–O bond distances are in the range of 2.1914 (16)–2.3684 (17)Å, which are comparable to those previously reported values (Inomata et al., 2004; Wang et al., 2008). The carboxylate group of 4-nitrobenzoxylate anion presents two different coordination modes: monodentate and asymmetric chelating bidentate fashions. In contrast, the carboxylate group of 4-piperidinecarboxylate only adopts an asymmetric chelating bidentate coordination mode. Additionally, the N atom of piperidine ring does not coordinate to a metal atom, and the protonated piperidine ring of 4-piperdinecarboxylate is in a chair conformation significantly resulted from the relatively lower energy (Delgado et al., 2001).

As shown in Fig. 2, the adjacent mononuclear entities are linked in to a two-dimensional (2-D) layer by threefold hydrogen bonding interactions between the protonated –NH₂⁺/coordinated water molecule and the carboxylate group of 4-piperdinecarboxylate /4-nitrobenzoxylate anion (Table 2.). The neighbour 2-D layers are further assembled into a 3-D supramolecular network (Fig. 3) also by the hydrogen bonding interaction between the coordinated water molecule and the carboxylate group of 4-nitrobenzoxylate anion (O11–H11A···O3). Thus, the abundant hydrogen bonds interactions significantly dominate the formation of 3-D supramolecular network of the title complex.

Related literature top

For the framework topologies and potential applications in ino-exchange of coordination complexes with mixed ligands, see: Muthu et al. (2002); Fujita et al. (1994); Zheng et al. (2004); Rosi et al. (2003). 4-piperidinecarboxylic acid exists as a zwitterion with the amino group protonated and the carboxylic group deprotonated in aqueous solution (Mora et al., 2002). It can selectively act as a bridge ligand linking different metal atoms into an infinite high-dimensional framework or as a terminal ligand forming a discrete complex (Inomata et al., 2002). For related structures, see: Adams et al. (2006a,b); Podesta et al. (2002); Delgado et al. (2001). For Cd—O bond lengths, see: Inomata et al. (2004); Wang et al. (2008).

Experimental top

To an aqueous solution (5 ml) of CdCl₂. 2.5H₂O (45.7 mg, 0.2 mmol) was slowly added a methanol solution (5 ml) containing 4-piperidinecarboxylic acid (12.9 mg, 0.1 mmol) and 4-nitrobenzoic acid (16.7 mg, 0.1 mmol) with constant stirring. And the pH value of the mixture was adjusted to 6 by NaOH solution (0.1 M). The resulting colorless solution was further stirred for half an hour and filtered. The filtrate was allowed to evaporate at room temperature. Pale-yellow block-shaped crystals were obtained within two weeks (yield 70% based on Cd^II salt).

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The 2-D layer of (I) formed by hydrogen bonding interactions. Only H atoms involved in hydrogen bonds are included.
	Fig. 3. The 3-D network of (I) formed by hydrogen bond interactions. Only H atoms involved in hydrogen bonds are included.

Aquabis(4-nitrobenzoato)-κ²O,O';κO-(piperidinium-4- carboxylato-κ²O,O')cadmium(II) top

Crystal data top

[Cd(C₆H₁₁NO₂)(C₇H₄NO₄)₂(H₂O)]	F(000) = 1192
M_r = 591.80	D_x = 1.745 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8249 reflections
a = 22.7135 (7) Å	θ = 2.9–27.8°
b = 6.6294 (2) Å	µ = 1.04 mm⁻¹
c = 14.9658 (5) Å	T = 296 K
β = 91.340 (1)°	Block, pale-yellow
V = 2252.89 (12) Å³	0.32 × 0.28 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3950 independent reflections
Radiation source: fine-focus sealed tube	3615 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ϕ and ω scans	θ_max = 25.0°, θ_min = 0.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→26
T_min = 0.733, T_max = 0.804	k = −7→7
10944 measured reflections	l = −17→17

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.056	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0248P)² + 1.8541P] where P = (F_o² + 2F_c²)/3
3950 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.37 e Å⁻³
18 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Cd(C₆H₁₁NO₂)(C₇H₄NO₄)₂(H₂O)]	V = 2252.89 (12) Å³
M_r = 591.80	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 22.7135 (7) Å	µ = 1.04 mm⁻¹
b = 6.6294 (2) Å	T = 296 K
c = 14.9658 (5) Å	0.32 × 0.28 × 0.22 mm
β = 91.340 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3950 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3615 reflections with I > 2σ(I)
T_min = 0.733, T_max = 0.804	R_int = 0.014
10944 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	18 restraints
wR(F²) = 0.056	H-atom parameters constrained
S = 1.05	Δρ_max = 0.37 e Å⁻³
3950 reflections	Δρ_min = −0.32 e Å⁻³
316 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	0.219460 (8)	0.68670 (3)	0.490995 (11)	0.03129 (7)
O1	0.11917 (8)	0.7419 (3)	0.45149 (12)	0.0458 (5)
O2	0.18499 (8)	0.7480 (3)	0.34618 (12)	0.0372 (4)
O3	−0.10379 (9)	0.7684 (4)	0.13243 (15)	0.0595 (6)
O4	−0.04142 (11)	0.7829 (5)	0.02901 (15)	0.0822 (9)
O5	0.30087 (8)	0.5260 (3)	0.46044 (13)	0.0450 (5)
O6	0.34464 (10)	0.7998 (3)	0.40672 (16)	0.0563 (6)
O7	0.59387 (12)	0.2162 (5)	0.3509 (3)	0.1201 (13)
O8	0.54181 (11)	−0.0455 (4)	0.3661 (2)	0.0759 (7)
O9	0.24780 (8)	0.7579 (3)	0.63847 (11)	0.0371 (4)
O10	0.23667 (10)	1.0130 (3)	0.54773 (12)	0.0506 (5)
O11	0.18002 (9)	0.3782 (3)	0.52820 (14)	0.0490 (5)
H11A	0.1486	0.3692	0.4963	0.073*
H11B	0.2007	0.2720	0.5342	0.073*
N1	−0.05315 (11)	0.7738 (4)	0.10707 (16)	0.0432 (6)
N2	0.54786 (12)	0.1355 (4)	0.3662 (2)	0.0637 (8)
N3	0.28125 (9)	1.4822 (3)	0.78005 (14)	0.0354 (5)
H3A	0.2604	1.5610	0.7420	0.043*
H3B	0.2946	1.5603	0.8253	0.043*
C1	0.08383 (11)	0.7676 (4)	0.30125 (16)	0.0297 (5)
C2	0.02551 (11)	0.7688 (4)	0.32711 (17)	0.0326 (5)
H2	0.0169	0.7675	0.3875	0.039*
C3	−0.01979 (11)	0.7717 (4)	0.26380 (17)	0.0342 (6)
H3	−0.0589	0.7730	0.2806	0.041*
C4	−0.00508 (11)	0.7727 (4)	0.17489 (17)	0.0331 (6)
C5	0.05237 (12)	0.7745 (4)	0.14668 (17)	0.0384 (6)
H5	0.0608	0.7779	0.0862	0.046*
C6	0.09691 (11)	0.7712 (4)	0.21095 (17)	0.0354 (6)
H6	0.1360	0.7713	0.1937	0.043*
C7	0.13244 (11)	0.7537 (4)	0.37115 (17)	0.0309 (5)
C8	0.39914 (11)	0.4942 (4)	0.41654 (17)	0.0356 (6)
C9	0.44834 (14)	0.5789 (5)	0.3783 (2)	0.0549 (8)
H9	0.4480	0.7144	0.3623	0.066*
C10	0.49774 (14)	0.4642 (5)	0.3638 (3)	0.0622 (9)
H10	0.5312	0.5217	0.3398	0.075*
C11	0.49655 (12)	0.2628 (5)	0.3857 (2)	0.0445 (7)
C12	0.44856 (12)	0.1744 (4)	0.42363 (18)	0.0402 (6)
H12	0.4488	0.0377	0.4377	0.048*
C13	0.39998 (12)	0.2921 (4)	0.44039 (17)	0.0367 (6)
H13	0.3676	0.2356	0.4679	0.044*
C14	0.34426 (12)	0.6197 (4)	0.42904 (17)	0.0372 (6)
C15	0.27278 (11)	1.0862 (4)	0.69599 (15)	0.0306 (5)
H15	0.2954	1.0078	0.7404	0.037*
C16	0.31251 (11)	1.2505 (4)	0.66016 (17)	0.0349 (6)
H16A	0.3469	1.1889	0.6342	0.042*
H16B	0.2915	1.3242	0.6133	0.042*
C17	0.33216 (12)	1.3960 (4)	0.73289 (18)	0.0399 (6)
H17A	0.3577	1.3262	0.7756	0.048*
H17B	0.3546	1.5045	0.7067	0.048*
C18	0.24177 (13)	1.3237 (4)	0.81621 (17)	0.0370 (6)
H18A	0.2081	1.3870	0.8434	0.044*
H18B	0.2629	1.2472	0.8620	0.044*
C19	0.22071 (11)	1.1830 (4)	0.74276 (17)	0.0341 (6)
H19A	0.1969	1.2576	0.6994	0.041*
H19B	0.1963	1.0783	0.7679	0.041*
C20	0.25127 (11)	0.9437 (4)	0.62321 (16)	0.0326 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03884 (12)	0.02632 (11)	0.02842 (11)	0.00414 (8)	−0.00520 (7)	−0.00244 (7)
O1	0.0443 (11)	0.0636 (13)	0.0294 (10)	0.0109 (10)	−0.0012 (8)	0.0033 (9)
O2	0.0321 (10)	0.0429 (10)	0.0364 (10)	0.0004 (8)	−0.0041 (8)	0.0006 (8)
O3	0.0341 (12)	0.0792 (16)	0.0646 (14)	0.0025 (11)	−0.0104 (10)	0.0013 (12)
O4	0.0595 (15)	0.149 (3)	0.0372 (13)	0.0001 (16)	−0.0105 (11)	0.0044 (15)
O5	0.0403 (11)	0.0396 (11)	0.0552 (12)	0.0066 (9)	0.0049 (9)	−0.0040 (9)
O6	0.0592 (13)	0.0369 (12)	0.0725 (15)	0.0100 (10)	−0.0061 (11)	0.0148 (10)
O7	0.0492 (15)	0.0736 (19)	0.240 (4)	0.0041 (14)	0.053 (2)	0.026 (2)
O8	0.0572 (14)	0.0516 (15)	0.120 (2)	0.0142 (12)	0.0266 (14)	0.0137 (14)
O9	0.0543 (11)	0.0239 (9)	0.0331 (9)	−0.0009 (8)	−0.0006 (8)	−0.0017 (7)
O10	0.0843 (14)	0.0275 (9)	0.0388 (10)	0.0071 (9)	−0.0225 (10)	−0.0030 (8)
O11	0.0479 (11)	0.0328 (10)	0.0650 (13)	−0.0032 (9)	−0.0228 (10)	0.0083 (9)
N1	0.0420 (14)	0.0409 (13)	0.0462 (15)	0.0022 (11)	−0.0101 (11)	0.0018 (11)
N2	0.0408 (14)	0.0533 (16)	0.098 (2)	0.0069 (12)	0.0211 (14)	0.0190 (15)
N3	0.0487 (13)	0.0225 (10)	0.0348 (11)	−0.0030 (9)	−0.0047 (9)	−0.0030 (9)
C1	0.0331 (13)	0.0233 (12)	0.0325 (13)	0.0020 (10)	−0.0009 (10)	0.0021 (10)
C2	0.0384 (14)	0.0297 (13)	0.0299 (13)	0.0030 (11)	0.0027 (11)	0.0025 (10)
C3	0.0301 (13)	0.0307 (13)	0.0418 (14)	0.0015 (10)	0.0034 (11)	0.0024 (11)
C4	0.0350 (14)	0.0280 (13)	0.0359 (14)	0.0012 (10)	−0.0067 (11)	0.0015 (10)
C5	0.0400 (15)	0.0461 (16)	0.0290 (13)	0.0027 (12)	0.0021 (11)	0.0029 (12)
C6	0.0306 (13)	0.0420 (15)	0.0338 (13)	0.0004 (11)	0.0028 (11)	0.0013 (11)
C7	0.0365 (14)	0.0211 (12)	0.0348 (14)	0.0027 (10)	−0.0035 (11)	0.0000 (10)
C8	0.0371 (14)	0.0330 (14)	0.0364 (13)	0.0006 (11)	−0.0047 (11)	0.0007 (11)
C9	0.0538 (19)	0.0326 (16)	0.079 (2)	−0.0024 (14)	0.0086 (16)	0.0141 (15)
C10	0.0452 (18)	0.0460 (19)	0.096 (3)	−0.0031 (15)	0.0208 (17)	0.0118 (18)
C11	0.0355 (15)	0.0420 (16)	0.0563 (18)	0.0032 (12)	0.0044 (13)	0.0059 (14)
C12	0.0409 (15)	0.0327 (14)	0.0469 (16)	0.0016 (12)	0.0012 (12)	0.0075 (12)
C13	0.0357 (14)	0.0367 (15)	0.0376 (14)	−0.0008 (11)	0.0015 (11)	0.0052 (11)
C14	0.0428 (15)	0.0368 (15)	0.0316 (13)	0.0036 (12)	−0.0089 (11)	−0.0015 (11)
C15	0.0397 (14)	0.0226 (12)	0.0293 (12)	0.0040 (10)	−0.0045 (10)	0.0004 (10)
C16	0.0326 (13)	0.0373 (14)	0.0348 (13)	0.0010 (11)	0.0039 (11)	−0.0015 (11)
C17	0.0365 (14)	0.0382 (15)	0.0447 (15)	−0.0071 (12)	−0.0039 (12)	0.0011 (12)
C18	0.0517 (16)	0.0265 (13)	0.0332 (13)	−0.0015 (11)	0.0082 (12)	−0.0019 (10)
C19	0.0386 (14)	0.0273 (13)	0.0367 (14)	−0.0066 (11)	0.0064 (11)	−0.0020 (11)
C20	0.0410 (13)	0.0248 (12)	0.0318 (12)	0.0055 (10)	−0.0035 (10)	−0.0039 (10)

Geometric parameters (Å, º) top

Cd1—O5	2.1917 (18)	C3—C4	1.379 (4)
Cd1—O11	2.3061 (19)	C3—H3	0.9300
Cd1—O2	2.3229 (17)	C4—C5	1.381 (4)
Cd1—O9	2.3327 (17)	C5—C6	1.380 (4)
Cd1—O10	2.3534 (18)	C5—H5	0.9300
Cd1—O1	2.3684 (19)	C6—H6	0.9300
Cd1—C7	2.675 (2)	C8—C9	1.386 (4)
Cd1—C20	2.697 (2)	C8—C13	1.387 (4)
O1—C7	1.249 (3)	C8—C14	1.514 (4)
O2—C7	1.260 (3)	C9—C10	1.377 (4)
O3—N1	1.220 (3)	C9—H9	0.9300
O4—N1	1.206 (3)	C10—C11	1.375 (4)
O5—C14	1.265 (3)	C10—H10	0.9300
O6—C14	1.240 (3)	C11—C12	1.372 (4)
O7—N2	1.201 (4)	C12—C13	1.379 (4)
O8—N2	1.207 (4)	C12—H12	0.9300
O9—C20	1.256 (3)	C13—H13	0.9300
O10—C20	1.257 (3)	C15—C20	1.514 (3)
O11—H11A	0.8504	C15—C16	1.520 (4)
O11—H11B	0.8500	C15—C19	1.529 (3)
N1—C4	1.473 (3)	C15—H15	0.9800
N2—C11	1.474 (4)	C16—C17	1.514 (4)
N3—C17	1.483 (3)	C16—H16A	0.9700
N3—C18	1.491 (3)	C16—H16B	0.9700
N3—H3A	0.9000	C17—H17A	0.9700
N3—H3B	0.9000	C17—H17B	0.9700
C1—C2	1.389 (4)	C18—C19	1.511 (3)
C1—C6	1.391 (3)	C18—H18A	0.9700
C1—C7	1.506 (3)	C18—H18B	0.9700
C2—C3	1.382 (4)	C19—H19A	0.9700
C2—H2	0.9300	C19—H19B	0.9700

O5—Cd1—O11	87.34 (7)	C1—C6—H6	119.7
O5—Cd1—O2	99.09 (7)	O1—C7—O2	122.4 (2)
O11—Cd1—O2	104.84 (7)	O1—C7—C1	118.9 (2)
O5—Cd1—O9	94.60 (7)	O2—C7—C1	118.7 (2)
O11—Cd1—O9	92.93 (7)	O1—C7—Cd1	62.30 (13)
O2—Cd1—O9	157.95 (7)	O2—C7—Cd1	60.23 (12)
O5—Cd1—O10	112.86 (8)	C1—C7—Cd1	173.83 (17)
O11—Cd1—O10	142.21 (7)	C9—C8—C13	119.4 (3)
O2—Cd1—O10	103.02 (6)	C9—C8—C14	120.2 (2)
O9—Cd1—O10	55.45 (6)	C13—C8—C14	120.4 (2)
O5—Cd1—O1	146.54 (7)	C10—C9—C8	120.6 (3)
O11—Cd1—O1	79.66 (7)	C10—C9—H9	119.7
O2—Cd1—O1	55.86 (6)	C8—C9—H9	119.7
O9—Cd1—O1	116.58 (6)	C11—C10—C9	118.6 (3)
O10—Cd1—O1	95.67 (7)	C11—C10—H10	120.7
O5—Cd1—C7	123.68 (7)	C9—C10—H10	120.7
O11—Cd1—C7	91.37 (7)	C12—C11—C10	122.3 (3)
O2—Cd1—C7	28.08 (7)	C12—C11—N2	118.4 (3)
O9—Cd1—C7	141.64 (7)	C10—C11—N2	119.3 (3)
O10—Cd1—C7	101.72 (7)	C11—C12—C13	118.7 (3)
O1—Cd1—C7	27.83 (7)	C11—C12—H12	120.7
O5—Cd1—C20	104.32 (7)	C13—C12—H12	120.7
O11—Cd1—C20	118.82 (7)	C12—C13—C8	120.4 (3)
O2—Cd1—C20	130.75 (7)	C12—C13—H13	119.8
O9—Cd1—C20	27.72 (7)	C8—C13—H13	119.8
O10—Cd1—C20	27.77 (7)	O6—C14—O5	125.7 (3)
O1—Cd1—C20	108.98 (7)	O6—C14—C8	119.0 (3)
C7—Cd1—C20	124.63 (7)	O5—C14—C8	115.3 (2)
C7—O1—Cd1	89.86 (15)	C20—C15—C16	112.2 (2)
C7—O2—Cd1	91.69 (15)	C20—C15—C19	110.6 (2)
C14—O5—Cd1	120.47 (17)	C16—C15—C19	109.4 (2)
C20—O9—Cd1	92.50 (14)	C20—C15—H15	108.2
C20—O10—Cd1	91.50 (15)	C16—C15—H15	108.2
Cd1—O11—H11A	104.6	C19—C15—H15	108.2
Cd1—O11—H11B	122.9	C17—C16—C15	111.8 (2)
H11A—O11—H11B	117.1	C17—C16—H16A	109.3
O4—N1—O3	122.3 (2)	C15—C16—H16A	109.3
O4—N1—C4	119.4 (2)	C17—C16—H16B	109.3
O3—N1—C4	118.3 (2)	C15—C16—H16B	109.3
O7—N2—O8	122.8 (3)	H16A—C16—H16B	107.9
O7—N2—C11	118.6 (3)	N3—C17—C16	111.6 (2)
O8—N2—C11	118.6 (3)	N3—C17—H17A	109.3
C17—N3—C18	112.6 (2)	C16—C17—H17A	109.3
C17—N3—H3A	109.1	N3—C17—H17B	109.3
C18—N3—H3A	109.1	C16—C17—H17B	109.3
C17—N3—H3B	109.1	H17A—C17—H17B	108.0
C18—N3—H3B	109.1	N3—C18—C19	110.7 (2)
H3A—N3—H3B	107.8	N3—C18—H18A	109.5
C2—C1—C6	119.8 (2)	C19—C18—H18A	109.5
C2—C1—C7	119.7 (2)	N3—C18—H18B	109.5
C6—C1—C7	120.4 (2)	C19—C18—H18B	109.5
C3—C2—C1	120.6 (2)	H18A—C18—H18B	108.1
C3—C2—H2	119.7	C18—C19—C15	110.9 (2)
C1—C2—H2	119.7	C18—C19—H19A	109.5
C4—C3—C2	117.9 (2)	C15—C19—H19A	109.5
C4—C3—H3	121.0	C18—C19—H19B	109.5
C2—C3—H3	121.0	C15—C19—H19B	109.5
C3—C4—C5	123.1 (2)	H19A—C19—H19B	108.0
C3—C4—N1	118.2 (2)	O9—C20—O10	120.4 (2)
C5—C4—N1	118.7 (2)	O9—C20—C15	120.1 (2)
C6—C5—C4	118.0 (2)	O10—C20—C15	119.5 (2)
C6—C5—H5	121.0	O9—C20—Cd1	59.78 (12)
C4—C5—H5	121.0	O10—C20—Cd1	60.73 (13)
C5—C6—C1	120.5 (2)	C15—C20—Cd1	176.71 (18)
C5—C6—H6	119.7

O5—Cd1—O1—C7	−44.7 (2)	C20—Cd1—C7—O2	113.00 (15)
O11—Cd1—O1—C7	−113.45 (16)	O5—Cd1—C7—C1	49.5 (17)
O2—Cd1—O1—C7	2.54 (14)	O11—Cd1—C7—C1	−38.2 (17)
O9—Cd1—O1—C7	158.45 (14)	O2—Cd1—C7—C1	81.7 (17)
O10—Cd1—O1—C7	104.44 (16)	O9—Cd1—C7—C1	−134.7 (17)
C20—Cd1—O1—C7	129.46 (15)	O10—Cd1—C7—C1	177.4 (17)
O5—Cd1—O2—C7	153.29 (15)	O1—Cd1—C7—C1	−102.8 (17)
O11—Cd1—O2—C7	63.65 (15)	C20—Cd1—C7—C1	−165.3 (17)
O9—Cd1—O2—C7	−79.0 (2)	C13—C8—C9—C10	0.1 (5)
O10—Cd1—O2—C7	−90.55 (15)	C14—C8—C9—C10	−177.8 (3)
O1—Cd1—O2—C7	−2.52 (14)	C8—C9—C10—C11	1.8 (5)
C20—Cd1—O2—C7	−88.77 (16)	C9—C10—C11—C12	−1.9 (5)
O11—Cd1—O5—C14	176.52 (19)	C9—C10—C11—N2	176.8 (3)
O2—Cd1—O5—C14	71.91 (19)	O7—N2—C11—C12	−164.7 (4)
O9—Cd1—O5—C14	−90.75 (19)	O8—N2—C11—C12	15.5 (5)
O10—Cd1—O5—C14	−36.4 (2)	O7—N2—C11—C10	16.6 (5)
O1—Cd1—O5—C14	109.9 (2)	O8—N2—C11—C10	−163.1 (4)
C7—Cd1—O5—C14	86.6 (2)	C10—C11—C12—C13	−0.1 (5)
C20—Cd1—O5—C14	−64.4 (2)	N2—C11—C12—C13	−178.8 (3)
O5—Cd1—O9—C20	112.35 (16)	C11—C12—C13—C8	2.1 (4)
O11—Cd1—O9—C20	−160.08 (16)	C9—C8—C13—C12	−2.1 (4)
O2—Cd1—O9—C20	−16.0 (3)	C14—C8—C13—C12	175.7 (2)
O10—Cd1—O9—C20	−2.34 (15)	Cd1—O5—C14—O6	−5.4 (4)
O1—Cd1—O9—C20	−80.19 (16)	Cd1—O5—C14—C8	176.17 (15)
C7—Cd1—O9—C20	−64.15 (19)	C9—C8—C14—O6	−1.8 (4)
O5—Cd1—O10—C20	−77.03 (17)	C13—C8—C14—O6	−179.6 (3)
O11—Cd1—O10—C20	40.4 (2)	C9—C8—C14—O5	176.7 (3)
O2—Cd1—O10—C20	177.09 (16)	C13—C8—C14—O5	−1.1 (4)
O9—Cd1—O10—C20	2.33 (15)	C20—C15—C16—C17	178.2 (2)
O1—Cd1—O10—C20	120.86 (16)	C19—C15—C16—C17	55.1 (3)
C7—Cd1—O10—C20	148.36 (16)	C18—N3—C17—C16	54.5 (3)
C6—C1—C2—C3	0.6 (4)	C15—C16—C17—N3	−54.3 (3)
C7—C1—C2—C3	−176.9 (2)	C17—N3—C18—C19	−56.0 (3)
C1—C2—C3—C4	0.2 (4)	N3—C18—C19—C15	57.1 (3)
C2—C3—C4—C5	−1.2 (4)	C20—C15—C19—C18	179.4 (2)
C2—C3—C4—N1	179.4 (2)	C16—C15—C19—C18	−56.6 (3)
O4—N1—C4—C3	177.0 (3)	Cd1—O9—C20—O10	4.2 (3)
O3—N1—C4—C3	−1.9 (4)	Cd1—O9—C20—C15	−176.2 (2)
O4—N1—C4—C5	−2.4 (4)	Cd1—O10—C20—O9	−4.1 (3)
O3—N1—C4—C5	178.7 (3)	Cd1—O10—C20—C15	176.2 (2)
C3—C4—C5—C6	1.3 (4)	C16—C15—C20—O9	140.5 (2)
N1—C4—C5—C6	−179.3 (2)	C19—C15—C20—O9	−97.1 (3)
C4—C5—C6—C1	−0.5 (4)	C16—C15—C20—O10	−39.9 (3)
C2—C1—C6—C5	−0.4 (4)	C19—C15—C20—O10	82.6 (3)
C7—C1—C6—C5	177.0 (2)	C16—C15—C20—Cd1	53 (3)
Cd1—O1—C7—O2	−4.6 (3)	C19—C15—C20—Cd1	175 (3)
Cd1—O1—C7—C1	173.1 (2)	O5—Cd1—C20—O9	−72.07 (16)
Cd1—O2—C7—O1	4.7 (3)	O11—Cd1—C20—O9	22.85 (18)
Cd1—O2—C7—C1	−173.03 (19)	O2—Cd1—C20—O9	172.13 (13)
C2—C1—C7—O1	0.5 (4)	O10—Cd1—C20—O9	175.9 (3)
C6—C1—C7—O1	−176.9 (2)	O1—Cd1—C20—O9	111.27 (15)
C2—C1—C7—O2	178.3 (2)	C7—Cd1—C20—O9	137.25 (15)
C6—C1—C7—O2	0.9 (4)	O5—Cd1—C20—O10	112.06 (16)
C2—C1—C7—Cd1	100.0 (17)	O11—Cd1—C20—O10	−153.02 (15)
C6—C1—C7—Cd1	−77.4 (17)	O2—Cd1—C20—O10	−3.7 (2)
O5—Cd1—C7—O1	152.24 (15)	O9—Cd1—C20—O10	−175.9 (3)
O11—Cd1—C7—O1	64.52 (16)	O1—Cd1—C20—O10	−64.60 (17)
O2—Cd1—C7—O1	−175.5 (2)	C7—Cd1—C20—O10	−38.62 (19)
O9—Cd1—C7—O1	−31.9 (2)	O5—Cd1—C20—C15	17 (3)
O10—Cd1—C7—O1	−79.80 (16)	O11—Cd1—C20—C15	112 (3)
C20—Cd1—C7—O1	−62.53 (18)	O2—Cd1—C20—C15	−99 (3)
O5—Cd1—C7—O2	−32.23 (17)	O9—Cd1—C20—C15	89 (3)
O11—Cd1—C7—O2	−119.95 (15)	O10—Cd1—C20—C15	−95 (3)
O9—Cd1—C7—O2	143.58 (14)	O1—Cd1—C20—C15	−159 (3)
O10—Cd1—C7—O2	95.73 (15)	C7—Cd1—C20—C15	−133 (3)
O1—Cd1—C7—O2	175.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11A···O3ⁱ	0.85	2.26	3.019 (3)	149
O11—H11B···O10ⁱⁱ	0.85	1.91	2.754 (3)	172
N3—H3A···O9ⁱⁱⁱ	0.90	2.04	2.887 (3)	156
N3—H3B···O6^iv	0.90	1.89	2.762 (3)	163

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) x, y+1, z; (iv) x, −y+5/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cd(C₆H₁₁NO₂)(C₇H₄NO₄)₂(H₂O)]
M_r	591.80
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	22.7135 (7), 6.6294 (2), 14.9658 (5)
β (°)	91.340 (1)
V (Å³)	2252.89 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.32 × 0.28 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.733, 0.804
No. of measured, independent and observed [I > 2σ(I)] reflections	10944, 3950, 3615
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.056, 1.05
No. of reflections	3950
No. of parameters	316
No. of restraints	18
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.32

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999).

Selected geometric parameters (Å, º) top

Cd1—O5	2.1917 (18)	Cd1—O9	2.3327 (17)
Cd1—O11	2.3061 (19)	Cd1—O10	2.3534 (18)
Cd1—O2	2.3229 (17)	Cd1—O1	2.3684 (19)

O5—Cd1—O11	87.34 (7)	O5—Cd1—C20	104.32 (7)
O5—Cd1—C7	123.68 (7)	O11—Cd1—C20	118.82 (7)
O11—Cd1—C7	91.37 (7)	C7—Cd1—C20	124.63 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11A···O3ⁱ	0.85	2.26	3.019 (3)	148.7
O11—H11B···O10ⁱⁱ	0.85	1.91	2.754 (3)	171.7
N3—H3A···O9ⁱⁱⁱ	0.90	2.04	2.887 (3)	156.2
N3—H3B···O6^iv	0.90	1.89	2.762 (3)	162.7

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) x, y+1, z; (iv) x, −y+5/2, z+1/2.

Acknowledgements

The authors gratefully acknowledge financial support from Tianjin Education Committee (2006ZD07).

References

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