catena-Poly[[diaqua­cadmium(II)]-μ-(methyl morpholino dichloro­methylene­diphospho­nato)-κ3O,O′:O′′-[tetra­aqua­cadmium(II)]-μ-(methyl morpholino dichloro­methyl­enediphospho­nato)-κ3O:O′,O′′]

Jokiniemi, J.; Vepsäläinen, J.; Ahlgrén, M.

doi:10.1107/S160053680901527X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages m600-m601

doi:10.1107/S160053680901527X

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catena-Poly[[diaquacadmium(II)]-μ-(methyl morpholino dichloromethylenediphosphonato)-κ³O,O′:O′′-[tetraaquacadmium(II)]-μ-(methyl morpholino dichloromethylenediphosphonato)-κ³O:O′,O′′]

Jonna Jokiniemi,^a ^* Jouko Vepsäläinen ^b and Markku Ahlgrén ^a

^aDepartment of Chemistry, University of Joensuu, PO Box 111, FI-80101 Joensuu, Finland, and ^bLaboratory of Chemistry, Department of Biosciences, University of Kuopio, PO Box 1627, FI-70211 Kuopio, Finland
^*Correspondence e-mail: Jonna.Jokiniemi@joensuu.fi

(Received 24 February 2009; accepted 23 April 2009; online 30 April 2009)

The asymmetric unit of the title compound, [Cd(C₆H₁₁Cl₂NO₆P₂)(H₂O)₃]_n, contains two octahedrally coordinated Cd atoms located in special positions, one on a twofold rotation axis and the other on a centre of symmetry. The metal atoms are connected by methyl morpholino dichloromethylenediphosphonate ligands into chains in the c-axis direction. These chains are further connected by O—H⋯O hydrogen bonds into a layer-like construction along (100).

Related literature

For applications of metal complexes of bisphosphonates, see: Clearfield (1998 ); Clearfield et al. (2001 ); Fu et al. (2007 ). For cadmium bisphosphonate complexes, see: Ying & Mao (2006 ); Man et al. (2006 ). For metal complexes of bisphosphonate ester derivatives, see: Jokiniemi et al. (2007 , 2008 ). For Mg, Zn and Cd complexes of the symmetrical diethyl ester derivative of (dichloromethylene)bisphosphonate, see: Kontturi et al. (2002 , 2005a ,b ).

Experimental

Crystal data

[Cd(C₆H₁₁Cl₂NO₆P₂)(H₂O)₃]
M_r = 492.45
Monoclinic, C 2/c
a = 26.2488 (8) Å
b = 7.6578 (3) Å
c = 17.5445 (7) Å
β = 116.002 (3)°
V = 3169.6 (2) Å³
Z = 8
Mo Kα radiation
μ = 1.96 mm⁻¹
T = 120 K
0.30 × 0.25 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008 ) T_min = 0.565, T_max = 0.676
21828 measured reflections
4053 independent reflections
3370 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.068
S = 1.06
4053 reflections
195 parameters
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −1.12 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cd1—O11	2.2256 (17)
Cd1—O21	2.3173 (16)
Cd1—O1	2.3409 (17)
Cd2—O12	2.1884 (17)
Cd2—O3	2.2795 (16)
Cd2—O2	2.3486 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2ⁱ	0.84	2.06	2.849 (2)	156
O1—H1B⋯O22ⁱⁱ	0.88	2.12	2.990 (2)	170
O2—H2A⋯O21ⁱⁱⁱ	0.86	2.04	2.844 (2)	155
O2—H2B⋯O22	0.86	1.84	2.662 (2)	159
O3—H3A⋯O22	0.83	2.03	2.773 (2)	149
O3—H3B⋯O13^iv	0.90	1.87	2.745 (2)	163
Symmetry codes: (i) $[-x+1, y-1, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iv) x, y+1, z.

Data collection: COLLECT (Nonius, 1997 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901527X/er2063sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901527X/er2063Isup2.hkl

checkCIF report

Comment top

Metal complexes with bisphosphonic acids have interesting structures with various coordination architectures, and properties that offer practical applications in catalysis, ion-exchange and sorption (Clearfield et al., 2001, Clearfield, 1998, Fu et al., 2007). In our recent investigations, we studied the complexing properties of amide ester derivatives of (dichloromethylene)bisphosphonate, Cl₂MBP (Jokiniemi et al., 2007, 2008). Introduction of these ester substituents to phosphorus groups can result in novel structures of metal bishosphonates and lead to interesting functionalities. We now present the crystal structure of the Cd(II) complex of the P-morpholinyl-P'-methyl ester derivative of Cl₂MBP obtained by gel crystallization.

The title compound is isomorphous with the earlier reported Mg complexes of (dichloromethylene)bisphosphonic acid methyl esters of piperidinyl and morpholinyl derivatives (Jokiniemi et al., 2007, 2008). The title compound is polymeric, consisting of chains in the direction of the c-axis. There are two crystallographically independent six-coordinated Cd²⁺ cations in the asymmetric unit, located in special positions: Cd1 on the twofold rotation axis and Cd2 on the centre of symmetry (Fig. 1). Two symmetrically related L₁ ligands, L₁ = (Cl₂CP2O₅MeNC₄H₈O), around the Cd1 atom form six-membered chelate rings. The L₁ ligand is further connected to Cd2 through one O atom, and thus acts as a triatomic bridge between the adjacent Cd atoms. The fourth phosphonate O atom remains non-coordinated but is involved in hydrogen bonding. The remaining coordination sites around the Cd1 atoms are occupied by aqua ligands in cis position; the geometry is a significantly distorted octahedron having Cd1–O bond distances 2.226 (2)–2.341 (2) Å (Table 1). The three trans angles are O11–Cd1–O11A 166.14 (9), O21–Cd1–O1A 174.23 (5) and O21A–Cd1–O1 174.23 (5)°. The Cd2 atom has a distorted octahedral geometry, and the binding sites around the metal atom are occupied by two phosphonate O atoms in axial positions and four aqua ligands having Cd2–O bond lengths 2.188 (2)–2.349 (2) Å. The three trans bond angles are 180°, while the cis bond angles around the Cd2 atom range from 82.50 (6) to 97.50 (6)°. In addition to isomorphous Mg complexes of monomethyl ester of morpholinyl and piperidinyl derivatives of Cl₂MBP (Jokiniemi et al., 2007 and 2008), the same kind of chain construction is found in Mg, Zn and Cd complexes of the symmetrical diethyl ester derivative of Cl₂MBP (Kontturi et al., 2002, 2005a and 2005b).

The polymeric chains are connected, in a layer-like structure parallel to the (100) plane, by hydrogen bonds [O···O 2.745 (2)–2.990 (2) Å, 149–170°, Table 2]. The morpholinyl rings and chlorine atoms of the L₁ ligands point out from the layers (Fig. 2), which are held together solely by weak Van der Waals interactions, with an interlayer distance of 11.7959 Å.

Related literature top

For applications of metal complexes of bisphosphonates, see: Clearfield (1998); Clearfield et al. (2001); Fu et al. (2007). For cadmium bisphosphonate complexes, see: Ying et al. (2006); Man et al. (2006). For metal complexes of bisphosphonate ester derivatives, see: Jokiniemi et al. (2007, 2008). For Mg, Zn and Cd complexes of the symmetrical diethyl ester derivative of (dichloromethylene)bisphosphonate, see: Kontturi et al. (2002, 2005a,b).

Experimental top

(H₂N[(CH₂)₂]₂O)₂CH₃PO₃CCl₂PO₂NC₄H₈O (19.8 mg, 0.039 mmol) and Cd(NO₃)₂×4H₂O (12.1 mg, 0.039 mmol) were dissolved separately in water (0.45 ml), the solutions were mixed, and tetramethoxysilane (TMOS 0.1 ml) was added. The two-phase system was shaken until homogeneous. After gel formation, a precipitant, acetone (1.0 ml), was added above the gel to induce crystallization. After about three weeks, large, colourless plank-shaped crystals suitable for X-ray analysis formed at the gel-liquid boundary. Anal. Found: C, 14.63; H, 3.48; N, 2.84; Cd, 22.83%. Calc. for C₆H₁₇Cl₂CdNO₉P₂: C, 14.74; H, 3.48; N, 2.86; Cd, 22.45%. Main IR absorptions (KBr pellet, cm^-1): 3432 (s), 2961 (m), 2926 (m), 2854 (m), 1627 (m), 1204 (versus), 1145 (m), 1101 (versus), 1072 (s), 1056 (s), 981 (s), 869 (m), 843 (m). ³¹P CP/MAS NMR: δ_P 8.4 and 4.3 p.p.m.. TGA (25–900 °C under a synthetic air): 30–110 °C 12.6% (calculated 11.0% for the loss of three aqua ligands). The second step (190–900 °C) is attributed to the release of organic groups, chlorine atoms and a methylene carbon atom. The observed total weight loss is 47.0% (calculated 45.1% if the final product is assumed to be Cd(PO₃)₂).

Computing details top

Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Structure of the title compound showing the atomic numbering scheme and 50% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity. Atoms labelled with suffixes A and B are at the symmetry postitions (1 - x, y, 1/2 - z) and (1 - x, 1 - y, - z) respectively.
	Fig. 2. Packing of the title compound viewed along the b-axis. CdO₆ octahedra are presented in medium grey and PO₃C and NPO₂C tetrahedra in dark grey. Hydrogen atoms are omitted for clarity.

catena-Poly[[diaquacadmium(II)]-µ-(methyl morpholino dichloromethylenediphosphonato)-κ³O,O':O''- [tetraaquacadmium(II)]-µ-(methyl morpholino dichloromethylenediphosphonato)-κ³O:O',O''] top

Crystal data top

[Cd(C₆H₁₁Cl₂NO₆P₂)(H₂O)₃]	F(000) = 1952
M_r = 492.45	D_x = 2.064 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 21828 reflections
a = 26.2488 (8) Å	θ = 2.8–28.7°
b = 7.6578 (3) Å	µ = 1.96 mm⁻¹
c = 17.5445 (7) Å	T = 120 K
β = 116.002 (3)°	Plank, colourles
V = 3169.6 (2) Å³	0.30 × 0.25 × 0.20 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer	4053 independent reflections
Radiation source: fine-focus sealed tube	3370 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
multi–scan	θ_max = 28.7°, θ_min = 2.8°
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008)	h = −35→35
T_min = 0.565, T_max = 0.676	k = −10→10
21828 measured reflections	l = −23→21

Refinement top

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
4053 reflections	Δρ_max = 1.04 e Å⁻³
195 parameters	Δρ_min = −1.12 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00053 (7)

Crystal data top

[Cd(C₆H₁₁Cl₂NO₆P₂)(H₂O)₃]	V = 3169.6 (2) Å³
M_r = 492.45	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 26.2488 (8) Å	µ = 1.96 mm⁻¹
b = 7.6578 (3) Å	T = 120 K
c = 17.5445 (7) Å	0.30 × 0.25 × 0.20 mm
β = 116.002 (3)°

Data collection top

Nonius KappaCCD diffractometer	4053 independent reflections
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008)	3370 reflections with I > 2σ(I)
T_min = 0.565, T_max = 0.676	R_int = 0.038
21828 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.06	Δρ_max = 1.04 e Å⁻³
4053 reflections	Δρ_min = −1.12 e Å⁻³
195 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
Cl1	0.33755 (3)	0.03444 (8)	0.08713 (4)	0.01735 (14)
Cl2	0.31951 (3)	0.31865 (8)	−0.03219 (3)	0.01910 (14)
P1	0.42845 (3)	0.12553 (8)	0.03696 (4)	0.01308 (14)
P2	0.39459 (2)	0.37248 (8)	0.15068 (4)	0.01129 (13)
Cd1	0.5000	0.05298 (3)	0.2500	0.01210 (8)
Cd2	0.5000	0.5000	0.0000	0.01366 (8)
O1	0.43819 (7)	−0.1737 (2)	0.24266 (10)	0.0170 (4)
H1A	0.4474	−0.2385	0.2856	0.025*
H1B	0.4298	−0.2517	0.2023	0.025*
O2	0.52362 (7)	0.5362 (2)	0.14457 (10)	0.0149 (4)
H2A	0.5420	0.4483	0.1748	0.022*
H2B	0.4929	0.5313	0.1507	0.022*
O3	0.41722 (7)	0.6409 (2)	−0.02767 (10)	0.0182 (4)
H3A	0.4041	0.6034	0.0045	0.027*
H3B	0.4177	0.7579	−0.0243	0.042 (9)*
O4	0.26897 (8)	0.6093 (3)	0.22336 (12)	0.0281 (4)
O11	0.46611 (8)	0.0179 (2)	0.11038 (11)	0.0182 (4)
O12	0.45203 (8)	0.2725 (2)	0.00769 (11)	0.0220 (4)
O13	0.39645 (7)	−0.0065 (2)	−0.03937 (10)	0.0172 (4)
O21	0.43465 (7)	0.2737 (2)	0.22805 (9)	0.0138 (3)
O22	0.41655 (7)	0.5285 (2)	0.12215 (10)	0.0142 (4)
N1	0.33955 (8)	0.4329 (3)	0.16396 (12)	0.0147 (4)
C1	0.37131 (10)	0.2129 (3)	0.06118 (14)	0.0130 (5)
C2	0.29966 (10)	0.5686 (3)	0.11230 (15)	0.0187 (5)
H2E	0.2634	0.5141	0.0731	0.022*
H2F	0.3155	0.6307	0.0781	0.022*
C3	0.28936 (12)	0.6969 (4)	0.16995 (17)	0.0246 (6)
H3E	0.3251	0.7585	0.2056	0.029*
H3F	0.2612	0.7851	0.1351	0.029*
C5	0.30950 (12)	0.4819 (4)	0.27479 (17)	0.0240 (6)
H5E	0.2955	0.4245	0.3125	0.029*
H5F	0.3457	0.5408	0.3109	0.029*
C6	0.31968 (11)	0.3450 (3)	0.22048 (15)	0.0188 (5)
H6E	0.3485	0.2601	0.2570	0.023*
H6F	0.2841	0.2808	0.1865	0.023*
C13	0.37843 (13)	0.0444 (4)	−0.12767 (15)	0.0267 (6)
H13A	0.3832	0.1707	−0.1308	0.040*
H13B	0.3384	0.0137	−0.1610	0.040*
H13C	0.4015	−0.0171	−0.1504	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0178 (3)	0.0143 (3)	0.0189 (3)	−0.0048 (2)	0.0070 (2)	0.0009 (2)
Cl2	0.0207 (3)	0.0164 (3)	0.0133 (3)	0.0014 (2)	0.0010 (2)	0.0018 (2)
P1	0.0172 (3)	0.0098 (3)	0.0123 (3)	−0.0019 (2)	0.0065 (2)	−0.0020 (2)
P2	0.0116 (3)	0.0097 (3)	0.0117 (3)	−0.0005 (2)	0.0042 (2)	−0.0006 (2)
Cd1	0.01370 (13)	0.00967 (13)	0.01166 (13)	0.000	0.00440 (9)	0.000
Cd2	0.01748 (14)	0.01108 (14)	0.01369 (14)	−0.00167 (9)	0.00800 (10)	−0.00030 (9)
O1	0.0202 (9)	0.0148 (9)	0.0144 (8)	−0.0028 (7)	0.0062 (7)	0.0010 (7)
O2	0.0155 (9)	0.0161 (9)	0.0129 (9)	0.0000 (7)	0.0060 (7)	0.0004 (7)
O3	0.0229 (10)	0.0124 (9)	0.0210 (9)	0.0016 (7)	0.0112 (7)	0.0029 (7)
O4	0.0294 (11)	0.0286 (11)	0.0380 (11)	0.0081 (9)	0.0254 (9)	0.0052 (9)
O11	0.0201 (9)	0.0220 (10)	0.0104 (9)	0.0041 (7)	0.0047 (7)	−0.0021 (7)
O12	0.0316 (11)	0.0129 (9)	0.0309 (10)	−0.0063 (8)	0.0225 (9)	−0.0042 (7)
O13	0.0257 (10)	0.0107 (9)	0.0117 (9)	−0.0015 (7)	0.0050 (7)	−0.0020 (6)
O21	0.0137 (8)	0.0132 (9)	0.0123 (8)	0.0013 (6)	0.0036 (6)	−0.0002 (6)
O22	0.0165 (9)	0.0120 (9)	0.0165 (9)	−0.0007 (7)	0.0094 (7)	0.0003 (6)
N1	0.0172 (11)	0.0143 (11)	0.0150 (10)	0.0018 (8)	0.0092 (8)	0.0031 (8)
C1	0.0142 (11)	0.0108 (12)	0.0111 (11)	−0.0021 (9)	0.0030 (9)	0.0015 (9)
C2	0.0159 (12)	0.0208 (14)	0.0187 (13)	0.0049 (10)	0.0071 (10)	0.0043 (10)
C3	0.0276 (15)	0.0210 (14)	0.0301 (15)	0.0069 (11)	0.0173 (12)	0.0027 (11)
C5	0.0303 (16)	0.0247 (15)	0.0247 (15)	−0.0005 (11)	0.0192 (12)	0.0025 (11)
C6	0.0202 (13)	0.0185 (13)	0.0212 (13)	−0.0030 (10)	0.0124 (10)	0.0025 (10)
C13	0.0457 (18)	0.0198 (14)	0.0107 (13)	0.0026 (12)	0.0088 (12)	−0.0007 (10)

Geometric parameters (Å, º) top

Cl1—C1	1.792 (2)	O1—H1B	0.8775
Cl2—C1	1.799 (2)	O2—H2A	0.8617
P1—O12	1.4803 (18)	O2—H2B	0.8598
P1—O11	1.4829 (18)	O3—H3A	0.8298
P1—O13	1.5922 (17)	O3—H3B	0.8982
P1—C1	1.854 (2)	O4—C3	1.433 (3)
P2—O22	1.5044 (17)	O4—C5	1.434 (3)
P2—O21	1.5062 (16)	O13—C13	1.460 (3)
P2—N1	1.628 (2)	N1—C6	1.470 (3)
P2—C1	1.869 (2)	N1—C2	1.472 (3)
Cd1—O11	2.2256 (17)	C2—C3	1.517 (3)
Cd1—O11ⁱ	2.2256 (17)	C2—H2E	0.9900
Cd1—O21ⁱ	2.3173 (16)	C2—H2F	0.9900
Cd1—O21	2.3173 (16)	C3—H3E	0.9900
Cd1—O1	2.3409 (17)	C3—H3F	0.9900
Cd1—O1ⁱ	2.3409 (17)	C5—C6	1.517 (4)
Cd2—O12ⁱⁱ	2.1884 (17)	C5—H5E	0.9900
Cd2—O12	2.1884 (17)	C5—H5F	0.9900
Cd2—O3ⁱⁱ	2.2795 (16)	C6—H6E	0.9900
Cd2—O3	2.2795 (16)	C6—H6F	0.9900
Cd2—O2	2.3486 (16)	C13—H13A	0.9800
Cd2—O2ⁱⁱ	2.3486 (16)	C13—H13B	0.9800
O1—H1A	0.8439	C13—H13C	0.9800

O12—P1—O11	120.19 (11)	Cd2—O3—H3A	109.4
O12—P1—O13	109.73 (10)	Cd2—O3—H3B	118.2
O11—P1—O13	106.42 (10)	H3A—O3—H3B	107.4
O12—P1—C1	107.98 (10)	C3—O4—C5	110.07 (19)
O11—P1—C1	107.43 (10)	P1—O11—Cd1	132.97 (10)
O13—P1—C1	103.90 (10)	P1—O12—Cd2	165.00 (12)
O22—P2—O21	118.72 (10)	C13—O13—P1	121.93 (16)
O22—P2—N1	108.40 (10)	P2—O21—Cd1	133.58 (9)
O21—P2—N1	109.04 (10)	C6—N1—C2	111.82 (19)
O22—P2—C1	105.77 (10)	C6—N1—P2	124.48 (17)
O21—P2—C1	105.72 (10)	C2—N1—P2	123.28 (16)
N1—P2—C1	108.80 (11)	Cl1—C1—Cl2	108.31 (12)
O11—Cd1—O11ⁱ	166.14 (9)	Cl1—C1—P1	108.85 (12)
O11—Cd1—O21ⁱ	100.40 (6)	Cl2—C1—P1	108.55 (12)
O11ⁱ—Cd1—O21ⁱ	89.75 (6)	Cl1—C1—P2	107.53 (11)
O11—Cd1—O21	89.75 (6)	Cl2—C1—P2	107.98 (12)
O11ⁱ—Cd1—O21	100.40 (6)	P1—C1—P2	115.42 (12)
O21ⁱ—Cd1—O21	86.31 (8)	N1—C2—C3	109.5 (2)
O11—Cd1—O1	85.24 (6)	N1—C2—H2E	109.8
O11ⁱ—Cd1—O1	84.49 (6)	C3—C2—H2E	109.8
O21ⁱ—Cd1—O1	174.23 (5)	N1—C2—H2F	109.8
O21—Cd1—O1	95.00 (6)	C3—C2—H2F	109.8
O11—Cd1—O1ⁱ	84.49 (6)	H2E—C2—H2F	108.2
O11ⁱ—Cd1—O1ⁱ	85.24 (6)	O4—C3—C2	111.1 (2)
O21ⁱ—Cd1—O1ⁱ	95.00 (6)	O4—C3—H3E	109.4
O21—Cd1—O1ⁱ	174.23 (5)	C2—C3—H3E	109.4
O1—Cd1—O1ⁱ	84.25 (8)	O4—C3—H3F	109.4
O12ⁱⁱ—Cd2—O12	180.00 (9)	C2—C3—H3F	109.4
O12ⁱⁱ—Cd2—O3ⁱⁱ	82.50 (6)	H3E—C3—H3F	108.0
O12—Cd2—O3ⁱⁱ	97.50 (6)	O4—C5—C6	111.2 (2)
O12ⁱⁱ—Cd2—O3	97.50 (6)	O4—C5—H5E	109.4
O12—Cd2—O3	82.50 (6)	C6—C5—H5E	109.4
O3ⁱⁱ—Cd2—O3	180.00 (8)	O4—C5—H5F	109.4
O12ⁱⁱ—Cd2—O2	94.94 (6)	C6—C5—H5F	109.4
O12—Cd2—O2	85.06 (6)	H5E—C5—H5F	108.0
O3ⁱⁱ—Cd2—O2	92.88 (6)	N1—C6—C5	108.6 (2)
O3—Cd2—O2	87.12 (6)	N1—C6—H6E	110.0
O12ⁱⁱ—Cd2—O2ⁱⁱ	85.06 (6)	C5—C6—H6E	110.0
O12—Cd2—O2ⁱⁱ	94.94 (6)	N1—C6—H6F	110.0
O3ⁱⁱ—Cd2—O2ⁱⁱ	87.12 (6)	C5—C6—H6F	110.0
O3—Cd2—O2ⁱⁱ	92.88 (6)	H6E—C6—H6F	108.3
O2—Cd2—O2ⁱⁱ	180.0	O13—C13—H13A	109.5
Cd1—O1—H1A	117.7	O13—C13—H13B	109.5
Cd1—O1—H1B	118.1	H13A—C13—H13B	109.5
H1A—O1—H1B	101.1	O13—C13—H13C	109.5
Cd2—O2—H2A	112.6	H13A—C13—H13C	109.5
Cd2—O2—H2B	108.2	H13B—C13—H13C	109.5
H2A—O2—H2B	101.1

O12—P1—O11—Cd1	82.84 (17)	O21—P2—N1—C2	163.49 (18)
O13—P1—O11—Cd1	−151.80 (14)	C1—P2—N1—C2	−81.7 (2)
C1—P1—O11—Cd1	−41.01 (18)	O12—P1—C1—Cl1	174.59 (11)
O11ⁱ—Cd1—O11—P1	151.44 (15)	O11—P1—C1—Cl1	−54.41 (14)
O21ⁱ—Cd1—O11—P1	−72.10 (16)	O13—P1—C1—Cl1	58.11 (13)
O21—Cd1—O11—P1	14.09 (16)	O12—P1—C1—Cl2	56.89 (14)
O1—Cd1—O11—P1	109.13 (16)	O11—P1—C1—Cl2	−172.11 (11)
O1ⁱ—Cd1—O11—P1	−166.20 (16)	O13—P1—C1—Cl2	−59.59 (13)
O11—P1—O12—Cd2	−39.7 (5)	O12—P1—C1—P2	−64.44 (15)
O13—P1—O12—Cd2	−163.4 (4)	O11—P1—C1—P2	66.56 (15)
C1—P1—O12—Cd2	83.9 (5)	O13—P1—C1—P2	179.07 (11)
O3ⁱⁱ—Cd2—O12—P1	77.6 (4)	O22—P2—C1—Cl1	−173.74 (11)
O3—Cd2—O12—P1	−102.4 (4)	O21—P2—C1—Cl1	59.52 (13)
O2—Cd2—O12—P1	−14.7 (4)	N1—P2—C1—Cl1	−57.47 (14)
O2ⁱⁱ—Cd2—O12—P1	165.3 (4)	O22—P2—C1—Cl2	−57.06 (14)
O12—P1—O13—C13	−18.2 (2)	O21—P2—C1—Cl2	176.19 (10)
O11—P1—O13—C13	−149.7 (2)	N1—P2—C1—Cl2	59.21 (14)
C1—P1—O13—C13	97.1 (2)	O22—P2—C1—P1	64.58 (14)
O22—P2—O21—Cd1	−84.54 (15)	O21—P2—C1—P1	−62.16 (14)
N1—P2—O21—Cd1	150.72 (12)	N1—P2—C1—P1	−179.15 (11)
C1—P2—O21—Cd1	33.90 (15)	C6—N1—C2—C3	55.4 (3)
O11—Cd1—O21—P2	−10.33 (14)	P2—N1—C2—C3	−131.8 (2)
O11ⁱ—Cd1—O21—P2	179.17 (13)	C5—O4—C3—C2	59.5 (3)
O21ⁱ—Cd1—O21—P2	90.11 (13)	N1—C2—C3—O4	−56.6 (3)
O1—Cd1—O21—P2	−95.53 (13)	C3—O4—C5—C6	−60.6 (3)
O22—P2—N1—C6	−155.22 (19)	C2—N1—C6—C5	−55.9 (3)
O21—P2—N1—C6	−24.6 (2)	P2—N1—C6—C5	131.4 (2)
C1—P2—N1—C6	90.2 (2)	O4—C5—C6—N1	58.1 (3)
O22—P2—N1—C2	32.9 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱⁱⁱ	0.84	2.06	2.849 (2)	156
O1—H1B···O22^iv	0.88	2.12	2.990 (2)	170
O2—H2A···O21ⁱ	0.86	2.04	2.844 (2)	155
O2—H2B···O22	0.86	1.84	2.662 (2)	159
O3—H3A···O22	0.83	2.03	2.773 (2)	149
O3—H3B···O13^v	0.90	1.87	2.745 (2)	163

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

Experimental details

Crystal data
Chemical formula	[Cd(C₆H₁₁Cl₂NO₆P₂)(H₂O)₃]
M_r	492.45
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	120
a, b, c (Å)	26.2488 (8), 7.6578 (3), 17.5445 (7)
β (°)	116.002 (3)
V (Å³)	3169.6 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.96
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (XPREP in SHELXTL; Sheldrick, 2008)
T_min, T_max	0.565, 0.676
No. of measured, independent and observed [I > 2σ(I)] reflections	21828, 4053, 3370
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.068, 1.06
No. of reflections	4053
No. of parameters	195
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.04, −1.12

Computer programs: COLLECT (Nonius, 1997), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005).

Selected geometric parameters (Å, º) top

Cl1—C1	1.792 (2)	P2—N1	1.628 (2)
Cl2—C1	1.799 (2)	P2—C1	1.869 (2)
P1—O12	1.4803 (18)	Cd1—O11	2.2256 (17)
P1—O11	1.4829 (18)	Cd1—O21	2.3173 (16)
P1—O13	1.5922 (17)	Cd1—O1	2.3409 (17)
P1—C1	1.854 (2)	Cd2—O12	2.1884 (17)
P2—O22	1.5044 (17)	Cd2—O3	2.2795 (16)
P2—O21	1.5062 (16)	Cd2—O2	2.3486 (16)

O12—P1—O11	120.19 (11)	O22—P2—N1	108.40 (10)
O12—P1—O13	109.73 (10)	O21—P2—N1	109.04 (10)
O11—P1—O13	106.42 (10)	Cl1—C1—Cl2	108.31 (12)
O22—P2—O21	118.72 (10)	P1—C1—P2	115.42 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱ	0.84	2.06	2.849 (2)	155.6
O1—H1B···O22ⁱⁱ	0.88	2.12	2.990 (2)	170.1
O2—H2A···O21ⁱⁱⁱ	0.86	2.04	2.844 (2)	155.4
O2—H2B···O22	0.86	1.84	2.662 (2)	159.3
O3—H3A···O22	0.83	2.03	2.773 (2)	149.4
O3—H3B···O13^iv	0.90	1.87	2.745 (2)	163.2

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

References

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