Poly[[μ-aqua-aqua­[μ4-ethyl (dichloro­methyl­ene)diphospho­nato]sesqui­calcium(II)] acetone hemisolvate 4.5-hydrate]

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

doi:10.1107/S1600536809010150

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages m436-m437

doi:10.1107/S1600536809010150

Open

access

Poly[[μ-aqua-aqua[μ₄-ethyl (dichloromethylene)diphosphonato]sesquicalcium(II)] acetone hemisolvate 4.5-hydrate]

Jonna Jokiniemi,^a ^* Sirpa Peräniemi,^b 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 19 March 2009; online 25 March 2009)

The title compound, {[Ca_1.5(C₃H₅Cl₂O₆P₂)(H₂O)₂]·0.5CH₃COCH₃·4.5H₂O}_n, has a two-dimensional polymeric structure. The asymmetric unit contains two crystallographically independent Ca²⁺ cations connected by a chelating and bridging ethyl (dichloromethylene)diphosphonate(3⁻) ligand and an aqua ligand. One of the Ca atoms, lying on a centre of symmetry, has a slightly distorted octahedral geometry, while the other Ca atom is seven-coordinated in a distorted monocapped trigonal-prismatic geometry. The polymeric layers are further connected by extensive O—H⋯O hydrogen bonding into a three-dimensional supramolecular network. The acetone solvent molecule and one uncoordinated water molecule are located on twofold rotation axes.

Related literature

For applications of metal complexes of bisphosphonates, see: Clearfield et al. (2001 ); Clearfield (1998 ); Fu et al. (2007 ); Serre et al. (2006 ). For calcium bisphosphonate complexes, see: Lin et al. (2007 ); Mathew et al. (1998 ). For metal complexes of bisphosphonate ester derivatives, see: Jokiniemi et al. (2007 , 2008 ).

Experimental

Crystal data

[Ca_1.5(C₃H₅Cl₂O₆P₂)(H₂O)₂]·0.5C₃H₆O·4.5H₂O
M_r = 476.17
Monoclinic, C 2/c
a = 31.2205 (3) Å
b = 10.1546 (1) Å
c = 11.6510 (1) Å
β = 103.107 (1)°
V = 3597.51 (6) Å³
Z = 8
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 150 K
0.25 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008 ) T_min = 0.823, T_max = 0.905
31118 measured reflections
4209 independent reflections
3617 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.073
S = 1.10
4209 reflections
213 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Selected bond lengths (Å)

Ca1—O1	2.3778 (14)
Ca1—O11	2.2278 (14)
Ca1—O21	2.3279 (15)
Ca2—O1	2.5726 (15)
Ca2—O2	2.4024 (15)
Ca2—O11ⁱ	2.4049 (15)
Ca2—O12	2.3466 (14)
Ca2—O13ⁱⁱ	2.3320 (15)
Ca2—O13ⁱ	2.5858 (15)
Ca2—O22	2.3158 (15)
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O3	0.99	1.81	2.794 (2)	171
O1—H1A⋯O12ⁱⁱ	0.99	1.83	2.637 (2)	137
O2—H2A⋯O3	0.84	1.88	2.717 (2)	172
O2—H2B⋯O21ⁱⁱⁱ	0.85	1.90	2.746 (2)	177
O3—H3A⋯O6^iv	0.86	1.93	2.782 (2)	175
O3—H3B⋯O4ⁱⁱⁱ	0.86	1.89	2.734 (2)	169
O4—H4A⋯O22	0.85	2.00	2.841 (2)	166
O4—H4B⋯O2^iv	0.85	1.93	2.754 (2)	163
O5—H5A⋯O4	0.85	2.02	2.838 (2)	163
O5—H5B⋯O6	0.85	2.05	2.901 (3)	171
O6—H6A⋯O8	0.85	2.02	2.831 (2)	161
O6—H6B⋯O7^v	0.84	2.26	2.832 (2)	125
O7—H7⋯O5	0.84	1.98	2.799 (2)	166
Symmetry codes: (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (v) -x, -y+1, -z+1.

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/S1600536809010150/xu2487sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010150/xu2487Isup2.hkl

checkCIF report

Comment top

Metal bisphosphonates have been attracting closer attention in light of their important applications in industrial processes such as ion-exchange, catalysis and sorption (Clearfield et al., 2001, Clearfield, 1998, Fu et al., 2007). Metal bisphosphonates usually adopt layered or pillared layered structures (Fu et al., 2007, Mathew et al., 1998). Other structural types, such as 1-D and 3-D open networks, have also been prepared in order to study the properties of bisphosphonate solid materials (Lin et al., 2007, Fu et al., 2007). Most of the effective materials consist of open frameworks and microporous structures (Fu et al., 2007, Serre et al., 2006). In recent investigations, we studied the complexing properties of amide ester derivatives of (dichloromethylene)bisphosphonate, Cl₂MBP (Jokiniemi et al., 2007, 2008). The introduction of various ester substituents into phosphonate groups can results in novel structures of metal bisphosphonates and lead to interesting functionalities. Of the numerous metal phosphonate compounds now known, only a small number have been prepared with alkali earth metals. We now present the crystal structure of the Ca(II) complex of the monoethyl ester derivative of Cl₂MBP obtained by gel crystallization.

The title compound consists of two-dimensional layers parallel to the (100) plane. The Ca1 atom lies on the centre of symmetry with two symmetrically chelating (Cl₂CP₂O₆Et)^3- ligands and two aqua ligands in axial positions; the geometry is slightly distorted octahedron with Ca1–O bond lengths of 2.228 (1)–2.378 (1) Å (Table 1, Fig. 1). The three trans bond angles are 180.0°, while the cis bond angles range from 84.12 (5) to 95.88 (5)°. The aqua ligand O1 bridges Ca1 and the adjacent Ca2 atom with Ca···Ca distance of 4.4283 (4) Å. The Ca2 atom is seven-coordinated in distorted monocapped trigonal prismatic geometry and is coordinated by five phosphonate O atoms from three different (Cl₂CP₂O₆Et)^3- ligands. The coordination sphere is completed by two aqua ligands. The Ca2–O bond lengths are 2.316 (2)–2.586 (2) Å. The (Cl₂CP₂O₆Et)^3- ligand is coordinated to four Ca²⁺ cations through five O atoms forming two six-membered chelate rings with Ca1 and Ca2 atoms, and the P1 atom forms a four-membered chelate ring with the adjacent Ca2D atom (x, -y, z - 1/2). Thus, the two oxygen atoms (O11, O13) act as monoatomic bridges between two Ca atoms.

The layers are further connected by extensive hydrogen bonding (O···O 2.637 (2)–2.901 (3) Å, 125–177°) into a 3-D network with the interlayer distance of 15.2036 (2) Å (Fig. 2, Table 2). The O8 and C2 atoms of the acetone molecule, as well as the water molecule O7, are located on the individual two-fold rotation axis. The ethyl groups and chlorine atoms point out from the layers.

Related literature top

For applications of metal complexes of bisphosphonates, see: Clearfield et al. (2001); Clearfield (1998); Fu et al. (2007); Serre et al. (2006). For calcium bisphosphonate complexes, see: Lin et al. (2007); Mathew et al. (1998). For metal complexes of bisphosphonate ester derivatives, see: Jokiniemi et al. (2007, 2008).

Experimental top

Na₃Cl₂CP₂O₆Et (10.0 mg, 0.030 mmol) and CaCl₂.2H₂O (4.3 mg, 0.030 mmol) were dissolved separately in water (2.25 ml), the solutions were mixed, and tetramethoxysilane (TMOS 0.5 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 months, colourless crystals suitable for X-ray analysis were formed uniformly throughout the gel as thin needles. The elemental analyses were performed several times and the results were consistent indicating that the acetone molecule and 3.5 water molecules were evaporated when the crystals were dried in air.

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. A part of the polymeric structure of the title compound showing the atomic numbering scheme and 50% probability displacement ellipsoids for non-H atoms. Hydrogen bonds are shown as dashed lines. Atoms labelled with suffixes A–F are at the symmetry positions (1/2 - x, 1/2 - y, -z), (1/2 - x, 1/2 + y, 1/2 - z), (x, -y, 1/2 + z), (x, -y, z - 1/2), (1/2 - x, y - 1/2, 1/2 - z) and (- x, y, 3/2 - z), respectively.

Fig. 2. Packing of the title compound viewed along the c-axis showing the hydrogen bond interactions. CaO₆ and CaO₇ polyhedra are presented in light grey and PO₃C tetrahedra in dark grey. Ethyl groups, chlorine atoms and H atoms of the acetone molecules are omitted for clarity.

Poly[[µ-aqua-aqua[µ₄-ethyl (dichloromethylene)diphosphonato]sesquicalcium(II)] acetone hemisolvate 4.5-hydrate] top

Crystal data top

[Ca_1.5(C₃H₅Cl₂O₆P₂)(H₂O)₂]·0.5C₃H₆O·4.5H₂O	F(000) = 1968
M_r = 476.17	D_x = 1.758 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 31118 reflections
a = 31.2205 (3) Å	θ = 2.7–28.0°
b = 10.1546 (1) Å	µ = 1.02 mm⁻¹
c = 11.6510 (1) Å	T = 150 K
β = 103.107 (1)°	Needle, colourless
V = 3597.51 (6) Å³	0.25 × 0.15 × 0.10 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer	4209 independent reflections
Radiation source: fine-focus sealed tube	3617 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ϕ scans, and ω scans with κ offsets	θ_max = 28.0°, θ_min = 2.7°
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008)	h = −40→40
T_min = 0.823, T_max = 0.905	k = −13→13
31118 measured reflections	l = −14→15

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.02P)² + 12P] where P = (F_o² + 2F_c²)/3
4209 reflections	(Δ/σ)_max = 0.001
213 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Ca_1.5(C₃H₅Cl₂O₆P₂)(H₂O)₂]·0.5C₃H₆O·4.5H₂O	V = 3597.51 (6) Å³
M_r = 476.17	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 31.2205 (3) Å	µ = 1.02 mm⁻¹
b = 10.1546 (1) Å	T = 150 K
c = 11.6510 (1) Å	0.25 × 0.15 × 0.10 mm
β = 103.107 (1)°

Data collection top

Nonius KappaCCD diffractometer	4209 independent reflections
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008)	3617 reflections with I > 2σ(I)
T_min = 0.823, T_max = 0.905	R_int = 0.055
31118 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.02P)² + 12P] where P = (F_o² + 2F_c²)/3
4209 reflections	Δρ_max = 0.47 e Å⁻³
213 parameters	Δρ_min = −0.58 e Å⁻³

Special details top

Experimental. These results are supported by the IR spectrum and TG analysis. Anal. Found: C, 9.30; H, 3.06%. Calc. for C₃H₁₁Cl₂Ca_1.5O₉P₂: C, 9.38; H, 2.89%. Main IR absorptions (KBr pellet, cm^-1): 3385 (b,s), 2995 (w), 1648 (b,m), 1389 (m), 1213 (s), 1148 (s), 1105 (versus), 1082 (versus), 1048 (m), 1008 (m), 959 (m), 871 (m), 852 (w), 760 (m). ³¹P CP/MAS NMR: δ_P 7.4 and 5.1 p.p.m.. TGA (25–700 °C under a synthetic air): 25–180 °C 13.1% (calculated 14.1% for the loss of three water molecules). The observed total weight loss is 40.0% (calculated 41.1% if the final product is assumed to be a mixture of Ca(PO₃)₂ and CaO in a molar ratio of 2:1).

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
Ca1	0.2500	0.2500	0.0000	0.00999 (12)
Ca2	0.248223 (14)	0.12782 (4)	0.36375 (3)	0.00930 (9)
Cl1	0.129792 (17)	−0.08747 (5)	0.13650 (4)	0.01375 (11)
Cl2	0.137474 (18)	0.01918 (5)	−0.08762 (4)	0.01548 (11)
P1	0.218448 (17)	−0.04904 (5)	0.08794 (4)	0.00900 (11)
P2	0.160183 (17)	0.18410 (5)	0.12307 (5)	0.00960 (11)
O1	0.28281 (5)	0.23098 (14)	0.20444 (12)	0.0126 (3)
H1A	0.2911	0.3217	0.2318	0.015*
H1B	0.3108	0.1830	0.2091	0.015*
O2	0.32098 (5)	0.03608 (14)	0.41612 (13)	0.0129 (3)
H2A	0.3353	0.0476	0.3639	0.019*
H2B	0.3198	−0.0467	0.4244	0.019*
O3	0.36311 (5)	0.09774 (16)	0.24321 (14)	0.0178 (3)
H3A	0.3899	0.1215	0.2683	0.027*
H3B	0.3643	0.0198	0.2163	0.027*
O4	0.13454 (5)	0.36331 (16)	0.37057 (14)	0.0180 (3)
H4A	0.1472	0.3000	0.3430	0.027*
H4B	0.1530	0.3864	0.4332	0.027*
O5	0.05044 (6)	0.30916 (18)	0.41409 (16)	0.0269 (4)
H5A	0.0775	0.3154	0.4142	0.040*
H5B	0.0476	0.3118	0.4851	0.040*
O6	0.05040 (6)	0.32700 (17)	0.66254 (16)	0.0238 (4)
H6A	0.0405	0.2579	0.6883	0.036*
H6B	0.0285	0.3765	0.6374	0.036*
O7	0.0000	0.4816 (2)	0.2500	0.0224 (5)
H7	0.0189	0.4385	0.2985	0.034*
O8	0.0000	0.1357 (2)	0.7500	0.0265 (6)
O11	0.24121 (5)	0.03290 (14)	0.00999 (12)	0.0107 (3)
O12	0.23607 (5)	−0.03674 (14)	0.21857 (12)	0.0108 (3)
O13	0.21597 (5)	−0.18636 (14)	0.04307 (12)	0.0103 (3)
O21	0.18181 (5)	0.26929 (14)	0.04781 (13)	0.0116 (3)
O22	0.17957 (5)	0.18469 (14)	0.25168 (12)	0.0115 (3)
O23	0.10987 (5)	0.21652 (15)	0.10779 (13)	0.0132 (3)
C1	0.16168 (7)	0.0176 (2)	0.06555 (17)	0.0104 (4)
C21	0.08235 (8)	0.2669 (2)	0.0003 (2)	0.0196 (5)
H21A	0.0615	0.1982	−0.0384	0.024*
H21B	0.1006	0.2944	−0.0548	0.024*
C22	0.05800 (9)	0.3813 (3)	0.0325 (3)	0.0292 (6)
H22A	0.0416	0.3541	0.0911	0.044*
H22B	0.0374	0.4143	−0.0380	0.044*
H22C	0.0788	0.4511	0.0656	0.044*
C2	0.0000	0.0182 (3)	0.7500	0.0228 (7)
C3	−0.02303 (10)	−0.0568 (3)	0.8273 (3)	0.0394 (7)
H3C	−0.0317	0.0033	0.8837	0.059*
H3D	−0.0033	−0.1244	0.8701	0.059*
H3E	−0.0493	−0.0990	0.7791	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0143 (3)	0.0066 (3)	0.0097 (3)	−0.0003 (2)	0.0041 (2)	0.0006 (2)
Ca2	0.0130 (2)	0.00660 (18)	0.00840 (19)	−0.00024 (15)	0.00261 (15)	0.00003 (14)
Cl1	0.0156 (2)	0.0112 (2)	0.0157 (3)	−0.00233 (19)	0.00603 (19)	0.00042 (18)
Cl2	0.0205 (3)	0.0151 (2)	0.0094 (2)	0.0024 (2)	0.00041 (19)	−0.00142 (18)
P1	0.0129 (3)	0.0059 (2)	0.0088 (3)	0.00034 (19)	0.00368 (19)	0.00012 (18)
P2	0.0122 (3)	0.0072 (2)	0.0097 (3)	0.00102 (19)	0.0030 (2)	0.00008 (18)
O1	0.0177 (8)	0.0088 (7)	0.0112 (7)	−0.0003 (6)	0.0030 (6)	−0.0011 (5)
O2	0.0160 (7)	0.0083 (7)	0.0154 (8)	−0.0001 (6)	0.0054 (6)	0.0010 (6)
O3	0.0171 (8)	0.0164 (8)	0.0199 (8)	0.0005 (6)	0.0045 (6)	0.0000 (6)
O4	0.0205 (8)	0.0176 (8)	0.0152 (8)	0.0029 (6)	0.0027 (6)	−0.0036 (6)
O5	0.0227 (9)	0.0291 (10)	0.0296 (10)	−0.0008 (8)	0.0074 (7)	−0.0014 (8)
O6	0.0200 (9)	0.0214 (9)	0.0297 (10)	−0.0012 (7)	0.0053 (7)	0.0032 (7)
O7	0.0205 (12)	0.0243 (13)	0.0216 (12)	0.000	0.0032 (10)	0.000
O8	0.0306 (14)	0.0174 (12)	0.0344 (15)	0.000	0.0130 (11)	0.000
O11	0.0159 (7)	0.0068 (7)	0.0109 (7)	0.0000 (6)	0.0057 (6)	0.0007 (5)
O12	0.0146 (7)	0.0086 (7)	0.0092 (7)	0.0005 (6)	0.0027 (6)	−0.0010 (5)
O13	0.0137 (7)	0.0072 (7)	0.0103 (7)	0.0009 (5)	0.0030 (6)	−0.0011 (5)
O21	0.0155 (7)	0.0068 (7)	0.0135 (7)	0.0009 (6)	0.0052 (6)	0.0003 (5)
O22	0.0146 (7)	0.0095 (7)	0.0102 (7)	0.0017 (6)	0.0025 (6)	−0.0010 (5)
O23	0.0130 (7)	0.0128 (7)	0.0138 (7)	0.0040 (6)	0.0031 (6)	0.0019 (6)
C1	0.0134 (10)	0.0085 (9)	0.0095 (10)	−0.0008 (8)	0.0031 (8)	0.0006 (7)
C21	0.0190 (11)	0.0221 (12)	0.0155 (11)	0.0052 (9)	−0.0009 (9)	0.0015 (9)
C22	0.0262 (13)	0.0223 (13)	0.0356 (15)	0.0100 (11)	−0.0002 (11)	0.0030 (11)
C2	0.0166 (16)	0.0189 (17)	0.033 (2)	0.000	0.0050 (14)	0.000
C3	0.0362 (16)	0.0276 (15)	0.061 (2)	0.0062 (13)	0.0253 (15)	0.0149 (14)

Geometric parameters (Å, º) top

Ca1—O1ⁱ	2.3778 (14)	P2—O22	1.4834 (15)
Ca1—O1	2.3778 (14)	P2—O21	1.4972 (15)
Ca1—O11	2.2278 (14)	P2—O23	1.5750 (15)
Ca1—O11ⁱ	2.2278 (14)	P2—C1	1.823 (2)
Ca1—O21ⁱ	2.3279 (15)	O1—H1A	0.9900
Ca1—O21	2.3279 (15)	O1—H1B	0.9900
Ca1—P2ⁱ	3.4915 (5)	O2—H2A	0.8414
Ca1—P2	3.4915 (5)	O2—H2B	0.8477
Ca1—P1ⁱ	3.4204 (5)	O3—H3A	0.8560
Ca1—P1	3.4204 (5)	O3—H3B	0.8554
Ca1—Ca2ⁱⁱ	4.1476 (4)	O4—H4A	0.8541
Ca1—Ca2ⁱⁱⁱ	4.1476 (4)	O4—H4B	0.8536
Ca2—O1	2.5726 (15)	O5—H5A	0.8468
Ca2—O2	2.4024 (15)	O5—H5B	0.8525
Ca2—O11^iv	2.4049 (15)	O6—H6A	0.8481
Ca2—O12	2.3466 (14)	O6—H6B	0.8448
Ca2—O13ⁱⁱⁱ	2.3320 (15)	O7—H7	0.8416
Ca2—O13^iv	2.5858 (15)	O8—C2	1.193 (4)
Ca2—O22	2.3158 (15)	O11—Ca2ⁱⁱ	2.4049 (15)
Ca2—P1^iv	3.0705 (6)	O13—Ca2^vi	2.3320 (15)
Ca2—P1ⁱⁱⁱ	3.4498 (6)	O13—Ca2ⁱⁱ	2.5858 (15)
Ca2—P2	3.4999 (7)	O23—C21	1.442 (3)
Ca2—Ca2^v	4.0111 (8)	C21—C22	1.482 (3)
Ca2—Ca1^vi	4.1476 (4)	C21—H21A	0.9900
Ca2—H2A	2.8382	C21—H21B	0.9900
Ca2—H2B	2.8142	C22—H22A	0.9800
Cl1—C1	1.785 (2)	C22—H22B	0.9800
Cl2—C1	1.773 (2)	C22—H22C	0.9800
P1—O13	1.4851 (15)	C2—C3^vii	1.484 (3)
P1—O12	1.5016 (15)	C2—C3	1.484 (3)
P1—O11	1.5216 (15)	C3—H3C	0.9800
P1—C1	1.860 (2)	C3—H3D	0.9800
P1—Ca2ⁱⁱ	3.0705 (6)	C3—H3E	0.9800
P1—Ca2^vi	3.4498 (6)

O21ⁱ—Ca1—O21	180.00 (6)	P2—Ca2—Ca2^v	114.135 (18)
O21ⁱ—Ca1—O11	93.40 (5)	O22—Ca2—Ca1^vi	112.14 (4)
O21—Ca1—O11	86.60 (5)	O13ⁱⁱⁱ—Ca2—Ca1^vi	127.37 (4)
O21ⁱ—Ca1—O11ⁱ	86.60 (5)	O2—Ca2—Ca1^vi	67.31 (4)
O21—Ca1—O11ⁱ	93.40 (5)	O12—Ca2—Ca1^vi	66.62 (4)
O11—Ca1—O11ⁱ	180.00 (8)	O11^iv—Ca2—Ca1^vi	25.39 (3)
O21ⁱ—Ca1—O1ⁱ	88.67 (5)	O1—Ca2—Ca1^vi	132.96 (4)
O21—Ca1—O1ⁱ	91.33 (5)	O13^iv—Ca2—Ca1^vi	82.95 (3)
O11—Ca1—O1ⁱ	95.88 (5)	P1^iv—Ca2—Ca1^vi	54.110 (11)
O11ⁱ—Ca1—O1ⁱ	84.12 (5)	P1ⁱⁱⁱ—Ca2—Ca1^vi	147.146 (14)
O21ⁱ—Ca1—O1	91.33 (5)	P2—Ca2—Ca1^vi	113.429 (13)
O21—Ca1—O1	88.67 (5)	Ca2^v—Ca2—Ca1^vi	105.887 (14)
O11—Ca1—O1	84.12 (5)	O22—Ca2—H2A	146.7
O11ⁱ—Ca1—O1	95.88 (5)	O13ⁱⁱⁱ—Ca2—H2A	82.8
O1ⁱ—Ca1—O1	180.00 (11)	O2—Ca2—H2A	15.8
O21ⁱ—Ca1—P2ⁱ	19.02 (4)	O12—Ca2—H2A	78.1
O21—Ca1—P2ⁱ	160.98 (4)	O11^iv—Ca2—H2A	92.6
O11—Ca1—P2ⁱ	109.33 (4)	O1—Ca2—H2A	63.8
O11ⁱ—Ca1—P2ⁱ	70.67 (4)	O13^iv—Ca2—H2A	127.9
O1ⁱ—Ca1—P2ⁱ	77.10 (4)	P1^iv—Ca2—H2A	113.6
O1—Ca1—P2ⁱ	102.90 (4)	P1ⁱⁱⁱ—Ca2—H2A	91.1
O21ⁱ—Ca1—P2	160.98 (4)	P2—Ca2—H2A	128.7
O21—Ca1—P2	19.02 (4)	Ca2^v—Ca2—H2A	108.8
O11—Ca1—P2	70.67 (4)	Ca1^vi—Ca2—H2A	78.7
O11ⁱ—Ca1—P2	109.33 (4)	O22—Ca2—H2B	151.6
O1ⁱ—Ca1—P2	102.90 (4)	O13ⁱⁱⁱ—Ca2—H2B	97.1
O1—Ca1—P2	77.10 (4)	O2—Ca2—H2B	16.4
P2ⁱ—Ca1—P2	180.000 (18)	O12—Ca2—H2B	73.8
O21ⁱ—Ca1—P1ⁱ	70.24 (4)	O11^iv—Ca2—H2B	65.8
O21—Ca1—P1ⁱ	109.76 (4)	O1—Ca2—H2B	89.9
O11—Ca1—P1ⁱ	160.29 (4)	O13^iv—Ca2—H2B	112.0
O11ⁱ—Ca1—P1ⁱ	19.71 (4)	P1^iv—Ca2—H2B	89.9
O1ⁱ—Ca1—P1ⁱ	73.49 (4)	P1ⁱⁱⁱ—Ca2—H2B	111.4
O1—Ca1—P1ⁱ	106.51 (4)	P2—Ca2—H2B	137.6
P2ⁱ—Ca1—P1ⁱ	52.709 (12)	Ca2^v—Ca2—H2B	108.2
P2—Ca1—P1ⁱ	127.291 (12)	Ca1^vi—Ca2—H2B	51.7
O21ⁱ—Ca1—P1	109.76 (4)	H2A—Ca2—H2B	27.5
O21—Ca1—P1	70.24 (4)	O13—P1—O12	114.38 (8)
O11—Ca1—P1	19.71 (4)	O13—P1—O11	107.30 (8)
O11ⁱ—Ca1—P1	160.29 (4)	O12—P1—O11	116.49 (8)
O1ⁱ—Ca1—P1	106.51 (4)	O13—P1—C1	108.70 (9)
O1—Ca1—P1	73.49 (4)	O12—P1—C1	103.32 (9)
P2ⁱ—Ca1—P1	127.291 (12)	O11—P1—C1	106.05 (9)
P2—Ca1—P1	52.709 (12)	O13—P1—Ca2ⁱⁱ	57.15 (6)
P1ⁱ—Ca1—P1	180.000 (17)	O12—P1—Ca2ⁱⁱ	140.52 (6)
O21ⁱ—Ca1—Ca2ⁱⁱ	76.36 (4)	O11—P1—Ca2ⁱⁱ	50.37 (6)
O21—Ca1—Ca2ⁱⁱ	103.64 (4)	C1—P1—Ca2ⁱⁱ	116.00 (7)
O11—Ca1—Ca2ⁱⁱ	27.57 (4)	O12—P1—Ca2^vi	83.46 (6)
O11ⁱ—Ca1—Ca2ⁱⁱ	152.43 (4)	O11—P1—Ca2^vi	116.94 (6)
O1ⁱ—Ca1—Ca2ⁱⁱ	74.12 (4)	C1—P1—Ca2^vi	127.72 (7)
O1—Ca1—Ca2ⁱⁱ	105.88 (4)	Ca2ⁱⁱ—P1—Ca2^vi	75.679 (16)
P2ⁱ—Ca1—Ca2ⁱⁱ	87.845 (10)	O13—P1—Ca1	136.36 (6)
P2—Ca1—Ca2ⁱⁱ	92.155 (10)	O12—P1—Ca1	99.53 (6)
P1ⁱ—Ca1—Ca2ⁱⁱ	133.342 (10)	C1—P1—Ca1	87.98 (6)
P1—Ca1—Ca2ⁱⁱ	46.658 (10)	Ca2ⁱⁱ—P1—Ca1	79.232 (14)
O21ⁱ—Ca1—Ca2ⁱⁱⁱ	103.64 (4)	Ca2^vi—P1—Ca1	142.808 (18)
O21—Ca1—Ca2ⁱⁱⁱ	76.36 (4)	O22—P2—O21	117.03 (9)
O11—Ca1—Ca2ⁱⁱⁱ	152.43 (4)	O22—P2—O23	106.35 (8)
O11ⁱ—Ca1—Ca2ⁱⁱⁱ	27.57 (4)	O21—P2—O23	112.56 (8)
O1ⁱ—Ca1—Ca2ⁱⁱⁱ	105.88 (4)	O22—P2—C1	109.66 (9)
O1—Ca1—Ca2ⁱⁱⁱ	74.12 (4)	O21—P2—C1	105.54 (9)
P2ⁱ—Ca1—Ca2ⁱⁱⁱ	92.155 (10)	O23—P2—C1	105.09 (9)
P2—Ca1—Ca2ⁱⁱⁱ	87.845 (10)	O22—P2—Ca1	103.43 (6)
P1ⁱ—Ca1—Ca2ⁱⁱⁱ	46.658 (10)	O23—P2—Ca1	141.89 (6)
P1—Ca1—Ca2ⁱⁱⁱ	133.342 (10)	C1—P2—Ca1	86.38 (7)
Ca2ⁱⁱ—Ca1—Ca2ⁱⁱⁱ	180.000 (14)	O21—P2—Ca2	100.78 (6)
O22—Ca2—O13ⁱⁱⁱ	110.21 (5)	O23—P2—Ca2	134.96 (6)
O22—Ca2—O2	160.19 (5)	C1—P2—Ca2	93.57 (7)
O13ⁱⁱⁱ—Ca2—O2	82.51 (5)	Ca1—P2—Ca2	78.603 (13)
O22—Ca2—O12	78.08 (5)	Ca1—O1—Ca2	126.86 (6)
O13ⁱⁱⁱ—Ca2—O12	153.36 (5)	Ca1—O1—H1A	105.6
O2—Ca2—O12	84.02 (5)	Ca2—O1—H1A	105.6
O22—Ca2—O11^iv	110.33 (5)	Ca1—O1—H1B	105.6
O13ⁱⁱⁱ—Ca2—O11^iv	109.29 (5)	Ca2—O1—H1B	105.6
O2—Ca2—O11^iv	77.85 (5)	H1A—O1—H1B	106.1
O12—Ca2—O11^iv	90.09 (5)	Ca2—O2—H2A	112.9
O22—Ca2—O1	88.74 (5)	Ca2—O2—H2B	110.5
O13ⁱⁱⁱ—Ca2—O1	76.76 (5)	H2A—O2—H2B	105.3
O2—Ca2—O1	79.26 (5)	H3A—O3—H3B	105.4
O12—Ca2—O1	78.20 (5)	H4A—O4—H4B	104.4
O11^iv—Ca2—O1	155.24 (5)	H5A—O5—H5B	108.6
O22—Ca2—O13^iv	85.30 (5)	H6A—O6—H6B	106.6
O13ⁱⁱⁱ—Ca2—O13^iv	70.81 (6)	P1—O11—Ca1	130.70 (8)
O2—Ca2—O13^iv	113.76 (5)	P1—O11—Ca2ⁱⁱ	100.46 (7)
O12—Ca2—O13^iv	135.83 (5)	Ca1—O11—Ca2ⁱⁱ	127.05 (6)
O11^iv—Ca2—O13^iv	57.92 (5)	P1—O12—Ca2	138.76 (9)
O1—Ca2—O13^iv	142.51 (5)	P1—O13—Ca2^vi	127.93 (8)
O22—Ca2—P1^iv	97.16 (4)	P1—O13—Ca2ⁱⁱ	94.01 (7)
O13ⁱⁱⁱ—Ca2—P1^iv	91.17 (4)	Ca2^vi—O13—Ca2ⁱⁱ	109.19 (6)
O2—Ca2—P1^iv	97.71 (4)	P2—O21—Ca1	130.53 (8)
O12—Ca2—P1^iv	113.39 (4)	P2—O22—Ca2	133.01 (9)
O11^iv—Ca2—P1^iv	29.16 (3)	C21—O23—P2	123.71 (14)
O1—Ca2—P1^iv	167.82 (4)	Cl2—C1—Cl1	108.43 (11)
O13^iv—Ca2—P1^iv	28.85 (3)	Cl2—C1—P1	108.63 (11)
O22—Ca2—P1ⁱⁱⁱ	93.51 (4)	Cl1—C1—P1	109.34 (11)
O13ⁱⁱⁱ—Ca2—P1ⁱⁱⁱ	19.85 (4)	Cl2—C1—P2	108.74 (11)
O2—Ca2—P1ⁱⁱⁱ	95.43 (4)	Cl1—C1—P2	108.71 (11)
O12—Ca2—P1ⁱⁱⁱ	142.04 (4)	P1—C1—P2	112.90 (11)
O11^iv—Ca2—P1ⁱⁱⁱ	127.05 (4)	O23—C21—C22	107.30 (19)
O1—Ca2—P1ⁱⁱⁱ	64.53 (3)	O23—C21—H21A	110.3
O13^iv—Ca2—P1ⁱⁱⁱ	78.92 (3)	C22—C21—H21A	110.3
P1^iv—Ca2—P1ⁱⁱⁱ	104.321 (16)	O23—C21—H21B	110.3
O22—Ca2—P2	18.06 (4)	C22—C21—H21B	110.3
O13ⁱⁱⁱ—Ca2—P2	116.57 (4)	H21A—C21—H21B	108.5
O2—Ca2—P2	142.41 (4)	C21—C22—H22A	109.5
O12—Ca2—P2	64.50 (4)	C21—C22—H22B	109.5
O11^iv—Ca2—P2	119.83 (4)	H22A—C22—H22B	109.5
O1—Ca2—P2	74.77 (4)	C21—C22—H22C	109.5
O13^iv—Ca2—P2	103.35 (3)	H22A—C22—H22C	109.5
P1^iv—Ca2—P2	112.947 (18)	H22B—C22—H22C	109.5
P1ⁱⁱⁱ—Ca2—P2	97.378 (15)	O8—C2—C3^vii	120.89 (17)
O22—Ca2—Ca2^v	98.51 (4)	O8—C2—C3	120.89 (17)
O13ⁱⁱⁱ—Ca2—Ca2^v	37.50 (4)	C3^vii—C2—C3	118.2 (3)
O2—Ca2—Ca2^v	100.60 (4)	C2—C3—H3C	109.5
O12—Ca2—Ca2^v	169.12 (4)	C2—C3—H3D	109.5
O11^iv—Ca2—Ca2^v	81.36 (4)	H3C—C3—H3D	109.5
O1—Ca2—Ca2^v	112.23 (4)	C2—C3—H3E	109.5
O13^iv—Ca2—Ca2^v	33.30 (3)	H3C—C3—H3E	109.5
P1^iv—Ca2—Ca2^v	56.443 (13)	H3D—C3—H3E	109.5
P1ⁱⁱⁱ—Ca2—Ca2^v	47.877 (12)

Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x, −y, z−1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, −y, z+1/2; (v) −x+1/2, −y+1/2, −z+1; (vi) −x+1/2, y−1/2, −z+1/2; (vii) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O3	0.99	1.81	2.794 (2)	171
O1—H1A···O12ⁱⁱⁱ	0.99	1.83	2.637 (2)	137
O2—H2A···O3	0.84	1.88	2.717 (2)	172
O2—H2B···O21^vi	0.85	1.90	2.746 (2)	177
O3—H3A···O6^v	0.86	1.93	2.782 (2)	175
O3—H3B···O4^vi	0.86	1.89	2.734 (2)	169
O4—H4A···O22	0.85	2.00	2.841 (2)	166
O4—H4B···O2^v	0.85	1.93	2.754 (2)	163
O5—H5A···O4	0.85	2.02	2.838 (2)	163
O5—H5B···O6	0.85	2.05	2.901 (3)	171
O6—H6A···O8	0.85	2.02	2.831 (2)	161
O6—H6B···O7^viii	0.84	2.26	2.832 (2)	125
O7—H7···O5	0.84	1.98	2.799 (2)	166

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

Experimental details

Crystal data
Chemical formula	[Ca_1.5(C₃H₅Cl₂O₆P₂)(H₂O)₂]·0.5C₃H₆O·4.5H₂O
M_r	476.17
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	31.2205 (3), 10.1546 (1), 11.6510 (1)
β (°)	103.107 (1)
V (Å³)	3597.51 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.25 × 0.15 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (XPREP in SHELXTL; Sheldrick, 2008)
T_min, T_max	0.823, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	31118, 4209, 3617
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.073, 1.10
No. of reflections	4209
No. of parameters	213
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.02P)² + 12P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.58

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

Selected bond lengths (Å) top

Ca1—O1	2.3778 (14)	Ca2—O11ⁱ	2.4049 (15)
Ca1—O11	2.2278 (14)	Ca2—O12	2.3466 (14)
Ca1—O21	2.3279 (15)	Ca2—O13ⁱⁱ	2.3320 (15)
Ca2—O1	2.5726 (15)	Ca2—O13ⁱ	2.5858 (15)
Ca2—O2	2.4024 (15)	Ca2—O22	2.3158 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O3	0.99	1.81	2.794 (2)	170.7
O1—H1A···O12ⁱⁱ	0.99	1.83	2.637 (2)	136.6
O2—H2A···O3	0.84	1.88	2.717 (2)	171.5
O2—H2B···O21ⁱⁱⁱ	0.85	1.90	2.746 (2)	176.8
O3—H3A···O6^iv	0.86	1.93	2.782 (2)	175.4
O3—H3B···O4ⁱⁱⁱ	0.86	1.89	2.734 (2)	169.3
O4—H4A···O22	0.85	2.00	2.841 (2)	166.2
O4—H4B···O2^iv	0.85	1.93	2.754 (2)	162.5
O5—H5A···O4	0.85	2.02	2.838 (2)	162.6
O5—H5B···O6	0.85	2.05	2.901 (3)	171.4
O6—H6A···O8	0.85	2.02	2.831 (2)	160.5
O6—H6B···O7^v	0.84	2.26	2.832 (2)	124.8
O7—H7···O5	0.84	1.98	2.799 (2)	165.6

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

References

Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Clearfield, A. (1998). Progress in Inorganic Chemistry: Metal Phosphonate Chemistry, Vol 47, edited by K. D. Karlin, pp. 371–510. New York: Wiley. Google Scholar
Clearfield, A., Krishnamohan Sharma, C. V. & Zhang, B. (2001). Chem. Mater. 13, 3099–3112. Web of Science CrossRef CAS Google Scholar
Fu, R., Hu, S. & Wu, X. (2007). Cryst. Growth Des. 7, 1134–1144. Web of Science CSD CrossRef CAS Google Scholar
Jokiniemi, J., Peräniemi, S., Vepsäläinen, J. J. & Ahlgrén, M. (2008). CrystEngComm, 10, 1011–1017. Web of Science CSD CrossRef CAS Google Scholar
Jokiniemi, J., Vuokila-Laine, E., Peräniemi, S., Vepsäläinen, J. J. & Ahlgrén, M. (2007). CrystEngComm, 9, 158–164. Web of Science CSD CrossRef CAS Google Scholar
Lin, L., Zhang, T.-J., Fan, Y.-T., Ding, D.-G. & Hou, H.-W. (2007). J. Mol. Struct. 837, 107–117. Web of Science CSD CrossRef CAS Google Scholar
Mathew, M., Fowler, B. O., Breuer, E., Golomb, G., Alferiev, I. S. & Eidelman, N. (1998). Inorg. Chem. 37, 6485–6494. Web of Science CSD CrossRef PubMed CAS Google Scholar
Nonius (1997). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Serre, C., Groves, J. A., Lightfoot, P., Slawin, A. M. Z., Wright, P. A., Stock, N., Bein, T., Haouas, M., Taulelle, F. & Férey, G. (2006). Chem. Mater. 18, 1451–1457. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.