Poly[(acetone)tetra­aqua­[μ₆-ethyl (dichloro­methyl­ene)diphospho­nato][μ₅-ethyl (dichloro­methylene)diphospho­nato]tribarium(II)]

The novel title compound, [Ba₃(C₃H₅Cl₂O₆P₂)₂(C₃H₆O)(H₂O)₄]_n, has a polymeric two-dimensional network structure which lies parallel to the (10) plane. The asymmetric unit consists of three independent Ba²⁺ ions, two of them eight-coordinated and the third nine-coordinated, and two independent ethyl (dichloro­methyl­ene)diphospho­nate(3−) lig­ands, one acetone ligand and four aqua ligands. The coordination environments around the BaO₈ polyhedra are best described as bicapped trigonal prismatic, while the BaO₉ polyhedron is in a distorted tricapped trigonal prismatic geometry. The two diphospho­nate ligands adopt different coordination modes. Both ligands chelate three metal cations, but one is coordinated to six metal cations in total and forms two six-membered and one four-membered chelate ring, while the other is coordinated to five metal cations in total and forms one six-membered and two four-membered chelate rings, the fifth unsubstituted O atom remaining uncoordinated.

S1. Comment

Bisphosphonic acids have attracted close attention because of their utility in supramolecular chemistry and crystal engineering (Clearfield et al., 2001; Fu et al., 2007). Usually, metal bisphosphonates form polymeric materials and microporous solids, with properties that offer a diversity of practical applications in catalysis, ion-exchange and sorption (Clearfield, 1998, and references therein; Fu et al., 2007; Serre et al., 2006). Clodronate, (dichloromethylene)bisphosphonate or Cl₂MBP, is one of the best documented bisphosphonates since it is widely used in therapeutics (Russell, 2007; Rodan & Martin, 2000). Several metal bisphosphonate complexes are known where the bisphosphonic ligand is fully ionic, but studies of the complexation of their ester derivatives are limited. The introduction of these ester substituents on phosphorus groups can result in novel structures of metal bishosphonates and produce interesting functionalities. However, of the numerous metal phosphonate compounds now known, only a small number have been prepared with alkali earth metals.

In earlier work, we developed a method for the preparation of partial amide esters of Cl₂MBP (Jokiniemi et al., 2006) and a novel synthesis for partial phenyl esters of Cl₂MBP (Jokiniemi et al., 2009). Several metal complexes of amide ester derivatives of clodronic acid have been reported by our group (Jokiniemi et al., 2007, 2008). We have also succeeded in preparing new Cd complexes with monophenyl, asymmetric diphenyl and monoethyl ester ligands of Cl₂MBP, and these will be reported shortly (Jokiniemi et al., 2009).

In this work, using the monoethyl ester anion of Cl₂MBP, we obtained the title novel layered Ba bisphosphonate complex, (I). The structure of (I) is different from the structures reported for other metal complexes of ester derivatives of Cl₂MBP.

The asymmetric unit of (I) consists of three crystallographically independent Ba²⁺ ions, two independent (Cl₂CP₂O₆Et)^3- ligands, one acetone molecule and four aqua ligands. As shown in Fig. 1, there are two coordination modes for the (Cl₂CP₂O₆Et)^3- ligands. The (Cl₂CP₂O₆Et)^3- ligand containing atoms P1 and P2 is coordinated to six Ba²⁺ cations through five O atoms, forming two six-membered chelate rings with atoms Ba1 and Ba3, while atom P1 forms a four-membered chelate ring with the adjacent atom Ba3C [symmetry code: (C) 1/2 - x, 1/2 + y, 1/2 - z]. The (Cl₂CP₂O₆Et)^3- ligand containing atoms P3 and P4 is coordinated to five Ba²⁺cations through four O atoms, forming a six-membered chelate ring with atom Ba2, while atom P3 forms two four-membered chelate rings with atoms Ba1A [symmetry code: (A) -x, 1 - y, -z] and Ba3C. Thus, atom O42 of the phosphonate group containing atom P4 remains uncoordinated but is involved in hydrogen bonding. In both (Cl₂CP₂O₆Et)^3- ligands, two O atoms (O13, O22 and O32, O33) act as monoatomic bridges between two Ba atoms, and one O atom (O11 and O31) is coordinated simultaneously to three Ba atoms (Ba1, Ba2 and Ba3C). The Ba1···Ba3C contact of 4.1404 (8) Å is shorter than the sum of the van der Waals radii of Ba (4.28 Å; Guo & Zhang, 2008; Srinivasan et al., 2007), indicating weak metal-to-metal interaction.

Both atoms Ba1 and Ba2 are eight-coordinated in a distorted bicapped trigonal prismatic geometry. The coordination environment around atom Ba1 consists of five phosphonate O atoms from three different (Cl₂CP₂O₆Et)^3- ligands and three aqua ligands. The Ba1—O bond distances range from 2.692 (3) to 2.889 (3) Å (Table 1). The aqua ligands O2 and O3 bridge atom Ba1 to the adjacent atoms Ba2 and Ba3E [symmetry code: (E) x - 1/2, 1/2 - y, z - 1/2], with a Ba1···Ba2 distance of 4.301 (1) Å and a Ba1···Ba3E distance of 4.502 (2) Å. The coordination environment around atom Ba2 consists of five phosphonate O atoms from four different (Cl₂CP₂O₆Et)^3- ligands, two bridging aqua ligands and one acetone ligand. The Ba2—O bond distances vary more widely, from 2.637 (3) to 3.226 (3) Å, compared with those involving atoms Ba1 and Ba3. Atom Ba3 is nine-coordinated in a distorted tricapped trigonal prismatic geometry. The coordination sites around the metal centre are occupied by seven phosphonate O atoms from five different (Cl₂CP₂O₆Et)^3- ligands, and two bridging aqua ligands. The Ba3—O bond distances range from 2.642 (3) to 3.023 (3) Å.

The infinite two-dimensional network of (I) can be thought of as formed through phosphonate atoms O12, O22 and O13, which link the Ba2 and Ba3 centres by acting as mono- and triatomic bridges. The µ-aqua ligand O4 also bridges atoms Ba2 and Ba3 [Ba2···Ba3 = 4.385 (1) Å] and is involved in forming the two-dimensional polymeric structure lying parallel to the (101) plane (Fig. 2). As presented in Fig. 3, the Cl atoms and ethyl groups point away from the layers, with an interlayer distance of 14.5492 (4) Å.

The layered structure of (I) is stabilized by intralayer hydrogen bonds involving all the aqua ligands and coordinated phosphonate O atoms (O12, O21, O32 and O41), and the non-coordinated phosphonate atom O42 (Table 2, wherein the following symmetry codes are defined). The aqua ligands O1 and O4ⁱⁱ donate H atoms to phosphonate atoms O12ⁱⁱ and O21, respectively, thereby closing a ring, Ba1—O1—H1B···O12ⁱⁱ—Ba3ⁱⁱ—O4ⁱⁱ—H4Aⁱⁱ···O21—Ba1, which has a graph-set motif of R²₂(8) (Bernstein et al., 1995). The aqua ligand O1 is also involved in hydrogen bonds with the phosphonate atom O41 and aqua ligand O2^v, which results in two further ring motifs, S(4) (Ba2—O1—H1A···O41—Ba2) and R²₂(6) (Ba3ⁱⁱ—O2^v—H2A^v···O1—H1B···O12ⁱⁱ—Ba3ⁱⁱ). As the aqua ligand O2 is involved in hydrogen bonding with atom O42, which further acts as an acceptor for two other H atoms of the aqua ligands O3^v and O4^vi [symmetry code: (vi) x-1/2, -y+1/2, z-1/2], a hydrogen-bonding network with several combined rings is formed.

S2. Experimental

The title compound was crystallized by the gel method. The starting materials Na₃Cl₂CP₂O₆Et (10 mg, 0.030 mmol) and BaCl₂.2H₂O (7.2 mg, 0.030 mmol) were dissolved separately in water (0.45 ml) and mixed, and tetramethoxysilane (0.1 ml) was added. The two-phase system was shaken until homogeneous. After gel formation, a precipitant, acetone (1 ml), was added above the gel to induce crystallization. Several months later, plate-like colourless crystals of (I) suitable for X-ray analysis were formed above the gel. Crystals for X-ray diffraction analysis were separated from the gel on a watch-glass under a microscope, washed with pure precipitant and dried in air.

S3. Refinement

C-bound H atoms were placed in calculated positions and refined using the riding-model approximation, with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms, and C—H 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene H atoms. Water H atoms were located in a difference Fourier map and treated as riding, with O—H = 0.83–0.86 Å, and their isotropic displacement parameters were refined. The C atoms (C4, C5, C22) of the coordinated acetone molecule and ethyl substituent have relatively high thermal motions, indicating disorder in the methyl groups. However, no residual electron density suitable for a split-atom model was found. The highest peak (2.99 e Å^-3) in the difference Fourier map is located 0.75 Å from atom H3B and the deepest hole (-0.92 e Å^-3) 0.88 Å from Ba1.

Computing details

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

	Fig. 1. The structure of the asymmetric unit of (I), expanded to show relevant symmetry-related atoms, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Atoms labelled with the suffixes A–E are at the symmetry postitions (-x, 1 - y, -z), (1/2 - x, y - 1/2, 1/2 - z), (1/2 - x, 1/2 + y, 1/2 - z), (1/2 + x, 1/2 - y, 1/2 + z) and (x - 1/2, 1/2 - y, z - 1/2), respectively.
	Fig. 2. The two-dimensional network of (I), viewed along the a axis. Dashed lines indicate hydrogen bonds. Ethyl groups and acetone molecules have been omitted for clarity.
	Fig. 3. The packing of the layers of (I) parallel to the (101) plane, viewed along the b axis. H atoms have been omitted for clarity.

Poly[acetonetetraaqua[µ₆-ethyl (dichloromethylene)diphosphonato][µ₅-ethyl (dichloromethylene)diphosphonato]tribarium(II)]

Crystal data

[Ba3(C3H5Cl2O6P2)2(C3H6O)(H2O)4]	F(000) = 2040
Mr = 1081.98	Dx = 2.393 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 41896 reflections
a = 16.635 (3) Å	θ = 2.0–26.0°
b = 9.814 (2) Å	µ = 4.52 mm^−1
c = 19.495 (4) Å	T = 150 K
β = 109.32 (3)°	Plate, colourless
V = 3003.5 (10) Å^3	0.25 × 0.10 × 0.05 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	5887 independent reflections
Radiation source: fine-focus sealed tube	5446 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ scans, and ω scans with κ offsets	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008)	h = −20→20
Tmin = 0.550, Tmax = 0.805	k = −12→11
41896 measured reflections	l = −24→24

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 11.7367P] where P = (Fo^2 + 2Fc^2)/3
5887 reflections	(Δ/σ)max = 0.001
346 parameters	Δρmax = 2.99 e Å^−3
0 restraints	Δρmin = −0.92 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
Ba1	0.019771 (16)	0.26522 (3)	0.099513 (13)	0.01081 (8)
Ba2	0.289813 (16)	0.29669 (3)	0.142021 (13)	0.01260 (8)
Ba3	0.366715 (15)	0.14599 (2)	0.366219 (13)	0.01024 (8)
Cl1	0.01132 (7)	0.38738 (12)	0.27129 (7)	0.0250 (3)
Cl2	0.14914 (9)	0.35471 (13)	0.40982 (6)	0.0293 (3)
Cl3	0.16658 (8)	0.47202 (13)	−0.15508 (6)	0.0233 (3)
Cl4	0.29450 (7)	0.46961 (12)	−0.01090 (6)	0.0184 (2)
P1	0.18991 (7)	0.41790 (11)	0.27614 (6)	0.0099 (2)
P2	0.11251 (7)	0.13395 (11)	0.29891 (6)	0.0118 (2)
P3	0.11161 (7)	0.47389 (11)	−0.02413 (6)	0.0102 (2)
P4	0.19592 (8)	0.21786 (12)	−0.06620 (6)	0.0153 (2)
O1	0.1405 (2)	0.0719 (3)	0.08929 (18)	0.0192 (7)
H1A	0.1593	0.0824	0.0537	0.06 (2)*
H1B	0.1699	0.0114	0.1181	0.028 (16)*
O2	−0.0217 (2)	0.1509 (3)	−0.04189 (17)	0.0163 (7)
H2B	0.0202	0.1529	−0.0561	0.030 (17)*
H2A	−0.0467	0.0755	−0.0522	0.037 (18)*
O3	−0.1216 (3)	0.1199 (5)	0.0992 (3)	0.0521 (13)
H3A	−0.1170	0.0458	0.0785	0.08 (3)*
H3B	−0.1648	0.1640	0.0729	0.10 (4)*
O4	0.4381 (2)	0.3239 (3)	0.28296 (18)	0.0212 (7)
H4A	0.4361	0.4101	0.2871	0.036 (18)*
H4B	0.4907	0.3045	0.2959	0.04 (2)*
O5	0.4486 (3)	0.2301 (5)	0.1284 (3)	0.0519 (13)
O11	0.1625 (2)	0.3742 (3)	0.19691 (16)	0.0148 (6)
O12	0.2790 (2)	0.3714 (3)	0.31911 (18)	0.0171 (7)
O13	0.1744 (2)	0.5675 (3)	0.28345 (16)	0.0147 (6)
O21	0.0663 (2)	0.1097 (3)	0.22002 (17)	0.0164 (7)
O22	0.2003 (2)	0.0768 (3)	0.33105 (17)	0.0172 (7)
O23	0.0600 (2)	0.0751 (4)	0.34690 (18)	0.0229 (8)
O31	0.13197 (19)	0.3919 (3)	0.04580 (16)	0.0140 (6)
O32	0.1285 (2)	0.6253 (3)	−0.00936 (17)	0.0149 (6)
O33	0.02446 (19)	0.4494 (3)	−0.07966 (16)	0.0150 (6)
O41	0.2406 (2)	0.1715 (3)	0.00992 (18)	0.0190 (7)
O42	0.1083 (2)	0.1641 (3)	−0.10433 (19)	0.0207 (7)
O43	0.2570 (2)	0.1865 (4)	−0.11226 (19)	0.0232 (8)
C1	0.1178 (3)	0.3215 (4)	0.3145 (2)	0.0127 (9)
C2	0.1907 (3)	0.4068 (5)	−0.0647 (2)	0.0137 (9)
C3	0.4902 (5)	0.1844 (8)	0.0943 (4)	0.0493 (17)
C4	0.5820 (5)	0.1414 (11)	0.1315 (5)	0.072 (3)
H4E	0.5959	0.1496	0.1832	0.108*
H4F	0.6190	0.1989	0.1155	0.108*
H4D	0.5891	0.0484	0.1193	0.108*
C5	0.4527 (6)	0.1626 (13)	0.0145 (5)	0.088 (3)
H5A	0.4014	0.2152	−0.0042	0.132*
H5B	0.4398	0.0678	0.0049	0.132*
H5C	0.4928	0.1909	−0.0086	0.132*
C41	0.2246 (4)	0.1476 (7)	−0.1876 (3)	0.0364 (14)
H41A	0.1666	0.1803	−0.2091	0.044*
H41B	0.2239	0.0491	−0.1916	0.044*
C42	0.2785 (5)	0.2060 (8)	−0.2271 (4)	0.0509 (18)
H42A	0.2759	0.3036	−0.2259	0.076*
H42C	0.2584	0.1754	−0.2767	0.076*
H42B	0.3364	0.1768	−0.2044	0.076*
C21	−0.0307 (4)	0.0476 (7)	0.3179 (4)	0.0395 (15)
H21B	−0.0587	0.1191	0.2841	0.047*
H21A	−0.0402	−0.0380	0.2916	0.047*
C22	−0.0669 (6)	0.0406 (12)	0.3758 (5)	0.078 (3)
H22B	−0.0389	−0.0298	0.4094	0.116*
H22A	−0.1266	0.0204	0.3556	0.116*
H22C	−0.0593	0.1264	0.4007	0.116*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.01297 (14)	0.00759 (13)	0.00938 (14)	−0.00045 (9)	0.00036 (10)	0.00050 (9)
Ba2	0.01570 (14)	0.00821 (14)	0.01153 (14)	0.00078 (9)	0.00132 (10)	0.00159 (9)
Ba3	0.01234 (14)	0.00667 (14)	0.00876 (13)	0.00068 (8)	−0.00050 (10)	0.00042 (9)
Cl1	0.0160 (5)	0.0179 (6)	0.0411 (7)	0.0053 (4)	0.0093 (5)	0.0012 (5)
Cl2	0.0479 (8)	0.0289 (7)	0.0131 (6)	−0.0071 (6)	0.0130 (5)	−0.0063 (5)
Cl3	0.0263 (6)	0.0305 (6)	0.0140 (5)	0.0059 (5)	0.0079 (5)	0.0069 (5)
Cl4	0.0127 (5)	0.0195 (6)	0.0214 (6)	−0.0022 (4)	0.0035 (4)	0.0006 (4)
P1	0.0123 (5)	0.0060 (5)	0.0089 (5)	0.0003 (4)	0.0000 (4)	−0.0006 (4)
P2	0.0139 (5)	0.0090 (5)	0.0113 (5)	−0.0003 (4)	0.0026 (4)	0.0016 (4)
P3	0.0107 (5)	0.0097 (5)	0.0091 (5)	0.0005 (4)	0.0016 (4)	0.0002 (4)
P4	0.0164 (6)	0.0142 (6)	0.0148 (6)	0.0007 (4)	0.0045 (5)	−0.0035 (4)
O1	0.0205 (17)	0.0175 (17)	0.0176 (17)	0.0057 (13)	0.0036 (14)	0.0048 (13)
O2	0.0162 (16)	0.0129 (17)	0.0189 (17)	0.0007 (12)	0.0045 (13)	−0.0003 (13)
O3	0.030 (2)	0.034 (3)	0.084 (4)	−0.010 (2)	0.009 (2)	0.013 (3)
O4	0.0255 (19)	0.0139 (17)	0.0247 (18)	−0.0001 (14)	0.0088 (15)	−0.0002 (14)
O5	0.043 (3)	0.058 (3)	0.063 (3)	0.013 (2)	0.030 (3)	−0.004 (3)
O11	0.0231 (17)	0.0122 (15)	0.0077 (14)	−0.0033 (12)	0.0034 (13)	−0.0021 (12)
O12	0.0144 (16)	0.0097 (15)	0.0229 (17)	−0.0010 (12)	0.0003 (13)	0.0021 (13)
O13	0.0187 (16)	0.0097 (15)	0.0137 (15)	0.0010 (12)	0.0026 (13)	−0.0005 (12)
O21	0.0203 (16)	0.0122 (15)	0.0117 (15)	−0.0019 (12)	−0.0015 (13)	0.0019 (12)
O22	0.0172 (16)	0.0087 (15)	0.0192 (16)	0.0002 (12)	−0.0025 (13)	0.0016 (12)
O23	0.0242 (18)	0.0277 (19)	0.0162 (16)	−0.0094 (15)	0.0059 (14)	0.0046 (14)
O31	0.0150 (15)	0.0136 (15)	0.0122 (15)	0.0036 (12)	0.0026 (12)	0.0027 (12)
O32	0.0169 (16)	0.0101 (15)	0.0138 (15)	−0.0009 (12)	0.0000 (13)	−0.0003 (12)
O33	0.0133 (15)	0.0159 (16)	0.0137 (15)	0.0000 (12)	0.0019 (12)	−0.0020 (12)
O41	0.0252 (18)	0.0116 (16)	0.0175 (17)	0.0029 (13)	0.0036 (14)	−0.0002 (13)
O42	0.0195 (17)	0.0176 (17)	0.0247 (18)	−0.0020 (13)	0.0070 (14)	−0.0044 (14)
O43	0.0210 (18)	0.029 (2)	0.0200 (18)	0.0027 (15)	0.0078 (14)	−0.0081 (15)
C1	0.017 (2)	0.012 (2)	0.009 (2)	0.0038 (17)	0.0035 (17)	−0.0019 (16)
C2	0.011 (2)	0.020 (2)	0.010 (2)	0.0000 (17)	0.0034 (16)	0.0033 (17)
C3	0.049 (4)	0.047 (4)	0.057 (5)	0.002 (3)	0.026 (4)	0.000 (3)
C4	0.054 (5)	0.095 (7)	0.063 (6)	0.020 (5)	0.014 (4)	0.000 (5)
C5	0.064 (6)	0.132 (10)	0.058 (6)	0.029 (6)	0.008 (5)	−0.006 (6)
C41	0.046 (4)	0.043 (4)	0.024 (3)	−0.005 (3)	0.018 (3)	−0.015 (2)
C42	0.048 (4)	0.068 (5)	0.042 (4)	0.003 (4)	0.022 (3)	−0.008 (3)
C21	0.021 (3)	0.048 (4)	0.051 (4)	−0.004 (3)	0.014 (3)	0.018 (3)
C22	0.053 (5)	0.124 (9)	0.069 (6)	−0.009 (5)	0.039 (4)	0.013 (6)

Geometric parameters (Å, º)

Ba1—O21	2.692 (3)	P3—O31	1.522 (3)
Ba1—O11	2.721 (3)	P3—O32	1.522 (3)
Ba1—O31	2.724 (3)	P3—C2	1.865 (5)
Ba1—O32^i	2.731 (3)	P3—Ba1^i	3.3715 (13)
Ba1—O3	2.748 (4)	P3—Ba3^ii	3.4242 (12)
Ba1—O1	2.817 (3)	P4—O41	1.494 (3)
Ba1—O2	2.842 (3)	P4—O42	1.496 (4)
Ba1—O33^i	2.889 (3)	P4—O43	1.593 (4)
Ba1—P3^i	3.3715 (13)	P4—C2	1.857 (5)
Ba1—Cl1	3.6031 (15)	O1—H1A	0.8565
Ba1—Ba3^ii	4.1404 (8)	O1—H1B	0.8516
Ba1—Ba2	4.3010 (10)	O2—Ba3^v	2.903 (3)
Ba2—O13^iii	2.637 (3)	O2—H2B	0.8314
Ba2—O41	2.723 (3)	O2—H2A	0.8403
Ba2—O11	2.777 (3)	O3—H3A	0.8476
Ba2—O22^ii	2.793 (3)	O3—H3B	0.8500
Ba2—O5	2.818 (5)	O4—H4A	0.8513
Ba2—O31	2.833 (3)	O4—H4B	0.8490
Ba2—O4	3.036 (4)	O5—C3	1.194 (8)
Ba2—O1	3.226 (3)	O11—Ba3^ii	2.910 (3)
Ba2—Cl4	3.4537 (13)	O13—Ba2^ii	2.637 (3)
Ba2—P2^ii	3.6992 (13)	O13—Ba3^ii	2.873 (3)
Ba2—P1	3.7269 (14)	O22—Ba2^iii	2.793 (3)
Ba2—Ba3^ii	4.2757 (7)	O23—C21	1.450 (6)
Ba3—O12	2.642 (3)	O31—Ba3^ii	3.023 (3)
Ba3—O33^iv	2.654 (3)	O32—Ba1^i	2.731 (3)
Ba3—O22	2.709 (3)	O32—Ba3^ii	2.772 (3)
Ba3—O32^iii	2.772 (3)	O33—Ba3^v	2.654 (3)
Ba3—O13^iii	2.873 (3)	O33—Ba1^i	2.889 (3)
Ba3—O4	2.892 (3)	O43—C41	1.439 (6)
Ba3—O2^iv	2.903 (3)	C3—C5	1.488 (12)
Ba3—O11^iii	2.910 (3)	C3—C4	1.517 (11)
Ba3—O31^iii	3.023 (3)	C4—H4E	0.9600
Ba3—P3^iii	3.4242 (12)	C4—H4F	0.9600
Ba3—P1^iii	3.4454 (12)	C4—H4D	0.9600
Ba3—Ba1^iii	4.1404 (8)	C5—H5A	0.9600
Cl1—C1	1.811 (4)	C5—H5B	0.9600
Cl2—C1	1.786 (4)	C5—H5C	0.9600
Cl3—C2	1.791 (4)	C41—C42	1.477 (9)
Cl4—C2	1.807 (4)	C41—H41A	0.9700
P1—O13	1.506 (3)	C41—H41B	0.9700
P1—O12	1.512 (3)	C42—H42A	0.9600
P1—O11	1.520 (3)	C42—H42C	0.9600
P1—C1	1.867 (5)	C42—H42B	0.9600
P1—Ba3^ii	3.4454 (12)	C21—C22	1.445 (10)
P2—O21	1.494 (3)	C21—H21B	0.9700
P2—O22	1.495 (3)	C21—H21A	0.9700
P2—O23	1.586 (3)	C22—H22B	0.9600
P2—C1	1.863 (5)	C22—H22A	0.9600
P2—Ba2^iii	3.6992 (13)	C22—H22C	0.9600
P3—O33	1.514 (3)
O21—Ba1—O11	71.42 (9)	O4—Ba3—P3^iii	149.49 (7)
O21—Ba1—O31	123.97 (9)	O2^iv—Ba3—P3^iii	85.88 (7)
O11—Ba1—O31	62.50 (9)	O11^iii—Ba3—P3^iii	83.18 (6)
O21—Ba1—O32^i	136.26 (10)	O31^iii—Ba3—P3^iii	26.37 (6)
O11—Ba1—O32^i	133.48 (9)	O12—Ba3—P1^iii	106.96 (8)
O31—Ba1—O32^i	99.25 (9)	O33^iv—Ba3—P1^iii	93.54 (7)
O21—Ba1—O3	72.91 (13)	O22—Ba3—P1^iii	69.45 (8)
O11—Ba1—O3	138.91 (14)	O32^iii—Ba3—P1^iii	132.24 (7)
O31—Ba1—O3	158.54 (14)	O13^iii—Ba3—P1^iii	25.58 (6)
O32^i—Ba1—O3	67.24 (12)	O4—Ba3—P1^iii	89.64 (7)
O21—Ba1—O1	70.97 (10)	O2^iv—Ba3—P1^iii	153.10 (7)
O11—Ba1—O1	80.59 (10)	O11^iii—Ba3—P1^iii	25.97 (6)
O31—Ba1—O1	71.65 (10)	O31^iii—Ba3—P1^iii	82.52 (6)
O32^i—Ba1—O1	137.10 (9)	P3^iii—Ba3—P1^iii	108.85 (3)
O3—Ba1—O1	106.24 (13)	O12—Ba3—Ba1^iii	169.06 (7)
O21—Ba1—O2	122.02 (9)	O33^iv—Ba3—Ba1^iii	43.88 (7)
O11—Ba1—O2	135.07 (10)	O22—Ba3—Ba1^iii	100.82 (7)
O31—Ba1—O2	77.56 (9)	O32^iii—Ba3—Ba1^iii	84.93 (6)
O32^i—Ba1—O2	69.71 (9)	O13^iii—Ba3—Ba1^iii	82.21 (6)
O3—Ba1—O2	81.97 (14)	O4—Ba3—Ba1^iii	112.67 (7)
O1—Ba1—O2	67.39 (9)	O2^iv—Ba3—Ba1^iii	110.85 (7)
O21—Ba1—O33^i	130.82 (9)	O11^iii—Ba3—Ba1^iii	40.92 (6)
O11—Ba1—O33^i	80.63 (9)	O31^iii—Ba3—Ba1^iii	41.10 (6)
O31—Ba1—O33^i	71.49 (9)	P3^iii—Ba3—Ba1^iii	60.20 (2)
O32^i—Ba1—O33^i	52.88 (9)	P1^iii—Ba3—Ba1^iii	62.10 (3)
O3—Ba1—O33^i	108.84 (13)	C1—Cl1—Ba1	88.88 (14)
O1—Ba1—O33^i	143.07 (9)	C2—Cl4—Ba2	92.48 (14)
O2—Ba1—O33^i	106.46 (9)	O13—P1—O12	114.18 (18)
O21—Ba1—P3^i	140.25 (8)	O13—P1—O11	111.59 (18)
O11—Ba1—P3^i	107.20 (7)	O12—P1—O11	112.78 (19)
O31—Ba1—P3^i	85.04 (7)	O13—P1—C1	107.67 (19)
O32^i—Ba1—P3^i	26.29 (7)	O12—P1—C1	105.48 (19)
O3—Ba1—P3^i	87.84 (11)	O11—P1—C1	104.31 (19)
O1—Ba1—P3^i	148.77 (7)	O13—P1—Ba3^ii	55.45 (12)
O2—Ba1—P3^i	87.85 (7)	O12—P1—Ba3^ii	126.81 (14)
O33^i—Ba1—P3^i	26.59 (6)	O11—P1—Ba3^ii	56.96 (12)
O21—Ba1—Cl1	57.72 (7)	C1—P1—Ba3^ii	127.68 (14)
O11—Ba1—Cl1	60.92 (7)	O13—P1—Ba2	120.52 (13)
O31—Ba1—Cl1	116.61 (7)	O12—P1—Ba2	73.09 (14)
O32^i—Ba1—Cl1	99.36 (7)	C1—P1—Ba2	127.85 (14)
O3—Ba1—Cl1	82.99 (13)	Ba3^ii—P1—Ba2	73.07 (3)
O1—Ba1—Cl1	122.53 (7)	O21—P2—O22	118.1 (2)
O2—Ba1—Cl1	164.01 (7)	O21—P2—O23	110.67 (19)
O33^i—Ba1—Cl1	73.47 (6)	O22—P2—O23	105.59 (19)
P3^i—Ba1—Cl1	86.18 (3)	O21—P2—C1	107.82 (19)
O21—Ba1—Ba3^ii	112.77 (7)	O22—P2—C1	108.39 (19)
O11—Ba1—Ba3^ii	44.48 (6)	O23—P2—C1	105.6 (2)
O31—Ba1—Ba3^ii	46.85 (7)	O21—P2—Ba2^iii	101.61 (13)
O32^i—Ba1—Ba3^ii	90.87 (7)	O23—P2—Ba2^iii	76.20 (14)
O3—Ba1—Ba3^ii	144.37 (12)	C1—P2—Ba2^iii	147.25 (14)
O1—Ba1—Ba3^ii	108.77 (7)	O33—P3—O31	115.68 (18)
O2—Ba1—Ba3^ii	117.66 (7)	O33—P3—O32	111.28 (18)
O33^i—Ba1—Ba3^ii	39.55 (6)	O31—P3—O32	111.99 (18)
P3^i—Ba1—Ba3^ii	65.17 (3)	O33—P3—C2	106.47 (19)
Cl1—Ba1—Ba3^ii	72.88 (2)	O31—P3—C2	102.37 (19)
O21—Ba1—Ba2	83.82 (7)	O32—P3—C2	108.3 (2)
O11—Ba1—Ba2	38.99 (7)	O33—P3—Ba1^i	58.63 (12)
O31—Ba1—Ba2	40.22 (6)	O31—P3—Ba1^i	135.42 (13)
O32^i—Ba1—Ba2	139.37 (7)	O32—P3—Ba1^i	52.65 (12)
O3—Ba1—Ba2	151.16 (11)	C2—P3—Ba1^i	121.98 (14)
O1—Ba1—Ba2	48.59 (7)	O33—P3—Ba3^ii	120.80 (13)
O2—Ba1—Ba2	96.79 (7)	O31—P3—Ba3^ii	61.93 (12)
O33^i—Ba1—Ba2	99.19 (6)	O32—P3—Ba3^ii	52.43 (12)
P3^i—Ba1—Ba2	120.97 (2)	C2—P3—Ba3^ii	132.55 (14)
Cl1—Ba1—Ba2	99.00 (3)	Ba1^i—P3—Ba3^ii	82.96 (3)
Ba3^ii—Ba1—Ba2	60.830 (9)	O41—P4—O42	118.0 (2)
O13^iii—Ba2—O41	94.52 (10)	O41—P4—O43	107.5 (2)
O13^iii—Ba2—O11	94.78 (9)	O42—P4—O43	110.5 (2)
O41—Ba2—O11	117.32 (10)	O41—P4—C2	107.39 (19)
O13^iii—Ba2—O22^ii	138.37 (9)	O42—P4—C2	108.5 (2)
O41—Ba2—O22^ii	127.03 (10)	O43—P4—C2	104.1 (2)
O11—Ba2—O22^ii	70.29 (9)	Ba1—O1—Ba2	90.49 (9)
O13^iii—Ba2—O5	78.83 (13)	Ba1—O1—H1A	115.8
O41—Ba2—O5	78.70 (13)	Ba2—O1—H1A	74.1
O11—Ba2—O5	163.40 (13)	Ba1—O1—H1B	133.7
O22^ii—Ba2—O5	104.33 (13)	Ba2—O1—H1B	93.0
O13^iii—Ba2—O31	129.57 (9)	H1A—O1—H1B	109.5
O41—Ba2—O31	66.41 (10)	Ba1—O2—Ba3^v	103.19 (10)
O11—Ba2—O31	60.45 (9)	Ba1—O2—H2B	110.6
O22^ii—Ba2—O31	77.51 (9)	Ba3^v—O2—H2B	102.4
O5—Ba2—O31	134.94 (13)	Ba1—O2—H2A	121.4
O13^iii—Ba2—O4	66.96 (9)	Ba3^v—O2—H2A	107.0
O41—Ba2—O4	142.71 (10)	H2B—O2—H2A	110.2
O11—Ba2—O4	97.00 (9)	Ba1—O3—H3A	103.5
O22^ii—Ba2—O4	76.34 (9)	Ba1—O3—H3B	106.8
O5—Ba2—O4	66.41 (13)	H3A—O3—H3B	109.9
O31—Ba2—O4	150.17 (9)	Ba3—O4—Ba2	95.37 (10)
O13^iii—Ba2—O1	66.54 (9)	Ba3—O4—H4A	120.7
O41—Ba2—O1	55.34 (10)	Ba2—O4—H4A	97.3
O11—Ba2—O1	72.84 (9)	Ba3—O4—H4B	105.8
O22^ii—Ba2—O1	136.39 (9)	Ba2—O4—H4B	134.3
O5—Ba2—O1	117.28 (13)	H4A—O4—H4B	105.2
O31—Ba2—O1	64.36 (9)	C3—O5—Ba2	150.9 (5)
O4—Ba2—O1	131.13 (9)	P1—O11—Ba1	135.99 (18)
O13^iii—Ba2—Cl4	146.04 (7)	P1—O11—Ba2	117.26 (17)
O41—Ba2—Cl4	59.40 (7)	Ba1—O11—Ba2	102.95 (10)
O11—Ba2—Cl4	115.85 (7)	P1—O11—Ba3^ii	97.07 (14)
O22^ii—Ba2—Cl4	70.24 (7)	Ba1—O11—Ba3^ii	94.60 (9)
O5—Ba2—Cl4	75.10 (11)	Ba2—O11—Ba3^ii	97.47 (10)
O31—Ba2—Cl4	63.07 (7)	P1—O12—Ba3	140.63 (18)
O4—Ba2—Cl4	119.63 (7)	P1—O13—Ba2^ii	150.39 (18)
O1—Ba2—Cl4	107.22 (7)	P1—O13—Ba3^ii	98.97 (15)
O13^iii—Ba2—P2^ii	126.58 (7)	Ba2^ii—O13—Ba3^ii	105.39 (10)
O41—Ba2—P2^ii	131.43 (7)	P2—O21—Ba1	135.20 (18)
O11—Ba2—P2^ii	86.98 (7)	P2—O22—Ba3	141.88 (18)
O22^ii—Ba2—P2^ii	21.32 (7)	P2—O22—Ba2^iii	115.89 (16)
O5—Ba2—P2^ii	84.73 (11)	Ba3—O22—Ba2^iii	101.99 (10)
O31—Ba2—P2^ii	97.26 (7)	C21—O23—P2	122.9 (3)
O4—Ba2—P2^ii	59.87 (7)	P3—O31—Ba1	127.46 (17)
O1—Ba2—P2^ii	157.49 (6)	P3—O31—Ba2	130.57 (17)
Cl4—Ba2—P2^ii	72.30 (3)	Ba1—O31—Ba2	101.41 (10)
O13^iii—Ba2—P1	87.56 (7)	P3—O31—Ba3^ii	91.70 (14)
O41—Ba2—P1	138.00 (8)	Ba1—O31—Ba3^ii	92.04 (9)
O11—Ba2—P1	21.26 (6)	Ba2—O31—Ba3^ii	93.74 (9)
O22^ii—Ba2—P1	64.28 (7)	P3—O32—Ba1^i	101.06 (15)
O5—Ba2—P1	142.17 (11)	P3—O32—Ba3^ii	101.78 (15)
O31—Ba2—P1	80.13 (7)	Ba1^i—O32—Ba3^ii	109.76 (11)
O4—Ba2—P1	75.77 (7)	P3—O33—Ba3^v	157.96 (19)
O1—Ba2—P1	88.09 (6)	P3—O33—Ba1^i	94.78 (14)
Cl4—Ba2—P1	126.26 (3)	Ba3^v—O33—Ba1^i	96.57 (10)
P2^ii—Ba2—P1	75.40 (3)	P4—O41—Ba2	134.21 (18)
O13^iii—Ba2—Ba3^ii	136.75 (7)	C41—O43—P4	122.2 (3)
O41—Ba2—Ba3^ii	109.71 (7)	Cl2—C1—Cl1	108.8 (2)
O11—Ba2—Ba3^ii	42.45 (6)	Cl2—C1—P2	109.4 (2)
O22^ii—Ba2—Ba3^ii	38.29 (7)	Cl1—C1—P2	106.9 (2)
O5—Ba2—Ba3^ii	139.53 (11)	Cl2—C1—P1	108.6 (2)
O31—Ba2—Ba3^ii	44.87 (6)	Cl1—C1—P1	107.0 (2)
O4—Ba2—Ba3^ii	105.41 (7)	P2—C1—P1	116.0 (2)
O1—Ba2—Ba3^ii	98.12 (6)	Cl3—C2—Cl4	108.0 (2)
Cl4—Ba2—Ba3^ii	76.17 (3)	Cl3—C2—P4	109.8 (2)
P2^ii—Ba2—Ba3^ii	59.57 (2)	Cl4—C2—P4	108.0 (2)
P1—Ba2—Ba3^ii	50.434 (19)	Cl3—C2—P3	109.3 (2)
O12—Ba3—O33^iv	142.50 (10)	Cl4—C2—P3	107.8 (2)
O12—Ba3—O22	73.83 (10)	P4—C2—P3	113.7 (2)
O33^iv—Ba3—O22	143.63 (10)	O5—C3—C5	121.1 (7)
O12—Ba3—O32^iii	103.89 (10)	O5—C3—C4	121.1 (7)
O33^iv—Ba3—O32^iii	83.02 (10)	C5—C3—C4	117.8 (7)
O22—Ba3—O32^iii	85.59 (10)	C3—C4—H4E	109.5
O12—Ba3—O13^iii	87.30 (10)	C3—C4—H4F	109.5
O33^iv—Ba3—O13^iii	100.42 (10)	H4E—C4—H4F	109.5
O22—Ba3—O13^iii	78.22 (10)	C3—C4—H4D	109.5
O32^iii—Ba3—O13^iii	156.99 (9)	H4E—C4—H4D	109.5
O12—Ba3—O4	65.25 (10)	H4F—C4—H4D	109.5
O33^iv—Ba3—O4	84.31 (10)	C3—C5—H5A	109.5
O22—Ba3—O4	125.73 (10)	C3—C5—H5B	109.5
O32^iii—Ba3—O4	136.76 (10)	H5A—C5—H5B	109.5
O13^iii—Ba3—O4	66.16 (9)	C3—C5—H5C	109.5
O12—Ba3—O2^iv	78.84 (9)	H5A—C5—H5C	109.5
O33^iv—Ba3—O2^iv	69.56 (10)	H5B—C5—H5C	109.5
O22—Ba3—O2^iv	136.02 (10)	O43—C41—C42	110.0 (5)
O32^iii—Ba3—O2^iv	68.26 (9)	O43—C41—H41A	109.7
O13^iii—Ba3—O2^iv	134.39 (9)	C42—C41—H41A	109.7
O4—Ba3—O2^iv	68.57 (9)	O43—C41—H41B	109.7
O12—Ba3—O11^iii	128.66 (9)	C42—C41—H41B	109.7
O33^iv—Ba3—O11^iii	81.34 (9)	H41A—C41—H41B	108.2
O22—Ba3—O11^iii	69.48 (9)	C41—C42—H42A	109.5
O32^iii—Ba3—O11^iii	107.67 (9)	C41—C42—H42C	109.5
O13^iii—Ba3—O11^iii	51.28 (8)	H42A—C42—H42C	109.5
O4—Ba3—O11^iii	110.98 (9)	C41—C42—H42B	109.5
O2^iv—Ba3—O11^iii	150.86 (9)	H42A—C42—H42B	109.5
O12—Ba3—O31^iii	141.96 (10)	H42C—C42—H42B	109.5
O33^iv—Ba3—O31^iii	70.29 (9)	C22—C21—O23	110.7 (6)
O22—Ba3—O31^iii	75.62 (9)	C22—C21—H21B	109.5
O32^iii—Ba3—O31^iii	51.39 (9)	O23—C21—H21B	109.5
O13^iii—Ba3—O31^iii	108.04 (8)	C22—C21—H21A	109.5
O4—Ba3—O31^iii	152.77 (9)	O23—C21—H21A	109.5
O2^iv—Ba3—O31^iii	109.46 (9)	H21B—C21—H21A	108.1
O11^iii—Ba3—O31^iii	56.81 (8)	C21—C22—H22B	109.5
O12—Ba3—P3^iii	127.40 (8)	C21—C22—H22A	109.5
O33^iv—Ba3—P3^iii	70.88 (7)	H22B—C22—H22A	109.5
O22—Ba3—P3^iii	84.18 (8)	C21—C22—H22C	109.5
O32^iii—Ba3—P3^iii	25.79 (7)	H22B—C22—H22C	109.5
O13^iii—Ba3—P3^iii	134.40 (6)	H22A—C22—H22C	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O41	0.86	2.02	2.798 (5)	150
O1—H1B···O12^iii	0.85	1.85	2.697 (4)	173
O2—H2B···O42	0.83	1.99	2.813 (5)	172
O2—H2A···O1^vi	0.84	2.07	2.886 (5)	163
O3—H3A···O42^vi	0.85	2.11	2.796 (6)	137
O3—H3B···O32^i	0.85	2.58	3.034 (6)	114
O4—H4A···O21^ii	0.85	1.96	2.806 (5)	170
O4—H4B···O42^iv	0.85	2.28	2.957 (5)	137

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