Poly[[aqua­([mu]-2,2-dimethyl­malonato)­barium(II)] 2,2-dimethyl­malonic acid solvate]

In the title complex, {[Ba(C₅H₆O₄)(H₂O)]·C₅H₈O₄}_n, the neutral dimethyl­malonic acid mol­ecules and the dianionic (dimethyl­malonato)barium metal-organic framework are linked by cocrystallization. The Ba atom, in a distorted monocapped square-anti­prismatic geometry, is nine-coordinated by seven O atoms of four different dimethyl­malonate groups and by two water mol­ecules. This arrangement generates a two-dimensional layer parallel to the bc plane. Two such layers sandwich another layer composed of neutral dimethyl­malonic acid mol­ecules that are involved in inter­molecular hydrogen bonds within this layer and to neighboring layers. This complex is different from the di­methyl­mal­on­ate-Ba complex reported previously. The title compound displays a novel structure type and represents a new member of the substituted malonate series of alkaline earth complexes.

S1. Comment

The characterization of alkaline earth carboxylates is an area of continuous interest owing to their relevance in a wide range of applications in materials science, including their use as processible oxide precursors by soft chemistry routes (Baggio et al., 2004; Bae et al., 2002) and in studies of heterobimetallic complexes (Guo & Guo, 2006; Guo & Cao, 2006; Guo & Zhang, 2008). Malonate and substituted malonate derivatives are often ligands of choice for the design of such metal-organic frameworks or molecular assemblies because of their manifold coordination modes and the variety of the resulting architectures. For the complexes of barium, two works have been published, one containing both malonate dianion and malonic acid molecule (Hodgson & Asplaund, 1991) and the other involving such as mono-deprotonation of benzylmalonic acid, benzylmalonate, dimethylmalonate dianion and hydrogen ethylmalonate anion (Yokomori et al., 1998) as ligands. In heterobimetallic malonate complexes involving transition and alkaline-earth metals, barium atoms have also been used to construct coordination polymers by acting as building blocks (Guo & Guo, 2006; Guo & Cao, 2006; Guo & Zhang, 2008). In the course of our studies of heterobimetallic malonate complexes involving Zn and Ba atoms, we used dimethylmalonic acid as a ligand, expecting to obtain a structure similar or isotypic to that of [BaZn(C₃H₂O₄)₂(H₂O)₄]_n (Guo & Guo, 2006). When we used only barium hydroxide and dimethylmalonic acid, a stoichiometric mixture proved unsuccessful, but interestingly, use of a slight excess of dimethylmalonic acid did allow the formation of the novel nine-coordinated dimethylmalonate–barium complex (I), which exhibits the unexpected result of co-crystallization of the neutral molecules of dimethylmalonic acid in addition to the dianionic dimethylmalonate barium metal–organic framework. We report here its crystal structure.

The asymmetric unit in the structure of (I) comprises one Ba atom, one complete dimethylmalonate dianion, one coordinated water molecule and one neutral dimethylmalonic acid molecule, and is shown in Fig. 1 in a symmetry-expanded view which displays the full coordination of the Ba atom. Selected geometric parameters are given in Table 1.

As can be seen in Fig. 1, the coordination polyhedron around barium is nine-coordinate. The Ba atom has a distorted monocapped square-antiprismatic environment. The four coordination sites of the basal plane are occupied by atoms O1, O4, O3ⁱⁱⁱ and O4ⁱⁱⁱ (see Fig. 1 for symmetry codes). The adjacent plane contains atoms O1ⁱ and O3ⁱⁱ and two coordinated water molecules (O9 and O9ⁱⁱⁱ). Finally, the capping site is occupied by atom O2ⁱ. The Ba—O(dimethylmalonate) distances are in the range 2.7072 (18)–2.916 (2) Å, which is not inconsistent with the distances in catena-poly[(µ₅-dimethylmalonato)(µ₃-dimethylmalonato)pentaaquadibarium], which has two crystallographically independent Ba atoms; the distances in (I) are a little longer than those for the eight-coordinate Ba atom but are somewhat shorter than those reported for the nine-coordinate Ba atom (Yokomori et al., 1998).

In the present structure, the variability of the substituted malonate ligand can be clearly seen (Fig. 1). Monodentate, bidentate–chelating, chelated six-membered and bridging bonding modes are all present. Atoms O1 and O2 of the O1/C1/O2 carboxylate group uses a bidentate 1,2-chelating mode to connect with atom Ba1ⁱ; atoms O3 and O4 are coordinated in a similar manner to atom Ba1^v (see Fig. 1 for symmetry codes). Atom O3ⁱⁱ adopts both a monodentate mode, to connect with atom Ba1, and a bridging bonding mode to link atoms Ba1^iv and Ba1. Furthermore, the whole dianionic dimethylmalonate ligand chelates atom Ba1 to form a six-membered ring. The bond angle at C2 [C3—C2—C1 = 102.7 (2)°] is smaller than the normal value, suggesting that there is greater strain in the six-membered ring than in the ten-coordinate catena-poly[(µ₂-aqua)-bis(µ₂-benzylhydrogenmalonato-O,O,O',O'')barium] complex (Yokomori et al., 1998). At the same time, atoms O1 and O4 also adopt a bridging bonding mode to connect with two different Ba atoms. In the dianionic dimethylmalonate ligand, the O—C—O angles for the two carboxylate groups are both 122.1 (2)°, and the four C—O bond distances are in the range 1.259 (3)–1.270 (3) Å. This indicates that both carboxylate groups have an evident mesomeric effect. As is observed in other alkylmalonate structure, the two carboxylate groups are non-coplanar (Yokomori et al., 1998). The O1/C1/O2 carboxylate group is rotated by 42.7 (4)° out of the C1/C2/C3 plane, while the O3/C3/O4 group forms an angle with the same plane of 80.9 (4)°; the dihedral angle between the two carboxylate groups is 89.3 (4)°.

As can be seen in Fig. 2, the structure as a whole consists of two distinct layers that stack alternatingly in the a direction. The first is composed entirely of Ba atoms, dimethylmalonate dianions and water molecules and occurs near x = 0 and x = 1. In this case, each dianionic dimethylmalonate ligand binds to four different Ba atoms, and each Ba atom binds to four different dimethylmalonate dianions. In the crystallographic c direction, the neighbouring Ba atoms are bridged via atom O4 and water molecule O9; in the crystallographic b direction, the connection between Ba atoms is achieved via bridging involving two O3 and two O1 atoms, which occur alternately. In this way, each group of four Ba atoms builds up a grid. These grids are further joined into a two-dimensional layer structure with a (4,4)-grid topology in the direction of the bc plane (Fig.2).

The other layer, alternating with the first and centered on x = 1/2, only contains neutral molecules of dimethylmalonic acid. Within this layer (Fig. 2), intermolecular O7—H7···O8^vii hydrogen-bond interactions form dimers of graph set D₂²(8) (Bernstein et al., 1995) comprising two molecules of dimethylmalonic acid (see Table 2). The connection between the neighbouring layers is mainly completed via a hydrogen-bond interaction between atom H9A of water molecule O9 and atom O6ⁱⁱ and a strong intramolecular O5—H5···O2 hydrogen-bond interaction (Brown, 1976). In addition, atom H9B of water molecule O9 and atom O4^vi engage in another distinct hydrogen-bonding interaction (see Table 2). These together make the structure a three-dimensional network.

In the dimethylmalonic acid molecule, the O—C—O angles for two carboxylate groups are almost the same [O6—C6—O5 = 123.8 (3)° and O8—C8—O7 = 124.0 (2)°]. Each carboxylate groups has one single and one double bond. The two C—O single-bond distances (O5—C6 and O7—C8) are 1.324 (3) and 1.322 (3) Å, respectively, while the two C—O double-bond distances (O6—C6 and O8—C8) are 1.213 (3) and 1.218 (3) Å, respectively; they are longer than the values of 1.308 (3) and 1.206 (2) Å reported for the free acid (Sheng-zhi & Mak, 1986). As is observed in the above dimethylmalonate structure, the two carboxylate groups are again non-coplanar; the dihedral angle between the O5/C6/O6 and O7/C8/O8 planes is 79.6 (4)°, the group at C6 lying 45.6 (4)° out of the C6/C7/C8 plane, while the other group forms an angle of 50.1 (4)° with this plane.

A comparison with other reported malonate and substituted malonate–barium compounds (Hodgson & Asplaund, 1991; Yokomori et al., 1998) reveals that the title compound has a novel structure type and represents a new member of the substituted malonate series of alkaline earth complexes. The previously reported complex catena-poly[(µ₅-dimethylmalonato)(µ₃-dimethylmalonato)pentaaquadibarium] (Yokomori et al., 1998) is quite different as two crystallographically independent Ba atoms are present. One is coordinated to five dimethylmalonate O atoms and three water molecules, while the other is bonded to six dimethylmalonate O atoms and three water molecules. Moreover the two independent dimethylmalonate dianions exhibit different coordination modes.

Related literature

For related literature, see: Bernstein et al. (1995); Brown (1976); Guo & Guo (2006a); Hodgson & Asplaund (1991); Sheng-zhi & Mak (1986); Yokomori et al. (1998).

S2. Experimental

The title complex was prepared under continuous stirring with successive addition of dimethylmalonic acid (0.53 g, 4 mmol) and Ba(OH)₂.8H₂O (0.63 g, 2 mmol) to distilled water (15 ml) at room temperature. After filtration, slow evaporation over a period of two weeks at room temperature provided colorless needle-shaped crystals of (I).

S3. Refinement

The H atoms of the water molecule were found in difference Fourier maps. However, during refinement, they were fixed at O–H distances of 0.86 Å and their U_iso(H) values were set at 1.2U_eq(O). The H atoms of CH₃ and OH groups were treated as riding [C—H = 0.96 Å, O—H = 0.82 Å and and U_iso(H) = 1.5U_eq(C,O)]. Please check changes to text.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the structure of (I), showing the atom-numbering scheme and coordination polyhedra for Ba atom; displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x, -y + 2, -z; (ii) -x, y - 1/2, -z + 1/2; (iii) x, -y + 3/2, z - 1/2; (iv) -x, -y + 1, -z; (v) x, -y + 3/2, z + 1/2.]
	Fig. 2. Packing diagram of (I), showing the two-dimensional polymeric layer in the bc plane and the hydrogen bonding interactions that link them in the a-axis direction as dashed lines.

Poly[[aqua(2,2-dimethylmalonato)barium(II)] 2,2-dimethylmalonic acid solvate]

Crystal data

[Ba(C5H6O4)(H2O)]·C5H8O4	F(000) = 816
Mr = 417.57	Dx = 1.941 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4236 reflections
a = 17.300 (3) Å	θ = 2.1–27.9°
b = 8.6107 (17) Å	µ = 2.82 mm^−1
c = 9.6027 (19) Å	T = 133 K
β = 92.41 (3)°	Needle, colorless
V = 1429.2 (5) Å^3	0.14 × 0.08 × 0.06 mm
Z = 4

Data collection

Rigaku Saturn diffractometer	2488 independent reflections
Radiation source: rotating anode	2224 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.030
Detector resolution: 27.873 pixels mm^-1	θmax = 25.0°, θmin = 2.6°
ω scans	h = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −8→10
Tmin = 0.738, Tmax = 0.852	l = −11→9
7812 measured reflections

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0444P)^2] where P = (Fo^2 + 2Fc^2)/3
2488 reflections	(Δ/σ)max = 0.001
187 parameters	Δρmax = 1.23 e Å^−3
0 restraints	Δρmin = −0.88 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	−0.030233 (10)	0.741550 (16)	0.030014 (16)	0.01787 (10)
O1	0.07501 (11)	0.9751 (2)	0.06517 (18)	0.0247 (4)
O2	0.17179 (11)	1.1406 (2)	0.09712 (19)	0.0232 (4)
O3	0.07639 (11)	0.95037 (19)	0.40554 (17)	0.0221 (4)
O4	0.06452 (13)	0.7286 (2)	0.2881 (2)	0.0208 (5)
C1	0.13815 (16)	1.0144 (3)	0.1250 (3)	0.0201 (6)
C2	0.17173 (15)	0.9021 (3)	0.2370 (3)	0.0200 (6)
C3	0.09984 (15)	0.8550 (3)	0.3157 (3)	0.0197 (6)
C4	0.2063 (2)	0.7638 (3)	0.1602 (4)	0.0254 (7)
H4A	0.2489	0.7987	0.1075	0.038*
H4B	0.1674	0.7188	0.0983	0.038*
H4C	0.2242	0.6873	0.2268	0.038*
C5	0.23316 (16)	0.9777 (3)	0.3338 (3)	0.0259 (6)
H5A	0.2482	0.9065	0.4070	0.039*
H5B	0.2124	1.0703	0.3736	0.039*
H5C	0.2775	1.0038	0.2817	0.039*
O9	−0.09323 (11)	0.9041 (2)	0.26237 (18)	0.0232 (4)
H9A	−0.1426	0.8906	0.2565	0.028*
H9B	−0.0826	1.0004	0.2479	0.028*
O5	0.30911 (14)	1.25906 (19)	0.1387 (3)	0.0266 (5)
H5	0.2661	1.2194	0.1311	0.040*
O6	0.25209 (11)	1.4111 (2)	0.2934 (2)	0.0279 (5)
O7	0.40271 (11)	1.5477 (2)	0.06535 (19)	0.0259 (4)
H7	0.4306	1.5643	0.0000	0.039*
O8	0.50343 (11)	1.4024 (2)	0.14196 (19)	0.0249 (4)
C6	0.30970 (16)	1.3659 (3)	0.2379 (3)	0.0219 (6)
C7	0.39149 (16)	1.4185 (3)	0.2814 (3)	0.0219 (6)
C8	0.43836 (16)	1.4529 (3)	0.1552 (3)	0.0211 (6)
C9	0.38863 (17)	1.5669 (3)	0.3704 (3)	0.0320 (7)
H9D	0.4403	1.5976	0.3985	0.048*
H9E	0.3596	1.5470	0.4516	0.048*
H9C	0.3642	1.6486	0.3167	0.048*
C10	0.4297 (2)	1.2853 (4)	0.3649 (3)	0.0313 (7)
H10A	0.4317	1.1944	0.3073	0.047*
H10B	0.4000	1.2632	0.4448	0.047*
H10C	0.4812	1.3148	0.3949	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.02030 (15)	0.01595 (14)	0.01761 (14)	−0.00054 (5)	0.00364 (9)	0.00016 (5)
O1	0.0255 (11)	0.0203 (9)	0.0279 (10)	−0.0035 (8)	−0.0013 (9)	0.0031 (8)
O2	0.0231 (11)	0.0193 (10)	0.0273 (10)	−0.0026 (8)	0.0023 (8)	0.0029 (8)
O3	0.0242 (10)	0.0197 (9)	0.0227 (10)	−0.0001 (8)	0.0068 (8)	−0.0021 (7)
O4	0.0211 (12)	0.0189 (10)	0.0225 (11)	−0.0014 (8)	0.0036 (9)	−0.0004 (7)
C1	0.0225 (15)	0.0187 (13)	0.0195 (13)	0.0002 (11)	0.0054 (11)	−0.0035 (10)
C2	0.0191 (14)	0.0197 (14)	0.0215 (13)	−0.0008 (11)	0.0031 (11)	0.0003 (10)
C3	0.0216 (15)	0.0197 (14)	0.0176 (13)	0.0022 (11)	−0.0006 (11)	0.0012 (10)
C4	0.0258 (19)	0.0224 (16)	0.0284 (18)	0.0038 (11)	0.0066 (15)	0.0029 (10)
C5	0.0233 (16)	0.0305 (15)	0.0238 (14)	−0.0035 (12)	0.0006 (12)	0.0042 (12)
O9	0.0230 (11)	0.0201 (9)	0.0265 (10)	−0.0022 (8)	0.0029 (8)	0.0016 (7)
O5	0.0192 (13)	0.0308 (13)	0.0302 (13)	−0.0071 (8)	0.0069 (10)	−0.0064 (7)
O6	0.0194 (11)	0.0283 (11)	0.0365 (11)	0.0014 (8)	0.0066 (9)	−0.0030 (8)
O7	0.0240 (11)	0.0278 (10)	0.0262 (10)	0.0003 (8)	0.0058 (8)	0.0072 (8)
O8	0.0206 (11)	0.0273 (10)	0.0272 (10)	0.0020 (8)	0.0063 (8)	0.0041 (8)
C6	0.0225 (15)	0.0178 (13)	0.0254 (14)	0.0000 (11)	0.0019 (12)	0.0041 (11)
C7	0.0188 (15)	0.0235 (14)	0.0235 (14)	−0.0014 (11)	0.0037 (11)	0.0006 (11)
C8	0.0217 (16)	0.0161 (13)	0.0255 (14)	−0.0042 (11)	0.0005 (11)	−0.0012 (10)
C9	0.0273 (17)	0.0355 (17)	0.0331 (16)	−0.0032 (13)	0.0020 (13)	−0.0090 (13)
C10	0.0222 (17)	0.0432 (17)	0.0289 (17)	0.0037 (14)	0.0055 (14)	0.0122 (15)

Geometric parameters (Å, º)

Ba1—O1^i	2.7072 (18)	C5—H5A	0.9600
Ba1—O3^ii	2.7108 (17)	C5—H5B	0.9600
Ba1—O1	2.7243 (18)	C5—H5C	0.9600
Ba1—O3^iii	2.7835 (18)	O9—H9A	0.8611
Ba1—O2^i	2.875 (2)	O9—H9B	0.8616
Ba1—O9	2.8861 (18)	O5—C6	1.324 (3)
Ba1—O4	2.916 (2)	O5—H5	0.8200
Ba1—O9^iii	3.0215 (19)	O6—C6	1.213 (3)
Ba1—Ba1^i	4.6138 (9)	O7—C8	1.322 (3)
Ba1—Ba1^iv	4.3338 (8)	O7—H7	0.8200
O4—Ba1^v	2.910 (2)	O8—C8	1.218 (3)
O1—C1	1.259 (3)	C6—C7	1.527 (4)
O2—C1	1.267 (3)	C7—C8	1.515 (4)
O3—C3	1.270 (3)	C7—C10	1.533 (4)
O4—C3	1.270 (3)	C7—C9	1.540 (4)
C1—C2	1.541 (4)	C9—H9D	0.9600
C2—C5	1.528 (4)	C9—H9E	0.9600
C2—C4	1.536 (4)	C9—H9C	0.9600
C2—C3	1.537 (4)	C10—H10A	0.9600
C4—H4A	0.9600	C10—H10B	0.9600
C4—H4B	0.9600	C10—H10C	0.9600
C4—H4C	0.9600
O1^i—Ba1—O3^ii	145.87 (6)	C1—O2—Ba1^i	90.11 (15)
O1^i—Ba1—O1	63.69 (7)	C3—O3—Ba1^vi	149.20 (16)
O3^ii—Ba1—O1	148.90 (6)	C3—O3—Ba1^v	98.27 (15)
O1^i—Ba1—O3^iii	125.13 (5)	Ba1^vi—O3—Ba1^v	104.13 (6)
O3^ii—Ba1—O3^iii	75.87 (6)	C3—O4—Ba1^v	92.30 (15)
O1—Ba1—O3^iii	92.29 (6)	C3—O4—Ba1	113.14 (16)
O1^i—Ba1—O2^i	46.52 (5)	Ba1^v—O4—Ba1	111.08 (7)
O3^ii—Ba1—O2^i	99.76 (5)	O1—C1—O2	122.1 (2)
O1—Ba1—O2^i	110.18 (5)	O1—C1—C2	116.4 (2)
O3^iii—Ba1—O2^i	126.53 (5)	O2—C1—C2	121.5 (2)
O1^i—Ba1—O9	73.26 (5)	O1—C1—Ba1^i	58.47 (13)
O3^ii—Ba1—O9	98.49 (5)	O2—C1—Ba1^i	66.13 (13)
O1—Ba1—O9	79.54 (6)	C2—C1—Ba1^i	161.53 (17)
O3^iii—Ba1—O9	153.96 (5)	C5—C2—C4	110.3 (2)
O2^i—Ba1—O9	79.31 (6)	C5—C2—C3	111.7 (2)
O1^i—Ba1—O4^iii	79.27 (5)	C4—C2—C3	111.8 (2)
O3^ii—Ba1—O4^iii	116.43 (5)	C5—C2—C1	112.9 (2)
O1—Ba1—O4^iii	68.77 (6)	C4—C2—C1	107.1 (2)
O3^iii—Ba1—O4^iii	45.89 (5)	C3—C2—C1	102.7 (2)
O2^i—Ba1—O4^iii	97.37 (6)	O3—C3—O4	122.1 (2)
O9—Ba1—O4^iii	144.89 (5)	O3—C3—C2	116.8 (2)
O1^i—Ba1—O4	117.65 (5)	O4—C3—C2	121.1 (2)
O3^ii—Ba1—O4	86.05 (5)	O3—C3—Ba1^v	58.76 (13)
O1—Ba1—O4	64.78 (5)	O4—C3—Ba1^v	64.50 (14)
O3^iii—Ba1—O4	89.05 (6)	C2—C3—Ba1^v	169.66 (17)
O2^i—Ba1—O4	144.37 (6)	C2—C4—H4A	109.5
O9—Ba1—O4	65.06 (6)	C2—C4—H4B	109.5
O4^iii—Ba1—O4	111.50 (7)	H4A—C4—H4B	109.5
O1^i—Ba1—O9^iii	89.94 (5)	C2—C4—H4C	109.5
O3^ii—Ba1—O9^iii	73.21 (5)	H4A—C4—H4C	109.5
O1—Ba1—O9^iii	128.83 (5)	H4B—C4—H4C	109.5
O3^iii—Ba1—O9^iii	67.06 (5)	C2—C5—H5A	109.5
O2^i—Ba1—O9^iii	60.99 (5)	C2—C5—H5B	109.5
O9—Ba1—O9^iii	136.42 (7)	H5A—C5—H5B	109.5
O4^iii—Ba1—O9^iii	63.44 (5)	C2—C5—H5C	109.5
O4—Ba1—O9^iii	151.28 (5)	H5A—C5—H5C	109.5
O1^i—Ba1—C1^i	23.35 (6)	H5B—C5—H5C	109.5
O3^ii—Ba1—C1^i	123.47 (6)	Ba1—O9—Ba1^v	108.78 (6)
O1—Ba1—C1^i	86.89 (6)	Ba1—O9—H9A	106.9
O3^iii—Ba1—C1^i	125.77 (6)	Ba1^v—O9—H9A	108.7
O2^i—Ba1—C1^i	23.76 (6)	Ba1—O9—H9B	104.6
O9—Ba1—C1^i	78.81 (6)	Ba1^v—O9—H9B	117.7
O4^iii—Ba1—C1^i	84.62 (6)	H9A—O9—H9B	109.6
O4—Ba1—C1^i	136.84 (6)	C6—O5—H5	109.5
O9^iii—Ba1—C1^i	71.87 (6)	C8—O7—H7	109.5
O1^i—Ba1—C3^iii	102.38 (6)	O6—C6—O5	123.8 (3)
O3^ii—Ba1—C3^iii	97.33 (6)	O6—C6—C7	123.6 (2)
O1—Ba1—C3^iii	77.78 (6)	O5—C6—C7	112.4 (2)
O3^iii—Ba1—C3^iii	22.96 (6)	C8—C7—C6	111.1 (2)
O2^i—Ba1—C3^iii	115.16 (6)	C8—C7—C10	109.3 (2)
O9—Ba1—C3^iii	156.28 (6)	C6—C7—C10	107.2 (2)
O4^iii—Ba1—C3^iii	23.20 (6)	C8—C7—C9	108.2 (2)
O4—Ba1—C3^iii	98.65 (6)	C6—C7—C9	110.3 (2)
O9^iii—Ba1—C3^iii	65.56 (6)	C10—C7—C9	110.7 (2)
C1^i—Ba1—C3^iii	106.66 (6)	O8—C8—O7	124.0 (2)
O1^i—Ba1—Ba1^iv	152.55 (4)	O8—C8—C7	122.8 (2)
O3^ii—Ba1—Ba1^iv	38.52 (4)	O7—C8—C7	113.1 (2)
O1—Ba1—Ba1^iv	124.14 (4)	C7—C9—H9D	109.5
O3^iii—Ba1—Ba1^iv	37.34 (3)	C7—C9—H9E	109.5
O2^i—Ba1—Ba1^iv	119.23 (4)	H9D—C9—H9E	109.5
O9—Ba1—Ba1^iv	132.02 (3)	C7—C9—H9C	109.5
O4^iii—Ba1—Ba1^iv	80.29 (3)	H9D—C9—H9C	109.5
O4—Ba1—Ba1^iv	86.92 (3)	H9E—C9—H9C	109.5
O9^iii—Ba1—Ba1^iv	64.47 (4)	C7—C10—H10A	109.5
C1^i—Ba1—Ba1^iv	136.09 (5)	C7—C10—H10B	109.5
C3^iii—Ba1—Ba1^iv	59.23 (5)	H10A—C10—H10B	109.5
C1—O1—Ba1^i	98.18 (15)	C7—C10—H10C	109.5
C1—O1—Ba1	144.83 (16)	H10A—C10—H10C	109.5
Ba1^i—O1—Ba1	116.31 (7)	H10B—C10—H10C	109.5
O1^i—Ba1—O1—C1	167.8 (3)	O1—C1—C2—C5	−162.6 (2)
O3^ii—Ba1—O1—C1	2.3 (3)	O2—C1—C2—C5	16.1 (3)
O3^iii—Ba1—O1—C1	−63.7 (3)	Ba1^i—C1—C2—C5	−93.6 (5)
O2^i—Ba1—O1—C1	165.8 (3)	O1—C1—C2—C4	75.8 (3)
O9—Ba1—O1—C1	91.4 (3)	O2—C1—C2—C4	−105.5 (3)
O4^iii—Ba1—O1—C1	−104.0 (3)	Ba1^i—C1—C2—C4	144.8 (5)
O4—Ba1—O1—C1	24.2 (3)	O1—C1—C2—C3	−42.1 (3)
O9^iii—Ba1—O1—C1	−125.8 (3)	O2—C1—C2—C3	136.6 (2)
C1^i—Ba1—O1—C1	170.6 (3)	Ba1^i—C1—C2—C3	26.9 (6)
C3^iii—Ba1—O1—C1	−81.6 (3)	Ba1^vi—O3—C3—O4	−123.5 (3)
Ba1^iv—Ba1—O1—C1	−42.8 (3)	Ba1^v—O3—C3—O4	13.0 (3)
O1^i—Ba1—O1—Ba1^i	0.0	Ba1^vi—O3—C3—C2	54.2 (4)
O3^ii—Ba1—O1—Ba1^i	−165.49 (7)	Ba1^v—O3—C3—C2	−169.29 (18)
O3^iii—Ba1—O1—Ba1^i	128.51 (7)	Ba1^vi—O3—C3—Ba1^v	−136.5 (3)
O2^i—Ba1—O1—Ba1^i	−1.98 (9)	Ba1^v—O4—C3—O3	−12.3 (3)
O9—Ba1—O1—Ba1^i	−76.39 (7)	Ba1—O4—C3—O3	101.8 (2)
O4^iii—Ba1—O1—Ba1^i	88.24 (8)	Ba1^v—O4—C3—C2	170.1 (2)
O4—Ba1—O1—Ba1^i	−143.62 (9)	Ba1—O4—C3—C2	−75.8 (3)
O9^iii—Ba1—O1—Ba1^i	66.46 (9)	Ba1—O4—C3—Ba1^v	114.12 (12)
C1^i—Ba1—O1—Ba1^i	2.80 (8)	C5—C2—C3—O3	41.4 (3)
C3^iii—Ba1—O1—Ba1^i	110.60 (8)	C4—C2—C3—O3	165.6 (2)
Ba1^iv—Ba1—O1—Ba1^i	149.41 (4)	C1—C2—C3—O3	−79.9 (3)
O1^i—Ba1—O4—C3	−22.0 (2)	C5—C2—C3—O4	−140.9 (3)
O3^ii—Ba1—O4—C3	−176.18 (18)	C4—C2—C3—O4	−16.7 (4)
O1—Ba1—O4—C3	14.94 (17)	C1—C2—C3—O4	97.9 (3)
O3^iii—Ba1—O4—C3	107.92 (18)	C5—C2—C3—Ba1^v	−20.8 (10)
O2^i—Ba1—O4—C3	−74.9 (2)	C4—C2—C3—Ba1^v	103.4 (9)
O9—Ba1—O4—C3	−74.93 (17)	C1—C2—C3—Ba1^v	−142.1 (9)
O4^iii—Ba1—O4—C3	66.93 (17)	O1^i—Ba1—O9—Ba1^v	−158.20 (7)
O9^iii—Ba1—O4—C3	140.58 (17)	O3^ii—Ba1—O9—Ba1^v	55.80 (7)
C1^i—Ba1—O4—C3	−38.9 (2)	O1—Ba1—O9—Ba1^v	−92.72 (7)
C3^iii—Ba1—O4—C3	87.0 (2)	O3^iii—Ba1—O9—Ba1^v	−19.31 (14)
Ba1^iv—Ba1—O4—C3	145.23 (18)	O2^i—Ba1—O9—Ba1^v	154.21 (7)
O1^i—Ba1—O4—Ba1^v	80.26 (7)	O4^iii—Ba1—O9—Ba1^v	−118.16 (9)
O3^ii—Ba1—O4—Ba1^v	−73.97 (6)	O4—Ba1—O9—Ba1^v	−25.80 (5)
O1—Ba1—O4—Ba1^v	117.15 (7)	O9^iii—Ba1—O9—Ba1^v	130.32 (7)
O3^iii—Ba1—O4—Ba1^v	−149.87 (6)	C1^i—Ba1—O9—Ba1^v	178.41 (7)
O2^i—Ba1—O4—Ba1^v	27.31 (11)	C3^iii—Ba1—O9—Ba1^v	−75.53 (15)
O9—Ba1—O4—Ba1^v	27.29 (5)	Ba1^iv—Ba1—O9—Ba1^v	34.28 (8)
O4^iii—Ba1—O4—Ba1^v	169.14 (7)	O6—C6—C7—C8	−136.7 (3)
O9^iii—Ba1—O4—Ba1^v	−117.20 (10)	O5—C6—C7—C8	46.9 (3)
C1^i—Ba1—O4—Ba1^v	63.31 (10)	O6—C6—C7—C10	103.8 (3)
C3^iii—Ba1—O4—Ba1^v	−170.80 (7)	O5—C6—C7—C10	−72.5 (3)
Ba1^iv—Ba1—O4—Ba1^v	−112.56 (5)	O6—C6—C7—C9	−16.7 (4)
Ba1^i—O1—C1—O2	−19.0 (3)	O5—C6—C7—C9	167.0 (2)
Ba1—O1—C1—O2	172.05 (17)	C6—C7—C8—O8	−131.6 (3)
Ba1^i—O1—C1—C2	159.69 (18)	C10—C7—C8—O8	−13.5 (4)
Ba1—O1—C1—C2	−9.3 (4)	C9—C7—C8—O8	107.2 (3)
Ba1—O1—C1—Ba1^i	−168.9 (3)	C6—C7—C8—O7	51.1 (3)
Ba1^i—O2—C1—O1	17.7 (2)	C10—C7—C8—O7	169.2 (2)
Ba1^i—O2—C1—C2	−161.0 (2)	C9—C7—C8—O7	−70.1 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O6^ii	0.86	1.94	2.778 (3)	163
O9—H9B···O4^vi	0.86	2.02	2.883 (2)	177
O5—H5···O2	0.82	1.78	2.601 (3)	174
O7—H7···O8^vii	0.82	1.84	2.656 (3)	178

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