Poly[[di­aqua­barium(II)]-μ₅-m-phenylenedioxydiacetato]: a three-dimensional barium(II) coordination polymer

In the title coordination polymer, [Ba(1,3-BDOA)(H₂O)₂]_n (where 1,3-BDOA²⁻ is the m-phenylenedioxydiacetate dianion, C₁₀H₈O₆), each Ba^II ion is ten-coordinated by six carboxyl O atoms and two ether O atoms from different 1,3-BDOA²⁻ ligands, as well as by two water mol­ecules, thus defining a dodeca­hedron. The Ba^II atoms are covalently linked by 1,3-BDOA²⁻ ligands in different crystallographic directions, giving rise to a three-dimensional open framework. The crystal structure is further stabilized by hydrogen bonds and π–π stacking inter­actions. In previously studied polymers of this type, the 1,3-BDOA²⁻ ligand showed multiple bridging modes with metal ions, including bi-, tri-, tetra- and hexa­dentate. The title Ba^II complex represents a novel three-dimensional coordination polymer constructed by octa­dentate bridging 1,3-BDOA²⁻ ligands.

S1. Comment

The field of metal-ion-directed assembly of organic molecular building blocks is giving access to new open-framework solid-state materials (Andrea, 2003). Compared with the extensively investigated transition metal coordination polymers, it is surprising to see the relatively small number of alkali earth coordination polymers in the literature (Guo et al., 2002). The oxidation states and atomic radii of alkali earth metals are comparable with those of the late divalent transition metals, which could, in principle, lead to similar networks in the solid state. However, the lack of d-orbital electrons in alkali earth metals could result in coordination numbers greater than six, and for the larger alkali earth metals, a higher coordination number is expected (Huo et al., 2004). Benzene-1,3-dioxyacetic acid (1,3-BDOAH₂) is a potential flexible multidentate ligand containing two oxyacetate groups, which could be used as a terminal ligand or a bridging ligand with different coordination modes when coordinated to various metal ions (see scheme). In addition to its versatile coordination modes, 1,3-BDOAH₂ may take part in hydrogen-bonding interactions by functioning as either a hydrogen-bond donor or an acceptor, and in π–π stacking interactions via its benzene ring. Recently, we have reported the structures of three one-dimensional chain polymers, namely [Cu(1,3-BDOA)(bipy)(H₂O)]_n (Liu et al., 2004), {[Zn(1,3-BDOA)(H₂O)₂](H₂O)₂}_n (Gao, Li et al., 2004) and {[Cu(1,3-BDOA)(phen)(H₂O)]·2H₂O}_n (Gao, Liu et al., 2004a), as well as three two-dimensional layer polymers, namely [Cd(1,3-BDOA)]_n (Gao, Liu et al., 2004b), [Cd(1,3-BDOA)(imidazole)₂]_n (Gao, Liu et al., 2004c) and [Mn(1,3-BDOA)(H₂O)₃]_n (Gao, Liu et al., 2004d), within which the metal ions have tetrahedral, square-pyramidal and octahedral configurations. The work described here is an investigation into the hydrothermal synthesis and structural characterization of the title novel three-dimensional Ba^II coordination polymer, [Ba(1,3-BDOA)(H₂O)₂]_n, (I), in which the Ba^II atom has tenfold coordination and the 1,3-BDOA²⁻ dianion adopts a novel octadentate bridging mode.

As shown in Fig. 1, the asymmetric building unit of complex (I) consists of one Ba^II atom, one 1,3-BDOA²⁻ dianion and two coordinated water molecules. Each Ba^II atom is ten-coordinated by two ether O atoms, six carboxyl O atoms from different 1,3-BDOA²⁻ ligands and two water molecules. The coordination geometry can best be described as a dodecahedron (Fig. 2). The O—Ba—O angles are distributed over a broad range, 43.13 (6)–148.23 (7)°. The Ba—O_carboxyl distances fall in the range 2.736 (2)–3.218 (2) Å (Table 1), within which the Ba—O3 and Ba—O6ⁱⁱⁱ [symmetry code: (iii) x − 1, 3/2 − y, z − 1/2] distances are considerably longer than the maximum Ba—O value of 3.161 (2) Å in the complex [Ba(H₂O)₅][Cu(C₂O₄)₂(H₂O)] (Bouayad et al., 1995). The Ba—O_water distances are similar to those of the complex [Ba(Hbtc)(H₂O)₂]·0.5H₂O [2.860 (6) and 2.877 (6) Å; Hbtc is benzene-1,3,5-tricarboxylate; Platers et al., 1997], (II). In (II), the Ba ion is coordinated by two bidentate carboxylate groups, three monodentate carboxylate groups and two water molecules.

In (I), the 1,3-BDOA²⁻ group adopts two coordination modes, namely bridging tridentate and bridging pentadentate. In the first case, the phenoxyacetate group (O1/C1/O2), in a bidentate chelating mode, is coordinated to atom Ba1 through ether atom O3 and carboxyl atom O1, and joins the adjacent atom Ba1A through the bridging atom O2, with a Ba1···Ba1A separation of 6.734 (3) Å [symmetry code: (A) x, 3/2 − y, z + 1/2]. In the second case, the phenoxyacetate group (O5/C10/O6) chelates to atom Ba1C through carboxyl atoms O5 and O6, bridges to a neighbouring atom Ba1D through atom O6, and chelates to atom Ba1B through ether atom O4 and carboxyl atom O5, with the Ba1B···Ba1C and Ba1C···Ba1D separations being 4.755 (3) Å [symmetry codes: (B) 1 − x, 1 − y, 1 − z; (C) x + 1, 3/2 − y, z + 1/2; (D) 1 − x, 2 − y, 1 − z]. The Ba1···Ba1C separation is 12.895 (3) Å. Thus, the 1,3-BDOA²⁻ ligand provides a total of eight binding sites to link five Ba atoms and give two five-membered chelate rings (O1/C1/C2/O3/Ba1 and O4/C9/C10/O5/Ba1B) and one four-membered ring (C10/O5/Ba1C/O6). The two five-membered chelate rings are non-planar, while the four-membered chelate ring is essentially planar, with an r.m.s. deviation of 0.07 (3) Å. The dihedral angles between the carboxyl groups and the aromatic ring are 11.30 (7)° (O1/C1/O2) and 62.28 (7)° (O6/C10/O5), respectively. One oxyacetate group and aromatic ring are almost coplanar, with a torsion angle of −177.7 (3) (C3—O3—C2—C1), while another oxyacetate group and benzene ring are not perfectly coplanar, with a torsion angle of −153.1 (3) ° (C7—O4—C9—C10).

Adjacent Ba^II atoms share the carboxyl atoms O6^iv and O5ⁱⁱⁱ [symmetry code: (iv) 1 − x, 2 − y, 1 − z], to afford a Ba₂O₂ four-membered ring [Ba···Ba 4.755 (3) Å], and are further linked by a pair of 1,3-BDOA²⁻ ligands to produce a centrosymmetric macrocyclic structure. As a consequence of the 1,3-BDOA²⁻ bridges, polymer (I) has an extended three-dimensional open framework, with alternating `organic' and `inorganic' sheets (Fig. 3). There are inorganic sheets lying parallel to the (011) plane at x = −1, 0, 1, etc., and which contain all the hydrogen bonds (Table 2). Intermolecular hydrogen-bond interactions are found between the water molecule and the carboxylate O atoms [O···O 2.748 (3)–3.085 (4) Å and O—H···O 127 (4)–176 (4)°]. Between these inorganic sheets there are organic sheets, which are also parallel to (011) at x = −1/2, 1/2, 3/2, etc. The shortest centroid–centroid separation between inversion-related aromatic rings is 3.495 (3) Å and the shortest plane–plane separation between aromatic rings at (x, y, z) and (1 − x, 1 − y, 1 − z) is 3.341 (3) Å, indicating some π–π stacking interactions between organic sheets. These weak supramolecular interactions, together with the coordinate-covalent interactions between metal ions and organic ligands, strengthen the stability of the whole crystal structure.

S2. Experimental

Benzene-1,3-dioxyacetic acid was prepared following the method described for the synthesis of benzene-1,2-dioxyacetic acid by Mirci (1990). BaCl₂·2H₂O (2.40 g, 10 mmol), pyridine (1 ml) and 1,3-BDOAH₂ (2.26 g, 10 mmol) were dissolved in water (30 ml). The mixture was sealed in a 50 ml Teflon-lined stainless steel bomb and held at 393 K for 5 d. The bomb was cooled naturally to room temperature, and colourless prismatic crystals of (I) were obtained. CH analysis: calculated for C₁₀H₁₂O₈Ba: C 30.21, H 3.04%; found: C 30.17, H 3.08%.

S3. Refinement

Water H atoms were located in a difference map and refined with O—H and H···H distance restraints of 0.85 (1) and 1.39 (1) Å, respectively, and with U_iso(H) = 1.5U_eq(O). C-bound H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å and U_iso(H) = 1.2U_eq(C), and were refined in the riding-model approximation. The largest residual peak (1.172 e Å⁻³) is close to the Ba atoms.

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: Please provide missing details.

Figures

	Fig. 1. A view of the title complex, with displacement ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, 3/2 − y, z − 1/2; (iii) x − 1, 3/2 − y, z − 1/2; (iv) 1 − x, 2 − y, 1 − z; (A) x, 3/2 − y, z + 1/2; (B) 1 − x, 1 − y, 1 − z; (C) x + 1, 3/2 − y, z + 1/2; (D) 1 − x, 2 − y, 1 − z.]
	Fig. 2. The coordination dodecahedron of the Ba atom in (I). [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, 3/2 − y, z − 1/2; (iii) x − 1, 3/2 − y, z − 1/2; (iv) 1 − x, 2 − y, 1 − z].
	Fig. 3. A packing diagram for (I). Intramolecular hydrogen bonds are shown as dashed lines. H atoms attached to C atoms have been omitted.

Poly[bisaquabarium(II)-µ-benzene-1,3-dioxyacetato-κ³O,O':O'']

Crystal data

[Ba(C10H8O6)(H2O)2]	F(000) = 768
Mr = 397.53	Dx = 2.158 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10381 reflections
a = 13.476 (3) Å	θ = 3.2–27.4°
b = 7.3396 (15) Å	µ = 3.28 mm^−1
c = 13.166 (3) Å	T = 295 K
β = 110.00 (3)°	Prism, colourless
V = 1223.7 (5) Å^3	0.38 × 0.25 × 0.19 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	2787 independent reflections
Radiation source: fine-focus sealed tube	2553 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 10 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −17→17
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→9
Tmin = 0.379, Tmax = 0.535	l = −17→17
10955 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.631P] where P = (Fo^2 + 2Fc^2)/3
2787 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 1.17 e Å^−3
6 restraints	Δρmin = −0.99 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ba1	0.120172 (12)	0.65340 (2)	0.302207 (13)	0.01977 (8)
O1	0.15957 (18)	0.8953 (3)	0.47376 (19)	0.0316 (5)
O2	0.22264 (19)	0.8979 (4)	0.6535 (2)	0.0413 (6)
O3	0.34616 (17)	0.7914 (3)	0.46229 (17)	0.0276 (5)
O4	0.72382 (18)	0.6765 (3)	0.6157 (2)	0.0310 (5)
O5	0.91956 (17)	0.7007 (3)	0.7640 (2)	0.0288 (5)
O6	0.89359 (19)	0.9954 (3)	0.78365 (19)	0.0339 (5)
O1W	0.1167 (2)	0.4928 (3)	0.4933 (2)	0.0355 (5)
O2W	−0.0107 (2)	0.6677 (3)	0.0780 (2)	0.0322 (5)
C1	0.2321 (2)	0.8814 (4)	0.5630 (3)	0.0233 (6)
C2	0.3444 (2)	0.8428 (4)	0.5663 (3)	0.0250 (7)
C3	0.4437 (2)	0.7466 (4)	0.4565 (2)	0.0225 (6)
C4	0.4441 (3)	0.6965 (5)	0.3556 (3)	0.0300 (7)
C5	0.5379 (3)	0.6398 (5)	0.3441 (3)	0.0329 (8)
C6	0.6321 (3)	0.6377 (5)	0.4315 (3)	0.0285 (7)
C7	0.6297 (2)	0.6901 (4)	0.5309 (3)	0.0231 (6)
C8	0.5367 (2)	0.7454 (5)	0.5447 (2)	0.0261 (6)
C9	0.7427 (2)	0.8128 (4)	0.6972 (3)	0.0283 (7)
C10	0.8613 (2)	0.8368 (4)	0.7515 (3)	0.0215 (6)
H1W1	0.111 (3)	0.525 (5)	0.553 (2)	0.053*
H1W2	0.082 (3)	0.395 (4)	0.472 (3)	0.053*
H2W1	−0.055 (2)	0.583 (4)	0.054 (3)	0.048*
H2W2	0.039 (2)	0.658 (5)	0.053 (4)	0.048*
H2A	0.3874	0.9507	0.5909	0.030*
H2B	0.3745	0.7455	0.6175	0.030*
H4	0.3822	0.7007	0.2960	0.036*
H5	0.5378	0.6023	0.2766	0.040*
H6	0.6950	0.6020	0.4228	0.034*
H8	0.5367	0.7813	0.6124	0.031*
H9A	0.7113	0.7766	0.7503	0.034*
H9B	0.7110	0.9270	0.6652	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.01834 (12)	0.01959 (12)	0.02083 (12)	0.00071 (6)	0.00598 (8)	−0.00118 (6)
O1	0.0230 (11)	0.0365 (12)	0.0293 (12)	0.0080 (10)	0.0012 (9)	−0.0089 (10)
O2	0.0306 (13)	0.0694 (17)	0.0291 (12)	0.0079 (13)	0.0168 (10)	−0.0004 (13)
O3	0.0174 (10)	0.0454 (13)	0.0193 (10)	0.0072 (10)	0.0054 (8)	−0.0007 (10)
O4	0.0180 (11)	0.0376 (12)	0.0309 (13)	0.0064 (9)	0.0001 (9)	−0.0135 (10)
O5	0.0188 (10)	0.0262 (10)	0.0389 (13)	−0.0007 (9)	0.0067 (9)	−0.0037 (10)
O6	0.0397 (13)	0.0230 (10)	0.0318 (12)	−0.0067 (10)	0.0027 (10)	−0.0026 (10)
O1W	0.0388 (14)	0.0379 (13)	0.0338 (13)	−0.0016 (11)	0.0176 (11)	−0.0013 (11)
O2W	0.0280 (12)	0.0321 (12)	0.0370 (14)	−0.0070 (9)	0.0117 (11)	−0.0115 (10)
C1	0.0186 (14)	0.0238 (13)	0.0279 (16)	0.0009 (11)	0.0084 (12)	−0.0043 (12)
C2	0.0191 (15)	0.0357 (18)	0.0191 (15)	0.0026 (11)	0.0049 (12)	−0.0021 (12)
C3	0.0151 (13)	0.0278 (15)	0.0245 (14)	0.0013 (11)	0.0067 (11)	−0.0005 (12)
C4	0.0212 (15)	0.0471 (18)	0.0210 (15)	0.0014 (14)	0.0062 (12)	0.0001 (14)
C5	0.0266 (17)	0.053 (2)	0.0202 (16)	0.0040 (14)	0.0099 (13)	−0.0008 (14)
C6	0.0208 (15)	0.0413 (19)	0.0261 (16)	0.0035 (13)	0.0115 (13)	−0.0001 (13)
C7	0.0165 (13)	0.0261 (14)	0.0230 (15)	0.0020 (11)	0.0022 (11)	−0.0021 (12)
C8	0.0196 (14)	0.0365 (17)	0.0212 (14)	0.0029 (12)	0.0057 (11)	−0.0064 (13)
C9	0.0167 (14)	0.0321 (15)	0.0325 (17)	0.0023 (12)	0.0038 (12)	−0.0121 (14)
C10	0.0226 (15)	0.0212 (14)	0.0216 (15)	−0.0028 (10)	0.0088 (12)	−0.0019 (11)

Geometric parameters (Å, º)

Ba1—O1	2.778 (2)	O6—Ba1^vii	3.173 (3)
Ba1—O2^i	2.781 (3)	O6—C10	1.264 (3)
Ba1—O3	3.218 (2)	O1W—H1W1	0.85 (3)
Ba1—O4^ii	3.146 (2)	O1W—H1W2	0.85 (3)
Ba1—O5^iii	2.789 (2)	O2W—H2W1	0.85 (3)
Ba1—O5^ii	2.736 (2)	O2W—H2W2	0.84 (3)
Ba1—O6^iv	2.795 (2)	C1—C2	1.526 (4)
Ba1—O6^iii	3.173 (3)	C2—H2A	0.9700
Ba1—O1W	2.794 (2)	C2—H2B	0.9700
Ba1—O2W	2.876 (3)	C3—C4	1.380 (4)
Ba1—Ba1^v	4.7752 (9)	C3—C8	1.386 (4)
Ba1—C10^iii	3.320 (3)	C4—C5	1.387 (5)
O1—C1	1.249 (4)	C4—H4	0.9300
O2—Ba1^vi	2.781 (3)	C5—C6	1.391 (5)
O2—C1	1.246 (4)	C5—H5	0.9300
O3—C2	1.428 (4)	C6—C7	1.375 (5)
O3—C3	1.383 (4)	C6—H6	0.9300
O4—Ba1^ii	3.146 (2)	C7—C8	1.388 (4)
O4—C7	1.377 (4)	C8—H8	0.9300
O4—C9	1.425 (4)	C9—C10	1.522 (4)
O5—Ba1^ii	2.736 (2)	C9—H9A	0.9700
O5—Ba1^vii	2.789 (2)	C9—H9B	0.9700
O5—C10	1.245 (4)	C10—Ba1^vii	3.320 (3)
O6—Ba1^iv	2.795 (2)
O1—Ba1—O2^i	131.02 (8)	O3—C3—C8	124.0 (3)
O1—Ba1—O3	52.50 (6)	O4^ii—Ba1—Ba1^v	79.35 (5)
O1—Ba1—O4^ii	107.05 (7)	O4^ii—Ba1—C10^iii	128.21 (7)
O1—Ba1—O5^iii	78.77 (7)	O4—C7—C8	122.5 (3)
O1—Ba1—O6^iv	72.98 (7)	O4—C9—C10	108.9 (2)
O1—Ba1—O6^iii	101.18 (7)	O4—C9—H9A	109.9
O1—Ba1—O1W	66.08 (8)	O4—C9—H9B	109.9
O1—Ba1—O2W	133.69 (7)	O5^iii—Ba1—Ba1^v	73.91 (5)
O2^i—Ba1—O3	85.25 (7)	O5^ii—Ba1—Ba1^v	30.51 (5)
O2^i—Ba1—O4^ii	72.74 (8)	O5^iii—Ba1—C10^iii	21.33 (6)
O2^i—Ba1—O5^iii	127.52 (8)	O5^ii—Ba1—C10^iii	83.04 (7)
O2^i—Ba1—O6^iv	79.64 (8)	O5—C10—Ba1^vii	54.54 (16)
O2^i—Ba1—O6^iii	126.57 (7)	O5—C10—O6	124.4 (3)
O2^i—Ba1—O1W	137.96 (8)	O5—C10—C9	118.8 (3)
O2^i—Ba1—O2W	63.91 (7)	O6—C10—Ba1^vii	72.27 (18)
O4^ii—Ba1—O3	69.24 (6)	O6^iii—Ba1—Ba1^v	34.22 (4)
O4^ii—Ba1—O6^iii	105.90 (6)	O6^iv—Ba1—Ba1^v	130.36 (5)
O5^ii—Ba1—O1	145.96 (8)	O6^iv—Ba1—C10^iii	88.79 (7)
O5^ii—Ba1—O2^i	74.76 (8)	O6^iii—Ba1—C10^iii	22.30 (6)
O5^ii—Ba1—O3	123.10 (6)	O6—C10—C9	116.7 (3)
O5^iii—Ba1—O3	129.74 (7)	O1W—Ba1—Ba1^v	73.53 (6)
O5^ii—Ba1—O4^ii	54.07 (6)	O1W—Ba1—C10^iii	81.38 (8)
O5^iii—Ba1—O4^ii	148.23 (7)	O2W—Ba1—Ba1^v	67.36 (5)
O5^ii—Ba1—O5^iii	103.61 (5)	O2W—Ba1—C10^iii	63.86 (8)
O5^ii—Ba1—O6^iv	140.23 (7)	C1—O1—Ba1	125.7 (2)
O5^iii—Ba1—O6^iv	69.32 (7)	C1—O2—Ba1^vi	153.8 (2)
O5^ii—Ba1—O6^iii	64.53 (6)	C1—C2—H2A	109.4
O5^iii—Ba1—O6^iii	43.13 (6)	C1—C2—H2B	109.4
O5^ii—Ba1—O1W	79.89 (7)	C2—O3—Ba1	112.88 (17)
O5^iii—Ba1—O1W	90.60 (8)	C3—O3—Ba1	126.45 (18)
O5^ii—Ba1—O2W	73.93 (7)	C3—O3—C2	116.3 (2)
O5^iii—Ba1—O2W	65.45 (8)	C3—C4—C5	119.2 (3)
O6^iv—Ba1—O3	83.78 (7)	C3—C4—H4	120.4
O6^iii—Ba1—O3	146.02 (6)	C3—C8—C7	119.3 (3)
O6^iv—Ba1—O4^ii	142.45 (7)	C3—C8—H8	120.3
O6^iv—Ba1—O6^iii	110.94 (6)	C4—C3—O3	115.6 (3)
O6^iv—Ba1—O2W	67.59 (6)	C4—C3—C8	120.3 (3)
O1W—Ba1—O3	81.17 (7)	C4—C5—C6	121.4 (3)
O1W—Ba1—O4^ii	65.23 (7)	C4—C5—H5	119.3
O1W—Ba1—O6^iv	137.23 (7)	C5—C4—H4	120.4
O1W—Ba1—O6^iii	67.16 (7)	C5—C6—H6	120.9
O1W—Ba1—O2W	138.28 (7)	C6—C5—H5	119.3
O2W—Ba1—O3	140.50 (7)	C6—C7—O4	115.9 (3)
O2W—Ba1—O4^ii	118.94 (6)	C6—C7—C8	121.5 (3)
O2W—Ba1—O6^iii	72.38 (7)	C7—O4—Ba1^ii	131.01 (17)
Ba1^ii—O5—Ba1^vii	119.62 (8)	C7—O4—C9	116.0 (2)
Ba1^iv—O6—Ba1^vii	106.12 (8)	C7—C6—C5	118.1 (3)
Ba1—O1W—H1W1	139 (3)	C7—C6—H6	120.9
Ba1—O1W—H1W2	103 (3)	C7—C8—H8	120.3
Ba1—O2W—H2W1	118 (3)	C9—O4—Ba1^ii	110.81 (18)
Ba1—O2W—H2W2	96 (3)	C9—C10—Ba1^vii	163.6 (2)
O1—Ba1—Ba1^v	130.36 (6)	C10^iii—Ba1—Ba1^v	52.87 (5)
O1—Ba1—C10^iii	92.59 (7)	C10—O5—Ba1^ii	132.36 (19)
O1—C1—C2	119.4 (3)	C10—O5—Ba1^vii	104.12 (18)
O2^i—Ba1—Ba1^v	98.31 (6)	C10—O6—Ba1^iv	138.3 (2)
O2^i—Ba1—C10^iii	127.00 (8)	C10—O6—Ba1^vii	85.42 (19)
O2—C1—O1	126.0 (3)	C10—C9—H9A	109.9
O2—C1—C2	114.5 (3)	C10—C9—H9B	109.9
O3—C2—H2B	109.4	H1W1—O1W—H1W2	109 (4)
O3—Ba1—Ba1^v	145.83 (4)	H2W1—O2W—H2W2	110 (4)
O3—Ba1—C10^iii	144.97 (7)	H2A—C2—H2B	108.0
O3—C2—C1	111.3 (3)	H9A—C9—H9B	108.3
O3—C2—H2A	109.4
Ba1^v—Ba1—O1—C1	96.1 (3)	O4—C7—C8—C3	−176.6 (3)
Ba1^v—Ba1—O3—C2	−81.7 (2)	O4—C9—C10—Ba1^vii	26.4 (9)
Ba1^v—Ba1—O3—C3	73.8 (2)	O4—C9—C10—O5	−35.2 (4)
Ba1—O1—C1—O2	−132.4 (3)	O4—C9—C10—O6	146.6 (3)
Ba1—O1—C1—C2	48.3 (4)	O5^ii—Ba1—O1—C1	55.7 (3)
Ba1^vi—O2—C1—O1	40.4 (8)	O5^iii—Ba1—O1—C1	153.5 (3)
Ba1^vi—O2—C1—C2	−140.3 (4)	O5^ii—Ba1—O3—C2	−111.15 (19)
Ba1—O3—C2—C1	−19.6 (3)	O5^iii—Ba1—O3—C2	44.0 (2)
Ba1—O3—C3—C4	25.0 (4)	O5^ii—Ba1—O3—C3	44.4 (3)
Ba1—O3—C3—C8	−153.3 (2)	O6^iv—Ba1—O1—C1	−134.9 (3)
Ba1^ii—O4—C7—C6	−53.4 (4)	O6^iii—Ba1—O1—C1	116.4 (3)
Ba1^ii—O4—C7—C8	123.9 (3)	O6^iv—Ba1—O3—C2	100.43 (19)
Ba1^ii—O4—C9—C10	41.9 (3)	O6^iii—Ba1—O3—C2	−18.4 (2)
Ba1^ii—O5—C10—Ba1^vii	−156.8 (3)	O6^iv—Ba1—O3—C3	−104.1 (2)
Ba1^ii—O5—C10—O6	−176.6 (2)	O6^iii—Ba1—O3—C3	137.2 (2)
Ba1^vii—O5—C10—O6	−19.7 (4)	O1W—Ba1—O1—C1	57.7 (3)
Ba1^ii—O5—C10—C9	5.5 (4)	O1W—Ba1—O3—C2	−39.40 (19)
Ba1^vii—O5—C10—C9	162.3 (2)	O1W—Ba1—O3—C3	116.1 (2)
Ba1^iv—O6—C10—Ba1^vii	109.2 (3)	O2W—Ba1—O1—C1	−167.4 (2)
Ba1^iv—O6—C10—O5	126.0 (3)	O2W—Ba1—O3—C2	143.12 (18)
Ba1^vii—O6—C10—O5	16.8 (3)	O2W—Ba1—O3—C3	−61.4 (3)
Ba1^iv—O6—C10—C9	−56.0 (4)	C2—O3—C3—C4	179.7 (3)
Ba1^vii—O6—C10—C9	−165.2 (3)	C2—O3—C3—C8	1.4 (5)
O1—Ba1—O3—C2	27.15 (18)	C3—O3—C2—C1	−177.7 (3)
O1—Ba1—O3—C3	−177.3 (3)	C3—C4—C5—C6	−2.0 (5)
O1—C1—C2—O3	−11.7 (4)	C4—C3—C8—C7	−1.2 (5)
O2^i—Ba1—O1—C1	−76.0 (3)	C4—C5—C6—C7	1.4 (5)
O2^i—Ba1—O3—C2	−179.5 (2)	C5—C6—C7—O4	176.7 (3)
O2^i—Ba1—O3—C3	−24.0 (2)	C5—C6—C7—C8	−0.6 (5)
O2—C1—C2—O3	168.9 (3)	C6—C7—C8—C3	0.6 (5)
O5^iii—Ba1—O3—C3	−160.5 (2)	C7—O4—C9—C10	−153.1 (3)
O3—Ba1—O1—C1	−39.6 (2)	C8—C3—C4—C5	1.9 (5)
O3—C3—C4—C5	−176.5 (3)	C9—O4—C7—C6	145.4 (3)
O3—C3—C8—C7	177.0 (3)	C9—O4—C7—C8	−37.4 (4)
O4^ii—Ba1—O1—C1	5.7 (3)	C10^iii—Ba1—O1—C1	137.1 (3)
O4^ii—Ba1—O3—C2	−106.2 (2)	C10^iii—Ba1—O3—C2	21.5 (2)
O4^ii—Ba1—O3—C3	49.3 (2)	C10^iii—Ba1—O3—C3	177.0 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O6^viii	0.85 (3)	2.18 (2)	2.986 (4)	158 (4)
O1W—H1W2···O2W^v	0.85 (3)	1.93 (3)	2.775 (4)	176 (4)
O2W—H2W1···O1^v	0.85 (3)	1.91 (3)	2.748 (3)	168 (4)
O2W—H2W2···O1^i	0.84 (3)	2.25 (4)	3.085 (4)	173 (3)
O2W—H2W2···O2^i	0.84 (3)	2.41 (4)	2.995 (4)	127 (4)

Symmetry codes: (i) x, −y+3/2, z−1/2; (v) −x, y−1/2, −z+1/2; (viii) −x+1, y−1/2, −z+3/2.