catena-Poly[[aqua­barium(II)]-μ-aqua-bis­(μ-2′-carboxy­biphenyl-2-carboxyl­ato)]

In the title compound, [Ba{HOOC(C₆H₄)₂CO₂}₂(H₂O)₂] or [Ba(C₁₄H₉O₄)₂(H₂O)₂], the Ba atoms are coordinated by nine O atoms, six from two 2′-carboxy­biphenyl-2-carboxyl­ate (Hbpdc⁻) ligands and three from three coordinated water mol­ecules, resulting in the formation of face-sharing distorted monocapped square anti­prisms. The Hbpdc⁻ ligands bridge the Ba atoms to form a one-dimensional helical polymer, with a Ba...Ba distance across the chain of 4.1386 (17) Å. Adjacent chains are parallel to each other. The two independent ligands are tetra­dentate and have the same coordination mode, exhibiting μ-oxo bridges and η⁸-chelation. The crystal structure is further stabilized by hydrogen bonds within each chain.

S1. Comment

The design of supra-molecular architectures employing dicarboxylic acids as ambidentate and templating ligands, with metals offering interesting connectivity, remains a topical research subject (Rao et al., 2004). The increasing interest is principally due to the tunability of the resulting extended frameworks, among them several layered compounds (Wan et al., 2002; Benmerad, Guehria-Laïdoudi, Bernardinelli & Balegroune, 2000), catena-polymers (Tu et al., 2005; Benmerad, Guehria-Laidoudi, Balegroune et al., 2000; Benmerad et al., 2004b) and three-dimensional cross-linked polynuclear units (Pan et al., 2001; Benmerad et al., 2004a; Djeghri et al., 2006). These compounds typically exhibit infinite M—O—M chains and several poly-membered rings, which favour interactions between the metals and create various kinds of voids.

Therefore, these materials are not only microporous, bringing out interesting chemical properties (ionic exchange), but have useful magnetic (Rueff et al., 2003; Mukherjee et al., 2004), electronic and optical (Kim et al., 2004; Thirumurugan et al., 2004; Millange et al., 2004) properties (electronic and/or magnetic exchange). These properties can be finely tuned, because the dimensionality of the framework, the interpenetration of pores and the orientation of the binding sites may be controlled, depending on synthesis conditions, as well as the characteristics of connectors and linkers.

Using this approach, we investigate the building-block methodology by using 2,2'-biphenyldicarboxylate as a relatively flexible ligand an and alkaline-earth metal as versatile connector. For this latter, a variable coordination number, in the range 7–12, provides the ability of adapting to many different environments. In the course of our studies on coordination polymers with interesting dimensionalities and functionalities, we have selected the barium–H₂bdpc (H₂bdpc is 2,2'-biphenyldicarboxylic acid) system, to extend this research with the title complex, [Ba(Hbdpc)₂(H₂O)₂], (I).

Complex (I) is a one-dimensional helical polymer. The asymmetric unit contains one Ba^II atom, two coordinating water molecules and two tritopic ligands (Hbpdc^-). As shown in Fig. 1, the Ba atom is nine-coordinate. Although they are crystallographically independent, the two ligands exhibit the same coordination mode, involving only one O atom from each end functional group, forming a µ-oxo bridge through atoms O4 and O7, respectively, for ligand L1 and ligand L2, and η⁸ chelation, analogous to the so-called `malonate mode' in the α,ω-aliphatic dicarboxylates.

In the present compound, and in the absence of any bridging exo ligand, this connectivity, seems to exist only with alkaline-earth and rare-earth biphenyldicarboxylates (Thirumurugan et al., 2003, 2004; Wang et al., 2004). As a consequence, a dramatic twist is observed, as shown by the helix formed by the spacer with torsion angles of -84.0 (2)° (C2—C7—C8—C13] in L1 and 84.8 (3)° [C16—C21—C22—C27] in L2.

A comparison with the biphenate compounds presenting the same connectivity shows the great distortions induced in the resulting nine-membered ring. The torsion angles between the two phenyl rings are far from what it has been reported (Thirumurugan et al., 2003,2004), being equal to -5.3 (3)° (C1—C2—C7—C8) and 10.3 (3)° (C14—C13—C8—C7) for L1, and 4.6 (3)° (C15—C16—C21—C22) and -10.9 (3)° (C28—C27—C22—C21) for L2. Several other twists are observed within each diphenyl unit. The functional ends are inclined at 52.28 and 55.52° to each other owing to the helical arrangement of the spacer; between the carboxylate or the carboxylic groups and the corresponding linking phenyl rings, the dihedral angles are small (40.15 and 39.29°, and 59.05 and 53.26°), and the two phenyl rings are nearly perpendicular to each other with dihedral angles of 82.32 and 81.86°. However this geometry is similar to those found in the pure acid (Fronczek et al., 1987) and is not unusual.

The formation of helical chains in one-dimensional coordination polymers is relatively common, particularly when the connectors are running in a zigzag fashion, as in this case. The metal lies in the centre of two square planes formed by atoms O4, O7ⁱ, O4ⁱ and O7 (see Table 1 for symmetry code), which are the O atoms of the carboxylate functional ends, and the set of atoms O1, O1W, O5 and OW2, comprising the O atoms of the second carboxylate groups.

The two square MO₄ and MO₂(H₂O)₂ structural features are almost planar [the maximum deviations being 0.0551 (8) and 0.0031 (3) Å, respectively] and nearly parallel to each other; the dihedral angle between them is 3.11 (7)°. The coordination environment of the Ba atom is completed by the water molecule O1Wⁱ at the apex position of these two squares. The resulting coordination polyhedron is a distorted monocapped square antiprism. The Ba—O bond lengths present a small dispersion [2.6922 (19)–2.9144 (15) Å] and remain within the range reported for barium carboxylate complexes (Bae et al., 2002). The 36 different bond angles around the metal lie in the range 66.35 (4)–142.99 (4)°, which is comparable to that for α,ω-aliphatic dicarboxylates, in the same connectivity. Fig. 2 shows the infinite one-dimensional chain and face-sharing barium polyhedra. Within the chain, each Ba atom is linked to two others, via three bridging O atoms, one from a water molecule (O1W) and two triply coordinated atoms (O4 and O7) from carboxylate groups.

From this point of view, this network, built up from decorated chains of BaO₉ monocapped square antiprisms, is somewhat similar to the recently reported tancoite-related structures (Thirumurugan et al., 2003, 2004). The Ba····Ba distance across the chain is 4.1386 (19) Å. The phenyl rings belonging to the same chain are parallel to each other and the distances between these parallel rings are in the range 3.90–4.42 Å. Adjacent chains are parallel to each other.

There are no direct π–π interactions between the biphenyl groups within the chain, nor along adjacent chains. Several intrachain hydrogen bonds are observed. They involve the two hydrogen-bonding acceptors from uncoordinated carboxylate atoms O3 from L1 and O8 from L2. In each ligand, the same H atom is shared between the protonated end and the deprotonated one of the symmetrical ligands [O3···H2 = 2.670 (2) Å and O8···H6A = 2.677 (2) Å]. Two other, weaker, hydrogen bonds involve the water molecule O1W and the atoms that are not bonded to the metal [O3···O1W = 2.753 (2) Å and O8···O1W = 2.755 (2) Å].

Related literature

For related literature, see: Bae et al. (2002); Benmerad et al. (2004a, 2004b); Benmerad, Guehria-Laïdoudi, Bernardinelli & Balegroune (2000); Benmerad, Guehria-Laidoudi, Balegroune, Birkedal & Chapuis (2000); Djeghri et al. (2006); Fronczek et al. (1987); Kim et al. (2004); Millange et al. (2004); Mukherjee et al. (2004); Pan et al. (2001); Rao et al. (2004); Rueff et al. (2003); Thirumurugan et al. (2003, 2004); Tu et al. (2005); Wan et al. (2002); Wang et al. (2004).

S2. Experimental

A mixture of diphenic acid (0.484 g, 2 mmol) and barium hydroxide octahydrate (0.473 g, 1.5 mmol) in water (20 ml) was heated (353–363 K) and stirred for 30 min, and the resulting mixture was filtered. Colourless single crystals were obtained after several weeks at 313 K.

S3. Refinement

H atoms attached to C atoms were placed in calculated positions and treated as riding, with C—H distances of 0.95 Å and the U_iso(H) values of 1.2U_eq(C). H atoms of water molecules and hydroxyl groups were located in a difference Fourier map and refined with an O—H distance restraint of 0.85 (1) Å and U_iso(H) values of 0.5 Ų.

Computing details

Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. : A view of the coordination environment around the Ba atom, including the labelling scheme, with 50% probability displacement ellipsoids. [Symmetry codes: (i) 1/2 - x, -1/2 + y, 1/2 - z; (ii) 1/2 - x, -1/2 + y, 1/2 - z.]
	Fig. 2. : The one-dimensional chain of BaO9 polyhedra, viewed along the b axis. [Symmetry codes: (i) 1/2 - x, -1/2 + y, 1/2 - z; (ii) 1/2 - x, -1/2 + y, 1/2 - z; (iii) x, y - 1, z.]

catena-Poly[aquabarium(II)]-µ-aqua-bis(µ-2-carboxybiphenyl-2- carboxylato)barium(II)]

Crystal data

[Ba(C14H9O4)2(H2O)2]	F(000) = 1304
Mr = 655.80	Dx = 1.690 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2140 reflections
a = 16.418 (5) Å	θ = 2.4–25.2°
b = 7.171 (4) Å	µ = 1.60 mm^−1
c = 22.428 (5) Å	T = 294 K
β = 102.543 (5)°	Prism, colourles
V = 2577.5 (17) Å^3	0.40 × 0.10 × 0.05 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	11547 independent reflections
Radiation source: fine-focus sealed tube	9372 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω and ϕ scans	θmax = 35.6°, θmin = 2.8°
Absorption correction: empirical (using intensity measurements) (DENZO–SMN; Otwinowski & Minor, 1997)	h = 0→26
Tmin = 0.619, Tmax = 0.917	k = 0→11
11569 measured reflections	l = −36→35

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0177P)^2 + 2.6715P] where P = (Fo^2 + 2Fc^2)/3
11547 reflections	(Δ/σ)max = 0.007
370 parameters	Δρmax = 0.80 e Å^−3
6 restraints	Δρmin = −0.90 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	0.222786 (6)	0.036792 (13)	0.203900 (4)	0.02144 (3)
O1	0.31678 (10)	−0.0351 (2)	0.11565 (6)	0.0368 (3)
O2	0.35314 (12)	−0.2308 (2)	0.04892 (7)	0.0422 (4)
O3	0.31488 (9)	0.4883 (2)	0.11605 (7)	0.0337 (3)
O4	0.32954 (9)	0.33399 (19)	0.20375 (6)	0.0293 (3)
O5	0.05186 (9)	−0.0355 (2)	0.16062 (7)	0.0397 (3)
O6	−0.04340 (11)	−0.2325 (2)	0.11083 (10)	0.0565 (5)
O7	0.13835 (8)	0.33648 (18)	0.23587 (6)	0.0283 (2)
O8	0.05696 (9)	0.4857 (2)	0.15822 (7)	0.0344 (3)
O1W	0.20646 (8)	−0.32653 (18)	0.17341 (6)	0.0275 (2)
O2W	0.15789 (12)	0.2371 (3)	0.09483 (8)	0.0465 (4)
C1	0.35535 (11)	0.3818 (2)	0.15706 (8)	0.0252 (3)
C2	0.43886 (11)	0.3092 (3)	0.15061 (9)	0.0277 (3)
C3	0.50233 (14)	0.3021 (3)	0.20294 (11)	0.0398 (5)
H3	0.4909	0.3367	0.2412	0.048*
C4	0.58206 (15)	0.2454 (4)	0.20004 (13)	0.0518 (6)
H4	0.6252	0.2431	0.2359	0.062*
C5	0.59833 (14)	0.1923 (4)	0.14474 (14)	0.0539 (7)
H5	0.6530	0.1545	0.1425	0.065*
C6	0.53558 (14)	0.1936 (4)	0.09252 (12)	0.0437 (5)
H6	0.5474	0.1540	0.0549	0.052*
C7	0.45477 (12)	0.2523 (3)	0.09428 (9)	0.0301 (3)
C8	0.39019 (12)	0.2419 (3)	0.03610 (8)	0.0282 (3)
C9	0.38657 (14)	0.3799 (3)	−0.00829 (10)	0.0365 (4)
H9	0.4221	0.4856	0.0003	0.044*
C10	0.33199 (16)	0.3649 (3)	−0.06465 (10)	0.0428 (5)
H10	0.3292	0.4622	−0.0938	0.051*
C11	0.28182 (15)	0.2107 (4)	−0.07876 (10)	0.0430 (5)
H11	0.2445	0.2015	−0.1175	0.052*
C12	0.28597 (14)	0.0686 (3)	−0.03624 (9)	0.0353 (4)
H12	0.2530	−0.0404	−0.0464	0.042*
C13	0.33864 (12)	0.0856 (3)	0.02143 (8)	0.0282 (3)
C14	0.33561 (11)	−0.0644 (3)	0.06736 (8)	0.0280 (3)
C15	0.06747 (10)	0.3828 (2)	0.20513 (8)	0.0255 (3)
C16	−0.00739 (11)	0.3109 (3)	0.22602 (8)	0.0269 (3)
C17	−0.00296 (14)	0.3050 (3)	0.28894 (10)	0.0378 (4)
H17	0.0475	0.3393	0.3163	0.045*
C18	−0.07065 (18)	0.2502 (4)	0.31188 (12)	0.0499 (6)
H18	−0.0672	0.2491	0.3547	0.060*
C19	−0.14327 (17)	0.1971 (4)	0.27222 (13)	0.0543 (7)
H19	−0.1905	0.1613	0.2877	0.065*
C20	−0.14756 (14)	0.1959 (4)	0.21005 (12)	0.0466 (5)
H20	−0.1975	0.1555	0.1833	0.056*
C21	−0.08038 (11)	0.2525 (3)	0.18556 (9)	0.0301 (4)
C22	−0.09045 (11)	0.2416 (3)	0.11774 (9)	0.0304 (4)
C23	−0.13609 (14)	0.3795 (3)	0.08145 (11)	0.0428 (5)
H23	−0.1554	0.4843	0.1003	0.051*
C24	−0.15393 (17)	0.3671 (4)	0.01836 (12)	0.0540 (7)
H24	−0.1834	0.4649	−0.0056	0.065*
C25	−0.12910 (15)	0.2138 (4)	−0.00959 (11)	0.0505 (6)
H25	−0.1412	0.2058	−0.0529	0.061*
C26	−0.08626 (13)	0.0704 (4)	0.02525 (10)	0.0412 (5)
H26	−0.0714	−0.0384	0.0059	0.049*
C27	−0.06497 (11)	0.0859 (3)	0.08876 (9)	0.0301 (4)
C28	−0.01266 (11)	−0.0646 (3)	0.12426 (9)	0.0304 (4)
H1A	0.1597 (10)	−0.381 (4)	0.1657 (12)	0.046*
H1B	0.2377 (14)	−0.383 (4)	0.1539 (11)	0.046*
H2A	0.1200 (13)	0.313 (3)	0.0983 (12)	0.046*
H2B	0.1956 (13)	0.301 (3)	0.0842 (12)	0.046*
H2	0.3444 (17)	−0.313 (3)	0.0737 (10)	0.046*
H6A	−0.0136 (14)	−0.319 (3)	0.1304 (11)	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.02512 (5)	0.01712 (4)	0.02099 (4)	0.00041 (3)	0.00260 (3)	0.00034 (3)
O1	0.0496 (9)	0.0365 (7)	0.0281 (6)	−0.0021 (7)	0.0168 (6)	0.0006 (6)
O2	0.0655 (11)	0.0275 (7)	0.0404 (8)	0.0039 (7)	0.0262 (8)	0.0044 (6)
O3	0.0367 (7)	0.0342 (7)	0.0331 (7)	0.0095 (6)	0.0139 (6)	0.0088 (5)
O4	0.0351 (7)	0.0276 (6)	0.0267 (6)	−0.0018 (5)	0.0105 (5)	0.0004 (5)
O5	0.0300 (7)	0.0401 (8)	0.0421 (8)	0.0031 (6)	−0.0073 (6)	−0.0012 (7)
O6	0.0419 (9)	0.0298 (8)	0.0823 (13)	0.0006 (7)	−0.0204 (9)	0.0002 (8)
O7	0.0233 (6)	0.0270 (6)	0.0318 (6)	0.0004 (5)	0.0001 (5)	−0.0026 (5)
O8	0.0277 (6)	0.0350 (7)	0.0383 (7)	−0.0008 (5)	0.0022 (5)	0.0104 (6)
O1W	0.0280 (6)	0.0227 (6)	0.0325 (6)	−0.0011 (5)	0.0080 (5)	−0.0035 (5)
O2W	0.0567 (11)	0.0433 (9)	0.0378 (8)	0.0056 (8)	0.0064 (8)	0.0067 (7)
C1	0.0289 (8)	0.0211 (7)	0.0265 (7)	−0.0018 (6)	0.0078 (6)	−0.0024 (6)
C2	0.0257 (8)	0.0244 (7)	0.0335 (9)	−0.0022 (6)	0.0079 (6)	−0.0014 (6)
C3	0.0354 (10)	0.0379 (11)	0.0422 (11)	0.0018 (8)	0.0001 (8)	−0.0037 (9)
C4	0.0328 (11)	0.0503 (14)	0.0644 (16)	0.0022 (10)	−0.0068 (10)	−0.0047 (12)
C5	0.0251 (9)	0.0552 (15)	0.0806 (19)	0.0050 (10)	0.0099 (11)	−0.0051 (14)
C6	0.0319 (10)	0.0459 (12)	0.0578 (14)	0.0010 (9)	0.0196 (9)	−0.0053 (11)
C7	0.0274 (8)	0.0274 (8)	0.0379 (9)	−0.0022 (7)	0.0123 (7)	−0.0009 (7)
C8	0.0308 (8)	0.0267 (8)	0.0306 (8)	0.0018 (7)	0.0146 (7)	−0.0011 (6)
C9	0.0472 (11)	0.0290 (9)	0.0391 (10)	−0.0010 (8)	0.0218 (9)	0.0028 (8)
C10	0.0586 (14)	0.0374 (11)	0.0370 (10)	0.0082 (10)	0.0208 (10)	0.0122 (9)
C11	0.0491 (12)	0.0498 (13)	0.0293 (9)	0.0050 (10)	0.0068 (9)	0.0071 (9)
C12	0.0399 (10)	0.0384 (11)	0.0281 (8)	−0.0024 (8)	0.0087 (7)	0.0014 (7)
C13	0.0317 (8)	0.0286 (8)	0.0270 (8)	0.0010 (7)	0.0123 (6)	0.0008 (6)
C14	0.0270 (8)	0.0297 (9)	0.0278 (8)	−0.0023 (6)	0.0072 (6)	0.0012 (6)
C15	0.0230 (7)	0.0234 (7)	0.0284 (8)	−0.0003 (6)	0.0021 (6)	−0.0038 (6)
C16	0.0251 (7)	0.0249 (7)	0.0306 (8)	0.0013 (6)	0.0057 (6)	−0.0022 (6)
C17	0.0410 (11)	0.0404 (11)	0.0331 (10)	−0.0059 (9)	0.0104 (8)	−0.0052 (8)
C18	0.0615 (16)	0.0529 (14)	0.0426 (12)	−0.0067 (12)	0.0274 (11)	−0.0046 (11)
C19	0.0445 (13)	0.0661 (17)	0.0605 (16)	−0.0079 (12)	0.0296 (12)	−0.0019 (13)
C20	0.0273 (9)	0.0586 (15)	0.0546 (14)	−0.0075 (10)	0.0104 (9)	−0.0039 (12)
C21	0.0236 (8)	0.0293 (8)	0.0369 (9)	0.0014 (6)	0.0051 (7)	−0.0017 (7)
C22	0.0226 (7)	0.0315 (9)	0.0336 (9)	−0.0024 (7)	−0.0015 (6)	0.0029 (7)
C23	0.0376 (10)	0.0319 (10)	0.0523 (13)	0.0006 (8)	−0.0048 (9)	0.0054 (9)
C24	0.0505 (14)	0.0505 (15)	0.0513 (14)	−0.0032 (11)	−0.0099 (11)	0.0223 (12)
C25	0.0433 (12)	0.0719 (18)	0.0316 (10)	−0.0061 (12)	−0.0026 (9)	0.0141 (11)
C26	0.0321 (9)	0.0577 (14)	0.0320 (9)	−0.0003 (9)	0.0033 (7)	−0.0001 (9)
C27	0.0224 (7)	0.0359 (9)	0.0297 (8)	−0.0007 (7)	0.0008 (6)	0.0015 (7)
C28	0.0250 (8)	0.0337 (9)	0.0313 (8)	0.0025 (7)	0.0031 (6)	−0.0022 (7)

Geometric parameters (Å, º)

Ba1—O1W	2.6922 (19)	C7—C8	1.494 (3)
Ba1—O7	2.7360 (16)	C8—C9	1.396 (3)
Ba1—O4	2.7598 (17)	C8—C13	1.400 (3)
Ba1—O7^i	2.7836 (14)	C9—C10	1.386 (3)
Ba1—O1	2.8091 (15)	C9—H9	0.9500
Ba1—O5	2.8113 (17)	C10—C11	1.374 (4)
Ba1—O4^i	2.8136 (14)	C10—H10	0.9500
Ba1—O2W	2.8373 (18)	C11—C12	1.387 (3)
Ba1—O1W^ii	2.9144 (15)	C11—H11	0.9500
Ba1—Ba1^ii	4.1386 (17)	C12—C13	1.396 (3)
Ba1—Ba1^i	4.1386 (17)	C12—H12	0.9500
O1—C14	1.208 (2)	C13—C14	1.498 (3)
O2—C14	1.315 (2)	C15—C16	1.499 (3)
O2—H2	0.84 (2)	C16—C17	1.398 (3)
O3—C1	1.267 (2)	C16—C21	1.401 (3)
O4—C1	1.259 (2)	C17—C18	1.379 (3)
O5—C28	1.206 (2)	C17—H17	0.9500
O6—C28	1.315 (3)	C18—C19	1.377 (4)
O6—H6A	0.853 (10)	C18—H18	0.9500
O7—C15	1.261 (2)	C19—C20	1.381 (4)
O8—C15	1.266 (2)	C19—H19	0.9500
O1W—H1A	0.85 (2)	C20—C21	1.395 (3)
O1W—H1B	0.85 (2)	C20—H20	0.9500
O2W—H2A	0.84 (2)	C21—C22	1.496 (3)
O2W—H2B	0.85 (2)	C22—C23	1.392 (3)
C1—C2	1.503 (3)	C22—C27	1.401 (3)
C2—C3	1.391 (3)	C23—C24	1.384 (4)
C2—C7	1.405 (3)	C23—H23	0.9500
C3—C4	1.386 (3)	C24—C25	1.371 (4)
C3—H3	0.9500	C24—H24	0.9500
C4—C5	1.378 (4)	C25—C26	1.387 (4)
C4—H4	0.9500	C25—H25	0.9500
C5—C6	1.382 (4)	C26—C27	1.395 (3)
C5—H5	0.9500	C26—H26	0.9500
C6—C7	1.401 (3)	C27—C28	1.497 (3)
C6—H6	0.9500
O1W—Ba1—O7	142.99 (4)	C7—C2—C1	122.61 (16)
O1W—Ba1—O4	140.83 (4)	C4—C3—C2	120.9 (2)
O7—Ba1—O4	75.63 (5)	C4—C3—H3	119.6
O1W—Ba1—O7^i	69.50 (4)	C2—C3—H3	119.6
O7—Ba1—O7^i	133.34 (3)	C5—C4—C3	119.6 (2)
O4—Ba1—O7^i	86.89 (5)	C5—C4—H4	120.2
O1W—Ba1—O1	71.53 (4)	C3—C4—H4	120.2
O7—Ba1—O1	135.71 (4)	C4—C5—C6	120.4 (2)
O4—Ba1—O1	72.22 (5)	C4—C5—H5	119.8
O7^i—Ba1—O1	74.33 (5)	C6—C5—H5	119.8
O1W—Ba1—O5	72.36 (4)	C5—C6—C7	121.0 (2)
O7—Ba1—O5	73.19 (5)	C5—C6—H6	119.5
O4—Ba1—O5	136.77 (4)	C7—C6—H6	119.5
O7^i—Ba1—O5	136.33 (5)	C6—C7—C2	118.34 (19)
O1—Ba1—O5	112.51 (5)	C6—C7—C8	117.20 (18)
O1W—Ba1—O4^i	69.96 (4)	C2—C7—C8	124.39 (16)
O7—Ba1—O4^i	87.71 (5)	C9—C8—C13	118.04 (18)
O4—Ba1—O4^i	134.07 (3)	C9—C8—C7	119.98 (18)
O7^i—Ba1—O4^i	74.03 (4)	C13—C8—C7	121.57 (17)
O1—Ba1—O4^i	136.57 (5)	C10—C9—C8	121.0 (2)
O5—Ba1—O4^i	73.58 (5)	C10—C9—H9	119.5
O1W—Ba1—O2W	105.83 (5)	C8—C9—H9	119.5
O7—Ba1—O2W	73.24 (5)	C11—C10—C9	120.6 (2)
O4—Ba1—O2W	74.20 (5)	C11—C10—H10	119.7
O7^i—Ba1—O2W	142.59 (5)	C9—C10—H10	119.7
O1—Ba1—O2W	69.28 (5)	C10—C11—C12	119.7 (2)
O5—Ba1—O2W	68.65 (5)	C10—C11—H11	120.2
O4^i—Ba1—O2W	141.15 (5)	C12—C11—H11	120.1
O1W—Ba1—O1W^ii	124.23 (4)	C11—C12—C13	120.0 (2)
O7—Ba1—O1W^ii	66.99 (4)	C11—C12—H12	120.0
O4—Ba1—O1W^ii	67.57 (4)	C13—C12—H12	120.0
O7^i—Ba1—O1W^ii	66.35 (4)	C12—C13—C8	120.58 (18)
O1—Ba1—O1W^ii	124.03 (5)	C12—C13—C14	117.91 (17)
O5—Ba1—O1W^ii	123.46 (4)	C8—C13—C14	121.47 (17)
O4^i—Ba1—O1W^ii	66.52 (4)	O1—C14—O2	123.80 (18)
O2W—Ba1—O1W^ii	129.93 (5)	O1—C14—C13	123.01 (18)
O1W—Ba1—Ba1^ii	164.61 (3)	O2—C14—C13	113.16 (16)
O7—Ba1—Ba1^ii	41.86 (3)	O7—C15—O8	123.42 (17)
O4—Ba1—Ba1^ii	42.55 (3)	O7—C15—C16	117.43 (16)
O7^i—Ba1—Ba1^ii	98.01 (4)	O8—C15—C16	119.15 (15)
O1—Ba1—Ba1^ii	114.77 (3)	C17—C16—C21	119.64 (18)
O5—Ba1—Ba1^ii	115.05 (3)	C17—C16—C15	117.36 (16)
O4^i—Ba1—Ba1^ii	98.47 (4)	C21—C16—C15	123.00 (17)
O2W—Ba1—Ba1^ii	89.55 (5)	C18—C17—C16	121.0 (2)
O1W^ii—Ba1—Ba1^ii	40.39 (3)	C18—C17—H17	119.5
O1W—Ba1—Ba1^i	44.54 (4)	C16—C17—H17	119.5
O7—Ba1—Ba1^i	128.04 (4)	C19—C18—C17	119.5 (2)
O4—Ba1—Ba1^i	126.97 (4)	C19—C18—H18	120.2
O7^i—Ba1—Ba1^i	40.99 (3)	C17—C18—H18	120.2
O1—Ba1—Ba1^i	95.80 (4)	C18—C19—C20	120.1 (2)
O5—Ba1—Ba1^i	95.95 (4)	C18—C19—H19	120.0
O4^i—Ba1—Ba1^i	41.55 (3)	C20—C19—H19	120.0
O2W—Ba1—Ba1^i	150.37 (4)	C19—C20—C21	121.6 (2)
O1W^ii—Ba1—Ba1^i	79.69 (4)	C19—C20—H20	119.2
Ba1^ii—Ba1—Ba1^i	120.08 (3)	C21—C20—H20	119.2
C14—O1—Ba1	161.94 (14)	C20—C21—C16	118.04 (19)
C14—O2—H2	110.3 (19)	C20—C21—C22	117.58 (18)
C1—O4—Ba1	122.66 (11)	C16—C21—C22	124.36 (17)
C1—O4—Ba1^ii	133.08 (12)	C23—C22—C27	118.17 (19)
Ba1—O4—Ba1^ii	95.90 (5)	C23—C22—C21	118.96 (19)
C28—O5—Ba1	158.34 (15)	C27—C22—C21	122.36 (17)
C28—O6—H6A	113.8 (18)	C24—C23—C22	121.3 (2)
C15—O7—Ba1	121.55 (11)	C24—C23—H23	119.4
C15—O7—Ba1^ii	133.67 (12)	C22—C23—H23	119.4
Ba1—O7—Ba1^ii	97.14 (5)	C25—C24—C23	120.1 (2)
Ba1—O1W—Ba1^i	95.07 (4)	C25—C24—H24	120.0
Ba1—O1W—H1A	122.3 (19)	C23—C24—H24	120.0
Ba1^i—O1W—H1A	101.3 (18)	C24—C25—C26	120.1 (2)
Ba1—O1W—H1B	124.0 (19)	C24—C25—H25	119.9
Ba1^i—O1W—H1B	99.4 (18)	C26—C25—H25	119.9
H1A—O1W—H1B	107 (3)	C25—C26—C27	120.0 (2)
Ba1—O2W—H2A	113.2 (19)	C25—C26—H26	120.0
Ba1—O2W—H2B	110.9 (19)	C27—C26—H26	120.0
H2A—O2W—H2B	106 (3)	C26—C27—C22	120.23 (19)
O4—C1—O3	123.33 (17)	C26—C27—C28	118.23 (19)
O4—C1—C2	117.69 (16)	C22—C27—C28	121.52 (17)
O3—C1—C2	118.98 (16)	O5—C28—O6	123.39 (19)
C3—C2—C7	119.79 (18)	O5—C28—C27	123.56 (19)
C3—C2—C1	117.60 (17)	O6—C28—C27	113.03 (16)
O1W—Ba1—O1—C14	77.3 (4)	O3—C1—C2—C7	−39.5 (3)
O7—Ba1—O1—C14	−72.4 (4)	C7—C2—C3—C4	2.1 (3)
O4—Ba1—O1—C14	−117.8 (4)	C1—C2—C3—C4	−176.8 (2)
O7^i—Ba1—O1—C14	150.5 (4)	C2—C3—C4—C5	−1.1 (4)
O5—Ba1—O1—C14	16.3 (4)	C3—C4—C5—C6	−0.6 (4)
O4^i—Ba1—O1—C14	105.9 (4)	C4—C5—C6—C7	1.3 (4)
O2W—Ba1—O1—C14	−38.4 (4)	C5—C6—C7—C2	−0.3 (3)
O1W^ii—Ba1—O1—C14	−163.3 (4)	C5—C6—C7—C8	−177.7 (2)
Ba1^ii—Ba1—O1—C14	−117.8 (4)	C3—C2—C7—C6	−1.4 (3)
Ba1^i—Ba1—O1—C14	115.2 (4)	C1—C2—C7—C6	177.52 (19)
O1W—Ba1—O4—C1	51.19 (16)	C3—C2—C7—C8	175.73 (19)
O7—Ba1—O4—C1	−120.93 (14)	C1—C2—C7—C8	−5.3 (3)
O7^i—Ba1—O4—C1	102.72 (14)	C6—C7—C8—C9	−79.4 (2)
O1—Ba1—O4—C1	28.19 (13)	C2—C7—C8—C9	103.4 (2)
O5—Ba1—O4—C1	−76.04 (15)	C6—C7—C8—C13	93.1 (2)
O4^i—Ba1—O4—C1	166.86 (13)	C2—C7—C8—C13	−84.0 (2)
O2W—Ba1—O4—C1	−44.64 (14)	C13—C8—C9—C10	1.6 (3)
O1W^ii—Ba1—O4—C1	168.38 (15)	C7—C8—C9—C10	174.46 (19)
Ba1^ii—Ba1—O4—C1	−151.87 (16)	C8—C9—C10—C11	−1.9 (3)
Ba1^i—Ba1—O4—C1	111.96 (13)	C9—C10—C11—C12	−0.1 (4)
O1W—Ba1—O4—Ba1^ii	−156.94 (5)	C10—C11—C12—C13	2.4 (3)
O7—Ba1—O4—Ba1^ii	30.94 (4)	C11—C12—C13—C8	−2.7 (3)
O7^i—Ba1—O4—Ba1^ii	−105.41 (5)	C11—C12—C13—C14	175.06 (19)
O1—Ba1—O4—Ba1^ii	−179.95 (5)	C9—C8—C13—C12	0.6 (3)
O5—Ba1—O4—Ba1^ii	75.83 (7)	C7—C8—C13—C12	−172.05 (18)
O4^i—Ba1—O4—Ba1^ii	−41.27 (6)	C9—C8—C13—C14	−177.01 (17)
O2W—Ba1—O4—Ba1^ii	107.23 (6)	C7—C8—C13—C14	10.3 (3)
O1W^ii—Ba1—O4—Ba1^ii	−39.75 (4)	Ba1—O1—C14—O2	−101.2 (4)
Ba1^i—Ba1—O4—Ba1^ii	−96.18 (4)	Ba1—O1—C14—C13	76.7 (5)
O1W—Ba1—O5—C28	−76.5 (4)	C12—C13—C14—O1	−119.4 (2)
O7—Ba1—O5—C28	117.2 (4)	C8—C13—C14—O1	58.4 (3)
O4—Ba1—O5—C28	71.6 (4)	C12—C13—C14—O2	58.8 (2)
O7^i—Ba1—O5—C28	−106.6 (4)	C8—C13—C14—O2	−123.5 (2)
O1—Ba1—O5—C28	−16.0 (4)	Ba1—O7—C15—O8	−85.0 (2)
O4^i—Ba1—O5—C28	−150.2 (4)	Ba1^ii—O7—C15—O8	57.0 (2)
O2W—Ba1—O5—C28	39.0 (4)	Ba1—O7—C15—C16	95.12 (17)
O1W^ii—Ba1—O5—C28	163.6 (4)	Ba1^ii—O7—C15—C16	−122.89 (15)
Ba1^ii—Ba1—O5—C28	118.0 (4)	O7—C15—C16—C17	39.2 (2)
Ba1^i—Ba1—O5—C28	−114.8 (4)	O8—C15—C16—C17	−140.73 (19)
O1W—Ba1—O7—C15	−49.80 (16)	O7—C15—C16—C21	−141.45 (18)
O4—Ba1—O7—C15	121.94 (14)	O8—C15—C16—C21	38.6 (3)
O7^i—Ba1—O7—C15	−166.66 (13)	C21—C16—C17—C18	−2.9 (3)
O1—Ba1—O7—C15	77.52 (15)	C15—C16—C17—C18	176.5 (2)
O5—Ba1—O7—C15	−27.73 (13)	C16—C17—C18—C19	1.2 (4)
O4^i—Ba1—O7—C15	−101.27 (14)	C17—C18—C19—C20	1.1 (4)
O2W—Ba1—O7—C15	44.43 (14)	C18—C19—C20—C21	−1.8 (4)
O1W^ii—Ba1—O7—C15	−166.67 (14)	C19—C20—C21—C16	0.2 (4)
Ba1^ii—Ba1—O7—C15	153.33 (16)	C19—C20—C21—C22	178.5 (2)
Ba1^i—Ba1—O7—C15	−112.06 (13)	C17—C16—C21—C20	2.1 (3)
O1W—Ba1—O7—Ba1^ii	156.87 (5)	C15—C16—C21—C20	−177.21 (19)
O4—Ba1—O7—Ba1^ii	−31.39 (4)	C17—C16—C21—C22	−176.12 (19)
O7^i—Ba1—O7—Ba1^ii	40.01 (6)	C15—C16—C21—C22	4.6 (3)
O1—Ba1—O7—Ba1^ii	−75.82 (7)	C20—C21—C22—C23	78.2 (3)
O5—Ba1—O7—Ba1^ii	178.93 (5)	C16—C21—C22—C23	−103.5 (2)
O4^i—Ba1—O7—Ba1^ii	105.40 (5)	C20—C21—C22—C27	−93.4 (2)
O2W—Ba1—O7—Ba1^ii	−108.90 (6)	C16—C21—C22—C27	84.8 (3)
O1W^ii—Ba1—O7—Ba1^ii	40.00 (4)	C27—C22—C23—C24	−1.9 (3)
Ba1^i—Ba1—O7—Ba1^ii	94.61 (4)	C21—C22—C23—C24	−173.9 (2)
O7—Ba1—O1W—Ba1^i	−96.41 (7)	C22—C23—C24—C25	2.3 (4)
O4—Ba1—O1W—Ba1^i	96.33 (6)	C23—C24—C25—C26	0.2 (4)
O7^i—Ba1—O1W—Ba1^i	39.75 (4)	C24—C25—C26—C27	−3.0 (4)
O1—Ba1—O1W—Ba1^i	119.43 (5)	C25—C26—C27—C22	3.3 (3)
O5—Ba1—O1W—Ba1^i	−118.58 (5)	C25—C26—C27—C28	−175.0 (2)
O4^i—Ba1—O1W—Ba1^i	−40.10 (4)	C23—C22—C27—C26	−0.9 (3)
O2W—Ba1—O1W—Ba1^i	−179.41 (5)	C21—C22—C27—C26	170.81 (18)
O1W^ii—Ba1—O1W—Ba1^i	0.330 (16)	C23—C22—C27—C28	177.38 (18)
Ba1^ii—Ba1—O1W—Ba1^i	2.65 (13)	C21—C22—C27—C28	−10.9 (3)
Ba1—O4—C1—O3	84.8 (2)	Ba1—O5—C28—O6	97.7 (4)
Ba1^ii—O4—C1—O3	−55.2 (2)	Ba1—O5—C28—C27	−80.9 (4)
Ba1—O4—C1—C2	−95.76 (17)	C26—C27—C28—O5	125.9 (2)
Ba1^ii—O4—C1—C2	124.20 (15)	C22—C27—C28—O5	−52.4 (3)
O4—C1—C2—C3	−40.0 (2)	C26—C27—C28—O6	−52.8 (3)
O3—C1—C2—C3	139.4 (2)	C22—C27—C28—O6	128.9 (2)
O4—C1—C2—C7	141.03 (18)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −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
O1W—H1A···O8^iii	0.85 (2)	1.91 (2)	2.755 (3)	173 (3)
O1W—H1B···O3^iii	0.85 (2)	1.91 (3)	2.753 (3)	175 (2)
O2—H2···O3^iii	0.84 (2)	1.84 (2)	2.670 (3)	170 (2)
O6—H6A···O8^iii	0.85 (2)	1.84 (2)	2.677 (3)	169 (2)

Symmetry code: (iii) x, y−1, z.