{[Ca₅(C₈H₄O₄)₅(H₂O)₉]·8H₂O}_n: the first crystallographically characterized non-transition metal salt of isophthalic acid

The reaction of CaCO₃ with isophthalic acid in water yields nona­aqua­penta-[mu]-isophthalato-pentacalcium octahydrate, {[Ca₅(C₈H₄O₄)₅(H₂O)₉]·8H₂O}_n, a complex polymeric one-dimensional column structure bearing metal-carboxyl­ate bonds and Ca-bound terminal and bridging water mol­ecules, in addition to hydrogen-bonded water mol­ecules of crystallization. The asymmetric unit comprises half of the formula unit, with one Ca²⁺ ion located on a twofold axis, and contains 16 unique strong O-H...O hydrogen bonds, some of which link the columns together.

S1. Comment

The benzenepolycarboxylic acid family has been extensively exploited in the challenge of creating functional porous supramolecular architectures (Yaghi et al., 1998; Janiak, 1997). While numerous examples of polymeric metal-organic frameworks (MOFs) exist in the literature, containing the more commonly used terephthalic (e.g. Groeneman et al., 1999) and trimesic (e.g. Yaghi et al., 1995) acids, a search of the Cambridge Structural Database (Version 5.24, July 2003 update; Allen, 2002) has highlighted the use of isophthalic acid (H₂IPA, benzene-1,3-dicarboxylic acid), predominantly in mixed-ligand metal complexes, for example in combination with derivatives of 4,4'-bipyridine (Bourne et al., 2001; Tao et al., 2000, 2002). Only two examples exist of solely hydrated salts of H₂IPA, namely those of Zn²⁺ (Otto & Wheeler, 2001) and La³⁺ (Kim et al., 2001), and this led us to investigate the synthesis of other hydrated metal salts of H₂IPA, including the title Ca²⁺ salt, (I), presented here. \sch

The asymmetric unit of (I), {[Ca(C₈H₄O₄)]₅.17H₂O}_n, contains half of a formula unit, with 2.5 Ca²⁺ cations, 2.5 IPA²⁻ anionic ligands and 8.5 H₂O molecules. The two full-weight Ca²⁺ ions (Ca1 and Ca2) both have a coordination number of eight, with the coordination sphere of atom Ca1 comprising six metal-carboxylate bonds and two terminal metal-OH₂ bonds, while atom Ca2 has six metal-carboxylate bonds, one terminal metal-OH₂ bond and one bridging metal-OH₂ bond, with the H₂O molecule (atom O15) bridging atoms Ca2 and Ca3, which lies on a twofold axis. In contrast, atom Ca3 has a coordination number of nine and makes six metal-carboxylate bonds, in addition to one terminal and two bridging metal-OH₂ bonds (Fig. 1 and Table 1). The Ca—O bond lengths are in the range 2.3252 (12)–2.7746 (13) Å for metal-carboxylate bonds and 2.3568 (13)–2.5800 (16) Å for metal-OH₂ bonds, which compare well with bond lengths observed in the literature, for example in calcium terephthalate trihydrate (Dale & Elsegood, 2003).

The carboxylate groups of the IPA²⁻ anions and their respective benzene rings lie close to coplanarity, with the greatest twist angle being 10.0 (3)°, while the aromatic rings of the anions lie at angles of roughly 60° to each other [dihedral angles with respect to the C1—C6 ring: carboxyl groups C7/O1/O2 6.5 (2) and C8/O3/O4 4.8 (2)°, and rings C9—C14 63.45 (6) and C17—C20 62.84 (6)°; dihedral angles with respect to the C9—C14 ring: carboxyl groups C15/O5/O6 6.3 (2) and C16/O7/O8 1.0 (2)°, and ring C17—C20 62.15 (5)°; dihedral angle with respect to the C17—C20 ring: carboxyl group C21/O9/O10 10.0 (3)°].

Each unique carboxylate group in (I) chelates one Ca²⁺ centre, with one of its O atoms also bridging a second Ca²⁺ centre, producing an η²:η¹:µ₂ motif. This creates an infinte one-dimensional coordination polymer which, viewed end on, approximates to a five-pointed star in cross-section. An extensive array of 16 unique strong O—H···O hydrogen bonds (Table 2) between metal-coordinated water molecules, water molecules of crystallization and carboxyl O atoms produces an extensive hydrogen-bonding network, too complex to describe here in detail. Packing plots reveal that each column (propagating parallel to the crystallographic a axis) is connected, either via direct or water-bridged hydrogen-bond paths, to five neighbouring columns (Fig. 2).

S2. Experimental

Isophthalic acid (1 equivalent) was refluxed with CaCO₃ (1 equivalent) in H₂O for 24 h, producing X-ray quality colourless crystals of (I), in quantitative yield, upon slow evaporation of the cooled filtered solution. The crystals were observed to desolvate at 318–323 K. Spectroscopic analysis: IR (KBr, ν_max, cm⁻¹): 3442 (br, OH), 3136 and 3118 (aromatic C—H), 1603 and 1533 (asymmetric CO₂⁻), 1479, 1448, 1394 (symmetric CO₂⁻), 1280, 1163, 1107, 1080 (C—O), 942, 916, 840, 833, 745, 725 (aromatic C—H). Analysis calculated for Ca₅C₄₀H₅₅O₃₇: C 36.17, H, 4.17%; found: C 36.39, H 3.63%.

S3. Refinement

In the refinement of the water molecules 1,2 and 1,3 distances were refined with the SHELX commands SADI 0.005 > and DFIX 1.33 0.005 respectively. Aromatic H atoms were placed in geometric positions (C—H distance = 0.95 Å) using a riding model, while the coordinates of the water H atoms were refined using geometric restraints on the O—H bond lengths and H—O—H bond angles. U_iso(H) values were set to 1.2U_eq for aryl H (1.5U_eq for water H). Atom O14 is disordered over two equally occupied sets of positions close to a twofold axis and restraints were applied to the anisotropic displacment parameters for this atom.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures

	Fig. 1. A view of (I), showing the atom-labelling scheme and the completed Ca^2+ coordination spheres. Displacement ellipsoids are drawn at the 50% probability level and all H atoms have been omitted for clarity. Atoms with the suffix A are at the symmetry position (-x, y, 1/2 − z), B at (1 − x, y, 1/2 − z) and C at (x + 1, y, z).
	Fig. 2. A packing plot of (I) showing the one-dimensional coordination polymer columns extending parallel to the crystallographic a axis. H atoms have been omitted for clarity and hydrogen-bond O···O contacts are shown by dashed lines.

Nonaaquapenta-µ-isophthalato-pentacalcium octahydrate

Crystal data

[Ca5(C8H4O4)5(H2O)9]·8H2O	F(000) = 2760
Mr = 1327.24	Dx = 1.666 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9880 reflections
a = 15.6289 (8) Å	θ = 2.4–28.9°
b = 21.2640 (11) Å	µ = 0.62 mm^−1
c = 17.1852 (9) Å	T = 150 K
β = 112.134 (2)°	Block, colourless
V = 5290.3 (5) Å^3	0.38 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	6434 independent reflections
Radiation source: sealed tube	5100 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω rotation with narrow frames scans	θmax = 29.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −20→21
Tmin = 0.836, Tmax = 0.941	k = −27→28
23336 measured reflections	l = −23→22

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0373P)^2 + 4.8388P] where P = (Fo^2 + 2Fc^2)/3
6434 reflections	(Δ/σ)max = 0.001
428 parameters	Δρmax = 0.46 e Å^−3
169 restraints	Δρmin = −0.33 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	Occ. (<1)
Ca1	0.07805 (2)	0.457932 (16)	0.18124 (2)	0.01297 (8)
O11	−0.00015 (9)	0.55510 (6)	0.15074 (9)	0.0230 (3)
H11A	−0.0562 (4)	0.5500 (10)	0.1297 (12)	0.034*
H11B	0.0140 (12)	0.5817 (8)	0.1233 (12)	0.034*
O12	0.12621 (9)	0.48871 (7)	0.06916 (8)	0.0243 (3)
H12A	0.1028 (12)	0.5119 (9)	0.0287 (10)	0.036*
H12B	0.1808 (5)	0.4842 (11)	0.0773 (13)	0.036*
Ca2	0.26313 (2)	0.350822 (16)	0.14830 (2)	0.01424 (8)
O13	0.16860 (9)	0.33877 (7)	0.00341 (8)	0.0226 (3)
H13A	0.1127 (5)	0.3397 (10)	−0.0085 (13)	0.034*
H13B	0.1816 (12)	0.3655 (8)	−0.0246 (12)	0.034*
Ca3	0.5000	0.29311 (2)	0.2500	0.01577 (11)
O14	0.5268 (2)	0.18294 (12)	0.2545 (3)	0.0328 (8)	0.50
H14A	0.5000	0.1493 (3)	0.2500	0.049*
H14B	0.5726 (10)	0.1776 (6)	0.2431 (17)	0.049*	0.5
O15	0.34963 (11)	0.26034 (8)	0.12884 (12)	0.0416 (4)
H15A	0.336 (2)	0.2240 (5)	0.1343 (15)	0.062*
H15B	0.349 (2)	0.2652 (12)	0.0814 (8)	0.062*
O16	0.80877 (9)	0.55494 (7)	0.08166 (8)	0.0273 (3)
H16A	0.7611 (9)	0.5487 (12)	0.0410 (7)	0.041*
H16B	0.7998 (14)	0.5464 (12)	0.1244 (7)	0.041*
O17	−0.63010 (12)	0.31325 (8)	−0.01361 (10)	0.0384 (4)
H17A	−0.5769 (8)	0.3056 (12)	0.0178 (12)	0.058*
H17B	−0.6430 (15)	0.2912 (11)	−0.0556 (10)	0.058*
O18	0.81026 (12)	0.66462 (8)	0.25007 (18)	0.0710 (7)
H18A	0.797 (2)	0.6273 (4)	0.244 (2)	0.107*
H18B	0.7630 (13)	0.6854 (12)	0.230 (2)	0.107*
O19	−0.48254 (9)	0.15049 (6)	0.04840 (8)	0.0217 (3)
H19A	−0.4629 (14)	0.1856 (5)	0.0651 (13)	0.033*
H19B	−0.4625 (14)	0.1394 (9)	0.0130 (11)	0.033*
C1	−0.20145 (12)	0.37312 (8)	0.07094 (11)	0.0154 (3)
C2	−0.25026 (11)	0.35537 (8)	0.12087 (11)	0.0146 (3)
H2	−0.2285	0.3680	0.1781	0.017*
C3	−0.33079 (11)	0.31929 (8)	0.08768 (11)	0.0154 (3)
C4	−0.36152 (12)	0.30049 (8)	0.00366 (11)	0.0179 (4)
H4	−0.4157	0.2756	−0.0194	0.021*
C5	−0.31343 (12)	0.31792 (9)	−0.04639 (11)	0.0201 (4)
H5	−0.3348	0.3048	−0.1034	0.024*
C6	−0.23420 (12)	0.35444 (9)	−0.01336 (11)	0.0184 (4)
H6	−0.2021	0.3668	−0.0481	0.022*
C7	−0.11385 (11)	0.41116 (8)	0.10758 (10)	0.0140 (3)
O1	−0.06599 (8)	0.42079 (6)	0.06309 (7)	0.0164 (3)
O2	−0.08804 (8)	0.43137 (6)	0.18196 (7)	0.0161 (2)
C8	−0.38557 (11)	0.30216 (8)	0.14082 (11)	0.0153 (3)
O3	−0.35612 (8)	0.31834 (6)	0.21711 (7)	0.0179 (3)
O4	−0.46099 (8)	0.27332 (6)	0.10720 (8)	0.0204 (3)
C9	0.46903 (12)	0.47596 (8)	0.11969 (10)	0.0154 (3)
C10	0.56102 (11)	0.46398 (8)	0.17083 (10)	0.0148 (3)
H10	0.5761	0.4273	0.2048	0.018*
C11	0.63094 (11)	0.50527 (8)	0.17253 (10)	0.0145 (3)
C12	0.60808 (12)	0.55805 (8)	0.12027 (11)	0.0160 (3)
H12	0.6553	0.5860	0.1198	0.019*
C13	0.51661 (12)	0.56986 (8)	0.06888 (11)	0.0179 (4)
H13	0.5017	0.6057	0.0332	0.022*
C14	0.44682 (12)	0.52953 (8)	0.06953 (11)	0.0172 (4)
H14	0.3842	0.5385	0.0359	0.021*
C15	0.39582 (11)	0.43069 (8)	0.12058 (10)	0.0153 (3)
O5	0.31161 (8)	0.44388 (6)	0.08099 (8)	0.0189 (3)
O6	0.42038 (8)	0.38049 (6)	0.16321 (8)	0.0169 (3)
C16	0.72924 (11)	0.49231 (8)	0.23008 (10)	0.0143 (3)
O7	0.74746 (8)	0.44345 (6)	0.27512 (7)	0.0157 (2)
O8	0.79235 (8)	0.53032 (6)	0.23120 (7)	0.0171 (3)
C17	0.05483 (11)	0.25618 (8)	0.21605 (10)	0.0140 (3)
C18	0.05440 (12)	0.19063 (8)	0.21597 (11)	0.0172 (4)
H18	0.0916	0.1684	0.1925	0.021*
C19	0.0000	0.15749 (12)	0.2500	0.0186 (5)
H19	0.0000	0.1128	0.2500	0.022*
C20	0.0000	0.28929 (11)	0.2500	0.0140 (5)
H20	0.0000	0.3340	0.2500	0.017*
C21	0.11630 (11)	0.29059 (8)	0.18050 (10)	0.0147 (3)
O9	0.10972 (8)	0.34960 (6)	0.17077 (8)	0.0166 (3)
O10	0.17496 (8)	0.25890 (6)	0.16277 (8)	0.0183 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.01177 (16)	0.01394 (17)	0.01339 (16)	0.00028 (12)	0.00496 (13)	0.00073 (13)
O11	0.0155 (6)	0.0224 (7)	0.0309 (7)	0.0017 (5)	0.0086 (6)	0.0066 (6)
O12	0.0204 (7)	0.0341 (8)	0.0211 (7)	0.0066 (6)	0.0109 (6)	0.0106 (6)
Ca2	0.01200 (16)	0.01587 (17)	0.01498 (16)	−0.00110 (13)	0.00525 (13)	0.00018 (13)
O13	0.0179 (7)	0.0276 (7)	0.0212 (7)	−0.0031 (6)	0.0060 (6)	0.0026 (6)
Ca3	0.0138 (2)	0.0149 (2)	0.0198 (2)	0.000	0.00779 (19)	0.000
O14	0.044 (3)	0.0184 (13)	0.0454 (18)	−0.0050 (11)	0.027 (2)	−0.0012 (14)
O15	0.0233 (8)	0.0412 (10)	0.0659 (12)	−0.0099 (7)	0.0234 (8)	−0.0331 (9)
O16	0.0159 (7)	0.0461 (9)	0.0190 (7)	0.0008 (6)	0.0057 (5)	0.0110 (7)
O17	0.0461 (10)	0.0345 (9)	0.0266 (8)	−0.0053 (8)	0.0044 (7)	−0.0028 (7)
O18	0.0283 (9)	0.0231 (9)	0.130 (2)	−0.0008 (7)	−0.0060 (11)	0.0034 (11)
O19	0.0239 (7)	0.0203 (7)	0.0251 (7)	−0.0039 (5)	0.0138 (6)	−0.0053 (6)
C1	0.0145 (8)	0.0163 (8)	0.0150 (8)	0.0012 (7)	0.0050 (7)	0.0011 (7)
C2	0.0143 (8)	0.0156 (8)	0.0138 (8)	0.0015 (6)	0.0052 (6)	−0.0004 (7)
C3	0.0143 (8)	0.0160 (8)	0.0160 (8)	0.0016 (7)	0.0057 (7)	−0.0005 (7)
C4	0.0141 (8)	0.0190 (9)	0.0188 (8)	−0.0009 (7)	0.0042 (7)	−0.0014 (7)
C5	0.0189 (9)	0.0268 (10)	0.0132 (8)	−0.0003 (7)	0.0044 (7)	−0.0039 (7)
C6	0.0175 (9)	0.0225 (9)	0.0166 (8)	0.0007 (7)	0.0081 (7)	0.0010 (7)
C7	0.0135 (8)	0.0143 (8)	0.0144 (8)	0.0035 (6)	0.0056 (6)	0.0031 (6)
O1	0.0144 (6)	0.0201 (6)	0.0161 (6)	−0.0008 (5)	0.0074 (5)	0.0001 (5)
O2	0.0159 (6)	0.0181 (6)	0.0141 (6)	−0.0011 (5)	0.0054 (5)	−0.0004 (5)
C8	0.0144 (8)	0.0132 (8)	0.0186 (8)	0.0019 (6)	0.0065 (7)	0.0003 (7)
O3	0.0181 (6)	0.0203 (7)	0.0161 (6)	−0.0019 (5)	0.0075 (5)	−0.0018 (5)
O4	0.0162 (6)	0.0228 (7)	0.0219 (6)	−0.0055 (5)	0.0070 (5)	−0.0036 (5)
C9	0.0143 (8)	0.0170 (8)	0.0150 (8)	−0.0009 (7)	0.0058 (7)	−0.0017 (7)
C10	0.0163 (8)	0.0129 (8)	0.0155 (8)	−0.0003 (6)	0.0064 (7)	0.0012 (6)
C11	0.0135 (8)	0.0151 (8)	0.0157 (8)	−0.0001 (6)	0.0063 (7)	−0.0017 (7)
C12	0.0148 (8)	0.0151 (8)	0.0194 (8)	−0.0017 (6)	0.0079 (7)	−0.0009 (7)
C13	0.0183 (9)	0.0159 (8)	0.0193 (9)	0.0028 (7)	0.0068 (7)	0.0033 (7)
C14	0.0122 (8)	0.0196 (9)	0.0183 (8)	0.0024 (7)	0.0040 (7)	0.0003 (7)
C15	0.0152 (8)	0.0191 (9)	0.0127 (8)	−0.0020 (7)	0.0064 (7)	−0.0032 (7)
O5	0.0123 (6)	0.0244 (7)	0.0189 (6)	−0.0012 (5)	0.0046 (5)	0.0024 (5)
O6	0.0156 (6)	0.0170 (6)	0.0180 (6)	−0.0015 (5)	0.0063 (5)	0.0012 (5)
C16	0.0152 (8)	0.0145 (8)	0.0147 (8)	0.0005 (6)	0.0074 (7)	−0.0020 (7)
O7	0.0137 (6)	0.0159 (6)	0.0168 (6)	0.0009 (5)	0.0049 (5)	0.0023 (5)
O8	0.0130 (6)	0.0181 (6)	0.0191 (6)	−0.0014 (5)	0.0049 (5)	0.0026 (5)
C17	0.0135 (8)	0.0148 (8)	0.0137 (8)	−0.0006 (6)	0.0050 (6)	0.0007 (6)
C18	0.0174 (9)	0.0153 (8)	0.0205 (9)	0.0022 (7)	0.0089 (7)	−0.0021 (7)
C19	0.0193 (13)	0.0132 (12)	0.0233 (13)	0.000	0.0080 (10)	0.000
C20	0.0137 (11)	0.0121 (11)	0.0167 (11)	0.000	0.0063 (9)	0.000
C21	0.0140 (8)	0.0163 (8)	0.0132 (8)	−0.0017 (6)	0.0044 (6)	−0.0013 (7)
O9	0.0178 (6)	0.0151 (6)	0.0191 (6)	−0.0004 (5)	0.0095 (5)	0.0006 (5)
O10	0.0177 (6)	0.0169 (6)	0.0241 (6)	0.0011 (5)	0.0122 (5)	−0.0011 (5)

Geometric parameters (Å, º)

Ca1—O11	2.3568 (13)	C1—C7	1.509 (2)
Ca1—O2^i	2.3652 (12)	C2—C3	1.399 (2)
Ca1—O9	2.3772 (12)	C2—H2	0.9500
Ca1—O12	2.4078 (13)	C3—C4	1.397 (2)
Ca1—O1	2.5238 (12)	C3—C8	1.513 (2)
Ca1—O8^ii	2.5377 (12)	C4—C5	1.389 (2)
Ca1—O7^ii	2.5600 (12)	C4—H4	0.9500
Ca1—O2	2.6610 (12)	C5—C6	1.389 (2)
O11—H11A	0.819 (5)	C5—H5	0.9500
O11—H11B	0.819 (5)	C6—H6	0.9500
O12—H12A	0.818 (5)	C7—O2	1.262 (2)
O12—H12B	0.817 (5)	C7—O1	1.272 (2)
Ca2—O3^i	2.3252 (12)	C8—O4	1.259 (2)
Ca2—O13	2.3824 (13)	C8—O3	1.263 (2)
Ca2—O7^ii	2.4089 (12)	C9—C14	1.391 (2)
Ca2—O15	2.4457 (16)	C9—C10	1.397 (2)
Ca2—O6	2.4555 (12)	C9—C15	1.500 (2)
Ca2—O10	2.4575 (13)	C10—C11	1.393 (2)
Ca2—O5	2.5473 (13)	C10—H10	0.9500
Ca2—O9	2.5682 (12)	C11—C12	1.397 (2)
O13—H13A	0.819 (5)	C11—C16	1.506 (2)
O13—H13B	0.819 (5)	C12—C13	1.391 (2)
Ca3—O14	2.376 (3)	C12—H12	0.9500
Ca3—O6	2.4138 (13)	C13—C14	1.391 (2)
Ca3—O3^i	2.5733 (12)	C13—H13	0.9500
Ca3—O15	2.5800 (16)	C14—H14	0.9500
Ca3—O4^i	2.7746 (13)	C15—O5	1.264 (2)
O14—H14A	0.818 (5)	C15—O6	1.270 (2)
O14—H14B	0.819 (5)	C16—O7	1.262 (2)
O15—H15A	0.817 (5)	C16—O8	1.270 (2)
O15—H15B	0.817 (5)	C17—C18	1.394 (2)
O16—H16A	0.818 (5)	C17—C20	1.395 (2)
O16—H16B	0.818 (5)	C17—C21	1.508 (2)
O17—H17A	0.819 (5)	C18—C19	1.391 (2)
O17—H17B	0.820 (5)	C18—H18	0.9500
O18—H18A	0.817 (5)	C19—C18^i	1.391 (2)
O18—H18B	0.817 (5)	C19—H19	0.9500
O19—H19A	0.818 (5)	C20—C17^i	1.395 (2)
O19—H19B	0.817 (5)	C20—H20	0.9500
C1—C2	1.398 (2)	C21—O10	1.264 (2)
C1—C6	1.400 (2)	C21—O9	1.265 (2)
O11—Ca1—O2^i	105.36 (5)	O6—Ca3—O4^iii	78.71 (4)
O11—Ca1—O9	159.72 (5)	O3^i—Ca3—O4^iii	136.66 (4)
O2^i—Ca1—O9	84.62 (4)	O3^iii—Ca3—O4^iii	48.39 (4)
O11—Ca1—O12	82.88 (5)	O15—Ca3—O4^iii	71.47 (4)
O2^i—Ca1—O12	159.49 (5)	O15^ii—Ca3—O4^iii	103.64 (5)
O9—Ca1—O12	93.79 (5)	O4^i—Ca3—O4^iii	162.55 (6)
O11—Ca1—O1	82.23 (4)	Ca3—O14—H14A	141.4 (3)
O2^i—Ca1—O1	115.45 (4)	O14^ii—O14—H14B	155 (2)
O9—Ca1—O1	77.52 (4)	Ca3—O14—H14B	106.8 (10)
O12—Ca1—O1	83.94 (4)	H14A—O14—H14B	108.6 (10)
O11—Ca1—O8^ii	80.29 (4)	Ca2—O15—Ca3	93.42 (5)
O2^i—Ca1—O8^ii	79.42 (4)	Ca2—O15—H15A	123 (2)
O9—Ca1—O8^ii	119.36 (4)	Ca3—O15—H15A	111 (2)
O12—Ca1—O8^ii	83.64 (5)	Ca2—O15—H15B	104 (2)
O1—Ca1—O8^ii	159.65 (4)	Ca3—O15—H15B	116 (2)
O11—Ca1—O7^ii	125.21 (4)	H15A—O15—H15B	109.1 (9)
O2^i—Ca1—O7^ii	90.92 (4)	H16A—O16—H16B	108.9 (10)
O9—Ca1—O7^ii	71.12 (4)	H17A—O17—H17B	108.6 (10)
O12—Ca1—O7^ii	69.36 (4)	H18A—O18—H18B	109.0 (10)
O1—Ca1—O7^ii	136.63 (4)	H19A—O19—H19B	109.1 (10)
O8^ii—Ca1—O7^ii	51.32 (4)	C2—C1—C6	119.16 (16)
O11—Ca1—O2	76.24 (4)	C2—C1—C7	120.53 (15)
O2^i—Ca1—O2	69.14 (5)	C6—C1—C7	120.30 (15)
O9—Ca1—O2	91.49 (4)	C1—C2—C3	120.87 (16)
O12—Ca1—O2	131.37 (4)	C1—C2—H2	119.6
O1—Ca1—O2	50.31 (4)	C3—C2—H2	119.6
O8^ii—Ca1—O2	133.48 (4)	C4—C3—C2	118.96 (16)
O7^ii—Ca1—O2	155.02 (4)	C4—C3—C8	120.17 (15)
Ca1—O11—H11A	111.1 (15)	C2—C3—C8	120.85 (15)
Ca1—O11—H11B	120.2 (16)	C5—C4—C3	120.53 (16)
H11A—O11—H11B	108.2 (10)	C5—C4—H4	119.7
Ca1—O12—H12A	132.0 (14)	C3—C4—H4	119.7
Ca1—O12—H12B	116.9 (14)	C6—C5—C4	120.22 (16)
H12A—O12—H12B	108.7 (10)	C6—C5—H5	119.9
O3^i—Ca2—O13	156.46 (5)	C4—C5—H5	119.9
O3^i—Ca2—O7^ii	81.10 (4)	C5—C6—C1	120.24 (16)
O13—Ca2—O7^ii	121.05 (5)	C5—C6—H6	119.9
O3^i—Ca2—O15	74.44 (6)	C1—C6—H6	119.9
O13—Ca2—O15	85.97 (6)	O2—C7—O1	121.22 (15)
O7^ii—Ca2—O15	150.83 (5)	O2—C7—C1	119.92 (15)
O3^i—Ca2—O6	75.32 (4)	O1—C7—C1	118.83 (15)
O13—Ca2—O6	109.81 (4)	C7—O1—Ca1	96.61 (10)
O7^ii—Ca2—O6	90.28 (4)	C7—O2—Ca1^i	164.64 (11)
O15—Ca2—O6	68.49 (5)	C7—O2—Ca1	90.44 (10)
O3^i—Ca2—O10	80.05 (4)	Ca1^i—O2—Ca1	104.76 (4)
O13—Ca2—O10	82.51 (4)	O4—C8—O3	121.40 (16)
O7^ii—Ca2—O10	116.01 (4)	O4—C8—C3	119.02 (15)
O15—Ca2—O10	75.41 (5)	O3—C8—C3	119.56 (15)
O6—Ca2—O10	140.45 (4)	C8—O3—Ca2^i	163.85 (11)
O3^i—Ca2—O5	120.08 (4)	C8—O3—Ca3^iv	99.47 (10)
O13—Ca2—O5	77.43 (4)	Ca2^i—O3—Ca3^iv	96.53 (4)
O7^ii—Ca2—O5	72.92 (4)	C8—O4—Ca3^iv	90.00 (10)
O15—Ca2—O5	105.94 (5)	C14—C9—C10	119.77 (16)
O6—Ca2—O5	52.45 (4)	C14—C9—C15	121.23 (15)
O10—Ca2—O5	159.71 (4)	C10—C9—C15	119.00 (15)
O3^i—Ca2—O9	96.69 (4)	C11—C10—C9	120.75 (16)
O13—Ca2—O9	84.81 (4)	C11—C10—H10	119.6
O7^ii—Ca2—O9	70.49 (4)	C9—C10—H10	119.6
O15—Ca2—O9	127.45 (5)	C10—C11—C12	118.95 (15)
O6—Ca2—O9	160.27 (4)	C10—C11—C16	119.75 (15)
O10—Ca2—O9	52.12 (4)	C12—C11—C16	121.29 (15)
O5—Ca2—O9	122.03 (4)	C13—C12—C11	120.38 (16)
Ca2—O13—H13A	116.2 (16)	C13—C12—H12	119.8
Ca2—O13—H13B	110.3 (15)	C11—C12—H12	119.8
H13A—O13—H13B	108.3 (10)	C14—C13—C12	120.33 (16)
O14^ii—Ca3—O14	19.22 (13)	C14—C13—H13	119.8
O14^ii—Ca3—O6^ii	145.34 (10)	C12—C13—H13	119.8
O14—Ca3—O6^ii	134.05 (9)	C13—C14—C9	119.76 (16)
O14^ii—Ca3—O6	134.05 (9)	C13—C14—H14	120.1
O14—Ca3—O6	145.34 (10)	C9—C14—H14	120.1
O6^ii—Ca3—O6	79.34 (6)	O5—C15—O6	121.62 (16)
O14^ii—Ca3—O3^i	93.12 (7)	O5—C15—C9	119.70 (15)
O14—Ca3—O3^i	110.88 (7)	O6—C15—C9	118.65 (15)
O6^ii—Ca3—O3^i	89.63 (4)	C15—O5—Ca2	90.61 (10)
O6—Ca3—O3^i	71.68 (4)	C15—O6—Ca3	167.75 (11)
O14^ii—Ca3—O3^iii	110.88 (7)	C15—O6—Ca2	94.74 (10)
O14—Ca3—O3^iii	93.12 (7)	Ca3—O6—Ca2	97.43 (4)
O6^ii—Ca3—O3^iii	71.68 (4)	O7—C16—O8	121.34 (15)
O6—Ca3—O3^iii	89.63 (4)	O7—C16—C11	119.45 (15)
O3^i—Ca3—O3^iii	155.94 (6)	O8—C16—C11	119.19 (15)
O14^ii—Ca3—O15	67.14 (10)	C16—O7—Ca2^ii	164.13 (11)
O14—Ca3—O15	81.71 (10)	C16—O7—Ca1^ii	92.86 (10)
O6^ii—Ca3—O15	143.83 (5)	Ca2^ii—O7—Ca1^ii	102.89 (4)
O6—Ca3—O15	66.95 (5)	C16—O8—Ca1^ii	93.71 (10)
O3^i—Ca3—O15	68.15 (4)	C18—C17—C20	120.10 (16)
O3^iii—Ca3—O15	118.99 (5)	C18—C17—C21	119.24 (15)
O14^ii—Ca3—O15^ii	81.71 (10)	C20—C17—C21	120.65 (16)
O14—Ca3—O15^ii	67.14 (10)	C19—C18—C17	120.63 (17)
O6^ii—Ca3—O15^ii	66.95 (5)	C19—C18—H18	119.7
O6—Ca3—O15^ii	143.83 (5)	C17—C18—H18	119.7
O3^i—Ca3—O15^ii	118.99 (5)	C18^i—C19—C18	119.2 (2)
O3^iii—Ca3—O15^ii	68.15 (4)	C18^i—C19—H19	120.4
O15—Ca3—O15^ii	148.66 (9)	C18—C19—H19	120.4
O14^ii—Ca3—O4^i	77.54 (9)	C17^i—C20—C17	119.4 (2)
O14—Ca3—O4^i	85.21 (9)	C17^i—C20—H20	120.3
O6^ii—Ca3—O4^i	78.71 (4)	C17—C20—H20	120.3
O6—Ca3—O4^i	115.43 (4)	O10—C21—O9	121.82 (16)
O3^i—Ca3—O4^i	48.39 (4)	O10—C21—C17	118.00 (15)
O3^iii—Ca3—O4^i	136.66 (4)	O9—C21—C17	120.17 (15)
O15—Ca3—O4^i	103.64 (5)	C21—O9—Ca1	163.76 (11)
O15^ii—Ca3—O4^i	71.47 (4)	C21—O9—Ca2	89.77 (10)
O14^ii—Ca3—O4^iii	85.21 (9)	Ca1—O9—Ca2	103.55 (4)
O14—Ca3—O4^iii	77.54 (9)	C21—O10—Ca2	94.91 (10)
O6^ii—Ca3—O4^iii	115.43 (4)
O3^i—Ca2—O15—Ca3	−39.27 (5)	C9—C15—O6—Ca2	170.18 (13)
O13—Ca2—O15—Ca3	153.91 (6)	O14^ii—Ca3—O6—C15	−141.6 (5)
O7^ii—Ca2—O15—Ca3	−5.19 (15)	O14—Ca3—O6—C15	−117.2 (5)
O6—Ca2—O15—Ca3	40.77 (5)	O6^ii—Ca3—O6—C15	49.1 (5)
O10—Ca2—O15—Ca3	−122.79 (6)	O3^i—Ca3—O6—C15	142.3 (5)
O5—Ca2—O15—Ca3	78.21 (6)	O3^iii—Ca3—O6—C15	−22.3 (5)
O9—Ca2—O15—Ca3	−125.77 (5)	O15—Ca3—O6—C15	−144.2 (5)
O14^ii—Ca3—O15—Ca2	139.87 (11)	O15^ii—Ca3—O6—C15	28.0 (6)
O14—Ca3—O15—Ca2	152.93 (10)	O4^i—Ca3—O6—C15	121.1 (5)
O6^ii—Ca3—O15—Ca2	−19.52 (12)	O4^iii—Ca3—O6—C15	−69.7 (5)
O6—Ca3—O15—Ca2	−42.19 (5)	O14^ii—Ca3—O6—Ca2	44.98 (12)
O3^i—Ca3—O15—Ca2	36.41 (5)	O14—Ca3—O6—Ca2	69.34 (13)
O3^iii—Ca3—O15—Ca2	−118.08 (5)	O6^ii—Ca3—O6—Ca2	−124.28 (6)
O15^ii—Ca3—O15—Ca2	146.64 (6)	O3^i—Ca3—O6—Ca2	−31.10 (4)
O4^i—Ca3—O15—Ca2	69.95 (6)	O3^iii—Ca3—O6—Ca2	164.30 (4)
O4^iii—Ca3—O15—Ca2	−127.50 (7)	O15—Ca3—O6—Ca2	42.33 (5)
C6—C1—C2—C3	0.1 (3)	O15^ii—Ca3—O6—Ca2	−145.44 (7)
C7—C1—C2—C3	−179.03 (15)	O4^i—Ca3—O6—Ca2	−52.34 (5)
C1—C2—C3—C4	0.7 (3)	O4^iii—Ca3—O6—Ca2	116.83 (4)
C1—C2—C3—C8	−177.69 (16)	O3^i—Ca2—O6—C15	−144.47 (10)
C2—C3—C4—C5	−0.7 (3)	O13—Ca2—O6—C15	59.61 (11)
C8—C3—C4—C5	177.70 (16)	O7^ii—Ca2—O6—C15	−63.76 (10)
C3—C4—C5—C6	−0.1 (3)	O15—Ca2—O6—C15	136.76 (11)
C4—C5—C6—C1	1.0 (3)	O10—Ca2—O6—C15	162.24 (9)
C2—C1—C6—C5	−1.0 (3)	O5—Ca2—O6—C15	4.27 (9)
C7—C1—C6—C5	178.19 (16)	O9—Ca2—O6—C15	−76.42 (16)
C2—C1—C7—O2	−5.5 (2)	O3^i—Ca2—O6—Ca3	34.13 (4)
C6—C1—C7—O2	175.31 (16)	O13—Ca2—O6—Ca3	−121.79 (5)
C2—C1—C7—O1	172.60 (16)	O7^ii—Ca2—O6—Ca3	114.85 (4)
C6—C1—C7—O1	−6.6 (2)	O15—Ca2—O6—Ca3	−44.64 (6)
O2—C7—O1—Ca1	12.67 (17)	O10—Ca2—O6—Ca3	−19.16 (8)
C1—C7—O1—Ca1	−165.44 (13)	O5—Ca2—O6—Ca3	−177.13 (7)
O11—Ca1—O1—C7	−85.17 (10)	O9—Ca2—O6—Ca3	102.18 (12)
O2^i—Ca1—O1—C7	18.19 (11)	C10—C11—C16—O7	1.3 (2)
O9—Ca1—O1—C7	95.97 (10)	C12—C11—C16—O7	−178.55 (16)
O12—Ca1—O1—C7	−168.78 (10)	C10—C11—C16—O8	−179.89 (15)
O8^ii—Ca1—O1—C7	−116.13 (13)	C12—C11—C16—O8	0.3 (2)
O7^ii—Ca1—O1—C7	140.17 (10)	O8—C16—O7—Ca2^ii	164.2 (3)
O2—Ca1—O1—C7	−6.64 (9)	C11—C16—O7—Ca2^ii	−17.0 (5)
O1—C7—O2—Ca1^i	176.2 (3)	O8—C16—O7—Ca1^ii	−8.91 (16)
C1—C7—O2—Ca1^i	−5.7 (5)	C11—C16—O7—Ca1^ii	169.88 (13)
O1—C7—O2—Ca1	−11.93 (16)	O7—C16—O8—Ca1^ii	9.00 (17)
C1—C7—O2—Ca1	166.16 (14)	C11—C16—O8—Ca1^ii	−169.80 (13)
O11—Ca1—O2—C7	97.93 (10)	C20—C17—C18—C19	−0.4 (2)
O2^i—Ca1—O2—C7	−149.42 (8)	C21—C17—C18—C19	178.58 (13)
O9—Ca1—O2—C7	−65.75 (10)	C17—C18—C19—C18^i	0.19 (11)
O12—Ca1—O2—C7	30.62 (12)	C18—C17—C20—C17^i	0.19 (11)
O1—Ca1—O2—C7	6.64 (9)	C21—C17—C20—C17^i	−178.75 (17)
O8^ii—Ca1—O2—C7	159.79 (9)	C18—C17—C21—O10	−9.9 (2)
O7^ii—Ca1—O2—C7	−110.45 (12)	C20—C17—C21—O10	169.07 (13)
O11—Ca1—O2—Ca1^i	−84.30 (5)	C18—C17—C21—O9	171.56 (16)
O2^i—Ca1—O2—Ca1^i	28.35 (6)	C20—C17—C21—O9	−9.5 (2)
O9—Ca1—O2—Ca1^i	112.02 (5)	O10—C21—O9—Ca1	−157.4 (3)
O12—Ca1—O2—Ca1^i	−151.61 (5)	C17—C21—O9—Ca1	21.1 (5)
O1—Ca1—O2—Ca1^i	−175.59 (7)	O10—C21—O9—Ca2	−11.86 (16)
O8^ii—Ca1—O2—Ca1^i	−22.44 (8)	C17—C21—O9—Ca2	166.64 (14)
O7^ii—Ca1—O2—Ca1^i	67.32 (11)	O11—Ca1—O9—C21	−94.7 (4)
C4—C3—C8—O4	−3.2 (2)	O2^i—Ca1—O9—C21	26.1 (4)
C2—C3—C8—O4	175.19 (16)	O12—Ca1—O9—C21	−174.4 (4)
C4—C3—C8—O3	178.59 (16)	O1—Ca1—O9—C21	−91.4 (4)
C2—C3—C8—O3	−3.0 (2)	O8^ii—Ca1—O9—C21	100.8 (4)
O4—C8—O3—Ca2^i	162.8 (3)	O7^ii—Ca1—O9—C21	119.0 (4)
C3—C8—O3—Ca2^i	−19.0 (5)	O2—Ca1—O9—C21	−42.7 (4)
O4—C8—O3—Ca3^iv	−9.36 (18)	O11—Ca1—O9—Ca2	120.91 (12)
C3—C8—O3—Ca3^iv	168.84 (13)	O2^i—Ca1—O9—Ca2	−118.25 (5)
O3—C8—O4—Ca3^iv	8.56 (17)	O12—Ca1—O9—Ca2	41.24 (5)
C3—C8—O4—Ca3^iv	−169.65 (14)	O1—Ca1—O9—Ca2	124.17 (5)
C14—C9—C10—C11	0.3 (3)	O8^ii—Ca1—O9—Ca2	−43.59 (6)
C15—C9—C10—C11	−179.24 (15)	O7^ii—Ca1—O9—Ca2	−25.43 (4)
C9—C10—C11—C12	−1.9 (3)	O2—Ca1—O9—Ca2	172.87 (4)
C9—C10—C11—C16	178.21 (15)	O3^i—Ca2—O9—C21	−65.30 (10)
C10—C11—C12—C13	1.5 (3)	O13—Ca2—O9—C21	91.07 (10)
C16—C11—C12—C13	−178.64 (15)	O7^ii—Ca2—O9—C21	−143.37 (10)
C11—C12—C13—C14	0.6 (3)	O15—Ca2—O9—C21	10.20 (12)
C12—C13—C14—C9	−2.2 (3)	O6—Ca2—O9—C21	−129.91 (13)
C10—C9—C14—C13	1.8 (3)	O10—Ca2—O9—C21	6.53 (9)
C15—C9—C14—C13	−178.67 (16)	O5—Ca2—O9—C21	162.74 (9)
C14—C9—C15—O5	−6.3 (3)	O3^i—Ca2—O9—Ca1	105.33 (5)
C10—C9—C15—O5	173.22 (16)	O13—Ca2—O9—Ca1	−98.30 (5)
C14—C9—C15—O6	175.44 (16)	O7^ii—Ca2—O9—Ca1	27.26 (4)
C10—C9—C15—O6	−5.0 (2)	O15—Ca2—O9—Ca1	−179.17 (6)
O6—C15—O5—Ca2	7.70 (16)	O6—Ca2—O9—Ca1	40.72 (14)
C9—C15—O5—Ca2	−170.48 (14)	O10—Ca2—O9—Ca1	177.16 (7)
O3^i—Ca2—O5—C15	31.19 (11)	O5—Ca2—O9—Ca1	−26.63 (6)
O13—Ca2—O5—C15	−131.81 (10)	O9—C21—O10—Ca2	12.44 (17)
O7^ii—Ca2—O5—C15	99.78 (10)	C17—C21—O10—Ca2	−166.09 (12)
O15—Ca2—O5—C15	−49.78 (11)	O3^i—Ca2—O10—C21	100.08 (10)
O6—Ca2—O5—C15	−4.27 (9)	O13—Ca2—O10—C21	−95.80 (10)
O10—Ca2—O5—C15	−140.76 (13)	O7^ii—Ca2—O10—C21	25.17 (11)
O9—Ca2—O5—C15	152.59 (9)	O15—Ca2—O10—C21	176.44 (11)
O5—C15—O6—Ca3	178.5 (4)	O6—Ca2—O10—C21	152.01 (9)
C9—C15—O6—Ca3	−3.3 (6)	O5—Ca2—O10—C21	−86.99 (15)
O5—C15—O6—Ca2	−8.02 (17)	O9—Ca2—O10—C21	−6.56 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11A···O16^iv	0.82 (2)	1.96 (2)	2.7670 (18)	169 (2)
O11—H11B···O19^v	0.82 (2)	1.96 (2)	2.7656 (19)	167 (2)
O12—H12A···O1^vi	0.82 (2)	2.05 (2)	2.8535 (18)	169 (2)
O12—H12B···O5	0.82 (2)	2.20 (2)	2.9836 (18)	162 (2)
O13—H13A···O19^vii	0.82 (2)	1.90 (2)	2.7110 (19)	172 (2)
O13—H13B···O16^viii	0.82 (2)	1.99 (2)	2.786 (2)	164 (2)
O14—H14B···O18^ix	0.82 (2)	1.81 (2)	2.606 (3)	164 (3)
O15—H15B···O17^iii	0.82 (2)	2.06 (2)	2.818 (3)	155 (2)
O16—H16A···O5^viii	0.82 (2)	1.98 (2)	2.7185 (18)	150 (2)
O16—H16B···O8	0.82 (2)	1.91 (2)	2.7278 (18)	174 (2)
O17—H17A···O4	0.82 (2)	2.00 (2)	2.808 (2)	167 (3)
O17—H17B···O10^vii	0.82 (2)	2.02 (2)	2.839 (2)	177 (3)
O18—H18A···O8	0.82 (2)	2.07 (2)	2.876 (2)	168 (3)
O18—H18B···O10^v	0.82 (2)	2.12 (2)	2.890 (2)	158 (3)
O19—H19A···O4	0.82 (2)	2.00 (2)	2.7747 (18)	159 (2)
O19—H19B···O1^vii	0.82 (2)	2.00 (2)	2.7639 (18)	156 (2)

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