Hexaaqua­cobalt(II) bis­[hydrogen bis­(4-carb­oxy­phenyl­phosphonate)] dihydrate

The Co^II ion in the title complex salt, [Co(H₂O)₆](C₁₄H₁₃O₁₀P₂)₂·2H₂O or [Co(H₂O)₆][H(C₇H₆O₅P)₂]·2H₂O, resides on an inversion centre and exhibits an octa­hedral environment formed by six aqua ligands. Two unique acid residues share an H atom between their phosphonate groups, forming a complex monoanion with a very short (P)O...H...O(P) hydrogen bond of 2.435 (2) Å. The crystal structure is layered and con­sists of thick organic bilayers with hydrated metal [Co(H₂O)₆]²⁺ ions arranged between them. The interior of the bilayer is occupied by the aromatic portions of the complex monoanions and the carboxyl groups, which form hydrogen-bonded R₂²(8) ring motifs. The phosphonate groups are arranged outwards in order to form the hydrogen-bonded surfaces of the bilayer. Electrostatic and multiple hydrogen-bond inter­actions, established between the coordination and solvent water mol­ecules and the phosphonate O atoms, hold neighbouring bilayers together.

S1. Comment

The chemistry of metal organophosphonates has attracted considerable attention for a long time, due to the potential applications of these materials as ion exchangers, catalysts, proton conductors and sensors (Clearfield, 1998; Alberti et al., 1996; Cao et al., 1992). Recently, consideration has been devoted to metal arylphosphonates, in which an additional functional group, especially a carboxyl group, is attached to the aromatic ring. The multifunctional acids have been found to be better ligands, since they provide additional coordination sites and allow the formation of novel complexes with variable structures and versatile properties. In particular, 4-carboxyphenylphosphonic acid has been widely used to form inorganic–organic hybrid compounds with the transition metal ions Ni²⁺ (one compound), Cu²⁺ (eight) and Zn²⁺ (16), as well as with main group metals (12) or rare earth metal ions (three). It has also been used as a ligand in three oxovanadium– and seven oxomolybdenum–organophosphonate/secondary metal–organonitrogen ligand systems. A literature survey has revealed that the majority of the 50 metal 4-carboxyphenylphosphonate structures reported to date were studied during the last two years. The acid moieties in them appear in different forms, from intact acid up to fully deprotonated trianion, and the metal ions are coordinated by O atoms from the phosphonate or from both phosphonate and carboxylate functional groups. However, to the best of our knowledge, there are no metal ion compounds of 4-carboxyphenylphosphonic acid in which both the anion and cation appear in complex form. A search of the Cambridge Structural Database (CSD, Version 5.31; Allen, 2002) returned only 24 organophosphonate crystal structures in which the H atom is shared between two neighbouring phosphonate sites in order to form a complex anionic unit via very short linear hydrogen bonds (O···O distances 2.37–2.45 Å and O—H—O angles 176–180°). In all but three of those compounds the hydrogen bond is symmetry-constrained. Here, we report the crystal structure of the title compound, (I), where there is no symmetry restriction imposed on the shared H atom.

The asymmetric unit of (I) contains half a Co^II ion, two acid moieties and four symmetry-independent water molecules (Fig. 1). The metal ion is six-coordinate with a slightly distorted octahedral geometry, and occupies a special position on the inversion centre at (1/2, 1/2, 0). Six water molecules, three of which are unique, fill the first coordination sphere of the Co^II ion in order to form the [Co(H₂O)₆]²⁺ unit. Atoms O2W, O2Wⁱ, O3W and O3Wⁱ (symmetry code as in Table 1) act as equatorial ligands and create two pairs of similar bonds (Co1—O2W and Co1—O3W), whereas the axial ligands O1W and O1Wⁱ form a somewhat longer bond (Co1—O1W) (Table 1).

The bond distances and angles observed in both acid moieties are within the usual ranges for carboxyl and phosphonic groups (Standard reference?), although the P11—O12 and P21—O22 bond distances are intermediate between single and double P—O bonds. This reflects the migration of the H atom from the formal phosphonic acid group to the phosphonate group of an adjacent moiety, in order to form a complex [H(HO₃PC₆H₄COOH)₂]^- monoanion via a very short (P)O22···H22O···O12(P) hydrogen bond (Fig. 1). Nevertheless, in the crystal structure there is only one position for atom H22O. Despite the very short distance of 2.435 (2) Å between the O sites in the dimeric unit, the position of H22O is not confined by any symmetry elements and its environment is asymmetric. The hydrogen bond is almost linear, but the two O—H distances are somewhat different (Table 2). The acid residues on both sides of the hydrogen bond are symmetry-unique and one of the carboxyl groups is rotated by 11.45 (12)° relative to the plane of the phenyl ring to which it is bonded, whereas the second group is almost coplanar with the corresponding ring. The acid dimers are organized into a polar monolayer with the help of two other hydrogen bonds, O13—H13O···O21ⁱⁱⁱ and O23—H23O···O11^vi (symmetry codes as in Table 2), established between the different phosphonate sites. The (P)O—H···O(P) hydrogen-bonded network is two-dimensional, parallel to the crystallographic bc plane, and is characterized by large R₆⁶(24) motifs (Bernstein et al., 1995) which are arranged in a herringbone fashion (Fig. 2a). The aromatic rings of the monoanions are arranged on one side of the monolayer. The para-carboxyl groups connect neighbouring inversion-related monolayers via two different carboxyl–carboxyl hydrogen-bond interactions, O15—H15O···O24^v and O25—H25O···O14^vii (symmetry codes as in Table 2), in order to form a thick organic bilayer. The phosphonate sites of the complex monoanion create the outer surfaces of the bilayer, while the aromatic rings and the R₂²(8) synthons form its interior (Fig. 2b).

The [Co(H₂O)₆]²⁺ units are arranged between the anionic bilayers. The aqua ligands serve both to complete the coordination environment of the Co^II ion and to cross-link the bilayers via water–phosphonate hydrogen bonds in order to construct the three-dimensional crystal structure. However, each hydrated Co^II ion is surrounded by six phosphonate groups from two neighbouring bilayers. Five different hydrogen bonds are formed between the water molecules in the first coordination sphere and the phosphonate O atoms of the second (Fig. 3b). Four of these, O2W—H1W2···O11^iv, O2W—H2W2···O21ⁱⁱⁱ, O2W—H2W2···O22ⁱⁱⁱ and O3W—H2W3···O23ⁱⁱ, are donated from the equatorial ligands, and the fifth, O1W—H2W1···O21ⁱⁱⁱ, from the axial ligands. The small channels generated along the b axis are occupied by the solvent water molecules OW4, which serve both to fill the empty spaces of the structure and to connect the coordination units into a two-dimensional network. There are six solvent water molecules OW4 around the [Co(H₂O)₆]²⁺ unit, and each of them is used to mediate three cationic units via three different hydrogen bonds from or to the aqua ligands: O1W—H1W1···O4Wⁱⁱ, O3W—H2W3···O4Wⁱⁱⁱ and O4W—H2W4···O1W. Two types of water ring motifs, R₄⁴(10) and R₄²(12), are formed around the Co^II ions, which tessellate in order to produce a two-dimensional hydrogen-bonded network of Co^II ions (Fig. 3a). An additional O4W—H1W4···O12 bond is established between the solvent water and the organic monolayer.

In conclusion, the title compound, (I), demonstrates a layered structure with thick organic bilayers and inorganic monolayers, which cross-link the bilayers via multiple hydrogen bonds. De facto, the crystal packing of the compound generates hydrophobic and hydrophilic regions that alternate along the crystallographic a axis. However, the hydrophilic regions, arranged on both sides of the aromatic region, are different: one of them contains hydrogen-bonded R₂²(8) ring motifs formed by the carboxyl groups of the monoanions, and the other consists of the phosphonate groups and hydrated metal ions (Fig. 3b). In this view, the structure of (I) resembles the packing patterns of some other metal 4-carboxyphenylphosphonate compounds with divalent metal ions like calcium (Svoboda et al., 2005), strontium (Zima et al., 2007), barium (Svoboda et al., 2008) and copper(II) ions (Li et al., 2008; Zima et al., 2009). The major structural difference observed in these structures is a direct metal–phosphonate contact via M—O bonds, making the inorganic monolayer more compact.

Related literature

For related literature, see: Alberti et al. (1996); Allen (2002); Bernstein et al. (1995); Cao et al. (1992); Clearfield (1998); Hirao et al. (1981); Li et al. (2008); Svoboda et al. (2005, 2008); Zima et al. (2007, 2009).

S2. Experimental

All chemicals were obtained commercially, with the exception of 4-carboxyphenylphosphonic acid, which was prepared according to the published procedure of Hirao et al. (1981). The title compound was synthesized by mixing 4-carboxyphenylphosphonic acid (30 mg, 0.15 mmol) dissolved in diethylamine (20 µl) and ethanol (1 ml) with cobalt(II) chloride (19 mg, 0.15 mmol) dissolved in ethanol (0.5 ml). A navy-blue solution was obtained and this was kept at room temperature to allow slow evaporation of the solvent. After one week, pink parallelepiped crystals of (I) of sufficient quality for X-ray diffraction measurements were obtained.

Spectroscopic analysis, FT–IR (KBr, cm^-1). Internal vibrations of the functional groups: νC═O 1687 (vs), 1628 (sh); δ(C)O—H and νC—OH 1427 (s), 1400 (m), 1375 (m), 1323 (s); νPO₃ 1172 (s, sh), 1143 (vs), 1115 (vs), 1090 (m, sh), 1029 (vs), 1013. PO₃ deformation vibrations: 580 (s, n), 546 (s, n), 518 (s, n), 460 (s, n), 448 (s, n). νOH of the hydrogen bonds: strong absorption in the region 3600–1800 cm^-1, with maxima at 3530 (s, b), 3408 (b, vs), 3095 (vb, vs), 2995 (vb, vs), 2895 (vb, vs), 2840 (vb, vs), 2676 (s, b), 2560 (s, b). Internal vibrations of the aromatic ring: νC—C 1560 (m, n), 1503 (vw), 1471 (vw). Out-of-plane ring deformations: 862 (m, n), 819 (w), 805 (w), 632 (w). Ring torsions 767 (m), 719 (n, vs), 646 (s, n).

S3. Refinement

Difference Fourier map plots showed a prolate shaped peak between O12 and O22 and while a two H-atom disorder model for this site was considered it was decided that nothing significant would obtained by doing so; the maximum was labelled as H22O and assigned unit occupancy. That position and those of the other H atoms bonded to O atoms, also located from difference Fourier maps, were refined with U_iso(H) = 1.5U_eq(O). The H atoms of the aromatic rings were located in geometric positions and refined as rigid, with C—H = 0.93 Å [Please check added text] and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates the short hydrogen bond between the two phosphonate portions of the complex monoanion. [Symmetry code: (i) -x + 1, -y + 1, -z.]
	Fig. 2. (a) The two-dimensional hydrogen-bonded network formed between the phosphonate sites of the hydrogen bis(4-carboxyphenylphosphonate) monoanions on the surface of the bilayer. Aromatic rings and carboxyl groups have been omitted for clarity. (b) The arrangement of the aromatic rings and the carboxyl groups in the interior of the bilayer. The H atoms of the aromatic rings have been omitted for clarity. [Symmetry codes: (iv) x, -y + 3/2, z - 1/2; (vi) x, -y + 3/2, z + 1/2; (viii) x, y + 1, z.]
	Fig. 3. (a) A view of the two-dimensional hydrogen-bonded network established between the [Co(H2O)6]^2+ cationic units and the solvent water molecules. (b) The three-dimensional packing arrangement of (I), viewed along the b axis. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 1, y - 1/2, -z + 1/2; (iii) x, -y + 1/2, z - 1/2; (iv) x, -y + 3/2, z - 1/2; (ix) -x + 1, y + 1/2, -z + 1/2].

Hexaaquacobalt(II) bis[hydrogen bis(4-carboxyphenylphosphonate)] dihydrate

Crystal data

[Co(H2O)6](C14H13O10P2)2·2H2O	F(000) = 1042
Mr = 1009.43	Dx = 1.654 Mg m^−3 Dm = 1.65 Mg m^−3 Dm measured by flotation
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1265 reflections
a = 21.053 (4) Å	θ = 3.0–28.5°
b = 7.2030 (14) Å	µ = 0.68 mm^−1
c = 13.370 (3) Å	T = 295 K
β = 92.00 (1)°	Parallelepiped, pink
V = 2026.3 (7) Å^3	0.36 × 0.22 × 0.17 mm
Z = 2

Data collection

Kuma KM-4 diffractometer with a CCD area detector	5087 independent reflections
Radiation source: fine-focus sealed tube	3294 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ω scans	θmax = 28.5°, θmin = 3.0°
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006)	h = −28→27
Tmin = 0.843, Tmax = 0.899	k = −9→9
26924 measured reflections	l = −16→17

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0351P)^2] where P = (Fo^2 + 2Fc^2)/3
5087 reflections	(Δ/σ)max = 0.001
316 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.28 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
Co1	0.5000	0.5000	0.0000	0.02365 (10)
O1W	0.47427 (7)	0.36143 (19)	0.13082 (11)	0.0305 (3)
H1W1	0.4897 (10)	0.259 (3)	0.1399 (16)	0.046*
H2W1	0.4372 (11)	0.345 (3)	0.1348 (16)	0.046*
O2W	0.41584 (7)	0.4247 (2)	−0.07416 (12)	0.0394 (4)
H1W2	0.3963 (11)	0.492 (3)	−0.1234 (17)	0.059*
H2W2	0.3900 (12)	0.363 (3)	−0.0524 (19)	0.059*
O3W	0.54242 (8)	0.2570 (2)	−0.04936 (13)	0.0452 (4)
H1W3	0.5250 (13)	0.179 (3)	−0.083 (2)	0.068*
H2W3	0.5766 (12)	0.216 (4)	−0.0402 (19)	0.068*
O4W	0.48215 (7)	0.5071 (2)	0.33196 (11)	0.0358 (3)
H1W4	0.4416 (11)	0.519 (3)	0.3385 (17)	0.054*
H2W4	0.4847 (11)	0.474 (3)	0.2752 (18)	0.054*
P11	0.31695 (2)	0.69294 (6)	0.30785 (3)	0.02222 (12)
O11	0.35444 (6)	0.86621 (17)	0.29064 (9)	0.0280 (3)
O12	0.35542 (6)	0.55568 (18)	0.37189 (9)	0.0327 (3)
O13	0.29499 (6)	0.60691 (18)	0.20704 (10)	0.0323 (3)
H13O	0.3155 (10)	0.517 (3)	0.1837 (16)	0.048*
C11	0.24504 (8)	0.7412 (2)	0.37050 (13)	0.0247 (4)
C12	0.24889 (9)	0.8279 (3)	0.46344 (14)	0.0321 (5)
H12	0.2882	0.8653	0.4901	0.038*
C13	0.19492 (9)	0.8591 (3)	0.51634 (14)	0.0333 (5)
H13	0.1977	0.9186	0.5781	0.040*
C14	0.13641 (9)	0.8013 (3)	0.47719 (15)	0.0305 (5)
C15	0.13251 (9)	0.7165 (3)	0.38461 (15)	0.0365 (5)
H15	0.0932	0.6792	0.3580	0.044*
C16	0.18640 (9)	0.6865 (3)	0.33120 (15)	0.0324 (5)
H16	0.1833	0.6296	0.2688	0.039*
C17	0.07912 (10)	0.8249 (3)	0.53689 (16)	0.0384 (5)
O14	0.08327 (7)	0.8922 (2)	0.62222 (11)	0.0526 (4)
O15	0.02712 (8)	0.7693 (3)	0.49572 (13)	0.0675 (6)
H15O	−0.0055 (15)	0.768 (4)	0.536 (2)	0.101*
P21	0.31449 (2)	0.33522 (6)	0.58978 (3)	0.02246 (12)
O21	0.34907 (6)	0.16758 (17)	0.62947 (11)	0.0385 (4)
O22	0.30471 (7)	0.32769 (17)	0.47738 (9)	0.0336 (3)
H22O	0.3268 (10)	0.438 (3)	0.4289 (15)	0.050*
O23	0.35217 (6)	0.51426 (18)	0.61278 (10)	0.0328 (3)
H23O	0.3562 (11)	0.546 (3)	0.6703 (16)	0.049*
C21	0.23998 (8)	0.3441 (2)	0.64937 (13)	0.0230 (4)
C22	0.24019 (9)	0.3130 (2)	0.75132 (13)	0.0263 (4)
H22	0.2785	0.2921	0.7863	0.032*
C23	0.18423 (9)	0.3126 (3)	0.80159 (14)	0.0308 (5)
H23	0.1847	0.2900	0.8701	0.037*
C24	0.12741 (9)	0.3460 (3)	0.74981 (14)	0.0297 (4)
C25	0.12665 (9)	0.3784 (3)	0.64868 (15)	0.0361 (5)
H25	0.0883	0.4010	0.6143	0.043*
C26	0.18278 (9)	0.3775 (3)	0.59750 (15)	0.0324 (5)
H26	0.1822	0.3992	0.5289	0.039*
C27	0.06846 (10)	0.3432 (3)	0.80791 (17)	0.0381 (5)
O24	0.07132 (7)	0.2848 (2)	0.89525 (12)	0.0583 (5)
O25	0.01789 (7)	0.4040 (3)	0.76446 (13)	0.0590 (5)
H25O	−0.0115 (13)	0.401 (4)	0.806 (2)	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01961 (19)	0.0257 (2)	0.0256 (2)	0.00138 (15)	0.00114 (15)	0.00295 (15)
O1W	0.0227 (7)	0.0341 (8)	0.0348 (8)	0.0010 (6)	0.0035 (7)	0.0054 (6)
O2W	0.0283 (8)	0.0481 (9)	0.0412 (9)	−0.0102 (7)	−0.0080 (7)	0.0198 (7)
O3W	0.0340 (9)	0.0422 (9)	0.0592 (11)	0.0112 (7)	−0.0018 (8)	−0.0147 (7)
O4W	0.0294 (7)	0.0405 (8)	0.0377 (9)	0.0000 (7)	0.0023 (7)	−0.0034 (7)
P11	0.0216 (3)	0.0255 (3)	0.0197 (3)	0.00267 (19)	0.0033 (2)	0.00198 (19)
O11	0.0280 (7)	0.0324 (7)	0.0237 (7)	−0.0036 (6)	0.0011 (6)	0.0008 (5)
O12	0.0241 (7)	0.0407 (8)	0.0338 (8)	0.0079 (6)	0.0087 (6)	0.0163 (6)
O13	0.0340 (8)	0.0331 (8)	0.0297 (8)	0.0049 (6)	0.0002 (6)	−0.0105 (6)
C11	0.0221 (10)	0.0287 (10)	0.0235 (10)	0.0037 (8)	0.0042 (8)	0.0022 (8)
C12	0.0241 (11)	0.0441 (12)	0.0282 (11)	−0.0023 (9)	0.0032 (9)	−0.0055 (9)
C13	0.0322 (11)	0.0416 (12)	0.0266 (11)	0.0026 (9)	0.0069 (9)	−0.0077 (9)
C14	0.0216 (10)	0.0388 (11)	0.0315 (11)	0.0025 (8)	0.0068 (9)	0.0018 (8)
C15	0.0217 (11)	0.0524 (13)	0.0354 (12)	−0.0008 (9)	0.0008 (9)	−0.0064 (10)
C16	0.0255 (11)	0.0451 (12)	0.0267 (11)	−0.0021 (9)	0.0021 (9)	−0.0072 (9)
C17	0.0263 (12)	0.0521 (14)	0.0372 (13)	0.0003 (10)	0.0057 (10)	0.0005 (10)
O14	0.0332 (9)	0.0873 (12)	0.0380 (9)	−0.0013 (8)	0.0120 (7)	−0.0176 (8)
O15	0.0254 (9)	0.1235 (16)	0.0545 (12)	−0.0084 (10)	0.0154 (8)	−0.0274 (11)
P21	0.0232 (3)	0.0233 (2)	0.0214 (3)	−0.00051 (19)	0.0079 (2)	0.00185 (19)
O21	0.0256 (8)	0.0348 (8)	0.0563 (10)	0.0047 (6)	0.0168 (7)	0.0186 (7)
O22	0.0443 (9)	0.0361 (8)	0.0209 (7)	−0.0142 (6)	0.0083 (6)	−0.0011 (6)
O23	0.0375 (8)	0.0384 (8)	0.0232 (7)	−0.0123 (6)	0.0106 (7)	−0.0082 (6)
C21	0.0251 (10)	0.0225 (9)	0.0219 (10)	−0.0003 (7)	0.0069 (8)	0.0009 (7)
C22	0.0212 (10)	0.0329 (10)	0.0249 (10)	0.0013 (8)	0.0015 (8)	0.0030 (8)
C23	0.0310 (11)	0.0378 (11)	0.0241 (11)	−0.0028 (9)	0.0093 (9)	0.0028 (8)
C24	0.0243 (10)	0.0328 (11)	0.0324 (11)	0.0005 (8)	0.0088 (9)	−0.0018 (8)
C25	0.0254 (11)	0.0455 (12)	0.0374 (13)	0.0043 (9)	−0.0002 (9)	0.0007 (9)
C26	0.0292 (11)	0.0450 (12)	0.0233 (10)	0.0042 (9)	0.0045 (9)	0.0056 (9)
C27	0.0260 (12)	0.0469 (13)	0.0419 (13)	0.0007 (9)	0.0098 (10)	0.0022 (10)
O24	0.0313 (9)	0.1004 (13)	0.0442 (10)	0.0015 (9)	0.0153 (7)	0.0184 (9)
O25	0.0269 (9)	0.0986 (14)	0.0522 (11)	0.0101 (9)	0.0135 (8)	0.0107 (10)

Geometric parameters (Å, º)

Co1—O2W^i	2.0722 (15)	C14—C17	1.479 (3)
Co1—O2W	2.0722 (15)	C15—C16	1.378 (3)
Co1—O3W^i	2.0828 (15)	C15—H15	0.9300
Co1—O3W	2.0828 (15)	C16—H16	0.9300
Co1—O1W	2.1012 (14)	C17—O14	1.240 (2)
Co1—O1W^i	2.1012 (14)	C17—O15	1.273 (3)
O1W—H1W1	0.81 (2)	O15—H15O	0.89 (3)
O1W—H2W1	0.79 (2)	P21—O21	1.4975 (13)
O2W—H1W2	0.91 (2)	P21—O22	1.5107 (13)
O2W—H2W2	0.77 (2)	P21—O23	1.5394 (14)
O3W—H1W3	0.80 (3)	P21—C21	1.7852 (19)
O3W—H2W3	0.78 (3)	O22—H22O	1.14 (2)
O4W—H1W4	0.86 (2)	O23—H23O	0.80 (2)
O4W—H2W4	0.80 (2)	C21—C22	1.381 (2)
P11—O11	1.4988 (13)	C21—C26	1.389 (3)
P11—O12	1.5225 (13)	C22—C23	1.377 (2)
P11—O13	1.5398 (14)	C22—H22	0.9300
P11—C11	1.7896 (19)	C23—C24	1.382 (3)
O12—H22O	1.30 (2)	C23—H23	0.9300
O13—H13O	0.84 (2)	C24—C25	1.372 (3)
C11—C16	1.382 (3)	C24—C27	1.487 (3)
C11—C12	1.391 (2)	C25—C26	1.386 (3)
C12—C13	1.378 (3)	C25—H25	0.9300
C12—H12	0.9300	C26—H26	0.9300
C13—C14	1.385 (3)	C27—O24	1.241 (2)
C13—H13	0.9300	C27—O25	1.273 (3)
C14—C15	1.380 (3)	O25—H25O	0.84 (3)
O2W^i—Co1—O2W	180.00 (10)	C15—C14—C17	120.71 (18)
O2W^i—Co1—O3W^i	89.85 (7)	C13—C14—C17	119.52 (18)
O2W—Co1—O3W^i	90.15 (7)	C16—C15—C14	120.63 (19)
O2W^i—Co1—O3W	90.15 (7)	C16—C15—H15	119.7
O2W—Co1—O3W	89.85 (7)	C14—C15—H15	119.7
O3W^i—Co1—O3W	180.00 (12)	C15—C16—C11	119.93 (18)
O2W^i—Co1—O1W	88.11 (6)	C15—C16—H16	120.0
O2W—Co1—O1W	91.89 (6)	C11—C16—H16	120.0
O3W^i—Co1—O1W	90.55 (7)	O14—C17—O15	123.57 (19)
O3W—Co1—O1W	89.45 (7)	O14—C17—C14	120.59 (19)
O2W^i—Co1—O1W^i	91.89 (6)	O15—C17—C14	115.84 (19)
O2W—Co1—O1W^i	88.11 (6)	C17—O15—H15O	114 (2)
O3W^i—Co1—O1W^i	89.45 (7)	O21—P21—O22	111.79 (8)
O3W—Co1—O1W^i	90.55 (7)	O21—P21—O23	111.35 (8)
O1W—Co1—O1W^i	180.00 (8)	O22—P21—O23	106.27 (7)
Co1—O1W—H1W1	116.2 (15)	O21—P21—C21	107.13 (8)
Co1—O1W—H2W1	114.1 (16)	O22—P21—C21	110.72 (9)
H1W1—O1W—H2W1	104 (2)	O23—P21—C21	109.61 (8)
Co1—O2W—H1W2	124.4 (14)	P21—O22—H22O	119.8 (10)
Co1—O2W—H2W2	125.1 (19)	P21—O23—H23O	117.9 (16)
H1W2—O2W—H2W2	106 (2)	C22—C21—C26	119.57 (17)
Co1—O3W—H1W3	124.9 (19)	C22—C21—P21	117.51 (14)
Co1—O3W—H2W3	132 (2)	C26—C21—P21	122.91 (14)
H1W3—O3W—H2W3	103 (3)	C23—C22—C21	120.58 (17)
H1W4—O4W—H2W4	103 (2)	C23—C22—H22	119.7
O11—P11—O12	110.76 (8)	C21—C22—H22	119.7
O11—P11—O13	110.14 (7)	C22—C23—C24	119.72 (18)
O12—P11—O13	111.62 (8)	C22—C23—H23	120.1
O11—P11—C11	111.64 (8)	C24—C23—H23	120.1
O12—P11—C11	107.75 (8)	C25—C24—C23	120.22 (17)
O13—P11—C11	104.77 (8)	C25—C24—C27	122.42 (19)
P11—O12—H22O	120.3 (9)	C23—C24—C27	117.36 (18)
P11—O13—H13O	119.4 (15)	C24—C25—C26	120.35 (19)
C16—C11—C12	119.42 (17)	C24—C25—H25	119.8
C16—C11—P11	121.71 (14)	C26—C25—H25	119.8
C12—C11—P11	118.79 (14)	C25—C26—C21	119.56 (18)
C13—C12—C11	120.56 (18)	C25—C26—H26	120.2
C13—C12—H12	119.7	C21—C26—H26	120.2
C11—C12—H12	119.7	O24—C27—O25	123.97 (19)
C12—C13—C14	119.71 (18)	O24—C27—C24	118.83 (19)
C12—C13—H13	120.1	O25—C27—C24	117.2 (2)
C14—C13—H13	120.1	C27—O25—H25O	108 (2)
C15—C14—C13	119.73 (18)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O4W^ii	0.81 (2)	1.94 (2)	2.752 (2)	174 (2)
O1W—H2W1···O21^iii	0.79 (2)	1.86 (2)	2.644 (2)	172 (2)
O2W—H1W2···O11^iv	0.91 (2)	1.75 (2)	2.654 (2)	174 (2)
O2W—H2W2···O22^iii	0.77 (2)	2.31 (2)	3.060 (2)	168 (3)
O2W—H2W2···O21^iii	0.77 (2)	2.62 (2)	3.178 (2)	131 (2)
O3W—H1W3···O4W^iii	0.80 (3)	1.96 (3)	2.758 (2)	179 (3)
O3W—H2W3···O23^ii	0.78 (3)	2.33 (3)	2.972 (2)	141 (2)
O4W—H1W4···O12	0.86 (2)	1.90 (2)	2.761 (2)	172 (2)
O4W—H2W4···O1W	0.80 (2)	2.10 (2)	2.886 (2)	169 (2)
O22—H22O···O12	1.14 (2)	1.30 (2)	2.435 (2)	176 (2)
O13—H13O···O21^iii	0.84 (2)	1.68 (2)	2.523 (2)	174 (2)
O15—H15O···O24^v	0.89 (3)	1.69 (3)	2.578 (2)	173 (3)
O23—H23O···O11^vi	0.80 (2)	1.73 (2)	2.528 (2)	171 (2)
O25—H25O···O14^vii	0.84 (3)	1.82 (3)	2.658 (2)	171 (3)

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