Dipotassium biphenyl-4,4′-disulfonate dihydrate: a coordination polymer

The polymeric structure of the title compound, poly[[diaquabis(μ-biphenyl-4,4′-disulfonato)tetrapotassium(I)] di­hydrate], {[K₂(C₁₂H₈O₆S₂)(H₂O)]·H₂O}_n, is based on an asymmetric unit comprising three independent and different potassium centres, one six-coordinate [K—O = 2.657 (3)–2.866 (5) Å], one seven-coordinate [K—O = 2.703 (3)–3.040 (4) Å], and the third ten-coordinate [K—O = 2.751 (3)–3.079 (4) Å], with two of these lying on crystallographic mirror planes. The four half-occupancy water mol­ecules also lie on the mirror planes with two coordinated (one monodentate, the other bidentate bridging) and two as mol­ecules of solvation. The inter­linked coordination polyhedra form chains which are joined laterally through the biphenyl residues as well as through head-to-tail water hydrogen-bonding inter­actions, giving a two-dimensional structure.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.031
• wR factor = 0.083
• Data-to-parameter ratio = 10.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O2W    -   H2W    ...          ?
PLAT420_ALERT_2_B D-H Without Acceptor       O1W    -   H12W   ...          ?
PLAT420_ALERT_2_B D-H Without Acceptor       O4W    -   H42W   ...          ?

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.61 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C5B
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C6B
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         K2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C1B
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C4B
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.56
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6
PLAT410_ALERT_2_C Short Intra H...H Contact  H6A    ..  H6B     ..       1.94 Ang.

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           27.50
           From the CIF: _reflns_number_total               2295
           Count of symmetry unique reflns         1973
           Completeness (_total/calc)            116.32%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       322
           Fraction of Friedel pairs measured     0.163
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  11 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Compounds of 4,4'-biphenyldisulfonic acid (BPDS) are not numerous in the crystallographic literature. The guanidinium salts have been used for the generation of 2-D structures for the formation of crystalline clathrates with aromatic hydrocarbons (Swift et al., 1998; Pivovar et al., 2002). The bis(alaninium) salt is also known (Liao et al., 2001). With coordination compounds, BDPDS is generally found as a dianionic counter ion (Cai et al., 2001; Usuki et al., 2002). We obtained X-ray diffraction quality crystals of the hydrated dipotassium salt of BPDS as an intermediate in the synthesis of BPDS, when recrystallized from water. The structure of this compound, K₂²⁺·C₁₂H₈O₆S₂^2-·2H₂O (I) is reported here.

The structure of (I) is based on an asymmetric unit comprising three independent and different potassium centres, one six-coordinate (K2) [K–O range, 2.657 (3)–2.866 (5) Å], one seven- coordinate (K1) [K–O range, 2.703 (3)–3.040 (4) Å] and the third ten-coordinate (K3) [K–O range, 2.751 (3)–3.079 (4) Å], with two of these (K2 and K3) lying on crystallographic mirror planes (Fig. 1). The four half-occupancy water molecules also lie on the mirror planes with two coordinated [one monodentate (O1W on K2), and one bidentate (O2W, bridging K2 and K3)], and the other two (OW3, OW4) as molecules of solvation. The structure has pseudo 2/m symmetry, the 2-fold rotational symmetry along the b axis being upset largely by the differing roles of the water molecules in the structure. This was also consistent with the failure to obtain a solution of the structure in the space group C2/m.

The interlinked potassium coordination polyhedra form chains which extend down the b axix and are linked laterally across the c cell direction through the biphenyl residues of the BPDS ligands, giving a 2-D structure (Fig. 2). This is somewhat analogous to the 2-D but hydrogen-bonded guanidinium-BPDS open framework structures (Swift et al., 1998; Pivovar et al., 2002) which accommodate interstitial inert aromatic molecules. With (I), the water molecules are similarly accommodated in the interstitial spaces along the crystallographic mirror planes in linear head-to-tail interactions (Table 1) and also link the coordination polymer chains. In addition, the coordinated water molecules give lateral O–H···O_sulfonate interactions within the polymer chains.

Within the BPDS anion, the two phenyl rings (A and B) are close to co-planar [torsion angle C2A–C1A–C1B–C6B, -178.3 (5) °], which is similar to that found in the alaninium salt where the two residues are inversion related (Liao et al., 2001).

Related literature

For other 4,4'-biphenyldisulfonate crystal structures, see: Swift et al. (1998); Liao et al. (2001); Cai et al. (2001); Usuki et al. (2002). For related literature, see: Pivovar et al. (2002). For synthesis, see: Feldmann (1931).

S2. Experimental

The title compound was obtained as colourless crystals from the room temperature evaporation of an aqueous solution of dipotassium 4,4-biphenyldisulfonate, an intermediate product in the synthesis of 4,4'-biphenyldisulfonic acid by the sulfonation of biphenyl using the procedure of Feldmann (1931).

S3. Refinement

Hydrogen atoms on the water molecules were located by difference methods but their positional and isotropic displacement parameters were fixed as located and U_iso(H) = 1.2U_eq(O), respectively; see Table 1 for distances. The aromatic H atoms were included in the refinement in their calculated positions (C–H = 0.94–0.95 Å) using a riding model approximation, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: MSC/AFC Diffractmeter Control Software (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC Diffractmeter Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures

Fig. 1. Molecular configuration and atom naming scheme for the BPDS ligand, the three independent potassium coordination polyhedra and the water molecules in the asymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen-bonding interactions associated with the water molecules. The two potassium ions (K2, K3) and the four water molecules (O1W–O4W) lie on a crystallographic mirror plane. Symmetry codes: (i) x - 1, y, z; (ii) x - 1, y, z + 1; (iii) x, y, z + 1; (iv) x - 1/2, -y + 1/2, z; (v) x - 1/2, -y + 1/2, z + 1; (vi) x - 1, -y, z + 1; (vii) x, -y, z + 1; (viii) x + 1, y, z; (ix) x, -y, z.

Fig. 2. The 2-D hydrogen-bonded structure of (I) viewed down the a axis, showing K–Osulfonate coordination-polymer chains with the biphenyl step linkages, together with the water mediated hydrogen-bonding associations lying on the mirror planes at y = 0, 1/2.

dipotassium biphenyl-4,4'-disulfonate dihydrate

Crystal data

2K^+·C12H8O6S2^2^−·2H2O	F(000) = 872
Mr = 426.56	Dx = 1.708 Mg m^−3
Monoclinic, Cm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2y	Cell parameters from 25 reflections
a = 5.8316 (10) Å	θ = 12.9–17.1°
b = 19.691 (7) Å	µ = 0.86 mm^−1
c = 14.623 (2) Å	T = 297 K
β = 98.953 (13)°	Block, colourless
V = 1658.7 (7) Å^3	0.32 × 0.25 × 0.20 mm
Z = 4

Data collection

Rigaku AFC 7R diffractometer	2196 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.016
Graphite monochromator	θmax = 27.5°, θmin = 2.5°
ω–2θ scans	h = −3→7
Absorption correction: ψ scan (TEXSAN for Windows; Molecular Structure Corporation, 1999)	k = 0→25
Tmin = 0.774, Tmax = 0.849	l = −18→18
2295 measured reflections	3 standard reflections every 150 min
2295 independent reflections	intensity decay: 0.6%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters not refined
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.1P)^2 + 15.7726P] where P = (Fo^2 + 2Fc^2)/3
S = 0.88	(Δ/σ)max = 0.002
2295 reflections	Δρmax = 0.40 e Å^−3
227 parameters	Δρmin = −0.39 e Å^−3
2 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (8)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
K1	0.27341 (18)	0.18494 (4)	0.50427 (7)	0.0306 (2)
K2	0.3806 (2)	0.00000	0.66340 (8)	0.0322 (3)
K3	0.8140 (2)	0.00000	0.48912 (8)	0.0331 (3)
S4A	0.85074 (12)	0.13645 (4)	−0.35496 (5)	0.0216 (2)
S4B	0.67991 (14)	0.14568 (5)	0.35851 (6)	0.0255 (2)
O1W	0.4854 (11)	0.00000	0.8501 (4)	0.080 (3)
O2W	0.2800 (7)	0.00000	0.4652 (3)	0.0354 (12)
O41A	0.8714 (6)	0.20502 (15)	−0.3888 (2)	0.0431 (9)
O41B	0.9000 (5)	0.12170 (17)	0.40854 (18)	0.0370 (9)
O42A	0.6357 (5)	0.10358 (17)	−0.39554 (19)	0.0374 (9)
O42B	0.4950 (6)	0.09558 (17)	0.3603 (2)	0.0404 (10)
O43A	1.0527 (5)	0.09479 (17)	−0.3630 (2)	0.0403 (10)
O43B	0.6088 (6)	0.21186 (17)	0.3865 (2)	0.0389 (9)
C1A	0.7952 (7)	0.15078 (19)	−0.0464 (3)	0.0274 (10)
C1B	0.7699 (7)	0.1525 (2)	0.0539 (3)	0.0285 (10)
C2A	0.6400 (8)	0.1846 (3)	−0.1132 (3)	0.0459 (15)
C2B	0.5868 (9)	0.1849 (2)	0.0848 (3)	0.0427 (14)
C3A	0.6591 (9)	0.1809 (2)	−0.2069 (3)	0.0424 (15)
C3B	0.5603 (8)	0.1853 (2)	0.1778 (3)	0.0429 (15)
C4A	0.8342 (7)	0.14383 (19)	−0.2346 (2)	0.0253 (10)
C4B	0.7182 (7)	0.1511 (2)	0.2407 (3)	0.0273 (10)
C5A	0.9927 (8)	0.1114 (3)	−0.1700 (3)	0.0497 (16)
C5B	0.9036 (10)	0.1196 (4)	0.2123 (3)	0.065 (2)
C6A	0.9716 (9)	0.1150 (3)	−0.0765 (3)	0.0533 (18)
C6B	0.9281 (9)	0.1203 (4)	0.1193 (3)	0.066 (2)
O3W	0.3491 (11)	0.00000	0.2133 (3)	0.0608 (19)
O4W	0.4275 (14)	0.00000	0.0351 (5)	0.083 (2)
H2A	0.51870	0.20980	−0.09300	0.0550*
H2B	0.47780	0.20740	0.04090	0.0510*
H2W	0.34800	0.03900	0.44000	0.0420*
H3A	0.55160	0.20360	−0.25180	0.0500*
H3B	0.43380	0.20770	0.19790	0.0510*
H5A	1.11400	0.08620	−0.19020	0.0600*
H5B	1.01260	0.09710	0.25620	0.0780*
H6A	1.07910	0.09230	−0.03160	0.0640*
H6B	1.05460	0.09790	0.09920	0.0790*
H11W	0.35600	0.00000	0.88400	0.0960*
H12W	0.61400	0.00000	0.88400	0.0960*
H3W	0.39700	0.03850	0.25200	0.0730*
H41W	0.40200	0.00000	0.09400	0.0970*
H42W	0.57940	0.00000	0.03750	0.0970*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0334 (4)	0.0286 (4)	0.0307 (3)	−0.0007 (4)	0.0082 (3)	0.0001 (4)
K2	0.0286 (6)	0.0346 (6)	0.0344 (6)	0.0000	0.0083 (5)	0.0000
K3	0.0357 (6)	0.0317 (5)	0.0325 (6)	0.0000	0.0076 (5)	0.0000
S4A	0.0243 (4)	0.0239 (4)	0.0174 (4)	0.0011 (3)	0.0058 (3)	0.0000 (3)
S4B	0.0310 (4)	0.0297 (4)	0.0166 (4)	−0.0042 (4)	0.0062 (3)	−0.0006 (3)
O1W	0.073 (4)	0.116 (6)	0.045 (3)	0.0000	−0.005 (3)	0.0000
O2W	0.038 (2)	0.036 (2)	0.035 (2)	0.0000	0.0147 (17)	0.0000
O41A	0.076 (2)	0.0276 (14)	0.0285 (14)	−0.0031 (16)	0.0174 (15)	0.0044 (11)
O41B	0.0383 (16)	0.0489 (17)	0.0230 (13)	0.0000 (14)	0.0020 (11)	0.0051 (12)
O42A	0.0328 (14)	0.0533 (18)	0.0267 (14)	−0.0133 (14)	0.0063 (11)	−0.0078 (12)
O42B	0.0453 (17)	0.0468 (19)	0.0302 (14)	−0.0183 (15)	0.0095 (13)	0.0004 (13)
O43A	0.0370 (16)	0.057 (2)	0.0279 (14)	0.0217 (15)	0.0085 (12)	0.0012 (13)
O43B	0.0518 (17)	0.0391 (16)	0.0277 (14)	0.0023 (14)	0.0120 (13)	−0.0056 (12)
C1A	0.0342 (19)	0.0320 (18)	0.0168 (15)	0.0031 (16)	0.0068 (14)	0.0009 (13)
C1B	0.0317 (19)	0.0359 (19)	0.0181 (16)	0.0004 (16)	0.0041 (14)	−0.0003 (14)
C2A	0.051 (3)	0.069 (3)	0.0196 (17)	0.030 (2)	0.0114 (18)	0.0024 (18)
C2B	0.049 (2)	0.058 (3)	0.0222 (19)	0.024 (2)	0.0086 (17)	0.0073 (19)
C3A	0.049 (3)	0.059 (3)	0.0196 (18)	0.025 (2)	0.0071 (17)	0.0072 (17)
C3B	0.050 (3)	0.056 (3)	0.0252 (19)	0.025 (2)	0.0140 (18)	0.0019 (17)
C4A	0.0306 (18)	0.0305 (17)	0.0154 (15)	−0.0001 (15)	0.0057 (14)	−0.0018 (13)
C4B	0.0318 (19)	0.0332 (19)	0.0170 (16)	−0.0034 (15)	0.0041 (14)	−0.0016 (13)
C5A	0.044 (2)	0.084 (4)	0.0220 (18)	0.036 (3)	0.0079 (17)	0.001 (2)
C5B	0.061 (3)	0.116 (5)	0.0188 (19)	0.048 (3)	0.012 (2)	0.016 (2)
C6A	0.052 (3)	0.085 (4)	0.0229 (18)	0.037 (3)	0.0059 (18)	0.006 (2)
C6B	0.054 (3)	0.122 (5)	0.023 (2)	0.053 (3)	0.014 (2)	0.016 (3)
O3W	0.080 (4)	0.057 (3)	0.040 (3)	0.0000	−0.008 (3)	0.0000
O4W	0.091 (5)	0.104 (6)	0.055 (4)	0.0000	0.003 (4)	0.0000

Geometric parameters (Å, º)

K1—O43B	2.850 (4)	S4B—C4B	1.775 (4)
K1—O41B^i	2.703 (3)	O1W—H12W	0.8300
K1—O41A^ii	3.040 (4)	O1W—H11W	0.9700
K1—O43A^ii	3.058 (3)	O2W—H2W^ix	0.9600
K1—O42A^iii	2.866 (3)	O2W—H2W	0.9600
K1—O43B^iv	2.739 (3)	O3W—H3W	0.9600
K1—O41A^v	2.681 (3)	O3W—H3W^ix	0.9600
K2—O1W	2.703 (6)	O4W—H41W	0.9000
K2—O2W	2.866 (5)	O4W—H42W	0.8800
K2—O43A^ii	2.657 (3)	C1A—C6A	1.375 (7)
K2—O42A^iii	2.741 (3)	C1A—C2A	1.393 (6)
K2—O43A^vi	2.657 (3)	C1A—C1B	1.497 (6)
K2—O42A^vii	2.741 (3)	C1B—C2B	1.379 (6)
K3—O2W	3.079 (4)	C1B—C6B	1.376 (7)
K3—O41B	2.751 (3)	C2A—C3A	1.394 (6)
K3—O42B	3.076 (4)	C2B—C3B	1.392 (6)
K3—O42A^iii	2.938 (3)	C3A—C4A	1.367 (6)
K3—O43A^iii	3.027 (3)	C3B—C4B	1.373 (6)
K3—O2W^viii	2.793 (4)	C4A—C5A	1.372 (6)
K3—O41B^ix	2.751 (3)	C4B—C5B	1.366 (7)
K3—O42B^ix	3.076 (4)	C5A—C6A	1.394 (6)
K3—O42A^vii	2.938 (3)	C5B—C6B	1.389 (6)
K3—O43A^vii	3.027 (3)	C2A—H2A	0.9500
S4A—O41A	1.450 (3)	C2B—H2B	0.9400
S4A—O42A	1.453 (3)	C3A—H3A	0.9500
S4A—O43A	1.455 (3)	C3B—H3B	0.9400
S4A—C4A	1.784 (3)	C5A—H5A	0.9500
S4B—O41B	1.454 (3)	C5B—H5B	0.9400
S4B—O42B	1.465 (4)	C6A—H6A	0.9500
S4B—O43B	1.446 (4)	C6B—H6B	0.9400
O41B^i—K1—O43B	110.25 (9)	O41B^ix—K3—O42B^ix	48.53 (9)
O41A^ii—K1—O43B	160.66 (9)	O41B^ix—K3—O42A^vii	75.26 (9)
O43A^ii—K1—O43B	152.59 (10)	O41B^ix—K3—O43A^vii	71.01 (8)
O42A^iii—K1—O43B	83.81 (9)	O42A^vii—K3—O42B^ix	72.09 (8)
O43B—K1—O43B^iv	71.84 (10)	O42B^ix—K3—O43A^vii	103.14 (9)
O41A^v—K1—O43B	95.63 (10)	O42A^vii—K3—O43A^vii	47.64 (8)
O41A^ii—K1—O41B^i	72.70 (9)	O41A—S4A—O42A	112.82 (19)
O41B^i—K1—O43A^ii	71.13 (9)	O41A—S4A—O43A	112.72 (19)
O41B^i—K1—O42A^iii	118.54 (10)	O41A—S4A—C4A	106.33 (17)
O41B^i—K1—O43B^iv	80.84 (10)	O42A—S4A—O43A	111.95 (18)
O41A^v—K1—O41B^i	139.11 (11)	O42A—S4A—C4A	105.28 (17)
O41A^ii—K1—O43A^ii	46.73 (8)	O43A—S4A—C4A	107.12 (18)
O41A^ii—K1—O42A^iii	112.09 (9)	K3—S4B—O41B	49.33 (13)
O41A^ii—K1—O43B^iv	90.23 (10)	K3—S4B—O42B	62.39 (13)
O41A^ii—K1—O41A^v	72.92 (10)	K3—S4B—O43B	129.77 (13)
O42A^iii—K1—O43A^ii	72.58 (9)	K3—S4B—C4B	122.20 (14)
O43A^ii—K1—O43B^iv	133.53 (10)	O41B—S4B—O42B	111.53 (19)
O41A^v—K1—O43A^ii	99.88 (9)	O41B—S4B—O43B	114.83 (19)
O42A^iii—K1—O43B^iv	153.45 (10)	O41B—S4B—C4B	105.87 (18)
O41A^v—K1—O42A^iii	94.61 (10)	O42B—S4B—O43B	111.0 (2)
O41A^v—K1—O43B^iv	77.83 (9)	O42B—S4B—C4B	105.19 (18)
O1W—K2—O2W	178.76 (17)	O43B—S4B—C4B	107.79 (18)
O1W—K2—O43A^ii	101.02 (12)	K2—O2W—K3	80.85 (11)
O1W—K2—O42A^iii	105.61 (11)	K2—O2W—K3^i	85.61 (12)
O1W—K2—O43A^vi	101.02 (12)	K3—O2W—K3^i	166.45 (17)
O1W—K2—O42A^vii	105.61 (11)	K1^x—O41A—S4A	99.57 (16)
O2W—K2—O43A^ii	79.84 (9)	K1^xi—O41A—S4A	158.5 (2)
O2W—K2—O42A^iii	73.61 (8)	K1^x—O41A—K1^xi	85.21 (9)
O2W—K2—O43A^vi	79.84 (9)	K3—O41B—S4B	107.04 (16)
O2W—K2—O42A^vii	73.61 (8)	K1^viii—O41B—K3	111.44 (10)
O42A^iii—K2—O43A^ii	81.09 (9)	K1^viii—O41B—S4B	133.48 (19)
O43A^ii—K2—O43A^vi	89.26 (10)	K1^xii—O42A—S4A	118.71 (18)
O42A^vii—K2—O43A^ii	152.93 (10)	K2^xii—O42A—S4A	132.77 (17)
O42A^iii—K2—O43A^vi	152.93 (10)	K3^xii—O42A—S4A	100.58 (15)
O42A^iii—K2—O42A^vii	96.15 (10)	K1^xii—O42A—K2^xii	100.58 (10)
O42A^vii—K2—O43A^vi	81.09 (9)	K1^xii—O42A—K3^xii	113.15 (10)
S4B—K3—O2W	78.47 (5)	K2^xii—O42A—K3^xii	85.52 (10)
S4B—K3—O41B	23.63 (6)	K3—O42B—S4B	92.65 (15)
S4B—K3—O42B	24.96 (7)	K3^xii—O43A—S4A	96.74 (14)
S4B—K3—O42A^iii	70.87 (6)	K1^x—O43A—S4A	98.62 (15)
S4B—K3—O43A^iii	85.56 (6)	K2^x—O43A—S4A	163.26 (19)
S4B—K3—O2W^viii	94.10 (6)	K1^x—O43A—K3^xii	95.55 (9)
S4B—K3—S4B^ix	111.64 (4)	K2^x—O43A—K3^xii	84.90 (9)
S4B—K3—O41B^ix	121.69 (7)	K1^x—O43A—K2^x	97.79 (9)
S4B—K3—O42B^ix	96.07 (7)	K1—O43B—S4B	104.92 (17)
S4B—K3—O42A^vii	145.18 (7)	K1—O43B—K1^xiii	87.96 (9)
S4B—K3—O43A^vii	160.55 (7)	K1^xiii—O43B—S4B	139.4 (2)
O2W—K3—O41B	101.53 (8)	H11W—O1W—H12W	113.00
O2W—K3—O42B	54.96 (9)	K2—O1W—H11W	117.00
O2W—K3—O42A^iii	67.86 (8)	K2—O1W—H12W	130.00
O2W—K3—O43A^iii	115.20 (9)	K2—O2W—H2W	111.00
O2W—K3—O2W^viii	166.45 (13)	K3—O2W—H2W^ix	65.00
S4B^ix—K3—O2W	78.47 (5)	K2—O2W—H2W^ix	111.00
O2W—K3—O41B^ix	101.53 (8)	K3—O2W—H2W	65.00
O2W—K3—O42B^ix	54.96 (9)	K3^i—O2W—H2W^ix	121.00
O2W—K3—O42A^vii	67.86 (8)	K3^i—O2W—H2W	121.00
O2W—K3—O43A^vii	115.20 (9)	H2W—O2W—H2W^ix	106.00
O41B—K3—O42B	48.53 (9)	H3W—O3W—H3W^ix	104.00
O41B—K3—O42A^iii	75.26 (9)	H41W—O4W—H42W	106.00
O41B—K3—O43A^iii	71.01 (8)	C2A—C1A—C6A	117.2 (4)
O2W^viii—K3—O41B	72.58 (8)	C1B—C1A—C6A	121.2 (4)
S4B^ix—K3—O41B	121.69 (7)	C1B—C1A—C2A	121.6 (4)
O41B—K3—O41B^ix	121.19 (10)	C1A—C1B—C6B	120.9 (4)
O41B—K3—O42B^ix	113.82 (9)	C1A—C1B—C2B	122.1 (4)
O41B—K3—O42A^vii	162.77 (10)	C2B—C1B—C6B	117.1 (4)
O41B—K3—O43A^vii	138.51 (9)	C1A—C2A—C3A	121.4 (4)
O42A^iii—K3—O42B	72.09 (8)	C1B—C2B—C3B	122.1 (4)
O42B—K3—O43A^iii	103.14 (9)	C2A—C3A—C4A	119.8 (4)
O2W^viii—K3—O42B	115.52 (10)	C2B—C3B—C4B	119.1 (4)
S4B^ix—K3—O42B	96.07 (7)	S4A—C4A—C3A	119.6 (3)
O41B^ix—K3—O42B	113.82 (9)	S4A—C4A—C5A	120.5 (3)
O42B—K3—O42B^ix	75.45 (9)	C3A—C4A—C5A	119.9 (3)
O42A^vii—K3—O42B	122.82 (10)	S4B—C4B—C3B	120.5 (3)
O42B—K3—O43A^vii	169.11 (9)	S4B—C4B—C5B	119.5 (3)
O42A^iii—K3—O43A^iii	47.64 (8)	C3B—C4B—C5B	120.0 (4)
O2W^viii—K3—O42A^iii	120.66 (8)	C4A—C5A—C6A	119.9 (4)
S4B^ix—K3—O42A^iii	145.18 (7)	C4B—C5B—C6B	120.0 (5)
O41B^ix—K3—O42A^iii	162.77 (10)	C1A—C6A—C5A	121.7 (5)
O42A^iii—K3—O42B^ix	122.82 (10)	C1B—C6B—C5B	121.7 (5)
O42A^iii—K3—O42A^vii	87.93 (9)	C1A—C2A—H2A	118.00
O42A^iii—K3—O43A^vii	100.51 (9)	C3A—C2A—H2A	121.00
O2W^viii—K3—O43A^iii	75.00 (9)	C1B—C2B—H2B	118.00
S4B^ix—K3—O43A^iii	160.55 (7)	C3B—C2B—H2B	120.00
O41B^ix—K3—O43A^iii	138.51 (9)	C4A—C3A—H3A	119.00
O42B^ix—K3—O43A^iii	169.11 (9)	C2A—C3A—H3A	121.00
O42A^vii—K3—O43A^iii	100.51 (9)	C2B—C3B—H3B	121.00
O43A^iii—K3—O43A^vii	76.15 (9)	C4B—C3B—H3B	120.00
S4B^ix—K3—O2W^viii	94.10 (6)	C4A—C5A—H5A	119.00
O2W^viii—K3—O41B^ix	72.58 (8)	C6A—C5A—H5A	121.00
O2W^viii—K3—O42B^ix	115.52 (10)	C6B—C5B—H5B	121.00
O2W^viii—K3—O42A^vii	120.66 (8)	C4B—C5B—H5B	119.00
O2W^viii—K3—O43A^vii	75.00 (9)	C1A—C6A—H6A	118.00
S4B^ix—K3—O41B^ix	23.63 (6)	C5A—C6A—H6A	120.00
S4B^ix—K3—O42B^ix	24.96 (7)	C5B—C6B—H6B	120.00
S4B^ix—K3—O42A^vii	70.87 (6)	C1B—C6B—H6B	118.00
S4B^ix—K3—O43A^vii	85.56 (6)
O41B^i—K1—O43B—S4B	−63.28 (18)	S4B—K3—O42A^iii—K1	36.28 (8)
O41B^i—K1—O43B—K1^xiii	155.80 (9)	S4B—K3—O42A^iii—K2	135.88 (8)
O43A^ii—K1—O43B—S4B	24.6 (3)	O2W—K3—O42A^iii—K1	−48.71 (11)
O43A^ii—K1—O43B—K1^xiii	−116.35 (19)	O41B—K3—O42A^iii—K1	60.57 (11)
O42A^iii—K1—O43B—S4B	54.89 (16)	O41B—K3—O42A^iii—K2	160.18 (10)
O42A^iii—K1—O43B—K1^xiii	−86.03 (10)	O42B—K3—O42A^iii—K1	9.96 (11)
O43B^iv—K1—O43B—S4B	−135.85 (18)	O42B—K3—O42A^iii—K2	109.57 (10)
O43B^iv—K1—O43B—K1^xiii	83.23 (10)	S4B—K3—O42A^vii—K2	−35.22 (15)
O41A^v—K1—O43B—S4B	148.94 (16)	O42B—K3—O42A^vii—K2	−51.07 (12)
O41A^v—K1—O43B—K1^xiii	8.02 (10)	O42A—S4A—O41A—K1^x	−112.87 (16)
O43B—K1—O41B^i—S4B^i	−92.7 (2)	O42A—S4A—O41A—K1^xi	−11.5 (6)
O43B—K1—O43A^ii—K2	10.8 (2)	O43A—S4A—O41A—K1^x	15.15 (19)
O43B—K1—O43A^ii—S4A^ii	−172.48 (16)	O43A—S4A—O41A—K1^xi	116.5 (5)
O43B—K1—O42A^iii—K2	−145.49 (11)	C4A—S4A—O41A—K1^x	132.23 (15)
O43B—K1—O42A^iii—K3	−55.87 (11)	C4A—S4A—O41A—K1^xi	−126.4 (5)
O43B—K1—O42A^iii—S4A^iii	61.65 (17)	O41A—S4A—O42A—K1^xii	−13.0 (2)
O43B—K1—O43B^iv—K1^iv	−165.58 (11)	O41A—S4A—O42A—K2^xii	−155.4 (2)
O43B—K1—O43B^iv—S4B^iv	−54.9 (3)	O41A—S4A—O42A—K3^xii	110.94 (17)
O43B—K1—O41A^v—S4A^v	96.8 (5)	O43A—S4A—O42A—K1^xii	−141.42 (17)
O43B—K1—O41A^v—K1^xiii	−7.24 (9)	O43A—S4A—O42A—K2^xii	76.2 (3)
O1W—K2—O43A^ii—K1	125.43 (12)	O43A—S4A—O42A—K3^xii	−17.47 (19)
O2W—K2—O43A^ii—K1	−53.67 (9)	C4A—S4A—O42A—K1^xii	102.53 (18)
O1W—K2—O42A^iii—K1	−121.86 (13)	C4A—S4A—O42A—K2^xii	−39.8 (3)
O2W—K2—O42A^iii—K1	59.14 (10)	C4A—S4A—O42A—K3^xii	−133.52 (14)
O2W—K3—S4B—O41B	167.29 (17)	O41A—S4A—O43A—K3^xii	−111.70 (15)
O2W—K3—S4B—O42B	−18.15 (16)	O41A—S4A—O43A—K1^x	−15.01 (18)
O2W—K3—S4B—O43B	77.0 (2)	O42A—S4A—O43A—K3^xii	16.77 (18)
O2W—K3—S4B—C4B	−109.31 (18)	O42A—S4A—O43A—K1^x	113.45 (15)
O41B—K3—S4B—O42B	174.6 (2)	C4A—S4A—O43A—K3^xii	131.69 (15)
O41B—K3—S4B—O43B	−90.3 (2)	C4A—S4A—O43A—K1^x	−131.62 (15)
O41B—K3—S4B—C4B	83.4 (2)	O41A—S4A—C4A—C3A	59.0 (4)
O42B—K3—S4B—O41B	−174.6 (2)	O41A—S4A—C4A—C5A	−122.4 (4)
O42B—K3—S4B—O43B	95.2 (2)	O42A—S4A—C4A—C3A	−60.9 (4)
O42B—K3—S4B—C4B	−91.2 (2)	O42A—S4A—C4A—C5A	117.7 (4)
O42A^iii—K3—S4B—O41B	96.94 (16)	O43A—S4A—C4A—C3A	179.8 (3)
O42A^iii—K3—S4B—O42B	−88.50 (16)	O43A—S4A—C4A—C5A	−1.6 (4)
O42A^iii—K3—S4B—O43B	6.6 (2)	K3—S4B—O41B—K1^viii	−144.8 (3)
O42A^iii—K3—S4B—C4B	−179.66 (18)	O42B—S4B—O41B—K3	−5.2 (2)
O43A^iii—K3—S4B—O41B	50.45 (16)	O42B—S4B—O41B—K1^viii	−150.0 (2)
O43A^iii—K3—S4B—O42B	−135.00 (15)	O43B—S4B—O41B—K3	122.13 (18)
O43A^iii—K3—S4B—O43B	−39.9 (2)	O43B—S4B—O41B—K1^viii	−22.7 (3)
O43A^iii—K3—S4B—C4B	133.85 (17)	C4B—S4B—O41B—K3	−119.08 (16)
O2W^viii—K3—S4B—O41B	−24.14 (17)	C4B—S4B—O41B—K1^viii	96.1 (2)
O2W^viii—K3—S4B—O42B	150.41 (16)	O41B—S4B—O42B—K3	4.44 (17)
O2W^viii—K3—S4B—O43B	−114.4 (2)	O43B—S4B—O42B—K3	−124.95 (15)
O2W^viii—K3—S4B—C4B	59.26 (18)	C4B—S4B—O42B—K3	118.76 (15)
S4B^ix—K3—S4B—O41B	−120.20 (16)	K3—S4B—O43B—K1	−44.0 (2)
S4B^ix—K3—S4B—O42B	54.36 (14)	K3—S4B—O43B—K1^xiii	60.7 (3)
S4B^ix—K3—S4B—O43B	149.50 (19)	O41B—S4B—O43B—K1	−100.68 (18)
S4B^ix—K3—S4B—C4B	−36.80 (17)	O41B—S4B—O43B—K1^xiii	4.0 (3)
O41B^ix—K3—S4B—O41B	−96.17 (17)	O42B—S4B—O43B—K1	26.9 (2)
O41B^ix—K3—S4B—O42B	78.38 (16)	O42B—S4B—O43B—K1^xiii	131.6 (3)
O41B^ix—K3—S4B—O43B	173.5 (2)	C4B—S4B—O43B—K1	141.61 (16)
O41B^ix—K3—S4B—C4B	−12.77 (19)	C4B—S4B—O43B—K1^xiii	−113.7 (3)
O42B^ix—K3—S4B—O41B	−140.37 (17)	K3—S4B—C4B—C3B	142.0 (3)
O42B^ix—K3—S4B—O42B	34.19 (16)	K3—S4B—C4B—C5B	−36.5 (5)
O42B^ix—K3—S4B—O43B	129.3 (2)	O41B—S4B—C4B—C3B	−166.4 (3)
O42B^ix—K3—S4B—C4B	−56.97 (18)	O41B—S4B—C4B—C5B	15.1 (5)
O42A^vii—K3—S4B—O41B	152.50 (19)	O42B—S4B—C4B—C3B	75.4 (4)
O42A^vii—K3—S4B—O42B	−32.95 (18)	O42B—S4B—C4B—C5B	−103.1 (5)
O42A^vii—K3—S4B—O43B	62.2 (2)	O43B—S4B—C4B—C3B	−43.0 (4)
O42A^vii—K3—S4B—C4B	−124.1 (2)	O43B—S4B—C4B—C5B	138.5 (4)
S4B—K3—O2W—K2	−122.40 (3)	C2A—C1A—C1B—C2B	3.0 (6)
O41B—K3—O2W—K2	−117.24 (7)	C2A—C1A—C1B—C6B	−178.3 (5)
O42B—K3—O2W—K2	−131.64 (8)	C6A—C1A—C1B—C2B	−176.3 (4)
S4B—K3—O41B—K1^viii	153.3 (2)	C6A—C1A—C1B—C6B	2.5 (7)
O2W—K3—O41B—S4B	−12.71 (17)	C1B—C1A—C2A—C3A	−177.7 (4)
O2W—K3—O41B—K1^viii	140.62 (11)	C6A—C1A—C2A—C3A	1.6 (7)
O42B—K3—O41B—S4B	3.06 (12)	C1B—C1A—C6A—C5A	178.1 (5)
O42B—K3—O41B—K1^viii	156.39 (16)	C2A—C1A—C6A—C5A	−1.2 (8)
O42A^iii—K3—O41B—S4B	−75.87 (15)	C1A—C1B—C2B—C3B	178.6 (4)
O43A^iii—K3—O41B—S4B	−125.62 (17)	C6B—C1B—C2B—C3B	−0.2 (7)
O2W^viii—K3—O41B—S4B	154.69 (18)	C1A—C1B—C6B—C5B	−178.0 (6)
S4B^ix—K3—O41B—S4B	70.76 (16)	C2B—C1B—C6B—C5B	0.8 (9)
O41B^ix—K3—O41B—S4B	98.52 (16)	C1A—C2A—C3A—C4A	−0.5 (7)
O42B^ix—K3—O41B—S4B	43.89 (18)	C1B—C2B—C3B—C4B	−1.5 (6)
O43A^vii—K3—O41B—S4B	−165.15 (13)	C2A—C3A—C4A—S4A	177.5 (4)
O2W—K3—O42B—S4B	158.11 (18)	C2A—C3A—C4A—C5A	−1.1 (7)
O41B—K3—O42B—S4B	−2.91 (11)	C2B—C3B—C4B—S4B	−175.8 (3)
O42A^iii—K3—O42B—S4B	83.00 (14)	C2B—C3B—C4B—C5B	2.7 (7)
O43A^iii—K3—O42B—S4B	46.38 (15)	S4A—C4A—C5A—C6A	−177.1 (4)
O2W^viii—K3—O42B—S4B	−33.08 (17)	C3A—C4A—C5A—C6A	1.5 (7)
S4B^ix—K3—O42B—S4B	−130.57 (13)	S4B—C4B—C5B—C6B	176.4 (5)
O41B^ix—K3—O42B—S4B	−114.34 (14)	C3B—C4B—C5B—C6B	−2.1 (9)
O42B^ix—K3—O42B—S4B	−144.75 (16)	C4A—C5A—C6A—C1A	−0.3 (8)
O42A^vii—K3—O42B—S4B	158.31 (12)	C4B—C5B—C6B—C1B	0.4 (10)

Symmetry codes: (i) x−1, y, z; (ii) x−1, y, z+1; (iii) x, y, z+1; (iv) x−1/2, −y+1/2, z; (v) x−1/2, −y+1/2, z+1; (vi) x−1, −y, z+1; (vii) x, −y, z+1; (viii) x+1, y, z; (ix) x, −y, z; (x) x+1, y, z−1; (xi) x+1/2, −y+1/2, z−1; (xii) x, y, z−1; (xiii) x+1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O4W^iii	0.97	2.18	2.778 (9)	119
O2W—H2W···O42B	0.96	1.91	2.840 (5)	162
O3W—H3W···O42B	0.96	1.95	2.884 (5)	162
O4W—H41W···O3W	0.90	1.82	2.715 (9)	180
O4W—H41W···O3W	0.90	1.82	2.715 (9)	180
C5A—H5A···O43A	0.95	2.50	2.916 (5)	106
C5B—H5B···O41B	0.94	2.47	2.873 (5)	106

Symmetry code: (iii) x, y, z+1.