Bis[hexa­aqua­cadmium(II)] 25,26,27,28-tetra­hydr­oxy-2,8,14,19-tetra­thia­calix[4]arene-5,11,17,23-tetra­sulfonate monohydrate clathrate

The title compound, [Cd(H₂O)₆]₂(C₂₄H₂O₁₆S₈)·H₂O, the bis­[hexa­aqua­cadmium(II)] salt of the p-sulfonatothia­calix[4]arene tetra­anion, crystallizes as a hydrate; two symmetry-independent cations inter­act with the tetra­anion via their coordinated water mol­ecules. The Cd atoms and water O atom lie on special positions of site symmetry m and the complete calixarene anion is generated by mirror symmetry. The water mol­ecule is weakly associated with the calixarene cavity by way of long O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.041
• wR factor = 0.130
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT731_ALERT_1_B Bond    Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O3W  -H3W2    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O4W  -H4W1    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.86(6), Rep   0.850(10) ......       6.00 su-Rat
              O4W  -H4W2    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O7W  -H7W1    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O8W  -H8W2    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O3W  -H4#     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O4W  -H5#     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.86(6), Rep   0.850(10) ......       6.00 su-Rat
              O4W  -H6#     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O7W  -H9#     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O8W  -H12#    1.555   1.555
PLAT736_ALERT_1_B H...A   Calc     1.91(5), Rep   1.910(10) ......       5.00 su-Rat
              H4#  -O3      1.555   1.455
PLAT736_ALERT_1_B H...A   Calc     1.92(6), Rep   1.930(10) ......       6.00 su-Rat
              H6#  -O8      1.555   3.666
PLAT736_ALERT_1_B H...A   Calc     1.95(5), Rep   1.960(10) ......       5.00 su-Rat
              H12# -O6      1.555   3.766

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.556     0.703
            Tmin(prime) and Tmax expected:      0.603     0.685
            RR(prime) =      0.897
            Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.88
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cd1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cd2
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         13
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O1W  -H1W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Rat
              O2W  -H2W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O3W  -H3W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O5W  -H5W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O6W  -H6W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O7W  -H7W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O8W  -H8W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.860(10) ......       3.00 su-Rat
              O9W  -H9W1    1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      125(4), Rep   125.0(10) ......       4.00 su-Rat
              CD1  -O1W  -H1W1    1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      109(6), Rep      109(2) ......       3.00 su-Rat
              H4W1 -O4W  -H4W2    1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      125(4), Rep   125.0(10) ......       4.00 su-Rat
              CD2  -O5W  -H5W1    1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      125(4), Rep   125.0(10) ......       4.00 su-Rat
              CD2  -O6W  -H6W1    1.555   1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O1W  -H1#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Rat
              O2W  -H2#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O3W  -H3#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O5W  -H7#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O6W  -H8#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O7W  -H10#    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O8W  -H11#    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.860(10) ......       3.00 su-Rat
              O9W  -H13#    1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.92(3), Rep   1.920(10) ......       3.00 su-Rat
              H1#  -O6      1.555   3.666
PLAT736_ALERT_1_C H...A   Calc     1.97(4), Rep   1.970(10) ......       4.00 su-Rat
              H3#  -O8      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.91(5), Rep     1.91(2) ......       2.50 su-Rat
              H5#  -O4      1.555   3.766
PLAT736_ALERT_1_C H...A   Calc     1.97(3), Rep   1.980(10) ......       3.00 su-Rat
              H7#  -O4      1.555   3.766
PLAT736_ALERT_1_C H...A   Calc     1.94(3), Rep   1.940(10) ......       3.00 su-Rat
              H8#  -O3      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.93(4), Rep   1.930(10) ......       4.00 su-Rat
              H10# -O5      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.96(5), Rep     1.96(2) ......       2.50 su-Rat
              H9#  -O7      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.94(4), Rep   1.940(10) ......       4.00 su-Rat
              H11# -O5      1.555   3.766
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O

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

  43 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   5 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The p-sulfonatocalix[4]arene (see scheme) tetraanion adopts a bowl-shaped conformation with the negatively charged sulfonate groups at the upper rim and the neutral/deprotonated hydroxyl groups at the lower rim. As such, it is capable of forming inclusion compounds through π-stacking, hydrogen-bonding and coordinative interactions (Atwood et al., 2001). A manganese(II) derivative of this species has been described (Gao et al., 2003) in which the hexaaquamanganese cations interact with the anionic p-sulfonatocalix[4]arene indirectly, via their coordinated water molecules. The compound was formulated as [Mn(H₂O)₆]₂(C₂₄H₂O₁₆S₈)·0.5H₂O.

The present cadmium complex, (I) (Fig. 1), is essentially isostructural with the manganese analogue (same cell dimensions and space group), but was modelled as [Cd(H₂O)₆]₂(C₂₄H₂O₁₆S₈)·H₂O, i.e. with full occupancy of the non-coordinatd water molecule. The hexaaquacadmium(II) species possess typical geometrical parameters (Table 1).

An extensive network of O—H···O hydrogen bonds (Table 2) help to stabilize the crystal packing in (I). The non-coordinated water molecule (O9w) lies on a special position of site symmetry m; as it forms long hydrogen bonds [H···O = 2.44 (2) Å] to neighboring acceptor calixarene hydroxide O atoms, its displacement factor is relatively large.

S2. Experimental

Tetrasodium p-sulfonatocalix[4]arene (Gao et al., 2003; Iki et al., 1998) (0.18 g, 0.2 mmol) was dissolved in water (10 ml) and cadmium nitrate (0.08 g, 0.4 mmol) was added to the solution. The filtered solution was set aside for several days resulting in the growth of colourless plates of (I).

S3. Refinement

The C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) = 1.2U_eq(C). The water H atoms were located in difference maps and were refined with the distance restraints O—H = 0.85 (1) Å and H···H = 1.39 (1) Å, and with U_iso(H) = 1.2U_eq(O). The two hydroxy H atoms of the anion are disordered over two positions. Two H-atom sites (H11 and H12 attached to O1 and H21 and H22 attached to O2), each of 50% occupancy, were generated for each O atom in idealized positions (O—H = 0.85 Å) and refined as riding with U_iso(H) = 1.2U_eq(O). This arrangment for the two orientations of the hydroxy groups leads to the formation of either a clockwise or an anticlockwise ring of O—H···O hydrogen bonds (Fig. 2 and Table 2). The deepest difference hole is 0.65 Å from atom Cd1 and the highest difference peak is 2.77 Å from atom H8, in a possible solvent-accessible void. Attempts to refine the electron density as an O atom were unsuccessful.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. View of (I), showing 50% displacement ellipsoids (arbitrary spheres for H atoms). [Symmetry codes: (i) x, 3/2 − y, z; (ii) x, 1/2 − y, z.]
	Fig. 2. Detail of (I), showing one possible `clockwise' cyclic arrangement of O—H···O hydrogen bonds within the calixarene moiety. As a result of the positional disorder of the hydroxy H atoms (not shown), the hydrogen bonds can also propagate in the reverse (anticlockwise) sense.

Bis[hexaaquacadmium(II)] 25,26,27,28-tetrahydroxy-2,8,14,19-tetrathiacalix[4]arene-5,11,17,23- tetrasulfonate monohydrate clathrate

Crystal data

[Cd(H2O)6]2(C24H2O16S8)·H2O	F(000) = 1276
Mr = 1271.82	Dx = 1.868 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 8025 reflections
a = 13.1183 (5) Å	θ = 2.8–28.4°
b = 14.2581 (6) Å	µ = 1.40 mm^−1
c = 13.1854 (5) Å	T = 295 K
β = 113.563 (1)°	Block, colorless
V = 2260.6 (2) Å^3	0.35 × 0.33 × 0.27 mm
Z = 2

Data collection

Bruker APEX2 area-detector diffractometer	5380 independent reflections
Radiation source: fine-focus sealed tube	5106 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.556, Tmax = 0.703	k = −18→18
19302 measured reflections	l = −17→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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0599P)^2 + 6.3407P] where P = (Fo^2 + 2Fc^2)/3
5380 reflections	(Δ/σ)max = 0.001
337 parameters	Δρmax = 1.76 e Å^−3
22 restraints	Δρmin = −1.74 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd1	0.47481 (3)	0.7500	0.44903 (4)	0.0371 (1)
Cd2	0.99024 (3)	0.7500	0.48290 (4)	0.0402 (1)
S1	1.12673 (7)	0.49239 (6)	0.33671 (7)	0.0298 (2)
S2	1.04713 (12)	0.2500	−0.0102 (1)	0.0386 (3)
S3	0.73831 (7)	0.52185 (8)	−0.03325 (8)	0.0408 (2)
S4	0.43955 (10)	0.2500	−0.0273 (1)	0.0363 (3)
S5	0.62754 (7)	0.48790 (6)	0.32418 (7)	0.03002 (19)
O1	0.8270 (2)	0.3504 (3)	−0.1018 (2)	0.0509 (8)
O2	0.5892 (3)	0.3531 (2)	−0.1125 (2)	0.0461 (7)
O3	1.1734 (2)	0.5838 (2)	0.3294 (3)	0.0422 (6)
O4	1.2104 (2)	0.4194 (2)	0.3828 (2)	0.0399 (6)
O5	1.0520 (2)	0.4983 (2)	0.3944 (2)	0.0410 (6)
O6	0.7017 (2)	0.4178 (2)	0.3976 (2)	0.0397 (6)
O7	0.6779 (2)	0.5810 (2)	0.3416 (3)	0.0421 (6)
O8	0.5180 (2)	0.4868 (2)	0.3282 (3)	0.0414 (6)
O1w	0.3633 (5)	0.7500	0.5411 (7)	0.075 (2)
O2w	0.5880 (6)	0.7500	0.3588 (7)	0.082 (2)
O3w	0.3760 (3)	0.6346 (2)	0.3296 (3)	0.0499 (8)
O4w	0.5741 (3)	0.6351 (3)	0.5675 (4)	0.078 (1)
O5w	0.8631 (5)	0.7500	0.5598 (7)	0.077 (2)
O6w	1.1035 (6)	0.7500	0.3926 (7)	0.079 (2)
O7w	0.8917 (3)	0.6326 (2)	0.3690 (3)	0.0556 (8)
O8w	1.0974 (3)	0.6417 (2)	0.6080 (3)	0.0504 (8)
O9w	1.1889 (18)	0.7500	0.8388 (10)	0.184 (5)
C1	1.0427 (3)	0.4555 (3)	0.2005 (3)	0.0311 (7)
C2	1.0746 (3)	0.3801 (3)	0.1536 (3)	0.0314 (7)
C3	1.0040 (3)	0.3460 (3)	0.0501 (3)	0.0323 (7)
C4	0.8993 (3)	0.3876 (3)	−0.0058 (3)	0.0347 (8)
C5	0.8698 (3)	0.4668 (3)	0.0398 (3)	0.0342 (8)
C6	0.9418 (3)	0.5007 (3)	0.1423 (3)	0.0345 (8)
C7	0.6085 (3)	0.4536 (2)	0.1891 (3)	0.0292 (7)
C8	0.5393 (3)	0.3784 (2)	0.1392 (3)	0.0296 (7)
C9	0.5307 (3)	0.3452 (3)	0.0371 (3)	0.0309 (7)
C10	0.5935 (3)	0.3876 (3)	−0.0159 (3)	0.0331 (7)
C11	0.6604 (3)	0.4651 (3)	0.0336 (3)	0.0321 (7)
C12	0.6670 (3)	0.4979 (2)	0.1354 (3)	0.0319 (7)
H1w1	0.339 (5)	0.7013 (4)	0.561 (5)	0.090*
H2w1	0.624 (3)	0.7012 (4)	0.358 (6)	0.099*
H3w1	0.416 (3)	0.589 (2)	0.327 (5)	0.060*
H3w2	0.317 (3)	0.615 (3)	0.335 (5)	0.060*
H4w1	0.638 (3)	0.617 (4)	0.573 (6)	0.093*
H4w2	0.547 (5)	0.594 (3)	0.597 (6)	0.093*
H5w1	0.834 (4)	0.7012 (4)	0.574 (6)	0.093*
H6w1	1.124 (5)	0.7012 (4)	0.369 (5)	0.094*
H7w1	0.833 (3)	0.614 (3)	0.376 (5)	0.067*
H7w2	0.934 (3)	0.586 (2)	0.375 (5)	0.067*
H8w1	1.052 (3)	0.598 (2)	0.605 (5)	0.060*
H8w2	1.154 (3)	0.618 (3)	0.601 (5)	0.060*
H9w1	1.176 (12)	0.7013 (4)	0.798 (2)	0.221*
H2	1.1435	0.3521	0.1913	0.038*
H6	0.9227	0.5536	0.1720	0.041*
H8	0.4985	0.3502	0.1745	0.036*
H121	0.7109	0.5498	0.1677	0.038*
H11	0.8449	0.3019	−0.1284	0.061*	0.50
H12	0.7636	0.3756	−0.1356	0.061*	0.50
H21	0.6273	0.3785	−0.1442	0.055*	0.50
H22	0.5484	0.3060	−0.1419	0.055*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0303 (2)	0.0309 (2)	0.0554 (3)	0.000	0.02266 (18)	0.000
Cd2	0.0288 (2)	0.0337 (2)	0.0603 (3)	0.000	0.02012 (18)	0.000
S1	0.0252 (4)	0.0308 (4)	0.0354 (4)	0.0003 (3)	0.0143 (3)	0.0017 (3)
S2	0.0415 (7)	0.0496 (8)	0.0348 (6)	0.000	0.0260 (6)	0.000
S3	0.0312 (4)	0.0483 (6)	0.0437 (5)	0.0083 (4)	0.0160 (4)	0.0262 (4)
S4	0.0241 (6)	0.0410 (7)	0.0364 (6)	0.000	0.0045 (5)	0.000
S5	0.0285 (4)	0.0265 (4)	0.0371 (4)	0.0023 (3)	0.0153 (3)	0.0005 (3)
O1	0.042 (2)	0.071 (2)	0.031 (1)	0.001 (2)	0.006 (1)	0.004 (1)
O2	0.051 (2)	0.055 (2)	0.035 (1)	−0.006 (1)	0.021 (1)	−0.001 (1)
O3	0.043 (2)	0.035 (1)	0.053 (2)	−0.008 (1)	0.024 (1)	−0.001 (1)
O4	0.032 (1)	0.041 (2)	0.042 (1)	0.008 (1)	0.010 (1)	0.001 (1)
O5	0.036 (1)	0.050 (2)	0.044 (2)	0.000 (1)	0.024 (1)	0.001 (1)
O6	0.040 (1)	0.038 (1)	0.039 (1)	0.007 (1)	0.014 (1)	0.006 (1)
O7	0.043 (2)	0.029 (1)	0.056 (2)	−0.003 (1)	0.023 (1)	−0.006 (1)
O8	0.037 (1)	0.045 (2)	0.051 (2)	0.004 (1)	0.026 (1)	0.000 (1)
O1w	0.090 (4)	0.036 (2)	0.15 (6)	0.000	0.095 (4)	0.000
O2w	0.100 (5)	0.029 (2)	0.172 (7)	0.000	0.112 (5)	0.000
O3w	0.038 (2)	0.038 (2)	0.078 (2)	−0.005 (1)	0.029 (2)	−0.009 (2)
O4w	0.049 (2)	0.083 (3)	0.116 (3)	0.030 (2)	0.048 (2)	0.057 (3)
O5w	0.088 (4)	0.037 (2)	0.150 (6)	0.000	0.093 (4)	0.000
O6w	0.097 (4)	0.039 (3)	0.144 (6)	0.000	0.095 (5)	0.000
O7w	0.036 (2)	0.047 (2)	0.082 (2)	−0.003 (1)	0.021 (2)	−0.011 (2)
O8w	0.040 (2)	0.039 (2)	0.076 (2)	0.004 (1)	0.027 (2)	0.009 (2)
O9w	0.27 (2)	0.15 (1)	0.15 (1)	0.000	0.10 (1)	0.000
C1	0.026 (2)	0.033 (2)	0.035 (2)	0.000 (1)	0.014 (1)	0.007 (1)
C2	0.026 (2)	0.035 (2)	0.035 (2)	0.002 (1)	0.013 (1)	0.007 (1)
C3	0.034 (2)	0.038 (2)	0.032 (2)	0.001 (1)	0.020 (1)	0.007 (1)
C4	0.033 (2)	0.045 (2)	0.028 (2)	−0.002 (2)	0.014 (1)	0.012 (2)
C5	0.027 (2)	0.040 (2)	0.039 (2)	0.004 (1)	0.016 (1)	0.018 (2)
C6	0.030 (2)	0.034 (2)	0.043 (2)	0.003 (1)	0.018 (2)	0.008 (2)
C7	0.025 (2)	0.028 (2)	0.034 (2)	0.005 (1)	0.012 (1)	0.006 (1)
C8	0.027 (2)	0.030 (2)	0.034 (2)	0.003 (1)	0.014 (1)	0.006 (1)
C9	0.024 (2)	0.033 (2)	0.033 (2)	0.004 (1)	0.008 (1)	0.005 (1)
C10	0.028 (2)	0.040 (2)	0.029 (2)	0.009 (1)	0.009 (1)	0.009 (1)
C11	0.025 (2)	0.036 (2)	0.038 (2)	0.007 (1)	0.014 (1)	0.017 (2)
C12	0.025 (2)	0.030 (2)	0.040 (2)	0.003 (1)	0.012 (1)	0.008 (1)

Geometric parameters (Å, º)

Cd1—O1w	2.243 (5)	C3—C4	1.405 (5)
Cd1—O2w	2.243 (5)	C4—C5	1.404 (6)
Cd1—O3w	2.288 (3)	C5—C6	1.390 (6)
Cd1—O3w^i	2.288 (3)	C7—C12	1.386 (5)
Cd1—O4w	2.279 (4)	C7—C8	1.388 (5)
Cd1—O4w^i	2.279 (4)	C8—C9	1.388 (5)
Cd2—O5w	2.272 (5)	C9—C10	1.411 (5)
Cd2—O6w	2.245 (5)	C10—C11	1.401 (5)
Cd2—O7w	2.275 (3)	C11—C12	1.391 (5)
Cd2—O7w^i	2.275 (3)	O1—H11	0.85
Cd2—O8w	2.287 (3)	O1—H12	0.85
Cd2—O8w^i	2.287 (3)	O2—H21	0.85
S1—O4	1.458 (3)	O2—H22	0.85
S1—O3	1.459 (3)	O1w—H1w1	0.85 (1)
S1—O5	1.464 (3)	O2w—H2w1	0.84 (1)
S1—C1	1.770 (4)	O3w—H3w1	0.85 (1)
S2—C3	1.785 (4)	O3w—H3w2	0.85 (1)
S2—C3^ii	1.785 (4)	O4w—H4w1	0.85 (1)
S3—C5	1.786 (4)	O4w—H4w2	0.85 (1)
S3—C11	1.788 (3)	O5w—H5w1	0.85 (1)
S4—C9	1.784 (4)	O6w—H6w1	0.85 (1)
S4—C9^ii	1.784 (4)	O7w—H7w1	0.85 (1)
S5—O6	1.459 (3)	O7w—H7w2	0.85 (1)
S5—O7	1.459 (3)	O8w—H8w1	0.85 (1)
S5—O8	1.459 (3)	O8w—H8w2	0.85 (1)
S5—C7	1.767 (4)	O9w—H9w1	0.86 (1)
O1—C4	1.349 (5)	C2—H2	0.93
O2—C10	1.346 (5)	C6—H6	0.93
C1—C6	1.394 (5)	C8—H8	0.93
C1—C2	1.386 (5)	C12—H121	0.93
C2—C3	1.394 (5)
O1w—Cd1—O2w	179.3 (3)	O1—C4—C3	120.0 (4)
O1w—Cd1—O3w	93.4 (2)	O1—C4—C5	120.4 (3)
O1w—Cd1—O3w^i	93.4 (2)	C3—C4—C5	119.6 (3)
O1w—Cd1—O4w	87.0 (2)	C6—C5—C4	119.9 (3)
O1w—Cd1—O4w^i	87.0 (2)	C6—C5—S3	120.4 (3)
O2w—Cd1—O3w	87.0 (2)	C4—C5—S3	119.6 (3)
O2w—Cd1—O3w^i	87.0 (2)	C5—C6—C1	120.1 (4)
O2w—Cd1—O4w	92.6 (2)	C12—C7—C8	120.1 (3)
O2w—Cd1—O4w^i	92.6 (2)	C12—C7—S5	120.3 (3)
O3w—Cd1—O3w^i	92.0 (2)	C8—C7—S5	119.6 (3)
O3w—Cd1—O4w	88.1 (2)	C9—C8—C7	120.4 (3)
O3w—Cd1—O4w^i	179.6 (1)	C8—C9—C10	119.8 (3)
O3w^i—Cd1—O4w	179.6 (1)	C8—C9—S4	120.0 (3)
O3w^i—Cd1—O4w^i	88.1 (2)	C10—C9—S4	120.2 (3)
O4w—Cd1—O4w^i	91.9 (3)	O2—C10—C11	120.7 (3)
O5w—Cd2—O6w	175.1 (3)	O2—C10—C9	120.1 (3)
O5w—Cd2—O7w	88.3 (2)	C11—C10—C9	119.2 (3)
O5w—Cd2—O7w^i	88.3 (2)	C12—C11—C10	120.0 (3)
O5w—Cd2—O8w	91.5 (2)	C12—C11—S3	119.8 (3)
O5w—Cd2—O8w^i	91.5 (2)	C10—C11—S3	120.2 (3)
O6w—Cd2—O7w	88.4 (2)	C11—C12—C7	120.4 (3)
O6w—Cd2—O7w^i	88.4 (2)	C4—O1—H11	120.0
O6w—Cd2—O8w	92.1 (2)	C4—O1—H12	120.0
O6w—Cd2—O8w^i	92.1 (2)	H11—O1—H12	120.0
O7w—Cd2—O7w^i	94.7 (2)	C10—O2—H21	120.0
O7w—Cd2—O8w	90.2 (1)	C10—O2—H22	120.0
O7w—Cd2—O8w^i	175.1 (1)	H21—O2—H22	120.0
O7w^i—Cd2—O8w	175.1 (1)	Cd1—O1w—H1w1	125 (1)
O7w^i—Cd2—O8w^i	90.2 (1)	Cd1—O2w—H2w1	120 (3)
O8w—Cd2—O8w^i	85.0 (2)	Cd1—O3w—H3w1	113 (3)
O4—S1—O3	113.5 (2)	Cd1—O3w—H3w2	117 (4)
O4—S1—O5	111.9 (2)	H3w1—O3w—H3w2	110 (2)
O3—S1—O5	111.6 (2)	Cd1—O4w—H4w1	123 (4)
O4—S1—C1	105.7 (2)	Cd1—O4w—H4w2	125 (4)
O3—S1—C1	107.8 (2)	H4w1—O4w—H4w2	109 (2)
O5—S1—C1	105.6 (2)	Cd2—O5w—H5w1	125 (1)
C3—S2—C3^ii	100.2 (2)	Cd2—O6w—H6w1	125 (1)
C5—S3—C11	98.9 (2)	Cd2—O7w—H7w1	117 (4)
C9—S4—C9^ii	99.1 (2)	Cd2—O7w—H7w2	110 (4)
O6—S5—O7	112.3 (2)	H7w1—O7w—H7w2	109 (2)
O6—S5—O8	111.9 (2)	Cd2—O8w—H8w1	104 (4)
O7—S5—O8	113.2 (2)	Cd2—O8w—H8w2	120 (4)
O6—S5—C7	105.5 (2)	H8w1—O8w—H8w2	110 (2)
O7—S5—C7	106.4 (2)	C1—C2—H2	119.8
O8—S5—C7	106.8 (2)	C3—C2—H2	119.8
C6—C1—C2	120.1 (3)	C5—C6—H6	119.9
C6—C1—S1	119.4 (3)	C1—C6—H6	119.9
C2—C1—S1	120.4 (3)	C9—C8—H8	119.8
C1—C2—C3	120.5 (3)	C7—C8—H8	119.8
C2—C3—C4	119.6 (3)	C11—C12—H121	119.8
C2—C3—S2	119.9 (3)	C7—C12—H121	119.8
C4—C3—S2	120.5 (3)
O4—S1—C1—C6	167.1 (3)	O6—S5—C7—C12	−100.9 (3)
O3—S1—C1—C6	−71.1 (3)	O7—S5—C7—C12	18.5 (3)
O5—S1—C1—C6	48.4 (3)	O8—S5—C7—C12	139.8 (3)
O4—S1—C1—C2	−10.4 (3)	O6—S5—C7—C8	75.5 (3)
O3—S1—C1—C2	111.3 (3)	O7—S5—C7—C8	−165.0 (3)
O5—S1—C1—C2	−129.2 (3)	O8—S5—C7—C8	−43.8 (3)
C6—C1—C2—C3	−3.0 (5)	C12—C7—C8—C9	2.0 (5)
S1—C1—C2—C3	174.5 (3)	S5—C7—C8—C9	−174.4 (3)
C1—C2—C3—C4	−1.1 (5)	C7—C8—C9—C10	0.6 (5)
C1—C2—C3—S2	179.1 (3)	C7—C8—C9—S4	−178.9 (3)
C3^ii—S2—C3—C2	86.5 (3)	C9^ii—S4—C9—C8	−86.0 (3)
C3^ii—S2—C3—C4	−93.4 (3)	C9^ii—S4—C9—C10	94.6 (3)
C2—C3—C4—O1	−174.8 (3)	C8—C9—C10—O2	177.1 (3)
S2—C3—C4—O1	5.1 (5)	S4—C9—C10—O2	−3.5 (5)
C2—C3—C4—C5	4.2 (5)	C8—C9—C10—C11	−2.5 (5)
S2—C3—C4—C5	−175.9 (3)	S4—C9—C10—C11	176.9 (3)
O1—C4—C5—C6	175.7 (3)	O2—C10—C11—C12	−177.7 (3)
C3—C4—C5—C6	−3.3 (5)	C9—C10—C11—C12	1.9 (5)
O1—C4—C5—S3	−2.9 (5)	O2—C10—C11—S3	1.8 (5)
C3—C4—C5—S3	178.1 (3)	C9—C10—C11—S3	−178.6 (3)
C11—S3—C5—C6	−83.3 (3)	C5—S3—C11—C12	81.7 (3)
C11—S3—C5—C4	95.4 (3)	C5—S3—C11—C10	−97.8 (3)
C4—C5—C6—C1	−0.8 (5)	C10—C11—C12—C7	0.6 (5)
S3—C5—C6—C1	177.8 (3)	S3—C11—C12—C7	−178.9 (3)
C2—C1—C6—C5	3.9 (5)	C8—C7—C12—C11	−2.6 (5)
S1—C1—C6—C5	−173.6 (3)	S5—C7—C12—C11	173.8 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O6^iii	0.85 (1)	1.92 (1)	2.767 (4)	172 (3)
O2w—H2w1···O7	0.84 (1)	1.90 (1)	2.732 (4)	169 (4)
O3w—H3w1···O8	0.85 (1)	1.97 (1)	2.817 (4)	176 (5)
O3w—H3w2···O3^iv	0.85 (1)	1.91 (1)	2.754 (4)	171 (5)
O4w—H4w1···O4^v	0.85 (1)	1.91 (2)	2.746 (4)	168 (7)
O4w—H4w2···O8^iii	0.85 (1)	1.93 (1)	2.775 (5)	174 (7)
O5w—H5w1···O4^v	0.85 (1)	1.98 (1)	2.814 (4)	172 (6)
O6w—H6w1···O3	0.85 (1)	1.94 (1)	2.786 (4)	175 (4)
O7w—H7w2···O5	0.85 (1)	1.93 (1)	2.764 (4)	169 (5)
O7w—H7w1···O7	0.85 (1)	1.96 (2)	2.781 (4)	162 (6)
O8w—H8w1···O5^v	0.85 (1)	1.94 (1)	2.788 (4)	176 (5)
O8w—H8w2···O6^v	0.85 (1)	1.96 (1)	2.798 (4)	170 (5)
O9w—H9w1···O8w	0.86 (1)	2.44 (2)	3.188 (12)	146 (3)
O1—H11···O1^ii	0.85	2.23	2.864 (7)	132
O1—H12···O2	0.85	2.45	3.066 (5)	130
O2—H21···O1	0.85	2.48	3.066 (4)	127
O2—H22···O2^ii	0.85	2.33	2.940 (4)	129

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