M_mH_n(XO₄)_(m+n)/2 crystals: structure, phase transitions, hydrogen bonds, conductivity. I. K₉H₇(SO₄)₈·H₂O crystals - a new representative of the family of solid acid conductors

To reveal the structural conditionality for anomalies in physical properties, including dielectric and optical properties, diffraction studies of K₉H₇(SO₄)₈·H₂O crystals were performed using synchrotron radiation in the temperature range 293-450 K and determined at 405 K, taking H atoms into account. The results indicate that the occurrence of high conductivity in K₉H₇(SO₄)₈·H₂O crystals with a temperature increase is associated with the outward diffusion of water molecules, hydrogen-bond network rearrangement and the formation of channels for the possible motion of K⁺ ions. A rearranged system of hydrogen bonds consists of permanent bonds and partly of dynamically disordered bonds. Hydrogen-bond rearrangement and the hindered back diffusion of water to the crystal bulk stabilize the high-temperature crystal structure right down to room temperature.

Computing details

For both compounds, data collection: CrysAlis PRO; cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: JANA 2006; program(s) used to refine structure: JANA 2006; molecular graphics: DIAMOND. Version. 3.

Figures

(I)

Crystal data

K9S8O33H9	F(000) = 2288
Mr = 1145.4	Dx = 2.326 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.696 Å
Hall symbol: -P 2ycb	Cell parameters from 7836 reflections
a = 7.0685 (4) Å	θ = 1.7–31.1°
b = 19.7920 (5) Å	µ = 1.68 mm^−1
c = 23.4724 (6) Å	T = 300 K
β = 95.372 (4)°	, colourless
V = 3269.4 (2) Å^3	0.27 × 0.27 × 0.27 mm
Z = 4

Data collection

Huber diffractometer	7239 reflections with I > 3σ(I)
Radiation source: synchrotron	Rint = 0.026
Mirror1-monochromator-Mirror2	θmax = 31.1°, θmin = 1.7°
w scans	h = −6→6
12521 measured reflections	k = −20→28
7657 independent reflections	l = −23→33

Refinement

Refinement on F	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.032	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
wR(F^2) = 0.046	(Δ/σ)max = 3.579
S = 2.99	Δρmax = 0.52 e Å^−3
7239 reflections	Δρmin = −0.51 e Å^−3
492 parameters	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 202E3 (3)
0 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
K1	0.97495 (8)	0.08283 (2)	0.596746 (19)	0.03029 (15)
K2	0.54128 (8)	0.07789 (2)	0.407281 (19)	0.02983 (15)
K3	0.19564 (7)	0.24728 (2)	0.333210 (19)	0.02871 (15)
K4	0.30880 (7)	0.23750 (2)	0.168128 (19)	0.03070 (15)
K5	0.36507 (8)	0.58408 (2)	0.40756 (2)	0.03078 (15)
K6	0.88086 (7)	0.41561 (2)	0.764090 (19)	0.02817 (15)
K7	0.63508 (8)	0.41031 (2)	0.229563 (19)	0.02976 (15)
K8	0.92007 (7)	0.41010 (2)	0.412193 (19)	0.02773 (15)
K9	0.76950 (8)	0.24689 (3)	0.501344 (18)	0.04241 (19)
S1	0.45897 (8)	0.10622 (3)	0.56839 (2)	0.02632 (16)
S2	0.04382 (8)	0.09454 (2)	0.42938 (2)	0.02532 (16)
S3	0.71499 (7)	0.24680 (2)	0.348889 (18)	0.02062 (14)
S4	0.81289 (8)	0.23899 (2)	0.150913 (19)	0.02277 (15)
S5	0.88182 (8)	0.58757 (2)	0.428693 (19)	0.02217 (15)
S6	0.38992 (8)	0.41223 (2)	0.745619 (18)	0.02260 (15)
S7	0.12913 (8)	0.40318 (2)	0.259011 (19)	0.02249 (15)
S8	0.41953 (7)	0.39065 (2)	0.430556 (18)	0.02069 (14)
O1	0.5479 (3)	0.36892 (9)	0.01960 (7)	0.0456 (6)
O2	0.5882 (3)	0.41209 (10)	0.11614 (7)	0.0479 (6)
O3	0.3371 (2)	0.45356 (7)	0.05162 (7)	0.0358 (5)
O4	0.3256 (2)	0.34011 (8)	0.08660 (7)	0.0411 (5)
O5	0.8295 (2)	0.64881 (8)	0.08637 (7)	0.0420 (6)
O6	0.0618 (3)	0.61535 (9)	0.02407 (7)	0.0419 (6)
O7	0.8253 (2)	0.53549 (7)	0.05004 (7)	0.0354 (5)
O8	0.0719 (3)	0.56883 (10)	0.11933 (7)	0.0442 (6)
O9	0.4013 (2)	0.80490 (7)	0.18299 (6)	0.0319 (5)
O10	0.1463 (2)	0.77708 (7)	0.10985 (6)	0.0289 (5)
O11	0.4189 (2)	0.70566 (8)	0.12408 (8)	0.0420 (6)
O12	0.1991 (2)	0.71331 (7)	0.19739 (6)	0.0327 (5)
O13	0.9343 (2)	0.28838 (8)	0.12794 (8)	0.0436 (6)
O14	0.7152 (3)	0.27511 (8)	0.20058 (6)	0.0372 (5)
O15	0.9150 (2)	0.18233 (8)	0.17711 (7)	0.0396 (5)
O16	0.6574 (2)	0.22037 (8)	0.10971 (6)	0.0354 (5)
O17	0.2214 (3)	0.02802 (7)	0.04361 (7)	0.0424 (5)
O18	0.9688 (2)	0.11216 (9)	0.03117 (7)	0.0389 (5)
O19	0.0466 (2)	0.05446 (7)	0.12047 (6)	0.0309 (5)
O20	0.2621 (2)	0.13750 (8)	0.08701 (7)	0.0370 (5)
O21	0.5150 (2)	0.11023 (8)	0.20460 (7)	0.0371 (5)
O22	0.4852 (2)	0.05112 (8)	0.29307 (6)	0.0336 (5)
O23	0.2669 (2)	0.14101 (8)	0.26178 (7)	0.0416 (6)
O24	0.2568 (3)	0.03185 (8)	0.21553 (7)	0.0397 (5)
O25	0.7429 (3)	0.95863 (8)	0.20790 (7)	0.0399 (5)
O26	0.9979 (2)	0.87796 (9)	0.20151 (7)	0.0404 (5)
O27	0.7425 (2)	0.85182 (9)	0.25765 (8)	0.0424 (6)
O28	0.9657 (2)	0.94087 (7)	0.28772 (6)	0.0336 (5)
O29	0.7177 (2)	0.83590 (7)	0.07734 (7)	0.0389 (5)
O30	0.5025 (2)	0.90455 (7)	0.12585 (6)	0.0281 (4)
O31	0.6798 (2)	0.95320 (7)	0.05504 (6)	0.0345 (5)
O32	0.4265 (2)	0.87446 (9)	0.02696 (6)	0.0371 (5)
O33	0.1929 (5)	0.24051 (13)	0.50353 (15)	0.0739 (11)
H1	0.757 (5)	0.547 (3)	0.0043 (16)	0.15 (2)*
H2	0.752 (4)	0.2513 (14)	0.2334 (14)	0.077 (11)*
H3	0.195 (5)	0.0502 (18)	0.1824 (16)	0.087 (12)*
H4	0.257 (4)	0.042 (2)	0.0078 (13)	0.097 (14)*
H5	0.437 (5)	0.8409 (17)	0.1524 (15)	0.094 (12)*
H6	0.684 (5)	0.9399 (17)	0.1800 (15)	0.073 (11)*
H7	0.292 (7)	0.216 (3)	0.539 (2)	0.18 (2)*
H8	0.176 (11)	0.209 (4)	0.466 (3)	0.15 (3)*	0.6667
H9	0.280 (9)	0.265 (4)	0.492 (3)	0.08 (2)*	0.6667
H10	0.219 (9)	0.270 (3)	0.514 (3)	0.052 (17)*	0.6667

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0311 (4)	0.0304 (2)	0.0301 (2)	−0.00137 (18)	0.0069 (2)	−0.00301 (15)
K2	0.0310 (4)	0.03055 (19)	0.0284 (2)	0.00115 (18)	0.0052 (2)	0.00265 (15)
K3	0.0259 (3)	0.02905 (19)	0.0313 (2)	−0.00082 (17)	0.0036 (2)	−0.00127 (14)
K4	0.0283 (3)	0.0300 (2)	0.0339 (2)	0.00030 (17)	0.0040 (2)	0.00103 (15)
K5	0.0267 (3)	0.02892 (19)	0.0368 (2)	−0.00068 (17)	0.0035 (2)	0.00425 (15)
K6	0.0257 (3)	0.02753 (19)	0.0307 (2)	−0.00046 (16)	−0.00033 (19)	0.00094 (14)
K7	0.0298 (3)	0.02981 (19)	0.0294 (2)	−0.00118 (17)	0.0011 (2)	−0.00083 (15)
K8	0.0259 (3)	0.02681 (18)	0.0299 (2)	−0.00072 (16)	−0.00072 (19)	−0.00309 (14)
K9	0.0615 (5)	0.0386 (2)	0.0286 (2)	0.0027 (2)	0.0117 (3)	0.00390 (17)
S1	0.0227 (4)	0.0337 (2)	0.0221 (2)	−0.0011 (2)	−0.0001 (2)	−0.00238 (16)
S2	0.0231 (4)	0.0307 (2)	0.0219 (2)	0.00097 (19)	0.0005 (2)	0.00158 (15)
S3	0.0201 (3)	0.02126 (18)	0.02027 (19)	0.00085 (16)	0.00070 (18)	0.00035 (13)
S4	0.0236 (3)	0.02163 (18)	0.0234 (2)	0.00032 (17)	0.0039 (2)	0.00123 (14)
S5	0.0200 (3)	0.0250 (2)	0.02092 (19)	0.00065 (17)	−0.00116 (19)	0.00158 (14)
S6	0.0216 (3)	0.0254 (2)	0.02012 (19)	0.00025 (17)	−0.00153 (19)	−0.00111 (14)
S7	0.0215 (3)	0.02414 (19)	0.02122 (19)	0.00061 (17)	−0.00117 (19)	0.00231 (14)
S8	0.0196 (3)	0.02239 (19)	0.01973 (19)	0.00065 (17)	−0.00030 (18)	−0.00108 (14)
O1	0.0516 (12)	0.0544 (10)	0.0333 (8)	0.0125 (9)	0.0164 (8)	0.0011 (7)
O2	0.0334 (12)	0.0756 (13)	0.0316 (8)	−0.0035 (9)	−0.0133 (8)	−0.0011 (8)
O3	0.0399 (11)	0.0307 (7)	0.0346 (7)	0.0047 (7)	−0.0083 (7)	−0.0022 (6)
O4	0.0372 (11)	0.0420 (8)	0.0454 (9)	−0.0039 (7)	0.0107 (8)	0.0112 (7)
O5	0.0382 (11)	0.0433 (9)	0.0449 (9)	0.0085 (7)	0.0067 (8)	−0.0127 (7)
O6	0.0428 (11)	0.0507 (9)	0.0344 (8)	−0.0097 (8)	0.0148 (8)	0.0005 (7)
O7	0.0406 (11)	0.0315 (7)	0.0320 (7)	−0.0068 (7)	−0.0076 (7)	0.0024 (6)
O8	0.0362 (11)	0.0648 (11)	0.0290 (8)	−0.0001 (8)	−0.0105 (7)	0.0032 (7)
O9	0.0393 (10)	0.0344 (7)	0.0218 (6)	−0.0163 (6)	0.0010 (6)	−0.0029 (5)
O10	0.0294 (10)	0.0326 (7)	0.0236 (6)	0.0023 (6)	−0.0031 (6)	0.0033 (5)
O11	0.0328 (11)	0.0399 (8)	0.0540 (10)	0.0088 (7)	0.0076 (8)	−0.0121 (7)
O12	0.0397 (10)	0.0328 (7)	0.0255 (6)	−0.0105 (6)	0.0020 (6)	0.0067 (5)
O13	0.0336 (11)	0.0385 (8)	0.0588 (11)	−0.0103 (7)	0.0043 (8)	0.0151 (7)
O14	0.0508 (12)	0.0373 (8)	0.0231 (6)	0.0190 (7)	0.0023 (7)	−0.0032 (6)
O15	0.0434 (11)	0.0352 (7)	0.0424 (8)	0.0167 (7)	0.0152 (8)	0.0124 (6)
O16	0.0350 (11)	0.0419 (8)	0.0285 (7)	−0.0075 (7)	−0.0011 (7)	−0.0080 (6)
O17	0.0649 (13)	0.0287 (7)	0.0373 (8)	0.0087 (7)	0.0242 (8)	0.0024 (6)
O18	0.0280 (11)	0.0553 (10)	0.0312 (8)	−0.0002 (8)	−0.0097 (7)	0.0065 (7)
O19	0.0302 (10)	0.0394 (7)	0.0232 (6)	−0.0018 (6)	0.0038 (6)	0.0009 (5)
O20	0.0303 (10)	0.0383 (8)	0.0412 (8)	−0.0102 (7)	−0.0033 (7)	−0.0035 (6)
O21	0.0295 (11)	0.0491 (9)	0.0333 (8)	−0.0031 (7)	0.0060 (7)	0.0102 (6)
O22	0.0342 (10)	0.0396 (8)	0.0248 (7)	0.0019 (7)	−0.0085 (6)	0.0058 (6)
O23	0.0379 (11)	0.0438 (9)	0.0434 (9)	0.0117 (7)	0.0048 (8)	−0.0067 (7)
O24	0.0487 (12)	0.0339 (7)	0.0329 (8)	−0.0146 (7)	−0.0152 (8)	0.0059 (6)
O25	0.0471 (12)	0.0293 (7)	0.0393 (8)	0.0095 (7)	−0.0178 (8)	−0.0052 (6)
O26	0.0366 (11)	0.0498 (9)	0.0359 (8)	0.0089 (8)	0.0088 (7)	−0.0103 (7)
O27	0.0350 (11)	0.0441 (9)	0.0475 (9)	−0.0144 (7)	0.0008 (8)	0.0080 (7)
O28	0.0353 (11)	0.0377 (7)	0.0258 (7)	−0.0030 (7)	−0.0074 (7)	−0.0067 (6)
O29	0.0410 (11)	0.0346 (7)	0.0407 (8)	0.0146 (7)	0.0019 (7)	0.0022 (6)
O30	0.0300 (10)	0.0319 (6)	0.0228 (6)	−0.0042 (6)	0.0045 (6)	−0.0009 (5)
O31	0.0454 (11)	0.0276 (6)	0.0327 (7)	−0.0082 (6)	0.0143 (7)	−0.0009 (5)
O32	0.0279 (10)	0.0532 (9)	0.0282 (7)	−0.0050 (7)	−0.0084 (7)	−0.0043 (6)
O33	0.106 (2)	0.0357 (11)	0.0808 (19)	0.0074 (13)	0.0158 (16)	0.0138 (12)

Bond lengths (Å)

K1—O2^i	2.815 (2)	O1—O4	2.394 (3)
K1—O3^ii	2.9498 (18)	O1—H1^xiv	2.74 (4)
K1—O4^ii	2.9388 (18)	O1—H7^xv	2.54 (5)
K1—O6^iii	2.8959 (17)	O2—O3	2.369 (2)
K1—O7^i	2.7545 (15)	O2—O4	2.391 (3)
K1—O13^i	2.6750 (17)	O3—O4	2.395 (2)
K1—O28^iv	2.7454 (15)	O3—O7^xiv	2.559 (2)
K2—O1^i	2.8350 (17)	O3—H1^xiv	1.41 (4)
K2—O3^iii	2.7514 (15)	O4—O33^xv	2.624 (4)
K2—O5^iii	2.9890 (18)	O4—H7^xv	1.58 (5)
K2—O7^iii	2.9847 (18)	O4—H10^xv	2.82 (6)
K2—O8^iii	2.867 (2)	O5—O6^xii	2.392 (3)
K2—O11^iii	2.6561 (17)	O5—O7	2.399 (2)
K2—O22	2.7250 (15)	O5—O8^xii	2.407 (2)
K3—O5^iii	2.7304 (18)	O5—O33^vii	2.777 (4)
K3—O10^v	2.9291 (16)	O5—H1	2.80 (5)
K3—O11^iii	2.9315 (18)	O5—H8^vii	1.71 (8)
K3—O12^v	2.8947 (17)	O5—H9^vii	3.00 (7)
K3—O23	2.7652 (18)	O6—O7^vi	2.419 (2)
K3—O29^iii	2.7602 (16)	O6—O8	2.413 (2)
K4—O4	2.8006 (18)	O6—H1^vi	2.55 (4)
K4—O13^vi	2.9056 (18)	O6—H8^viii	2.52 (8)
K4—O14	2.9960 (19)	O7—O8^xii	2.364 (2)
K4—O16	2.9498 (17)	O7—H1	1.16 (4)
K4—O20	2.7447 (16)	O9—O10	2.433 (2)
K4—O21	2.9947 (17)	O9—O11	2.412 (2)
K4—O23	2.9476 (18)	O9—O12	2.352 (2)
K4—O27^iii	2.8991 (18)	O9—O14^vii	2.986 (2)
K5—O16^vii	2.7301 (16)	O9—O27	2.993 (2)
K5—O18^vii	2.9298 (18)	O9—O30	2.526 (2)
K5—O19^viii	2.9807 (16)	O9—H2^vii	2.56 (3)
K5—O20^vii	2.8312 (17)	O9—H5	1.06 (3)
K5—O21^vii	2.8871 (17)	O10—O11	2.388 (2)
K5—O31^iii	2.7628 (14)	O10—O12	2.4105 (19)
K5—O32^ix	2.9136 (15)	O10—H5	2.54 (3)
K6—O8^x	2.7429 (17)	O11—O12	2.429 (2)
K6—O12^x	2.7827 (15)	O11—H5	2.76 (3)
K6—O15^i	2.8419 (16)	O12—O14^vii	2.707 (2)
K6—O21^i	2.8678 (17)	O12—H2^vii	1.79 (3)
K6—O23^ii	2.9552 (18)	O13—O14	2.423 (3)
K6—O25^ix	2.9403 (16)	O13—O15	2.405 (2)
K6—O28^ix	2.9451 (15)	O13—O16	2.381 (2)
K7—O2	2.6522 (17)	O13—H2	2.99 (3)
K7—O9^iii	2.9547 (15)	O14—O15	2.412 (2)
K7—O14	2.8312 (16)	O14—O16	2.393 (2)
K7—O22^vii	2.9475 (16)	O14—H2	0.92 (3)
K7—O24^vii	2.8013 (16)	O15—O16	2.418 (2)
K7—O26^xi	2.9954 (17)	O15—H2	2.29 (3)
K7—O27^iii	2.9501 (18)	O16—H2	2.98 (3)
K7—O28^xi	2.9511 (18)	O17—O18^vi	2.439 (2)
K8—O10^iii	2.7154 (14)	O17—O19	2.340 (2)
K8—O17^vii	2.7781 (16)	O17—O20	2.400 (2)
K8—O18^i	2.8162 (16)	O17—O31^xiv	2.508 (2)
K8—O19^vii	2.9733 (15)	O17—H4	0.94 (3)
K8—O26^xi	2.8555 (17)	O18—O19^xii	2.405 (2)
K8—O29^xi	2.9418 (17)	O18—O20^xii	2.400 (2)
K8—O31^xi	2.9855 (17)	O18—H4^xii	2.57 (3)
K9—O1^i	2.8313 (19)	O18—H10^xvi	2.98 (6)
K9—O6^iii	2.9479 (18)	O19—O20	2.422 (2)
K9—O10^iii	2.7955 (15)	O19—O24	2.601 (2)
K9—O16^i	2.8097 (16)	O19—H3	1.71 (3)
K9—O32^iii	2.9262 (17)	O20—H3	2.90 (4)
K9—O33^xii	2.991 (4)	O20—H4	2.66 (4)
S1—O1^i	1.4435 (18)	O20—H9^xv	2.96 (7)
S1—O2^i	1.4249 (18)	O20—H10^xv	2.51 (6)
S1—O3^i	1.4944 (16)	O21—O22	2.410 (2)
S1—O4^i	1.5084 (18)	O21—O23	2.385 (2)
S1—H1^iii	2.47 (4)	O21—O24	2.427 (2)
S1—H7	2.54 (5)	O21—H3	2.57 (4)
S2—O5^iii	1.4678 (18)	O22—O23	2.424 (2)
S2—O6^v	1.4399 (18)	O22—O24	2.348 (2)
S2—O7^iii	1.5397 (16)	O23—O24	2.416 (2)
S2—O8^v	1.4352 (17)	O23—H3	2.60 (4)
S2—H1^iii	2.21 (4)	O24—H3	0.93 (4)
S2—H8	2.56 (8)	O25—O26	2.423 (2)
S3—O9^iii	1.5627 (15)	O25—O27	2.415 (2)
S3—O10^iii	1.4425 (14)	O25—O28	2.358 (2)
S3—O11^iii	1.4403 (18)	O25—O30	2.670 (2)
S3—O12^iii	1.4530 (16)	O25—H6	0.83 (3)
S3—H2	2.75 (3)	O26—O27	2.389 (2)
S3—H5^iii	2.15 (3)	O26—O28	2.405 (2)
S4—O13	1.4387 (18)	O26—H6	2.54 (3)
S4—O14	1.5805 (17)	O27—O28	2.426 (2)
S4—O15	1.4401 (16)	O27—H6	2.53 (3)
S4—O16	1.4420 (16)	O29—O30	2.405 (2)
S4—H2	2.04 (3)	O29—O31	2.390 (2)
S5—O17^vii	1.5599 (17)	O29—O32	2.401 (2)
S5—O18^xiii	1.4327 (16)	O29—O33^vii	2.791 (4)
S5—O19^vii	1.4584 (15)	O29—H5	2.77 (4)
S5—O20^vii	1.4413 (16)	O29—H8^vii	2.85 (8)
S5—H3^vii	2.72 (4)	O29—H9^vii	2.16 (7)
S5—H4^vii	2.07 (3)	O29—H10^vii	2.59 (6)
S6—O21^i	1.4371 (17)	O30—O31	2.377 (2)
S6—O22^i	1.4422 (15)	O30—O32	2.4078 (19)
S6—O23^i	1.4396 (18)	O30—H5	1.50 (3)
S6—O24^i	1.5762 (17)	O30—H6	1.86 (3)
S6—H3^i	2.07 (3)	O31—O32	2.418 (2)
S7—O25^iii	1.5794 (17)	O31—H4^xiv	1.58 (3)
S7—O26^iii	1.4386 (18)	O31—H6	2.94 (3)
S7—O27^iii	1.4409 (18)	O32—H4^xiv	2.96 (3)
S7—O28^iii	1.4391 (15)	O33—H7	1.14 (5)
S7—H6^iii	1.99 (3)	O33—H8	1.08 (8)
S8—O29^iii	1.4548 (16)	O33—H9	0.84 (7)
S8—O30^iii	1.5064 (15)	O33—H10	0.65 (6)
S8—O31^iii	1.4778 (15)	H5—H6	2.66 (5)
S8—O32^iii	1.4418 (16)	H7—H8	1.82 (9)
S8—H4^i	2.61 (3)	H7—H9	1.45 (9)
S8—H5^iii	2.48 (3)	H7—H10	1.29 (8)
S8—H6^iii	2.81 (3)	H8—H9	1.43 (10)
O1—O2	2.414 (2)	H8—H10	1.66 (10)
O1—O3	2.409 (2)	H9—H10	0.71 (9)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x+1, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, −y+1, −z+1; (v) −x, y−1/2, −z+1/2; (vi) x−1, y, z; (vii) −x+1, y+1/2, −z+1/2; (viii) −x, y+1/2, −z+1/2; (ix) x, −y+3/2, z+1/2; (x) −x+1, −y+1, −z+1; (xi) −x+2, y−1/2, −z+1/2; (xii) x+1, y, z; (xiii) −x+2, y+1/2, −z+1/2; (xiv) −x+1, −y+1, −z; (xv) x, −y+1/2, z−1/2; (xvi) x+1, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1···O3^xiv	1.16 (4)	1.41 (4)	2.559 (2)	168 (5)
O14—H2···O12^iii	0.92 (3)	1.79 (3)	2.707 (2)	172 (3)
O24—H3···O19	0.93 (4)	1.71 (3)	2.601 (2)	159 (3)
O17—H4···O31^xiv	0.94 (3)	1.58 (3)	2.508 (2)	167 (4)
O9—H5···O30	1.06 (3)	1.50 (3)	2.526 (2)	162 (3)
O25—H6···O30	0.83 (3)	1.86 (3)	2.670 (2)	166 (4)
O33—H7···O4^i	1.14 (5)	1.58 (5)	2.624 (4)	149 (4)
O33—H8···O5^iii	1.08 (8)	1.71 (8)	2.777 (4)	171 (6)
O33—H9···O29^iii	0.84 (7)	2.16 (7)	2.791 (4)	132 (5)
O33—H10···O20^i	0.65 (6)	2.51 (6)	3.119 (3)	158 (7)

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

(II)

Crystal data

K9S8O32H7	F(000) = 2291
Mr = 1127.4	Dx = 2.314 Mg m^−3
Orthorhombic, Pcan	Synchrotron radiation, λ = 0.696 Å
Hall symbol: -P -2xc;-2yab;-2zabc	Cell parameters from 7649 reflections
a = 7.1474 (3) Å	θ = 1.7–31.1°
b = 19.7761 (4) Å	µ = 1.67 mm^−1
c = 23.2542 (5) Å	T = 405 K
V = 3286.9 (2) Å^3	, colourless
Z = 4	0.27 × 0.27 × 0.27 mm

Data collection

Huber diffractometer	3911 reflections with I > 3σ(I)
Radiation source: synchrotron	Rint = 0.011
Mirror1-monochromator-Mirror2	θmax = 31.1°, θmin = 1.7°
w scans	h = −6→6
12037 measured reflections	k = −20→28
4316 independent reflections	l = −22→34

Refinement

Refinement on F	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.000025F^2)
wR(F^2) = 0.048	(Δ/σ)max = 3.785
S = 4.69	Δρmax = 0.55 e Å^−3
3911 reflections	Δρmin = −0.35 e Å^−3
255 parameters	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 136E2 (9)
0 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
K1	0.58615 (9)	0.83338 (3)	0.15907 (3)	0.0519 (2)
K2	0.22960 (9)	0.16927 (3)	0.15604 (3)	0.04979 (19)
K3	0.91408 (8)	0.99868 (3)	0.08242 (3)	0.0511 (2)
K4	0.61615 (9)	0.16342 (3)	0.01800 (3)	0.0524 (2)
K5	0.3560 (8)	0	0.25	0.1269 (17)	0.8371
K6	0.8491 (15)	0	0.25	0.216 (4)	0.7317
S1	0.08786 (9)	0.85128 (4)	0.18052 (3)	0.0454 (2)
S2	0.73096 (9)	0.14809 (3)	0.17962 (2)	0.04211 (19)
S3	0.42004 (9)	0.99687 (3)	0.10031 (3)	0.0428 (2)
S4	0.13281 (9)	0.15770 (3)	0.99236 (2)	0.03831 (18)
O1	0.2240 (3)	0.86657 (12)	0.22346 (9)	0.0720 (8)
O2	0.1835 (3)	0.82936 (15)	0.12749 (9)	0.0868 (10)
O3	0.9707 (3)	0.79375 (11)	0.19836 (10)	0.0732 (8)
O4	0.9643 (3)	0.90662 (14)	0.16842 (11)	0.0856 (9)
O5	0.8711 (3)	0.10048 (11)	0.16249 (11)	0.0761 (9)
O6	0.6200 (3)	0.12228 (12)	0.22588 (9)	0.0734 (8)
O7	0.3410 (3)	0.28990 (9)	0.20126 (9)	0.0668 (7)
O8	0.6220 (3)	0.17480 (13)	0.13337 (10)	0.0824 (10)
O9	0.3234 (3)	0.94023 (11)	0.06873 (10)	0.0675 (8)
O10	0.5477 (3)	0.97040 (10)	0.14176 (8)	0.0576 (6)
O11	0.2804 (3)	0.03924 (10)	0.12569 (10)	0.0703 (8)
O12	0.5264 (3)	0.03161 (10)	0.05366 (9)	0.0673 (7)
O13	0.0037 (3)	0.10571 (11)	0.00797 (9)	0.0701 (8)
O14	0.2104 (3)	0.19481 (10)	0.03965 (8)	0.0575 (6)
O15	0.2716 (3)	0.13406 (11)	0.95291 (9)	0.0662 (8)
O16	0.0160 (3)	0.21278 (10)	0.96026 (10)	0.0653 (8)
H1	0.881 (5)	0.206 (2)	0.2471 (16)	0.127 (16)*
H2	0.5	0	0.5	0.18 (3)*
H3	0.032 (5)	0.201 (2)	0.4311 (16)	0.097 (14)*
H4	0.267 (6)	0.082 (3)	0.403 (2)	0.17 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0528 (4)	0.0463 (3)	0.0567 (3)	0.0006 (2)	0.0000 (3)	0.0032 (2)
K2	0.0521 (4)	0.0453 (3)	0.0519 (3)	−0.0038 (2)	0.0078 (3)	−0.0058 (2)
K3	0.0512 (4)	0.0488 (3)	0.0531 (3)	−0.0019 (2)	0.0036 (3)	0.0015 (2)
K4	0.0516 (4)	0.0486 (3)	0.0569 (3)	−0.0009 (2)	−0.0028 (3)	0.0056 (2)
K5	0.276 (5)	0.0590 (7)	0.0460 (6)	0	0	−0.0064 (5)
K6	0.537 (11)	0.0485 (8)	0.0624 (12)	0	0	0.0001 (9)
S1	0.0374 (4)	0.0627 (4)	0.0361 (3)	−0.0004 (3)	−0.0012 (2)	0.0071 (2)
S2	0.0398 (4)	0.0488 (3)	0.0377 (3)	0.0011 (3)	−0.0015 (2)	−0.0047 (2)
S3	0.0393 (4)	0.0399 (3)	0.0492 (3)	0.0018 (2)	0.0025 (3)	0.0001 (2)
S4	0.0395 (4)	0.0373 (3)	0.0381 (3)	−0.0003 (2)	−0.0018 (2)	−0.00251 (19)
O1	0.0620 (14)	0.0989 (16)	0.0552 (12)	−0.0092 (12)	−0.0170 (10)	−0.0046 (11)
O2	0.0484 (13)	0.168 (3)	0.0437 (11)	0.0119 (14)	0.0069 (10)	−0.0149 (13)
O3	0.0812 (15)	0.0632 (12)	0.0753 (14)	−0.0142 (11)	0.0250 (12)	−0.0197 (11)
O4	0.0756 (15)	0.0982 (18)	0.0830 (16)	0.0328 (14)	0.0036 (13)	0.0312 (13)
O5	0.0562 (13)	0.0648 (13)	0.1073 (18)	0.0062 (10)	0.0162 (13)	−0.0253 (12)
O6	0.0773 (15)	0.0912 (16)	0.0517 (11)	−0.0182 (12)	0.0173 (10)	0.0020 (11)
O7	0.0942 (16)	0.0429 (9)	0.0635 (12)	0.0079 (10)	−0.0247 (12)	−0.0053 (8)
O8	0.0737 (16)	0.115 (2)	0.0586 (13)	0.0011 (14)	−0.0248 (11)	0.0146 (13)
O9	0.0697 (14)	0.0677 (13)	0.0650 (13)	−0.0259 (11)	0.0138 (11)	−0.0211 (10)
O10	0.0567 (12)	0.0566 (10)	0.0597 (11)	0.0078 (9)	−0.0064 (9)	0.0089 (9)
O11	0.0528 (13)	0.0601 (11)	0.0979 (17)	0.0168 (10)	−0.0018 (11)	−0.0222 (11)
O12	0.0739 (14)	0.0642 (12)	0.0638 (12)	−0.0201 (11)	0.0014 (11)	0.0189 (10)
O13	0.0655 (14)	0.0707 (13)	0.0742 (14)	−0.0257 (11)	−0.0026 (11)	0.0123 (11)
O14	0.0671 (13)	0.0598 (11)	0.0455 (10)	−0.0029 (9)	−0.0133 (9)	−0.0107 (8)
O15	0.0560 (13)	0.0812 (14)	0.0615 (12)	0.0098 (11)	0.0111 (10)	−0.0163 (10)
O16	0.0829 (16)	0.0474 (10)	0.0655 (13)	0.0162 (10)	−0.0259 (12)	−0.0075 (9)

Geometric parameters (Å, º)

K1—O2	2.971 (2)	S2—O7^viii	1.541 (2)
K1—O3^i	2.800 (2)	S2—O8	1.429 (2)
K1—O6^ii	2.826 (2)	S3—O9	1.507 (2)
K1—O10	2.753 (2)	S3—O10	1.427 (2)
K1—O15^iii	2.869 (2)	S3—O11^v	1.430 (2)
K2—O1^ii	2.891 (2)	S3—O12^v	1.492 (2)
K2—O5^iv	2.905 (2)	S4—O13^xiii	1.428 (2)
K2—O7	2.726 (2)	S4—O14^xiii	1.4335 (19)
K2—O8	2.856 (2)	S4—O15	1.430 (2)
K2—O11	2.691 (2)	S4—O16	1.562 (2)
K2—O14	2.7567 (18)	O1—O2	2.368 (3)
K3—O4	2.728 (3)	O1—O3^iv	2.386 (3)
K3—O5^v	2.759 (2)	O1—O4^iv	2.390 (3)
K3—O11^vi	2.918 (2)	O2—O3^iv	2.350 (3)
K3—O12^v	2.924 (2)	O2—O4^iv	2.386 (4)
K3—O13^vi	2.809 (2)	O2—O9	2.770 (3)
K4—O8	2.693 (2)	O2—O16^xiv	2.625 (3)
K4—O9^vii	2.908 (2)	O3—O4	2.339 (3)
K4—O12	2.810 (2)	O3—O7^xv	2.513 (3)
K4—O14^viii	2.927 (2)	O5—O6	2.362 (3)
K4—O15^ix	2.948 (2)	O5—O7^viii	2.358 (3)
K4—O16^x	2.882 (2)	O5—O8	2.406 (3)
K5—O1^xi	2.870 (3)	O6—O7^viii	2.416 (3)
K5—O1^ii	2.870 (3)	O6—O8	2.389 (3)
K5—O10^xi	2.925 (3)	O7—O8^xvi	2.330 (3)
K5—O10^ii	2.925 (3)	O9—O10	2.411 (3)
K6—O4^xi	2.773 (4)	O9—O11^v	2.384 (3)
K6—O4^ii	2.773 (4)	O9—O12^v	2.344 (3)
K6—O5	2.849 (2)	O10—O11^v	2.376 (3)
K6—O5^xii	2.849 (2)	O10—O12^v	2.385 (3)
K6—O6	2.974 (6)	O11—O12	2.433 (3)
K6—O6^xii	2.974 (6)	O12—O12^xvii	2.817 (3)
S1—O1	1.427 (2)	O13—O14	2.414 (3)
S1—O2	1.475 (2)	O13—O15^ix	2.371 (3)
S1—O3^iv	1.472 (2)	O13—O16^ix	2.392 (3)
S1—O4^iv	1.434 (3)	O14—O15^ix	2.388 (3)
S2—O5	1.431 (2)	O14—O16^ix	2.338 (3)
S2—O6	1.431 (2)	O15—O16	2.406 (3)
O2—K1—O3^i	76.76 (7)	O5^xvi—O7—O8^xvi	61.76 (10)
O2—K1—O6^ii	108.98 (6)	O6^xvi—O7—O8^xvi	60.41 (9)
O2—K1—O10	83.90 (7)	K2—O8—K4	99.53 (8)
O2—K1—O15^iii	97.18 (6)	K2—O8—S2	112.47 (12)
O3^i—K1—O6^ii	89.71 (7)	K2—O8—O5	130.65 (11)
O3^i—K1—O10	154.46 (7)	K2—O8—O6	79.13 (9)
O3^i—K1—O15^iii	127.03 (7)	K2—O8—O7^viii	123.10 (11)
O6^ii—K1—O10	80.88 (6)	K4—O8—S2	136.66 (14)
O6^ii—K1—O15^iii	139.41 (7)	K4—O8—O5	103.93 (11)
O10—K1—O15^iii	71.44 (6)	K4—O8—O6	149.41 (13)
O1^ii—K2—O5^iv	79.80 (7)	K4—O8—O7^viii	135.27 (12)
O1^ii—K2—O7	81.06 (7)	S2—O8—O5	32.76 (9)
O1^ii—K2—O8	101.65 (6)	S2—O8—O6	33.37 (8)
O1^ii—K2—O11	91.25 (7)	S2—O8—O7^viii	40.07 (8)
O1^ii—K2—O14	174.86 (6)	O5—O8—O6	59.02 (10)
O5^iv—K2—O7	130.35 (7)	O5—O8—O7^viii	59.68 (9)
O5^iv—K2—O8	153.34 (7)	O6—O8—O7^viii	61.58 (9)
O5^iv—K2—O11	71.65 (6)	K4^vii—O9—S3	142.54 (13)
O5^iv—K2—O14	95.31 (7)	K4^vii—O9—O2	80.67 (8)
O7—K2—O8	75.57 (7)	K4^vii—O9—O10	124.35 (10)
O7—K2—O11	153.89 (7)	K4^vii—O9—O11^v	169.58 (11)
O7—K2—O14	103.47 (6)	K4^vii—O9—O12^v	110.36 (10)
O8—K2—O11	81.70 (7)	S3—O9—O2	120.88 (13)
O8—K2—O14	81.99 (6)	S3—O9—O10	33.68 (7)
O11—K2—O14	85.66 (6)	S3—O9—O11^v	34.69 (7)
O4—K3—O5^v	90.40 (8)	S3—O9—O12^v	38.38 (8)
O4—K3—O11^vi	79.20 (7)	O2—O9—O10	95.07 (10)
O4—K3—O12^v	116.17 (7)	O2—O9—O11^v	109.24 (11)
O4—K3—O13^vi	157.63 (7)	O2—O9—O12^v	155.15 (12)
O5^v—K3—O11^vi	70.53 (6)	O10—O9—O11^v	59.40 (8)
O5^v—K3—O12^v	83.47 (6)	O10—O9—O12^v	60.18 (9)
O5^v—K3—O13^vi	83.77 (7)	O11^v—O9—O12^v	61.93 (9)
O11^vi—K3—O12^v	150.24 (6)	K1—O10—K5^v	96.77 (6)
O11^vi—K3—O13^vi	78.50 (6)	K1—O10—S3	121.58 (11)
O12^v—K3—O13^vi	84.68 (6)	K1—O10—O9	85.74 (8)
O8—K4—O9^vii	138.39 (7)	K1—O10—O11^v	131.86 (9)
O8—K4—O12	77.70 (7)	K1—O10—O12^v	129.17 (9)
O8—K4—O14^viii	75.23 (7)	K5^v—O10—S3	102.02 (13)
O8—K4—O15^ix	122.74 (7)	K5^v—O10—O9	110.13 (13)
O8—K4—O16^x	113.39 (7)	K5^v—O10—O11^v	69.14 (11)
O9^vii—K4—O12	65.46 (6)	K5^v—O10—O12^v	127.43 (10)
O9^vii—K4—O14^viii	139.49 (6)	S3—O10—O9	35.85 (7)
O9^vii—K4—O15^ix	68.24 (6)	S3—O10—O11^v	33.80 (8)
O9^vii—K4—O16^x	108.21 (6)	S3—O10—O12^v	36.15 (7)
O12—K4—O14^viii	152.92 (6)	O9—O10—O11^v	59.74 (9)
O12—K4—O15^ix	77.18 (6)	O9—O10—O12^v	58.52 (9)
O12—K4—O16^x	150.32 (7)	O11^v—O10—O12^v	61.47 (9)
O14^viii—K4—O15^ix	117.98 (6)	K2—O11—K3^xxi	103.42 (7)
O14^viii—K4—O16^x	47.45 (6)	K2—O11—S3^xi	139.65 (12)
O15^ix—K4—O16^x	73.78 (6)	K2—O11—O9^xi	161.43 (11)
O1^xi—K5—O1^ii	141.6 (2)	K2—O11—O10^xi	127.95 (10)
O1^xi—K5—O10^xi	77.58 (6)	K2—O11—O12	109.72 (9)
O1^xi—K5—O10^ii	121.55 (6)	K3^xxi—O11—S3^xi	108.83 (11)
O1^ii—K5—O10^xi	121.55 (6)	K3^xxi—O11—O9^xi	72.43 (8)
O1^ii—K5—O10^ii	77.58 (6)	K3^xxi—O11—O10^xi	128.20 (9)
O10^xi—K5—O10^ii	124.1 (2)	K3^xxi—O11—O12	113.21 (10)
O4^xi—K6—O4^ii	145.5 (4)	S3^xi—O11—O9^xi	36.85 (8)
O4^xi—K6—O5	87.68 (10)	S3^xi—O11—O10^xi	33.71 (7)
O4^xi—K6—O5^xii	90.45 (11)	S3^xi—O11—O12	34.46 (8)
O4^xi—K6—O6	125.18 (13)	O9^xi—O11—O10^xi	60.86 (9)
O4^xi—K6—O6^xii	75.58 (8)	O9^xi—O11—O12	58.23 (9)
O4^ii—K6—O5	90.45 (11)	O10^xi—O11—O12	59.44 (8)
O4^ii—K6—O5^xii	87.68 (10)	K3^xi—O12—K4	93.32 (6)
O4^ii—K6—O6	75.58 (8)	K3^xi—O12—S3^xi	102.36 (10)
O4^ii—K6—O6^xii	125.18 (13)	K3^xi—O12—O9^xi	112.38 (9)
O5—K6—O5^xii	173.7 (4)	K3^xi—O12—O10^xi	68.27 (7)
O5—K6—O6	47.81 (8)	K3^xi—O12—O11	122.76 (9)
O5—K6—O6^xii	137.1 (3)	K3^xi—O12—O12^xvii	103.35 (8)
O5^xii—K6—O6	137.1 (3)	K4—O12—S3^xi	139.29 (12)
O5^xii—K6—O6^xii	47.81 (8)	K4—O12—O9^xi	154.25 (11)
O6—K6—O6^xii	113.2 (4)	K4—O12—O10^xi	135.24 (10)
O1—S1—O2	109.34 (13)	K4—O12—O11	108.09 (9)
O1—S1—O3^iv	110.76 (13)	K4—O12—O12^xvii	100.42 (8)
O1—S1—O4^iv	113.31 (15)	S3^xi—O12—O9^xi	38.83 (8)
O2—S1—O3^iv	105.78 (15)	S3^xi—O12—O10^xi	34.34 (7)
O2—S1—O4^iv	110.22 (15)	S3^xi—O12—O11	32.85 (7)
O3^iv—S1—O4^iv	107.14 (14)	S3^xi—O12—O12^xvii	111.81 (11)
O5—S2—O6	111.25 (14)	O9^xi—O12—O10^xi	61.30 (9)
O5—S2—O7^viii	104.90 (13)	O9^xi—O12—O11	59.84 (9)
O5—S2—O8	114.53 (14)	O9^xi—O12—O12^xvii	72.98 (9)
O6—S2—O7^viii	108.73 (13)	O10^xi—O12—O11	59.08 (8)
O6—S2—O8	113.31 (14)	O10^xi—O12—O12^xvii	122.99 (10)
O7^viii—S2—O8	103.29 (14)	O11—O12—O12^xvii	122.73 (11)
O9—S3—O10	110.46 (12)	K3^xxi—O13—S4^ix	147.83 (13)
O9—S3—O11^v	108.46 (12)	K3^xxi—O13—O14	120.10 (9)
O9—S3—O12^v	102.79 (12)	K3^xxi—O13—O15^ix	134.06 (10)
O10—S3—O11^v	112.49 (13)	K3^xxi—O13—O16^ix	164.03 (11)
O10—S3—O12^v	109.52 (12)	S4^ix—O13—O14	32.54 (7)
O11^v—S3—O12^v	112.68 (12)	S4^ix—O13—O15^ix	33.98 (8)
O13^xiii—S4—O14^xiii	115.05 (12)	S4^ix—O13—O16^ix	38.85 (8)
O13^xiii—S4—O15	112.08 (13)	O14—O13—O15^ix	59.87 (8)
O13^xiii—S4—O16	106.15 (12)	O14—O13—O16^ix	58.20 (9)
O14^xiii—S4—O15	113.03 (12)	O15^ix—O13—O16^ix	60.69 (9)
O14^xiii—S4—O16	102.49 (11)	K2—O14—K4^xvi	110.85 (6)
O15—S4—O16	106.98 (12)	K2—O14—S4^ix	132.73 (11)
K2^ii—O1—K5^v	90.71 (6)	K2—O14—O13	101.32 (8)
K2^ii—O1—S1	129.48 (12)	K2—O14—O15^ix	136.72 (10)
K2^ii—O1—O2	147.05 (12)	K2—O14—O16^ix	146.39 (10)
K2^ii—O1—O3^iv	95.71 (9)	K4^xvi—O14—S4^ix	105.63 (9)
K2^ii—O1—O4^iv	127.67 (10)	K4^xvi—O14—O13	120.38 (9)
K5^v—O1—S1	124.72 (15)	K4^xvi—O14—O15^ix	112.25 (8)
K5^v—O1—O2	121.92 (11)	K4^xvi—O14—O16^ix	65.28 (7)
K5^v—O1—O3^iv	148.99 (15)	S4^ix—O14—O13	32.41 (7)
K5^v—O1—O4^iv	93.77 (13)	S4^ix—O14—O15^ix	33.44 (7)
S1—O1—O2	36.00 (8)	S4^ix—O14—O16^ix	40.73 (7)
S1—O1—O3^iv	35.24 (8)	O13—O14—O15^ix	59.15 (8)
S1—O1—O4^iv	33.44 (9)	O13—O14—O16^ix	60.42 (8)
O2—O1—O3^iv	59.27 (10)	O15^ix—O14—O16^ix	61.20 (8)
O2—O1—O4^iv	60.21 (10)	K1^iii—O15—K4^xiii	97.23 (6)
O3^iv—O1—O4^iv	58.64 (10)	K1^iii—O15—S4	139.03 (12)
K1—O2—S1	103.55 (11)	K1^iii—O15—O13^xiii	146.06 (10)
K1—O2—O1	68.91 (8)	K1^iii—O15—O14^xiii	135.95 (10)
K1—O2—O3^iv	117.49 (10)	K1^iii—O15—O16	100.86 (9)
K1—O2—O4^iv	121.34 (11)	K4^xiii—O15—S4	100.70 (10)
K1—O2—O9	75.58 (8)	K4^xiii—O15—O13^xiii	116.35 (9)
K1—O2—O16^xiv	136.61 (10)	K4^xiii—O15—O14^xiii	67.69 (7)
S1—O2—O1	34.66 (8)	K4^xiii—O15—O16	118.05 (10)
S1—O2—O3^iv	37.07 (8)	S4—O15—O13^xiii	33.94 (8)
S1—O2—O4^iv	34.33 (9)	S4—O15—O14^xiii	33.53 (7)
S1—O2—O9	110.31 (16)	S4—O15—O16	38.39 (8)
S1—O2—O16^xiv	119.44 (13)	O13^xiii—O15—O14^xiii	60.97 (9)
O1—O2—O3^iv	60.76 (9)	O13^xiii—O15—O16	60.10 (9)
O1—O2—O4^iv	60.36 (10)	O14^xiii—O15—O16	58.36 (9)
O1—O2—O9	100.07 (12)	K4^xxii—O16—S4	103.70 (11)
O1—O2—O16^xiv	153.88 (12)	K4^xxii—O16—O2^xiv	140.05 (10)
O3^iv—O2—O4^iv	59.17 (10)	K4^xxii—O16—O13^xiii	123.02 (10)
O3^iv—O2—O9	144.74 (14)	K4^xxii—O16—O14^xiii	67.28 (7)
O3^iv—O2—O16^xiv	95.65 (11)	K4^xxii—O16—O15	113.21 (10)
O4^iv—O2—O9	85.81 (12)	S4—O16—O2^xiv	116.13 (12)
O4^iv—O2—O16^xiv	99.02 (11)	S4—O16—O13^xiii	35.00 (7)
O9—O2—O16^xiv	93.66 (9)	S4—O16—O14^xiii	36.78 (7)
K1^xviii—O3—S1^xix	115.74 (12)	S4—O16—O15	34.63 (7)
K1^xviii—O3—O1^xix	113.46 (10)	O2^xiv—O16—O13^xiii	93.41 (11)
K1^xviii—O3—O2^xix	81.34 (10)	O2^xiv—O16—O14^xiii	152.67 (12)
K1^xviii—O3—O4	139.98 (12)	O2^xiv—O16—O15	98.73 (10)
K1^xviii—O3—O7^xv	112.63 (9)	O13^xiii—O16—O14^xiii	61.38 (9)
S1^xix—O3—O1^xix	34.00 (8)	O13^xiii—O16—O15	59.21 (9)
S1^xix—O3—O2^xix	37.14 (9)	O14^xiii—O16—O15	60.43 (9)
S1^xix—O3—O4	35.87 (8)	S1^xxiii—H1—S2	121.7 (19)
S1^xix—O3—O7^xv	119.67 (13)	S1^xxiii—H1—O1^xxiii	29.2 (5)
O1^xix—O3—O2^xix	59.97 (9)	S1^xxiii—H1—O3^ii	30.4 (10)
O1^xix—O3—O4	60.76 (10)	S1^xxiii—H1—O5	98.4 (14)
O1^xix—O3—O7^xv	94.07 (10)	S1^xxiii—H1—O6	105.5 (16)
O2^xix—O3—O4	61.18 (11)	S1^xxiii—H1—O7^viii	146 (3)
O2^xix—O3—O7^xv	154.04 (13)	S2—H1—O1^xxiii	108.5 (16)
O4—O3—O7^xv	107.36 (11)	S2—H1—O3^ii	148 (3)
K3—O4—K6^v	91.03 (9)	S2—H1—O5	29.3 (5)
K3—O4—S1^xix	137.23 (14)	S2—H1—O6	34.1 (6)
K3—O4—O1^xix	135.72 (11)	S2—H1—O7^viii	39.7 (15)
K3—O4—O2^xix	102.79 (11)	O1^xxiii—H1—O3^ii	54.2 (13)
K3—O4—O3	149.06 (13)	O1^xxiii—H1—O5	79.9 (11)
K6^v—O4—S1^xix	123.84 (18)	O1^xxiii—H1—O6	109.9 (16)
K6^v—O4—O1^xix	94.9 (2)	O1^xxiii—H1—O7^viii	119 (3)
K6^v—O4—O2^xix	153.4 (2)	O3^ii—H1—O5	129 (2)
K6^v—O4—O3	115.96 (11)	O3^ii—H1—O6	120 (2)
S1^xix—O4—O1^xix	33.25 (8)	O3^ii—H1—O7^viii	168 (4)
S1^xix—O4—O2^xix	35.45 (9)	O5—H1—O6	51.3 (8)
S1^xix—O4—O3	36.99 (9)	O5—H1—O7^viii	52.1 (19)
O1^xix—O4—O2^xix	59.43 (9)	O6—H1—O7^viii	71 (2)
O1^xix—O4—O3	60.60 (10)	S3^ii—H2—S3^xxiv	180.0 (5)
O2^xix—O4—O3	59.66 (11)	S3^ii—H2—O9^ii	36.92 (6)
K2^xix—O5—K3^xi	102.04 (7)	S3^ii—H2—O9^xxiv	143.08 (6)
K2^xix—O5—K6	114.3 (2)	S3^ii—H2—O12^xii	35.22 (9)
K2^xix—O5—S2	108.88 (11)	S3^ii—H2—O12^xxv	144.78 (9)
K2^xix—O5—O6	128.09 (11)	S3^xxiv—H2—O9^ii	143.08 (6)
K2^xix—O5—O7^viii	70.71 (8)	S3^xxiv—H2—O9^xxiv	36.92 (6)
K2^xix—O5—O8	110.62 (10)	S3^xxiv—H2—O12^xii	144.78 (9)
K3^xi—O5—K6	88.81 (7)	S3^xxiv—H2—O12^xxv	35.22 (9)
K3^xi—O5—S2	138.22 (13)	O9^ii—H2—O9^xxiv	180.0 (5)
K3^xi—O5—O6	129.70 (10)	O9^ii—H2—O12^xii	72.14 (10)
K3^xi—O5—O7^viii	159.89 (12)	O9^ii—H2—O12^xxv	107.86 (10)
K3^xi—O5—O8	109.76 (11)	O9^xxiv—H2—O12^xii	107.86 (10)
K6—O5—S2	102.8 (2)	O9^xxiv—H2—O12^xxv	72.14 (10)
K6—O5—O6	68.87 (19)	O12^xii—H2—O12^xxv	180.0 (5)
K6—O5—O7^viii	111.30 (11)	S1^ii—H3—S4^xxvi	124.9 (17)
K6—O5—O8	125.9 (2)	S1^ii—H3—O2^ii	28.0 (6)
S2—O5—O6	34.37 (8)	S1^ii—H3—O13^xxvii	112.3 (14)
S2—O5—O7^viii	39.18 (9)	S1^ii—H3—O15^xxvi	96.4 (12)
S2—O5—O8	32.71 (8)	S1^ii—H3—O16^xxvi	163 (4)
O6—O5—O7^viii	61.59 (10)	S4^xxvi—H3—O2^ii	136 (2)
O6—O5—O8	60.13 (9)	S4^xxvi—H3—O13^xxvii	33.0 (6)
O7^viii—O5—O8	58.57 (10)	S4^xxvi—H3—O15^xxvi	33.4 (6)
K1^ii—O6—K6	96.95 (6)	S4^xxvi—H3—O16^xxvi	44 (2)
K1^ii—O6—S2	130.45 (13)	O2^ii—H3—O13^xxvii	109.2 (17)
K1^ii—O6—O5	135.45 (11)	O2^ii—H3—O15^xxvi	118.1 (18)
K1^ii—O6—O7^viii	93.29 (9)	O2^ii—H3—O16^xxvi	169 (4)
K1^ii—O6—O8	135.90 (12)	O13^xxvii—H3—O15^xxvi	54.3 (8)
K6—O6—S2	97.28 (17)	O13^xxvii—H3—O16^xxvi	66 (3)
K6—O6—O5	63.32 (14)	O15^xxvi—H3—O16^xxvi	68 (3)
K6—O6—O7^viii	105.6 (2)	S1^ii—H4—S3^ii	130 (2)
K6—O6—O8	121.34 (12)	S1^ii—H4—O2^ii	32.9 (8)
S2—O6—O5	34.38 (8)	S1^ii—H4—O4^xxviii	30.7 (6)
S2—O6—O7^viii	37.16 (8)	S1^ii—H4—O9^ii	179 (4)
S2—O6—O8	33.33 (8)	S1^ii—H4—O10^ii	106.6 (18)
O5—O6—O7^viii	59.11 (9)	S1^ii—H4—O11^xii	107.2 (18)
O5—O6—O8	60.85 (10)	S3^ii—H4—O2^ii	152 (3)
O7^viii—O6—O8	58.02 (9)	S3^ii—H4—O4^xxviii	119 (2)
K2—O7—S2^xvi	114.91 (11)	S3^ii—H4—O9^ii	50 (3)
K2—O7—O3^xx	119.52 (9)	S3^ii—H4—O10^ii	34.7 (8)
K2—O7—O5^xvi	133.14 (11)	S3^ii—H4—O11^xii	34.7 (9)
K2—O7—O6^xvi	121.97 (11)	O2^ii—H4—O4^xxviii	58.2 (12)
K2—O7—O8^xvi	78.73 (9)	O2^ii—H4—O9^ii	148 (5)
S2^xvi—O7—O3^xx	117.87 (12)	O2^ii—H4—O10^ii	117 (2)
S2^xvi—O7—O5^xvi	35.92 (7)	O2^ii—H4—O11^xii	140 (2)
S2^xvi—O7—O6^xvi	34.11 (7)	O4^xxviii—H4—O9^ii	148 (4)
S2^xvi—O7—O8^xvi	36.65 (9)	O4^xxviii—H4—O10^ii	114.5 (19)
O3^xx—O7—O5^xvi	107.08 (11)	O4^xxviii—H4—O11^xii	86.8 (15)
O3^xx—O7—O6^xvi	89.96 (10)	O9^ii—H4—O10^ii	74 (3)
O3^xx—O7—O8^xvi	150.24 (12)	O9^ii—H4—O11^xii	72 (3)
O5^xvi—O7—O6^xvi	59.30 (9)	O10^ii—H4—O11^xii	56.8 (11)

Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) x, −y+1, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z; (v) x, y+1, z; (vi) x+1, y+1, z; (vii) −x+1, −y+1, −z; (viii) x+1/2, −y+1/2, z; (ix) x, y, z−1; (x) x+1/2, −y+1/2, z−1; (xi) x, y−1, z; (xii) x, −y, −z+1/2; (xiii) x, y, z+1; (xiv) −x, −y+1, −z+1; (xv) x+1/2, y+1/2, −z+1/2; (xvi) x−1/2, −y+1/2, z; (xvii) −x+1, −y, −z; (xviii) x+1/2, −y+3/2, z; (xix) x+1, y, z; (xx) x−1/2, y−1/2, −z+1/2; (xxi) x−1, y−1, z; (xxii) x−1/2, −y+1/2, z+1; (xxiii) x+1, −y+1, −z+1/2; (xxiv) −x+1, y−1, z+1/2; (xxv) −x+1, y, z+1/2; (xxvi) −x, y, z−1/2; (xxvii) −x, y, z+1/2; (xxviii) x−1, −y+1, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7^viii—H1···O3^ii	1.11 (4)	1.42 (4)	2.513 (3)	168 (4)
O12^xii—H2···O12^xxv	1.408 (2)	1.408 (2)	2.817 (3)	**
O16^xxvi—H3···O2^ii	0.79 (4)	1.84 (4)	2.625 (3)	169 (4)
O9^ii—H4···O2^ii	0.89 (5)	1.98 (5)	2.770 (3)	148 (5)

Symmetry codes: (ii) x, −y+1, −z+1/2; (viii) x+1/2, −y+1/2, z; (xii) x, −y, −z+1/2; (xxv) −x+1, y, z+1/2; (xxvi) −x, y, z−1/2.