Thia­minium chloride perchlorate

In the title compound, C₁₂H₁₈N₄OS²⁺·Cl⁻·ClO₄⁻, the thia­minium cations form `head-to-tail' N—H...O hydrogen-bonded dimers about inversion centres. N—H...Cl and O—H...Cl hydrogen bonds further stabilize the structure, forming a one-dimensional chain running along the diagonal of the ac plane. Both anions are located adjacent to `anion holes' in the thia­minium cation. The perchlorate anions show rotational disorder about a Cl—O bond.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.029
• wR factor = 0.082
• Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.03
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      33.00 Perc.
PLAT430_ALERT_2_C Short Inter D...A Contact  N8     ..  O12'    ..       2.90 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12    ..  O11     ..       2.78 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12    ..  O13     ..       2.84 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6     ..  CL2     ..       2.85 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              Cl

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

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

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S1. Comment

Thiamine (vitamin B1) deficiency leads to an number of medical problems, including wet beri-beri and heart failure, and hence vitamin B1 supplements are commonly admistered (Suter, 2004). Thiamine, in the form of pyrophosphate cocarboxylase, is the coenzyme for many reactions, including the oxidative decarboxylation of pyruvic acid (Breslow, 1958). Derivatives of thiamine disulfides are also used as therapeutic provitamins, due to their high absorptivity in the gastrointestinal tract (Suzuoki et al., 1965). Protonation on one of the N atoms of monovalent thiamine (Th⁺) leads to a divalent cation with a protonated pyrimidine ring and a monovalent thiazolium ring. Numerous crystal structures of mono- and divalent thiamine cations with a variety of anions have been reported previously (Kraut & Reed, 1962; Ishida et al., 1984; Shin & Chun, 1987; Koziol et al., 1987; Aoki et al., 1988; Cramer & Carrie, 1989; Casas et al., 1994).

The title compound, (I), crystallizes with a divalent thiaminium cation, and Cl⁻ and perchlorate anions in the asymmetric unit (Fig. 1). The pyrimidine ring is protonated at N1, with C—N bond distances and the C—N—C bond angle being typical for a protonated N atom (Hu et al., 2000). The planar pyridimine and thiazolium rings are inclined to one another at a dihedral angle of 71.8 (1)°. Two conformation angles about the C7 methylene group [ϕ_T (C5—C7—N8—C12) and ϕ_P (C4—C5—C7—N8)] define three possible forms of thiamine, namely F, S and V (Shin et al., 1977). Our statistical analysis from the Cambridge Structural Database (Version 5.26 of November 2004; Allen, 2002) indicates that the F form occurs frequently when atom C12 in the thiazolium ring carries no substituents. In (I), the thiamine is in the preferred F conformation, with ϕ_T = −8.6 (3)° and ϕ_P = 79.2 (2)°, close to the ideal values (ϕ_T = 0° and ϕ_P = ±90°). The conformation of the 5-(β-hydroxyethyl) side chain is also described by the two torsion angles ϕ_5α (S11—C10—C13—C14) and ϕ_5β (C10—C13—C14—O15) (Table 1), which result in a close contact between the electronegative atom O15 and the electropositive atom S11 of 2.921 (2) Å, a common structural feature of thiamine compounds (Shin et al., 1977), causing the hydroxyethyl side-chain to fold back towards the thaizolium ring.

Stabilization in the crystal structure of (I) results from interactions between adjacent thiamine units, both with themselves and through the anions. This occurs through a range of classical and non-classical hydrogen bonding interactions (Table 2), augmented by a weak S···O interaction [S1···O11(−x + 1, −y + 1, −z + 2) 3.117 (2) Å] and electrostatic interactions. In the title compound, however, classical hydrogen bonding dominates. `Head-to-tail' dimers form around inversion centres through N—H41A···O15 hydrogen bonds (Fig. 3), to form a closed hydrogen-bonding network in the bc plane. This results in a cavity of approximate dimensions 5.52 × 5.24 Å running along the a axis. In addition, N41—H41B···O interactions link the perchlorate anion to the cation in a location described as anion hole II (Hu et al., 2000). Further strong N1—H1···Cl2 and O15—H15···Cl2 hydrogen bonds complete the network, forming infinite chains along the diagonal of the ac plane. C12—H12···O interactions are also of interest because of the importance of the acidic atom H12 in hydroxyethyl thiamine pyrophosphate reactions (Krampitz, 1969). Weak intermolecular C12—H12···O11/O13 bifurcated hydrogen bonds lock an alternative perchlorate into `anion hole I', characteristic of thiamine systems in the F conformation (Hu et al., 2001), with a final weak C6—H6···Cl2 interaction designating the Cl⁻ anion to `anion hole III' (Hu et al., 2000).

S2. Experimental

The title compound was crystallized from a liquid mixture of thiamine chloride and perchloric acid in the stoichiometric ratio of 1:1 at room temperature by the technique of slow evaporation. CAUTION: Although no problems were encountered in this work, perchlorate compounds are potentially explosive. They should be prepared in small amounts and handled with care.

S3. Refinement

The H atom on atom O15 of the hydroxyethyl substituent in the thiamine moiety was located and refined isotropically. All other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and N—H = 0.86 Å, and U_iso(H) = 1.2–1.5U_eq(parent atom). The perchlorate anion shows `rotational' disorder around the axis of the Cl1—O11 bond, which leads to occupancy factors of 0.63 (2) and 0.37 (6) for O12/O13/O14 and O12'/O13'/O14', respectively.

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecular structure of compound (I), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. A packing diagram of (I), viewed down the a axis. Hydrogen bonds are drawn as dashed lines.
	Fig. 3. The inversion-related closed hydrogen-bonding loop formed by the cations. Hydrogen bonds are drawn as dashed lines.

Thiaminium chloride perchlorate

Crystal data

C12H18N4OS^2+·Cl^−·ClO4^−	Z = 2
Mr = 401.26	F(000) = 416
Triclinic, P1	Dx = 1.527 Mg m^−3 Dm = 1.514 Mg m^−3 Dm measured by flotation, using a mixture of xylene and carbon tetrachloride
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.076 (3) Å	Cell parameters from 25 reflections
b = 10.896 (4) Å	θ = 10.2–14.1°
c = 11.594 (5) Å	µ = 0.52 mm^−1
α = 107.61 (3)°	T = 293 K
β = 97.39 (3)°	Block, colourless
γ = 111.30 (3)°	0.21 × 0.19 × 0.16 mm
V = 872.7 (7) Å^3

Data collection

Nonius MACH3 sealed-tube diffractometer	2474 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.011
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω/2θ scans	h = −1→9
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
Tmin = 0.902, Tmax = 0.926	l = −13→13
3775 measured reflections	3 standard reflections every 60 min
3065 independent reflections	intensity decay: none

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0416P)^2 + 0.338P] where P = (Fo^2 + 2Fc^2)/3
3065 reflections	(Δ/σ)max = 0.001
248 parameters	Δρmax = 0.24 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	Occ. (<1)
N1	−0.2519 (2)	0.29966 (19)	0.58224 (16)	0.0407 (4)
H1	−0.3676	0.2684	0.5479	0.049*
C2	−0.1398 (3)	0.4370 (2)	0.61258 (18)	0.0394 (5)
C21	−0.2287 (3)	0.5311 (3)	0.5953 (2)	0.0544 (6)
H21A	−0.2926	0.5471	0.6587	0.082*
H21B	−0.3149	0.4862	0.5137	0.082*
H21C	−0.1359	0.6204	0.6025	0.082*
N3	0.0388 (2)	0.48969 (18)	0.65775 (16)	0.0393 (4)
C4	0.1130 (3)	0.4014 (2)	0.67884 (18)	0.0354 (4)
N41	0.2928 (2)	0.45598 (19)	0.72131 (17)	0.0458 (4)
H41A	0.3585	0.5437	0.7346	0.055*
H41B	0.3452	0.4041	0.7359	0.055*
C5	−0.0021 (3)	0.2568 (2)	0.65576 (17)	0.0337 (4)
C6	−0.1851 (3)	0.2102 (2)	0.60504 (18)	0.0370 (4)
H6	−0.2649	0.1159	0.5859	0.044*
C7	0.0708 (3)	0.1562 (2)	0.67989 (18)	0.0363 (4)
H7A	−0.0201	0.0594	0.6310	0.044*
H7B	0.1814	0.1695	0.6513	0.044*
N8	0.1148 (2)	0.17545 (16)	0.81449 (15)	0.0315 (3)
C9	0.1692 (3)	0.0820 (2)	0.85155 (19)	0.0365 (4)
C91	0.1703 (3)	−0.0435 (2)	0.7539 (2)	0.0543 (6)
H91A	0.2660	−0.0117	0.7143	0.082*
H91B	0.0531	−0.0951	0.6920	0.082*
H91C	0.1925	−0.1045	0.7926	0.082*
C10	0.2123 (3)	0.1217 (2)	0.9777 (2)	0.0392 (5)
S11	0.18620 (8)	0.27557 (6)	1.04821 (5)	0.04205 (15)
C12	0.1154 (3)	0.2801 (2)	0.90818 (18)	0.0356 (4)
H12	0.0803	0.3493	0.8977	0.043*
C13	0.2753 (3)	0.0508 (2)	1.0559 (2)	0.0493 (5)
H13A	0.1819	0.0166	1.0975	0.059*
H13B	0.2863	−0.0311	1.0006	0.059*
C14	0.4567 (3)	0.1467 (3)	1.1534 (2)	0.0521 (6)
H14A	0.4910	0.0933	1.1978	0.063*
H14B	0.5516	0.1798	1.1124	0.063*
O15	0.4466 (2)	0.26551 (17)	1.24080 (17)	0.0539 (4)
H15	0.412 (4)	0.244 (3)	1.298 (3)	0.079 (10)*
Cl1	0.65996 (7)	0.32484 (5)	0.88251 (5)	0.04121 (14)
O11	0.8239 (2)	0.42779 (16)	0.87423 (15)	0.0507 (4)
O12	0.5156 (8)	0.2984 (9)	0.7803 (5)	0.0760 (17)	0.63
O12'	0.5013 (17)	0.3274 (16)	0.8330 (14)	0.139 (7)	0.37
O13	0.6123 (9)	0.3805 (7)	0.9943 (6)	0.0859 (19)	0.63
O13'	0.6878 (18)	0.3501 (17)	1.0096 (11)	0.142 (6)	0.37
O14	0.6728 (14)	0.1959 (11)	0.8660 (11)	0.096 (3)	0.63
O14'	0.654 (3)	0.1938 (18)	0.830 (2)	0.133 (7)	0.37
Cl2	−0.66976 (7)	0.16989 (6)	0.45121 (5)	0.04722 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0301 (9)	0.0499 (10)	0.0415 (10)	0.0163 (8)	0.0041 (7)	0.0194 (8)
C2	0.0418 (12)	0.0488 (12)	0.0329 (10)	0.0220 (10)	0.0098 (9)	0.0192 (9)
C21	0.0588 (15)	0.0609 (15)	0.0583 (14)	0.0358 (12)	0.0143 (12)	0.0296 (12)
N3	0.0396 (10)	0.0391 (9)	0.0409 (9)	0.0147 (8)	0.0099 (8)	0.0202 (8)
C4	0.0324 (10)	0.0402 (10)	0.0323 (10)	0.0129 (9)	0.0068 (8)	0.0159 (8)
N41	0.0329 (9)	0.0421 (10)	0.0571 (11)	0.0090 (8)	0.0033 (8)	0.0237 (9)
C5	0.0324 (10)	0.0376 (10)	0.0317 (10)	0.0151 (8)	0.0069 (8)	0.0143 (8)
C6	0.0325 (10)	0.0399 (11)	0.0362 (10)	0.0132 (9)	0.0060 (8)	0.0151 (9)
C7	0.0328 (10)	0.0375 (10)	0.0360 (10)	0.0151 (8)	0.0054 (8)	0.0118 (8)
N8	0.0249 (8)	0.0326 (8)	0.0381 (9)	0.0136 (7)	0.0062 (7)	0.0140 (7)
C9	0.0266 (10)	0.0327 (10)	0.0475 (12)	0.0129 (8)	0.0028 (8)	0.0143 (9)
C91	0.0560 (14)	0.0459 (13)	0.0588 (14)	0.0319 (11)	0.0008 (11)	0.0103 (11)
C10	0.0345 (11)	0.0350 (10)	0.0492 (12)	0.0162 (9)	0.0054 (9)	0.0182 (9)
S11	0.0513 (3)	0.0433 (3)	0.0386 (3)	0.0271 (3)	0.0085 (2)	0.0176 (2)
C12	0.0353 (11)	0.0363 (10)	0.0414 (11)	0.0197 (9)	0.0091 (9)	0.0179 (9)
C13	0.0525 (14)	0.0416 (12)	0.0579 (14)	0.0232 (11)	0.0056 (11)	0.0243 (11)
C14	0.0431 (13)	0.0663 (15)	0.0646 (15)	0.0294 (12)	0.0127 (11)	0.0410 (13)
O15	0.0596 (11)	0.0472 (9)	0.0511 (10)	0.0146 (8)	0.0073 (8)	0.0267 (8)
Cl1	0.0369 (3)	0.0433 (3)	0.0442 (3)	0.0162 (2)	0.0102 (2)	0.0189 (2)
O11	0.0373 (8)	0.0485 (9)	0.0635 (10)	0.0139 (7)	0.0157 (7)	0.0218 (8)
O12	0.031 (3)	0.121 (4)	0.070 (2)	0.026 (2)	−0.0013 (17)	0.043 (2)
O12'	0.040 (4)	0.144 (11)	0.31 (2)	0.054 (6)	0.055 (10)	0.162 (14)
O13	0.097 (4)	0.077 (2)	0.067 (4)	0.021 (3)	0.049 (3)	0.013 (2)
O13'	0.134 (11)	0.186 (13)	0.052 (4)	−0.003 (8)	0.025 (6)	0.062 (7)
O14	0.071 (3)	0.057 (4)	0.175 (7)	0.032 (3)	0.013 (4)	0.067 (4)
O14'	0.160 (15)	0.043 (5)	0.215 (16)	0.045 (8)	0.124 (12)	0.042 (8)
Cl2	0.0364 (3)	0.0506 (3)	0.0487 (3)	0.0116 (2)	0.0057 (2)	0.0217 (2)

Geometric parameters (Å, º)

N1—C2	1.341 (3)	C9—C91	1.492 (3)
N1—C6	1.346 (3)	C91—H91A	0.9600
N1—H1	0.8600	C91—H91B	0.9600
C2—N3	1.306 (3)	C91—H91C	0.9600
C2—C21	1.493 (3)	C10—C13	1.506 (3)
C21—H21A	0.9600	C10—S11	1.731 (2)
C21—H21B	0.9600	S11—C12	1.672 (2)
C21—H21C	0.9600	C12—H12	0.9300
N3—C4	1.367 (3)	C13—C14	1.505 (3)
C4—N41	1.310 (3)	C13—H13A	0.9700
C4—C5	1.426 (3)	C13—H13B	0.9700
N41—H41A	0.8600	C14—O15	1.419 (3)
N41—H41B	0.8600	C14—H14A	0.9700
C5—C6	1.355 (3)	C14—H14B	0.9700
C5—C7	1.496 (3)	O15—H15	0.82 (3)
C6—H6	0.9300	Cl1—O12'	1.348 (12)
C7—N8	1.487 (3)	Cl1—O14'	1.352 (15)
C7—H7A	0.9700	Cl1—O13'	1.387 (11)
C7—H7B	0.9700	Cl1—O14	1.404 (9)
N8—C12	1.314 (2)	Cl1—O13	1.420 (6)
N8—C9	1.398 (2)	Cl1—O11	1.4281 (17)
C9—C10	1.351 (3)	Cl1—O12	1.429 (6)
C2—N1—C6	120.67 (18)	H91B—C91—H91C	109.5
C2—N1—H1	119.7	C9—C10—C13	128.73 (19)
C6—N1—H1	119.7	C9—C10—S11	110.62 (15)
N3—C2—N1	122.93 (19)	C13—C10—S11	120.64 (17)
N3—C2—C21	120.2 (2)	C12—S11—C10	91.10 (10)
N1—C2—C21	116.84 (19)	N8—C12—S11	112.71 (14)
C2—C21—H21A	109.5	N8—C12—H12	123.6
C2—C21—H21B	109.5	S11—C12—H12	123.6
H21A—C21—H21B	109.5	C14—C13—C10	113.82 (19)
C2—C21—H21C	109.5	C14—C13—H13A	108.8
H21A—C21—H21C	109.5	C10—C13—H13A	108.8
H21B—C21—H21C	109.5	C14—C13—H13B	108.8
C2—N3—C4	118.18 (18)	C10—C13—H13B	108.8
N41—C4—N3	116.95 (18)	H13A—C13—H13B	107.7
N41—C4—C5	122.22 (19)	O15—C14—C13	111.39 (19)
N3—C4—C5	120.83 (18)	O15—C14—H14A	109.3
C4—N41—H41A	120.0	C13—C14—H14A	109.3
C4—N41—H41B	120.0	O15—C14—H14B	109.3
H41A—N41—H41B	120.0	C13—C14—H14B	109.3
C6—C5—C4	116.83 (18)	H14A—C14—H14B	108.0
C6—C5—C7	119.90 (18)	C14—O15—H15	109 (2)
C4—C5—C7	123.22 (17)	O12'—Cl1—O14'	110.4 (11)
N1—C6—C5	120.37 (19)	O12'—Cl1—O13'	112.2 (8)
N1—C6—H6	119.8	O14'—Cl1—O13'	104.5 (11)
C5—C6—H6	119.8	O12'—Cl1—O14	121.3 (8)
N8—C7—C5	113.38 (16)	O13'—Cl1—O14	87.4 (8)
N8—C7—H7A	108.9	O12'—Cl1—O13	80.0 (7)
C5—C7—H7A	108.9	O14'—Cl1—O13	127.8 (9)
N8—C7—H7B	108.9	O14—Cl1—O13	113.6 (6)
C5—C7—H7B	108.9	O12'—Cl1—O11	115.4 (5)
H7A—C7—H7B	107.7	O14'—Cl1—O11	109.2 (9)
C12—N8—C9	114.03 (16)	O13'—Cl1—O11	104.6 (6)
C12—N8—C7	125.33 (16)	O14—Cl1—O11	111.3 (5)
C9—N8—C7	120.58 (16)	O13—Cl1—O11	111.3 (3)
C10—C9—N8	111.52 (17)	O14'—Cl1—O12	92.4 (10)
C10—C9—C91	129.09 (19)	O13'—Cl1—O12	137.7 (6)
N8—C9—C91	119.38 (19)	O14—Cl1—O12	107.6 (5)
C9—C91—H91A	109.5	O13—Cl1—O12	106.6 (3)
C9—C91—H91B	109.5	O11—Cl1—O12	105.9 (3)
H91A—C91—H91B	109.5	Cl1—O12'—O13	51.8 (5)
C9—C91—H91C	109.5	Cl1—O13—O12'	48.2 (4)
H91A—C91—H91C	109.5
C6—N1—C2—N3	4.4 (3)	O13'—Cl1—O12—O12'	19 (2)
C6—N1—C2—C21	−174.23 (19)	O14—Cl1—O12—O12'	125.6 (19)
N1—C2—N3—C4	−2.3 (3)	O13—Cl1—O12—O12'	3 (2)
C21—C2—N3—C4	176.23 (19)	O11—Cl1—O12—O12'	−115.2 (18)
C2—N3—C4—N41	178.41 (18)	Cl1—O12—O12'—O13	−4 (2)
C2—N3—C4—C5	−1.9 (3)	O14'—Cl1—O12'—O12	−50 (2)
N41—C4—C5—C6	−176.31 (18)	O13'—Cl1—O12'—O12	−166.0 (17)
N3—C4—C5—C6	4.0 (3)	O14—Cl1—O12'—O12	−65 (2)
N41—C4—C5—C7	1.2 (3)	O13—Cl1—O12'—O12	−176.7 (19)
N3—C4—C5—C7	−178.53 (17)	O11—Cl1—O12'—O12	74 (2)
C2—N1—C6—C5	−2.0 (3)	O14'—Cl1—O12'—O13	126.7 (10)
C4—C5—C6—N1	−2.0 (3)	O13'—Cl1—O12'—O13	10.7 (10)
C7—C5—C6—N1	−179.59 (18)	O14—Cl1—O12'—O13	111.7 (8)
C6—C5—C7—N8	−103.4 (2)	O11—Cl1—O12'—O13	−108.9 (4)
C4—C5—C7—N8	79.2 (2)	O12—Cl1—O12'—O13	176.7 (19)
C5—C7—N8—C12	−8.6 (3)	O12'—Cl1—O13—O13'	162.0 (16)
C5—C7—N8—C9	174.45 (16)	O14'—Cl1—O13—O13'	53.9 (19)
C12—N8—C9—C10	−0.5 (2)	O14—Cl1—O13—O13'	42.1 (16)
C7—N8—C9—C10	176.71 (17)	O11—Cl1—O13—O13'	−84.5 (15)
C12—N8—C9—C91	178.61 (19)	O12—Cl1—O13—O13'	160.5 (14)
C7—N8—C9—C91	−4.2 (3)	O14'—Cl1—O13—O12'	−108.1 (12)
N8—C9—C10—C13	179.5 (2)	O13'—Cl1—O13—O12'	−162.0 (16)
C91—C9—C10—C13	0.5 (4)	O14—Cl1—O13—O12'	−119.9 (7)
N8—C9—C10—S11	−0.5 (2)	O11—Cl1—O13—O12'	113.5 (6)
C91—C9—C10—S11	−179.48 (19)	O12—Cl1—O13—O12'	−1.5 (9)
C9—C10—S11—C12	0.98 (16)	O12—O12'—O13—O13'	−14 (4)
C13—C10—S11—C12	−178.98 (18)	Cl1—O12'—O13—O13'	−19.0 (17)
C9—N8—C12—S11	1.3 (2)	O12—O12'—O13—Cl1	5 (3)
C7—N8—C12—S11	−175.79 (14)	O12'—O13—O13'—Cl1	14.9 (13)
C10—S11—C12—N8	−1.30 (16)	O12'—Cl1—O13'—O13	−19.1 (17)
C9—C10—C13—C14	123.7 (3)	O14'—Cl1—O13'—O13	−138.7 (15)
S11—C10—C13—C14	−56.3 (3)	O14—Cl1—O13'—O13	−142.0 (14)
C10—C13—C14—O15	61.2 (3)	O11—Cl1—O13'—O13	106.6 (13)
O14'—Cl1—O12—O12'	134 (2)	O12—Cl1—O13'—O13	−28 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.86	2.24	3.100 (2)	176
N41—H41A···O15^i	0.86	2.01	2.854 (3)	168
N41—H41B···O12	0.86	2.19	3.048 (8)	172
N41—H41B···O12′	0.86	2.13	2.955 (12)	161
O15—H15···Cl2^ii	0.82 (3)	2.24 (3)	3.056 (2)	174 (3)
C12—H12···O11^i	0.93	2.78	3.229 (3)	111
C12—H12···O13^i	0.93	2.84	3.273 (7)	110
C6—H6···Cl2^iii	0.93	2.85	3.687 (3)	151

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