7-Chloro-2-methyl-3-methyl­amino-2H-1,2,4-benzo­thia­diazine 1,1-dioxide

The title compound, C₉H₁₀ClN₃O₂S, was prepared for structural comparison with analogous products known as myorelaxants and inhibitors of insulin release. The 2H-tautomeric form is imposed by the presence of a methyl group in the 2-position. There are four independent mol­ecules (A, B, C and D) in the asymmetric unit which have almost the same geometry. The C-N distances in the four thia­diazine rings [C-N single- and double-bond mean values of 1.405 (3) and 1.304 (3) Å, respectively] may serve as reference to characterize the 2H-tautomeric form in analogous structures. The NH group of the methyl­amino substituent of each mol­ecule participates in an intermolecular hydrogen bond with a sulfoxide O atom acting as acceptor. These four independent hydrogen bonds give rise to two types of infinite chains, both stretching along the a axis and having molecular compositions of ...ABABAB... and ...CDCDCD...

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.106
• Data-to-parameter ratio = 10.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



THETM_01  Alert B The value of sine(theta_max)/wavelength is less than 0.575
          Calculated sin(theta_max)/wavelength =    0.5566


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           23.30
         From the CIF: _reflns_number_total               6008
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         6497
         Completeness (_total/calc)             92.47%
          Alert C: < 95% complete


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The title compound is a structural analogue of diazoxide (7-chloro-3-methyl-4H-1,2,4-benzothiadiazine 1,1-dioxide; Bandoli & Nicolini, 1977) and other 3-alkylamino-7-chloro-4H-1,2,4-benzothiadiazine 1,1-dioxides known to exert important biological properties (smooth muscle myorelaxants and inhibitors of insulin release) like 7-chloro-(R/S)-3-[1-(cyclohexyl)ethylamino]-4H-1,2,4-benzothiadiazine 1,1-dioxide (Dupont et al., 1999). A typical 2H-tautomeric form results from the presence of the metyl substituent in the 2-position of the thiadiazine ring. There are four independent molecules (A, B, C and D) in the asymmetric unit with essentially identical geometry: even the most flexible N2—C3—N11—C12 torsion angles do not deviate from the mean value of -172.7 (2)° by more than 2.1 (2)°. The C3—N2 (A—D) distances are within the range 1.402 (3)–1.408 (3) Å, and C3—N4 within 1.301 (3)–1.309 (3) Å. They are useful references with respect to C3—N2 single- and C3—N4 double-bond length in such a ring system. The corresponding distances in diazoxide are 1.300 (9) and 1.335 (9) Å, respectively, and 1.325 (5) and 1.368 (4) Å in 7-chloro-(S)-3-[1-(cyclohexyl)ethylamino]-4H-1,2,4-benzothiadiazine 1,1-dioxide (Dupont et al., 1999). Typical values for C3—N2 double-bond [1.326 (4)] and C3—N4 single-bond [1.381 (4) Å] have been observed in the molecular structure of 3-isopropylamino-4-methyl-4H-pyrido[4,3 e][1,2,4]thiadiazine 1,1-dioxide (Dupont et al., 1996) where a 4H-tautomeric form is imposed by a 4-methyl substituent.

The crystal packing is dominated by two symmetry independent types of hydrogen-bonded infinite chains. The chains of the first type are made up of alternating A and B molecules linked via N—H···O bonds formed by the methylamino NH groups and sulfoxide oxygen atoms. The chains of the second type are built in the analogous way and involve alternating C and D molecules. Both chains are stretching along the shortest axis, i.e. a, of the unit cell.

S2. Experimental

A solution of 7-chloro-2-methyl-3-methylsulfanyl-2H-1,2,4-benzothiadiazine 1,1-dioxide [obtained as described in Di Bella et al. (1973)] (0.6 g) in a 33% w/v solution of methylamine in methanol (15 ml) was heated in a closed vessel at 373 K for 4 h. The excess solvent and amine were removed by distillation under reduced pressure and the resulting residue was suspended in distilled water (40 ml) and stirred for 15 min. The insoluble material (final compound) was collected by filtration, washed with water and recrystallized from the methanol–water (1:2) mixture (yield: 60%; m.p. 456–457 K)..

S3. Refinement

The diffraction data are limited because of a rather poor quality of the crystal. The data collection was stopped when the R_int of the equivalent reflections became too high. All H atoms [with the exception of the nitrogen-bound atoms H11(A—D)] were included in the refinement in the riding model approximation with isotropic displacement parameters fixed at 1.2U_eq of the parent atom (1.5U_eq for methyl H atoms). The H11(A—D) atoms were refined isotropically (their displacement parameters being fixed at 1.2U_eq of the corresponding nitogen atom). The N—H distances are in the range 0.78–0.86 Å. Even though their geometrical similarity and peculiar relative disposition suggest that the crystallographically independent molecules are pairwise related by the local symmetry elements, the thorough check for additional genuine crystal symmetry yielded no result.

Computing details

Data collection: MAR software; cell refinement: marHKL software; data reduction: marHKL software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure with atom-labelling scheme of molecule A. Displacement ellipsoids are shown at 50% probability levels and H atoms are drawn as small circles of arbitrary radii.

7-chloro-2-methyl-3-methylamino-2H-1,2,4-benzothiadiazine 1,1-dioxide

Crystal data

C9H10ClN3O2S	F(000) = 2144
Mr = 259.71	Dx = 1.534 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71069 Å
a = 10.096 (1) Å	Cell parameters from 219 reflections
b = 26.316 (2) Å	θ = 2.6–23.3°
c = 16.927 (2) Å	µ = 0.51 mm^−1
β = 90.070 (2)°	T = 293 K
V = 4497.3 (8) Å^3	Prism, colourless
Z = 16	0.30 × 0.30 × 0.30 mm

Data collection

MAR345 image-plate diffractometer	4970 reflections with I > 2σ(I)
Radiation source: RU200 rotating anode	Rint = 0.039
Graphite monochromator	θmax = 23.3°, θmin = 2.6°
Detector resolution: 6.66 pixels mm^-1	h = 0→10
119 images, 130 mm, ΔΦ 3° scans	k = 0→29
38152 measured reflections	l = −18→18
6008 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: H atoms were placed at standard calculated positions, except atoms H(N11) which were obtained from difference map.
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.064P)^2 + 0.5031P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.002
6008 reflections	Δρmax = 0.25 e Å^−3
598 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0065 (4)

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
S1A	0.73080 (5)	0.313750 (19)	0.06113 (3)	0.03802 (17)
O1A	0.65228 (15)	0.31544 (6)	−0.00935 (10)	0.0526 (4)
O2A	0.73479 (16)	0.26694 (5)	0.10321 (10)	0.0531 (4)
N2A	0.88417 (16)	0.33030 (6)	0.04059 (11)	0.0387 (4)
C3A	0.9039 (2)	0.38088 (7)	0.01607 (13)	0.0347 (5)
N4A	0.83590 (17)	0.41918 (6)	0.04278 (11)	0.0385 (4)
C5A	0.7424 (2)	0.41131 (7)	0.10169 (13)	0.0355 (5)
C6A	0.6964 (2)	0.45310 (8)	0.14525 (14)	0.0431 (6)
H6A	0.7285	0.4854	0.1337	0.052*
C7A	0.6051 (2)	0.44725 (8)	0.20447 (14)	0.0458 (6)
H7A	0.5758	0.4755	0.2323	0.055*
C8A	0.5559 (2)	0.39952 (9)	0.22323 (13)	0.0431 (6)
C9A	0.5951 (2)	0.35730 (8)	0.18139 (13)	0.0428 (5)
H9A	0.5610	0.3253	0.1928	0.051*
C10A	0.6877 (2)	0.36406 (7)	0.12133 (13)	0.0358 (5)
N11A	1.00236 (18)	0.38852 (7)	−0.03531 (12)	0.0422 (5)
H11A	1.034 (2)	0.3641 (9)	−0.0535 (14)	0.051*
C12A	1.0459 (2)	0.43882 (9)	−0.05774 (14)	0.0501 (6)
H121	0.9754	0.4561	−0.0847	0.075*
H122	1.1211	0.4361	−0.0922	0.075*
H123	1.0702	0.4576	−0.0113	0.075*
C13A	0.9800 (2)	0.28951 (9)	0.02487 (17)	0.0631 (7)
H131	0.9690	0.2776	−0.0283	0.095*
H132	0.9654	0.2620	0.0610	0.095*
H133	1.0684	0.3023	0.0316	0.095*
Cl1A	0.44215 (6)	0.39293 (3)	0.29959 (4)	0.0644 (2)
S1B	−0.23939 (5)	0.689769 (19)	0.20463 (4)	0.03986 (18)
O1B	−0.16326 (15)	0.68925 (6)	0.13292 (10)	0.0525 (4)
O2B	−0.25017 (15)	0.73676 (5)	0.24575 (10)	0.0550 (4)
N2B	−0.39074 (16)	0.66897 (6)	0.18613 (11)	0.0392 (4)
C3B	−0.4006 (2)	0.61801 (7)	0.16201 (13)	0.0344 (5)
N4B	−0.32518 (17)	0.58175 (6)	0.18860 (11)	0.0377 (4)
C5B	−0.2314 (2)	0.59229 (7)	0.24640 (13)	0.0360 (5)
C6B	−0.1741 (2)	0.55231 (8)	0.28929 (13)	0.0431 (6)
H6B	−0.1982	0.5191	0.2775	0.052*
C7B	−0.0836 (2)	0.56106 (9)	0.34807 (14)	0.0481 (6)
H7B	−0.0475	0.5338	0.3756	0.058*
C8B	−0.0454 (2)	0.61018 (9)	0.36680 (14)	0.0469 (6)
C9B	−0.0943 (2)	0.65075 (9)	0.32491 (13)	0.0445 (6)
H9B	−0.0672	0.6837	0.3363	0.053*
C10B	−0.1854 (2)	0.64117 (8)	0.26504 (13)	0.0373 (5)
N11B	−0.49807 (19)	0.60782 (7)	0.11092 (12)	0.0432 (5)
H11B	−0.534 (2)	0.6322 (9)	0.0900 (15)	0.052*
C12B	−0.5316 (2)	0.55651 (9)	0.08651 (15)	0.0525 (6)
H124	−0.4598	0.5424	0.0565	0.079*
H125	−0.6102	0.5573	0.0545	0.079*
H126	−0.5471	0.5359	0.1324	0.079*
C13B	−0.4944 (2)	0.70673 (8)	0.17262 (16)	0.0553 (7)
H134	−0.4888	0.7190	0.1193	0.083*
H135	−0.4830	0.7345	0.2087	0.083*
H136	−0.5796	0.6914	0.1809	0.083*
Cl1B	0.06561 (6)	0.62083 (3)	0.44353 (4)	0.0696 (2)
S1C	0.47269 (5)	0.683672 (19)	0.43689 (3)	0.03947 (18)
O1C	0.39406 (16)	0.68284 (6)	0.50731 (10)	0.0529 (4)
O2C	0.47578 (16)	0.72969 (6)	0.39342 (10)	0.0565 (5)
N2C	0.62665 (17)	0.66763 (6)	0.45840 (11)	0.0402 (4)
C3C	0.6481 (2)	0.61749 (7)	0.48337 (13)	0.0361 (5)
N4C	0.58043 (17)	0.57849 (6)	0.45763 (11)	0.0402 (4)
C5C	0.4858 (2)	0.58533 (8)	0.39925 (13)	0.0376 (5)
C6C	0.4384 (2)	0.54298 (8)	0.35812 (14)	0.0457 (6)
H6C	0.4698	0.5108	0.3712	0.055*
C7C	0.3459 (2)	0.54785 (9)	0.29853 (14)	0.0508 (6)
H7C	0.3158	0.5191	0.2720	0.061*
C8C	0.2977 (2)	0.59518 (9)	0.27803 (14)	0.0469 (6)
C9C	0.3371 (2)	0.63789 (9)	0.31803 (14)	0.0461 (6)
H9C	0.3028	0.6697	0.3054	0.055*
C10C	0.4303 (2)	0.63221 (8)	0.37840 (13)	0.0382 (5)
N11C	0.74755 (18)	0.61037 (7)	0.53443 (12)	0.0442 (5)
H11C	0.779 (2)	0.6373 (9)	0.5527 (14)	0.053*
C12C	0.7926 (2)	0.56032 (9)	0.55669 (15)	0.0524 (6)
H127	0.7253	0.5437	0.5872	0.079*
H128	0.8720	0.5632	0.5877	0.079*
H129	0.8106	0.5408	0.5100	0.079*
C13C	0.7195 (2)	0.70916 (9)	0.47544 (17)	0.0600 (7)
H137	0.7075	0.7204	0.5289	0.090*
H138	0.7029	0.7369	0.4400	0.090*
H139	0.8086	0.6973	0.4685	0.090*
Cl1C	0.18374 (7)	0.60094 (3)	0.20151 (4)	0.0697 (2)
S1D	0.02320 (5)	0.313087 (19)	0.29261 (3)	0.04001 (18)
O1D	0.10049 (15)	0.31330 (6)	0.36374 (10)	0.0527 (4)
O2D	0.01531 (16)	0.26663 (5)	0.25003 (10)	0.0554 (5)
N2D	−0.12931 (16)	0.33185 (6)	0.31213 (10)	0.0388 (4)
C3D	−0.1436 (2)	0.38230 (7)	0.33810 (13)	0.0342 (5)
N4D	−0.07141 (16)	0.41999 (6)	0.31175 (11)	0.0381 (4)
C5D	0.0215 (2)	0.41125 (7)	0.25310 (13)	0.0365 (5)
C6D	0.0729 (2)	0.45212 (8)	0.20993 (14)	0.0463 (6)
H6D	0.0442	0.4849	0.2215	0.056*
C7D	0.1645 (2)	0.44526 (9)	0.15092 (14)	0.0510 (6)
H7D	0.1968	0.4732	0.1233	0.061*
C8D	0.2089 (2)	0.39695 (10)	0.13245 (14)	0.0492 (6)
C9D	0.1646 (2)	0.35526 (9)	0.17372 (14)	0.0468 (6)
H9D	0.1955	0.3228	0.1622	0.056*
C10D	0.0723 (2)	0.36322 (8)	0.23319 (13)	0.0397 (5)
N11D	−0.23932 (18)	0.39073 (7)	0.39063 (12)	0.0419 (5)
H11D	−0.278 (2)	0.3649 (9)	0.4113 (14)	0.050*
C12D	−0.2739 (2)	0.44116 (9)	0.41822 (15)	0.0536 (6)
H12A	−0.1998	0.4557	0.4457	0.080*
H12B	−0.3483	0.4390	0.4534	0.080*
H12C	−0.2966	0.4622	0.3739	0.080*
C13D	−0.2284 (2)	0.29255 (8)	0.32816 (16)	0.0569 (7)
H13A	−0.2197	0.2812	0.3818	0.085*
H13B	−0.2149	0.2644	0.2931	0.085*
H13C	−0.3154	0.3063	0.3201	0.085*
Cl1D	0.32229 (7)	0.38835 (3)	0.05652 (4)	0.0739 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1A	0.0420 (3)	0.0297 (3)	0.0424 (4)	−0.0012 (2)	−0.0026 (3)	−0.0017 (2)
O1A	0.0566 (10)	0.0529 (10)	0.0483 (11)	−0.0019 (7)	−0.0146 (8)	−0.0101 (7)
O2A	0.0619 (10)	0.0308 (9)	0.0667 (12)	−0.0022 (7)	0.0035 (8)	0.0065 (7)
N2A	0.0387 (10)	0.0297 (9)	0.0478 (12)	0.0058 (7)	0.0032 (8)	−0.0001 (8)
C3A	0.0390 (12)	0.0321 (12)	0.0331 (14)	0.0012 (9)	−0.0041 (9)	−0.0011 (9)
N4A	0.0417 (10)	0.0339 (10)	0.0399 (12)	0.0022 (8)	0.0046 (8)	−0.0001 (8)
C5A	0.0377 (12)	0.0337 (12)	0.0351 (14)	0.0031 (9)	−0.0026 (10)	0.0004 (9)
C6A	0.0480 (13)	0.0340 (12)	0.0474 (16)	0.0043 (9)	0.0022 (11)	−0.0033 (10)
C7A	0.0489 (14)	0.0467 (14)	0.0419 (16)	0.0080 (10)	0.0002 (11)	−0.0097 (11)
C8A	0.0382 (13)	0.0562 (15)	0.0350 (15)	0.0036 (10)	0.0018 (10)	−0.0036 (11)
C9A	0.0408 (13)	0.0471 (14)	0.0405 (15)	−0.0049 (10)	−0.0026 (10)	0.0043 (11)
C10A	0.0367 (12)	0.0360 (12)	0.0347 (14)	0.0026 (9)	−0.0017 (9)	0.0008 (9)
N11A	0.0462 (11)	0.0372 (11)	0.0432 (13)	0.0017 (8)	0.0095 (9)	−0.0033 (9)
C12A	0.0561 (15)	0.0465 (14)	0.0477 (17)	−0.0045 (11)	0.0086 (12)	0.0032 (11)
C13A	0.0641 (16)	0.0413 (14)	0.084 (2)	0.0182 (12)	0.0193 (14)	0.0006 (13)
Cl1A	0.0530 (4)	0.0894 (5)	0.0510 (5)	−0.0038 (3)	0.0163 (3)	−0.0065 (3)
S1B	0.0430 (3)	0.0296 (3)	0.0471 (4)	−0.0022 (2)	0.0059 (3)	−0.0009 (2)
O1B	0.0577 (10)	0.0488 (10)	0.0510 (11)	−0.0034 (7)	0.0157 (8)	0.0076 (7)
O2B	0.0624 (10)	0.0323 (9)	0.0705 (13)	−0.0019 (7)	0.0017 (9)	−0.0101 (8)
N2B	0.0382 (10)	0.0312 (10)	0.0482 (12)	0.0043 (7)	0.0008 (8)	−0.0015 (8)
C3B	0.0363 (12)	0.0322 (12)	0.0347 (14)	−0.0017 (9)	0.0047 (10)	0.0010 (9)
N4B	0.0419 (10)	0.0311 (10)	0.0399 (12)	0.0008 (8)	−0.0006 (8)	−0.0009 (8)
C5B	0.0382 (12)	0.0342 (12)	0.0358 (14)	0.0003 (9)	0.0051 (10)	−0.0026 (9)
C6B	0.0499 (14)	0.0371 (13)	0.0424 (16)	0.0022 (10)	0.0018 (11)	0.0045 (10)
C7B	0.0473 (14)	0.0547 (15)	0.0424 (16)	0.0052 (11)	−0.0006 (11)	0.0087 (11)
C8B	0.0408 (13)	0.0618 (16)	0.0380 (16)	0.0001 (11)	−0.0002 (10)	−0.0021 (11)
C9B	0.0441 (13)	0.0474 (14)	0.0421 (15)	−0.0062 (10)	0.0033 (10)	−0.0087 (11)
C10B	0.0367 (12)	0.0364 (12)	0.0388 (14)	0.0007 (9)	0.0048 (10)	−0.0036 (9)
N11B	0.0461 (11)	0.0390 (12)	0.0445 (14)	0.0013 (8)	−0.0051 (9)	0.0035 (9)
C12B	0.0590 (15)	0.0454 (14)	0.0529 (17)	−0.0097 (11)	−0.0096 (12)	−0.0033 (11)
C13B	0.0596 (15)	0.0428 (14)	0.0635 (18)	0.0174 (11)	−0.0120 (12)	−0.0001 (12)
Cl1B	0.0540 (4)	0.1031 (6)	0.0516 (5)	−0.0078 (3)	−0.0142 (3)	−0.0016 (4)
S1C	0.0420 (3)	0.0340 (3)	0.0424 (4)	0.0011 (2)	0.0040 (3)	−0.0003 (2)
O1C	0.0566 (10)	0.0547 (10)	0.0475 (11)	0.0024 (7)	0.0154 (8)	−0.0085 (8)
O2C	0.0656 (11)	0.0366 (9)	0.0673 (13)	0.0019 (7)	−0.0024 (9)	0.0107 (8)
N2C	0.0401 (10)	0.0337 (10)	0.0467 (12)	−0.0066 (8)	0.0003 (8)	−0.0008 (8)
C3C	0.0389 (12)	0.0343 (12)	0.0353 (14)	−0.0004 (9)	0.0032 (10)	−0.0010 (9)
N4C	0.0419 (10)	0.0372 (10)	0.0415 (12)	−0.0030 (8)	−0.0019 (8)	−0.0017 (8)
C5C	0.0378 (12)	0.0387 (13)	0.0363 (14)	−0.0031 (9)	0.0033 (10)	−0.0009 (10)
C6C	0.0485 (14)	0.0397 (13)	0.0489 (16)	−0.0050 (10)	−0.0008 (11)	−0.0075 (11)
C7C	0.0478 (14)	0.0570 (16)	0.0476 (17)	−0.0099 (11)	0.0016 (11)	−0.0127 (12)
C8C	0.0381 (13)	0.0659 (17)	0.0365 (16)	−0.0060 (11)	−0.0012 (10)	−0.0050 (11)
C9C	0.0418 (13)	0.0550 (15)	0.0414 (16)	0.0027 (10)	0.0032 (11)	0.0059 (11)
C10C	0.0374 (12)	0.0420 (13)	0.0351 (14)	−0.0035 (9)	0.0046 (9)	0.0001 (10)
N11C	0.0479 (12)	0.0416 (12)	0.0433 (13)	−0.0038 (8)	−0.0072 (9)	−0.0034 (9)
C12C	0.0536 (15)	0.0522 (15)	0.0514 (17)	0.0070 (11)	−0.0077 (12)	0.0033 (12)
C13C	0.0605 (16)	0.0434 (14)	0.076 (2)	−0.0160 (11)	−0.0121 (13)	−0.0044 (13)
Cl1C	0.0532 (4)	0.1048 (6)	0.0509 (5)	−0.0024 (3)	−0.0146 (3)	−0.0059 (4)
S1D	0.0425 (3)	0.0327 (3)	0.0448 (4)	0.0039 (2)	−0.0041 (3)	−0.0021 (2)
O1D	0.0567 (10)	0.0512 (10)	0.0502 (11)	0.0064 (7)	−0.0162 (8)	0.0047 (8)
O2D	0.0653 (11)	0.0342 (9)	0.0666 (12)	0.0046 (7)	0.0006 (9)	−0.0134 (8)
N2D	0.0398 (10)	0.0316 (10)	0.0451 (12)	−0.0035 (7)	0.0006 (8)	−0.0007 (8)
C3D	0.0369 (12)	0.0323 (12)	0.0335 (14)	0.0019 (9)	−0.0030 (9)	0.0024 (9)
N4D	0.0420 (10)	0.0338 (10)	0.0385 (12)	0.0001 (8)	0.0027 (8)	0.0008 (8)
C5D	0.0371 (12)	0.0367 (12)	0.0358 (14)	−0.0022 (9)	−0.0022 (10)	−0.0024 (9)
C6D	0.0481 (14)	0.0419 (13)	0.0489 (16)	−0.0032 (10)	0.0026 (11)	0.0049 (11)
C7D	0.0458 (14)	0.0604 (16)	0.0468 (17)	−0.0080 (11)	0.0010 (11)	0.0081 (12)
C8D	0.0386 (13)	0.0694 (17)	0.0396 (16)	−0.0003 (11)	0.0008 (11)	0.0004 (12)
C9D	0.0402 (13)	0.0558 (15)	0.0444 (16)	0.0078 (10)	−0.0023 (11)	−0.0085 (12)
C10D	0.0364 (12)	0.0434 (13)	0.0392 (15)	−0.0003 (9)	−0.0050 (10)	−0.0048 (10)
N11D	0.0461 (11)	0.0382 (11)	0.0415 (13)	−0.0001 (8)	0.0066 (9)	0.0034 (9)
C12D	0.0611 (15)	0.0469 (15)	0.0528 (17)	0.0111 (11)	0.0125 (12)	0.0008 (11)
C13D	0.0609 (15)	0.0406 (14)	0.0694 (19)	−0.0151 (11)	0.0104 (13)	0.0031 (12)
Cl1D	0.0531 (4)	0.1160 (6)	0.0526 (5)	0.0097 (4)	0.0169 (3)	0.0048 (4)

Geometric parameters (Å, º)

S1A—O1A	1.4322 (16)	S1C—O1C	1.4332 (16)
S1A—O2A	1.4235 (16)	S1C—O2C	1.4173 (16)
S1A—N2A	1.6461 (18)	S1C—N2C	1.6509 (18)
S1A—C10A	1.727 (2)	S1C—C10C	1.731 (2)
N2A—C3A	1.408 (3)	N2C—C3C	1.402 (3)
N2A—C13A	1.470 (3)	N2C—C13C	1.468 (3)
C3A—N4A	1.301 (3)	C3C—N4C	1.307 (3)
C3A—N11A	1.337 (3)	C3C—N11C	1.337 (3)
N4A—C5A	1.390 (3)	N4C—C5C	1.386 (3)
C5A—C10A	1.401 (3)	C5C—C6C	1.398 (3)
C5A—C6A	1.403 (3)	C5C—C10C	1.400 (3)
C6A—C7A	1.371 (3)	C6C—C7C	1.379 (3)
C6A—H6A	0.9300	C6C—H6C	0.9300
C7A—C8A	1.387 (3)	C7C—C8C	1.381 (3)
C7A—H7A	0.9300	C7C—H7C	0.9300
C8A—C9A	1.376 (3)	C8C—C9C	1.371 (3)
C8A—Cl1A	1.739 (2)	C8C—Cl1C	1.738 (2)
C9A—C10A	1.393 (3)	C9C—C10C	1.396 (3)
C9A—H9A	0.9300	C9C—H9C	0.9300
N11A—C12A	1.446 (3)	N11C—C12C	1.444 (3)
N11A—H11A	0.78 (2)	N11C—H11C	0.84 (2)
C12A—H121	0.9600	C12C—H127	0.9600
C12A—H122	0.9600	C12C—H128	0.9600
C12A—H123	0.9600	C12C—H129	0.9600
C13A—H131	0.9600	C13C—H137	0.9600
C13A—H132	0.9600	C13C—H138	0.9600
C13A—H133	0.9600	C13C—H139	0.9600
S1B—O1B	1.4376 (16)	S1D—O1D	1.4340 (16)
S1B—O2B	1.4233 (15)	S1D—O2D	1.4214 (15)
S1B—N2B	1.6526 (17)	S1D—N2D	1.6508 (17)
S1B—C10B	1.725 (2)	S1D—C10D	1.732 (2)
N2B—C3B	1.405 (2)	N2D—C3D	1.406 (3)
N2B—C13B	1.461 (3)	N2D—C13D	1.464 (3)
C3B—N4B	1.301 (3)	C3D—N4D	1.309 (3)
C3B—N11B	1.336 (3)	C3D—N11D	1.333 (3)
N4B—C5B	1.389 (3)	N4D—C5D	1.386 (3)
C5B—C6B	1.402 (3)	C5D—C6D	1.401 (3)
C5B—C10B	1.403 (3)	C5D—C10D	1.405 (3)
C6B—C7B	1.370 (3)	C6D—C7D	1.374 (3)
C6B—H6B	0.9300	C6D—H6D	0.9300
C7B—C8B	1.386 (3)	C7D—C8D	1.384 (3)
C7B—H7B	0.9300	C7D—H7D	0.9300
C8B—C9B	1.373 (3)	C8D—C9D	1.376 (3)
C8B—Cl1B	1.737 (2)	C8D—Cl1D	1.737 (2)
C9B—C10B	1.391 (3)	C9D—C10D	1.389 (3)
C9B—H9B	0.9300	C9D—H9D	0.9300
N11B—C12B	1.452 (3)	N11D—C12D	1.450 (3)
N11B—H11B	0.82 (2)	N11D—H11D	0.86 (2)
C12B—H124	0.9600	C12D—H12A	0.9600
C12B—H125	0.9600	C12D—H12B	0.9600
C12B—H126	0.9600	C12D—H12C	0.9600
C13B—H134	0.9600	C13D—H13A	0.9600
C13B—H135	0.9600	C13D—H13B	0.9600
C13B—H136	0.9600	C13D—H13C	0.9600
O2A—S1A—O1A	117.32 (9)	O2C—S1C—O1C	117.22 (10)
O2A—S1A—N2A	107.97 (9)	O2C—S1C—N2C	108.16 (9)
O1A—S1A—N2A	109.62 (10)	O1C—S1C—N2C	109.57 (10)
O2A—S1A—C10A	112.03 (10)	O2C—S1C—C10C	112.15 (11)
O1A—S1A—C10A	109.14 (9)	O1C—S1C—C10C	109.09 (10)
N2A—S1A—C10A	99.20 (9)	N2C—S1C—C10C	99.09 (9)
C3A—N2A—C13A	122.90 (18)	C3C—N2C—C13C	122.90 (18)
C3A—N2A—S1A	116.48 (13)	C3C—N2C—S1C	116.88 (13)
C13A—N2A—S1A	117.70 (15)	C13C—N2C—S1C	116.96 (15)
N4A—C3A—N11A	120.17 (19)	N4C—C3C—N11C	119.81 (19)
N4A—C3A—N2A	123.69 (19)	N4C—C3C—N2C	123.91 (19)
N11A—C3A—N2A	116.09 (17)	N11C—C3C—N2C	116.24 (18)
C3A—N4A—C5A	119.55 (17)	C3C—N4C—C5C	119.69 (18)
N4A—C5A—C10A	124.83 (18)	N4C—C5C—C6C	119.14 (19)
N4A—C5A—C6A	119.05 (18)	N4C—C5C—C10C	124.73 (19)
C10A—C5A—C6A	116.1 (2)	C6C—C5C—C10C	116.1 (2)
C7A—C6A—C5A	121.3 (2)	C7C—C6C—C5C	121.4 (2)
C7A—C6A—H6A	119.4	C7C—C6C—H6C	119.3
C5A—C6A—H6A	119.4	C5C—C6C—H6C	119.3
C6A—C7A—C8A	120.7 (2)	C6C—C7C—C8C	120.4 (2)
C6A—C7A—H7A	119.7	C6C—C7C—H7C	119.8
C8A—C7A—H7A	119.7	C8C—C7C—H7C	119.8
C9A—C8A—C7A	120.7 (2)	C9C—C8C—C7C	120.9 (2)
C9A—C8A—Cl1A	119.52 (18)	C9C—C8C—Cl1C	119.19 (19)
C7A—C8A—Cl1A	119.82 (17)	C7C—C8C—Cl1C	119.90 (18)
C8A—C9A—C10A	117.8 (2)	C8C—C9C—C10C	117.9 (2)
C8A—C9A—H9A	121.1	C8C—C9C—H9C	121.0
C10A—C9A—H9A	121.1	C10C—C9C—H9C	121.0
C9A—C10A—C5A	123.47 (19)	C9C—C10C—C5C	123.2 (2)
C9A—C10A—S1A	120.18 (16)	C9C—C10C—S1C	120.04 (17)
C5A—C10A—S1A	116.14 (16)	C5C—C10C—S1C	116.53 (16)
C3A—N11A—C12A	122.37 (19)	C3C—N11C—C12C	122.19 (19)
C3A—N11A—H11A	116.0 (19)	C3C—N11C—H11C	114.0 (17)
C12A—N11A—H11A	121.7 (19)	C12C—N11C—H11C	123.8 (17)
N11A—C12A—H121	109.5	N11C—C12C—H127	109.5
N11A—C12A—H122	109.5	N11C—C12C—H128	109.5
H121—C12A—H122	109.5	H127—C12C—H128	109.5
N11A—C12A—H123	109.5	N11C—C12C—H129	109.5
H121—C12A—H123	109.5	H127—C12C—H129	109.5
H122—C12A—H123	109.5	H128—C12C—H129	109.5
N2A—C13A—H131	109.5	N2C—C13C—H137	109.5
N2A—C13A—H132	109.5	N2C—C13C—H138	109.5
H131—C13A—H132	109.5	H137—C13C—H138	109.5
N2A—C13A—H133	109.5	N2C—C13C—H139	109.5
H131—C13A—H133	109.5	H137—C13C—H139	109.5
H132—C13A—H133	109.5	H138—C13C—H139	109.5
O2B—S1B—O1B	117.54 (9)	O2D—S1D—O1D	117.34 (9)
O2B—S1B—N2B	108.01 (9)	O2D—S1D—N2D	107.88 (9)
O1B—S1B—N2B	109.38 (10)	O1D—S1D—N2D	109.73 (10)
O2B—S1B—C10B	112.24 (10)	O2D—S1D—C10D	112.13 (11)
O1B—S1B—C10B	108.94 (10)	O1D—S1D—C10D	109.20 (10)
N2B—S1B—C10B	99.10 (9)	N2D—S1D—C10D	98.97 (9)
C3B—N2B—C13B	123.56 (17)	C3D—N2D—C13D	122.58 (17)
C3B—N2B—S1B	115.87 (13)	C3D—N2D—S1D	116.17 (13)
C13B—N2B—S1B	117.82 (14)	C13D—N2D—S1D	117.60 (14)
N4B—C3B—N11B	120.46 (19)	N4D—C3D—N11D	120.38 (19)
N4B—C3B—N2B	123.93 (19)	N4D—C3D—N2D	123.45 (19)
N11B—C3B—N2B	115.56 (18)	N11D—C3D—N2D	116.14 (18)
C3B—N4B—C5B	119.71 (17)	C3D—N4D—C5D	119.73 (17)
N4B—C5B—C6B	119.68 (18)	N4D—C5D—C6D	119.88 (19)
N4B—C5B—C10B	124.51 (19)	N4D—C5D—C10D	124.64 (19)
C6B—C5B—C10B	115.8 (2)	C6D—C5D—C10D	115.5 (2)
C7B—C6B—C5B	121.6 (2)	C7D—C6D—C5D	121.9 (2)
C7B—C6B—H6B	119.2	C7D—C6D—H6D	119.0
C5B—C6B—H6B	119.2	C5D—C6D—H6D	119.0
C6B—C7B—C8B	120.6 (2)	C6D—C7D—C8D	120.2 (2)
C6B—C7B—H7B	119.7	C6D—C7D—H7D	119.9
C8B—C7B—H7B	119.7	C8D—C7D—H7D	119.9
C9B—C8B—C7B	120.5 (2)	C9D—C8D—C7D	120.8 (2)
C9B—C8B—Cl1B	119.46 (18)	C9D—C8D—Cl1D	119.12 (19)
C7B—C8B—Cl1B	120.06 (18)	C7D—C8D—Cl1D	120.04 (19)
C8B—C9B—C10B	118.2 (2)	C8D—C9D—C10D	117.8 (2)
C8B—C9B—H9B	120.9	C8D—C9D—H9D	121.1
C10B—C9B—H9B	120.9	C10D—C9D—H9D	121.1
C9B—C10B—C5B	123.2 (2)	C9D—C10D—C5D	123.7 (2)
C9B—C10B—S1B	120.37 (16)	C9D—C10D—S1D	119.93 (17)
C5B—C10B—S1B	116.24 (17)	C5D—C10D—S1D	116.19 (17)
C3B—N11B—C12B	122.83 (19)	C3D—N11D—C12D	122.86 (19)
C3B—N11B—H11B	116.9 (17)	C3D—N11D—H11D	118.1 (16)
C12B—N11B—H11B	120.0 (17)	C12D—N11D—H11D	118.9 (16)
N11B—C12B—H124	109.5	N11D—C12D—H12A	109.5
N11B—C12B—H125	109.5	N11D—C12D—H12B	109.5
H124—C12B—H125	109.5	H12A—C12D—H12B	109.5
N11B—C12B—H126	109.5	N11D—C12D—H12C	109.5
H124—C12B—H126	109.5	H12A—C12D—H12C	109.5
H125—C12B—H126	109.5	H12B—C12D—H12C	109.5
N2B—C13B—H134	109.5	N2D—C13D—H13A	109.5
N2B—C13B—H135	109.5	N2D—C13D—H13B	109.5
H134—C13B—H135	109.5	H13A—C13D—H13B	109.5
N2B—C13B—H136	109.5	N2D—C13D—H13C	109.5
H134—C13B—H136	109.5	H13A—C13D—H13C	109.5
H135—C13B—H136	109.5	H13B—C13D—H13C	109.5
O2A—S1A—N2A—C3A	−165.34 (15)	O2C—S1C—N2C—C3C	−164.34 (16)
O1A—S1A—N2A—C3A	65.76 (17)	O1C—S1C—N2C—C3C	66.80 (17)
C10A—S1A—N2A—C3A	−48.47 (17)	C10C—S1C—N2C—C3C	−47.31 (17)
O2A—S1A—N2A—C13A	33.4 (2)	O2C—S1C—N2C—C13C	35.4 (2)
O1A—S1A—N2A—C13A	−95.49 (19)	O1C—S1C—N2C—C13C	−93.42 (18)
C10A—S1A—N2A—C13A	150.28 (18)	C10C—S1C—N2C—C13C	152.48 (18)
C13A—N2A—C3A—N4A	−165.2 (2)	C13C—N2C—C3C—N4C	−167.4 (2)
S1A—N2A—C3A—N4A	34.6 (3)	S1C—N2C—C3C—N4C	33.6 (3)
C13A—N2A—C3A—N11A	12.2 (3)	C13C—N2C—C3C—N11C	10.1 (3)
S1A—N2A—C3A—N11A	−147.97 (16)	S1C—N2C—C3C—N11C	−148.83 (16)
N11A—C3A—N4A—C5A	−173.92 (19)	N11C—C3C—N4C—C5C	−173.97 (19)
N2A—C3A—N4A—C5A	3.4 (3)	N2C—C3C—N4C—C5C	3.5 (3)
C3A—N4A—C5A—C10A	−18.2 (3)	C3C—N4C—C5C—C6C	163.9 (2)
C3A—N4A—C5A—C6A	162.5 (2)	C3C—N4C—C5C—C10C	−17.4 (3)
N4A—C5A—C6A—C7A	−179.39 (19)	N4C—C5C—C6C—C7C	−178.82 (19)
C10A—C5A—C6A—C7A	1.2 (3)	C10C—C5C—C6C—C7C	2.3 (3)
C5A—C6A—C7A—C8A	0.3 (3)	C5C—C6C—C7C—C8C	0.0 (4)
C6A—C7A—C8A—C9A	−1.8 (4)	C6C—C7C—C8C—C9C	−2.3 (4)
C6A—C7A—C8A—Cl1A	179.00 (17)	C6C—C7C—C8C—Cl1C	178.72 (17)
C7A—C8A—C9A—C10A	1.5 (3)	C7C—C8C—C9C—C10C	2.0 (3)
Cl1A—C8A—C9A—C10A	−179.22 (16)	Cl1C—C8C—C9C—C10C	−179.02 (16)
C8A—C9A—C10A—C5A	0.1 (3)	C8C—C9C—C10C—C5C	0.6 (3)
C8A—C9A—C10A—S1A	−174.57 (16)	C8C—C9C—C10C—S1C	−174.16 (17)
N4A—C5A—C10A—C9A	179.21 (19)	N4C—C5C—C10C—C9C	178.57 (19)
C6A—C5A—C10A—C9A	−1.4 (3)	C6C—C5C—C10C—C9C	−2.7 (3)
N4A—C5A—C10A—S1A	−5.9 (3)	N4C—C5C—C10C—S1C	−6.5 (3)
C6A—C5A—C10A—S1A	173.42 (16)	C6C—C5C—C10C—S1C	172.24 (16)
O2A—S1A—C10A—C9A	−36.3 (2)	O2C—S1C—C10C—C9C	−36.4 (2)
O1A—S1A—C10A—C9A	95.34 (18)	O1C—S1C—C10C—C9C	95.12 (18)
N2A—S1A—C10A—C9A	−150.06 (17)	N2C—S1C—C10C—C9C	−150.40 (17)
O2A—S1A—C10A—C5A	148.65 (16)	O2C—S1C—C10C—C5C	148.48 (16)
O1A—S1A—C10A—C5A	−79.69 (18)	O1C—S1C—C10C—C5C	−79.96 (18)
N2A—S1A—C10A—C5A	34.91 (17)	N2C—S1C—C10C—C5C	34.52 (18)
N4A—C3A—N11A—C12A	5.9 (3)	N4C—C3C—N11C—C12C	6.4 (3)
N2A—C3A—N11A—C12A	−171.59 (19)	N2C—C3C—N11C—C12C	−171.3 (2)
O2B—S1B—N2B—C3B	−166.15 (15)	O2D—S1D—N2D—C3D	−166.24 (15)
O1B—S1B—N2B—C3B	64.81 (17)	O1D—S1D—N2D—C3D	64.84 (17)
C10B—S1B—N2B—C3B	−49.07 (17)	C10D—S1D—N2D—C3D	−49.39 (17)
O2B—S1B—N2B—C13B	31.9 (2)	O2D—S1D—N2D—C13D	34.7 (2)
O1B—S1B—N2B—C13B	−97.10 (18)	O1D—S1D—N2D—C13D	−94.25 (18)
C10B—S1B—N2B—C13B	149.02 (17)	C10D—S1D—N2D—C13D	151.52 (18)
C13B—N2B—C3B—N4B	−163.6 (2)	C13D—N2D—C3D—N4D	−165.9 (2)
S1B—N2B—C3B—N4B	35.6 (3)	S1D—N2D—C3D—N4D	36.2 (3)
C13B—N2B—C3B—N11B	13.8 (3)	C13D—N2D—C3D—N11D	12.2 (3)
S1B—N2B—C3B—N11B	−146.99 (16)	S1D—N2D—C3D—N11D	−145.80 (16)
N11B—C3B—N4B—C5B	−174.83 (19)	N11D—C3D—N4D—C5D	−175.49 (19)
N2B—C3B—N4B—C5B	2.5 (3)	N2D—C3D—N4D—C5D	2.5 (3)
C3B—N4B—C5B—C6B	163.8 (2)	C3D—N4D—C5D—C6D	162.8 (2)
C3B—N4B—C5B—C10B	−17.7 (3)	C3D—N4D—C5D—C10D	−18.4 (3)
N4B—C5B—C6B—C7B	−178.43 (19)	N4D—C5D—C6D—C7D	−179.6 (2)
C10B—C5B—C6B—C7B	2.9 (3)	C10D—C5D—C6D—C7D	1.5 (3)
C5B—C6B—C7B—C8B	−0.2 (3)	C5D—C6D—C7D—C8D	0.0 (4)
C6B—C7B—C8B—C9B	−2.2 (4)	C6D—C7D—C8D—C9D	−1.5 (4)
C6B—C7B—C8B—Cl1B	178.00 (17)	C6D—C7D—C8D—Cl1D	178.76 (17)
C7B—C8B—C9B—C10B	1.7 (3)	C7D—C8D—C9D—C10D	1.3 (3)
Cl1B—C8B—C9B—C10B	−178.49 (16)	Cl1D—C8D—C9D—C10D	−178.92 (16)
C8B—C9B—C10B—C5B	1.2 (3)	C8D—C9D—C10D—C5D	0.3 (3)
C8B—C9B—C10B—S1B	−174.26 (17)	C8D—C9D—C10D—S1D	−174.62 (17)
N4B—C5B—C10B—C9B	177.99 (19)	N4D—C5D—C10D—C9D	179.47 (19)
C6B—C5B—C10B—C9B	−3.4 (3)	C6D—C5D—C10D—C9D	−1.6 (3)
N4B—C5B—C10B—S1B	−6.4 (3)	N4D—C5D—C10D—S1D	−5.4 (3)
C6B—C5B—C10B—S1B	172.19 (16)	C6D—C5D—C10D—S1D	173.45 (16)
O2B—S1B—C10B—C9B	−35.0 (2)	O2D—S1D—C10D—C9D	−36.2 (2)
O1B—S1B—C10B—C9B	96.97 (18)	O1D—S1D—C10D—C9D	95.60 (19)
N2B—S1B—C10B—C9B	−148.80 (17)	N2D—S1D—C10D—C9D	−149.76 (18)
O2B—S1B—C10B—C5B	149.25 (16)	O2D—S1D—C10D—C5D	148.51 (16)
O1B—S1B—C10B—C5B	−78.79 (18)	O1D—S1D—C10D—C5D	−79.69 (18)
N2B—S1B—C10B—C5B	35.44 (18)	N2D—S1D—C10D—C5D	34.95 (18)
N4B—C3B—N11B—C12B	4.4 (3)	N4D—C3D—N11D—C12D	3.4 (3)
N2B—C3B—N11B—C12B	−173.12 (19)	N2D—C3D—N11D—C12D	−174.73 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11A—H11A···O1B^i	0.78 (2)	2.34 (2)	3.093 (2)	161 (2)
N11B—H11B···O1A^ii	0.82 (2)	2.27 (2)	3.074 (2)	165 (2)
N11C—H11C···O1D^iii	0.84 (2)	2.27 (2)	3.058 (2)	157 (2)
N11D—H11D···O1C^iv	0.86 (2)	2.20 (2)	3.030 (2)	162 (2)

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