Synthesis, structure and sulfonamide–sulfonimide tautomerism of sulfonamide–1,2,4-triazine derivatives

Two new 1,2,4-triazine-containing sulfonamide derivatives, namely, 4-bromo-N-(5,6-diphenyl-2H-1,2,4-triazin-3-yl­idene)benzene­sulfonamide, C₂₁H₁₅BrN₄O₄S, 3a, and methyl 2-{[(5,6-diphenyl-1,2,4-triazin-3-yl)sulfamo­yl]meth­yl}benzoate, C₂₄H₂₀N₄O₄S, 3b, which crystallize in the different sulfonimide and sulfonamide tautomeric forms, respectively, were synthesized and characterized by spectroscopic, X-ray diffraction and theoretical calculation methods. Both mol­ecules adopt a very similar conformation of the common part of the structure and the differences occur within the substituents on the sulfonamide group. The amino groups characteristic for the existing tautomeric forms are involved in strong inter­molecular N—H...N and N—H...O hydrogen bonds in 3a and 3b, respectively. The Hirshfeld surface analysis showed that H...H contacts constitute a high percentage of the inter­molecular inter­actions. Theoretical calculations at the ab initio DFT/B3LYP/6-311++G(d,p) level showed that the two tautomeric forms observed for 3a and 3b can co-exist in chloro­form, ethanol and water solutions, with a distinct predominance of the sulfonamide form; the participation of the sulfonimide form increases with increasing solvent polarity.

Computing details

For both structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and WinGX (Farrugia, 2012).

4-Bromo-N-(5,6-diphenyl-2H-1,2,4-triazin-3-ylidene)benzenesulfonamide (3a)

Crystal data

C21H15BrN4O2S	Z = 2
Mr = 467.34	F(000) = 472
Triclinic, P1	Dx = 1.589 Mg m^−3
a = 5.781 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 12.717 (2) Å	Cell parameters from 1543 reflections
c = 14.655 (3) Å	θ = 3.8–74.9°
α = 67.751 (18)°	µ = 4.09 mm^−1
β = 78.78 (3)°	T = 120 K
γ = 82.94 (2)°	Needle, yellow
V = 976.7 (5) Å^3	0.25 × 0.10 × 0.05 mm

Data collection

Agilent SuperNova Single Source diffractometer with an Atlas detector	3828 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	2377 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.061
Detector resolution: 5.2763 pixels mm^-1	θmax = 80.3°, θmin = 3.3°
ω scans	h = −7→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −15→15
Tmin = 0.589, Tmax = 1.000	l = −18→17
6490 measured reflections

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)] = 0.079	Hydrogen site location: difference Fourier map
wR(F^2) = 0.251	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0949P)^2 + 2.6148P] where P = (Fo^2 + 2Fc^2)/3
3828 reflections	(Δ/σ)max < 0.001
275 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.65 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C3	0.8158 (12)	0.4867 (4)	0.8997 (4)	0.0338 (13)
C5	1.0892 (11)	0.3917 (5)	0.8175 (4)	0.0341 (13)
C6	0.9554 (11)	0.2917 (5)	0.8682 (4)	0.0334 (13)
C51	1.3032 (12)	0.3995 (5)	0.7422 (5)	0.0379 (13)
C52	1.4683 (12)	0.4794 (5)	0.7265 (5)	0.0411 (14)
H52	1.4412	0.5260	0.7638	0.062*
C53	1.6713 (14)	0.4895 (6)	0.6561 (6)	0.0546 (18)
H53	1.7842	0.5395	0.6487	0.082*
C54	1.7041 (14)	0.4237 (7)	0.5964 (6)	0.061 (2)
H54	1.8388	0.4304	0.5485	0.091*
C55	1.5355 (14)	0.3483 (6)	0.6086 (6)	0.0522 (18)
H55	1.5562	0.3061	0.5675	0.078*
C56	1.3386 (12)	0.3355 (5)	0.6809 (5)	0.0414 (14)
H56	1.2283	0.2840	0.6890	0.062*
C61	1.0298 (11)	0.1768 (4)	0.8656 (4)	0.0326 (12)
C62	1.2389 (12)	0.1228 (5)	0.8983 (4)	0.0364 (13)
H62	1.3356	0.1595	0.9192	0.055*
C63	1.3023 (12)	0.0127 (5)	0.8993 (4)	0.0365 (13)
H63	1.4413	−0.0242	0.9214	0.055*
C64	1.1595 (12)	−0.0408 (5)	0.8678 (5)	0.0423 (15)
H64	1.2015	−0.1145	0.8698	0.063*
C65	0.9543 (11)	0.0134 (5)	0.8332 (5)	0.0368 (13)
H65	0.8603	−0.0228	0.8104	0.055*
C66	0.8903 (12)	0.1218 (5)	0.8328 (5)	0.0372 (13)
H66	0.7515	0.1583	0.8101	0.056*
C81	0.8559 (12)	0.7498 (5)	0.7498 (4)	0.0374 (13)
C82	0.6485 (15)	0.8025 (9)	0.7173 (6)	0.072 (3)
H82	0.5157	0.8087	0.7627	0.108*
C83	0.6411 (19)	0.8462 (11)	0.6155 (8)	0.092 (4)
H83	0.5009	0.8800	0.5927	0.138*
C84	0.8372 (18)	0.8401 (7)	0.5487 (5)	0.059 (2)
C85	1.0393 (18)	0.7889 (6)	0.5817 (6)	0.067 (3)
H85	1.1736	0.7848	0.5362	0.100*
C86	1.0478 (15)	0.7428 (6)	0.6822 (6)	0.062 (2)
H86	1.1872	0.7062	0.7043	0.093*
N1	0.7504 (10)	0.2960 (4)	0.9250 (3)	0.0356 (12)
N2	0.6833 (10)	0.3961 (4)	0.9355 (4)	0.0365 (12)
H2	0.587 (15)	0.400 (7)	0.974 (6)	0.055*
N4	1.0171 (10)	0.4866 (4)	0.8345 (4)	0.0364 (11)
N7	0.7303 (10)	0.5754 (4)	0.9250 (4)	0.0374 (12)
O1	1.1136 (9)	0.6745 (4)	0.8896 (4)	0.0514 (12)
O2	0.7214 (10)	0.7651 (4)	0.9239 (4)	0.0515 (13)
S8	0.8673 (3)	0.69186 (12)	0.87965 (11)	0.0406 (4)
Br1A	0.879 (3)	0.8881 (9)	0.4094 (4)	0.061 (2)	0.47 (4)
Br1B	0.780 (4)	0.9120 (11)	0.4108 (5)	0.079 (3)	0.53 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C3	0.048 (4)	0.017 (2)	0.037 (3)	0.006 (2)	−0.012 (3)	−0.011 (2)
C5	0.046 (4)	0.022 (3)	0.035 (3)	−0.002 (2)	−0.007 (2)	−0.011 (2)
C6	0.048 (4)	0.023 (3)	0.032 (3)	−0.001 (2)	−0.006 (2)	−0.015 (2)
C51	0.044 (4)	0.028 (3)	0.040 (3)	−0.003 (3)	−0.008 (3)	−0.009 (2)
C52	0.048 (4)	0.027 (3)	0.046 (3)	0.000 (3)	−0.013 (3)	−0.008 (2)
C53	0.049 (4)	0.044 (4)	0.060 (4)	−0.008 (3)	−0.010 (3)	−0.004 (3)
C54	0.048 (5)	0.052 (4)	0.062 (5)	−0.002 (3)	0.012 (4)	−0.010 (4)
C55	0.056 (5)	0.045 (4)	0.052 (4)	−0.005 (3)	0.008 (3)	−0.020 (3)
C56	0.047 (4)	0.029 (3)	0.048 (3)	−0.004 (3)	0.000 (3)	−0.017 (3)
C61	0.047 (4)	0.019 (2)	0.033 (3)	0.000 (2)	−0.002 (2)	−0.013 (2)
C62	0.044 (4)	0.027 (3)	0.039 (3)	0.007 (2)	−0.008 (3)	−0.016 (2)
C63	0.048 (4)	0.023 (3)	0.038 (3)	0.004 (2)	−0.003 (3)	−0.014 (2)
C64	0.053 (4)	0.028 (3)	0.043 (3)	−0.001 (3)	0.008 (3)	−0.017 (2)
C65	0.041 (4)	0.033 (3)	0.040 (3)	−0.005 (3)	−0.004 (3)	−0.017 (2)
C66	0.042 (4)	0.028 (3)	0.044 (3)	0.003 (2)	−0.003 (3)	−0.020 (2)
C81	0.049 (4)	0.031 (3)	0.033 (3)	−0.005 (3)	0.000 (3)	−0.015 (2)
C82	0.045 (5)	0.099 (7)	0.048 (4)	0.008 (4)	0.002 (3)	−0.009 (4)
C83	0.063 (7)	0.126 (10)	0.062 (6)	−0.010 (6)	−0.017 (5)	−0.002 (6)
C84	0.102 (7)	0.045 (4)	0.030 (3)	−0.030 (4)	−0.005 (4)	−0.008 (3)
C85	0.091 (7)	0.040 (4)	0.051 (4)	0.002 (4)	0.024 (4)	−0.017 (3)
C86	0.062 (5)	0.037 (4)	0.063 (5)	0.007 (3)	0.017 (4)	−0.009 (3)
N1	0.057 (3)	0.020 (2)	0.031 (2)	0.008 (2)	−0.006 (2)	−0.0141 (18)
N2	0.050 (3)	0.025 (2)	0.036 (3)	0.001 (2)	0.001 (2)	−0.017 (2)
N4	0.049 (3)	0.022 (2)	0.040 (3)	0.002 (2)	−0.006 (2)	−0.0140 (19)
N7	0.053 (3)	0.022 (2)	0.042 (3)	−0.002 (2)	−0.002 (2)	−0.018 (2)
O1	0.061 (3)	0.035 (2)	0.070 (3)	−0.001 (2)	−0.032 (3)	−0.023 (2)
O2	0.082 (4)	0.027 (2)	0.048 (3)	−0.008 (2)	0.011 (2)	−0.0251 (19)
S8	0.0618 (11)	0.0247 (7)	0.0400 (8)	−0.0034 (6)	−0.0078 (7)	−0.0169 (6)
Br1A	0.095 (5)	0.049 (2)	0.0379 (11)	−0.004 (2)	−0.0069 (15)	−0.0163 (11)
Br1B	0.127 (7)	0.062 (2)	0.0464 (11)	−0.009 (4)	−0.022 (2)	−0.0139 (13)

Geometric parameters (Å, º)

C3—N7	1.328 (7)	C63—H63	0.9300
C3—N2	1.340 (8)	C64—C65	1.381 (10)
C3—N4	1.354 (8)	C64—H64	0.9300
C5—N4	1.326 (7)	C65—C66	1.381 (8)
C5—C6	1.439 (8)	C65—H65	0.9300
C5—C51	1.474 (9)	C66—H66	0.9300
C6—N1	1.317 (8)	C81—C86	1.354 (9)
C6—C61	1.485 (7)	C81—C82	1.377 (11)
C51—C56	1.397 (8)	C81—S8	1.772 (6)
C51—C52	1.404 (9)	C82—C83	1.388 (13)
C52—C53	1.388 (10)	C82—H82	0.9300
C52—H52	0.9300	C83—C84	1.361 (14)
C53—C54	1.396 (12)	C83—H83	0.9300
C53—H53	0.9300	C84—C85	1.348 (13)
C54—C55	1.391 (11)	C84—Br1A	1.870 (9)
C54—H54	0.9300	C84—Br1B	1.954 (9)
C55—C56	1.374 (9)	C85—C86	1.372 (12)
C55—H55	0.9300	C85—H85	0.9300
C56—H56	0.9300	C86—H86	0.9300
C61—C66	1.384 (9)	N1—N2	1.341 (6)
C61—C62	1.391 (9)	N2—H2	0.72 (8)
C62—C63	1.397 (7)	N7—S8	1.612 (5)
C62—H62	0.9300	O1—S8	1.441 (5)
C63—C64	1.372 (9)	O2—S8	1.432 (4)
N7—C3—N2	117.0 (6)	C66—C65—C64	119.2 (6)
N7—C3—N4	123.9 (5)	C66—C65—H65	120.4
N2—C3—N4	118.9 (5)	C64—C65—H65	120.4
N4—C5—C6	120.0 (6)	C65—C66—C61	120.9 (6)
N4—C5—C51	115.4 (5)	C65—C66—H66	119.5
C6—C5—C51	124.5 (5)	C61—C66—H66	119.5
N1—C6—C5	120.6 (5)	C86—C81—C82	119.5 (7)
N1—C6—C61	113.8 (5)	C86—C81—S8	121.0 (6)
C5—C6—C61	125.6 (5)	C82—C81—S8	119.4 (5)
C56—C51—C52	118.8 (6)	C81—C82—C83	118.9 (8)
C56—C51—C5	121.9 (6)	C81—C82—H82	120.6
C52—C51—C5	119.1 (6)	C83—C82—H82	120.6
C53—C52—C51	120.8 (6)	C84—C83—C82	120.6 (10)
C53—C52—H52	119.6	C84—C83—H83	119.7
C51—C52—H52	119.6	C82—C83—H83	119.7
C52—C53—C54	119.3 (7)	C85—C84—C83	119.7 (8)
C52—C53—H53	120.4	C85—C84—Br1A	110.0 (9)
C54—C53—H53	120.4	C83—C84—Br1A	130.2 (10)
C55—C54—C53	120.0 (7)	C85—C84—Br1B	128.1 (10)
C55—C54—H54	120.0	C83—C84—Br1B	112.1 (11)
C53—C54—H54	120.0	C84—C85—C86	120.3 (7)
C56—C55—C54	120.5 (7)	C84—C85—H85	119.9
C56—C55—H55	119.7	C86—C85—H85	119.9
C54—C55—H55	119.7	C81—C86—C85	120.9 (8)
C55—C56—C51	120.4 (6)	C81—C86—H86	119.6
C55—C56—H56	119.8	C85—C86—H86	119.6
C51—C56—H56	119.8	C6—N1—N2	116.0 (5)
C66—C61—C62	119.6 (5)	C3—N2—N1	125.0 (6)
C66—C61—C6	120.5 (6)	C3—N2—H2	112 (7)
C62—C61—C6	119.8 (5)	N1—N2—H2	120 (7)
C61—C62—C63	119.3 (6)	C5—N4—C3	118.4 (5)
C61—C62—H62	120.3	C3—N7—S8	120.8 (5)
C63—C62—H62	120.3	O2—S8—O1	118.1 (3)
C64—C63—C62	120.0 (6)	O2—S8—N7	103.9 (3)
C64—C63—H63	120.0	O1—S8—N7	113.2 (3)
C62—C63—H63	120.0	O2—S8—C81	107.5 (3)
C63—C64—C65	120.9 (6)	O1—S8—C81	106.7 (3)
C63—C64—H64	119.5	N7—S8—C81	106.8 (3)
C65—C64—H64	119.5
N4—C5—C6—N1	6.0 (9)	C81—C82—C83—C84	−1.9 (18)
C51—C5—C6—N1	−171.4 (6)	C82—C83—C84—C85	1.4 (17)
N4—C5—C6—C61	−172.3 (6)	C82—C83—C84—Br1A	178.6 (9)
C51—C5—C6—C61	10.3 (10)	C82—C83—C84—Br1B	−178.2 (10)
N4—C5—C51—C56	−148.0 (6)	C83—C84—C85—C86	0.2 (14)
C6—C5—C51—C56	29.5 (10)	Br1A—C84—C85—C86	−177.5 (7)
N4—C5—C51—C52	27.3 (9)	Br1B—C84—C85—C86	179.8 (7)
C6—C5—C51—C52	−155.2 (6)	C82—C81—C86—C85	1.0 (12)
C56—C51—C52—C53	−4.3 (10)	S8—C81—C86—C85	−179.2 (6)
C5—C51—C52—C53	−179.8 (6)	C84—C85—C86—C81	−1.4 (13)
C51—C52—C53—C54	3.6 (11)	C5—C6—N1—N2	−3.0 (8)
C52—C53—C54—C55	−0.6 (12)	C61—C6—N1—N2	175.5 (5)
C53—C54—C55—C56	−1.7 (13)	N7—C3—N2—N1	−173.8 (6)
C54—C55—C56—C51	1.0 (12)	N4—C3—N2—N1	11.3 (9)
C52—C51—C56—C55	2.0 (10)	C6—N1—N2—C3	−5.6 (9)
C5—C51—C56—C55	177.3 (7)	C6—C5—N4—C3	−0.4 (9)
N1—C6—C61—C66	59.1 (8)	C51—C5—N4—C3	177.2 (5)
C5—C6—C61—C66	−122.5 (7)	N7—C3—N4—C5	177.9 (6)
N1—C6—C61—C62	−119.5 (6)	N2—C3—N4—C5	−7.6 (9)
C5—C6—C61—C62	58.9 (8)	N2—C3—N7—S8	−175.7 (5)
C66—C61—C62—C63	−1.3 (9)	N4—C3—N7—S8	−1.0 (9)
C6—C61—C62—C63	177.4 (5)	C3—N7—S8—O2	179.8 (5)
C61—C62—C63—C64	0.4 (9)	C3—N7—S8—O1	−50.7 (6)
C62—C63—C64—C65	1.1 (9)	C3—N7—S8—C81	66.4 (6)
C63—C64—C65—C66	−1.6 (9)	C86—C81—S8—O2	144.6 (6)
C64—C65—C66—C61	0.6 (9)	C82—C81—S8—O2	−35.5 (7)
C62—C61—C66—C65	0.8 (9)	C86—C81—S8—O1	17.0 (6)
C6—C61—C66—C65	−177.8 (6)	C82—C81—S8—O1	−163.1 (7)
C86—C81—C82—C83	0.6 (15)	C86—C81—S8—N7	−104.3 (6)
S8—C81—C82—C83	−179.2 (9)	C82—C81—S8—N7	75.5 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C86—H86···O1	0.93	2.55	2.917 (10)	104
N2—H2···N7^i	0.72 (8)	2.19 (9)	2.911 (8)	173 (9)
C83—H83···Br1B^ii	0.93	2.92	3.63 (2)	134

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

Methyl 2-{[(5,6-diphenyl-1,2,4-triazin-3-yl)sulfamoyl]methyl}benzoate (3b)

Crystal data

C24H20N4O4S	F(000) = 960
Mr = 460.50	Dx = 1.402 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 10.919 (2) Å	Cell parameters from 3956 reflections
b = 8.0871 (16) Å	θ = 4.6–75.6°
c = 24.875 (5) Å	µ = 1.66 mm^−1
β = 96.65 (3)°	T = 120 K
V = 2181.9 (8) Å^3	Plate, yellow
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection

Agilent SuperNova Single Source diffractometer with an Atlas detector	4438 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	3507 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.049
Detector resolution: 5.2763 pixels mm^-1	θmax = 76.5°, θmin = 3.6°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −8→10
Tmin = 0.782, Tmax = 1.000	l = −31→31
8470 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.070	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.253	w = 1/[σ^2(Fo^2) + (0.128P)^2 + 2.0409P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max < 0.001
4438 reflections	Δρmax = 0.64 e Å^−3
302 parameters	Δρmin = −1.16 e Å^−3
18 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0015 (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.

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

	x	y	z	Uiso*/Ueq
C3	0.5856 (3)	0.3397 (4)	0.63161 (13)	0.0288 (5)
C5	0.5785 (3)	0.3612 (4)	0.72213 (13)	0.0277 (5)
C6	0.7094 (3)	0.3482 (4)	0.72907 (14)	0.0270 (7)
C9	0.3271 (3)	0.5231 (5)	0.59242 (14)	0.0313 (7)
H9A	0.3491	0.5177	0.6313	0.047*
H9B	0.3699	0.6167	0.5789	0.047*
C10	0.2111 (3)	0.7638 (4)	0.50776 (13)	0.0317 (7)
C12	0.2140 (4)	0.9891 (5)	0.44913 (17)	0.0437 (10)
H12A	0.1599	1.0719	0.4319	0.066*
H12B	0.2800	1.0417	0.4717	0.066*
H12C	0.2473	0.9239	0.4220	0.066*
C51	0.4987 (3)	0.3849 (4)	0.76596 (13)	0.0275 (7)
C52	0.3845 (4)	0.3033 (5)	0.76124 (15)	0.0357 (8)
H52	0.3623	0.2328	0.7322	0.054*
C53	0.3049 (4)	0.3280 (6)	0.80003 (17)	0.0434 (10)
H53	0.2306	0.2708	0.7977	0.065*
C54	0.3355 (4)	0.4375 (6)	0.84228 (16)	0.0437 (10)
H54	0.2810	0.4554	0.8678	0.066*
C55	0.4468 (4)	0.5200 (5)	0.84652 (15)	0.0409 (9)
H55	0.4672	0.5929	0.8750	0.061*
C56	0.5284 (4)	0.4948 (5)	0.80845 (15)	0.0347 (8)
H56	0.6030	0.5515	0.8114	0.052*
C61	0.7902 (3)	0.3471 (4)	0.78100 (14)	0.0269 (7)
C62	0.7635 (3)	0.2545 (4)	0.82579 (13)	0.0294 (7)
H62	0.6918	0.1916	0.8237	0.044*
C63	0.8441 (4)	0.2566 (5)	0.87351 (14)	0.0358 (8)
H63	0.8266	0.1933	0.9029	0.054*
C64	0.9502 (4)	0.3522 (5)	0.87750 (16)	0.0366 (8)
H64	1.0025	0.3554	0.9098	0.055*
C65	0.9778 (3)	0.4429 (5)	0.83323 (16)	0.0361 (8)
H65	1.0487	0.5074	0.8358	0.054*
C66	0.9003 (3)	0.4378 (4)	0.78517 (15)	0.0328 (7)
H66	0.9214	0.4954	0.7552	0.049*
C91	0.1909 (3)	0.5496 (4)	0.58061 (13)	0.0292 (7)
C92	0.1358 (3)	0.6610 (4)	0.54204 (14)	0.0311 (7)
C93	0.0076 (4)	0.6795 (5)	0.53476 (17)	0.0387 (9)
H93	−0.0289	0.7537	0.5092	0.058*
C94	−0.0648 (4)	0.5872 (5)	0.56568 (18)	0.0435 (9)
H94	−0.1501	0.5989	0.5605	0.065*
C95	−0.0117 (4)	0.4778 (5)	0.60419 (17)	0.0393 (9)
H95	−0.0608	0.4162	0.6249	0.059*
C96	0.1151 (4)	0.4607 (5)	0.61166 (15)	0.0373 (8)
H96	0.1507	0.3883	0.6380	0.056*
N1	0.7690 (3)	0.3342 (4)	0.68541 (12)	0.0294 (6)
N2	0.7092 (3)	0.3326 (4)	0.63565 (12)	0.0312 (7)
N4	0.5187 (3)	0.3534 (4)	0.67275 (11)	0.0280 (5)
N7	0.5258 (3)	0.3388 (4)	0.57955 (11)	0.0300 (5)
H7	0.574 (4)	0.320 (6)	0.553 (2)	0.045*
O1	0.3236 (2)	0.1997 (3)	0.58655 (11)	0.0370 (6)
O2	0.3626 (3)	0.3521 (4)	0.50456 (10)	0.0386 (7)
O10	0.3196 (2)	0.7421 (4)	0.50363 (11)	0.0386 (6)
O11	0.1456 (3)	0.8832 (3)	0.48194 (12)	0.0413 (7)
S8	0.37658 (8)	0.33808 (11)	0.56239 (3)	0.0303 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C3	0.0326 (10)	0.0314 (10)	0.0231 (10)	0.0025 (8)	0.0067 (9)	0.0005 (8)
C5	0.0343 (11)	0.0256 (11)	0.0237 (11)	0.0008 (9)	0.0061 (10)	0.0001 (9)
C6	0.0354 (17)	0.0196 (14)	0.0279 (16)	−0.0004 (12)	0.0117 (13)	0.0002 (11)
C9	0.0347 (17)	0.0321 (17)	0.0268 (15)	−0.0030 (14)	0.0022 (13)	−0.0003 (13)
C10	0.0399 (18)	0.0305 (17)	0.0257 (15)	0.0045 (15)	0.0079 (13)	−0.0025 (13)
C12	0.065 (3)	0.0289 (18)	0.039 (2)	0.0013 (18)	0.0127 (18)	0.0037 (16)
C51	0.0317 (16)	0.0265 (15)	0.0254 (15)	0.0038 (13)	0.0084 (12)	0.0011 (12)
C52	0.0380 (19)	0.0368 (18)	0.0333 (17)	−0.0025 (16)	0.0080 (15)	−0.0022 (15)
C53	0.041 (2)	0.050 (2)	0.043 (2)	−0.0018 (18)	0.0226 (18)	−0.0023 (17)
C54	0.045 (2)	0.053 (2)	0.0350 (19)	0.0118 (19)	0.0165 (16)	0.0044 (17)
C55	0.051 (2)	0.040 (2)	0.0324 (18)	0.0123 (18)	0.0098 (16)	−0.0068 (15)
C56	0.0414 (19)	0.0305 (17)	0.0330 (17)	0.0014 (15)	0.0079 (15)	−0.0030 (14)
C61	0.0316 (17)	0.0214 (15)	0.0285 (16)	0.0025 (12)	0.0068 (13)	−0.0023 (12)
C62	0.0341 (17)	0.0272 (16)	0.0269 (15)	0.0023 (14)	0.0036 (13)	−0.0002 (12)
C63	0.049 (2)	0.0330 (18)	0.0258 (16)	0.0070 (16)	0.0042 (15)	0.0000 (13)
C64	0.0399 (19)	0.0347 (19)	0.0334 (18)	0.0083 (16)	−0.0041 (15)	−0.0067 (14)
C65	0.0339 (18)	0.0318 (18)	0.0405 (19)	0.0019 (15)	−0.0042 (15)	−0.0021 (15)
C66	0.0357 (18)	0.0272 (16)	0.0359 (17)	0.0033 (14)	0.0058 (14)	0.0015 (14)
C91	0.0319 (16)	0.0303 (16)	0.0270 (15)	0.0016 (14)	0.0101 (13)	−0.0046 (13)
C92	0.0344 (18)	0.0293 (17)	0.0320 (17)	0.0018 (14)	0.0135 (14)	−0.0048 (13)
C93	0.039 (2)	0.0352 (19)	0.043 (2)	0.0082 (16)	0.0110 (16)	−0.0042 (16)
C94	0.0368 (19)	0.042 (2)	0.055 (2)	0.0007 (17)	0.0168 (17)	−0.0087 (18)
C95	0.0359 (19)	0.0380 (19)	0.048 (2)	−0.0018 (16)	0.0204 (16)	−0.0038 (17)
C96	0.046 (2)	0.0319 (18)	0.0366 (18)	0.0013 (16)	0.0165 (16)	0.0013 (15)
N1	0.0338 (15)	0.0297 (14)	0.0246 (13)	0.0019 (11)	0.0028 (11)	0.0006 (11)
N2	0.0337 (15)	0.0329 (15)	0.0279 (14)	0.0024 (12)	0.0077 (12)	−0.0017 (11)
N4	0.0333 (10)	0.0285 (10)	0.0228 (9)	0.0018 (8)	0.0051 (8)	0.0004 (7)
N7	0.0327 (11)	0.0357 (11)	0.0219 (10)	0.0033 (9)	0.0045 (9)	0.0007 (9)
O1	0.0402 (14)	0.0316 (13)	0.0391 (14)	0.0023 (11)	0.0042 (11)	0.0011 (11)
O2	0.0453 (15)	0.0470 (16)	0.0231 (12)	0.0057 (12)	0.0027 (11)	−0.0033 (10)
O10	0.0352 (13)	0.0476 (16)	0.0354 (13)	0.0066 (12)	0.0144 (11)	0.0093 (12)
O11	0.0489 (16)	0.0319 (13)	0.0445 (15)	0.0081 (12)	0.0109 (12)	0.0083 (12)
S8	0.0347 (5)	0.0320 (5)	0.0248 (4)	0.0016 (3)	0.0063 (3)	−0.0021 (3)

Geometric parameters (Å, º)

C3—N4	1.329 (4)	C55—H55	0.9300
C3—N2	1.342 (5)	C56—H56	0.9300
C3—N7	1.381 (4)	C61—C62	1.401 (5)
C5—N4	1.324 (4)	C61—C66	1.401 (5)
C5—C6	1.424 (5)	C62—C63	1.394 (5)
C5—C51	1.484 (4)	C62—H62	0.9300
C6—N1	1.334 (4)	C63—C64	1.387 (6)
C6—C61	1.478 (5)	C63—H63	0.9300
C9—C91	1.498 (5)	C64—C65	1.385 (6)
C9—S8	1.784 (4)	C64—H64	0.9300
C9—H9A	0.9700	C65—C66	1.383 (5)
C9—H9B	0.9700	C65—H65	0.9300
C10—O10	1.213 (4)	C66—H66	0.9300
C10—O11	1.323 (5)	C91—C96	1.395 (5)
C10—C92	1.502 (5)	C91—C92	1.400 (5)
C12—O11	1.448 (5)	C92—C93	1.398 (5)
C12—H12A	0.9600	C93—C94	1.384 (6)
C12—H12B	0.9600	C93—H93	0.9300
C12—H12C	0.9600	C94—C95	1.381 (6)
C51—C56	1.390 (5)	C94—H94	0.9300
C51—C52	1.404 (5)	C95—C96	1.382 (6)
C52—C53	1.386 (5)	C95—H95	0.9300
C52—H52	0.9300	C96—H96	0.9300
C53—C54	1.385 (6)	N1—N2	1.331 (4)
C53—H53	0.9300	N7—S8	1.636 (3)
C54—C55	1.379 (6)	N7—H7	0.90 (5)
C54—H54	0.9300	O1—S8	1.425 (3)
C55—C56	1.389 (5)	O2—S8	1.434 (3)
N4—C3—N2	125.7 (3)	C63—C62—H62	119.9
N4—C3—N7	118.7 (3)	C61—C62—H62	119.9
N2—C3—N7	115.6 (3)	C64—C63—C62	120.5 (3)
N4—C5—C6	119.3 (3)	C64—C63—H63	119.7
N4—C5—C51	114.8 (3)	C62—C63—H63	119.7
C6—C5—C51	125.9 (3)	C65—C64—C63	119.7 (4)
N1—C6—C5	119.0 (3)	C65—C64—H64	120.2
N1—C6—C61	114.4 (3)	C63—C64—H64	120.2
C5—C6—C61	126.6 (3)	C66—C65—C64	120.3 (4)
C91—C9—S8	112.3 (2)	C66—C65—H65	119.9
C91—C9—H9A	109.1	C64—C65—H65	119.9
S8—C9—H9A	109.1	C65—C66—C61	120.9 (3)
C91—C9—H9B	109.1	C65—C66—H66	119.6
S8—C9—H9B	109.1	C61—C66—H66	119.6
H9A—C9—H9B	107.9	C96—C91—C92	118.3 (3)
O10—C10—O11	122.9 (3)	C96—C91—C9	117.2 (3)
O10—C10—C92	124.9 (3)	C92—C91—C9	124.4 (3)
O11—C10—C92	112.2 (3)	C93—C92—C91	120.1 (3)
O11—C12—H12A	109.5	C93—C92—C10	118.2 (3)
O11—C12—H12B	109.5	C91—C92—C10	121.6 (3)
H12A—C12—H12B	109.5	C94—C93—C92	119.9 (4)
O11—C12—H12C	109.5	C94—C93—H93	120.1
H12A—C12—H12C	109.5	C92—C93—H93	120.1
H12B—C12—H12C	109.5	C95—C94—C93	120.6 (4)
C56—C51—C52	119.4 (3)	C95—C94—H94	119.7
C56—C51—C5	122.4 (3)	C93—C94—H94	119.7
C52—C51—C5	118.0 (3)	C94—C95—C96	119.4 (4)
C53—C52—C51	119.8 (4)	C94—C95—H95	120.3
C53—C52—H52	120.1	C96—C95—H95	120.3
C51—C52—H52	120.1	C95—C96—C91	121.6 (4)
C54—C53—C52	120.3 (4)	C95—C96—H96	119.2
C54—C53—H53	119.8	C91—C96—H96	119.2
C52—C53—H53	119.8	N2—N1—C6	121.7 (3)
C55—C54—C53	120.0 (3)	N1—N2—C3	116.7 (3)
C55—C54—H54	120.0	C5—N4—C3	117.5 (3)
C53—C54—H54	120.0	C3—N7—S8	126.4 (3)
C54—C55—C56	120.4 (4)	C3—N7—H7	116 (3)
C54—C55—H55	119.8	S8—N7—H7	117 (3)
C56—C55—H55	119.8	C10—O11—C12	114.8 (3)
C55—C56—C51	120.0 (4)	O1—S8—O2	118.97 (18)
C55—C56—H56	120.0	O1—S8—N7	109.51 (16)
C51—C56—H56	120.0	O2—S8—N7	104.40 (16)
C62—C61—C66	118.5 (3)	O1—S8—C9	108.95 (17)
C62—C61—C6	122.7 (3)	O2—S8—C9	110.58 (17)
C66—C61—C6	118.8 (3)	N7—S8—C9	103.20 (16)
C63—C62—C61	120.1 (3)
N4—C5—C6—N1	2.4 (5)	C96—C91—C92—C10	178.8 (3)
C51—C5—C6—N1	−177.1 (3)	C9—C91—C92—C10	1.1 (5)
N4—C5—C6—C61	−177.2 (3)	O10—C10—C92—C93	−167.7 (4)
C51—C5—C6—C61	3.3 (5)	O11—C10—C92—C93	12.3 (5)
N4—C5—C51—C56	−136.7 (4)	O10—C10—C92—C91	12.6 (6)
C6—C5—C51—C56	42.8 (5)	O11—C10—C92—C91	−167.4 (3)
N4—C5—C51—C52	37.7 (5)	C91—C92—C93—C94	−0.2 (6)
C6—C5—C51—C52	−142.8 (4)	C10—C92—C93—C94	−179.9 (3)
C56—C51—C52—C53	−2.5 (6)	C92—C93—C94—C95	0.7 (6)
C5—C51—C52—C53	−177.1 (4)	C93—C94—C95—C96	−0.1 (6)
C51—C52—C53—C54	2.4 (7)	C94—C95—C96—C91	−1.0 (6)
C52—C53—C54—C55	−1.3 (7)	C92—C91—C96—C95	1.5 (6)
C53—C54—C55—C56	0.4 (6)	C9—C91—C96—C95	179.4 (3)
C54—C55—C56—C51	−0.5 (6)	C5—C6—N1—N2	0.1 (5)
C52—C51—C56—C55	1.6 (6)	C61—C6—N1—N2	179.7 (3)
C5—C51—C56—C55	175.9 (3)	C6—N1—N2—C3	−2.3 (5)
N1—C6—C61—C62	−135.4 (3)	N4—C3—N2—N1	2.2 (5)
C5—C6—C61—C62	44.2 (5)	N7—C3—N2—N1	179.6 (3)
N1—C6—C61—C66	42.4 (4)	C6—C5—N4—C3	−2.5 (5)
C5—C6—C61—C66	−138.0 (3)	C51—C5—N4—C3	177.1 (3)
C66—C61—C62—C63	1.3 (5)	N2—C3—N4—C5	0.2 (5)
C6—C61—C62—C63	179.1 (3)	N7—C3—N4—C5	−177.1 (3)
C61—C62—C63—C64	1.2 (5)	N4—C3—N7—S8	−5.3 (5)
C62—C63—C64—C65	−1.7 (6)	N2—C3—N7—S8	177.1 (3)
C63—C64—C65—C66	−0.2 (6)	O10—C10—O11—C12	−1.3 (5)
C64—C65—C66—C61	2.7 (6)	C92—C10—O11—C12	178.6 (3)
C62—C61—C66—C65	−3.2 (5)	C3—N7—S8—O1	−56.5 (3)
C6—C61—C66—C65	178.9 (3)	C3—N7—S8—O2	175.0 (3)
S8—C9—C91—C96	79.8 (3)	C3—N7—S8—C9	59.4 (3)
S8—C9—C91—C92	−102.5 (4)	C91—C9—S8—O1	−64.9 (3)
C96—C91—C92—C93	−0.9 (5)	C91—C9—S8—O2	67.6 (3)
C9—C91—C92—C93	−178.6 (3)	C91—C9—S8—N7	178.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N4	0.97	2.41	3.047 (4)	123
C9—H9B···O10	0.97	2.14	2.825 (5)	126
C93—H93···O11	0.93	2.34	2.678 (5)	101
N7—H7···O10^i	0.90 (5)	1.99 (5)	2.893 (4)	175 (4)
C12—H12···N2^i	0.96	2.60	3.512 (5)	159
C63—H63···O2^ii	0.93	2.54	3.360 (4)	147
C95—H95···N1^iii	0.93	2.61	3.505 (5)	162

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