The different modes of chiral [1,2,3]tri­az­olo[5,1-b][1,3,4]thia­dia­zines: crystal packing, conformation investigation and cellular activity

The crystal structures of four new chiral [1,2,3]triazolo[5,1-b][1,3,4]thia­diazines are described, namely, ethyl 5′-benzoyl-5′H,7′H-spiro­[cyclo­hexane-1,6′-[1,2,3]triazolo[5,1-b][1,3,4]thia­diazine]-3′-carboxyl­ate, C₁₉H₂₂N₄O₃S, ethyl 5′-(4-meth­oxy­benzo­yl)-5′H,7′H-spiro­[cyclo­hexane-1,6′-[1,2,3]triazolo[5,1-b][1,3,4]thia­dia­zine]-3′-carboxyl­ate, C₂₀H₂₄N₄O₄S, ethyl 6,6-dimethyl-5-(4-methyl­benzo­yl)-6,7-di­hydro-5H-[1,2,3]triazolo[5,1-b][1,3,4]thia­diazine-3-carboxyl­ate, C₁₇H₂₀N₄O₃S, and ethyl 5-benzoyl-6-(4-meth­oxy­phen­yl)-6,7-di­hydro-5H-[1,2,3]triazolo[5,1-b][1,3,4]thia­diazine-3-carboxyl­ate, C₂₁H₂₀N₄O₄S. The crystallographic data and cell activities of these four com­pounds and of the structures of three previously reported similar com­pounds, namely, ethyl 5′-(4-methyl­benzo­yl)-5′H,7′H-spiro­[cyclo­pentane-1,6′-[1,2,3]triazolo[5,1-b][1,3,4]thia­diazine]-3′-carboxyl­ate, C₁₉H₂₂N₄O₃S, ethyl 5′-(4-meth­oxy­benzo­yl)-5′H,7′H-spiro­[cyclo­pentane-1,6′-[1,2,3]triazolo[5,1-b][1,3,4]thia­diazine]-3′-carboxyl­ate, C₁₉H₂₂N₄O₄S, and ethyl 6-methyl-5-(4-methyl­benzo­yl)-6-phenyl-6,7-di­hydro-5H-[1,2,3]triazolo[5,1-b][1,3,4]thia­diazine-3-carboxyl­ate, C₂₂H₂₂N₄O₃S, are contrasted and com­pared. For both crystallization and an MTT assay, racemic mixtures of the corresponding [1,2,3]triazolo[5,1-b][1,3,4]thia­diazines were used. The main manner of mol­ecular packing in these com­pounds is the organization of either enanti­omeric pairs or dimers. In both cases, the formation of two three-centre hydrogen bonds can be detected resulting from intra­molecular N—H...O and inter­molecular N—H...O or N—H...N inter­actions. Mol­ecules of different enanti­omeric forms can also form chains through N—H...O hydrogen bonds or form layers between which only weak hydro­phobic contacts exist. Unlike other [1,2,3]triazolo[5,1-b][1,3,4]thia­diazines, ethyl 5′-benzoyl-5′H,7′H-spiro­[cyclo­hexane-1,6′-[1,2,3]triazolo[5,1-b][1,3,4]thia­diazine]-3′-carboxyl­ate contains mol­ecules of only the (R)-enanti­omer; moreover, the N—H group does not participate in any significant inter­molecular inter­actions. Mol­ecular mechanics methods (force field OPLS3e) and the DFT B3LYP/6-31G+(d,p) method show that the com­pound forming enanti­omeric pairs via weak N—H...N hydrogen bonds is subject to greater distortion of the geometry under the influence of the inter­molecular inter­actions in the crystal. For intra­molecular N—H...O and S...O inter­actions, an analysis of the noncovalent inter­actions (NCIs) was carried out. The cellular activities of the com­pounds were tested by evaluating their anti­proliferative effect against two normal human cell lines and two cancer cell lines in terms of half-maximum inhibitory con­centration (IC₅₀). Some derivatives have been found to be very effective in inhibiting the growth of Hela cells at nanomolar and submicromolar con­centrations with minimal cytotoxicity in relation to normal cells.

Computing details

Data collection: FRAMBO (Bruker, 2009) for (I); CrysAlis PRO (Agilent, 2013) for (II), (III), (IV), (V), (VI), (VII). Cell refinement: FRAMBO (Bruker, 2009) for (I); CrysAlis PRO (Agilent, 2013) for (II), (III), (IV), (V), (VI), (VII). Data reduction: SHELXTL (Bruker, 2000) for (I); CrysAlis PRO (Agilent, 2013) for (II), (III), (IV), (V), (VI), (VII). Program(s) used to solve structure: olex2.solve (Bourhis et al., 2015) for (I), (VI), (VII); SUPERFLIP (Palatinus & Chapuis, 2007; Palatinus & van der Lee, 2008; Palatinus et al., 2012) for (II); SHELXS97 (Sheldrick, 2008) for (III), (IV), (V). For all structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2020) and publCIF (Westrip, 2010).

Ethyl 5'-(4-methylbenzoyl)-5'H,7'H-spiro[cyclopentane-1,6'-[1,2,3]triazolo[5,1-b][1,3,4]thiadiazine]-3'-carboxylate (I)

Crystal data

C19H22N4O3S	Z = 2
Mr = 386.46	F(000) = 408
Triclinic, P1	Dx = 1.339 Mg m^−3
a = 9.1209 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6732 (19) Å	Cell parameters from 2041 reflections
c = 11.958 (2) Å	θ = 2.8–26.4°
α = 104.763 (17)°	µ = 0.20 mm^−1
β = 100.147 (15)°	T = 295 K
γ = 103.858 (17)°	Prism, colourless
V = 958.4 (3) Å^3	0.4 × 0.35 × 0.25 mm

Data collection

Xcalibur 3 diffractometer	2037 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.032
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	θmax = 26.4°, θmin = 2.8°
Tmin = 0.957, Tmax = 1.038	h = −11→11
8686 measured reflections	k = −8→12
3842 independent reflections	l = −14→14

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.038P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3842 reflections	Δρmax = 0.35 e Å^−3
246 parameters	Δρmin = −0.21 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
S1	0.11874 (7)	0.35535 (6)	0.31730 (5)	0.04464 (19)
N3	0.2652 (2)	0.59934 (17)	0.26016 (14)	0.0411 (4)
N4	0.1350 (2)	0.64544 (16)	0.22494 (14)	0.0419 (4)
H4	0.101492	0.601422	0.134228	0.050*
O1	0.41191 (19)	0.28613 (16)	0.38001 (13)	0.0595 (4)
C4	−0.0408 (2)	0.4147 (2)	0.24743 (17)	0.0381 (5)
H4A	−0.120437	0.385988	0.292629	0.046*
O2	0.6474 (2)	0.40289 (18)	0.36494 (16)	0.0718 (5)
O3	−0.0416 (2)	0.36910 (16)	0.04306 (13)	0.0814 (6)
C6	−0.1853 (3)	0.1605 (2)	0.08551 (18)	0.0428 (5)
C3	0.0039 (3)	0.5855 (2)	0.27300 (18)	0.0401 (5)
C1	0.2740 (3)	0.4807 (2)	0.29763 (16)	0.0380 (5)
N2	0.4072 (2)	0.68261 (19)	0.25891 (16)	0.0532 (5)
N1	0.5076 (2)	0.6166 (2)	0.29365 (17)	0.0567 (5)
C5	−0.0883 (3)	0.3188 (2)	0.11743 (18)	0.0477 (6)
C16	0.0406 (3)	0.6683 (2)	0.40761 (18)	0.0491 (6)
H16A	0.003856	0.599086	0.449901	0.059*
H16B	0.152176	0.714255	0.440283	0.059*
C2	0.4315 (3)	0.4941 (2)	0.31995 (18)	0.0442 (6)
C13	0.5124 (3)	0.3939 (2)	0.35769 (19)	0.0500 (6)
C19	−0.1307 (3)	0.6353 (2)	0.2181 (2)	0.0543 (6)
H19A	−0.128684	0.635789	0.137327	0.065*
H19B	−0.230308	0.569130	0.215974	0.065*
C9	−0.3552 (3)	−0.1424 (2)	0.0197 (2)	0.0538 (6)
C11	−0.2743 (3)	0.1071 (2)	0.1555 (2)	0.0548 (6)
H11	−0.277717	0.172522	0.226352	0.066*
C10	−0.3586 (3)	−0.0417 (2)	0.1221 (2)	0.0601 (7)
H10	−0.419297	−0.074697	0.170471	0.072*
C7	−0.1838 (3)	0.0602 (3)	−0.0197 (2)	0.0669 (8)
H7	−0.127390	0.093846	−0.070222	0.080*
C12	−0.4474 (3)	−0.3062 (2)	−0.0144 (2)	0.0762 (8)
H12A	−0.487335	−0.324810	0.051173	0.114*
H12B	−0.380675	−0.367180	−0.033165	0.114*
H12C	−0.532739	−0.330427	−0.082948	0.114*
C14	0.4675 (3)	0.1682 (3)	0.4071 (3)	0.0756 (8)
H14A	0.521152	0.130667	0.348304	0.091*
H14B	0.540784	0.206663	0.485161	0.091*
C8	−0.2656 (3)	−0.0892 (3)	−0.0500 (2)	0.0719 (8)
H8	−0.259940	−0.155680	−0.119493	0.086*
C18	−0.1049 (3)	0.7919 (3)	0.2988 (2)	0.0713 (8)
H18A	−0.030864	0.865374	0.278094	0.086*
H18B	−0.202171	0.817029	0.293947	0.086*
C17	−0.0417 (4)	0.7849 (3)	0.4199 (2)	0.0914 (10)
H17A	−0.126059	0.759870	0.457539	0.110*
H17B	0.030244	0.881408	0.469485	0.110*
C15	0.3388 (4)	0.0503 (3)	0.4058 (4)	0.1248 (14)
H15A	0.375739	−0.027836	0.425164	0.187*
H15B	0.268026	0.010891	0.327765	0.187*
H15C	0.285693	0.088182	0.463689	0.187*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0409 (4)	0.0449 (3)	0.0521 (4)	0.0107 (3)	0.0138 (3)	0.0225 (3)
N3	0.0359 (13)	0.0399 (10)	0.0468 (10)	0.0069 (9)	0.0145 (9)	0.0139 (8)
N4	0.0378 (13)	0.0435 (10)	0.0467 (10)	0.0106 (9)	0.0122 (9)	0.0185 (8)
O1	0.0495 (12)	0.0582 (10)	0.0791 (11)	0.0218 (9)	0.0134 (9)	0.0320 (9)
C4	0.0323 (14)	0.0435 (12)	0.0406 (12)	0.0081 (10)	0.0110 (10)	0.0184 (10)
O2	0.0445 (13)	0.0784 (11)	0.1012 (14)	0.0281 (10)	0.0247 (11)	0.0291 (10)
O3	0.1188 (18)	0.0608 (10)	0.0455 (10)	−0.0142 (10)	0.0224 (10)	0.0213 (8)
C6	0.0414 (16)	0.0433 (12)	0.0387 (13)	0.0065 (11)	0.0059 (11)	0.0130 (11)
C3	0.0344 (15)	0.0424 (12)	0.0466 (13)	0.0116 (11)	0.0123 (11)	0.0177 (10)
C1	0.0415 (16)	0.0358 (11)	0.0367 (12)	0.0112 (11)	0.0136 (11)	0.0092 (9)
N2	0.0410 (14)	0.0520 (11)	0.0698 (13)	0.0087 (11)	0.0228 (11)	0.0236 (10)
N1	0.0403 (14)	0.0578 (12)	0.0733 (14)	0.0112 (11)	0.0228 (11)	0.0201 (10)
C5	0.0498 (17)	0.0493 (13)	0.0412 (13)	0.0073 (12)	0.0093 (12)	0.0180 (11)
C16	0.0515 (17)	0.0456 (12)	0.0495 (14)	0.0131 (12)	0.0165 (12)	0.0123 (11)
C2	0.0392 (17)	0.0445 (13)	0.0498 (13)	0.0129 (12)	0.0169 (12)	0.0119 (11)
C13	0.0444 (19)	0.0548 (15)	0.0495 (14)	0.0187 (14)	0.0158 (13)	0.0075 (12)
C19	0.0432 (17)	0.0587 (14)	0.0693 (16)	0.0191 (13)	0.0150 (13)	0.0299 (13)
C9	0.0592 (19)	0.0438 (13)	0.0482 (15)	0.0064 (13)	0.0045 (13)	0.0119 (12)
C11	0.0616 (19)	0.0418 (13)	0.0580 (15)	0.0080 (12)	0.0248 (13)	0.0105 (11)
C10	0.066 (2)	0.0473 (14)	0.0674 (17)	0.0078 (13)	0.0298 (14)	0.0186 (13)
C7	0.078 (2)	0.0596 (16)	0.0490 (15)	−0.0036 (15)	0.0232 (14)	0.0098 (13)
C12	0.097 (3)	0.0433 (14)	0.0704 (18)	0.0018 (15)	0.0118 (16)	0.0122 (12)
C14	0.071 (2)	0.0674 (17)	0.097 (2)	0.0291 (17)	0.0133 (17)	0.0370 (15)
C8	0.088 (2)	0.0551 (15)	0.0532 (16)	0.0034 (15)	0.0233 (15)	−0.0024 (12)
C18	0.0583 (19)	0.0560 (15)	0.114 (2)	0.0263 (14)	0.0247 (17)	0.0405 (16)
C17	0.138 (3)	0.0692 (17)	0.083 (2)	0.060 (2)	0.035 (2)	0.0176 (15)
C15	0.088 (3)	0.073 (2)	0.203 (4)	0.017 (2)	−0.007 (3)	0.060 (2)

Geometric parameters (Å, º)

S1—C4	1.834 (2)	C19—H19A	0.9700
S1—C1	1.724 (2)	C19—H19B	0.9700
N3—N4	1.400 (2)	C19—C18	1.512 (3)
N3—C1	1.348 (2)	C9—C10	1.367 (3)
N3—N2	1.356 (2)	C9—C12	1.515 (3)
N4—H4	1.0182	C9—C8	1.373 (3)
N4—C3	1.475 (2)	C11—H11	0.9300
O1—C13	1.329 (3)	C11—C10	1.376 (3)
O1—C14	1.439 (2)	C10—H10	0.9300
C4—H4A	1.0074	C7—H7	0.9300
C4—C3	1.538 (3)	C7—C8	1.377 (3)
C4—C5	1.517 (3)	C12—H12A	0.9600
O2—C13	1.200 (3)	C12—H12B	0.9600
O3—C5	1.210 (2)	C12—H12C	0.9600
C6—C5	1.486 (3)	C14—H14A	0.9700
C6—C11	1.372 (3)	C14—H14B	0.9700
C6—C7	1.384 (3)	C14—C15	1.423 (4)
C3—C16	1.539 (3)	C8—H8	0.9300
C3—C19	1.527 (3)	C18—H18A	0.9700
C1—C2	1.382 (3)	C18—H18B	0.9700
N2—N1	1.304 (2)	C18—C17	1.487 (3)
N1—C2	1.363 (2)	C17—H17A	0.9700
C16—H16A	0.9700	C17—H17B	0.9700
C16—H16B	0.9700	C15—H15A	0.9600
C16—C17	1.489 (3)	C15—H15B	0.9600
C2—C13	1.461 (3)	C15—H15C	0.9600
C1—S1—C4	99.09 (9)	C18—C19—H19A	110.8
C1—N3—N4	129.70 (17)	C18—C19—H19B	110.8
C1—N3—N2	111.99 (17)	C10—C9—C12	120.7 (2)
N2—N3—N4	118.31 (15)	C10—C9—C8	117.5 (2)
N3—N4—H4	105.0	C8—C9—C12	121.8 (2)
N3—N4—C3	112.38 (14)	C6—C11—H11	119.6
C3—N4—H4	108.3	C6—C11—C10	120.9 (2)
C13—O1—C14	117.3 (2)	C10—C11—H11	119.6
S1—C4—H4A	100.7	C9—C10—C11	121.6 (2)
C3—C4—S1	112.18 (14)	C9—C10—H10	119.2
C3—C4—H4A	108.1	C11—C10—H10	119.2
C5—C4—S1	104.56 (13)	C6—C7—H7	119.9
C5—C4—H4A	113.0	C8—C7—C6	120.3 (2)
C5—C4—C3	117.07 (15)	C8—C7—H7	119.9
C11—C6—C5	123.79 (19)	C9—C12—H12A	109.5
C11—C6—C7	118.0 (2)	C9—C12—H12B	109.5
C7—C6—C5	118.2 (2)	C9—C12—H12C	109.5
N4—C3—C4	113.75 (15)	H12A—C12—H12B	109.5
N4—C3—C16	109.63 (18)	H12A—C12—H12C	109.5
N4—C3—C19	105.38 (15)	H12B—C12—H12C	109.5
C4—C3—C16	111.48 (15)	O1—C14—H14A	109.8
C19—C3—C4	112.14 (18)	O1—C14—H14B	109.8
C19—C3—C16	103.83 (17)	H14A—C14—H14B	108.3
N3—C1—S1	124.99 (16)	C15—C14—O1	109.3 (2)
N3—C1—C2	103.18 (17)	C15—C14—H14A	109.8
C2—C1—S1	131.74 (16)	C15—C14—H14B	109.8
N1—N2—N3	106.66 (15)	C9—C8—C7	121.7 (2)
N2—N1—C2	109.1 (2)	C9—C8—H8	119.2
O3—C5—C4	120.18 (19)	C7—C8—H8	119.2
O3—C5—C6	121.28 (19)	C19—C18—H18A	111.1
C6—C5—C4	118.46 (17)	C19—C18—H18B	111.1
C3—C16—H16A	110.4	H18A—C18—H18B	109.0
C3—C16—H16B	110.4	C17—C18—C19	103.51 (18)
H16A—C16—H16B	108.6	C17—C18—H18A	111.1
C17—C16—C3	106.58 (18)	C17—C18—H18B	111.1
C17—C16—H16A	110.4	C16—C17—H17A	110.0
C17—C16—H16B	110.4	C16—C17—H17B	110.0
C1—C2—C13	128.8 (2)	C18—C17—C16	108.5 (2)
N1—C2—C1	109.02 (19)	C18—C17—H17A	110.0
N1—C2—C13	122.0 (2)	C18—C17—H17B	110.0
O1—C13—C2	109.6 (2)	H17A—C17—H17B	108.4
O2—C13—O1	124.2 (2)	C14—C15—H15A	109.5
O2—C13—C2	126.2 (2)	C14—C15—H15B	109.5
C3—C19—H19A	110.8	C14—C15—H15C	109.5
C3—C19—H19B	110.8	H15A—C15—H15B	109.5
H19A—C19—H19B	108.8	H15A—C15—H15C	109.5
C18—C19—C3	104.97 (19)	H15B—C15—H15C	109.5
S1—C4—C3—N4	62.33 (19)	C1—N3—N2—N1	1.0 (2)
S1—C4—C3—C16	−62.3 (2)	C1—C2—C13—O1	−5.8 (3)
S1—C4—C3—C19	−178.20 (14)	C1—C2—C13—O2	172.4 (2)
S1—C4—C5—O3	−99.3 (2)	N2—N3—N4—C3	−157.68 (16)
S1—C4—C5—C6	77.3 (2)	N2—N3—C1—S1	176.81 (14)
S1—C1—C2—N1	−177.44 (15)	N2—N3—C1—C2	−0.1 (2)
S1—C1—C2—C13	6.5 (3)	N2—N1—C2—C1	1.5 (2)
N3—N4—C3—C4	−52.2 (2)	N2—N1—C2—C13	177.90 (18)
N3—N4—C3—C16	73.37 (18)	N1—C2—C13—O1	178.64 (18)
N3—N4—C3—C19	−175.44 (15)	N1—C2—C13—O2	−3.2 (3)
N3—C1—C2—N1	−0.8 (2)	C5—C4—C3—N4	−58.6 (2)
N3—C1—C2—C13	−176.89 (19)	C5—C4—C3—C16	176.86 (19)
N3—N2—N1—C2	−1.5 (2)	C5—C4—C3—C19	60.9 (2)
N4—N3—C1—S1	−2.8 (3)	C5—C6—C11—C10	−178.3 (2)
N4—N3—C1—C2	−179.70 (17)	C5—C6—C7—C8	176.7 (2)
N4—N3—N2—N1	−179.33 (16)	C16—C3—C19—C18	30.5 (2)
N4—C3—C16—C17	98.7 (2)	C13—O1—C14—C15	−169.0 (2)
N4—C3—C19—C18	−84.7 (2)	C19—C3—C16—C17	−13.5 (2)
C4—S1—C1—N3	10.11 (18)	C19—C18—C17—C16	27.8 (3)
C4—S1—C1—C2	−173.91 (19)	C11—C6—C5—C4	20.9 (3)
C4—C3—C16—C17	−134.4 (2)	C11—C6—C5—O3	−162.5 (2)
C4—C3—C19—C18	151.00 (18)	C11—C6—C7—C8	−2.2 (4)
C6—C11—C10—C9	1.0 (4)	C10—C9—C8—C7	−1.1 (4)
C6—C7—C8—C9	2.6 (4)	C7—C6—C5—C4	−157.9 (2)
C3—C4—C5—O3	25.5 (3)	C7—C6—C5—O3	18.8 (3)
C3—C4—C5—C6	−157.87 (19)	C7—C6—C11—C10	0.4 (4)
C3—C16—C17—C18	−8.8 (3)	C12—C9—C10—C11	179.2 (2)
C3—C19—C18—C17	−36.0 (3)	C12—C9—C8—C7	179.0 (3)
C1—S1—C4—C3	−37.08 (15)	C14—O1—C13—O2	−4.1 (3)
C1—S1—C4—C5	90.78 (14)	C14—O1—C13—C2	174.04 (18)
C1—N3—N4—C3	21.9 (3)	C8—C9—C10—C11	−0.7 (4)

Ethyl 5'-(4-methoxybenzoyl)-5'H,7'H-spiro[cyclopentane-1,6'-[1,2,3]triazolo[5,1-b][1,3,4]thiadiazine]-3'-carboxylate (II)

Crystal data

C19H22N4O4S	Z = 2
Mr = 402.46	F(000) = 424
Triclinic, P1	Dx = 1.349 Mg m^−3
a = 9.1304 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9986 (6) Å	Cell parameters from 3031 reflections
c = 11.8551 (6) Å	θ = 2.7–29.5°
α = 107.458 (5)°	µ = 0.20 mm^−1
β = 99.719 (4)°	T = 295 K
γ = 99.414 (5)°	Block, colourless
V = 990.84 (10) Å^3	0.3 × 0.25 × 0.2 mm

Data collection

Agilent Xcalibur Eos diffractometer	4047 reflections with I > 2σ(I)
Detector resolution: 15.9555 pixels mm^-1	Rint = 0.020
ω scans	θmax = 30.7°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013),	h = −12→12
Tmin = 0.934, Tmax = 1.000	k = −12→14
9553 measured reflections	l = −16→16
5400 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0544P)^2 + 0.1655P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
5400 reflections	Δρmax = 0.32 e Å^−3
272 parameters	Δρmin = −0.21 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.63535 (4)	0.86556 (4)	0.82226 (4)	0.03722 (12)
N2	0.90546 (17)	1.16932 (17)	0.76171 (15)	0.0515 (4)
C1	0.78297 (17)	0.98041 (16)	0.80070 (13)	0.0347 (3)
O1	0.92725 (13)	0.78557 (14)	0.87498 (12)	0.0508 (3)
N4	0.63771 (15)	1.14353 (15)	0.73287 (14)	0.0382 (3)
O2	1.15593 (14)	0.89089 (16)	0.85833 (15)	0.0655 (4)
N1	1.00736 (17)	1.10155 (17)	0.79347 (16)	0.0534 (4)
C12	0.0156 (3)	0.1971 (2)	0.5076 (2)	0.0743 (7)
H12A	−0.036149	0.099927	0.458967	0.112*
H12B	−0.058204	0.252542	0.529254	0.112*
H12C	0.081284	0.197405	0.579980	0.112*
C13	1.02212 (19)	0.8865 (2)	0.85262 (16)	0.0458 (4)
N3	0.76841 (14)	1.09486 (14)	0.76596 (12)	0.0381 (3)
O4	0.10375 (19)	0.25848 (15)	0.44031 (14)	0.0732 (4)
O3	0.4853 (2)	0.88148 (15)	0.54493 (12)	0.0732 (5)
C16	0.3732 (2)	1.13968 (19)	0.72729 (17)	0.0476 (4)
H16A	0.374347	1.137104	0.645002	0.057*
H16B	0.277945	1.079346	0.726216	0.057*
C4	0.47563 (17)	0.92418 (16)	0.75138 (13)	0.0330 (3)
C2	0.93840 (18)	0.98674 (18)	0.81912 (15)	0.0418 (4)
C3	0.51001 (17)	1.08856 (17)	0.78081 (14)	0.0347 (3)
C9	0.1828 (2)	0.39803 (19)	0.49218 (17)	0.0503 (4)
C8	0.1839 (2)	0.4856 (2)	0.60699 (18)	0.0539 (5)
H8	0.129162	0.450442	0.655490	0.065*
C7	0.2675 (2)	0.62695 (19)	0.64941 (17)	0.0487 (4)
H7	0.269886	0.685551	0.727534	0.058*
C6	0.34717 (18)	0.68262 (17)	0.57834 (14)	0.0378 (3)
C18A	0.5057 (5)	1.3133 (5)	0.9303 (5)	0.0613 (11)	0.65
H18A	0.597960	1.384310	0.941642	0.074*	0.65
H18B	0.460490	1.345109	0.999246	0.074*	0.65
C10	0.2649 (3)	0.4508 (2)	0.42086 (18)	0.0631 (6)
H10	0.265687	0.390760	0.344087	0.076*
C5	0.43644 (19)	0.83273 (18)	0.61724 (14)	0.0410 (4)
C19	0.5410 (2)	1.16907 (18)	0.91834 (15)	0.0437 (4)
H19A	0.476060	1.117195	0.955590	0.052*	0.65
H19B	0.646746	1.179966	0.957093	0.052*	0.65
H19C	0.517173	1.102225	0.960925	0.052*	0.35
H19D	0.647308	1.219471	0.950308	0.052*	0.35
C11	0.3453 (2)	0.5914 (2)	0.46265 (16)	0.0562 (5)
H11	0.398985	0.626304	0.413460	0.067*
C14	0.9854 (2)	0.6676 (2)	0.8971 (2)	0.0666 (6)
H14A	1.065507	0.703226	0.971078	0.080*
H14B	1.027817	0.620407	0.830224	0.080*
C17	0.3920 (3)	1.2929 (2)	0.8106 (2)	0.0684 (6)
H17A	0.294461	1.309069	0.826719	0.082*	0.65
H17B	0.430991	1.360782	0.773085	0.082*	0.65
H17C	0.471304	1.359416	0.796846	0.082*	0.35
H17D	0.297243	1.324813	0.801311	0.082*	0.35
C15	0.8590 (3)	0.5655 (3)	0.9090 (3)	0.0860 (8)
H15A	0.774900	0.540705	0.840237	0.129*
H15B	0.827479	0.608743	0.982153	0.129*
H15C	0.891961	0.480098	0.912494	0.129*
C18	0.4372 (11)	1.2761 (10)	0.9336 (8)	0.063 (2)	0.35
H18C	0.347571	1.239491	0.958602	0.075*	0.35
H18D	0.491215	1.367970	0.994353	0.075*	0.35
H4A	0.3936 (19)	0.8947 (18)	0.7901 (15)	0.038 (4)*
H4	0.614 (2)	1.109 (2)	0.6536 (18)	0.051 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0358 (2)	0.0378 (2)	0.0424 (2)	0.00641 (15)	0.01321 (15)	0.01855 (17)
N2	0.0406 (8)	0.0467 (9)	0.0699 (10)	0.0007 (6)	0.0259 (7)	0.0214 (8)
C1	0.0344 (7)	0.0335 (8)	0.0342 (8)	0.0054 (6)	0.0129 (6)	0.0071 (6)
O1	0.0401 (6)	0.0557 (8)	0.0622 (8)	0.0173 (6)	0.0129 (5)	0.0239 (6)
N4	0.0391 (7)	0.0360 (7)	0.0434 (8)	0.0066 (5)	0.0150 (6)	0.0173 (6)
O2	0.0363 (7)	0.0715 (10)	0.0876 (10)	0.0181 (6)	0.0182 (6)	0.0202 (8)
N1	0.0391 (8)	0.0506 (9)	0.0701 (10)	0.0045 (7)	0.0245 (7)	0.0164 (8)
C12	0.0762 (15)	0.0478 (12)	0.0870 (17)	−0.0081 (10)	0.0044 (12)	0.0249 (12)
C13	0.0366 (8)	0.0500 (10)	0.0442 (9)	0.0102 (7)	0.0124 (7)	0.0047 (8)
N3	0.0351 (7)	0.0348 (7)	0.0458 (7)	0.0029 (5)	0.0177 (5)	0.0137 (6)
O4	0.0939 (12)	0.0378 (8)	0.0668 (10)	−0.0104 (7)	0.0165 (8)	0.0019 (7)
O3	0.1223 (13)	0.0494 (9)	0.0388 (7)	−0.0118 (8)	0.0243 (8)	0.0150 (6)
C16	0.0406 (9)	0.0494 (10)	0.0588 (11)	0.0138 (8)	0.0137 (8)	0.0238 (9)
C4	0.0322 (7)	0.0343 (8)	0.0339 (7)	0.0045 (6)	0.0119 (6)	0.0125 (6)
C2	0.0343 (8)	0.0434 (9)	0.0443 (9)	0.0066 (7)	0.0159 (6)	0.0073 (7)
C3	0.0348 (7)	0.0348 (8)	0.0368 (8)	0.0067 (6)	0.0134 (6)	0.0132 (6)
C9	0.0562 (11)	0.0345 (9)	0.0490 (10)	0.0026 (8)	0.0051 (8)	0.0060 (8)
C8	0.0648 (12)	0.0397 (10)	0.0530 (11)	−0.0002 (8)	0.0232 (9)	0.0110 (8)
C7	0.0603 (11)	0.0381 (9)	0.0422 (9)	0.0025 (8)	0.0200 (8)	0.0061 (8)
C6	0.0406 (8)	0.0354 (8)	0.0346 (8)	0.0056 (6)	0.0069 (6)	0.0101 (7)
C18A	0.073 (3)	0.038 (2)	0.074 (3)	0.0157 (19)	0.032 (2)	0.0104 (18)
C10	0.0841 (15)	0.0456 (11)	0.0437 (10)	−0.0010 (10)	0.0190 (10)	−0.0019 (9)
C5	0.0493 (9)	0.0382 (9)	0.0342 (8)	0.0052 (7)	0.0099 (7)	0.0126 (7)
C19	0.0490 (9)	0.0406 (9)	0.0390 (8)	0.0095 (7)	0.0167 (7)	0.0067 (7)
C11	0.0729 (13)	0.0474 (11)	0.0388 (9)	−0.0020 (9)	0.0191 (9)	0.0061 (8)
C14	0.0580 (12)	0.0662 (14)	0.0840 (16)	0.0262 (11)	0.0131 (11)	0.0328 (12)
C17	0.0754 (15)	0.0510 (12)	0.0891 (16)	0.0297 (11)	0.0233 (12)	0.0281 (12)
C15	0.0782 (17)	0.0805 (18)	0.111 (2)	0.0172 (14)	0.0099 (15)	0.0563 (16)
C18	0.095 (7)	0.053 (5)	0.048 (3)	0.034 (5)	0.027 (5)	0.015 (4)

Geometric parameters (Å, º)

S1—C1	1.7282 (16)	C8—C7	1.387 (2)
S1—C4	1.8269 (15)	C7—H7	0.9300
N2—N1	1.307 (2)	C7—C6	1.380 (2)
N2—N3	1.3644 (18)	C6—C5	1.479 (2)
C1—N3	1.346 (2)	C6—C11	1.396 (2)
C1—C2	1.387 (2)	C18A—H18A	0.9700
O1—C13	1.338 (2)	C18A—H18B	0.9700
O1—C14	1.444 (2)	C18A—C19	1.499 (5)
N4—N3	1.4005 (18)	C18A—C17	1.547 (6)
N4—C3	1.4785 (19)	C10—H10	0.9300
N4—H4	0.872 (19)	C10—C11	1.372 (3)
O2—C13	1.205 (2)	C19—H19A	0.9700
N1—C2	1.358 (2)	C19—H19B	0.9700
C12—H12A	0.9600	C19—H19C	0.9700
C12—H12B	0.9600	C19—H19D	0.9700
C12—H12C	0.9600	C19—C18	1.533 (9)
C12—O4	1.417 (3)	C11—H11	0.9300
C13—C2	1.461 (2)	C14—H14A	0.9700
O4—C9	1.361 (2)	C14—H14B	0.9700
O3—C5	1.217 (2)	C14—C15	1.467 (3)
C16—H16A	0.9700	C17—H17A	0.9700
C16—H16B	0.9700	C17—H17B	0.9700
C16—C3	1.536 (2)	C17—H17C	0.9700
C16—C17	1.517 (3)	C17—H17D	0.9700
C4—C3	1.540 (2)	C17—C18	1.513 (9)
C4—C5	1.524 (2)	C15—H15A	0.9600
C4—H4A	0.991 (17)	C15—H15B	0.9600
C3—C19	1.539 (2)	C15—H15C	0.9600
C9—C8	1.377 (3)	C18—H18C	0.9700
C9—C10	1.381 (3)	C18—H18D	0.9700
C8—H8	0.9300
C1—S1—C4	98.57 (7)	C19—C18A—H18A	110.5
N1—N2—N3	106.29 (14)	C19—C18A—H18B	110.5
N3—C1—S1	124.90 (11)	C19—C18A—C17	106.1 (3)
N3—C1—C2	103.44 (14)	C17—C18A—H18A	110.5
C2—C1—S1	131.57 (13)	C17—C18A—H18B	110.5
C13—O1—C14	118.02 (14)	C9—C10—H10	119.8
N3—N4—C3	112.01 (12)	C11—C10—C9	120.36 (18)
N3—N4—H4	104.0 (13)	C11—C10—H10	119.8
C3—N4—H4	110.0 (13)	O3—C5—C4	119.70 (15)
N2—N1—C2	109.59 (14)	O3—C5—C6	121.02 (15)
H12A—C12—H12B	109.5	C6—C5—C4	119.17 (14)
H12A—C12—H12C	109.5	C3—C19—H19A	110.6
H12B—C12—H12C	109.5	C3—C19—H19B	110.6
O4—C12—H12A	109.5	C3—C19—H19C	110.5
O4—C12—H12B	109.5	C3—C19—H19D	110.5
O4—C12—H12C	109.5	C18A—C19—C3	105.6 (3)
O1—C13—C2	109.81 (14)	C18A—C19—H19A	110.6
O2—C13—O1	124.13 (18)	C18A—C19—H19B	110.6
O2—C13—C2	126.06 (18)	H19A—C19—H19B	108.8
N2—N3—N4	118.02 (13)	H19C—C19—H19D	108.7
C1—N3—N2	111.86 (13)	C18—C19—C3	105.9 (4)
C1—N3—N4	130.10 (13)	C18—C19—H19C	110.5
C9—O4—C12	118.65 (17)	C18—C19—H19D	110.5
H16A—C16—H16B	108.8	C6—C11—H11	119.7
C3—C16—H16A	110.7	C10—C11—C6	120.61 (18)
C3—C16—H16B	110.7	C10—C11—H11	119.7
C17—C16—H16A	110.7	O1—C14—H14A	110.0
C17—C16—H16B	110.7	O1—C14—H14B	110.0
C17—C16—C3	105.13 (15)	O1—C14—C15	108.26 (17)
S1—C4—H4A	102.3 (9)	H14A—C14—H14B	108.4
C3—C4—S1	112.08 (10)	C15—C14—H14A	110.0
C3—C4—H4A	109.8 (10)	C15—C14—H14B	110.0
C5—C4—S1	105.53 (11)	C16—C17—C18A	107.3 (2)
C5—C4—C3	116.35 (13)	C16—C17—H17A	110.3
C5—C4—H4A	109.7 (10)	C16—C17—H17B	110.3
C1—C2—C13	128.74 (16)	C16—C17—H17C	111.7
N1—C2—C1	108.80 (15)	C16—C17—H17D	111.7
N1—C2—C13	122.35 (15)	C18A—C17—H17A	110.3
N4—C3—C16	105.40 (13)	C18A—C17—H17B	110.3
N4—C3—C4	113.65 (12)	H17A—C17—H17B	108.5
N4—C3—C19	109.47 (13)	H17C—C17—H17D	109.4
C16—C3—C4	112.43 (13)	C18—C17—C16	100.6 (4)
C16—C3—C19	103.66 (13)	C18—C17—H17C	111.7
C19—C3—C4	111.59 (13)	C18—C17—H17D	111.7
O4—C9—C8	124.53 (19)	C14—C15—H15A	109.5
O4—C9—C10	115.39 (17)	C14—C15—H15B	109.5
C8—C9—C10	120.07 (17)	C14—C15—H15C	109.5
C9—C8—H8	120.4	H15A—C15—H15B	109.5
C9—C8—C7	119.23 (18)	H15A—C15—H15C	109.5
C7—C8—H8	120.4	H15B—C15—H15C	109.5
C8—C7—H7	119.2	C19—C18—H18C	110.5
C6—C7—C8	121.51 (17)	C19—C18—H18D	110.5
C6—C7—H7	119.2	C17—C18—C19	106.1 (5)
C7—C6—C5	124.25 (15)	C17—C18—H18C	110.5
C7—C6—C11	118.18 (16)	C17—C18—H18D	110.5
C11—C6—C5	117.57 (15)	H18C—C18—H18D	108.7
H18A—C18A—H18B	108.7
S1—C1—N3—N2	177.24 (11)	C4—S1—C1—N3	12.52 (15)
S1—C1—N3—N4	−4.2 (2)	C4—S1—C1—C2	−171.49 (15)
S1—C1—C2—N1	−177.35 (13)	C4—C3—C19—C18A	−156.3 (2)
S1—C1—C2—C13	6.4 (3)	C4—C3—C19—C18	−129.1 (4)
S1—C4—C3—N4	63.45 (15)	C2—C1—N3—N2	0.32 (18)
S1—C4—C3—C16	−176.92 (11)	C2—C1—N3—N4	178.90 (15)
S1—C4—C3—C19	−60.93 (14)	C3—N4—N3—N2	−160.09 (14)
S1—C4—C5—O3	−98.04 (18)	C3—N4—N3—C1	21.4 (2)
S1—C4—C5—C6	78.26 (16)	C3—C16—C17—C18A	−17.2 (3)
N2—N1—C2—C1	0.9 (2)	C3—C16—C17—C18	−43.1 (4)
N2—N1—C2—C13	177.44 (15)	C3—C4—C5—O3	26.9 (2)
C1—S1—C4—C3	−39.23 (11)	C3—C4—C5—C6	−156.77 (14)
C1—S1—C4—C5	88.35 (11)	C3—C19—C18—C17	−18.8 (6)
O1—C13—C2—C1	−5.3 (2)	C9—C8—C7—C6	1.3 (3)
O1—C13—C2—N1	178.91 (16)	C9—C10—C11—C6	0.9 (3)
N4—C3—C19—C18A	77.0 (2)	C8—C9—C10—C11	−1.4 (3)
N4—C3—C19—C18	104.2 (4)	C8—C7—C6—C5	179.01 (17)
O2—C13—C2—C1	173.82 (18)	C8—C7—C6—C11	−1.8 (3)
O2—C13—C2—N1	−2.0 (3)	C7—C6—C5—O3	−168.99 (18)
N1—N2—N3—C1	0.2 (2)	C7—C6—C5—C4	14.8 (2)
N1—N2—N3—N4	−178.55 (14)	C7—C6—C11—C10	0.6 (3)
C12—O4—C9—C8	0.1 (3)	C10—C9—C8—C7	0.3 (3)
C12—O4—C9—C10	−179.39 (19)	C5—C4—C3—N4	−58.11 (18)
C13—O1—C14—C15	−175.32 (19)	C5—C4—C3—C16	61.52 (18)
N3—N2—N1—C2	−0.7 (2)	C5—C4—C3—C19	177.51 (13)
N3—C1—C2—N1	−0.73 (18)	C5—C6—C11—C10	179.93 (19)
N3—C1—C2—C13	−176.97 (16)	C19—C18A—C17—C16	−4.4 (3)
N3—N4—C3—C16	−174.98 (13)	C11—C6—C5—O3	11.8 (3)
N3—N4—C3—C4	−51.42 (17)	C11—C6—C5—C4	−164.48 (16)
N3—N4—C3—C19	74.09 (16)	C14—O1—C13—O2	−5.5 (3)
O4—C9—C8—C7	−179.16 (19)	C14—O1—C13—C2	173.60 (16)
O4—C9—C10—C11	178.1 (2)	C17—C16—C3—N4	−83.17 (17)
C16—C3—C19—C18A	−35.0 (2)	C17—C16—C3—C4	152.51 (15)
C16—C3—C19—C18	−7.9 (4)	C17—C16—C3—C19	31.84 (18)
C16—C17—C18—C19	37.8 (6)	C17—C18A—C19—C3	24.4 (3)

Ethyl 5'-benzoyl-5'H,7'H-spiro[cyclohexane-1,6'-[1,2,3]triazolo[5,1-b][1,3,4]thiadiazine]-3'-carboxylate (III)

Crystal data

C19H22N4O3S	F(000) = 408
Mr = 386.46	Dx = 1.356 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 5.8289 (6) Å	Cell parameters from 2546 reflections
b = 18.0940 (18) Å	θ = 3.2–28.3°
c = 9.0173 (8) Å	µ = 0.20 mm^−1
β = 95.799 (8)°	T = 295 K
V = 946.17 (16) Å^3	Prism, colourless
Z = 2	0.25 × 0.2 × 0.15 mm

Data collection

Xcalibur 3 diffractometer	Rint = 0.018
Graphite monochromator	θmax = 28.3°, θmin = 3.2°
phi and ω scans	h = −7→6
6254 measured reflections	k = −24→23
4285 independent reflections	l = −12→11
2544 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.018P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.055	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.35 e Å^−3
4285 reflections	Δρmin = −0.17 e Å^−3
248 parameters	Absolute structure: Flack x determined using 908 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.02 (4)
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
S1	0.36652 (11)	0.60607 (4)	0.42819 (7)	0.05628 (19)
N4	0.7935 (4)	0.72176 (13)	0.4776 (2)	0.0508 (5)
O2	0.2896 (3)	0.62515 (12)	−0.08442 (19)	0.0837 (6)
C11	0.8701 (5)	0.44206 (18)	0.6728 (3)	0.0716 (9)
H11	0.997368	0.451200	0.621087	0.086*
N3	0.6869 (3)	0.70046 (11)	0.3383 (2)	0.0483 (5)
O3	0.9198 (4)	0.57769 (12)	0.5526 (3)	0.1050 (8)
C10	0.8512 (7)	0.37557 (19)	0.7430 (5)	0.0943 (12)
H10	0.966230	0.340088	0.740841	0.113*
N2	0.7662 (4)	0.73095 (12)	0.2163 (3)	0.0592 (6)
O1	0.1707 (3)	0.58020 (10)	0.12459 (19)	0.0687 (6)
C9	0.6622 (8)	0.36191 (19)	0.8160 (4)	0.0957 (12)
H9	0.649362	0.316911	0.864339	0.115*
N1	0.6394 (4)	0.70367 (13)	0.1026 (2)	0.0622 (6)
C8	0.4936 (6)	0.41267 (18)	0.8193 (3)	0.0800 (9)
H8	0.364350	0.402166	0.868084	0.096*
C7	0.5123 (5)	0.48037 (14)	0.7501 (3)	0.0589 (7)
H7	0.395967	0.515363	0.752823	0.071*
C6	0.7023 (5)	0.49584 (14)	0.6778 (3)	0.0499 (6)
C5	0.7399 (5)	0.56704 (15)	0.6064 (3)	0.0529 (7)
C14	−0.0157 (5)	0.5406 (2)	0.0433 (3)	0.0818 (9)
H14A	0.044129	0.505773	−0.024936	0.098*
H14B	−0.117890	0.574749	−0.013907	0.098*
C15	−0.1415 (5)	0.50110 (19)	0.1526 (4)	0.0909 (11)
H15A	−0.267320	0.474084	0.101443	0.136*
H15B	−0.038924	0.467386	0.208389	0.136*
H15C	−0.200264	0.536072	0.219372	0.136*
C19	0.8007 (4)	0.71901 (17)	0.7426 (3)	0.0602 (7)
H19A	0.720747	0.700856	0.824554	0.072*
H19B	0.940185	0.689966	0.740126	0.072*
C12	0.8676 (5)	0.79896 (18)	0.7729 (3)	0.0774 (9)
H12A	0.954194	0.802957	0.870237	0.093*
H12B	0.965394	0.815854	0.698876	0.093*
C18	0.6552 (6)	0.84698 (17)	0.7678 (4)	0.0833 (10)
H18A	0.700099	0.898134	0.784989	0.100*
H18B	0.561634	0.832065	0.845682	0.100*
C17	0.5169 (5)	0.83971 (15)	0.6174 (3)	0.0697 (8)
H17A	0.380600	0.870654	0.614750	0.084*
H17B	0.608726	0.856651	0.540201	0.084*
C16	0.4458 (4)	0.76090 (13)	0.5875 (3)	0.0514 (7)
H16A	0.364179	0.757671	0.488446	0.062*
H16B	0.339679	0.746261	0.658346	0.062*
C3	0.6485 (4)	0.70683 (14)	0.5982 (2)	0.0448 (6)
C4	0.5561 (4)	0.62651 (13)	0.5941 (2)	0.0448 (6)
H4A	0.466012	0.620596	0.679352	0.054*
C13	0.3082 (5)	0.62070 (16)	0.0483 (3)	0.0588 (7)
C2	0.4797 (5)	0.65724 (14)	0.1501 (2)	0.0501 (6)
C1	0.5114 (4)	0.65376 (13)	0.3023 (3)	0.0452 (6)
H4	0.914 (5)	0.6921 (15)	0.495 (3)	0.069 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0583 (4)	0.0631 (4)	0.0490 (4)	−0.0158 (4)	0.0131 (3)	0.0044 (4)
N4	0.0485 (13)	0.0625 (15)	0.0430 (13)	−0.0080 (12)	0.0121 (11)	0.0012 (11)
O2	0.1033 (15)	0.1071 (19)	0.0405 (11)	0.0101 (12)	0.0068 (10)	−0.0045 (11)
C11	0.0572 (19)	0.056 (2)	0.098 (2)	0.0079 (16)	−0.0074 (17)	−0.0132 (18)
N3	0.0588 (13)	0.0491 (14)	0.0397 (13)	−0.0044 (11)	0.0171 (11)	0.0054 (10)
O3	0.0796 (14)	0.0821 (17)	0.167 (2)	0.0246 (11)	0.0776 (16)	0.0360 (14)
C10	0.072 (3)	0.048 (2)	0.156 (3)	0.0110 (17)	−0.026 (2)	−0.011 (2)
N2	0.0759 (15)	0.0569 (15)	0.0487 (13)	−0.0080 (12)	0.0251 (13)	0.0045 (11)
O1	0.0769 (13)	0.0750 (15)	0.0523 (11)	−0.0086 (11)	−0.0037 (10)	−0.0120 (10)
C9	0.091 (3)	0.054 (2)	0.132 (3)	−0.017 (2)	−0.037 (3)	0.018 (2)
N1	0.0823 (16)	0.0585 (15)	0.0492 (14)	0.0034 (12)	0.0243 (13)	0.0048 (11)
C8	0.084 (2)	0.062 (2)	0.093 (2)	−0.014 (2)	0.0020 (17)	0.0200 (19)
C7	0.0652 (19)	0.0485 (18)	0.0632 (18)	−0.0043 (14)	0.0076 (15)	0.0032 (14)
C6	0.0483 (16)	0.0450 (17)	0.0555 (16)	0.0002 (13)	0.0001 (14)	−0.0078 (13)
C5	0.0527 (16)	0.0560 (18)	0.0527 (16)	0.0050 (13)	0.0189 (14)	0.0048 (12)
C14	0.079 (2)	0.089 (3)	0.075 (2)	−0.0019 (19)	−0.0061 (19)	−0.0233 (19)
C15	0.075 (2)	0.080 (2)	0.115 (3)	−0.0035 (18)	−0.006 (2)	−0.013 (2)
C19	0.0522 (16)	0.080 (2)	0.0483 (16)	0.0017 (15)	0.0054 (13)	0.0008 (15)
C12	0.071 (2)	0.089 (3)	0.071 (2)	−0.0135 (19)	−0.0028 (18)	−0.0224 (17)
C18	0.089 (3)	0.070 (2)	0.092 (2)	−0.0146 (19)	0.016 (2)	−0.0276 (18)
C17	0.071 (2)	0.0532 (19)	0.086 (2)	0.0013 (15)	0.0174 (18)	−0.0036 (16)
C16	0.0513 (15)	0.0538 (18)	0.0504 (15)	−0.0001 (13)	0.0112 (13)	0.0037 (12)
C3	0.0442 (13)	0.0495 (16)	0.0423 (14)	−0.0010 (12)	0.0126 (12)	0.0041 (11)
C4	0.0461 (14)	0.0510 (18)	0.0400 (13)	−0.0010 (12)	0.0175 (11)	0.0072 (11)
C13	0.0751 (19)	0.058 (2)	0.0443 (17)	0.0170 (16)	0.0114 (16)	−0.0044 (15)
C2	0.0634 (17)	0.0482 (16)	0.0403 (16)	0.0029 (14)	0.0131 (14)	−0.0009 (13)
C1	0.0498 (15)	0.0441 (15)	0.0424 (14)	−0.0056 (12)	0.0083 (12)	−0.0010 (12)

Geometric parameters (Å, º)

S1—C4	1.806 (2)	C14—H14A	0.9700
S1—C1	1.715 (2)	C14—H14B	0.9700
N4—N3	1.398 (3)	C14—C15	1.472 (4)
N4—C3	1.468 (3)	C15—H15A	0.9600
N4—H4	0.88 (3)	C15—H15B	0.9600
O2—C13	1.194 (3)	C15—H15C	0.9600
C11—H11	0.9300	C19—H19A	0.9700
C11—C10	1.369 (4)	C19—H19B	0.9700
C11—C6	1.383 (4)	C19—C12	1.516 (4)
N3—N2	1.353 (3)	C19—C3	1.516 (3)
N3—C1	1.341 (3)	C12—H12A	0.9700
O3—C5	1.214 (3)	C12—H12B	0.9700
C10—H10	0.9300	C12—C18	1.509 (4)
C10—C9	1.362 (5)	C18—H18A	0.9700
N2—N1	1.300 (3)	C18—H18B	0.9700
O1—C14	1.439 (3)	C18—C17	1.512 (4)
O1—C13	1.328 (3)	C17—H17A	0.9700
C9—H9	0.9300	C17—H17B	0.9700
C9—C8	1.348 (4)	C17—C16	1.502 (3)
N1—C2	1.355 (3)	C16—H16A	0.9700
C8—H8	0.9300	C16—H16B	0.9700
C8—C7	1.384 (4)	C16—C3	1.530 (3)
C7—H7	0.9300	C3—C4	1.549 (3)
C7—C6	1.370 (4)	C4—H4A	0.9800
C6—C5	1.467 (4)	C13—C2	1.447 (4)
C5—C4	1.515 (3)	C2—C1	1.368 (3)
C1—S1—C4	98.29 (11)	C3—C19—H19A	108.7
N3—N4—C3	112.22 (18)	C3—C19—H19B	108.7
N3—N4—H4	105.1 (18)	C19—C12—H12A	109.6
C3—N4—H4	105.4 (17)	C19—C12—H12B	109.6
C10—C11—H11	119.6	H12A—C12—H12B	108.1
C10—C11—C6	120.8 (3)	C18—C12—C19	110.4 (2)
C6—C11—H11	119.6	C18—C12—H12A	109.6
N2—N3—N4	117.4 (2)	C18—C12—H12B	109.6
C1—N3—N4	130.53 (19)	C12—C18—H18A	109.7
C1—N3—N2	112.0 (2)	C12—C18—H18B	109.7
C11—C10—H10	120.3	C12—C18—C17	109.8 (3)
C9—C10—C11	119.3 (3)	H18A—C18—H18B	108.2
C9—C10—H10	120.3	C17—C18—H18A	109.7
N1—N2—N3	105.9 (2)	C17—C18—H18B	109.7
C13—O1—C14	118.4 (2)	C18—C17—H17A	109.5
C10—C9—H9	119.5	C18—C17—H17B	109.5
C8—C9—C10	120.9 (3)	H17A—C17—H17B	108.1
C8—C9—H9	119.5	C16—C17—C18	110.9 (2)
N2—N1—C2	109.87 (19)	C16—C17—H17A	109.5
C9—C8—H8	119.9	C16—C17—H17B	109.5
C9—C8—C7	120.2 (3)	C17—C16—H16A	108.9
C7—C8—H8	119.9	C17—C16—H16B	108.9
C8—C7—H7	120.0	C17—C16—C3	113.5 (2)
C6—C7—C8	120.0 (3)	H16A—C16—H16B	107.7
C6—C7—H7	120.0	C3—C16—H16A	108.9
C11—C6—C5	117.8 (3)	C3—C16—H16B	108.9
C7—C6—C11	118.7 (3)	N4—C3—C19	106.19 (19)
C7—C6—C5	123.5 (2)	N4—C3—C16	109.5 (2)
O3—C5—C6	119.2 (2)	N4—C3—C4	112.32 (18)
O3—C5—C4	119.4 (2)	C19—C3—C16	110.0 (2)
C6—C5—C4	121.3 (2)	C19—C3—C4	109.21 (19)
O1—C14—H14A	110.2	C16—C3—C4	109.50 (19)
O1—C14—H14B	110.2	S1—C4—H4A	107.2
O1—C14—C15	107.6 (2)	C5—C4—S1	106.53 (16)
H14A—C14—H14B	108.5	C5—C4—C3	115.02 (19)
C15—C14—H14A	110.2	C5—C4—H4A	107.2
C15—C14—H14B	110.2	C3—C4—S1	113.23 (15)
C14—C15—H15A	109.5	C3—C4—H4A	107.2
C14—C15—H15B	109.5	O2—C13—O1	123.9 (3)
C14—C15—H15C	109.5	O2—C13—C2	126.3 (3)
H15A—C15—H15B	109.5	O1—C13—C2	109.8 (2)
H15A—C15—H15C	109.5	N1—C2—C13	122.4 (2)
H15B—C15—H15C	109.5	N1—C2—C1	108.6 (2)
H19A—C19—H19B	107.6	C1—C2—C13	129.0 (2)
C12—C19—H19A	108.7	N3—C1—S1	124.85 (18)
C12—C19—H19B	108.7	N3—C1—C2	103.7 (2)
C12—C19—C3	114.3 (2)	C2—C1—S1	131.4 (2)

Ethyl 5'-(4-methoxybenzoyl)-5'H,7'H-spiro[cyclohexane-1,6'-[1,2,3]triazolo[5,1-b][1,3,4]thiadiazine]-3'-carboxylate (IV)

Crystal data

C20H24N4O4S	Dx = 1.320 Mg m^−3
Mr = 416.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 2233 reflections
a = 28.5394 (14) Å	θ = 2.7–27.0°
b = 8.0288 (3) Å	µ = 0.19 mm^−1
c = 9.1435 (4) Å	T = 295 K
V = 2095.12 (16) Å^3	Block, light yellow
Z = 4	0.25 × 0.2 × 0.15 mm
F(000) = 880

Data collection

Xcalibur 3 diffractometer	2926 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
phi and ω scans	θmax = 27.1°, θmin = 2.5°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −17→36
Tmin = 0.822, Tmax = 1.000	k = −10→10
6492 measured reflections	l = −5→11
3439 independent reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.070P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.040	(Δ/σ)max < 0.001
wR(F^2) = 0.112	Δρmax = 0.22 e Å^−3
S = 1.00	Δρmin = −0.19 e Å^−3
3439 reflections	Absolute structure: Flack x determined using 735 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
272 parameters	Absolute structure parameter: 0.04 (5)
1 restraint

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
S1	0.36348 (3)	0.71255 (10)	0.46005 (10)	0.0492 (2)
N4	0.36707 (11)	0.7878 (3)	0.1100 (3)	0.0444 (6)
C1	0.35711 (11)	0.8968 (3)	0.3637 (3)	0.0384 (7)
N3	0.35821 (9)	0.9092 (3)	0.2163 (3)	0.0402 (6)
O2	0.33641 (12)	1.2673 (3)	0.5873 (3)	0.0718 (8)
N2	0.35044 (10)	1.0690 (3)	0.1705 (3)	0.0472 (7)
O1	0.33760 (10)	0.9973 (3)	0.6510 (3)	0.0571 (7)
O3	0.45378 (9)	0.7191 (3)	0.2518 (4)	0.0673 (8)
C16	0.37673 (12)	0.5009 (4)	0.0447 (4)	0.0468 (8)
H16B	0.409392	0.527921	0.027425	0.056*
H16A	0.375257	0.386855	0.079373	0.056*
N1	0.34453 (10)	1.1582 (3)	0.2878 (3)	0.0487 (6)
C5	0.43595 (11)	0.5895 (4)	0.2961 (4)	0.0467 (7)
C7	0.44955 (11)	0.3132 (4)	0.4193 (4)	0.0526 (9)
H7	0.419895	0.319820	0.461145	0.063*
C4	0.38270 (11)	0.5783 (3)	0.3105 (4)	0.0412 (7)
C3	0.35734 (11)	0.6170 (3)	0.1636 (4)	0.0395 (7)
C2	0.34765 (11)	1.0583 (4)	0.4079 (4)	0.0426 (7)
C13	0.34010 (12)	1.1229 (4)	0.5558 (4)	0.0469 (8)
C14	0.32623 (14)	1.0351 (5)	0.8032 (4)	0.0592 (9)
H14B	0.339278	1.142591	0.829565	0.071*
H14A	0.339951	0.951550	0.866715	0.071*
C17	0.34998 (16)	0.5143 (5)	−0.0985 (5)	0.0652 (11)
H17B	0.354257	0.624772	−0.139336	0.078*
H17A	0.362346	0.434085	−0.167790	0.078*
C6	0.46502 (11)	0.4411 (4)	0.3287 (4)	0.0446 (7)
C8	0.47782 (11)	0.1751 (4)	0.4486 (5)	0.0625 (10)
H8	0.467273	0.090747	0.510040	0.075*
C20	0.30446 (10)	0.5909 (4)	0.1820 (4)	0.0478 (8)
H20B	0.298953	0.482636	0.225788	0.057*
H20A	0.292267	0.674762	0.248284	0.057*
C18	0.29826 (16)	0.4821 (5)	−0.0752 (6)	0.0801 (14)
H18B	0.293810	0.368436	−0.041939	0.096*
H18A	0.281765	0.495076	−0.167221	0.096*
C19	0.27799 (14)	0.6014 (5)	0.0368 (5)	0.0681 (11)
H19B	0.245232	0.574834	0.052930	0.082*
H19A	0.279755	0.714218	−0.000664	0.082*
C11	0.50950 (11)	0.4284 (4)	0.2654 (5)	0.0602 (10)
H11	0.520498	0.512528	0.204470	0.072*
O4	0.55220 (10)	0.0387 (4)	0.4082 (5)	0.0987 (13)
C9	0.52138 (13)	0.1658 (5)	0.3856 (6)	0.0672 (11)
C10	0.53684 (13)	0.2916 (5)	0.2933 (6)	0.0722 (12)
H10	0.566188	0.283053	0.249744	0.087*
C15	0.27435 (16)	1.0380 (6)	0.8236 (6)	0.0812 (13)
H15B	0.261339	1.130770	0.771299	0.122*
H15A	0.267212	1.048667	0.925773	0.122*
H15C	0.261125	0.936319	0.786839	0.122*
C12	0.53770 (17)	−0.0976 (6)	0.4963 (10)	0.117 (3)
H12C	0.511001	−0.150343	0.452321	0.176*
H12B	0.529452	−0.057995	0.591976	0.176*
H12A	0.562837	−0.176519	0.504190	0.176*
H4	0.3983 (11)	0.801 (3)	0.086 (4)	0.037 (9)*
H4A	0.3710 (10)	0.468 (4)	0.346 (4)	0.035 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0752 (5)	0.0374 (4)	0.0352 (4)	0.0037 (4)	0.0008 (4)	0.0049 (4)
N4	0.0679 (19)	0.0311 (13)	0.0342 (13)	−0.0018 (12)	0.0043 (13)	−0.0045 (12)
C1	0.0505 (16)	0.0305 (14)	0.0342 (15)	−0.0022 (12)	0.0014 (13)	−0.0019 (13)
N3	0.0612 (15)	0.0267 (12)	0.0328 (13)	−0.0008 (10)	0.0001 (12)	−0.0023 (11)
O2	0.126 (2)	0.0362 (13)	0.0536 (18)	−0.0062 (13)	0.0154 (17)	−0.0137 (12)
N2	0.0729 (18)	0.0250 (12)	0.0436 (16)	0.0001 (11)	0.0017 (14)	0.0043 (12)
O1	0.0946 (18)	0.0437 (12)	0.0330 (13)	−0.0003 (11)	0.0071 (13)	−0.0035 (11)
O3	0.0633 (14)	0.0502 (14)	0.089 (2)	−0.0177 (11)	−0.0049 (15)	0.0155 (15)
C16	0.0567 (18)	0.0350 (16)	0.049 (2)	0.0004 (13)	0.0049 (16)	−0.0081 (15)
N1	0.0741 (17)	0.0290 (11)	0.0429 (15)	−0.0039 (12)	0.0037 (15)	−0.0022 (13)
C5	0.0544 (17)	0.0414 (15)	0.0441 (17)	−0.0089 (13)	−0.0056 (17)	0.0018 (15)
C7	0.0447 (17)	0.0556 (19)	0.058 (2)	−0.0023 (13)	−0.0017 (16)	0.0133 (17)
C4	0.0526 (16)	0.0257 (13)	0.0454 (18)	−0.0004 (12)	0.0006 (15)	0.0024 (13)
C3	0.0548 (16)	0.0242 (13)	0.0396 (16)	0.0002 (11)	−0.0017 (14)	−0.0037 (14)
C2	0.0545 (17)	0.0353 (15)	0.0380 (16)	−0.0082 (12)	−0.0002 (15)	−0.0010 (14)
C13	0.064 (2)	0.0365 (16)	0.0405 (17)	−0.0057 (14)	0.0045 (16)	−0.0067 (15)
C14	0.084 (2)	0.057 (2)	0.0366 (18)	−0.0046 (17)	0.003 (2)	−0.0085 (17)
C17	0.085 (3)	0.056 (2)	0.054 (2)	0.0049 (19)	−0.005 (2)	−0.022 (2)
C6	0.0413 (15)	0.0506 (17)	0.0420 (18)	−0.0069 (13)	−0.0066 (14)	0.0035 (15)
C8	0.0494 (19)	0.063 (2)	0.075 (3)	0.0013 (14)	−0.014 (2)	0.021 (2)
C20	0.0496 (17)	0.0383 (16)	0.055 (2)	0.0042 (13)	−0.0009 (16)	−0.0020 (16)
C18	0.083 (3)	0.083 (3)	0.074 (3)	0.003 (2)	−0.021 (2)	−0.033 (3)
C19	0.062 (2)	0.068 (2)	0.074 (3)	0.0071 (18)	−0.016 (2)	−0.003 (2)
C11	0.0471 (17)	0.072 (2)	0.061 (3)	−0.0054 (16)	−0.0025 (17)	0.015 (2)
O4	0.0584 (16)	0.092 (2)	0.146 (4)	0.0247 (14)	−0.0116 (19)	0.030 (2)
C9	0.050 (2)	0.068 (2)	0.083 (3)	0.0096 (17)	−0.018 (2)	0.004 (2)
C10	0.0424 (18)	0.090 (3)	0.084 (3)	0.0054 (17)	0.005 (2)	0.013 (3)
C15	0.086 (3)	0.089 (3)	0.069 (3)	−0.016 (2)	0.012 (3)	−0.002 (3)
C12	0.081 (3)	0.074 (3)	0.197 (8)	0.014 (2)	−0.046 (4)	0.040 (4)

Geometric parameters (Å, º)

S1—C1	1.731 (3)	C14—H14B	0.9700
S1—C4	1.826 (3)	C14—H14A	0.9700
N4—N3	1.399 (4)	C17—C18	1.514 (6)
N4—C3	1.482 (4)	C17—H17B	0.9700
N4—H4	0.92 (3)	C17—H17A	0.9700
C1—N3	1.352 (4)	C6—C11	1.399 (5)
C1—C2	1.385 (4)	C8—C9	1.372 (5)
N3—N2	1.368 (3)	C8—H8	0.9300
O2—C13	1.199 (4)	C20—C19	1.530 (6)
N2—N1	1.301 (4)	C20—H20B	0.9700
O1—C13	1.334 (4)	C20—H20A	0.9700
O1—C14	1.461 (4)	C18—C19	1.517 (6)
O3—C5	1.227 (4)	C18—H18B	0.9700
C16—C17	1.520 (6)	C18—H18A	0.9700
C16—C3	1.535 (4)	C19—H19B	0.9700
C16—H16B	0.9700	C19—H19A	0.9700
C16—H16A	0.9700	C11—C10	1.371 (5)
N1—C2	1.362 (4)	C11—H11	0.9300
C5—C6	1.482 (5)	O4—C9	1.363 (4)
C5—C4	1.528 (5)	O4—C12	1.421 (7)
C7—C6	1.391 (5)	C9—C10	1.389 (6)
C7—C8	1.397 (5)	C10—H10	0.9300
C7—H7	0.9300	C15—H15B	0.9600
C4—C3	1.557 (5)	C15—H15A	0.9600
C4—H4A	1.00 (3)	C15—H15C	0.9600
C3—C20	1.533 (4)	C12—H12C	0.9600
C2—C13	1.464 (5)	C12—H12B	0.9600
C14—C15	1.492 (6)	C12—H12A	0.9600
C1—S1—C4	98.91 (15)	C16—C17—H17B	109.5
N3—N4—C3	112.4 (3)	C18—C17—H17A	109.5
N3—N4—H4	105.0 (19)	C16—C17—H17A	109.5
C3—N4—H4	111.2 (18)	H17B—C17—H17A	108.1
N3—C1—C2	103.1 (3)	C7—C6—C11	118.7 (3)
N3—C1—S1	124.6 (2)	C7—C6—C5	122.4 (3)
C2—C1—S1	132.2 (3)	C11—C6—C5	118.9 (3)
C1—N3—N2	111.7 (3)	C9—C8—C7	119.1 (4)
C1—N3—N4	130.2 (3)	C9—C8—H8	120.5
N2—N3—N4	118.0 (3)	C7—C8—H8	120.5
N1—N2—N3	106.5 (3)	C19—C20—C3	112.5 (3)
C13—O1—C14	118.4 (3)	C19—C20—H20B	109.1
C17—C16—C3	112.7 (3)	C3—C20—H20B	109.1
C17—C16—H16B	109.0	C19—C20—H20A	109.1
C3—C16—H16B	109.0	C3—C20—H20A	109.1
C17—C16—H16A	109.0	H20B—C20—H20A	107.8
C3—C16—H16A	109.0	C17—C18—C19	111.0 (3)
H16B—C16—H16A	107.8	C17—C18—H18B	109.4
N2—N1—C2	109.4 (2)	C19—C18—H18B	109.4
O3—C5—C6	121.1 (3)	C17—C18—H18A	109.4
O3—C5—C4	119.4 (3)	C19—C18—H18A	109.4
C6—C5—C4	119.5 (3)	H18B—C18—H18A	108.0
C6—C7—C8	121.1 (3)	C18—C19—C20	111.3 (3)
C6—C7—H7	119.5	C18—C19—H19B	109.4
C8—C7—H7	119.5	C20—C19—H19B	109.4
C5—C4—C3	112.1 (3)	C18—C19—H19A	109.4
C5—C4—S1	109.2 (2)	C20—C19—H19A	109.4
C3—C4—S1	112.88 (19)	H19B—C19—H19A	108.0
C5—C4—H4A	114.3 (17)	C10—C11—C6	119.8 (4)
C3—C4—H4A	107.6 (19)	C10—C11—H11	120.1
S1—C4—H4A	100.3 (18)	C6—C11—H11	120.1
N4—C3—C20	110.3 (2)	C9—O4—C12	118.3 (4)
N4—C3—C16	105.1 (3)	O4—C9—C8	124.2 (4)
C20—C3—C16	110.5 (3)	O4—C9—C10	115.6 (4)
N4—C3—C4	112.5 (2)	C8—C9—C10	120.2 (3)
C20—C3—C4	109.6 (3)	C11—C10—C9	121.0 (4)
C16—C3—C4	108.8 (2)	C11—C10—H10	119.5
N1—C2—C1	109.2 (3)	C9—C10—H10	119.5
N1—C2—C13	121.8 (3)	C14—C15—H15B	109.5
C1—C2—C13	129.0 (3)	C14—C15—H15A	109.5
O2—C13—O1	124.7 (3)	H15B—C15—H15A	109.5
O2—C13—C2	125.3 (3)	C14—C15—H15C	109.5
O1—C13—C2	110.1 (3)	H15B—C15—H15C	109.5
O1—C14—C15	110.0 (3)	H15A—C15—H15C	109.5
O1—C14—H14B	109.7	O4—C12—H12C	109.5
C15—C14—H14B	109.7	O4—C12—H12B	109.5
O1—C14—H14A	109.7	H12C—C12—H12B	109.5
C15—C14—H14A	109.7	O4—C12—H12A	109.5
H14B—C14—H14A	108.2	H12C—C12—H12A	109.5
C18—C17—C16	110.9 (4)	H12B—C12—H12A	109.5
C18—C17—H17B	109.5
C4—S1—C1—N3	11.0 (3)	N3—C1—C2—C13	176.9 (3)
C4—S1—C1—C2	−172.9 (3)	S1—C1—C2—C13	0.2 (6)
C2—C1—N3—N2	0.6 (4)	C14—O1—C13—O2	4.7 (5)
S1—C1—N3—N2	177.7 (2)	C14—O1—C13—C2	−175.0 (3)
C2—C1—N3—N4	178.7 (3)	N1—C2—C13—O2	−9.6 (6)
S1—C1—N3—N4	−4.3 (5)	C1—C2—C13—O2	172.5 (3)
C3—N4—N3—C1	23.5 (5)	N1—C2—C13—O1	170.0 (3)
C3—N4—N3—N2	−158.5 (3)	C1—C2—C13—O1	−7.8 (5)
C1—N3—N2—N1	0.1 (4)	C13—O1—C14—C15	87.2 (4)
N4—N3—N2—N1	−178.2 (3)	C3—C16—C17—C18	−55.7 (4)
N3—N2—N1—C2	−0.9 (3)	C8—C7—C6—C11	0.7 (5)
O3—C5—C4—C3	56.5 (4)	C8—C7—C6—C5	−179.7 (4)
C6—C5—C4—C3	−120.4 (3)	O3—C5—C6—C7	159.5 (4)
O3—C5—C4—S1	−69.4 (4)	C4—C5—C6—C7	−23.7 (5)
C6—C5—C4—S1	113.7 (3)	O3—C5—C6—C11	−20.9 (5)
C1—S1—C4—C5	87.5 (2)	C4—C5—C6—C11	155.9 (3)
C1—S1—C4—C3	−37.9 (2)	C6—C7—C8—C9	−0.5 (6)
N3—N4—C3—C20	70.4 (3)	N4—C3—C20—C19	64.1 (4)
N3—N4—C3—C16	−170.6 (3)	C16—C3—C20—C19	−51.6 (4)
N3—N4—C3—C4	−52.4 (3)	C4—C3—C20—C19	−171.5 (3)
C17—C16—C3—N4	−66.4 (4)	C16—C17—C18—C19	57.1 (5)
C17—C16—C3—C20	52.5 (4)	C17—C18—C19—C20	−56.5 (5)
C17—C16—C3—C4	172.9 (3)	C3—C20—C19—C18	54.3 (5)
C5—C4—C3—N4	−61.1 (3)	C7—C6—C11—C10	0.0 (6)
S1—C4—C3—N4	62.7 (3)	C5—C6—C11—C10	−179.6 (4)
C5—C4—C3—C20	175.8 (2)	C12—O4—C9—C8	3.5 (7)
S1—C4—C3—C20	−60.5 (3)	C12—O4—C9—C10	−177.2 (5)
C5—C4—C3—C16	54.9 (3)	C7—C8—C9—O4	178.9 (4)
S1—C4—C3—C16	178.6 (2)	C7—C8—C9—C10	−0.4 (7)
N2—N1—C2—C1	1.4 (4)	C6—C11—C10—C9	−1.0 (7)
N2—N1—C2—C13	−176.9 (3)	O4—C9—C10—C11	−178.2 (4)
N3—C1—C2—N1	−1.2 (4)	C8—C9—C10—C11	1.1 (7)
S1—C1—C2—N1	−177.9 (3)

Ethyl 6,6-dimethyl-5-(4-methylbenzoyl)-6,7-dihydro-5H-[1,2,3]triazolo[5,1-b][1,3,4]thiadiazine-3-carboxylate (V)

Crystal data

C17H20N4O3S	F(000) = 760
Mr = 360.43	Dx = 1.349 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.0154 (3) Å	Cell parameters from 2433 reflections
b = 14.2211 (11) Å	θ = 2.6–28.0°
c = 15.9349 (7) Å	µ = 0.21 mm^−1
β = 102.337 (4)°	T = 295 K
V = 1774.45 (17) Å^3	Prism, colourless
Z = 4	0.25 × 0.2 × 0.15 mm

Data collection

Xcalibur 3 diffractometer	2950 reflections with I > 2σ(I)
Detector resolution: 15.9555 pixels mm^-1	Rint = 0.029
ω scans	θmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −10→10
Tmin = 0.947, Tmax = 1.000	k = −18→9
8945 measured reflections	l = −21→14
4411 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 0.3794P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
4411 reflections	Δρmax = 0.21 e Å^−3
238 parameters	Δρmin = −0.24 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
S1	0.50827 (6)	0.22721 (4)	0.01390 (3)	0.05234 (17)
C4	0.6010 (2)	0.26169 (14)	−0.07639 (11)	0.0386 (4)
N1	0.02928 (17)	0.16111 (12)	−0.08035 (10)	0.0458 (4)
O1	−0.00287 (16)	0.12860 (13)	0.08540 (9)	0.0624 (4)
N3	0.25078 (16)	0.20179 (11)	−0.12616 (9)	0.0387 (4)
C3	0.5292 (2)	0.20261 (14)	−0.15855 (12)	0.0423 (4)
N4	0.34350 (17)	0.21692 (15)	−0.18997 (10)	0.0440 (4)
O2	0.27457 (18)	0.15983 (13)	0.13615 (9)	0.0655 (5)
N2	0.08279 (16)	0.17734 (13)	−0.15086 (10)	0.0463 (4)
O3	0.43032 (15)	0.39760 (11)	−0.10475 (11)	0.0676 (5)
C17	0.6082 (2)	0.23682 (18)	−0.23221 (12)	0.0553 (6)
H17A	0.579393	0.301730	−0.243888	0.083*
H17B	0.564743	0.199979	−0.282620	0.083*
H17C	0.730099	0.230270	−0.216419	0.083*
C1	0.30372 (19)	0.20152 (14)	−0.04058 (11)	0.0384 (4)
C5	0.5753 (2)	0.36639 (14)	−0.09285 (12)	0.0423 (4)
C13	0.1525 (2)	0.15400 (15)	0.07757 (13)	0.0472 (5)
C9	0.9843 (2)	0.54966 (16)	−0.12010 (11)	0.0484 (5)
C6	0.72125 (19)	0.42822 (13)	−0.09868 (10)	0.0369 (4)
C10	1.0153 (2)	0.45553 (16)	−0.10392 (12)	0.0469 (5)
H10	1.125065	0.432148	−0.100003	0.056*
C2	0.1604 (2)	0.17345 (14)	−0.01173 (11)	0.0409 (4)
C16	0.5654 (2)	0.09863 (16)	−0.14211 (15)	0.0599 (6)
H16A	0.686219	0.089120	−0.123424	0.090*
H16B	0.524214	0.063962	−0.194098	0.090*
H16C	0.508610	0.077087	−0.098397	0.090*
C7	0.6911 (2)	0.52377 (15)	−0.11324 (12)	0.0482 (5)
H7	0.582126	0.547719	−0.115878	0.058*
C14	−0.0201 (3)	0.0980 (2)	0.17049 (14)	0.0732 (8)
H14A	−0.004393	0.150829	0.209896	0.088*
H14B	0.065166	0.050716	0.192637	0.088*
C11	0.8864 (2)	0.39512 (15)	−0.09341 (12)	0.0431 (4)
H11	0.910296	0.331712	−0.082695	0.052*
C12	1.1244 (3)	0.6148 (2)	−0.13432 (15)	0.0740 (8)
H12A	1.233299	0.585176	−0.114247	0.111*
H12B	1.119913	0.672236	−0.103252	0.111*
H12C	1.109229	0.628345	−0.194493	0.111*
C15	−0.1919 (3)	0.05879 (18)	0.16181 (15)	0.0638 (6)
H15A	−0.274969	0.107703	0.145378	0.096*
H15B	−0.203474	0.032372	0.215708	0.096*
H15C	−0.209781	0.010573	0.118643	0.096*
C8	0.8204 (3)	0.58335 (16)	−0.12379 (13)	0.0550 (5)
H8	0.797663	0.647010	−0.133527	0.066*
H4A	0.714 (2)	0.2460 (13)	−0.0590 (11)	0.041 (5)*
H4	0.325 (2)	0.2727 (15)	−0.2042 (13)	0.043 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0366 (2)	0.0798 (4)	0.0373 (2)	−0.0182 (2)	0.00045 (17)	0.0070 (2)
C4	0.0257 (8)	0.0481 (12)	0.0413 (9)	−0.0022 (7)	0.0054 (6)	0.0042 (8)
N1	0.0308 (7)	0.0564 (11)	0.0506 (9)	−0.0038 (7)	0.0100 (6)	−0.0008 (8)
O1	0.0477 (8)	0.0929 (13)	0.0503 (8)	−0.0160 (7)	0.0185 (6)	0.0067 (8)
N3	0.0262 (6)	0.0508 (10)	0.0381 (7)	−0.0037 (6)	0.0046 (5)	0.0015 (7)
C3	0.0292 (8)	0.0510 (12)	0.0465 (10)	−0.0017 (8)	0.0075 (7)	−0.0023 (9)
N4	0.0311 (7)	0.0614 (13)	0.0391 (8)	−0.0026 (7)	0.0066 (6)	0.0047 (8)
O2	0.0547 (8)	0.0902 (13)	0.0484 (8)	−0.0222 (8)	0.0041 (7)	0.0056 (8)
N2	0.0263 (7)	0.0619 (12)	0.0484 (9)	−0.0028 (7)	0.0030 (6)	−0.0017 (8)
O3	0.0320 (7)	0.0611 (11)	0.1126 (13)	0.0067 (6)	0.0221 (7)	0.0039 (9)
C17	0.0416 (10)	0.0794 (17)	0.0483 (11)	−0.0062 (10)	0.0170 (8)	−0.0062 (11)
C1	0.0306 (8)	0.0450 (11)	0.0383 (9)	−0.0047 (7)	0.0046 (7)	0.0013 (8)
C5	0.0310 (8)	0.0495 (12)	0.0480 (10)	0.0000 (8)	0.0117 (7)	−0.0012 (9)
C13	0.0450 (10)	0.0475 (13)	0.0510 (11)	−0.0077 (8)	0.0147 (9)	0.0024 (10)
C9	0.0472 (10)	0.0575 (14)	0.0373 (9)	−0.0163 (9)	0.0020 (8)	0.0044 (9)
C6	0.0316 (8)	0.0421 (11)	0.0367 (8)	−0.0007 (7)	0.0069 (6)	−0.0006 (8)
C10	0.0324 (8)	0.0612 (14)	0.0481 (10)	−0.0054 (8)	0.0106 (7)	−0.0003 (10)
C2	0.0337 (8)	0.0448 (12)	0.0446 (10)	−0.0032 (7)	0.0092 (7)	0.0004 (9)
C16	0.0455 (11)	0.0517 (14)	0.0807 (15)	−0.0015 (9)	0.0096 (10)	−0.0081 (12)
C7	0.0387 (9)	0.0495 (13)	0.0544 (11)	0.0047 (8)	0.0051 (8)	0.0003 (10)
C14	0.0659 (14)	0.107 (2)	0.0498 (12)	−0.0202 (14)	0.0192 (10)	0.0143 (13)
C11	0.0342 (8)	0.0433 (12)	0.0527 (11)	0.0003 (8)	0.0113 (7)	0.0006 (9)
C12	0.0693 (14)	0.088 (2)	0.0611 (13)	−0.0377 (13)	0.0048 (11)	0.0158 (14)
C15	0.0595 (13)	0.0705 (17)	0.0665 (13)	0.0012 (11)	0.0249 (10)	0.0161 (13)
C8	0.0585 (12)	0.0438 (13)	0.0567 (12)	−0.0062 (10)	−0.0011 (9)	0.0050 (10)

Geometric parameters (Å, º)

S1—C1	1.7225 (16)	C9—C10	1.376 (3)
S1—C4	1.8218 (17)	C9—C8	1.388 (3)
C4—C5	1.518 (3)	C9—C12	1.510 (3)
C4—C3	1.559 (3)	C6—C11	1.391 (2)
C4—H4A	0.920 (18)	C6—C7	1.391 (3)
N1—N2	1.306 (2)	C10—C11	1.381 (2)
N1—C2	1.356 (2)	C10—H10	0.9300
O1—C13	1.328 (2)	C16—H16A	0.9600
O1—C14	1.458 (2)	C16—H16B	0.9600
N3—C1	1.339 (2)	C16—H16C	0.9600
N3—N2	1.3647 (18)	C7—C8	1.377 (3)
N3—N4	1.398 (2)	C7—H7	0.9300
C3—N4	1.480 (2)	C14—C15	1.464 (3)
C3—C16	1.519 (3)	C14—H14A	0.9700
C3—C17	1.527 (2)	C14—H14B	0.9700
N4—H4	0.83 (2)	C11—H11	0.9300
O2—C13	1.202 (2)	C12—H12A	0.9600
O3—C5	1.220 (2)	C12—H12B	0.9600
C17—H17A	0.9600	C12—H12C	0.9600
C17—H17B	0.9600	C15—H15A	0.9600
C17—H17C	0.9600	C15—H15B	0.9600
C1—C2	1.384 (2)	C15—H15C	0.9600
C5—C6	1.482 (2)	C8—H8	0.9300
C13—C2	1.464 (3)
C1—S1—C4	99.44 (8)	C11—C6—C5	123.33 (17)
C5—C4—C3	111.80 (15)	C7—C6—C5	118.59 (15)
C5—C4—S1	109.71 (12)	C9—C10—C11	121.20 (17)
C3—C4—S1	112.27 (12)	C9—C10—H10	119.4
C5—C4—H4A	112.2 (12)	C11—C10—H10	119.4
C3—C4—H4A	106.7 (11)	N1—C2—C1	108.94 (15)
S1—C4—H4A	103.9 (11)	N1—C2—C13	124.90 (15)
N2—N1—C2	109.29 (13)	C1—C2—C13	126.05 (15)
C13—O1—C14	116.46 (15)	C3—C16—H16A	109.5
C1—N3—N2	111.80 (13)	C3—C16—H16B	109.5
C1—N3—N4	129.72 (13)	H16A—C16—H16B	109.5
N2—N3—N4	118.33 (13)	C3—C16—H16C	109.5
N4—C3—C16	109.47 (16)	H16A—C16—H16C	109.5
N4—C3—C17	104.38 (15)	H16B—C16—H16C	109.5
C16—C3—C17	110.35 (17)	C8—C7—C6	120.86 (17)
N4—C3—C4	111.95 (15)	C8—C7—H7	119.6
C16—C3—C4	110.94 (16)	C6—C7—H7	119.6
C17—C3—C4	109.56 (15)	O1—C14—C15	107.44 (17)
N3—N4—C3	112.67 (14)	O1—C14—H14A	110.2
N3—N4—H4	104.8 (14)	C15—C14—H14A	110.2
C3—N4—H4	109.2 (13)	O1—C14—H14B	110.2
N1—N2—N3	106.39 (13)	C15—C14—H14B	110.2
C3—C17—H17A	109.5	H14A—C14—H14B	108.5
C3—C17—H17B	109.5	C10—C11—C6	120.61 (19)
H17A—C17—H17B	109.5	C10—C11—H11	119.7
C3—C17—H17C	109.5	C6—C11—H11	119.7
H17A—C17—H17C	109.5	C9—C12—H12A	109.5
H17B—C17—H17C	109.5	C9—C12—H12B	109.5
N3—C1—C2	103.54 (14)	H12A—C12—H12B	109.5
N3—C1—S1	124.97 (12)	C9—C12—H12C	109.5
C2—C1—S1	131.45 (14)	H12A—C12—H12C	109.5
O3—C5—C6	120.84 (18)	H12B—C12—H12C	109.5
O3—C5—C4	118.23 (16)	C14—C15—H15A	109.5
C6—C5—C4	120.85 (14)	C14—C15—H15B	109.5
O2—C13—O1	124.74 (18)	H15A—C15—H15B	109.5
O2—C13—C2	123.01 (16)	C14—C15—H15C	109.5
O1—C13—C2	112.25 (16)	H15A—C15—H15C	109.5
C10—C9—C8	118.38 (17)	H15B—C15—H15C	109.5
C10—C9—C12	120.97 (19)	C7—C8—C9	120.9 (2)
C8—C9—C12	120.6 (2)	C7—C8—H8	119.6
C11—C6—C7	118.04 (16)	C9—C8—H8	119.6
C1—S1—C4—C5	89.15 (13)	C14—O1—C13—C2	173.7 (2)
C1—S1—C4—C3	−35.81 (15)	O3—C5—C6—C11	−174.04 (18)
C5—C4—C3—N4	−60.68 (19)	C4—C5—C6—C11	2.8 (3)
S1—C4—C3—N4	63.12 (19)	O3—C5—C6—C7	3.6 (3)
C5—C4—C3—C16	176.70 (14)	C4—C5—C6—C7	−179.54 (17)
S1—C4—C3—C16	−59.50 (17)	C8—C9—C10—C11	1.4 (3)
C5—C4—C3—C17	54.63 (19)	C12—C9—C10—C11	−178.05 (18)
S1—C4—C3—C17	178.42 (13)	N2—N1—C2—C1	1.7 (2)
C1—N3—N4—C3	19.7 (3)	N2—N1—C2—C13	−174.70 (19)
N2—N3—N4—C3	−155.47 (16)	N3—C1—C2—N1	−1.7 (2)
C16—C3—N4—N3	70.4 (2)	S1—C1—C2—N1	−179.43 (16)
C17—C3—N4—N3	−171.51 (17)	N3—C1—C2—C13	174.59 (19)
C4—C3—N4—N3	−53.1 (2)	S1—C1—C2—C13	−3.1 (3)
C2—N1—N2—N3	−0.9 (2)	O2—C13—C2—N1	174.9 (2)
C1—N3—N2—N1	−0.3 (2)	O1—C13—C2—N1	−4.4 (3)
N4—N3—N2—N1	175.74 (17)	O2—C13—C2—C1	−0.9 (4)
N2—N3—C1—C2	1.2 (2)	O1—C13—C2—C1	179.84 (19)
N4—N3—C1—C2	−174.19 (19)	C11—C6—C7—C8	1.3 (3)
N2—N3—C1—S1	179.12 (14)	C5—C6—C7—C8	−176.47 (17)
N4—N3—C1—S1	3.7 (3)	C13—O1—C14—C15	−170.7 (2)
C4—S1—C1—N3	5.1 (2)	C9—C10—C11—C6	−0.2 (3)
C4—S1—C1—C2	−177.6 (2)	C7—C6—C11—C10	−1.1 (3)
C3—C4—C5—O3	70.1 (2)	C5—C6—C11—C10	176.48 (17)
S1—C4—C5—O3	−55.1 (2)	C6—C7—C8—C9	−0.1 (3)
C3—C4—C5—C6	−106.85 (18)	C10—C9—C8—C7	−1.3 (3)
S1—C4—C5—C6	127.92 (14)	C12—C9—C8—C7	178.18 (19)
C14—O1—C13—O2	−5.6 (3)

Ethyl 6-methyl-5-(4-methylbenzoyl)-6-phenyl-6,7-dihydro-5H-[1,2,3]triazolo[5,1-b][1,3,4]thiadiazine-3-carboxylate (VI)

Crystal data

C22H22N4O3S	F(000) = 1776
Mr = 422.49	Dx = 1.379 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.4485 (8) Å	Cell parameters from 5356 reflections
b = 8.9445 (3) Å	θ = 2.3–30.6°
c = 19.0694 (7) Å	µ = 0.19 mm^−1
β = 110.315 (4)°	T = 120 K
V = 4070.7 (3) Å^3	Prism, colourless
Z = 8	0.23 × 0.17 × 0.11 mm

Data collection

Xcalibur 3 diffractometer	4741 reflections with I > 2σ(I)
ω scans	Rint = 0.023
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	θmax = 30.6°, θmin = 2.3°
Tmin = 0.910, Tmax = 1.000	h = −34→35
11216 measured reflections	k = −11→12
5585 independent reflections	l = −25→23

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	All H-atom parameters refined
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0477P)^2 + 1.5461P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.034
5585 reflections	Δρmax = 0.36 e Å^−3
359 parameters	Δρmin = −0.38 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
S1	0.65910 (2)	0.94662 (3)	0.44763 (2)	0.01637 (8)
O1	0.69571 (3)	1.23970 (10)	0.52105 (5)	0.02019 (18)
O3	0.52336 (3)	0.90853 (11)	0.33534 (5)	0.02281 (19)
N4	0.60219 (4)	0.94690 (11)	0.26559 (5)	0.0170 (2)
O2	0.66735 (4)	1.46459 (10)	0.46724 (5)	0.0258 (2)
N1	0.63265 (4)	1.31188 (11)	0.32499 (6)	0.0200 (2)
N3	0.62007 (4)	1.07568 (11)	0.30903 (5)	0.01564 (19)
N2	0.61422 (4)	1.20953 (11)	0.27332 (6)	0.0193 (2)
C1	0.64299 (4)	1.09160 (13)	0.38398 (6)	0.0150 (2)
C4	0.61572 (4)	0.80525 (13)	0.38539 (6)	0.0152 (2)
C5	0.55610 (4)	0.83396 (13)	0.38535 (6)	0.0166 (2)
C17	0.71379 (5)	0.66138 (14)	0.35588 (7)	0.0201 (2)
C6	0.54063 (4)	0.78023 (13)	0.44934 (6)	0.0174 (2)
C19	0.58743 (5)	0.68169 (14)	0.25935 (7)	0.0193 (2)
H19A	0.5488 (6)	0.6938 (16)	0.2577 (8)	0.024 (4)*
H19B	0.5893 (7)	0.6897 (19)	0.2080 (9)	0.036 (4)*
H19C	0.6014 (6)	0.5879 (18)	0.2822 (8)	0.027 (4)*
C22	0.71192 (5)	0.87969 (14)	0.28202 (7)	0.0189 (2)
C16	0.68484 (4)	0.78516 (13)	0.31644 (6)	0.0155 (2)
C13	0.67193 (5)	1.33091 (14)	0.46291 (7)	0.0189 (2)
C18	0.76882 (5)	0.63411 (15)	0.36073 (7)	0.0225 (3)
C21	0.76685 (5)	0.85048 (14)	0.28648 (7)	0.0219 (2)
C2	0.65100 (4)	1.24501 (13)	0.39334 (6)	0.0170 (2)
C3	0.62291 (4)	0.80784 (13)	0.30748 (6)	0.0152 (2)
C9	0.50806 (5)	0.69838 (15)	0.57086 (7)	0.0217 (2)
C10	0.47362 (5)	0.78772 (16)	0.51333 (7)	0.0244 (3)
C8	0.55887 (5)	0.65101 (16)	0.56638 (7)	0.0254 (3)
C15	0.66259 (5)	1.31684 (17)	0.62039 (8)	0.0251 (3)
H15A	0.6341 (6)	1.3802 (18)	0.5868 (9)	0.029 (4)*
H15B	0.6470 (7)	1.2121 (19)	0.6223 (9)	0.033 (4)*
H15C	0.6744 (6)	1.3609 (18)	0.6698 (9)	0.033 (4)*
C11	0.48936 (5)	0.82794 (15)	0.45345 (7)	0.0221 (2)
C14	0.71232 (5)	1.30910 (16)	0.59496 (7)	0.0228 (3)
H14A	0.7417 (6)	1.2432 (16)	0.6257 (8)	0.018 (3)*
H14B	0.7287 (6)	1.4089 (17)	0.5922 (8)	0.026 (4)*
C20	0.79551 (5)	0.72839 (15)	0.32584 (7)	0.0221 (3)
C12	0.49107 (6)	0.6556 (2)	0.63625 (8)	0.0303 (3)
H12A	0.4804 (8)	0.747 (2)	0.6592 (11)	0.057 (6)*
H12B	0.4588 (8)	0.590 (2)	0.6214 (11)	0.055 (6)*
H12C	0.5215 (8)	0.610 (2)	0.6735 (10)	0.049 (5)*
C7	0.57527 (5)	0.69069 (15)	0.50668 (7)	0.0235 (3)
H20	0.8325 (7)	0.7082 (18)	0.3283 (9)	0.031 (4)*
H21	0.7849 (6)	0.9175 (17)	0.2593 (8)	0.027 (4)*
H8	0.5832 (7)	0.592 (2)	0.6066 (10)	0.041 (5)*
H11	0.4667 (6)	0.8917 (17)	0.4165 (8)	0.025 (4)*
H4A	0.6300 (5)	0.7088 (15)	0.4108 (7)	0.014 (3)*
H22	0.6938 (6)	0.9633 (16)	0.2541 (8)	0.020 (3)*
H7	0.6109 (6)	0.6559 (18)	0.5066 (9)	0.031 (4)*
H4	0.5651 (7)	0.9512 (18)	0.2501 (9)	0.032 (4)*
H18	0.7880 (6)	0.5474 (18)	0.3861 (9)	0.029 (4)*
H10	0.4378 (7)	0.8241 (19)	0.5153 (9)	0.040 (5)*
H17	0.6953 (6)	0.5931 (17)	0.3796 (8)	0.023 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01890 (13)	0.01565 (14)	0.01378 (13)	−0.00052 (10)	0.00468 (10)	0.00203 (10)
O1	0.0230 (4)	0.0194 (4)	0.0191 (4)	−0.0002 (3)	0.0085 (3)	−0.0016 (3)
O3	0.0202 (4)	0.0290 (5)	0.0193 (4)	0.0050 (3)	0.0070 (3)	0.0038 (4)
N4	0.0184 (4)	0.0163 (5)	0.0154 (4)	0.0004 (4)	0.0048 (3)	0.0006 (4)
O2	0.0390 (5)	0.0163 (4)	0.0285 (5)	−0.0013 (4)	0.0196 (4)	−0.0010 (4)
N1	0.0241 (5)	0.0173 (5)	0.0229 (5)	0.0033 (4)	0.0135 (4)	0.0033 (4)
N3	0.0180 (4)	0.0149 (5)	0.0153 (4)	0.0017 (3)	0.0074 (3)	0.0031 (4)
N2	0.0229 (4)	0.0169 (5)	0.0207 (5)	0.0041 (4)	0.0109 (4)	0.0056 (4)
C1	0.0147 (4)	0.0162 (5)	0.0157 (5)	0.0014 (4)	0.0072 (4)	0.0015 (4)
C4	0.0160 (5)	0.0151 (5)	0.0156 (5)	0.0004 (4)	0.0068 (4)	0.0009 (4)
C5	0.0165 (5)	0.0161 (5)	0.0182 (5)	−0.0019 (4)	0.0072 (4)	−0.0027 (4)
C17	0.0219 (5)	0.0221 (6)	0.0184 (5)	0.0016 (5)	0.0098 (4)	0.0025 (5)
C6	0.0174 (5)	0.0181 (6)	0.0179 (5)	−0.0020 (4)	0.0077 (4)	−0.0022 (4)
C19	0.0192 (5)	0.0193 (6)	0.0201 (6)	−0.0018 (4)	0.0076 (4)	−0.0029 (5)
C22	0.0223 (5)	0.0174 (6)	0.0190 (5)	−0.0013 (4)	0.0096 (4)	−0.0005 (5)
C16	0.0170 (5)	0.0163 (5)	0.0141 (5)	−0.0010 (4)	0.0066 (4)	−0.0022 (4)
C13	0.0203 (5)	0.0175 (6)	0.0239 (6)	−0.0013 (4)	0.0140 (4)	0.0001 (5)
C18	0.0220 (5)	0.0278 (7)	0.0176 (5)	0.0062 (5)	0.0069 (4)	0.0013 (5)
C21	0.0227 (5)	0.0228 (6)	0.0236 (6)	−0.0070 (5)	0.0123 (5)	−0.0045 (5)
C2	0.0182 (5)	0.0154 (5)	0.0208 (5)	0.0020 (4)	0.0110 (4)	0.0020 (4)
C3	0.0173 (5)	0.0151 (5)	0.0147 (5)	0.0007 (4)	0.0073 (4)	0.0009 (4)
C9	0.0197 (5)	0.0267 (6)	0.0211 (6)	−0.0040 (5)	0.0098 (4)	−0.0008 (5)
C10	0.0170 (5)	0.0341 (7)	0.0247 (6)	0.0009 (5)	0.0104 (4)	−0.0005 (5)
C8	0.0240 (6)	0.0304 (7)	0.0248 (6)	0.0054 (5)	0.0121 (5)	0.0081 (6)
C15	0.0266 (6)	0.0290 (7)	0.0226 (6)	−0.0001 (5)	0.0123 (5)	−0.0010 (5)
C11	0.0179 (5)	0.0278 (7)	0.0208 (6)	0.0023 (5)	0.0069 (4)	0.0014 (5)
C14	0.0219 (5)	0.0269 (7)	0.0202 (6)	−0.0044 (5)	0.0079 (4)	−0.0048 (5)
C20	0.0166 (5)	0.0310 (7)	0.0193 (6)	−0.0015 (5)	0.0069 (4)	−0.0072 (5)
C12	0.0243 (6)	0.0459 (9)	0.0254 (7)	−0.0005 (6)	0.0146 (5)	0.0055 (6)
C7	0.0206 (5)	0.0281 (7)	0.0257 (6)	0.0058 (5)	0.0130 (5)	0.0054 (5)

Geometric parameters (Å, º)

S1—C1	1.7255 (11)	C22—C21	1.3953 (16)
S1—C4	1.8212 (11)	C22—H22	0.941 (14)
O1—C13	1.3399 (15)	C16—C3	1.5386 (14)
O1—C14	1.4618 (14)	C13—C2	1.4641 (17)
O3—C5	1.2235 (14)	C18—C20	1.3887 (18)
N4—N3	1.3994 (13)	C18—H18	0.954 (16)
N4—C3	1.4734 (14)	C21—C20	1.3812 (18)
N4—H4	0.886 (16)	C21—H21	1.002 (16)
O2—C13	1.2069 (15)	C9—C10	1.3936 (18)
N1—N2	1.3069 (14)	C9—C8	1.3914 (16)
N1—C2	1.3608 (15)	C9—C12	1.5043 (18)
N3—N2	1.3596 (13)	C10—C11	1.3826 (17)
N3—C1	1.3507 (14)	C10—H10	0.980 (17)
C1—C2	1.3896 (16)	C8—C7	1.3877 (17)
C4—C5	1.5386 (15)	C8—H8	0.957 (17)
C4—C3	1.5588 (15)	C15—H15A	0.967 (16)
C4—H4A	0.995 (13)	C15—H15B	1.022 (17)
C5—C6	1.4860 (16)	C15—H15C	0.968 (16)
C17—C16	1.3963 (16)	C15—C14	1.5058 (17)
C17—C18	1.3926 (16)	C11—H11	0.934 (15)
C17—H17	0.972 (15)	C14—H14A	0.972 (14)
C6—C11	1.4005 (16)	C14—H14B	0.994 (16)
C6—C7	1.3946 (17)	C20—H20	0.944 (16)
C19—H19A	0.979 (15)	C12—H12A	1.01 (2)
C19—H19B	0.999 (17)	C12—H12B	0.97 (2)
C19—H19C	0.955 (16)	C12—H12C	0.942 (19)
C19—C3	1.5347 (16)	C7—H7	0.960 (16)
C22—C16	1.3911 (16)
C1—S1—C4	96.96 (5)	C20—C21—C22	120.66 (11)
C13—O1—C14	115.82 (10)	C20—C21—H21	120.2 (9)
N3—N4—C3	113.10 (8)	N1—C2—C1	108.95 (10)
N3—N4—H4	104.6 (10)	N1—C2—C13	122.21 (11)
C3—N4—H4	110.9 (10)	C1—C2—C13	128.72 (11)
N2—N1—C2	109.15 (10)	N4—C3—C4	113.02 (9)
N2—N3—N4	118.15 (9)	N4—C3—C19	105.72 (9)
C1—N3—N4	130.19 (9)	N4—C3—C16	109.35 (9)
C1—N3—N2	111.66 (9)	C19—C3—C4	108.65 (9)
N1—N2—N3	106.92 (9)	C19—C3—C16	109.68 (9)
N3—C1—S1	125.10 (9)	C16—C3—C4	110.29 (9)
N3—C1—C2	103.30 (10)	C10—C9—C12	121.01 (11)
C2—C1—S1	131.56 (9)	C8—C9—C10	118.04 (11)
S1—C4—H4A	104.4 (7)	C8—C9—C12	120.95 (12)
C5—C4—S1	105.01 (7)	C9—C10—H10	119.9 (10)
C5—C4—C3	116.05 (9)	C11—C10—C9	121.07 (11)
C5—C4—H4A	109.8 (7)	C11—C10—H10	119.0 (10)
C3—C4—S1	111.45 (7)	C9—C8—H8	118.3 (10)
C3—C4—H4A	109.5 (8)	C7—C8—C9	121.54 (12)
O3—C5—C4	119.73 (10)	C7—C8—H8	120.2 (10)
O3—C5—C6	120.90 (10)	H15A—C15—H15B	110.5 (13)
C6—C5—C4	119.21 (9)	H15A—C15—H15C	108.3 (13)
C16—C17—H17	119.9 (8)	H15B—C15—H15C	109.3 (13)
C18—C17—C16	120.34 (11)	C14—C15—H15A	109.5 (9)
C18—C17—H17	119.8 (8)	C14—C15—H15B	110.4 (9)
C11—C6—C5	117.70 (10)	C14—C15—H15C	108.7 (9)
C7—C6—C5	123.64 (10)	C6—C11—H11	119.1 (9)
C7—C6—C11	118.60 (11)	C10—C11—C6	120.63 (11)
H19A—C19—H19B	110.5 (13)	C10—C11—H11	120.2 (9)
H19A—C19—H19C	108.8 (12)	O1—C14—C15	109.63 (10)
H19B—C19—H19C	111.9 (13)	O1—C14—H14A	103.2 (8)
C3—C19—H19A	108.2 (9)	O1—C14—H14B	108.4 (9)
C3—C19—H19B	108.4 (10)	C15—C14—H14A	112.9 (8)
C3—C19—H19C	108.9 (9)	C15—C14—H14B	112.9 (9)
C16—C22—C21	120.50 (11)	H14A—C14—H14B	109.2 (12)
C16—C22—H22	121.6 (9)	C18—C20—H20	120.4 (10)
C21—C22—H22	117.9 (9)	C21—C20—C18	119.12 (11)
C17—C16—C3	119.54 (10)	C21—C20—H20	120.5 (10)
C22—C16—C17	118.73 (10)	C9—C12—H12A	110.6 (11)
C22—C16—C3	121.59 (10)	C9—C12—H12B	111.7 (12)
O1—C13—C2	110.36 (10)	C9—C12—H12C	109.8 (11)
O2—C13—O1	124.98 (11)	H12A—C12—H12B	106.8 (16)
O2—C13—C2	124.65 (12)	H12A—C12—H12C	107.4 (15)
C17—C18—H18	120.1 (9)	H12B—C12—H12C	110.4 (16)
C20—C18—C17	120.64 (12)	C6—C7—H7	121.7 (9)
C20—C18—H18	119.2 (9)	C8—C7—C6	120.12 (11)
C22—C21—H21	119.1 (9)	C8—C7—H7	118.2 (9)
S1—C1—C2—N1	177.95 (8)	C5—C4—C3—C16	177.27 (9)
S1—C1—C2—C13	−5.80 (18)	C5—C6—C11—C10	−176.99 (11)
S1—C4—C5—O3	96.55 (11)	C5—C6—C7—C8	176.93 (12)
S1—C4—C5—C6	−78.82 (11)	C17—C16—C3—N4	178.71 (10)
S1—C4—C3—N4	−65.60 (10)	C17—C16—C3—C4	53.84 (13)
S1—C4—C3—C19	177.40 (7)	C17—C16—C3—C19	−65.78 (13)
S1—C4—C3—C16	57.15 (11)	C17—C18—C20—C21	0.37 (18)
O1—C13—C2—N1	−169.89 (9)	C22—C16—C3—N4	−5.59 (14)
O1—C13—C2—C1	14.30 (16)	C22—C16—C3—C4	−130.46 (11)
O3—C5—C6—C11	−5.06 (17)	C22—C16—C3—C19	109.92 (12)
O3—C5—C6—C7	177.73 (12)	C22—C21—C20—C18	0.37 (18)
N4—N3—N2—N1	178.89 (9)	C16—C17—C18—C20	−0.71 (19)
N4—N3—C1—S1	2.83 (16)	C16—C22—C21—C20	−0.78 (18)
N4—N3—C1—C2	−179.27 (10)	C13—O1—C14—C15	83.47 (13)
O2—C13—C2—N1	11.46 (17)	C18—C17—C16—C22	0.30 (17)
O2—C13—C2—C1	−164.35 (11)	C18—C17—C16—C3	176.12 (11)
N3—N4—C3—C4	46.41 (12)	C21—C22—C16—C17	0.44 (17)
N3—N4—C3—C19	165.13 (9)	C21—C22—C16—C3	−175.29 (11)
N3—N4—C3—C16	−76.86 (11)	C2—N1—N2—N3	0.87 (11)
N3—C1—C2—N1	0.25 (12)	C3—N4—N3—N2	165.77 (9)
N3—C1—C2—C13	176.50 (10)	C3—N4—N3—C1	−14.69 (15)
N2—N1—C2—C1	−0.71 (12)	C3—C4—C5—O3	−26.98 (15)
N2—N1—C2—C13	−177.26 (10)	C3—C4—C5—C6	157.65 (10)
N2—N3—C1—S1	−177.61 (8)	C9—C10—C11—C6	−0.3 (2)
N2—N3—C1—C2	0.29 (12)	C9—C8—C7—C6	0.1 (2)
C1—S1—C4—C5	−80.97 (8)	C10—C9—C8—C7	0.0 (2)
C1—S1—C4—C3	45.46 (8)	C8—C9—C10—C11	0.1 (2)
C1—N3—N2—N1	−0.73 (12)	C11—C6—C7—C8	−0.25 (19)
C4—S1—C1—N3	−17.68 (10)	C14—O1—C13—O2	5.73 (16)
C4—S1—C1—C2	165.05 (11)	C14—O1—C13—C2	−172.92 (9)
C4—C5—C6—C11	170.25 (11)	C12—C9—C10—C11	179.56 (13)
C4—C5—C6—C7	−6.95 (17)	C12—C9—C8—C7	−179.46 (13)
C5—C4—C3—N4	54.52 (13)	C7—C6—C11—C10	0.36 (19)
C5—C4—C3—C19	−62.49 (12)

Ethyl 5-benzoyl-6-(4-methoxyphenyl)-6,7-dihydro-5H-[1,2,3]triazolo[5,1-b][1,3,4]thiadiazine-3-carboxylate (VII)

Crystal data

C21H20N4O4S	Z = 2
Mr = 424.47	F(000) = 444
Triclinic, P1	Dx = 1.386 Mg m^−3
a = 9.2791 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1445 (8) Å	Cell parameters from 2384 reflections
c = 11.4872 (7) Å	θ = 2.3–29.0°
α = 65.567 (7)°	µ = 0.20 mm^−1
β = 73.829 (5)°	T = 295 K
γ = 73.034 (6)°	Block, colourless
V = 1017.32 (13) Å^3	0.25 × 0.2 × 0.15 mm

Data collection

Xcalibur 3 diffractometer	3602 reflections with I > 2σ(I)
Detector resolution: 15.9555 pixels mm^-1	Rint = 0.027
ω scans	θmax = 30.9°, θmin = 2.3°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −13→11
Tmin = 0.866, Tmax = 1.000	k = −15→15
9054 measured reflections	l = −16→9
5427 independent reflections

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.062P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
5427 reflections	Δρmax = 0.30 e Å^−3
310 parameters	Δρmin = −0.20 e Å^−3
6 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.01471 (5)	0.17117 (5)	0.95568 (5)	0.04083 (15)
N4	0.26879 (16)	0.29948 (16)	0.98216 (17)	0.0362 (3)
O3	0.29401 (19)	0.34182 (16)	0.71394 (15)	0.0627 (4)
N1	−0.07717 (18)	0.39801 (16)	1.16385 (15)	0.0405 (4)
N2	0.07010 (17)	0.39179 (16)	1.12322 (15)	0.0391 (4)
N3	0.11700 (15)	0.31678 (14)	1.04658 (14)	0.0326 (3)
O4	0.3697 (2)	−0.22355 (18)	1.47527 (16)	0.0705 (5)
O2	−0.31207 (14)	0.22927 (16)	1.10730 (16)	0.0572 (4)
O1	−0.38398 (15)	0.40175 (16)	1.17780 (15)	0.0550 (4)
C1	0.00038 (18)	0.27216 (17)	1.04057 (17)	0.0313 (4)
C21	0.4027 (2)	0.0710 (2)	1.1830 (2)	0.0455 (5)
C4	0.22106 (19)	0.14792 (19)	0.88939 (18)	0.0356 (4)
C2	−0.12400 (19)	0.32472 (18)	1.11656 (17)	0.0345 (4)
C17	0.2656 (2)	−0.0573 (2)	1.1495 (2)	0.0458 (5)
C18	0.2779 (2)	−0.1540 (2)	1.2736 (2)	0.0494 (5)
C19	0.3527 (2)	−0.1367 (2)	1.3517 (2)	0.0482 (5)
C5	0.2402 (2)	0.2432 (2)	0.7475 (2)	0.0425 (4)
C20	0.4160 (2)	−0.0237 (2)	1.3049 (2)	0.0545 (6)
C13	−0.2814 (2)	0.3110 (2)	1.13464 (19)	0.0412 (4)
C7	0.1750 (3)	0.0862 (3)	0.6713 (2)	0.0598 (6)
H7	0.195651	0.014749	0.747528	0.072*
C16	0.32559 (18)	0.05698 (18)	1.10229 (18)	0.0353 (4)
C6	0.1867 (2)	0.2137 (2)	0.65276 (19)	0.0450 (5)
C8	0.1321 (3)	0.0645 (3)	0.5753 (3)	0.0780 (8)
H8	0.124491	−0.021450	0.587646	0.094*
C3	0.31661 (19)	0.16617 (18)	0.96903 (19)	0.0352 (4)
C11	0.1529 (3)	0.3190 (3)	0.5391 (2)	0.0661 (6)
H11	0.159920	0.405455	0.525701	0.079*
C9	0.1016 (3)	0.1689 (4)	0.4639 (3)	0.0795 (9)
H9	0.075501	0.153425	0.399577	0.095*
C12	0.3316 (3)	−0.3507 (3)	1.5184 (3)	0.0749 (7)
H12A	0.391564	−0.396838	1.460787	0.112*
H12B	0.224700	−0.338963	1.518982	0.112*
H12C	0.352441	−0.402616	1.604627	0.112*
C10	0.1088 (3)	0.2965 (4)	0.4456 (3)	0.0823 (9)
H10	0.084155	0.367866	0.370521	0.099*
C15	−0.6366 (3)	0.5280 (3)	1.2066 (3)	0.0806 (8)
H15A	−0.622938	0.525189	1.287548	0.121*	0.75
H15B	−0.743132	0.535243	1.209633	0.121*	0.75
H15C	−0.601871	0.604452	1.137012	0.121*	0.75
H15D	−0.603411	0.573668	1.246166	0.121*	0.25
H15E	−0.742403	0.523453	1.241932	0.121*	0.25
H15F	−0.624680	0.576346	1.114369	0.121*	0.25
C14	−0.5474 (7)	0.4041 (6)	1.1843 (4)	0.0515 (11)	0.75
H14A	−0.561651	0.404642	1.103602	0.062*	0.75
H14B	−0.579485	0.325730	1.254974	0.062*	0.75
H18	0.229 (3)	−0.226 (3)	1.299 (2)	0.067 (7)*
H17	0.215 (2)	−0.070 (2)	1.099 (2)	0.048 (6)*
H3	0.420 (2)	0.1674 (19)	0.9164 (18)	0.037 (5)*
H20	0.465 (2)	−0.010 (2)	1.361 (2)	0.067 (7)*
H21	0.444 (2)	0.143 (2)	1.150 (2)	0.051 (6)*
H4A	0.2541 (18)	0.056 (2)	0.8909 (18)	0.035 (5)*
H4	0.270 (2)	0.367 (2)	0.899 (2)	0.062 (7)*
C22	−0.537 (2)	0.381 (2)	1.2348 (15)	0.061 (4)	0.25
H22A	−0.546110	0.330789	1.327585	0.074*	0.25
H22B	−0.567804	0.333378	1.194959	0.074*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0377 (2)	0.0408 (3)	0.0562 (3)	−0.0079 (2)	−0.0093 (2)	−0.0287 (3)
N4	0.0348 (7)	0.0290 (8)	0.0462 (10)	−0.0107 (6)	−0.0072 (7)	−0.0120 (8)
O3	0.0942 (11)	0.0457 (9)	0.0495 (9)	−0.0308 (9)	−0.0124 (8)	−0.0077 (8)
N1	0.0506 (9)	0.0345 (9)	0.0384 (9)	−0.0076 (7)	−0.0090 (7)	−0.0152 (8)
N2	0.0511 (9)	0.0328 (9)	0.0398 (9)	−0.0080 (7)	−0.0138 (7)	−0.0161 (8)
N3	0.0367 (7)	0.0251 (8)	0.0393 (8)	−0.0060 (6)	−0.0108 (6)	−0.0124 (7)
O4	0.1018 (12)	0.0549 (11)	0.0487 (10)	−0.0126 (9)	−0.0251 (9)	−0.0075 (9)
O2	0.0440 (7)	0.0499 (9)	0.0876 (12)	−0.0118 (7)	−0.0074 (7)	−0.0356 (9)
O1	0.0428 (7)	0.0515 (9)	0.0736 (11)	−0.0070 (6)	0.0015 (7)	−0.0349 (9)
C1	0.0363 (8)	0.0224 (8)	0.0353 (9)	−0.0058 (7)	−0.0115 (7)	−0.0075 (8)
C21	0.0489 (11)	0.0369 (11)	0.0548 (13)	−0.0095 (9)	−0.0176 (9)	−0.0147 (10)
C4	0.0390 (9)	0.0268 (9)	0.0401 (10)	−0.0026 (7)	−0.0078 (7)	−0.0136 (9)
C2	0.0421 (9)	0.0256 (9)	0.0347 (9)	−0.0069 (7)	−0.0071 (7)	−0.0097 (8)
C17	0.0475 (10)	0.0389 (11)	0.0541 (13)	−0.0125 (9)	−0.0186 (9)	−0.0114 (10)
C18	0.0538 (11)	0.0365 (12)	0.0538 (13)	−0.0152 (10)	−0.0124 (10)	−0.0065 (10)
C19	0.0533 (11)	0.0411 (12)	0.0427 (12)	−0.0013 (9)	−0.0120 (9)	−0.0114 (10)
C5	0.0483 (10)	0.0330 (11)	0.0435 (11)	−0.0059 (8)	−0.0071 (8)	−0.0136 (9)
C20	0.0630 (13)	0.0509 (14)	0.0569 (14)	−0.0068 (11)	−0.0252 (11)	−0.0205 (12)
C13	0.0431 (10)	0.0340 (10)	0.0419 (11)	−0.0056 (8)	−0.0053 (8)	−0.0121 (9)
C7	0.0770 (15)	0.0524 (14)	0.0569 (14)	−0.0099 (12)	−0.0219 (12)	−0.0223 (13)
C16	0.0302 (8)	0.0308 (10)	0.0438 (10)	−0.0034 (7)	−0.0080 (7)	−0.0135 (9)
C6	0.0453 (10)	0.0490 (13)	0.0393 (11)	−0.0078 (9)	−0.0054 (8)	−0.0174 (10)
C8	0.099 (2)	0.081 (2)	0.0758 (19)	−0.0243 (16)	−0.0233 (16)	−0.0410 (18)
C3	0.0325 (8)	0.0299 (10)	0.0439 (10)	−0.0069 (7)	−0.0068 (7)	−0.0136 (9)
C11	0.0834 (16)	0.0640 (17)	0.0479 (14)	−0.0252 (13)	−0.0188 (12)	−0.0060 (13)
C9	0.0811 (17)	0.122 (3)	0.0545 (16)	−0.0370 (18)	−0.0122 (13)	−0.0398 (19)
C12	0.100 (2)	0.0496 (16)	0.0548 (16)	−0.0078 (14)	−0.0187 (14)	−0.0014 (13)
C10	0.0972 (19)	0.108 (3)	0.0421 (14)	−0.0416 (18)	−0.0225 (13)	−0.0068 (16)
C15	0.0596 (14)	0.074 (2)	0.095 (2)	0.0038 (13)	−0.0094 (14)	−0.0331 (18)
C14	0.0417 (18)	0.055 (3)	0.056 (3)	−0.0119 (17)	−0.002 (2)	−0.021 (3)
C22	0.045 (6)	0.062 (8)	0.076 (9)	−0.009 (5)	0.004 (7)	−0.034 (7)

Geometric parameters (Å, º)

S1—C1	1.7274 (16)	C5—C6	1.493 (3)
S1—C4	1.8371 (17)	C20—H20	0.96 (2)
N4—N3	1.3955 (19)	C7—H7	0.9300
N4—C3	1.480 (2)	C7—C6	1.380 (3)
N4—H4	0.94 (2)	C7—C8	1.397 (3)
O3—C5	1.212 (2)	C16—C3	1.517 (3)
N1—N2	1.306 (2)	C6—C11	1.388 (3)
N1—C2	1.363 (2)	C8—H8	0.9300
N2—N3	1.3587 (18)	C8—C9	1.360 (4)
N3—C1	1.344 (2)	C3—H3	0.983 (18)
O4—C19	1.369 (3)	C11—H11	0.9300
O4—C12	1.411 (3)	C11—C10	1.382 (3)
O2—C13	1.203 (2)	C9—H9	0.9300
O1—C13	1.328 (2)	C9—C10	1.368 (4)
O1—C14	1.491 (6)	C12—H12A	0.9600
O1—C22	1.429 (19)	C12—H12B	0.9600
C1—C2	1.380 (2)	C12—H12C	0.9600
C21—C20	1.374 (3)	C10—H10	0.9300
C21—C16	1.396 (3)	C15—H15A	0.9600
C21—H21	0.89 (2)	C15—H15B	0.9600
C4—C5	1.528 (3)	C15—H15C	0.9600
C4—C3	1.541 (2)	C15—H15D	0.9600
C4—H4A	0.974 (18)	C15—H15E	0.9600
C2—C13	1.461 (2)	C15—H15F	0.9600
C17—C18	1.398 (3)	C15—C14	1.471 (7)
C17—C16	1.378 (3)	C15—C22	1.57 (2)
C17—H17	0.916 (19)	C14—H14A	0.9700
C18—C19	1.376 (3)	C14—H14B	0.9700
C18—H18	0.93 (3)	C22—H22A	0.9700
C19—C20	1.384 (3)	C22—H22B	0.9700
C1—S1—C4	100.18 (8)	C7—C6—C5	122.9 (2)
N3—N4—C3	109.92 (13)	C7—C6—C11	118.9 (2)
N3—N4—H4	105.6 (13)	C11—C6—C5	118.1 (2)
C3—N4—H4	109.3 (13)	C7—C8—H8	119.9
N2—N1—C2	108.93 (13)	C9—C8—C7	120.1 (3)
N1—N2—N3	106.92 (12)	C9—C8—H8	119.9
N2—N3—N4	120.02 (13)	N4—C3—C4	113.34 (14)
C1—N3—N4	128.47 (13)	N4—C3—C16	109.27 (14)
C1—N3—N2	111.46 (13)	N4—C3—H3	103.5 (11)
C19—O4—C12	117.90 (19)	C4—C3—H3	105.7 (10)
C13—O1—C14	115.8 (3)	C16—C3—C4	114.90 (15)
C13—O1—C22	119.9 (8)	C16—C3—H3	109.4 (11)
N3—C1—S1	125.34 (12)	C6—C11—H11	119.7
N3—C1—C2	103.81 (14)	C10—C11—C6	120.6 (3)
C2—C1—S1	130.85 (13)	C10—C11—H11	119.7
C20—C21—C16	121.6 (2)	C8—C9—H9	119.7
C20—C21—H21	122.3 (14)	C8—C9—C10	120.7 (2)
C16—C21—H21	116.1 (14)	C10—C9—H9	119.7
S1—C4—H4A	106.5 (10)	O4—C12—H12A	109.5
C5—C4—S1	106.99 (12)	O4—C12—H12B	109.5
C5—C4—C3	113.15 (16)	O4—C12—H12C	109.5
C5—C4—H4A	108.0 (11)	H12A—C12—H12B	109.5
C3—C4—S1	113.58 (12)	H12A—C12—H12C	109.5
C3—C4—H4A	108.3 (10)	H12B—C12—H12C	109.5
N1—C2—C1	108.86 (15)	C11—C10—H10	120.1
N1—C2—C13	126.13 (15)	C9—C10—C11	119.7 (3)
C1—C2—C13	124.88 (16)	C9—C10—H10	120.1
C18—C17—H17	118.5 (14)	H15A—C15—H15B	109.5
C16—C17—C18	121.92 (19)	H15A—C15—H15C	109.5
C16—C17—H17	119.6 (14)	H15B—C15—H15C	109.5
C17—C18—H18	116.0 (15)	H15D—C15—H15E	109.5
C19—C18—C17	119.8 (2)	H15D—C15—H15F	109.5
C19—C18—H18	124.1 (15)	H15E—C15—H15F	109.5
O4—C19—C18	124.9 (2)	C14—C15—H15A	109.5
O4—C19—C20	116.1 (2)	C14—C15—H15B	109.5
C18—C19—C20	119.0 (2)	C14—C15—H15C	109.5
O3—C5—C4	120.47 (17)	C22—C15—H15D	109.5
O3—C5—C6	121.20 (19)	C22—C15—H15E	109.5
C6—C5—C4	118.30 (17)	C22—C15—H15F	109.5
C21—C20—C19	120.7 (2)	O1—C14—H14A	110.5
C21—C20—H20	120.6 (15)	O1—C14—H14B	110.5
C19—C20—H20	118.6 (15)	C15—C14—O1	106.3 (4)
O2—C13—O1	124.75 (17)	C15—C14—H14A	110.5
O2—C13—C2	122.45 (16)	C15—C14—H14B	110.5
O1—C13—C2	112.73 (16)	H14A—C14—H14B	108.7
C6—C7—H7	120.1	O1—C22—C15	104.0 (12)
C6—C7—C8	119.9 (2)	O1—C22—H22A	111.0
C8—C7—H7	120.1	O1—C22—H22B	111.0
C21—C16—C3	118.08 (18)	C15—C22—H22A	111.0
C17—C16—C21	117.03 (19)	C15—C22—H22B	111.0
C17—C16—C3	124.87 (16)	H22A—C22—H22B	109.0
S1—C1—C2—N1	179.63 (14)	C17—C18—C19—O4	179.02 (18)
S1—C1—C2—C13	−4.4 (3)	C17—C18—C19—C20	−0.6 (3)
S1—C4—C5—O3	108.89 (18)	C17—C16—C3—N4	133.70 (17)
S1—C4—C5—C6	−69.27 (17)	C17—C16—C3—C4	5.0 (2)
S1—C4—C3—N4	−57.59 (19)	C18—C17—C16—C21	1.4 (3)
S1—C4—C3—C16	69.04 (17)	C18—C17—C16—C3	−179.93 (18)
N4—N3—C1—S1	4.1 (3)	C18—C19—C20—C21	0.9 (3)
N4—N3—C1—C2	−176.46 (17)	C5—C4—C3—N4	64.64 (19)
O3—C5—C6—C7	157.0 (2)	C5—C4—C3—C16	−168.73 (14)
O3—C5—C6—C11	−20.6 (3)	C5—C6—C11—C10	177.4 (2)
N1—N2—N3—N4	176.01 (15)	C20—C21—C16—C17	−1.1 (3)
N1—N2—N3—C1	−1.5 (2)	C20—C21—C16—C3	−179.89 (17)
N1—C2—C13—O2	−168.5 (2)	C13—O1—C14—C15	−168.1 (2)
N1—C2—C13—O1	14.5 (3)	C13—O1—C22—C15	−151.9 (5)
N2—N1—C2—C1	−1.1 (2)	C7—C6—C11—C10	−0.3 (4)
N2—N1—C2—C13	−177.04 (17)	C7—C8—C9—C10	−1.5 (4)
N2—N3—C1—S1	−178.70 (13)	C16—C21—C20—C19	0.0 (3)
N2—N3—C1—C2	0.77 (19)	C16—C17—C18—C19	−0.5 (3)
N3—N4—C3—C4	61.1 (2)	C6—C7—C8—C9	−0.2 (4)
N3—N4—C3—C16	−68.45 (17)	C6—C11—C10—C9	−1.4 (4)
N3—C1—C2—N1	0.2 (2)	C8—C7—C6—C5	−176.5 (2)
N3—C1—C2—C13	176.18 (18)	C8—C7—C6—C11	1.1 (3)
O4—C19—C20—C21	−178.78 (19)	C8—C9—C10—C11	2.3 (4)
C1—S1—C4—C5	−101.32 (13)	C3—N4—N3—N2	148.39 (15)
C1—S1—C4—C3	24.26 (15)	C3—N4—N3—C1	−34.6 (2)
C1—C2—C13—O2	16.2 (3)	C3—C4—C5—O3	−16.9 (2)
C1—C2—C13—O1	−160.81 (18)	C3—C4—C5—C6	164.89 (15)
C21—C16—C3—N4	−47.6 (2)	C12—O4—C19—C18	11.3 (3)
C21—C16—C3—C4	−176.32 (15)	C12—O4—C19—C20	−169.0 (2)
C4—S1—C1—N3	1.11 (18)	C14—O1—C13—O2	−3.6 (4)
C4—S1—C1—C2	−178.20 (18)	C14—O1—C13—C2	173.3 (3)
C4—C5—C6—C7	−24.9 (3)	C22—O1—C13—O2	20.5 (8)
C4—C5—C6—C11	157.56 (18)	C22—O1—C13—C2	−162.5 (7)
C2—N1—N2—N3	1.6 (2)