Three closely related 4,5,6,7-tetra­hydro-1H-pyrazolo­[4,3-c]pyridines: synthesis, mol­ecular conformations and hydrogen bonding in zero, one and two dimensions

In each of 1-(4-fluoro­phen­yl)-5-methyl­sulfonyl-3-[4-(tri­fluoro­meth­yl)phen­yl]-4,5,6,7-tetra­hydro-1H-pyrazolo­[4,3-c]pyridine, C₂₁H₁₉F₄N₃O₂S, (I), 1-(4-chloro­phen­yl)-5-methyl­sulfonyl-3-[4-(tri­fluoro­meth­yl)phen­yl]-4,5,6,7-tetra­hydro-1H-pyrazolo­[4,3-c]pyridine, C₂₁H₁₉ClF₃N₃O₂S, (II), and 1-(3-methyl­phen­yl)-5-methyl­sulfonyl-3-[4-(tri­fluoro­meth­yl)phen­yl]-4,5,6,7-tetra­hydro-1H-pyrazolo[4,3-c]pyridine, C₂₂H₂₂F₃N₃O₂S, (III), the reduced pyridine ring adopts a half-chair conformation with the methyl­sulfonyl substituent occupying an equatorial site. Although compounds (I) and (II) are not isostructural, having the space groups Pbca and P2₁2₁2₁, respectively, their mol­ecular conformations are very similar, but the conformation of compound (III) differs from those of (I) and (II) in the relative orientation of the N-benzyl and methyl­sulfonyl substituents. In compounds (II) and (III), but not in (I), the tri­fluoro­methyl groups are disordered over two sets of atomic sites. Mol­ecules of (I) are linked into centrosymmetric dimers by C—H...π(arene) hydrogen bonds, molecules of (II) are linked by two C—H...O hydrogen bonds to form ribbons of R₃³(18) rings, which are themselves further linked by a C—Cl...π(arene) inter­action, and a combination of C—H...O and C—H...π(arene) hydrogen bonds links the mol­ecules of (III) into sheets. Comparisons are made with the structures of some related compounds.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2012); cell refinement: APEX2 (Bruker, 2012); data reduction: SAINT-Plus (Bruker, 2012); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009). Software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009) for (I), (III); SHELXL2014 (Sheldrick, 2015 and PLATON (Spek, 2009) for (II).

(I) 1-(4-Fluorophenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine

Crystal data

C21H19F4N3O2S	Dx = 1.510 Mg m^−3
Mr = 453.45	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 4704 reflections
a = 19.7282 (6) Å	θ = 2.1–27.8°
b = 9.7644 (3) Å	µ = 0.22 mm^−1
c = 20.7157 (7) Å	T = 296 K
V = 3990.5 (2) Å^3	Block, colourless
Z = 8	0.31 × 0.29 × 0.28 mm
F(000) = 1872

Data collection

Bruker Kappa APEXII diffractometer	2738 reflections with I > 2σ(I)
Radiation source: fine focus sealed tube	Rint = 0.039
φ and ω scans	θmax = 26.6°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 20012)	h = −22→24
Tmin = 0.926, Tmax = 0.939	k = −12→12
50117 measured reflections	l = −25→26
4148 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.058	w = 1/[σ^2(Fo^2) + (0.1039P)^2 + 2.7804P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.210	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 0.35 e Å^−3
4148 reflections	Δρmin = −0.53 e Å^−3
282 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0032 (8)

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
N1	0.38650 (11)	0.7471 (3)	0.45255 (12)	0.0452 (6)
N2	0.37282 (12)	0.6640 (3)	0.50338 (13)	0.0464 (6)
C3	0.43251 (13)	0.6512 (3)	0.53422 (14)	0.0412 (7)
C3A	0.48364 (14)	0.7256 (3)	0.50227 (14)	0.0402 (6)
C4	0.55757 (14)	0.7426 (3)	0.51515 (15)	0.0435 (7)
H4A	0.5649	0.7621	0.5605	0.052*
H4B	0.5815	0.6588	0.5044	0.052*
N5	0.58350 (12)	0.8571 (3)	0.47532 (12)	0.0450 (6)
C6	0.56076 (15)	0.8565 (4)	0.40750 (15)	0.0498 (7)
H6A	0.5721	0.7694	0.3877	0.060*
H6B	0.5839	0.9283	0.3838	0.060*
C7	0.48439 (16)	0.8792 (3)	0.40391 (16)	0.0492 (7)
H7A	0.4736	0.9736	0.4143	0.059*
H7B	0.4681	0.8599	0.3607	0.059*
C7A	0.45184 (14)	0.7861 (3)	0.45089 (14)	0.0430 (7)
C17	0.33306 (15)	0.7798 (3)	0.40629 (16)	0.0512 (8)
H17A	0.3421	0.8691	0.3876	0.061*
H17B	0.2901	0.7850	0.4289	0.061*
C11	0.32736 (14)	0.6760 (4)	0.35284 (15)	0.0482 (8)
C12	0.31506 (16)	0.5384 (4)	0.36714 (18)	0.0562 (8)
H12	0.3117	0.5110	0.4100	0.067*
C13	0.30780 (18)	0.4429 (4)	0.3189 (2)	0.0704 (11)
H13	0.3004	0.3512	0.3288	0.084*
C14	0.31172 (19)	0.4851 (6)	0.2564 (2)	0.0766 (12)
F14	0.30351 (16)	0.3926 (4)	0.20841 (14)	0.1188 (11)
C15	0.3238 (2)	0.6185 (6)	0.2395 (2)	0.0806 (13)
H15	0.3265	0.6444	0.1964	0.097*
C16	0.33188 (17)	0.7143 (4)	0.28874 (18)	0.0650 (10)
H16	0.3404	0.8053	0.2783	0.078*
C31	0.43545 (14)	0.5722 (3)	0.59446 (14)	0.0413 (7)
C32	0.49679 (14)	0.5259 (3)	0.61880 (14)	0.0452 (7)
H32	0.5364	0.5422	0.5957	0.054*
C33	0.50019 (16)	0.4561 (3)	0.67656 (15)	0.0484 (7)
H33	0.5419	0.4273	0.6926	0.058*
C34	0.44176 (16)	0.4290 (3)	0.71045 (15)	0.0480 (7)
C35	0.37958 (16)	0.4711 (3)	0.68658 (16)	0.0531 (8)
H35	0.3400	0.4507	0.7089	0.064*
C36	0.37683 (15)	0.5435 (3)	0.62941 (16)	0.0506 (8)
H36	0.3351	0.5736	0.6140	0.061*
C37	0.4453 (2)	0.3459 (4)	0.76991 (18)	0.0622 (9)
F31	0.44298 (18)	0.2127 (2)	0.75781 (13)	0.1069 (10)
F32	0.39575 (15)	0.3710 (3)	0.81152 (12)	0.1023 (9)
F33	0.50207 (14)	0.3661 (3)	0.80380 (11)	0.0960 (8)
S51	0.66482 (4)	0.88817 (9)	0.48509 (4)	0.0538 (3)
O51	0.67969 (14)	1.0121 (3)	0.45186 (16)	0.0803 (8)
O52	0.67724 (13)	0.8798 (3)	0.55280 (13)	0.0733 (8)
C51	0.70896 (16)	0.7557 (4)	0.44678 (18)	0.0609 (9)
H51A	0.7567	0.7676	0.4536	0.091*
H51B	0.6994	0.7576	0.4013	0.091*
H51C	0.6949	0.6694	0.4644	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0343 (12)	0.0517 (14)	0.0497 (14)	0.0055 (10)	−0.0031 (10)	0.0008 (12)
N2	0.0351 (12)	0.0520 (15)	0.0521 (15)	0.0015 (11)	−0.0016 (10)	0.0044 (12)
C3	0.0310 (13)	0.0428 (15)	0.0499 (17)	0.0013 (11)	0.0000 (11)	−0.0025 (13)
C3A	0.0331 (14)	0.0419 (16)	0.0458 (15)	0.0040 (11)	0.0001 (11)	−0.0036 (12)
C4	0.0348 (14)	0.0476 (16)	0.0481 (17)	−0.0029 (12)	−0.0013 (11)	0.0006 (13)
N5	0.0363 (13)	0.0474 (14)	0.0513 (15)	−0.0052 (11)	−0.0002 (10)	−0.0043 (11)
C6	0.0439 (16)	0.0561 (18)	0.0495 (18)	−0.0020 (14)	0.0024 (13)	0.0025 (14)
C7	0.0453 (17)	0.0516 (18)	0.0508 (18)	0.0004 (13)	0.0006 (13)	0.0051 (14)
C7A	0.0358 (14)	0.0469 (16)	0.0462 (16)	0.0041 (12)	−0.0003 (12)	−0.0023 (13)
C17	0.0357 (15)	0.0591 (19)	0.059 (2)	0.0086 (13)	−0.0078 (13)	0.0046 (15)
C11	0.0294 (14)	0.067 (2)	0.0482 (18)	0.0074 (13)	−0.0031 (12)	0.0018 (15)
C12	0.0427 (17)	0.068 (2)	0.058 (2)	−0.0061 (15)	0.0052 (14)	−0.0056 (17)
C13	0.052 (2)	0.081 (3)	0.078 (3)	−0.0109 (19)	0.0098 (18)	−0.015 (2)
C14	0.049 (2)	0.112 (4)	0.068 (3)	−0.003 (2)	0.0007 (17)	−0.029 (3)
F14	0.103 (2)	0.166 (3)	0.088 (2)	−0.0128 (19)	−0.0001 (15)	−0.062 (2)
C15	0.065 (3)	0.129 (4)	0.047 (2)	0.016 (3)	−0.0060 (17)	−0.005 (2)
C16	0.053 (2)	0.079 (3)	0.062 (2)	0.0121 (17)	−0.0017 (16)	0.014 (2)
C31	0.0370 (14)	0.0416 (15)	0.0455 (16)	−0.0011 (12)	−0.0004 (11)	−0.0043 (13)
C32	0.0358 (14)	0.0487 (16)	0.0511 (17)	−0.0020 (12)	0.0021 (12)	0.0038 (14)
C33	0.0461 (16)	0.0489 (17)	0.0503 (17)	0.0006 (13)	−0.0069 (13)	−0.0001 (14)
C34	0.0543 (18)	0.0451 (16)	0.0445 (17)	−0.0033 (13)	0.0017 (13)	−0.0016 (13)
C35	0.0470 (17)	0.0554 (19)	0.057 (2)	−0.0004 (14)	0.0135 (14)	0.0025 (16)
C36	0.0364 (15)	0.0564 (19)	0.059 (2)	0.0045 (13)	0.0035 (13)	0.0036 (16)
C37	0.077 (2)	0.059 (2)	0.050 (2)	−0.0042 (18)	0.0008 (17)	0.0042 (17)
F31	0.181 (3)	0.0580 (14)	0.0817 (17)	−0.0065 (16)	−0.0127 (17)	0.0183 (13)
F32	0.108 (2)	0.137 (2)	0.0623 (15)	0.0034 (17)	0.0266 (14)	0.0241 (15)
F33	0.0966 (19)	0.130 (2)	0.0617 (14)	−0.0050 (16)	−0.0185 (13)	0.0194 (14)
S51	0.0414 (5)	0.0556 (5)	0.0644 (6)	−0.0143 (3)	0.0013 (3)	−0.0099 (4)
O51	0.0717 (17)	0.0566 (15)	0.113 (2)	−0.0264 (13)	0.0075 (15)	0.0034 (15)
O52	0.0542 (15)	0.107 (2)	0.0590 (15)	−0.0233 (13)	−0.0064 (11)	−0.0212 (14)
C51	0.0395 (16)	0.075 (2)	0.068 (2)	−0.0023 (16)	0.0020 (15)	−0.0066 (18)

Geometric parameters (Å, º)

N1—C7A	1.344 (4)	C13—H13	0.9300
N1—N2	1.356 (4)	C14—F14	1.353 (5)
N1—C17	1.460 (4)	C14—C15	1.369 (7)
N2—C3	1.345 (4)	C15—C16	1.392 (6)
C3—C3A	1.408 (4)	C15—H15	0.9300
C3—C31	1.468 (4)	C16—H16	0.9300
C3A—C7A	1.369 (4)	C31—C32	1.387 (4)
C3A—C4	1.492 (4)	C31—C36	1.393 (4)
C4—N5	1.480 (4)	C32—C33	1.379 (4)
C4—H4A	0.9700	C32—H32	0.9300
C4—H4B	0.9700	C33—C34	1.375 (4)
N5—C6	1.475 (4)	C33—H33	0.9300
N5—S51	1.645 (2)	C34—C35	1.385 (4)
C6—C7	1.525 (4)	C34—C37	1.477 (5)
C6—H6A	0.9700	C35—C36	1.380 (5)
C6—H6B	0.9700	C35—H35	0.9300
C7—C7A	1.479 (4)	C36—H36	0.9300
C7—H7A	0.9700	C37—F31	1.325 (4)
C7—H7B	0.9700	C37—F32	1.326 (5)
C17—C11	1.505 (5)	C37—F33	1.337 (4)
C17—H17A	0.9700	S51—O51	1.423 (3)
C17—H17B	0.9700	S51—O52	1.426 (3)
C11—C16	1.383 (5)	S51—C51	1.749 (4)
C11—C12	1.397 (5)	C51—H51A	0.9600
C12—C13	1.374 (5)	C51—H51B	0.9600
C12—H12	0.9300	C51—H51C	0.9600
C13—C14	1.361 (6)
C7A—N1—N2	112.3 (2)	C14—C13—H13	120.7
C7A—N1—C17	127.8 (3)	C12—C13—H13	120.7
N2—N1—C17	119.8 (2)	F14—C14—C13	119.4 (5)
C3—N2—N1	104.5 (2)	F14—C14—C15	117.9 (4)
N2—C3—C3A	110.9 (3)	C13—C14—C15	122.7 (4)
N2—C3—C31	119.1 (2)	C14—C15—C16	118.2 (4)
C3A—C3—C31	130.0 (3)	C14—C15—H15	120.9
C7A—C3A—C3	105.0 (2)	C16—C15—H15	120.9
C7A—C3A—C4	122.6 (3)	C11—C16—C15	120.9 (4)
C3—C3A—C4	132.4 (3)	C11—C16—H16	119.5
N5—C4—C3A	108.8 (2)	C15—C16—H16	119.5
N5—C4—H4A	109.9	C32—C31—C36	118.0 (3)
C3A—C4—H4A	109.9	C32—C31—C3	121.0 (3)
N5—C4—H4B	109.9	C36—C31—C3	121.0 (3)
C3A—C4—H4B	109.9	C33—C32—C31	121.3 (3)
H4A—C4—H4B	108.3	C33—C32—H32	119.4
C6—N5—C4	115.0 (2)	C31—C32—H32	119.4
C6—N5—S51	114.5 (2)	C34—C33—C32	119.8 (3)
C4—N5—S51	114.06 (19)	C34—C33—H33	120.1
N5—C6—C7	110.3 (3)	C32—C33—H33	120.1
N5—C6—H6A	109.6	C33—C34—C35	120.2 (3)
C7—C6—H6A	109.6	C33—C34—C37	119.5 (3)
N5—C6—H6B	109.6	C35—C34—C37	120.2 (3)
C7—C6—H6B	109.6	C36—C35—C34	119.5 (3)
H6A—C6—H6B	108.1	C36—C35—H35	120.2
C7A—C7—C6	107.9 (3)	C34—C35—H35	120.2
C7A—C7—H7A	110.1	C35—C36—C31	121.1 (3)
C6—C7—H7A	110.1	C35—C36—H36	119.5
C7A—C7—H7B	110.1	C31—C36—H36	119.5
C6—C7—H7B	110.1	F31—C37—F32	106.2 (3)
H7A—C7—H7B	108.4	F31—C37—F33	105.9 (3)
N1—C7A—C3A	107.3 (3)	F32—C37—F33	104.4 (3)
N1—C7A—C7	127.4 (3)	F31—C37—C34	112.4 (3)
C3A—C7A—C7	125.3 (3)	F32—C37—C34	113.9 (3)
N1—C17—C11	112.9 (2)	F33—C37—C34	113.3 (3)
N1—C17—H17A	109.0	O51—S51—O52	119.30 (18)
C11—C17—H17A	109.0	O51—S51—N5	107.37 (16)
N1—C17—H17B	109.0	O52—S51—N5	106.14 (14)
C11—C17—H17B	109.0	O51—S51—C51	107.85 (19)
H17A—C17—H17B	107.8	O52—S51—C51	108.55 (18)
C16—C11—C12	118.4 (3)	N5—S51—C51	107.04 (15)
C16—C11—C17	121.3 (3)	S51—C51—H51A	109.5
C12—C11—C17	120.3 (3)	S51—C51—H51B	109.5
C13—C12—C11	121.1 (4)	H51A—C51—H51B	109.5
C13—C12—H12	119.4	S51—C51—H51C	109.5
C11—C12—H12	119.4	H51A—C51—H51C	109.5
C14—C13—C12	118.7 (4)	H51B—C51—H51C	109.5
C7A—N1—N2—C3	−0.1 (3)	C12—C13—C14—C15	1.2 (6)
C17—N1—N2—C3	177.8 (3)	F14—C14—C15—C16	179.6 (3)
N1—N2—C3—C3A	−0.5 (3)	C13—C14—C15—C16	−0.4 (6)
N1—N2—C3—C31	176.9 (3)	C12—C11—C16—C15	0.5 (5)
N2—C3—C3A—C7A	0.9 (3)	C17—C11—C16—C15	−177.4 (3)
C31—C3—C3A—C7A	−176.2 (3)	C14—C15—C16—C11	−0.4 (6)
N2—C3—C3A—C4	−178.3 (3)	N2—C3—C31—C32	162.9 (3)
C31—C3—C3A—C4	4.6 (5)	C3A—C3—C31—C32	−20.2 (5)
C7A—C3A—C4—N5	13.9 (4)	N2—C3—C31—C36	−18.1 (4)
C3—C3A—C4—N5	−167.0 (3)	C3A—C3—C31—C36	158.7 (3)
C3A—C4—N5—C6	−45.2 (3)	C36—C31—C32—C33	−1.4 (5)
C3A—C4—N5—S51	179.6 (2)	C3—C31—C32—C33	177.5 (3)
C4—N5—C6—C7	65.6 (3)	C31—C32—C33—C34	1.3 (5)
S51—N5—C6—C7	−159.4 (2)	C32—C33—C34—C35	0.3 (5)
N5—C6—C7—C7A	−47.9 (3)	C32—C33—C34—C37	175.7 (3)
N2—N1—C7A—C3A	0.7 (3)	C33—C34—C35—C36	−1.7 (5)
C17—N1—C7A—C3A	−177.0 (3)	C37—C34—C35—C36	−177.1 (3)
N2—N1—C7A—C7	−178.0 (3)	C34—C35—C36—C31	1.5 (5)
C17—N1—C7A—C7	4.3 (5)	C32—C31—C36—C35	0.0 (5)
C3—C3A—C7A—N1	−0.9 (3)	C3—C31—C36—C35	−178.9 (3)
C4—C3A—C7A—N1	178.4 (3)	C33—C34—C37—F31	−85.3 (4)
C3—C3A—C7A—C7	177.8 (3)	C35—C34—C37—F31	90.1 (4)
C4—C3A—C7A—C7	−2.9 (5)	C33—C34—C37—F32	153.9 (3)
C6—C7—C7A—N1	−161.8 (3)	C35—C34—C37—F32	−30.7 (5)
C6—C7—C7A—C3A	19.7 (4)	C33—C34—C37—F33	34.7 (5)
C7A—N1—C17—C11	90.4 (4)	C35—C34—C37—F33	−149.9 (3)
N2—N1—C17—C11	−87.2 (3)	C6—N5—S51—O51	53.3 (3)
N1—C17—C11—C16	−124.1 (3)	C4—N5—S51—O51	−171.2 (2)
N1—C17—C11—C12	58.1 (4)	C6—N5—S51—O52	−178.0 (2)
C16—C11—C12—C13	0.2 (5)	C4—N5—S51—O52	−42.6 (3)
C17—C11—C12—C13	178.1 (3)	C6—N5—S51—C51	−62.2 (3)
C11—C12—C13—C14	−1.1 (5)	C4—N5—S51—C51	73.2 (2)
C12—C13—C14—F14	−178.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cg2^i	0.97	2.76	3.694 (4)	161
C33—H33···Cg1^i	0.93	2.73	3.595 (3)	154
C51—H51A···N2^ii	0.96	2.55	3.483 (4)	165

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+3/2, −z+1.

(II) 1-(4-Chlorophenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine

Crystal data

C21H19ClF3N3O2S	Dx = 1.464 Mg m^−3
Mr = 469.90	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 5856 reflections
a = 5.4468 (2) Å	θ = 1.2–29.3°
b = 11.4102 (4) Å	µ = 0.33 mm^−1
c = 34.3009 (9) Å	T = 296 K
V = 2131.77 (12) Å^3	Block, colourless
Z = 4	0.40 × 0.30 × 0.30 mm
F(000) = 968

Data collection

Bruker Kappa APEXII diffractometer	3587 reflections with I > 2σ(I)
Radiation source: fine focus sealed tube	Rint = 0.032
φ and ω scans	θmax = 27.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −3→7
Tmin = 0.879, Tmax = 0.907	k = −14→14
15002 measured reflections	l = −44→29
4920 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0426P)^2 + 0.0545P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.093	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.16 e Å^−3
4920 reflections	Δρmin = −0.22 e Å^−3
309 parameters	Absolute structure: Flack x determined using 1208 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.03 (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)
N1	0.6422 (4)	0.5128 (2)	0.64083 (7)	0.0435 (6)
N2	0.7153 (4)	0.5746 (2)	0.60944 (7)	0.0430 (6)
C3	0.5874 (5)	0.6739 (3)	0.61079 (7)	0.0363 (6)
C3A	0.4302 (5)	0.6749 (3)	0.64357 (7)	0.0355 (6)
C4	0.2561 (5)	0.7637 (3)	0.65979 (8)	0.0393 (7)
H4A	0.3280	0.8414	0.6585	0.047*
H4B	0.1045	0.7639	0.6450	0.047*
N5	0.2071 (4)	0.7314 (2)	0.70082 (7)	0.0401 (6)
C6	0.1312 (6)	0.6083 (3)	0.70578 (9)	0.0506 (8)
H6A	−0.0004	0.5900	0.6877	0.061*
H6B	0.0712	0.5961	0.7321	0.061*
C7	0.3479 (6)	0.5294 (3)	0.69817 (9)	0.0502 (8)
H7A	0.4623	0.5333	0.7198	0.060*
H7B	0.2934	0.4489	0.6953	0.060*
C7A	0.4698 (5)	0.5696 (3)	0.66161 (8)	0.0395 (7)
C17	0.7330 (6)	0.3936 (3)	0.64656 (10)	0.0556 (9)
H17A	0.7849	0.3841	0.6734	0.067*
H17B	0.8748	0.3808	0.6300	0.067*
C11	0.5399 (6)	0.3036 (3)	0.63724 (9)	0.0497 (8)
C12	0.4368 (8)	0.2988 (3)	0.60081 (10)	0.0666 (10)
H12	0.4922	0.3496	0.5815	0.080*
C13	0.2532 (9)	0.2204 (3)	0.59234 (11)	0.0733 (12)
H13	0.1822	0.2191	0.5677	0.088*
C14	0.1756 (7)	0.1438 (3)	0.62071 (11)	0.0611 (10)
Cl14	−0.0571 (2)	0.04450 (10)	0.61044 (4)	0.0892 (4)
C15	0.2776 (8)	0.1455 (3)	0.65713 (11)	0.0694 (11)
H15	0.2257	0.0930	0.6762	0.083*
C16	0.4585 (8)	0.2263 (3)	0.66515 (10)	0.0646 (10)
H16	0.5270	0.2286	0.6900	0.078*
C31	0.6213 (5)	0.7627 (3)	0.58017 (8)	0.0377 (7)
C32	0.4564 (6)	0.8528 (3)	0.57475 (9)	0.0494 (8)
H32	0.3189	0.8575	0.5908	0.059*
C33	0.4902 (6)	0.9359 (3)	0.54621 (9)	0.0549 (9)
H33	0.3775	0.9964	0.5432	0.066*
C34	0.6925 (7)	0.9287 (3)	0.52216 (9)	0.0529 (9)
C35	0.8556 (6)	0.8382 (3)	0.52649 (9)	0.0575 (9)
H35	0.9899	0.8323	0.5099	0.069*
C36	0.8215 (6)	0.7563 (3)	0.55522 (9)	0.0485 (8)
H36	0.9341	0.6957	0.5580	0.058*
C37	0.7371 (10)	1.0200 (5)	0.49169 (13)	0.0752 (12)
F31A	0.875 (5)	1.0995 (15)	0.5014 (5)	0.134 (7)	0.51 (2)
F32A	0.812 (4)	0.9771 (12)	0.4588 (4)	0.143 (9)	0.51 (2)
F33A	0.537 (3)	1.073 (2)	0.4812 (5)	0.129 (6)	0.51 (2)
F31B	0.974 (3)	1.050 (2)	0.4901 (7)	0.147 (9)	0.49 (2)
F32B	0.680 (6)	0.995 (2)	0.4590 (4)	0.183 (10)	0.49 (2)
F33B	0.635 (7)	1.1226 (14)	0.5013 (9)	0.188 (11)	0.49 (2)
S51	0.07584 (13)	0.83056 (8)	0.72794 (2)	0.0464 (2)
O51	0.0454 (5)	0.7815 (3)	0.76567 (6)	0.0724 (8)
O52	0.2154 (4)	0.9352 (2)	0.72410 (7)	0.0565 (6)
C51	−0.2150 (6)	0.8583 (4)	0.70770 (11)	0.0795 (14)
H51A	−0.2939	0.9200	0.7220	0.119*
H51B	−0.3132	0.7885	0.7091	0.119*
H51C	−0.1967	0.8815	0.6810	0.119*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0500 (15)	0.0338 (15)	0.0467 (14)	0.0050 (12)	0.0004 (12)	0.0033 (11)
N2	0.0479 (14)	0.0397 (15)	0.0415 (13)	0.0025 (12)	0.0018 (11)	0.0005 (11)
C3	0.0369 (13)	0.0354 (16)	0.0367 (14)	0.0011 (14)	−0.0013 (12)	−0.0024 (12)
C3A	0.0378 (13)	0.0335 (16)	0.0351 (13)	−0.0019 (14)	0.0004 (12)	−0.0016 (12)
C4	0.0377 (14)	0.0417 (18)	0.0386 (15)	0.0010 (14)	0.0025 (12)	0.0002 (13)
N5	0.0378 (12)	0.0459 (16)	0.0367 (12)	−0.0060 (12)	0.0070 (10)	−0.0030 (11)
C6	0.053 (2)	0.049 (2)	0.0502 (18)	−0.0140 (16)	0.0085 (15)	0.0020 (15)
C7	0.059 (2)	0.044 (2)	0.0474 (18)	−0.0066 (16)	0.0040 (15)	0.0090 (15)
C7A	0.0430 (16)	0.0348 (17)	0.0406 (15)	−0.0022 (13)	−0.0013 (13)	0.0005 (13)
C17	0.061 (2)	0.039 (2)	0.066 (2)	0.0127 (17)	−0.0060 (18)	0.0059 (16)
C11	0.069 (2)	0.0321 (17)	0.0482 (17)	0.0109 (16)	−0.0067 (16)	−0.0002 (14)
C12	0.103 (3)	0.046 (2)	0.0510 (19)	0.001 (2)	−0.014 (2)	0.0062 (16)
C13	0.113 (3)	0.048 (2)	0.059 (2)	0.005 (2)	−0.033 (2)	−0.0026 (18)
C14	0.073 (2)	0.037 (2)	0.073 (2)	0.0063 (18)	−0.0073 (19)	−0.0168 (18)
Cl14	0.0822 (7)	0.0607 (7)	0.1248 (9)	−0.0037 (6)	−0.0140 (7)	−0.0279 (7)
C15	0.099 (3)	0.047 (2)	0.062 (2)	−0.013 (2)	0.004 (2)	0.0018 (18)
C16	0.098 (3)	0.049 (2)	0.0466 (18)	−0.006 (2)	−0.0124 (19)	0.0037 (16)
C31	0.0379 (15)	0.0381 (17)	0.0370 (14)	−0.0030 (13)	0.0011 (12)	−0.0026 (13)
C32	0.0515 (18)	0.050 (2)	0.0467 (17)	0.0068 (17)	0.0100 (14)	0.0082 (15)
C33	0.063 (2)	0.046 (2)	0.055 (2)	0.0091 (17)	0.0020 (16)	0.0097 (16)
C34	0.069 (2)	0.051 (2)	0.0389 (17)	−0.0099 (19)	0.0052 (16)	0.0052 (15)
C35	0.061 (2)	0.059 (2)	0.0528 (19)	−0.0081 (19)	0.0214 (15)	0.0021 (17)
C36	0.0509 (17)	0.046 (2)	0.0482 (17)	0.0046 (16)	0.0109 (14)	−0.0010 (15)
C37	0.096 (3)	0.066 (3)	0.064 (3)	−0.016 (3)	0.009 (3)	0.017 (2)
F31A	0.19 (2)	0.084 (9)	0.130 (9)	−0.075 (11)	−0.025 (11)	0.029 (7)
F32A	0.260 (19)	0.093 (7)	0.077 (8)	0.022 (10)	0.103 (12)	0.025 (6)
F33A	0.144 (8)	0.141 (13)	0.101 (8)	0.046 (8)	0.029 (6)	0.081 (8)
F31B	0.102 (8)	0.172 (18)	0.165 (16)	−0.057 (8)	−0.009 (6)	0.120 (14)
F32B	0.290 (19)	0.193 (19)	0.065 (9)	−0.167 (16)	−0.075 (11)	0.069 (9)
F33B	0.32 (3)	0.081 (8)	0.166 (15)	0.041 (12)	0.110 (19)	0.069 (8)
S51	0.0359 (4)	0.0627 (5)	0.0406 (4)	−0.0030 (4)	0.0025 (3)	−0.0132 (4)
O51	0.0878 (16)	0.092 (2)	0.0379 (12)	−0.0073 (16)	0.0147 (12)	−0.0082 (12)
O52	0.0480 (12)	0.0539 (16)	0.0676 (14)	−0.0022 (11)	0.0040 (11)	−0.0185 (12)
C51	0.0346 (17)	0.123 (4)	0.080 (3)	0.011 (2)	−0.0040 (17)	−0.034 (3)

Geometric parameters (Å, º)

N1—C7A	1.346 (4)	C14—C15	1.367 (5)
N1—N2	1.347 (3)	C14—Cl14	1.736 (4)
N1—C17	1.461 (4)	C15—C16	1.377 (5)
N2—C3	1.332 (4)	C15—H15	0.9300
C3—C3A	1.413 (4)	C16—H16	0.9300
C3—C31	1.471 (4)	C31—C32	1.378 (4)
C3A—C7A	1.368 (4)	C31—C36	1.388 (4)
C3A—C4	1.496 (4)	C32—C33	1.375 (4)
C4—N5	1.479 (4)	C32—H32	0.9300
C4—H4A	0.9700	C33—C34	1.379 (5)
C4—H4B	0.9700	C33—H33	0.9300
N5—C6	1.473 (4)	C34—C35	1.370 (5)
N5—S51	1.630 (3)	C34—C37	1.495 (5)
C6—C7	1.507 (4)	C35—C36	1.371 (5)
C6—H6A	0.9700	C35—H35	0.9300
C6—H6B	0.9700	C36—H36	0.9300
C7—C7A	1.491 (4)	C37—F32B	1.199 (12)
C7—H7A	0.9700	C37—F31A	1.224 (15)
C7—H7B	0.9700	C37—F32A	1.297 (10)
C17—C11	1.504 (5)	C37—F33A	1.302 (13)
C17—H17A	0.9700	C37—F31B	1.336 (15)
C17—H17B	0.9700	C37—F33B	1.338 (16)
C11—C12	1.371 (5)	S51—O51	1.420 (2)
C11—C16	1.375 (5)	S51—O52	1.421 (2)
C12—C13	1.373 (6)	S51—C51	1.758 (3)
C12—H12	0.9300	C51—H51A	0.9600
C13—C14	1.374 (5)	C51—H51B	0.9600
C13—H13	0.9300	C51—H51C	0.9600
C7A—N1—N2	112.2 (2)	C15—C14—Cl14	119.4 (3)
C7A—N1—C17	127.9 (3)	C13—C14—Cl14	119.7 (3)
N2—N1—C17	119.7 (3)	C14—C15—C16	118.8 (4)
C3—N2—N1	105.3 (2)	C14—C15—H15	120.6
N2—C3—C3A	110.5 (3)	C16—C15—H15	120.6
N2—C3—C31	119.7 (2)	C11—C16—C15	121.4 (3)
C3A—C3—C31	129.7 (3)	C11—C16—H16	119.3
C7A—C3A—C3	104.9 (2)	C15—C16—H16	119.3
C7A—C3A—C4	121.8 (2)	C32—C31—C36	117.9 (3)
C3—C3A—C4	133.3 (3)	C32—C31—C3	121.9 (2)
N5—C4—C3A	107.4 (2)	C36—C31—C3	120.2 (3)
N5—C4—H4A	110.2	C33—C32—C31	121.5 (3)
C3A—C4—H4A	110.2	C33—C32—H32	119.2
N5—C4—H4B	110.2	C31—C32—H32	119.2
C3A—C4—H4B	110.2	C32—C33—C34	119.5 (3)
H4A—C4—H4B	108.5	C32—C33—H33	120.3
C6—N5—C4	113.5 (2)	C34—C33—H33	120.3
C6—N5—S51	118.21 (19)	C35—C34—C33	119.9 (3)
C4—N5—S51	116.6 (2)	C35—C34—C37	119.7 (3)
N5—C6—C7	109.2 (2)	C33—C34—C37	120.4 (4)
N5—C6—H6A	109.8	C34—C35—C36	120.2 (3)
C7—C6—H6A	109.8	C34—C35—H35	119.9
N5—C6—H6B	109.8	C36—C35—H35	119.9
C7—C6—H6B	109.8	C35—C36—C31	120.9 (3)
H6A—C6—H6B	108.3	C35—C36—H36	119.5
C7A—C7—C6	108.1 (3)	C31—C36—H36	119.5
C7A—C7—H7A	110.1	F31A—C37—F32A	108.8 (10)
C6—C7—H7A	110.1	F31A—C37—F33A	104.0 (10)
C7A—C7—H7B	110.1	F32A—C37—F33A	101.6 (9)
C6—C7—H7B	110.1	F32B—C37—F31B	105.9 (11)
H7A—C7—H7B	108.4	F32B—C37—F33B	109.3 (13)
N1—C7A—C3A	107.1 (2)	F31B—C37—F33B	100.7 (12)
N1—C7A—C7	127.4 (3)	F32B—C37—C34	116.4 (8)
C3A—C7A—C7	125.5 (3)	F31A—C37—C34	115.2 (8)
N1—C17—C11	111.7 (3)	F32A—C37—C34	113.4 (7)
N1—C17—H17A	109.3	F33A—C37—C34	112.6 (7)
C11—C17—H17A	109.3	F31B—C37—C34	111.5 (7)
N1—C17—H17B	109.3	F33B—C37—C34	111.7 (8)
C11—C17—H17B	109.3	O51—S51—O52	118.56 (16)
H17A—C17—H17B	107.9	O51—S51—N5	107.30 (15)
C12—C11—C16	118.5 (3)	O52—S51—N5	107.20 (13)
C12—C11—C17	120.5 (3)	O51—S51—C51	109.00 (19)
C16—C11—C17	121.0 (3)	O52—S51—C51	107.11 (19)
C11—C12—C13	121.1 (4)	N5—S51—C51	107.16 (16)
C11—C12—H12	119.4	S51—C51—H51A	109.5
C13—C12—H12	119.4	S51—C51—H51B	109.5
C12—C13—C14	119.2 (3)	H51A—C51—H51B	109.5
C12—C13—H13	120.4	S51—C51—H51C	109.5
C14—C13—H13	120.4	H51A—C51—H51C	109.5
C15—C14—C13	120.9 (4)	H51B—C51—H51C	109.5
C7A—N1—N2—C3	0.8 (3)	C12—C11—C16—C15	−0.1 (6)
C17—N1—N2—C3	175.0 (3)	C17—C11—C16—C15	178.4 (3)
N1—N2—C3—C3A	−0.1 (3)	C14—C15—C16—C11	−0.9 (6)
N1—N2—C3—C31	−179.5 (2)	N2—C3—C31—C32	164.3 (3)
N2—C3—C3A—C7A	−0.5 (3)	C3A—C3—C31—C32	−15.0 (5)
C31—C3—C3A—C7A	178.8 (3)	N2—C3—C31—C36	−14.6 (4)
N2—C3—C3A—C4	177.5 (3)	C3A—C3—C31—C36	166.1 (3)
C31—C3—C3A—C4	−3.1 (5)	C36—C31—C32—C33	−1.5 (5)
C7A—C3A—C4—N5	16.3 (4)	C3—C31—C32—C33	179.6 (3)
C3—C3A—C4—N5	−161.6 (3)	C31—C32—C33—C34	0.6 (5)
C3A—C4—N5—C6	−51.5 (3)	C32—C33—C34—C35	1.0 (5)
C3A—C4—N5—S51	165.85 (18)	C32—C33—C34—C37	−178.2 (4)
C4—N5—C6—C7	70.6 (3)	C33—C34—C35—C36	−1.6 (5)
S51—N5—C6—C7	−147.5 (2)	C37—C34—C35—C36	177.7 (4)
N5—C6—C7—C7A	−46.5 (3)	C34—C35—C36—C31	0.6 (5)
N2—N1—C7A—C3A	−1.2 (3)	C32—C31—C36—C35	1.0 (5)
C17—N1—C7A—C3A	−174.8 (3)	C3—C31—C36—C35	179.9 (3)
N2—N1—C7A—C7	−179.3 (3)	C35—C34—C37—F32B	80 (2)
C17—N1—C7A—C7	7.0 (5)	C33—C34—C37—F32B	−100 (2)
C3—C3A—C7A—N1	1.0 (3)	C35—C34—C37—F31A	−84.2 (17)
C4—C3A—C7A—N1	−177.4 (2)	C33—C34—C37—F31A	95.0 (17)
C3—C3A—C7A—C7	179.2 (3)	C35—C34—C37—F32A	42.1 (13)
C4—C3A—C7A—C7	0.8 (4)	C33—C34—C37—F32A	−138.7 (13)
C6—C7—C7A—N1	−167.7 (3)	C35—C34—C37—F33A	156.8 (14)
C6—C7—C7A—C3A	14.5 (4)	C33—C34—C37—F33A	−24.0 (15)
C7A—N1—C17—C11	68.1 (4)	C35—C34—C37—F31B	−41.3 (17)
N2—N1—C17—C11	−105.1 (3)	C33—C34—C37—F31B	137.9 (17)
N1—C17—C11—C12	59.0 (4)	C35—C34—C37—F33B	−153 (2)
N1—C17—C11—C16	−119.4 (4)	C33—C34—C37—F33B	26 (2)
C16—C11—C12—C13	1.2 (5)	C6—N5—S51—O51	38.9 (3)
C17—C11—C12—C13	−177.3 (3)	C4—N5—S51—O51	179.7 (2)
C11—C12—C13—C14	−1.4 (6)	C6—N5—S51—O52	167.3 (2)
C12—C13—C14—C15	0.4 (6)	C4—N5—S51—O52	−51.9 (2)
C12—C13—C14—Cl14	179.8 (3)	C6—N5—S51—C51	−78.0 (3)
C13—C14—C15—C16	0.7 (6)	C4—N5—S51—C51	62.8 (3)
Cl14—C14—C15—C16	−178.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O52^i	0.93	2.44	3.339 (4)	163
C17—H17A···O51^ii	0.97	2.57	3.487 (4)	158

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+3/2.

(III) 1-(3-<ethylphenyl)-5-methylsulfonyl-3-[4-(trifluoromethyl)phenyl]-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine

Crystal data

C22H22F3N3O2S	F(000) = 936
Mr = 449.48	Dx = 1.427 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.8408 (10) Å	Cell parameters from 4392 reflections
b = 8.7145 (6) Å	θ = 1.7–26.7°
c = 18.0898 (13) Å	µ = 0.21 mm^−1
β = 106.470 (2)°	T = 296 K
V = 2092.4 (3) Å^3	Block, colourless
Z = 4	0.34 × 0.24 × 0.22 mm

Data collection

Bruker Kappa APEXII diffractometer	2953 reflections with I > 2σ(I)
Radiation source: fine focus sealed tube	Rint = 0.045
φ and ω scans	θmax = 26.7°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −17→17
Tmin = 0.946, Tmax = 0.956	k = −10→10
33310 measured reflections	l = −22→22
4391 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.0394P)^2 + 1.101P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4391 reflections	Δρmax = 0.33 e Å^−3
310 parameters	Δρmin = −0.29 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)
N1	0.73177 (12)	0.6156 (2)	0.51672 (9)	0.0328 (4)
N2	0.69346 (12)	0.6065 (2)	0.57743 (9)	0.0331 (4)
C3	0.59874 (14)	0.6585 (2)	0.55104 (11)	0.0292 (4)
C3A	0.57717 (14)	0.7005 (2)	0.47255 (11)	0.0301 (4)
C4	0.48518 (15)	0.7636 (3)	0.41515 (11)	0.0364 (5)
H4A	0.4267	0.7024	0.4153	0.044*
H4B	0.4733	0.8682	0.4286	0.044*
N5	0.50150 (13)	0.7597 (2)	0.33856 (10)	0.0383 (4)
C6	0.60024 (16)	0.8150 (3)	0.33435 (13)	0.0443 (6)
H6A	0.6132	0.9164	0.3571	0.053*
H6B	0.6006	0.8220	0.2809	0.053*
C7	0.68157 (16)	0.7042 (3)	0.37754 (12)	0.0406 (5)
H7A	0.6783	0.6100	0.3484	0.049*
H7B	0.7477	0.7495	0.3850	0.049*
C7A	0.66397 (15)	0.6718 (2)	0.45297 (11)	0.0321 (5)
C17	0.83560 (14)	0.5690 (3)	0.52546 (13)	0.0375 (5)
H17A	0.8755	0.5907	0.5778	0.045*
H17B	0.8624	0.6301	0.4910	0.045*
C11	0.84674 (14)	0.4017 (3)	0.50869 (12)	0.0369 (5)
C12	0.81108 (16)	0.2891 (3)	0.54804 (13)	0.0419 (5)
H12	0.7796	0.3181	0.5850	0.050*
C13	0.82091 (18)	0.1344 (3)	0.53402 (15)	0.0527 (7)
C14	0.8700 (2)	0.0946 (4)	0.47966 (18)	0.0693 (9)
H14	0.8783	−0.0086	0.4697	0.083*
C15	0.9063 (2)	0.2042 (4)	0.44039 (19)	0.0704 (9)
H15	0.9393	0.1749	0.4044	0.084*
C16	0.89437 (17)	0.3587 (3)	0.45389 (14)	0.0529 (7)
H16	0.9181	0.4330	0.4265	0.063*
C18	0.7774 (2)	0.0146 (3)	0.57530 (18)	0.0787 (9)
H18A	0.7133	−0.0185	0.5427	0.118*
H18B	0.7687	0.0573	0.6219	0.118*
H18C	0.8223	−0.0716	0.5876	0.118*
C31	0.53696 (14)	0.6687 (2)	0.60515 (11)	0.0294 (4)
C32	0.43873 (16)	0.7240 (3)	0.58234 (13)	0.0447 (6)
H19	0.4102	0.7532	0.5314	0.054*
C33	0.38283 (17)	0.7360 (3)	0.63451 (13)	0.0460 (6)
H33	0.3171	0.7729	0.6185	0.055*
C34	0.42433 (16)	0.6936 (3)	0.70989 (12)	0.0375 (5)
C35	0.52071 (18)	0.6367 (3)	0.73315 (13)	0.0446 (6)
H35	0.5484	0.6059	0.7840	0.054*
C36	0.57651 (16)	0.6253 (3)	0.68124 (12)	0.0401 (5)
H36	0.6420	0.5876	0.6977	0.048*
C37	0.3650 (2)	0.7116 (4)	0.76638 (15)	0.0552 (7)
F31A	0.2712 (4)	0.7447 (19)	0.7364 (3)	0.120 (5)	0.579 (19)
F32A	0.3654 (11)	0.5891 (10)	0.8068 (8)	0.143 (6)	0.579 (19)
F33A	0.3997 (8)	0.8211 (16)	0.8150 (7)	0.142 (6)	0.579 (19)
F31B	0.2894 (10)	0.6221 (17)	0.7546 (8)	0.109 (7)	0.421 (19)
F32B	0.4157 (6)	0.689 (2)	0.8372 (3)	0.102 (6)	0.421 (19)
F33B	0.3293 (14)	0.8486 (10)	0.7660 (10)	0.120 (7)	0.421 (19)
S51	0.40470 (4)	0.79046 (7)	0.26402 (3)	0.04040 (17)
O51	0.43430 (14)	0.7467 (2)	0.19768 (9)	0.0603 (5)
O52	0.32052 (12)	0.71828 (19)	0.27996 (10)	0.0542 (5)
C51	0.38223 (19)	0.9882 (3)	0.25797 (15)	0.0562 (7)
H51A	0.3247	1.0095	0.2150	0.084*
H51B	0.4401	1.0402	0.2509	0.084*
H51C	0.3696	1.0234	0.3046	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0276 (9)	0.0379 (10)	0.0354 (9)	0.0034 (8)	0.0130 (7)	−0.0004 (8)
N2	0.0299 (9)	0.0393 (10)	0.0330 (9)	0.0046 (8)	0.0137 (7)	0.0014 (8)
C3	0.0292 (10)	0.0278 (10)	0.0318 (11)	0.0004 (8)	0.0107 (8)	−0.0014 (8)
C3A	0.0290 (10)	0.0321 (11)	0.0303 (10)	0.0007 (9)	0.0103 (8)	−0.0014 (9)
C4	0.0335 (11)	0.0458 (13)	0.0314 (11)	0.0052 (10)	0.0115 (9)	0.0029 (9)
N5	0.0335 (10)	0.0495 (12)	0.0315 (10)	0.0003 (8)	0.0085 (8)	0.0067 (8)
C6	0.0425 (13)	0.0543 (15)	0.0402 (13)	−0.0027 (11)	0.0185 (10)	0.0090 (11)
C7	0.0361 (12)	0.0517 (14)	0.0382 (12)	−0.0014 (11)	0.0177 (10)	−0.0002 (11)
C7A	0.0331 (11)	0.0341 (11)	0.0302 (11)	−0.0012 (9)	0.0108 (9)	−0.0030 (9)
C17	0.0253 (10)	0.0477 (13)	0.0420 (12)	0.0030 (10)	0.0135 (9)	−0.0011 (10)
C11	0.0245 (10)	0.0472 (14)	0.0373 (12)	0.0056 (10)	0.0056 (9)	−0.0071 (10)
C12	0.0359 (12)	0.0476 (14)	0.0382 (12)	0.0058 (11)	0.0041 (10)	−0.0038 (11)
C13	0.0444 (14)	0.0435 (15)	0.0582 (16)	0.0070 (12)	−0.0051 (12)	−0.0065 (12)
C14	0.0532 (17)	0.0545 (18)	0.090 (2)	0.0176 (14)	0.0040 (16)	−0.0264 (16)
C15	0.0517 (17)	0.081 (2)	0.083 (2)	0.0128 (16)	0.0265 (15)	−0.0307 (18)
C16	0.0378 (13)	0.0697 (18)	0.0546 (15)	0.0042 (12)	0.0189 (11)	−0.0131 (13)
C18	0.089 (2)	0.0484 (17)	0.085 (2)	−0.0031 (16)	0.0013 (18)	0.0071 (15)
C31	0.0307 (11)	0.0292 (10)	0.0309 (10)	−0.0009 (8)	0.0131 (8)	−0.0023 (8)
C32	0.0328 (12)	0.0695 (17)	0.0319 (12)	0.0070 (11)	0.0095 (9)	0.0032 (11)
C33	0.0315 (12)	0.0662 (17)	0.0444 (14)	0.0044 (11)	0.0174 (10)	−0.0034 (12)
C34	0.0405 (12)	0.0385 (13)	0.0400 (12)	−0.0033 (10)	0.0216 (10)	−0.0022 (10)
C35	0.0543 (15)	0.0486 (14)	0.0352 (12)	0.0073 (12)	0.0195 (11)	0.0085 (10)
C36	0.0394 (12)	0.0445 (13)	0.0381 (12)	0.0104 (10)	0.0137 (10)	0.0072 (10)
C37	0.0575 (17)	0.0675 (19)	0.0504 (16)	0.0015 (16)	0.0314 (13)	−0.0003 (15)
F31A	0.051 (3)	0.249 (15)	0.073 (3)	0.037 (5)	0.040 (2)	0.029 (5)
F32A	0.206 (13)	0.130 (6)	0.153 (11)	0.059 (7)	0.150 (11)	0.079 (6)
F33A	0.136 (8)	0.186 (11)	0.139 (9)	−0.060 (7)	0.099 (7)	−0.115 (8)
F31B	0.099 (9)	0.144 (11)	0.120 (9)	−0.068 (8)	0.087 (8)	−0.048 (7)
F32B	0.079 (4)	0.201 (16)	0.033 (3)	0.028 (7)	0.029 (3)	0.006 (5)
F33B	0.177 (15)	0.071 (5)	0.174 (13)	0.046 (7)	0.152 (12)	0.027 (6)
S51	0.0433 (3)	0.0389 (3)	0.0345 (3)	−0.0008 (3)	0.0037 (2)	0.0037 (2)
O51	0.0725 (12)	0.0735 (13)	0.0317 (9)	0.0111 (10)	0.0095 (8)	−0.0011 (8)
O52	0.0430 (9)	0.0535 (10)	0.0580 (11)	−0.0130 (8)	0.0009 (8)	0.0122 (8)
C51	0.0569 (16)	0.0429 (14)	0.0644 (16)	0.0032 (12)	0.0099 (13)	0.0096 (12)

Geometric parameters (Å, º)

N1—N2	1.351 (2)	C15—C16	1.387 (4)
N1—C7A	1.355 (2)	C15—H15	0.9300
N1—C17	1.458 (2)	C16—H16	0.9300
N2—C3	1.341 (2)	C18—H18A	0.9600
C3—C3A	1.414 (3)	C18—H18B	0.9600
C3—C31	1.474 (3)	C18—H18C	0.9600
C3A—C7A	1.368 (3)	C31—C36	1.382 (3)
C3A—C4	1.501 (3)	C31—C32	1.390 (3)
C4—N5	1.466 (3)	C32—C33	1.384 (3)
C4—H4A	0.9700	C32—H19	0.9300
C4—H4B	0.9700	C33—C34	1.372 (3)
N5—C6	1.471 (3)	C33—H33	0.9300
N5—S51	1.6311 (17)	C34—C35	1.373 (3)
C6—C7	1.520 (3)	C34—C37	1.489 (3)
C6—H6A	0.9700	C35—C36	1.378 (3)
C6—H6B	0.9700	C35—H35	0.9300
C7—C7A	1.480 (3)	C36—H36	0.9300
C7—H7A	0.9700	C37—F31B	1.275 (6)
C7—H7B	0.9700	C37—F32B	1.289 (7)
C17—C11	1.506 (3)	C37—F31A	1.290 (5)
C17—H17A	0.9700	C37—F33B	1.291 (7)
C17—H17B	0.9700	C37—F32A	1.293 (5)
C11—C12	1.382 (3)	C37—F33A	1.294 (6)
C11—C16	1.388 (3)	S51—O52	1.4237 (17)
C12—C13	1.386 (3)	S51—O51	1.4255 (18)
C12—H12	0.9300	S51—C51	1.749 (2)
C13—C14	1.388 (4)	C51—H51A	0.9600
C13—C18	1.506 (4)	C51—H51B	0.9600
C14—C15	1.369 (4)	C51—H51C	0.9600
C14—H14	0.9300
N2—N1—C7A	112.11 (15)	C14—C15—H15	119.8
N2—N1—C17	119.84 (16)	C16—C15—H15	119.8
C7A—N1—C17	128.05 (17)	C15—C16—C11	119.5 (3)
C3—N2—N1	105.09 (15)	C15—C16—H16	120.3
N2—C3—C3A	110.61 (17)	C11—C16—H16	120.3
N2—C3—C31	118.47 (17)	C13—C18—H18A	109.5
C3A—C3—C31	130.88 (18)	C13—C18—H18B	109.5
C7A—C3A—C3	105.18 (17)	H18A—C18—H18B	109.5
C7A—C3A—C4	121.52 (18)	C13—C18—H18C	109.5
C3—C3A—C4	133.30 (18)	H18A—C18—H18C	109.5
N5—C4—C3A	108.52 (16)	H18B—C18—H18C	109.5
N5—C4—H4A	110.0	C36—C31—C32	117.93 (19)
C3A—C4—H4A	110.0	C36—C31—C3	120.29 (18)
N5—C4—H4B	110.0	C32—C31—C3	121.77 (18)
C3A—C4—H4B	110.0	C33—C32—C31	120.9 (2)
H4A—C4—H4B	108.4	C33—C32—H19	119.6
C4—N5—C6	115.83 (17)	C31—C32—H19	119.6
C4—N5—S51	117.84 (14)	C34—C33—C32	120.0 (2)
C6—N5—S51	117.44 (14)	C34—C33—H33	120.0
N5—C6—C7	109.18 (18)	C32—C33—H33	120.0
N5—C6—H6A	109.8	C33—C34—C35	119.9 (2)
C7—C6—H6A	109.8	C33—C34—C37	119.8 (2)
N5—C6—H6B	109.8	C35—C34—C37	120.3 (2)
C7—C6—H6B	109.8	C34—C35—C36	120.1 (2)
H6A—C6—H6B	108.3	C34—C35—H35	120.0
C7A—C7—C6	107.69 (17)	C36—C35—H35	120.0
C7A—C7—H7A	110.2	C35—C36—C31	121.2 (2)
C6—C7—H7A	110.2	C35—C36—H36	119.4
C7A—C7—H7B	110.2	C31—C36—H36	119.4
C6—C7—H7B	110.2	F31B—C37—F32B	105.2 (6)
H7A—C7—H7B	108.5	F31B—C37—F33B	105.7 (6)
N1—C7A—C3A	107.02 (17)	F32B—C37—F33B	104.2 (6)
N1—C7A—C7	126.75 (18)	F31A—C37—F32A	105.3 (5)
C3A—C7A—C7	126.15 (19)	F31A—C37—F33A	104.8 (5)
N1—C17—C11	113.69 (17)	F32A—C37—F33A	106.4 (5)
N1—C17—H17A	108.8	F31B—C37—C34	114.0 (3)
C11—C17—H17A	108.8	F32B—C37—C34	114.6 (4)
N1—C17—H17B	108.8	F31A—C37—C34	114.9 (3)
C11—C17—H17B	108.8	F33B—C37—C34	112.2 (3)
H17A—C17—H17B	107.7	F32A—C37—C34	112.7 (3)
C12—C11—C16	119.2 (2)	F33A—C37—C34	112.0 (3)
C12—C11—C17	120.74 (19)	O52—S51—O51	119.96 (11)
C16—C11—C17	120.1 (2)	O52—S51—N5	106.72 (9)
C11—C12—C13	121.9 (2)	O51—S51—N5	106.70 (10)
C11—C12—H12	119.1	O52—S51—C51	107.87 (12)
C13—C12—H12	119.1	O51—S51—C51	107.40 (12)
C12—C13—C14	117.8 (3)	N5—S51—C51	107.65 (11)
C12—C13—C18	120.7 (3)	S51—C51—H51A	109.5
C14—C13—C18	121.5 (3)	S51—C51—H51B	109.5
C15—C14—C13	121.2 (3)	H51A—C51—H51B	109.5
C15—C14—H14	119.4	S51—C51—H51C	109.5
C13—C14—H14	119.4	H51A—C51—H51C	109.5
C14—C15—C16	120.4 (3)	H51B—C51—H51C	109.5
C7A—N1—N2—C3	0.0 (2)	C14—C15—C16—C11	1.2 (4)
C17—N1—N2—C3	179.28 (17)	C12—C11—C16—C15	−0.8 (3)
N1—N2—C3—C3A	0.2 (2)	C17—C11—C16—C15	178.4 (2)
N1—N2—C3—C31	−177.72 (17)	N2—C3—C31—C36	0.0 (3)
N2—C3—C3A—C7A	−0.3 (2)	C3A—C3—C31—C36	−177.4 (2)
C31—C3—C3A—C7A	177.3 (2)	N2—C3—C31—C32	178.9 (2)
N2—C3—C3A—C4	179.7 (2)	C3A—C3—C31—C32	1.5 (3)
C31—C3—C3A—C4	−2.7 (4)	C36—C31—C32—C33	0.5 (3)
C7A—C3A—C4—N5	9.7 (3)	C3—C31—C32—C33	−178.4 (2)
C3—C3A—C4—N5	−170.3 (2)	C31—C32—C33—C34	0.2 (4)
C3A—C4—N5—C6	−45.2 (2)	C32—C33—C34—C35	−1.1 (4)
C3A—C4—N5—S51	168.19 (14)	C32—C33—C34—C37	178.0 (2)
C4—N5—C6—C7	67.6 (2)	C33—C34—C35—C36	1.4 (4)
S51—N5—C6—C7	−145.72 (16)	C37—C34—C35—C36	−177.8 (2)
N5—C6—C7—C7A	−47.5 (2)	C34—C35—C36—C31	−0.7 (4)
N2—N1—C7A—C3A	−0.2 (2)	C32—C31—C36—C35	−0.3 (3)
C17—N1—C7A—C3A	−179.38 (19)	C3—C31—C36—C35	178.7 (2)
N2—N1—C7A—C7	176.8 (2)	C33—C34—C37—F31B	68.1 (11)
C17—N1—C7A—C7	−2.4 (3)	C35—C34—C37—F31B	−112.8 (11)
C3—C3A—C7A—N1	0.3 (2)	C33—C34—C37—F32B	−170.6 (10)
C4—C3A—C7A—N1	−179.72 (18)	C35—C34—C37—F32B	8.5 (11)
C3—C3A—C7A—C7	−176.7 (2)	C33—C34—C37—F31A	10.4 (9)
C4—C3A—C7A—C7	3.3 (3)	C35—C34—C37—F31A	−170.4 (9)
C6—C7—C7A—N1	−160.2 (2)	C33—C34—C37—F33B	−52.1 (12)
C6—C7—C7A—C3A	16.2 (3)	C35—C34—C37—F33B	127.1 (11)
N2—N1—C17—C11	89.5 (2)	C33—C34—C37—F32A	131.1 (10)
C7A—N1—C17—C11	−91.3 (3)	C35—C34—C37—F32A	−49.8 (10)
N1—C17—C11—C12	−56.3 (3)	C33—C34—C37—F33A	−108.9 (9)
N1—C17—C11—C16	124.5 (2)	C35—C34—C37—F33A	70.2 (10)
C16—C11—C12—C13	−0.4 (3)	C4—N5—S51—O52	−37.73 (19)
C17—C11—C12—C13	−179.62 (19)	C6—N5—S51—O52	176.24 (17)
C11—C12—C13—C14	1.2 (3)	C4—N5—S51—O51	−167.12 (16)
C11—C12—C13—C18	−177.3 (2)	C6—N5—S51—O51	46.85 (19)
C12—C13—C14—C15	−0.8 (4)	C4—N5—S51—C51	77.85 (19)
C18—C13—C14—C15	177.7 (3)	C6—N5—S51—C51	−68.2 (2)
C13—C14—C15—C16	−0.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17A···O51^i	0.97	2.52	3.426 (3)	155
C33—H33···Cg1^ii	0.93	2.70	3.488 (3)	144

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1.