Isomorphous methyl- and chloro-substituted small heterocyclic analogues obeying the chlorine-methyl (Cl-Me) exchange rule

The two new isomorphous structures [3-methyl-4-(4-methyl­phen­yl)-1-phenyl-6-trifluoro­methyl-1H-pyrazolo­[3,4-b]pyri­din-5-yl](thio­phen-2-yl)methanone, C₂₆H₁₈F₃N₃OS, (I), and [4-(4-chloro­phen­yl)-3-methyl-1-phenyl-6-trifluoro­methyl-1H-pyrazolo­[3,4-b]pyridin-5-yl](thio­phen-2-yl)methanone, C₂₅H₁₅ClF₃N₃OS, (II), are shown to obey the chlorine-methyl exchange rule. Both structures show extensive disorder, treatment of which greatly improves the quality of the description of the structures. In addition, it is worth noting that the presence of extensive disorder may make it difficult to detect the isomorphism automatically during data-mining procedures (such as searches of the Cambridge Structural Database).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

(I) [3-Methyl-4-(4-methylphenyl)-1-phenyl-6-trifluoromethyl-1H-pyrazolo[3,4-b]pyridin-5-yl](thiophen-2-yl)methanone

Crystal data

C26H18F3N3OS	Z = 2
Mr = 477.49	F(000) = 492
Triclinic, P1	Dx = 1.397 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0323 (4) Å	Cell parameters from 10124 reflections
b = 10.3715 (5) Å	θ = 2.1–28.0°
c = 11.7411 (5) Å	µ = 0.19 mm^−1
α = 109.211 (2)°	T = 298 K
β = 96.105 (2)°	Needle, yellow
γ = 95.676 (2)°	0.28 × 0.18 × 0.12 mm
V = 1135.36 (9) Å^3

Data collection

Bruker APEXII CCD diffractometer	6692 independent reflections
Radiation source: fine-focus sealed tube	4773 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω and φ scans	θmax = 30.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→13
Tmin = 0.900, Tmax = 0.989	k = −14→14
25018 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 0.2446P] where P = (Fo^2 + 2Fc^2)/3
6692 reflections	(Δ/σ)max < 0.001
382 parameters	Δρmax = 0.19 e Å^−3
345 restraints	Δρmin = −0.25 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.22031 (13)	0.53727 (13)	0.43932 (10)	0.0649 (3)
N1	0.45272 (11)	0.20561 (11)	−0.02588 (10)	0.0423 (3)
N2	0.57941 (12)	0.28107 (12)	−0.00452 (11)	0.0469 (3)
N3	0.24775 (11)	0.23106 (11)	0.06404 (10)	0.0438 (3)
C1	0.58186 (13)	0.39452 (14)	0.08892 (12)	0.0436 (3)
C2	0.45472 (12)	0.39688 (12)	0.13287 (11)	0.0376 (3)
C3	0.39830 (13)	0.48555 (12)	0.22745 (11)	0.0368 (3)
C4	0.26395 (13)	0.44530 (13)	0.23546 (12)	0.0401 (3)
C5	0.19596 (13)	0.31823 (14)	0.15358 (12)	0.0436 (3)
C25	0.0502 (6)	0.2683 (7)	0.1625 (6)	0.0624 (15)	0.569 (7)
F1	−0.0332 (3)	0.3069 (8)	0.0918 (5)	0.1235 (18)	0.569 (7)
F2	0.0218 (5)	0.3180 (6)	0.2697 (3)	0.1110 (19)	0.569 (7)
F3	0.0284 (4)	0.1350 (3)	0.1241 (7)	0.132 (3)	0.569 (7)
C25A	0.0600 (8)	0.2512 (9)	0.1634 (7)	0.0580 (18)	0.431 (7)
F1A	0.0660 (5)	0.1633 (9)	0.2197 (9)	0.133 (3)	0.431 (7)
F2A	−0.0196 (6)	0.1901 (10)	0.0643 (4)	0.125 (3)	0.431 (7)
F3A	−0.0148 (6)	0.3372 (5)	0.2272 (9)	0.129 (3)	0.431 (7)
C6	0.37445 (13)	0.27416 (13)	0.05595 (11)	0.0383 (3)
C7	0.19828 (13)	0.53776 (14)	0.33622 (12)	0.0431 (3)
C8	0.11091 (13)	0.62838 (14)	0.30385 (12)	0.0423 (3)
S1	0.00886 (7)	0.71013 (8)	0.40507 (6)	0.05390 (18)	0.845 (2)
C9	−0.0533 (5)	0.7880 (5)	0.3084 (4)	0.0586 (7)	0.845 (2)
H9	−0.1191	0.8461	0.3248	0.070*	0.845 (2)
C10	0.0032 (6)	0.7563 (7)	0.2051 (5)	0.0626 (9)	0.845 (2)
H10	−0.0168	0.7917	0.1431	0.075*	0.845 (2)
C11	0.0958 (6)	0.6631 (6)	0.2031 (3)	0.0589 (9)	0.845 (2)
H11	0.1426	0.6285	0.1378	0.071*	0.845 (2)
S1A	0.1045 (8)	0.6501 (9)	0.1657 (5)	0.0652 (13)	0.155 (2)
C9A	−0.012 (3)	0.761 (3)	0.203 (3)	0.064 (3)	0.155 (2)
H9A	−0.0535	0.8001	0.1510	0.077*	0.155 (2)
C10A	−0.036 (3)	0.783 (3)	0.318 (3)	0.074 (4)	0.155 (2)
H10A	−0.0898	0.8463	0.3581	0.089*	0.155 (2)
C11A	0.0292 (16)	0.7016 (18)	0.3688 (14)	0.064 (3)	0.155 (2)
H11A	0.0163	0.6982	0.4451	0.077*	0.155 (2)
C12	0.42500 (14)	0.07335 (13)	−0.11801 (11)	0.0420 (3)
C13	0.29410 (17)	0.01699 (15)	−0.17233 (14)	0.0551 (4)
H13	0.2222	0.0638	−0.1471	0.066*
C14	0.2707 (2)	−0.11019 (17)	−0.26499 (16)	0.0665 (5)
H14	0.1825	−0.1488	−0.3020	0.080*
C15	0.3765 (2)	−0.17989 (16)	−0.30278 (15)	0.0665 (5)
H15	0.3603	−0.2645	−0.3660	0.080*
C16	0.5059 (2)	−0.12383 (16)	−0.24672 (14)	0.0606 (4)
H16	0.5773	−0.1716	−0.2716	0.073*
C17	0.53208 (17)	0.00274 (15)	−0.15371 (13)	0.0502 (3)
H17	0.6202	0.0398	−0.1158	0.060*
C18	0.48269 (13)	0.61143 (12)	0.31676 (11)	0.0370 (3)
C19	0.57813 (15)	0.59816 (14)	0.40508 (12)	0.0459 (3)
H19	0.5852	0.5115	0.4104	0.055*
C20	0.66267 (15)	0.71197 (14)	0.48505 (13)	0.0477 (3)
H20	0.7261	0.7010	0.5437	0.057*
C21	0.65478 (14)	0.84204 (14)	0.47957 (13)	0.0454 (3)
C22	0.55912 (16)	0.85475 (14)	0.39198 (13)	0.0488 (3)
H22	0.5521	0.9416	0.3871	0.059*
C23	0.47327 (15)	0.74156 (13)	0.31123 (13)	0.0447 (3)
H23	0.4092	0.7529	0.2532	0.054*
C24	0.70538 (16)	0.49990 (18)	0.13200 (16)	0.0614 (4)
H24A	0.7675	0.4777	0.0739	0.092*
H24B	0.7477	0.5006	0.2095	0.092*
H24C	0.6805	0.5892	0.1403	0.092*
C26	0.74974 (18)	0.96556 (17)	0.56560 (17)	0.0671 (5)
H26A	0.8087	0.9370	0.6198	0.101*	0.50
H26B	0.6982	1.0319	0.6121	0.101*	0.50
H26C	0.8028	1.0065	0.5196	0.101*	0.50
H26D	0.7311	1.0466	0.5479	0.101*	0.50
H26E	0.8416	0.9517	0.5556	0.101*	0.50
H26F	0.7370	0.9771	0.6481	0.101*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0818 (8)	0.0745 (8)	0.0431 (6)	0.0340 (6)	0.0136 (5)	0.0184 (5)
N1	0.0433 (6)	0.0362 (6)	0.0394 (6)	0.0070 (4)	0.0074 (4)	0.0017 (4)
N2	0.0434 (6)	0.0457 (6)	0.0437 (6)	0.0061 (5)	0.0088 (5)	0.0043 (5)
N3	0.0417 (6)	0.0390 (6)	0.0431 (6)	0.0055 (4)	0.0048 (5)	0.0044 (5)
C1	0.0422 (6)	0.0417 (7)	0.0412 (7)	0.0068 (5)	0.0063 (5)	0.0063 (6)
C2	0.0399 (6)	0.0324 (6)	0.0371 (6)	0.0071 (5)	0.0050 (5)	0.0072 (5)
C3	0.0434 (6)	0.0307 (6)	0.0346 (6)	0.0098 (5)	0.0042 (5)	0.0081 (5)
C4	0.0414 (6)	0.0378 (6)	0.0378 (6)	0.0113 (5)	0.0055 (5)	0.0071 (5)
C5	0.0393 (6)	0.0443 (7)	0.0422 (7)	0.0079 (5)	0.0057 (5)	0.0078 (6)
C25	0.037 (2)	0.051 (2)	0.070 (3)	−0.0051 (17)	0.0084 (19)	−0.014 (2)
F1	0.0400 (11)	0.197 (5)	0.130 (3)	0.0192 (19)	0.0018 (15)	0.054 (3)
F2	0.091 (3)	0.135 (3)	0.0646 (15)	−0.050 (2)	0.0421 (15)	−0.0126 (15)
F3	0.084 (3)	0.0425 (15)	0.227 (6)	−0.0171 (13)	0.076 (4)	−0.018 (2)
C25A	0.053 (3)	0.072 (5)	0.048 (3)	0.017 (3)	0.018 (2)	0.014 (3)
F1A	0.073 (2)	0.155 (5)	0.231 (7)	0.007 (3)	0.034 (3)	0.144 (5)
F2A	0.070 (3)	0.187 (8)	0.070 (2)	−0.054 (4)	0.0078 (16)	0.000 (3)
F3A	0.064 (3)	0.058 (2)	0.225 (7)	0.0022 (16)	0.076 (4)	−0.020 (3)
C6	0.0417 (6)	0.0338 (6)	0.0354 (6)	0.0103 (5)	0.0046 (5)	0.0054 (5)
C7	0.0435 (7)	0.0422 (7)	0.0392 (7)	0.0089 (5)	0.0075 (5)	0.0069 (5)
C8	0.0389 (6)	0.0419 (7)	0.0402 (7)	0.0090 (5)	0.0079 (5)	0.0047 (5)
S1	0.0491 (3)	0.0574 (3)	0.0532 (3)	0.0188 (2)	0.0195 (2)	0.0095 (3)
C9	0.0450 (15)	0.0563 (14)	0.0718 (16)	0.0218 (11)	0.0097 (12)	0.0140 (12)
C10	0.059 (2)	0.0703 (19)	0.0619 (14)	0.0234 (14)	0.0057 (13)	0.0246 (13)
C11	0.0599 (15)	0.0662 (16)	0.0500 (19)	0.0214 (11)	0.0140 (15)	0.0138 (17)
S1A	0.062 (2)	0.081 (3)	0.060 (3)	0.0340 (18)	0.011 (2)	0.027 (3)
C9A	0.044 (6)	0.058 (7)	0.089 (7)	0.028 (5)	0.006 (6)	0.019 (6)
C10A	0.053 (7)	0.069 (7)	0.084 (6)	0.026 (5)	0.005 (5)	0.000 (6)
C11A	0.056 (6)	0.063 (6)	0.066 (6)	0.015 (4)	0.021 (5)	0.005 (5)
C12	0.0571 (8)	0.0333 (6)	0.0335 (6)	0.0109 (5)	0.0091 (5)	0.0068 (5)
C13	0.0578 (9)	0.0455 (8)	0.0509 (8)	0.0054 (6)	0.0099 (7)	0.0018 (7)
C14	0.0796 (12)	0.0485 (9)	0.0542 (9)	−0.0112 (8)	0.0098 (8)	0.0005 (7)
C15	0.1101 (15)	0.0331 (7)	0.0490 (9)	0.0069 (8)	0.0196 (9)	0.0031 (6)
C16	0.0974 (13)	0.0447 (8)	0.0466 (8)	0.0328 (8)	0.0240 (8)	0.0144 (7)
C17	0.0648 (9)	0.0473 (8)	0.0405 (7)	0.0220 (7)	0.0118 (6)	0.0123 (6)
C18	0.0431 (6)	0.0309 (6)	0.0346 (6)	0.0079 (5)	0.0088 (5)	0.0062 (5)
C19	0.0577 (8)	0.0319 (6)	0.0439 (7)	0.0113 (6)	0.0002 (6)	0.0082 (5)
C20	0.0510 (7)	0.0434 (7)	0.0413 (7)	0.0101 (6)	−0.0014 (6)	0.0062 (6)
C21	0.0474 (7)	0.0386 (7)	0.0422 (7)	0.0020 (5)	0.0113 (6)	0.0032 (6)
C22	0.0629 (9)	0.0305 (6)	0.0516 (8)	0.0041 (6)	0.0099 (7)	0.0124 (6)
C23	0.0540 (8)	0.0371 (7)	0.0424 (7)	0.0077 (6)	0.0029 (6)	0.0137 (6)
C24	0.0469 (8)	0.0621 (10)	0.0588 (9)	−0.0044 (7)	0.0119 (7)	0.0013 (8)
C26	0.0645 (10)	0.0500 (9)	0.0660 (11)	−0.0093 (7)	0.0033 (8)	−0.0007 (8)

Geometric parameters (Å, º)

O1—C7	1.2090 (17)	C9A—H9A	0.9300
N1—C6	1.3662 (15)	C10A—C11A	1.360 (18)
N1—N2	1.3773 (16)	C10A—H10A	0.9300
N1—C12	1.4188 (16)	C11A—H11A	0.9300
N2—C1	1.3145 (17)	C12—C13	1.378 (2)
N3—C6	1.3288 (17)	C12—C17	1.3840 (19)
N3—C5	1.3327 (16)	C13—C14	1.385 (2)
C1—C2	1.4254 (18)	C13—H13	0.9300
C1—C24	1.490 (2)	C14—C15	1.374 (3)
C2—C3	1.4014 (16)	C14—H14	0.9300
C2—C6	1.4036 (17)	C15—C16	1.369 (3)
C3—C4	1.3933 (18)	C15—H15	0.9300
C3—C18	1.4874 (17)	C16—C17	1.383 (2)
C4—C5	1.4055 (19)	C16—H16	0.9300
C4—C7	1.5157 (17)	C17—H17	0.9300
C5—C25A	1.502 (8)	C18—C23	1.3843 (18)
C5—C25	1.529 (6)	C18—C19	1.3857 (18)
C25—F2	1.268 (7)	C19—C20	1.3775 (19)
C25—F3	1.293 (7)	C19—H19	0.9300
C25—F1	1.298 (7)	C20—C21	1.381 (2)
C25A—F2A	1.270 (8)	C20—H20	0.9300
C25A—F1A	1.293 (9)	C21—C22	1.378 (2)
C25A—F3A	1.316 (9)	C21—C26	1.507 (2)
C7—C8	1.4572 (19)	C22—C23	1.3830 (19)
C8—C11A	1.306 (12)	C22—H22	0.9300
C8—C11	1.344 (4)	C23—H23	0.9300
C8—S1A	1.705 (6)	C24—H24A	0.9600
C8—S1	1.7166 (13)	C24—H24B	0.9600
S1—C9	1.698 (3)	C24—H24C	0.9600
C9—C10	1.349 (4)	C26—H26A	0.9600
C9—H9	0.9300	C26—H26B	0.9600
C10—C11	1.402 (6)	C26—H26C	0.9600
C10—H10	0.9300	C26—H26D	0.9600
C11—H11	0.9300	C26—H26E	0.9600
S1A—C9A	1.706 (19)	C26—H26F	0.9600
C9A—C10A	1.344 (17)
C6—N1—N2	110.02 (10)	C8—C11A—H11A	122.0
C6—N1—C12	130.48 (11)	C10A—C11A—H11A	122.0
N2—N1—C12	119.38 (10)	C13—C12—C17	120.52 (13)
C1—N2—N1	107.65 (11)	C13—C12—N1	120.67 (12)
C6—N3—C5	114.01 (11)	C17—C12—N1	118.81 (13)
N2—C1—C2	110.33 (12)	C12—C13—C14	119.32 (15)
N2—C1—C24	120.30 (12)	C12—C13—H13	120.3
C2—C1—C24	129.36 (12)	C14—C13—H13	120.3
C3—C2—C6	118.43 (12)	C15—C14—C13	120.63 (17)
C3—C2—C1	136.61 (12)	C15—C14—H14	119.7
C6—C2—C1	104.96 (11)	C13—C14—H14	119.7
C4—C3—C2	116.51 (11)	C16—C15—C14	119.48 (14)
C4—C3—C18	123.14 (11)	C16—C15—H15	120.3
C2—C3—C18	120.27 (11)	C14—C15—H15	120.3
C3—C4—C5	119.12 (11)	C15—C16—C17	121.10 (15)
C3—C4—C7	118.53 (11)	C15—C16—H16	119.5
C5—C4—C7	122.29 (12)	C17—C16—H16	119.5
N3—C5—C4	125.57 (12)	C16—C17—C12	118.93 (16)
N3—C5—C25A	109.0 (4)	C16—C17—H17	120.5
C4—C5—C25A	125.0 (3)	C12—C17—H17	120.5
N3—C5—C25	113.8 (3)	C23—C18—C19	118.63 (12)
C4—C5—C25	120.6 (3)	C23—C18—C3	122.02 (11)
F2—C25—F3	110.8 (6)	C19—C18—C3	119.28 (11)
F2—C25—F1	107.1 (6)	C20—C19—C18	120.67 (12)
F3—C25—F1	106.6 (5)	C20—C19—H19	119.7
F2—C25—C5	112.3 (4)	C18—C19—H19	119.7
F3—C25—C5	110.1 (5)	C19—C20—C21	121.11 (13)
F1—C25—C5	109.7 (5)	C19—C20—H20	119.4
F2A—C25A—F1A	106.1 (8)	C21—C20—H20	119.4
F2A—C25A—F3A	101.9 (7)	C22—C21—C20	117.98 (12)
F1A—C25A—F3A	102.2 (6)	C22—C21—C26	121.25 (14)
F2A—C25A—C5	116.6 (6)	C20—C21—C26	120.76 (14)
F1A—C25A—C5	114.0 (6)	C21—C22—C23	121.62 (13)
F3A—C25A—C5	114.3 (7)	C21—C22—H22	119.2
N3—C6—N1	126.63 (11)	C23—C22—H22	119.2
N3—C6—C2	126.30 (11)	C22—C23—C18	119.99 (13)
N1—C6—C2	107.04 (11)	C22—C23—H23	120.0
O1—C7—C8	121.97 (12)	C18—C23—H23	120.0
O1—C7—C4	120.76 (12)	C1—C24—H24A	109.5
C8—C7—C4	117.25 (12)	C1—C24—H24B	109.5
C11A—C8—C11	101.5 (8)	H24A—C24—H24B	109.5
C11A—C8—C7	128.4 (7)	C1—C24—H24C	109.5
C11—C8—C7	130.1 (2)	H24A—C24—H24C	109.5
C11A—C8—S1A	110.5 (7)	H24B—C24—H24C	109.5
C7—C8—S1A	121.2 (2)	C21—C26—H26A	109.5
C11—C8—S1	110.73 (19)	C21—C26—H26B	109.5
C7—C8—S1	119.16 (11)	H26A—C26—H26B	109.5
S1A—C8—S1	119.6 (2)	C21—C26—H26C	109.5
C9—S1—C8	91.27 (14)	H26A—C26—H26C	109.5
C10—C9—S1	112.5 (3)	H26B—C26—H26C	109.5
C10—C9—H9	123.7	C21—C26—H26D	109.5
S1—C9—H9	123.7	H26A—C26—H26D	141.1
C9—C10—C11	111.5 (3)	H26B—C26—H26D	56.3
C9—C10—H10	124.3	H26C—C26—H26D	56.3
C11—C10—H10	124.3	C21—C26—H26E	109.5
C8—C11—C10	114.0 (3)	H26A—C26—H26E	56.3
C8—C11—H11	123.0	H26B—C26—H26E	141.1
C10—C11—H11	123.0	H26C—C26—H26E	56.3
C8—S1A—C9A	90.6 (9)	H26D—C26—H26E	109.5
C10A—C9A—S1A	111.3 (17)	C21—C26—H26F	109.5
C10A—C9A—H9A	124.4	H26A—C26—H26F	56.3
S1A—C9A—H9A	124.4	H26B—C26—H26F	56.3
C9A—C10A—C11A	111.3 (19)	H26C—C26—H26F	141.1
C9A—C10A—H10A	124.3	H26D—C26—H26F	109.5
C11A—C10A—H10A	124.3	H26E—C26—H26F	109.5
C8—C11A—C10A	116.0 (14)

Hydrogen-bond geometry (Å, º)

Cg2 is the centroid of the C12–C17 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O1^i	0.93	2.66	3.531 (2)	156
C20—H20···O1^ii	0.93	2.65	3.2769 (18)	126
C22—H22···Cg2^iii	0.93	2.76	3.4509 (17)	132

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

(II) [4-(4-Chlorophenyl)-3-methyl-1-phenyl-6-trifluoromethyl-1H-pyrazolo[3,4-b]pyridin-5-yl](thiophen-2-yl)methanone

Crystal data

C25H15ClF3N3OS	Z = 2
Mr = 497.91	F(000) = 508
Triclinic, P1	Dx = 1.469 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0018 (7) Å	Cell parameters from 1226 reflections
b = 10.3503 (8) Å	θ = 2.3–28.0°
c = 11.6309 (10) Å	µ = 0.31 mm^−1
α = 108.607 (4)°	T = 298 K
β = 95.295 (4)°	Needle, yellow
γ = 95.628 (4)°	0.30 × 0.14 × 0.12 mm
V = 1125.82 (15) Å^3

Data collection

Bruker APEXII CCD diffractometer	5407 independent reflections
Radiation source: fine-focus sealed tube	3912 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω and φ scans	θmax = 28.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→13
Tmin = 0.890, Tmax = 0.978	k = −13→13
22298 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0372P)^2 + 0.2614P] where P = (Fo^2 + 2Fc^2)/3
5407 reflections	(Δ/σ)max < 0.001
382 parameters	Δρmax = 0.21 e Å^−3
345 restraints	Δρmin = −0.19 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.75890 (5)	0.97291 (5)	1.07183 (5)	0.07168 (16)
O1	0.21636 (14)	0.53523 (13)	0.94144 (11)	0.0652 (3)
N1	0.45432 (12)	0.20812 (12)	0.47402 (11)	0.0433 (3)
N2	0.58047 (13)	0.28291 (13)	0.49460 (12)	0.0474 (3)
N3	0.24730 (12)	0.23298 (12)	0.56487 (12)	0.0447 (3)
C1	0.58184 (15)	0.39550 (15)	0.58813 (14)	0.0439 (3)
C2	0.45390 (14)	0.39739 (14)	0.63292 (13)	0.0385 (3)
C3	0.39551 (14)	0.48487 (13)	0.72757 (13)	0.0380 (3)
C4	0.26054 (15)	0.44524 (14)	0.73639 (13)	0.0408 (3)
C5	0.19383 (15)	0.31888 (16)	0.65423 (14)	0.0447 (3)
C25	0.0486 (7)	0.2706 (7)	0.6617 (7)	0.0635 (17)	0.577 (9)
F1	−0.0340 (3)	0.3145 (7)	0.5947 (5)	0.1198 (17)	0.577 (9)
F2	0.0183 (6)	0.3142 (7)	0.7715 (4)	0.122 (2)	0.577 (9)
F3	0.0232 (4)	0.1376 (4)	0.6197 (7)	0.115 (2)	0.577 (9)
C25A	0.0556 (9)	0.2528 (10)	0.6666 (9)	0.058 (2)	0.423 (9)
F1A	0.0618 (6)	0.1588 (9)	0.7157 (12)	0.138 (3)	0.423 (9)
F2A	−0.0234 (7)	0.2003 (14)	0.5664 (4)	0.143 (4)	0.423 (9)
F3A	−0.0143 (8)	0.3372 (6)	0.7361 (10)	0.122 (3)	0.423 (9)
C6	0.37455 (14)	0.27573 (14)	0.55613 (13)	0.0393 (3)
C7	0.19409 (15)	0.53713 (15)	0.83811 (14)	0.0447 (3)
C8	0.10869 (15)	0.63006 (15)	0.80710 (14)	0.0435 (3)
S1	0.01384 (8)	0.72012 (8)	0.91303 (6)	0.0549 (2)	0.860 (2)
C9	−0.0460 (5)	0.7999 (5)	0.8160 (5)	0.0601 (8)	0.860 (2)
H9	−0.1075	0.8631	0.8348	0.072*	0.860 (2)
C10	0.0049 (6)	0.7621 (6)	0.7093 (5)	0.0638 (8)	0.860 (2)
H10	−0.0156	0.7967	0.6461	0.077*	0.860 (2)
C11	0.0923 (6)	0.6643 (6)	0.7051 (3)	0.0595 (9)	0.860 (2)
H11	0.1356	0.6259	0.6373	0.071*	0.860 (2)
S1A	0.0992 (11)	0.6482 (11)	0.6658 (6)	0.0630 (16)	0.140 (2)
C9A	−0.011 (4)	0.765 (4)	0.708 (3)	0.066 (4)	0.140 (2)
H9A	−0.0521	0.8055	0.6563	0.079*	0.140 (2)
C10A	−0.033 (4)	0.791 (3)	0.826 (3)	0.069 (4)	0.140 (2)
H10A	−0.0853	0.8560	0.8663	0.083*	0.140 (2)
C11A	0.033 (2)	0.707 (2)	0.8773 (16)	0.065 (3)	0.140 (2)
H11A	0.0240	0.7057	0.9559	0.078*	0.140 (2)
C12	0.42790 (16)	0.07661 (14)	0.38187 (13)	0.0426 (3)
C13	0.29746 (18)	0.02172 (17)	0.32764 (16)	0.0562 (4)
H13	0.2251	0.0689	0.3528	0.067*
C14	0.2754 (2)	−0.10428 (18)	0.23531 (17)	0.0676 (5)
H14	0.1876	−0.1420	0.1984	0.081*
C15	0.3813 (2)	−0.17437 (17)	0.19751 (17)	0.0659 (5)
H15	0.3657	−0.2584	0.1343	0.079*
C16	0.5103 (2)	−0.11993 (17)	0.25340 (16)	0.0610 (5)
H16	0.5822	−0.1681	0.2286	0.073*
C17	0.53523 (18)	0.00572 (16)	0.34624 (14)	0.0504 (4)
H17	0.6230	0.0420	0.3842	0.061*
C18	0.47870 (14)	0.60931 (14)	0.81689 (13)	0.0380 (3)
C19	0.57629 (16)	0.59314 (15)	0.90202 (14)	0.0459 (4)
H19	0.5845	0.5057	0.9055	0.055*
C20	0.66101 (16)	0.70477 (16)	0.98134 (14)	0.0483 (4)
H20	0.7261	0.6935	1.0386	0.058*
C21	0.64805 (16)	0.83317 (15)	0.97480 (14)	0.0452 (4)
C22	0.55173 (17)	0.85244 (15)	0.89245 (15)	0.0483 (4)
H22	0.5440	0.9403	0.8899	0.058*
C23	0.46635 (16)	0.74027 (14)	0.81336 (14)	0.0443 (3)
H23	0.4003	0.7525	0.7575	0.053*
C24	0.70480 (17)	0.49984 (19)	0.63054 (17)	0.0612 (5)
H24A	0.7464	0.4992	0.7081	0.092*
H24B	0.6797	0.5893	0.6391	0.092*
H24C	0.7677	0.4784	0.5718	0.092*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0683 (3)	0.0525 (3)	0.0723 (3)	−0.0107 (2)	0.0014 (2)	−0.0019 (2)
O1	0.0821 (9)	0.0753 (8)	0.0450 (7)	0.0340 (7)	0.0143 (6)	0.0207 (6)
N1	0.0422 (7)	0.0404 (6)	0.0417 (7)	0.0089 (5)	0.0075 (5)	0.0043 (5)
N2	0.0430 (7)	0.0486 (7)	0.0455 (7)	0.0083 (6)	0.0091 (6)	0.0068 (6)
N3	0.0430 (7)	0.0412 (7)	0.0441 (7)	0.0059 (5)	0.0052 (5)	0.0063 (5)
C1	0.0417 (8)	0.0450 (8)	0.0428 (8)	0.0079 (6)	0.0073 (6)	0.0101 (7)
C2	0.0405 (8)	0.0353 (7)	0.0388 (8)	0.0087 (6)	0.0052 (6)	0.0101 (6)
C3	0.0440 (8)	0.0326 (7)	0.0377 (7)	0.0108 (6)	0.0052 (6)	0.0107 (6)
C4	0.0418 (8)	0.0398 (7)	0.0404 (8)	0.0129 (6)	0.0057 (6)	0.0102 (6)
C5	0.0400 (8)	0.0464 (8)	0.0441 (8)	0.0086 (6)	0.0064 (6)	0.0088 (7)
C25	0.047 (3)	0.058 (3)	0.061 (3)	−0.004 (2)	0.006 (3)	−0.010 (3)
F1	0.0395 (13)	0.172 (4)	0.146 (3)	0.020 (2)	−0.0024 (17)	0.052 (3)
F2	0.098 (3)	0.159 (5)	0.0644 (18)	−0.060 (3)	0.0409 (16)	−0.0118 (19)
F3	0.071 (3)	0.0492 (17)	0.184 (6)	−0.0163 (13)	0.050 (3)	−0.017 (2)
C25A	0.045 (4)	0.068 (5)	0.063 (4)	0.014 (3)	0.019 (3)	0.018 (4)
F1A	0.075 (3)	0.142 (5)	0.260 (9)	0.013 (3)	0.043 (4)	0.147 (6)
F2A	0.069 (4)	0.241 (11)	0.071 (3)	−0.059 (5)	0.0060 (19)	0.010 (4)
F3A	0.071 (3)	0.058 (2)	0.201 (7)	0.0016 (19)	0.080 (5)	−0.020 (4)
C6	0.0422 (8)	0.0361 (7)	0.0381 (8)	0.0108 (6)	0.0065 (6)	0.0083 (6)
C7	0.0450 (8)	0.0457 (8)	0.0417 (9)	0.0101 (6)	0.0089 (6)	0.0100 (7)
C8	0.0392 (8)	0.0455 (8)	0.0419 (8)	0.0104 (6)	0.0087 (6)	0.0067 (6)
S1	0.0520 (3)	0.0591 (4)	0.0539 (4)	0.0211 (2)	0.0210 (3)	0.0110 (3)
C9	0.0496 (17)	0.0575 (16)	0.0739 (18)	0.0240 (12)	0.0110 (13)	0.0171 (13)
C10	0.059 (2)	0.0739 (19)	0.0658 (16)	0.0250 (14)	0.0066 (15)	0.0286 (14)
C11	0.0586 (17)	0.0710 (19)	0.049 (2)	0.0238 (13)	0.0129 (18)	0.0140 (19)
S1A	0.065 (3)	0.078 (3)	0.056 (3)	0.036 (2)	0.013 (3)	0.026 (3)
C9A	0.056 (8)	0.065 (8)	0.074 (7)	0.032 (6)	0.003 (7)	0.015 (6)
C10A	0.058 (8)	0.064 (7)	0.080 (7)	0.026 (5)	0.015 (6)	0.008 (6)
C11A	0.065 (8)	0.066 (7)	0.057 (6)	0.024 (5)	0.017 (5)	0.004 (6)
C12	0.0563 (9)	0.0355 (7)	0.0347 (8)	0.0111 (6)	0.0089 (6)	0.0076 (6)
C13	0.0586 (10)	0.0484 (9)	0.0526 (10)	0.0061 (8)	0.0113 (8)	0.0036 (8)
C14	0.0782 (13)	0.0525 (10)	0.0573 (11)	−0.0086 (9)	0.0095 (9)	0.0025 (8)
C15	0.1069 (16)	0.0345 (8)	0.0506 (10)	0.0066 (9)	0.0181 (10)	0.0051 (7)
C16	0.0960 (15)	0.0470 (9)	0.0481 (10)	0.0339 (10)	0.0234 (10)	0.0161 (8)
C17	0.0639 (10)	0.0494 (9)	0.0413 (9)	0.0225 (8)	0.0107 (7)	0.0142 (7)
C18	0.0434 (8)	0.0335 (7)	0.0362 (7)	0.0088 (6)	0.0100 (6)	0.0081 (6)
C19	0.0566 (9)	0.0342 (7)	0.0457 (9)	0.0131 (7)	0.0028 (7)	0.0108 (6)
C20	0.0507 (9)	0.0466 (8)	0.0433 (9)	0.0112 (7)	0.0008 (7)	0.0090 (7)
C21	0.0468 (8)	0.0395 (8)	0.0429 (8)	0.0015 (6)	0.0114 (7)	0.0043 (6)
C22	0.0611 (10)	0.0332 (7)	0.0512 (9)	0.0076 (7)	0.0121 (8)	0.0131 (7)
C23	0.0510 (9)	0.0393 (8)	0.0442 (8)	0.0109 (6)	0.0053 (7)	0.0148 (6)
C24	0.0468 (9)	0.0633 (11)	0.0608 (11)	−0.0017 (8)	0.0137 (8)	0.0039 (9)

Geometric parameters (Å, º)

Cl1—C21	1.7342 (15)	C10—H10	0.9300
O1—C7	1.2087 (19)	C11—H11	0.9300
N1—C6	1.3645 (17)	S1A—C9A	1.703 (19)
N1—N2	1.3722 (18)	C9A—C10A	1.346 (17)
N1—C12	1.4204 (18)	C9A—H9A	0.9300
N2—C1	1.3140 (18)	C10A—C11A	1.387 (19)
N3—C5	1.3277 (18)	C10A—H10A	0.9300
N3—C6	1.3297 (19)	C11A—H11A	0.9300
C1—C2	1.425 (2)	C12—C13	1.377 (2)
C1—C24	1.486 (2)	C12—C17	1.380 (2)
C2—C3	1.3997 (19)	C13—C14	1.382 (2)
C2—C6	1.403 (2)	C13—H13	0.9300
C3—C4	1.395 (2)	C14—C15	1.369 (3)
C3—C18	1.4855 (19)	C14—H14	0.9300
C4—C5	1.408 (2)	C15—C16	1.369 (3)
C4—C7	1.516 (2)	C15—H15	0.9300
C5—C25	1.509 (7)	C16—C17	1.382 (2)
C5—C25A	1.522 (9)	C16—H16	0.9300
C25—F2	1.287 (7)	C17—H17	0.9300
C25—F1	1.295 (8)	C18—C19	1.386 (2)
C25—F3	1.295 (7)	C18—C23	1.3863 (19)
C25A—F2A	1.272 (10)	C19—C20	1.374 (2)
C25A—F1A	1.279 (10)	C19—H19	0.9300
C25A—F3A	1.296 (10)	C20—C21	1.373 (2)
C7—C8	1.453 (2)	C20—H20	0.9300
C8—C11A	1.300 (13)	C21—C22	1.369 (2)
C8—C11	1.343 (4)	C22—C23	1.379 (2)
C8—S1A	1.708 (6)	C22—H22	0.9300
C8—S1	1.7155 (15)	C23—H23	0.9300
S1—C9	1.698 (4)	C24—H24A	0.9600
C9—C10	1.341 (4)	C24—H24B	0.9600
C9—H9	0.9300	C24—H24C	0.9600
C10—C11	1.393 (5)
C6—N1—N2	110.16 (11)	C8—C11—C10	114.4 (3)
C6—N1—C12	130.36 (13)	C8—C11—H11	122.8
N2—N1—C12	119.37 (12)	C10—C11—H11	122.8
C1—N2—N1	107.76 (12)	C9A—S1A—C8	89.8 (10)
C5—N3—C6	114.27 (12)	C10A—C9A—S1A	112.5 (18)
N2—C1—C2	110.16 (13)	C10A—C9A—H9A	123.7
N2—C1—C24	120.38 (14)	S1A—C9A—H9A	123.7
C2—C1—C24	129.45 (14)	C9A—C10A—C11A	111 (2)
C3—C2—C6	118.22 (13)	C9A—C10A—H10A	124.6
C3—C2—C1	136.80 (14)	C11A—C10A—H10A	124.6
C6—C2—C1	104.98 (12)	C8—C11A—C10A	114.5 (15)
C4—C3—C2	116.91 (13)	C8—C11A—H11A	122.7
C4—C3—C18	122.91 (12)	C10A—C11A—H11A	122.7
C2—C3—C18	120.10 (13)	C13—C12—C17	120.56 (14)
C3—C4—C5	118.74 (13)	C13—C12—N1	120.49 (13)
C3—C4—C7	118.39 (13)	C17—C12—N1	118.94 (14)
C5—C4—C7	122.80 (13)	C12—C13—C14	119.17 (16)
N3—C5—C4	125.59 (14)	C12—C13—H13	120.4
N3—C5—C25	113.8 (3)	C14—C13—H13	120.4
C4—C5—C25	120.6 (3)	C15—C14—C13	120.81 (19)
N3—C5—C25A	110.0 (4)	C15—C14—H14	119.6
C4—C5—C25A	123.9 (4)	C13—C14—H14	119.6
F2—C25—F1	107.0 (6)	C16—C15—C14	119.53 (16)
F2—C25—F3	109.3 (6)	C16—C15—H15	120.2
F1—C25—F3	106.0 (5)	C14—C15—H15	120.2
F2—C25—C5	112.4 (5)	C15—C16—C17	120.85 (16)
F1—C25—C5	110.8 (5)	C15—C16—H16	119.6
F3—C25—C5	111.0 (5)	C17—C16—H16	119.6
F2A—C25A—F1A	106.9 (9)	C12—C17—C16	119.05 (17)
F2A—C25A—F3A	103.5 (8)	C12—C17—H17	120.5
F1A—C25A—F3A	103.3 (8)	C16—C17—H17	120.5
F2A—C25A—C5	114.4 (7)	C19—C18—C23	119.13 (14)
F1A—C25A—C5	113.5 (7)	C19—C18—C3	118.89 (12)
F3A—C25A—C5	114.1 (8)	C23—C18—C3	121.89 (13)
N3—C6—N1	126.82 (13)	C20—C19—C18	120.78 (14)
N3—C6—C2	126.21 (13)	C20—C19—H19	119.6
N1—C6—C2	106.93 (12)	C18—C19—H19	119.6
O1—C7—C8	122.15 (14)	C21—C20—C19	118.96 (15)
O1—C7—C4	120.33 (14)	C21—C20—H20	120.5
C8—C7—C4	117.47 (13)	C19—C20—H20	120.5
C11A—C8—C11	102.8 (9)	C22—C21—C20	121.55 (14)
C11A—C8—C7	126.9 (9)	C22—C21—Cl1	119.71 (12)
C11—C8—C7	130.2 (2)	C20—C21—Cl1	118.73 (13)
C11A—C8—S1A	112.2 (9)	C21—C22—C23	119.35 (14)
C7—C8—S1A	120.8 (3)	C21—C22—H22	120.3
C11—C8—S1	110.3 (2)	C23—C22—H22	120.3
C7—C8—S1	119.44 (12)	C22—C23—C18	120.21 (15)
S1A—C8—S1	119.7 (3)	C22—C23—H23	119.9
C9—S1—C8	91.16 (16)	C18—C23—H23	119.9
C10—C9—S1	112.7 (3)	C1—C24—H24A	109.5
C10—C9—H9	123.6	C1—C24—H24B	109.5
S1—C9—H9	123.6	H24A—C24—H24B	109.5
C9—C10—C11	111.4 (4)	C1—C24—H24C	109.5
C9—C10—H10	124.3	H24A—C24—H24C	109.5
C11—C10—H10	124.3	H24B—C24—H24C	109.5

Hydrogen-bond geometry (Å, º)

Cg2 is the centroid of the C12–C17 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O1^i	0.93	2.74	3.610 (2)	156
C20—H20···O1^ii	0.93	2.57	3.209 (2)	127
C22—H22···Cg2^iii	0.93	2.74	3.4075 (18)	129

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