Supra­molecular inter­actions in cocrystals of benzoic acid derivatives with selective COX-2 inhibitor etoricoxib

The structures of three 1:1 cocrystal forms of etoricoxib {ETR; systematic name: 5-chloro-2-(6-methyl­pyridin-3-yl)-3-[4-(methyl­sulfon­yl)phen­yl]pyridine, C₁₈H₁₅ClN₂O₂S} have been synthesized and characterized by single-crystal X-ray diffraction; these are etoricoxib–benzoic acid (1/1), C₁₈H₁₅ClN₂O₂S·C₇H₆O₂ (ETR–Bz), etoricoxib–4-fluoro­benzoic acid (1/1), C₁₈H₁₅ClN₂O₂S·C₇H₅FO₂ (ETR–PFB), and etoricoxib–4-nitro­benzoic acid (1/1), C₁₈H₁₅ClN₂O₂S·C₇H₅NO₄ (ETR–PNB). Powder X-ray diffraction and thermal differential scanning calorimetry–thermogravimetry (DSC–TG) techniques were also used to characterize these multicom­ponent systems. Due to the influence of the corresponding acids, ETR shows different conformations. Furthermore, the energetic contributions of the supra­molecular motifs have been established by energy framework studies of the stabilizing inter­action forces and are consistent with the thermal stability of the cocrystals.

Computing details

5-Chloro-2-(6-methylpyridin-3-yl)-3-[4-(methylsulfonyl)phenyl]pyridine–\ benzoic acid (etr-bz)

Crystal data

C18H15ClN2O2S·C7H6O2	Dx = 1.358 Mg m^−3
Mr = 480.95	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 25 reflections
a = 10.7920 (2) Å	θ = 9–13°
b = 18.7130 (4) Å	µ = 0.29 mm^−1
c = 23.2990 (5) Å	T = 293 K
V = 4705.25 (17) Å^3	Needle, colourless
Z = 8	0.46 × 0.1 × 0.08 mm
F(000) = 2000

Data collection

Nonius CAD4 diffractometer	Rint = 0.094
ω/2θ scans	θmax = 25.4°, θmin = 2.6°
Absorption correction: ψ scan (North et al., 1968)	h = 0→13
Tmin = 0.919, Tmax = 0.972	k = 0→22
7760 measured reflections	l = −18→28
4277 independent reflections	3 standard reflections every 200 reflections
2113 reflections with I > 2σ(I)	intensity decay: 1%

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.068	H-atom parameters constrained
wR(F^2) = 0.192	w = 1/[σ^2(Fo^2) + (0.0778P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
4277 reflections	Δρmax = 0.29 e Å^−3
301 parameters	Δρmin = −0.57 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.

Refinement. Single-crystal diffraction data were collected on a Nonius CAD4 (ENRAF, Netherlands) with an enhanced Mo Kα X-ray source (λ=0.71073Å) at 293K. The structure was solved using ShelXT(Sheldrick, Sect. A, 2015; Sheldrick, Sect. C, 2015), via the Olex2 (Dolomanov et al.2009; Bourhis et al., 2015) graphical interface. All nonhydrogen atoms were refined anisotropically.

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

	x	y	z	Uiso*/Ueq
Cl1	0.69880 (12)	0.04504 (7)	0.28406 (5)	0.0686 (4)
S1	0.43493 (12)	0.26556 (7)	−0.04738 (5)	0.0593 (4)
O2	0.5202 (5)	0.3218 (3)	−0.05469 (17)	0.159 (2)
O1	0.4503 (4)	0.2032 (2)	−0.08033 (14)	0.1122 (17)
N1	0.4139 (4)	0.17588 (19)	0.30043 (14)	0.0509 (10)
N2	0.2036 (3)	0.35792 (18)	0.28756 (15)	0.0470 (9)
C12	0.3966 (4)	0.2005 (2)	0.24637 (17)	0.0413 (10)
C1	0.4362 (4)	0.2405 (2)	0.02586 (17)	0.0458 (11)
C13	0.2995 (4)	0.2565 (2)	0.24155 (16)	0.0402 (10)
C4	0.4522 (4)	0.1998 (2)	0.13969 (16)	0.0416 (10)
C2	0.4733 (4)	0.2893 (2)	0.06679 (18)	0.0548 (13)
H2	0.493560	0.335778	0.056123	0.066*
C9	0.5596 (4)	0.1248 (2)	0.21168 (17)	0.0485 (12)
H9	0.607309	0.106448	0.181901	0.058*
C3	0.4802 (4)	0.2688 (2)	0.12403 (17)	0.0506 (12)
H3	0.503856	0.301751	0.151813	0.061*
C8	0.4672 (4)	0.1750 (2)	0.20075 (16)	0.0401 (10)
C10	0.5790 (4)	0.1031 (2)	0.26724 (18)	0.0469 (11)
C6	0.4054 (5)	0.1727 (2)	0.04086 (18)	0.0588 (13)
H6	0.378621	0.140473	0.013133	0.071*
C15	0.1287 (4)	0.3666 (2)	0.2419 (2)	0.0482 (11)
C11	0.5029 (5)	0.1289 (2)	0.31015 (19)	0.0532 (12)
H11	0.514870	0.112605	0.347448	0.064*
C5	0.4142 (5)	0.1518 (2)	0.09801 (18)	0.0591 (13)
H5	0.394291	0.105184	0.108323	0.071*
C14	0.2859 (4)	0.3051 (2)	0.28645 (17)	0.0455 (11)
H14	0.338253	0.300286	0.317904	0.055*
C7	0.2888 (6)	0.2973 (4)	−0.0603 (2)	0.111 (2)
H7A	0.274659	0.339342	−0.037574	0.167*
H7B	0.228992	0.261414	−0.050318	0.167*
H7C	0.280659	0.309029	−0.100238	0.167*
C18	0.0374 (4)	0.4265 (3)	0.2453 (2)	0.0736 (15)
H18A	−0.029677	0.413189	0.270127	0.110*
H18B	0.005813	0.436600	0.207650	0.110*
H18C	0.077569	0.468353	0.260301	0.110*
C16	0.1339 (4)	0.3203 (3)	0.19594 (18)	0.0528 (12)
H16	0.079794	0.326161	0.165236	0.063*
C17	0.2185 (4)	0.2659 (2)	0.19531 (17)	0.0471 (11)
H17	0.222059	0.234995	0.164074	0.057*
O3	0.1819 (3)	0.4239 (2)	0.38961 (14)	0.0761 (10)
H3A	0.192143	0.411321	0.356220	0.114*
O4	0.3542 (4)	0.4850 (2)	0.37304 (17)	0.1071 (16)
C19	0.2708 (5)	0.4670 (3)	0.4047 (2)	0.0593 (13)
C20	0.2605 (4)	0.4933 (2)	0.46513 (18)	0.0484 (11)
C21	0.1651 (6)	0.4758 (3)	0.5004 (2)	0.0719 (16)
H21	0.102760	0.445771	0.486944	0.086*
C23	0.2507 (6)	0.5453 (3)	0.5757 (2)	0.0795 (17)
H23	0.246163	0.563413	0.612840	0.095*
C25	0.3521 (5)	0.5365 (3)	0.4866 (2)	0.0765 (16)
H25	0.418658	0.548698	0.463158	0.092*
C22	0.1589 (6)	0.5016 (3)	0.5558 (2)	0.0870 (18)
H22	0.092771	0.489347	0.579407	0.104*
C24	0.3482 (6)	0.5623 (3)	0.5418 (2)	0.0820 (17)
H24	0.411671	0.591152	0.555678	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0738 (9)	0.0628 (8)	0.0692 (8)	0.0095 (7)	−0.0136 (7)	0.0043 (6)
S1	0.0650 (9)	0.0829 (9)	0.0299 (6)	0.0018 (7)	−0.0004 (6)	0.0080 (6)
O2	0.186 (5)	0.227 (5)	0.063 (3)	−0.139 (5)	−0.036 (3)	0.068 (3)
O1	0.190 (5)	0.114 (3)	0.033 (2)	0.079 (3)	0.010 (2)	−0.004 (2)
N1	0.077 (3)	0.045 (2)	0.0303 (19)	0.002 (2)	0.0010 (19)	0.0033 (17)
N2	0.052 (2)	0.044 (2)	0.045 (2)	0.0006 (19)	−0.0029 (19)	−0.0055 (17)
C12	0.056 (3)	0.039 (2)	0.029 (2)	−0.005 (2)	0.000 (2)	−0.0013 (19)
C1	0.055 (3)	0.057 (3)	0.025 (2)	−0.003 (2)	0.006 (2)	0.001 (2)
C13	0.045 (3)	0.042 (2)	0.033 (2)	−0.004 (2)	0.003 (2)	0.0001 (19)
C4	0.049 (3)	0.049 (3)	0.027 (2)	−0.001 (2)	0.0020 (19)	−0.0022 (19)
C2	0.071 (3)	0.051 (3)	0.042 (3)	−0.009 (3)	−0.005 (2)	0.008 (2)
C9	0.065 (3)	0.044 (3)	0.036 (3)	0.006 (2)	0.004 (2)	−0.005 (2)
C3	0.071 (3)	0.048 (3)	0.034 (2)	−0.015 (2)	−0.007 (2)	−0.001 (2)
C8	0.051 (3)	0.040 (2)	0.029 (2)	−0.004 (2)	0.000 (2)	−0.0027 (18)
C10	0.060 (3)	0.037 (2)	0.043 (3)	0.000 (2)	−0.012 (2)	0.000 (2)
C6	0.090 (4)	0.054 (3)	0.033 (3)	−0.011 (3)	0.003 (2)	−0.008 (2)
C15	0.043 (3)	0.050 (3)	0.051 (3)	−0.005 (2)	0.006 (2)	0.004 (2)
C11	0.076 (4)	0.047 (3)	0.037 (3)	0.003 (3)	−0.008 (2)	0.005 (2)
C5	0.092 (4)	0.045 (3)	0.040 (3)	−0.016 (3)	0.001 (3)	−0.004 (2)
C14	0.055 (3)	0.048 (3)	0.034 (2)	−0.005 (2)	−0.002 (2)	−0.001 (2)
C7	0.114 (5)	0.161 (6)	0.058 (3)	0.065 (5)	−0.008 (4)	0.009 (4)
C18	0.069 (4)	0.062 (3)	0.090 (4)	0.007 (3)	−0.006 (3)	−0.003 (3)
C16	0.054 (3)	0.066 (3)	0.038 (3)	−0.007 (3)	−0.006 (2)	0.002 (2)
C17	0.050 (3)	0.057 (3)	0.034 (2)	−0.011 (2)	0.005 (2)	−0.006 (2)
O3	0.079 (2)	0.088 (2)	0.061 (2)	−0.018 (2)	0.0132 (19)	−0.030 (2)
O4	0.129 (4)	0.129 (4)	0.064 (3)	−0.054 (3)	0.034 (3)	−0.014 (2)
C19	0.068 (4)	0.056 (3)	0.054 (3)	−0.007 (3)	0.002 (3)	−0.005 (3)
C20	0.058 (3)	0.039 (2)	0.047 (3)	−0.005 (2)	−0.005 (2)	0.000 (2)
C21	0.085 (4)	0.073 (4)	0.058 (3)	−0.023 (3)	0.005 (3)	−0.015 (3)
C23	0.115 (5)	0.071 (4)	0.053 (3)	−0.003 (4)	−0.004 (4)	−0.006 (3)
C25	0.082 (4)	0.075 (4)	0.073 (4)	−0.023 (3)	−0.001 (3)	−0.001 (3)
C22	0.100 (5)	0.099 (4)	0.062 (4)	−0.024 (4)	0.020 (3)	−0.016 (3)
C24	0.095 (5)	0.086 (4)	0.065 (4)	−0.022 (4)	−0.019 (3)	−0.014 (3)

Geometric parameters (Å, º)

Cl1—C10	1.733 (4)	C15—C16	1.379 (6)
S1—O2	1.409 (4)	C11—H11	0.9300
S1—O1	1.407 (4)	C5—H5	0.9300
S1—C1	1.770 (4)	C14—H14	0.9300
S1—C7	1.712 (6)	C7—H7A	0.9600
N1—C12	1.354 (5)	C7—H7B	0.9600
N1—C11	1.322 (5)	C7—H7C	0.9600
N2—C15	1.346 (5)	C18—H18A	0.9600
N2—C14	1.328 (5)	C18—H18B	0.9600
C12—C13	1.486 (5)	C18—H18C	0.9600
C12—C8	1.392 (5)	C16—H16	0.9300
C1—C2	1.380 (6)	C16—C17	1.368 (6)
C1—C6	1.357 (6)	C17—H17	0.9300
C13—C14	1.395 (5)	O3—H3A	0.8200
C13—C17	1.398 (5)	O3—C19	1.302 (5)
C4—C3	1.375 (5)	O4—C19	1.211 (6)
C4—C8	1.505 (5)	C19—C20	1.497 (6)
C4—C5	1.385 (5)	C20—C21	1.358 (6)
C2—H2	0.9300	C20—C25	1.372 (6)
C2—C3	1.390 (6)	C21—H21	0.9300
C9—H9	0.9300	C21—C22	1.381 (7)
C9—C8	1.393 (6)	C23—H23	0.9300
C9—C10	1.373 (6)	C23—C22	1.365 (7)
C3—H3	0.9300	C23—C24	1.355 (8)
C10—C11	1.381 (6)	C25—H25	0.9300
C6—H6	0.9300	C25—C24	1.375 (7)
C6—C5	1.391 (6)	C22—H22	0.9300
C15—C18	1.494 (6)	C24—H24	0.9300
O2—S1—C1	108.0 (2)	C4—C5—H5	119.7
O2—S1—C7	108.7 (4)	C6—C5—H5	119.7
O1—S1—O2	118.5 (3)	N2—C14—C13	124.8 (4)
O1—S1—C1	107.8 (2)	N2—C14—H14	117.6
O1—S1—C7	107.5 (3)	C13—C14—H14	117.6
C7—S1—C1	105.6 (2)	S1—C7—H7A	109.5
C11—N1—C12	119.1 (4)	S1—C7—H7B	109.5
C14—N2—C15	118.4 (4)	S1—C7—H7C	109.5
N1—C12—C13	114.0 (3)	H7A—C7—H7B	109.5
N1—C12—C8	121.2 (4)	H7A—C7—H7C	109.5
C8—C12—C13	124.7 (4)	H7B—C7—H7C	109.5
C2—C1—S1	119.6 (3)	C15—C18—H18A	109.5
C6—C1—S1	119.6 (3)	C15—C18—H18B	109.5
C6—C1—C2	120.8 (4)	C15—C18—H18C	109.5
C14—C13—C12	118.5 (4)	H18A—C18—H18B	109.5
C14—C13—C17	115.5 (4)	H18A—C18—H18C	109.5
C17—C13—C12	126.0 (4)	H18B—C18—H18C	109.5
C3—C4—C8	121.1 (4)	C15—C16—H16	119.9
C3—C4—C5	119.2 (4)	C17—C16—C15	120.2 (4)
C5—C4—C8	119.7 (4)	C17—C16—H16	119.9
C1—C2—H2	120.2	C13—C17—H17	119.9
C1—C2—C3	119.7 (4)	C16—C17—C13	120.1 (4)
C3—C2—H2	120.2	C16—C17—H17	119.9
C8—C9—H9	120.6	C19—O3—H3A	109.5
C10—C9—H9	120.6	O3—C19—C20	113.8 (4)
C10—C9—C8	118.8 (4)	O4—C19—O3	123.8 (5)
C4—C3—C2	120.2 (4)	O4—C19—C20	122.4 (5)
C4—C3—H3	119.9	C21—C20—C19	123.1 (5)
C2—C3—H3	119.9	C21—C20—C25	118.0 (5)
C12—C8—C4	123.9 (4)	C25—C20—C19	118.9 (5)
C12—C8—C9	118.9 (4)	C20—C21—H21	119.4
C9—C8—C4	117.2 (4)	C20—C21—C22	121.1 (5)
C9—C10—Cl1	120.8 (4)	C22—C21—H21	119.4
C9—C10—C11	119.2 (4)	C22—C23—H23	119.8
C11—C10—Cl1	119.9 (3)	C24—C23—H23	119.8
C1—C6—H6	120.2	C24—C23—C22	120.4 (5)
C1—C6—C5	119.5 (4)	C20—C25—H25	119.2
C5—C6—H6	120.2	C20—C25—C24	121.7 (5)
N2—C15—C18	116.5 (4)	C24—C25—H25	119.2
N2—C15—C16	120.9 (4)	C21—C22—H22	120.2
C16—C15—C18	122.6 (4)	C23—C22—C21	119.6 (6)
N1—C11—C10	122.7 (4)	C23—C22—H22	120.2
N1—C11—H11	118.6	C23—C24—C25	119.2 (5)
C10—C11—H11	118.6	C23—C24—H24	120.4
C4—C5—C6	120.6 (4)	C25—C24—H24	120.4
Cl1—C10—C11—N1	176.7 (3)	C10—C9—C8—C12	−0.9 (6)
S1—C1—C2—C3	−176.8 (4)	C10—C9—C8—C4	177.5 (4)
S1—C1—C6—C5	175.8 (4)	C6—C1—C2—C3	0.5 (7)
O2—S1—C1—C2	24.4 (5)	C15—N2—C14—C13	−1.3 (6)
O2—S1—C1—C6	−153.0 (5)	C15—C16—C17—C13	0.5 (6)
O1—S1—C1—C2	153.5 (4)	C11—N1—C12—C13	−176.1 (4)
O1—S1—C1—C6	−23.8 (5)	C11—N1—C12—C8	2.8 (6)
N1—C12—C13—C14	35.2 (5)	C5—C4—C3—C2	−1.6 (7)
N1—C12—C13—C17	−145.1 (4)	C5—C4—C8—C12	−116.3 (5)
N1—C12—C8—C4	179.7 (4)	C5—C4—C8—C9	65.4 (6)
N1—C12—C8—C9	−2.0 (6)	C14—N2—C15—C18	179.8 (4)
N2—C15—C16—C17	−2.0 (6)	C14—N2—C15—C16	2.3 (6)
C12—N1—C11—C10	−0.6 (7)	C14—C13—C17—C16	0.5 (6)
C12—C13—C14—N2	179.6 (4)	C7—S1—C1—C2	−91.8 (5)
C12—C13—C17—C16	−179.2 (4)	C7—S1—C1—C6	90.8 (5)
C1—C2—C3—C4	1.1 (7)	C18—C15—C16—C17	−179.3 (4)
C1—C6—C5—C4	0.9 (8)	C17—C13—C14—N2	−0.2 (6)
C13—C12—C8—C4	−1.5 (6)	O3—C19—C20—C21	−2.1 (7)
C13—C12—C8—C9	176.8 (4)	O3—C19—C20—C25	177.0 (4)
C2—C1—C6—C5	−1.5 (8)	O4—C19—C20—C21	177.5 (5)
C9—C10—C11—N1	−2.3 (7)	O4—C19—C20—C25	−3.4 (8)
C3—C4—C8—C12	66.2 (6)	C19—C20—C21—C22	−179.6 (5)
C3—C4—C8—C9	−112.2 (5)	C19—C20—C25—C24	−179.9 (5)
C3—C4—C5—C6	0.6 (7)	C20—C21—C22—C23	−0.4 (9)
C8—C12—C13—C14	−143.7 (4)	C20—C25—C24—C23	−0.7 (9)
C8—C12—C13—C17	36.0 (6)	C21—C20—C25—C24	−0.7 (8)
C8—C4—C3—C2	175.9 (4)	C25—C20—C21—C22	1.2 (8)
C8—C4—C5—C6	−176.9 (4)	C22—C23—C24—C25	1.6 (9)
C8—C9—C10—Cl1	−176.0 (3)	C24—C23—C22—C21	−1.0 (10)
C8—C9—C10—C11	2.9 (6)

5-Chloro-2-(6-methylpyridin-3-yl)-3-[4-(methylsulfonyl)phenyl]pyridine–\ 4-fluorobenzoic acid (etr-pfb)

Crystal data

C18H15ClN2O2S·C7H5FO2	Dx = 1.400 Mg m^−3
Mr = 498.94	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 25 reflections
a = 10.536 (2) Å	θ = 9–14°
b = 19.246 (4) Å	µ = 0.29 mm^−1
c = 23.343 (5) Å	T = 293 K
V = 4733.4 (17) Å^3	Needle, colourless
Z = 8	0.52 × 0.1 × 0.08 mm
F(000) = 2064

Data collection

Nonius CAD4 diffractometer	Rint = 0.041
ω/2θ scans	θmax = 25.4°, θmin = 2.1°
Absorption correction: ψ scan (North et al., 1968)	h = 0→12
Tmin = 0.917, Tmax = 0.971	k = 0→23
4796 measured reflections	l = −2→28
4338 independent reflections	3 standard reflections every 200 reflections
2105 reflections with I > 2σ(I)	intensity decay: 1%

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.073	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.191	w = 1/[σ^2(Fo^2) + (0.0731P)^2 + 1.4818P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
4338 reflections	Δρmax = 0.24 e Å^−3
313 parameters	Δρmin = −0.32 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.

Refinement. Single-crystal diffraction data were collected on a Nonius CAD4 (ENRAF, Netherlands) with an enhanced Mo Kα X-ray source (λ=0.71073Å) at 293K. The structure was solved using ShelXT(Sheldrick, Sect. A, 2015; Sheldrick, Sect. C, 2015), via the Olex2 (Dolomanov et al.2009; Bourhis et al., 2015) graphical interface. All nonhydrogen atoms were refined anisotropically.

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

	x	y	z	Uiso*/Ueq
Cl1	0.30295 (14)	0.04782 (7)	0.28308 (6)	0.0730 (5)
S1	0.56423 (14)	0.26876 (8)	−0.04501 (5)	0.0608 (4)
O1	0.5281 (5)	0.2109 (2)	−0.07779 (15)	0.1189 (19)
O2	0.4915 (5)	0.3303 (3)	−0.04963 (17)	0.141 (2)
N2	0.7973 (4)	0.3564 (2)	0.29038 (16)	0.0483 (10)
N1	0.5921 (4)	0.1765 (2)	0.30139 (16)	0.0547 (11)
C4	0.5532 (4)	0.2011 (2)	0.14117 (18)	0.0437 (12)
C1	0.5665 (4)	0.2432 (3)	0.02798 (18)	0.0473 (12)
C8	0.5386 (4)	0.1762 (2)	0.20105 (18)	0.0423 (12)
C10	0.4247 (5)	0.1046 (2)	0.2669 (2)	0.0510 (13)
C16	0.8738 (5)	0.3204 (3)	0.19949 (19)	0.0496 (13)
H16	0.929738	0.326787	0.169118	0.060*
C18	0.9653 (5)	0.4259 (3)	0.2494 (3)	0.0716 (16)
H18A	0.920597	0.466219	0.262756	0.107*
H18B	1.000170	0.434969	0.212195	0.107*
H18C	1.032657	0.414954	0.275622	0.107*
C2	0.5935 (5)	0.1755 (3)	0.0419 (2)	0.0624 (15)
H2	0.616189	0.144001	0.013459	0.075*
C12	0.6103 (5)	0.2008 (2)	0.24798 (19)	0.0452 (12)
C14	0.7163 (4)	0.3031 (2)	0.28868 (18)	0.0454 (12)
H14	0.662675	0.296873	0.319900	0.054*
C6	0.5353 (4)	0.2905 (2)	0.06959 (19)	0.0510 (13)
H6	0.518402	0.336501	0.060017	0.061*
C9	0.4457 (5)	0.1262 (2)	0.21179 (19)	0.0492 (12)
H9	0.398441	0.107712	0.181796	0.059*
C7	0.7199 (6)	0.2874 (4)	−0.0623 (2)	0.105 (2)
H7A	0.771643	0.247223	−0.055524	0.157*
H7B	0.749415	0.325226	−0.038988	0.157*
H7C	0.725101	0.300260	−0.101965	0.157*
C13	0.7066 (4)	0.2566 (2)	0.24382 (18)	0.0404 (11)
C17	0.7902 (4)	0.2665 (2)	0.19849 (17)	0.0447 (12)
H17	0.788943	0.236266	0.167416	0.054*
C11	0.5005 (5)	0.1295 (3)	0.3102 (2)	0.0583 (14)
H11	0.487568	0.113045	0.347229	0.070*
C5	0.5294 (4)	0.2687 (3)	0.12624 (19)	0.0505 (13)
H5	0.508996	0.300697	0.154649	0.061*
C15	0.8760 (5)	0.3661 (2)	0.2459 (2)	0.0499 (12)
C3	0.5868 (5)	0.1547 (3)	0.09814 (19)	0.0614 (15)
H3	0.605027	0.108798	0.107550	0.074*
F1	0.7694 (5)	0.57415 (18)	0.62516 (14)	0.1201 (15)
O3	0.8136 (4)	0.4195 (2)	0.39115 (17)	0.0800 (13)
O4	0.6423 (5)	0.4817 (3)	0.3736 (2)	0.125 (2)
C21	0.8332 (6)	0.4717 (3)	0.5003 (2)	0.0758 (18)
H21	0.892409	0.439269	0.487709	0.091*
C20	0.7371 (5)	0.4911 (3)	0.4647 (2)	0.0555 (13)
C22	0.8443 (7)	0.4992 (3)	0.5547 (3)	0.092 (2)
H22	0.910117	0.485950	0.578952	0.110*
C24	0.6602 (7)	0.5660 (3)	0.5394 (3)	0.097 (2)
H24	0.600674	0.597481	0.553148	0.117*
C23	0.7568 (8)	0.5458 (3)	0.5715 (2)	0.081 (2)
C19	0.7267 (6)	0.4627 (3)	0.4056 (2)	0.0655 (16)
C25	0.6501 (6)	0.5387 (3)	0.4843 (3)	0.092 (2)
H25	0.583950	0.552738	0.460600	0.110*
H3A	0.801 (5)	0.403 (3)	0.349 (3)	0.11 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0793 (10)	0.0608 (8)	0.0789 (10)	−0.0071 (8)	0.0132 (8)	0.0086 (8)
S1	0.0638 (9)	0.0855 (11)	0.0330 (6)	−0.0011 (8)	−0.0020 (7)	0.0055 (7)
O1	0.181 (5)	0.141 (4)	0.035 (2)	−0.090 (4)	−0.020 (3)	0.001 (2)
O2	0.174 (5)	0.192 (5)	0.057 (3)	0.113 (4)	0.025 (3)	0.046 (3)
N2	0.053 (3)	0.050 (2)	0.043 (2)	0.001 (2)	0.002 (2)	−0.006 (2)
N1	0.075 (3)	0.053 (3)	0.036 (2)	−0.003 (2)	−0.004 (2)	0.004 (2)
C4	0.056 (3)	0.044 (3)	0.032 (2)	0.000 (2)	−0.007 (2)	−0.004 (2)
C1	0.045 (3)	0.064 (3)	0.033 (2)	−0.002 (3)	−0.005 (2)	0.001 (2)
C8	0.052 (3)	0.041 (3)	0.034 (2)	0.007 (2)	0.003 (2)	−0.004 (2)
C10	0.065 (3)	0.039 (3)	0.049 (3)	0.004 (3)	0.008 (3)	0.002 (2)
C16	0.050 (3)	0.067 (3)	0.032 (3)	0.010 (3)	0.000 (2)	0.004 (2)
C18	0.073 (4)	0.064 (3)	0.077 (4)	−0.009 (3)	0.004 (3)	0.001 (3)
C2	0.091 (4)	0.060 (3)	0.037 (3)	0.009 (3)	−0.003 (3)	−0.012 (3)
C12	0.058 (3)	0.046 (3)	0.031 (2)	0.013 (3)	−0.001 (2)	−0.002 (2)
C14	0.048 (3)	0.054 (3)	0.034 (2)	0.006 (3)	0.007 (2)	0.001 (2)
C6	0.064 (3)	0.049 (3)	0.040 (3)	0.009 (3)	0.005 (3)	0.003 (2)
C9	0.059 (3)	0.045 (3)	0.044 (3)	0.004 (3)	0.001 (3)	−0.002 (2)
C7	0.089 (5)	0.167 (7)	0.057 (4)	−0.041 (5)	0.016 (3)	0.008 (4)
C13	0.050 (3)	0.040 (2)	0.031 (2)	0.008 (2)	−0.005 (2)	0.001 (2)
C17	0.049 (3)	0.052 (3)	0.033 (2)	0.007 (3)	−0.007 (2)	−0.007 (2)
C11	0.084 (4)	0.053 (3)	0.038 (3)	0.001 (3)	0.008 (3)	0.006 (3)
C5	0.063 (3)	0.051 (3)	0.038 (3)	0.008 (3)	0.003 (2)	−0.006 (2)
C15	0.050 (3)	0.051 (3)	0.049 (3)	0.004 (3)	−0.010 (3)	0.005 (3)
C3	0.093 (4)	0.052 (3)	0.039 (3)	0.009 (3)	−0.009 (3)	−0.008 (2)
F1	0.211 (5)	0.095 (3)	0.054 (2)	0.033 (3)	0.006 (3)	−0.017 (2)
O3	0.096 (3)	0.083 (3)	0.061 (3)	0.027 (3)	−0.011 (2)	−0.032 (2)
O4	0.139 (4)	0.157 (5)	0.079 (3)	0.067 (4)	−0.038 (3)	−0.033 (3)
C21	0.096 (5)	0.076 (4)	0.054 (3)	0.032 (4)	−0.001 (3)	−0.020 (3)
C20	0.066 (4)	0.050 (3)	0.050 (3)	0.003 (3)	0.001 (3)	0.003 (3)
C22	0.117 (6)	0.099 (5)	0.059 (4)	0.035 (4)	−0.013 (4)	−0.007 (4)
C24	0.132 (6)	0.081 (5)	0.079 (5)	0.045 (5)	0.012 (5)	−0.013 (4)
C23	0.140 (6)	0.054 (4)	0.047 (3)	0.015 (4)	0.010 (4)	−0.005 (3)
C19	0.075 (4)	0.067 (4)	0.054 (3)	0.004 (3)	−0.009 (3)	−0.012 (3)
C25	0.101 (5)	0.100 (5)	0.074 (4)	0.041 (4)	0.002 (4)	−0.013 (4)

Geometric parameters (Å, º)

Cl1—C10	1.727 (5)	C14—H14	0.9300
S1—O1	1.405 (4)	C14—C13	1.382 (6)
S1—O2	1.414 (5)	C6—H6	0.9300
S1—C1	1.774 (4)	C6—C5	1.389 (6)
S1—C7	1.727 (6)	C9—H9	0.9300
N2—C14	1.335 (5)	C7—H7A	0.9600
N2—C15	1.341 (6)	C7—H7B	0.9600
N1—C12	1.346 (5)	C7—H7C	0.9600
N1—C11	1.338 (6)	C13—C17	1.390 (6)
C4—C8	1.485 (6)	C17—H17	0.9300
C4—C5	1.371 (6)	C11—H11	0.9300
C4—C3	1.390 (6)	C5—H5	0.9300
C1—C2	1.372 (6)	C3—H3	0.9300
C1—C6	1.372 (6)	F1—C23	1.372 (6)
C8—C12	1.412 (6)	O3—C19	1.282 (6)
C8—C9	1.395 (6)	O3—H3A	1.04 (6)
C10—C9	1.370 (6)	O4—C19	1.216 (6)
C10—C11	1.375 (7)	C21—H21	0.9300
C16—H16	0.9300	C21—C20	1.362 (7)
C16—C17	1.361 (6)	C21—C22	1.382 (7)
C16—C15	1.396 (6)	C20—C19	1.488 (7)
C18—H18A	0.9600	C20—C25	1.373 (7)
C18—H18B	0.9600	C22—H22	0.9300
C18—H18C	0.9600	C22—C23	1.345 (8)
C18—C15	1.489 (6)	C24—H24	0.9300
C2—H2	0.9300	C24—C23	1.323 (9)
C2—C3	1.375 (6)	C24—C25	1.393 (8)
C12—C13	1.480 (6)	C25—H25	0.9300
O1—S1—O2	118.4 (3)	S1—C7—H7B	109.5
O1—S1—C1	107.9 (2)	S1—C7—H7C	109.5
O1—S1—C7	107.2 (3)	H7A—C7—H7B	109.5
O2—S1—C1	108.2 (2)	H7A—C7—H7C	109.5
O2—S1—C7	108.8 (4)	H7B—C7—H7C	109.5
C7—S1—C1	105.6 (3)	C14—C13—C12	118.1 (4)
C14—N2—C15	118.6 (4)	C14—C13—C17	116.2 (4)
C11—N1—C12	118.7 (4)	C17—C13—C12	125.7 (4)
C5—C4—C8	121.8 (4)	C16—C17—C13	120.1 (4)
C5—C4—C3	118.2 (4)	C16—C17—H17	119.9
C3—C4—C8	120.0 (4)	C13—C17—H17	119.9
C2—C1—S1	119.6 (4)	N1—C11—C10	122.8 (4)
C6—C1—S1	119.5 (4)	N1—C11—H11	118.6
C6—C1—C2	120.8 (4)	C10—C11—H11	118.6
C12—C8—C4	124.5 (4)	C4—C5—C6	121.4 (4)
C9—C8—C4	117.6 (4)	C4—C5—H5	119.3
C9—C8—C12	117.8 (4)	C6—C5—H5	119.3
C9—C10—Cl1	121.2 (4)	N2—C15—C16	120.3 (4)
C9—C10—C11	119.4 (5)	N2—C15—C18	117.0 (4)
C11—C10—Cl1	119.4 (4)	C16—C15—C18	122.7 (5)
C17—C16—H16	119.9	C4—C3—H3	119.5
C17—C16—C15	120.2 (4)	C2—C3—C4	121.1 (5)
C15—C16—H16	119.9	C2—C3—H3	119.5
H18A—C18—H18B	109.5	C19—O3—H3A	111 (3)
H18A—C18—H18C	109.5	C20—C21—H21	119.4
H18B—C18—H18C	109.5	C20—C21—C22	121.3 (5)
C15—C18—H18A	109.5	C22—C21—H21	119.4
C15—C18—H18B	109.5	C21—C20—C19	121.3 (5)
C15—C18—H18C	109.5	C21—C20—C25	118.4 (5)
C1—C2—H2	120.3	C25—C20—C19	120.3 (5)
C1—C2—C3	119.5 (5)	C21—C22—H22	121.1
C3—C2—H2	120.3	C23—C22—C21	117.7 (6)
N1—C12—C8	121.7 (4)	C23—C22—H22	121.1
N1—C12—C13	114.3 (4)	C23—C24—H24	120.9
C8—C12—C13	124.0 (4)	C23—C24—C25	118.2 (6)
N2—C14—H14	117.7	C25—C24—H24	120.9
N2—C14—C13	124.6 (4)	C22—C23—F1	117.7 (6)
C13—C14—H14	117.7	C24—C23—F1	118.4 (6)
C1—C6—H6	120.5	C24—C23—C22	123.9 (6)
C1—C6—C5	119.0 (4)	O3—C19—C20	115.4 (5)
C5—C6—H6	120.5	O4—C19—O3	123.8 (5)
C8—C9—H9	120.3	O4—C19—C20	120.8 (6)
C10—C9—C8	119.4 (4)	C20—C25—C24	120.5 (6)
C10—C9—H9	120.3	C20—C25—H25	119.7
S1—C7—H7A	109.5	C24—C25—H25	119.7
Cl1—C10—C9—C8	175.0 (3)	C9—C10—C11—N1	2.5 (8)
Cl1—C10—C11—N1	−176.3 (4)	C7—S1—C1—C2	−84.7 (5)
S1—C1—C2—C3	−175.6 (4)	C7—S1—C1—C6	98.3 (5)
S1—C1—C6—C5	175.9 (4)	C17—C16—C15—N2	1.3 (7)
O1—S1—C1—C2	29.7 (5)	C17—C16—C15—C18	180.0 (4)
O1—S1—C1—C6	−147.3 (4)	C11—N1—C12—C8	−2.3 (7)
O2—S1—C1—C2	158.9 (5)	C11—N1—C12—C13	175.2 (4)
O2—S1—C1—C6	−18.1 (5)	C11—C10—C9—C8	−3.8 (7)
N2—C14—C13—C12	−179.0 (4)	C5—C4—C8—C12	−62.7 (7)
N2—C14—C13—C17	1.5 (6)	C5—C4—C8—C9	115.9 (5)
N1—C12—C13—C14	−34.9 (6)	C5—C4—C3—C2	−1.4 (8)
N1—C12—C13—C17	144.6 (4)	C15—N2—C14—C13	−0.4 (7)
C4—C8—C12—N1	179.6 (4)	C15—C16—C17—C13	−0.1 (7)
C4—C8—C12—C13	2.3 (7)	C3—C4—C8—C12	119.9 (5)
C4—C8—C9—C10	−176.6 (4)	C3—C4—C8—C9	−61.5 (6)
C1—C2—C3—C4	−0.1 (8)	C3—C4—C5—C6	1.7 (8)
C1—C6—C5—C4	−0.5 (7)	C21—C20—C19—O3	−0.1 (8)
C8—C4—C5—C6	−175.8 (4)	C21—C20—C19—O4	−178.2 (6)
C8—C4—C3—C2	176.1 (5)	C21—C20—C25—C24	−0.2 (9)
C8—C12—C13—C14	142.6 (4)	C21—C22—C23—F1	−178.7 (6)
C8—C12—C13—C17	−37.9 (7)	C21—C22—C23—C24	1.0 (11)
C2—C1—C6—C5	−1.0 (7)	C20—C21—C22—C23	0.2 (10)
C12—N1—C11—C10	0.6 (7)	C22—C21—C20—C19	178.6 (6)
C12—C8—C9—C10	2.1 (7)	C22—C21—C20—C25	−0.5 (9)
C12—C13—C17—C16	179.4 (4)	C23—C24—C25—C20	1.3 (11)
C14—N2—C15—C16	−1.0 (6)	C19—C20—C25—C24	−179.3 (6)
C14—N2—C15—C18	−179.8 (4)	C25—C20—C19—O3	179.0 (5)
C14—C13—C17—C16	−1.1 (6)	C25—C20—C19—O4	0.9 (9)
C6—C1—C2—C3	1.3 (8)	C25—C24—C23—F1	178.0 (6)
C9—C8—C12—N1	1.0 (6)	C25—C24—C23—C22	−1.7 (12)
C9—C8—C12—C13	−176.3 (4)

5-Chloro-2-(6-methylpyridin-3-yl)-3-[4-(methylsulfonyl)phenyl]pyridine–4-nitrobenzoic acid (1/1) (etr-pnb)

Crystal data

C18H15ClN2O2S·C7H5NO4	Z = 2
Mr = 525.95	F(000) = 544
Triclinic, P1	Dx = 1.413 Mg m^−3
a = 7.4890 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.3020 (17) Å	Cell parameters from 25 reflections
c = 21.384 (4) Å	θ = 9–13°
α = 93.03 (3)°	µ = 0.28 mm^−1
β = 91.61 (3)°	T = 293 K
γ = 111.17 (3)°	Needle, colourless
V = 1236.5 (5) Å^3	0.36 × 0.1 × 0.08 mm

Data collection

Nonius CAD4 diffractometer	Rint = 0.020
ω/2θ scans	θmax = 25.4°, θmin = 1.9°
Absorption correction: ψ scan (North et al., 1968)	h = 0→9
Tmin = 0.919, Tmax = 0.972	k = −10→9
4893 measured reflections	l = −25→25
4518 independent reflections	3 standard reflections every 200 reflections
3212 reflections with I > 2σ(I)	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.158	w = 1/[σ^2(Fo^2) + (0.0798P)^2 + 0.5419P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4518 reflections	Δρmax = 0.27 e Å^−3
328 parameters	Δρmin = −0.37 e Å^−3
0 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.

Refinement. Single-crystal diffraction data were collected on a Nonius CAD4 (ENRAF, Netherlands) with an enhanced Mo Kα X-ray source (λ=0.71073Å) at 293K. The structure was solved using ShelXT(Sheldrick, Sect. A, 2015; Sheldrick, Sect. C, 2015), via the Olex2 (Dolomanov et al.2009; Bourhis et al., 2015) graphical interface. All nonhydrogen atoms were refined anisotropically.

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

	x	y	z	Uiso*/Ueq
S1	0.84792 (11)	0.35666 (9)	0.09457 (4)	0.0460 (2)
Cl1	0.14061 (14)	1.07681 (12)	0.06711 (4)	0.0640 (3)
O2	0.7985 (4)	0.2309 (3)	0.14008 (13)	0.0667 (7)
O1	0.8129 (4)	0.2986 (3)	0.02949 (12)	0.0695 (7)
N1	0.3878 (4)	1.0575 (3)	0.23088 (12)	0.0471 (6)
N2	0.6676 (4)	0.8806 (4)	0.37348 (12)	0.0561 (7)
C12	0.4868 (4)	0.9552 (4)	0.21632 (13)	0.0384 (7)
O3	0.4310 (4)	0.7719 (5)	0.46640 (13)	0.0890 (10)
H3A	0.520030	0.802104	0.442875	0.133*
C4	0.5659 (4)	0.7456 (4)	0.14127 (13)	0.0378 (6)
C9	0.3688 (4)	0.9149 (4)	0.10970 (14)	0.0417 (7)
H9	0.362521	0.868856	0.068731	0.050*
C8	0.4746 (4)	0.8742 (4)	0.15637 (13)	0.0385 (7)
O4	0.6423 (4)	0.7157 (5)	0.52756 (15)	0.0977 (11)
C13	0.6184 (4)	0.9410 (4)	0.26716 (14)	0.0414 (7)
C10	0.2733 (4)	1.0240 (4)	0.12479 (15)	0.0428 (7)
C6	0.6307 (4)	0.4912 (4)	0.16525 (14)	0.0421 (7)
H6	0.619751	0.402610	0.191480	0.051*
C1	0.7312 (4)	0.5045 (4)	0.11089 (14)	0.0416 (7)
C5	0.5477 (4)	0.6110 (4)	0.17977 (14)	0.0411 (7)
H5	0.478626	0.601896	0.215731	0.049*
C11	0.2821 (4)	1.0898 (4)	0.18611 (15)	0.0465 (8)
H11	0.211616	1.158857	0.196183	0.056*
C17	0.8096 (4)	0.9697 (4)	0.25774 (15)	0.0506 (8)
H17	0.858868	0.999414	0.218755	0.061*
C14	0.5580 (5)	0.9002 (4)	0.32673 (15)	0.0509 (8)
H14	0.431732	0.885342	0.334677	0.061*
N3	−0.0899 (6)	0.5132 (5)	0.69685 (17)	0.0816 (10)
C2	0.7491 (5)	0.6353 (4)	0.07218 (16)	0.0558 (9)
H2	0.816541	0.642902	0.035911	0.067*
C3	0.6668 (5)	0.7557 (4)	0.08718 (15)	0.0510 (8)
H3	0.678967	0.844300	0.060855	0.061*
C7	1.0917 (5)	0.4851 (4)	0.10655 (17)	0.0560 (9)
H7A	1.115330	0.538391	0.148418	0.084*
H7B	1.125870	0.573141	0.077017	0.084*
H7C	1.167265	0.413990	0.100761	0.084*
C16	0.9264 (5)	0.9544 (5)	0.30591 (15)	0.0543 (9)
H16	1.055057	0.975342	0.299770	0.065*
C15	0.8527 (5)	0.9079 (5)	0.36326 (15)	0.0542 (8)
C23	0.0587 (5)	0.5695 (5)	0.65012 (17)	0.0598 (9)
C20	0.3313 (5)	0.6675 (5)	0.56405 (16)	0.0572 (9)
O6	−0.0718 (6)	0.4182 (6)	0.73611 (18)	0.1230 (14)
O5	−0.2235 (6)	0.5608 (6)	0.6942 (2)	0.1325 (16)
C22	0.0161 (6)	0.6334 (6)	0.59694 (19)	0.0724 (11)
H22	−0.102393	0.643520	0.589932	0.087*
C19	0.4864 (6)	0.7211 (6)	0.51759 (18)	0.0668 (10)
C21	0.1562 (6)	0.6827 (6)	0.55364 (19)	0.0733 (11)
H21	0.131596	0.727085	0.516712	0.088*
C18	0.9747 (6)	0.8849 (6)	0.41709 (18)	0.0776 (12)
H18A	1.051335	0.996260	0.436688	0.116*
H18B	1.056925	0.827720	0.401533	0.116*
H18C	0.893310	0.816257	0.447215	0.116*
C25	0.3677 (6)	0.6009 (6)	0.61798 (18)	0.0773 (12)
H25	0.486119	0.590826	0.625341	0.093*
C24	0.2296 (6)	0.5486 (6)	0.66136 (19)	0.0807 (13)
H24	0.251841	0.500153	0.697601	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0463 (5)	0.0315 (4)	0.0590 (5)	0.0131 (3)	0.0042 (4)	0.0001 (3)
Cl1	0.0725 (6)	0.0638 (6)	0.0671 (6)	0.0394 (5)	−0.0098 (5)	0.0057 (4)
O2	0.0634 (16)	0.0456 (13)	0.099 (2)	0.0240 (12)	0.0260 (14)	0.0275 (13)
O1	0.0810 (18)	0.0636 (15)	0.0654 (16)	0.0332 (14)	−0.0119 (13)	−0.0249 (13)
N1	0.0455 (15)	0.0513 (15)	0.0454 (15)	0.0187 (13)	0.0107 (12)	0.0002 (12)
N2	0.0552 (18)	0.073 (2)	0.0379 (15)	0.0202 (15)	0.0042 (13)	0.0035 (13)
C12	0.0328 (15)	0.0407 (16)	0.0381 (16)	0.0083 (13)	0.0090 (12)	0.0049 (13)
O3	0.082 (2)	0.140 (3)	0.0570 (18)	0.050 (2)	0.0214 (15)	0.0336 (18)
C4	0.0341 (15)	0.0368 (15)	0.0416 (16)	0.0119 (12)	0.0022 (12)	0.0010 (12)
C9	0.0428 (17)	0.0344 (15)	0.0439 (17)	0.0094 (13)	0.0012 (13)	0.0022 (13)
C8	0.0357 (15)	0.0355 (15)	0.0414 (17)	0.0091 (12)	0.0076 (12)	0.0034 (12)
O4	0.067 (2)	0.154 (3)	0.079 (2)	0.045 (2)	0.0150 (16)	0.037 (2)
C13	0.0392 (17)	0.0435 (16)	0.0389 (16)	0.0122 (13)	0.0051 (13)	−0.0002 (13)
C10	0.0394 (16)	0.0376 (16)	0.0496 (18)	0.0114 (13)	0.0028 (14)	0.0051 (13)
C6	0.0411 (16)	0.0353 (15)	0.0474 (18)	0.0101 (13)	0.0014 (14)	0.0084 (13)
C1	0.0445 (17)	0.0350 (15)	0.0463 (17)	0.0156 (13)	0.0040 (14)	0.0011 (13)
C5	0.0374 (16)	0.0425 (16)	0.0415 (17)	0.0113 (13)	0.0062 (13)	0.0065 (13)
C11	0.0403 (17)	0.0438 (17)	0.058 (2)	0.0178 (14)	0.0109 (15)	0.0032 (15)
C17	0.0445 (18)	0.065 (2)	0.0382 (17)	0.0143 (16)	0.0062 (14)	0.0057 (15)
C14	0.0442 (18)	0.065 (2)	0.0427 (18)	0.0182 (16)	0.0082 (15)	0.0023 (15)
N3	0.085 (3)	0.094 (3)	0.059 (2)	0.023 (2)	0.023 (2)	0.0100 (19)
C2	0.076 (2)	0.056 (2)	0.0474 (19)	0.0354 (18)	0.0229 (17)	0.0117 (16)
C3	0.073 (2)	0.0471 (18)	0.0445 (18)	0.0331 (17)	0.0195 (16)	0.0162 (14)
C7	0.0484 (19)	0.0470 (19)	0.069 (2)	0.0137 (16)	0.0039 (17)	0.0002 (16)
C16	0.0419 (18)	0.072 (2)	0.0447 (19)	0.0156 (17)	0.0046 (15)	0.0004 (16)
C15	0.052 (2)	0.065 (2)	0.0423 (19)	0.0197 (17)	−0.0034 (15)	−0.0045 (16)
C23	0.059 (2)	0.065 (2)	0.050 (2)	0.0155 (18)	0.0138 (17)	−0.0007 (17)
C20	0.053 (2)	0.064 (2)	0.051 (2)	0.0171 (17)	0.0066 (16)	0.0017 (17)
O6	0.136 (3)	0.157 (4)	0.087 (2)	0.057 (3)	0.048 (2)	0.050 (3)
O5	0.110 (3)	0.188 (4)	0.133 (3)	0.083 (3)	0.066 (3)	0.055 (3)
C22	0.072 (3)	0.092 (3)	0.068 (3)	0.045 (2)	0.018 (2)	0.020 (2)
C19	0.059 (2)	0.088 (3)	0.053 (2)	0.026 (2)	0.0029 (18)	0.006 (2)
C21	0.080 (3)	0.095 (3)	0.056 (2)	0.042 (2)	0.013 (2)	0.025 (2)
C18	0.073 (3)	0.109 (3)	0.053 (2)	0.037 (3)	−0.010 (2)	0.003 (2)
C25	0.060 (2)	0.122 (4)	0.054 (2)	0.036 (2)	0.0021 (19)	0.018 (2)
C24	0.079 (3)	0.117 (4)	0.047 (2)	0.034 (3)	0.005 (2)	0.017 (2)

Geometric parameters (Å, º)

S1—O2	1.422 (2)	C17—H17	0.9300
S1—O1	1.434 (3)	C17—C16	1.373 (4)
S1—C1	1.772 (3)	C14—H14	0.9300
S1—C7	1.753 (3)	N3—C23	1.480 (5)
Cl1—C10	1.733 (3)	N3—O6	1.219 (5)
N1—C12	1.344 (4)	N3—O5	1.202 (5)
N1—C11	1.324 (4)	C2—H2	0.9300
N2—C14	1.329 (4)	C2—C3	1.380 (4)
N2—C15	1.348 (4)	C3—H3	0.9300
C12—C8	1.401 (4)	C7—H7A	0.9600
C12—C13	1.485 (4)	C7—H7B	0.9600
O3—H3A	0.8200	C7—H7C	0.9600
O3—C19	1.303 (4)	C16—H16	0.9300
C4—C8	1.488 (4)	C16—C15	1.375 (5)
C4—C5	1.392 (4)	C15—C18	1.512 (5)
C4—C3	1.389 (4)	C23—C22	1.357 (5)
C9—H9	0.9300	C23—C24	1.368 (6)
C9—C8	1.387 (4)	C20—C19	1.507 (5)
C9—C10	1.374 (4)	C20—C21	1.375 (5)
O4—C19	1.198 (5)	C20—C25	1.367 (5)
C13—C17	1.387 (4)	C22—H22	0.9300
C13—C14	1.382 (4)	C22—C21	1.382 (5)
C10—C11	1.384 (4)	C21—H21	0.9300
C6—H6	0.9300	C18—H18A	0.9600
C6—C1	1.390 (4)	C18—H18B	0.9600
C6—C5	1.377 (4)	C18—H18C	0.9600
C1—C2	1.371 (4)	C25—H25	0.9300
C5—H5	0.9300	C25—C24	1.375 (6)
C11—H11	0.9300	C24—H24	0.9300
O2—S1—O1	118.61 (17)	O5—N3—O6	122.9 (4)
O2—S1—C1	108.51 (15)	C1—C2—H2	120.1
O2—S1—C7	108.62 (17)	C1—C2—C3	119.8 (3)
O1—S1—C1	108.75 (15)	C3—C2—H2	120.1
O1—S1—C7	107.90 (18)	C4—C3—H3	119.7
C7—S1—C1	103.38 (15)	C2—C3—C4	120.6 (3)
C11—N1—C12	118.8 (3)	C2—C3—H3	119.7
C14—N2—C15	118.3 (3)	S1—C7—H7A	109.5
N1—C12—C8	122.5 (3)	S1—C7—H7B	109.5
N1—C12—C13	115.5 (3)	S1—C7—H7C	109.5
C8—C12—C13	121.9 (3)	H7A—C7—H7B	109.5
C19—O3—H3A	109.5	H7A—C7—H7C	109.5
C5—C4—C8	121.0 (3)	H7B—C7—H7C	109.5
C3—C4—C8	120.1 (3)	C17—C16—H16	120.0
C3—C4—C5	118.9 (3)	C17—C16—C15	119.9 (3)
C8—C9—H9	120.5	C15—C16—H16	120.0
C10—C9—H9	120.5	N2—C15—C16	120.9 (3)
C10—C9—C8	119.1 (3)	N2—C15—C18	117.4 (3)
C12—C8—C4	123.2 (3)	C16—C15—C18	121.7 (3)
C9—C8—C12	117.6 (3)	C22—C23—N3	118.3 (4)
C9—C8—C4	119.2 (3)	C22—C23—C24	123.0 (4)
C17—C13—C12	121.9 (3)	C24—C23—N3	118.6 (4)
C14—C13—C12	122.0 (3)	C21—C20—C19	122.2 (3)
C14—C13—C17	116.2 (3)	C25—C20—C19	118.2 (3)
C9—C10—Cl1	119.8 (2)	C25—C20—C21	119.6 (3)
C9—C10—C11	119.8 (3)	C23—C22—H22	121.4
C11—C10—Cl1	120.4 (2)	C23—C22—C21	117.2 (4)
C1—C6—H6	120.4	C21—C22—H22	121.4
C5—C6—H6	120.4	O3—C19—C20	112.6 (3)
C5—C6—C1	119.1 (3)	O4—C19—O3	124.8 (4)
C6—C1—S1	118.9 (2)	O4—C19—C20	122.6 (4)
C2—C1—S1	120.2 (2)	C20—C21—C22	121.3 (4)
C2—C1—C6	120.8 (3)	C20—C21—H21	119.3
C4—C5—H5	119.6	C22—C21—H21	119.3
C6—C5—C4	120.8 (3)	C15—C18—H18A	109.5
C6—C5—H5	119.6	C15—C18—H18B	109.5
N1—C11—C10	122.0 (3)	C15—C18—H18C	109.5
N1—C11—H11	119.0	H18A—C18—H18B	109.5
C10—C11—H11	119.0	H18A—C18—H18C	109.5
C13—C17—H17	120.0	H18B—C18—H18C	109.5
C16—C17—C13	120.1 (3)	C20—C25—H25	119.9
C16—C17—H17	120.0	C20—C25—C24	120.1 (4)
N2—C14—C13	124.6 (3)	C24—C25—H25	119.9
N2—C14—H14	117.7	C23—C24—C25	118.7 (4)
C13—C14—H14	117.7	C23—C24—H24	120.7
O6—N3—C23	118.0 (4)	C25—C24—H24	120.7
O5—N3—C23	119.1 (4)
S1—C1—C2—C3	−176.3 (3)	C11—N1—C12—C8	−3.4 (4)
Cl1—C10—C11—N1	−177.4 (2)	C11—N1—C12—C13	173.4 (3)
O2—S1—C1—C6	6.2 (3)	C17—C13—C14—N2	−2.7 (5)
O2—S1—C1—C2	−177.4 (3)	C17—C16—C15—N2	−1.4 (5)
O1—S1—C1—C6	136.5 (3)	C17—C16—C15—C18	178.4 (4)
O1—S1—C1—C2	−47.1 (3)	C14—N2—C15—C16	−0.2 (5)
N1—C12—C8—C4	−173.0 (3)	C14—N2—C15—C18	180.0 (3)
N1—C12—C8—C9	5.7 (4)	C14—C13—C17—C16	1.0 (5)
N1—C12—C13—C17	−128.3 (3)	N3—C23—C22—C21	−179.1 (4)
N1—C12—C13—C14	51.1 (4)	N3—C23—C24—C25	−180.0 (4)
C12—N1—C11—C10	−1.1 (4)	C3—C4—C8—C12	−135.2 (3)
C12—C13—C17—C16	−179.6 (3)	C3—C4—C8—C9	46.2 (4)
C12—C13—C14—N2	177.9 (3)	C3—C4—C5—C6	1.1 (4)
C9—C10—C11—N1	3.2 (5)	C7—S1—C1—C6	−109.0 (3)
C8—C12—C13—C17	48.6 (4)	C7—S1—C1—C2	67.4 (3)
C8—C12—C13—C14	−132.1 (3)	C15—N2—C14—C13	2.4 (5)
C8—C4—C5—C6	179.3 (3)	C23—C22—C21—C20	0.0 (7)
C8—C4—C3—C2	−178.9 (3)	C20—C25—C24—C23	−1.8 (7)
C8—C9—C10—Cl1	179.9 (2)	O6—N3—C23—C22	162.1 (4)
C8—C9—C10—C11	−0.8 (4)	O6—N3—C23—C24	−15.5 (6)
C13—C12—C8—C4	10.3 (4)	O5—N3—C23—C22	−17.0 (6)
C13—C12—C8—C9	−171.0 (3)	O5—N3—C23—C24	165.4 (5)
C13—C17—C16—C15	1.0 (5)	C22—C23—C24—C25	2.6 (7)
C10—C9—C8—C12	−3.4 (4)	C19—C20—C21—C22	−179.8 (4)
C10—C9—C8—C4	175.3 (3)	C19—C20—C25—C24	−179.3 (4)
C6—C1—C2—C3	0.0 (5)	C21—C20—C19—O3	−3.8 (6)
C1—C6—C5—C4	−1.0 (4)	C21—C20—C19—O4	176.5 (5)
C1—C2—C3—C4	0.1 (5)	C21—C20—C25—C24	0.3 (7)
C5—C4—C8—C12	46.6 (4)	C25—C20—C19—O3	175.8 (4)
C5—C4—C8—C9	−132.1 (3)	C25—C20—C19—O4	−3.9 (6)
C5—C4—C3—C2	−0.6 (5)	C25—C20—C21—C22	0.6 (7)
C5—C6—C1—S1	176.8 (2)	C24—C23—C22—C21	−1.7 (7)
C5—C6—C1—C2	0.4 (5)