1-[4-(Methyl­sulfonyl)­phenyl]-5-phenyl-1H-pyrazole derivatives

Three related compounds containing a pyrazole moiety with vicinal phenyl rings featuring a methyl­sulfonyl substituent are described, namely 3-methyl-1-[4-(methyl­sulfonyl)­phenyl]-5-phenyl-1H-pyrazole, C₁₇H₁₆N₂O₂S, ethyl 1-[4-(methyl­sul­fonyl)­phenyl]-5-phenyl-1H-pyrazole-3-carboxyl­ate, C₁₉H₁₈N₂O₄S, and 1-[4-(methyl­sulfonyl)­phenyl]-3-[3-(morpholino)­phenoxy­methyl]-5-phenyl-1H-pyrazole, C₂₇H₂₇N₃O₄S. The design of these compounds was based on celecoxib, a selective cyclo­oxy­genase-2 (COX-2) inhibitor, in order to study the influence of various substituents on COX-2 and 5-lipoxy­genase (5-LOX) inhibition.

S1. Comment

The three title compounds, i.e. C₁₇H₁₆N₂O₂S (I), C₁₉H₁₈N₂O₄S, (II), and C₂₇H₂₇N₃O₄S, (III), have been investigated as part of a project aimed at the design of new dual 5-LOX/COX-2 inhibitors (Barbey et al., 2002; Pommery et al., 2004). Besides selective COX-2 inhibition, this strategy appears to be a promising approach to providing safer non-steroidal anti-inflammatory drugs (Charlier & Michaux, 2003). Moreover, it opens up new perspectives in the prophylactic treatment of several types of cancer (Romano & Claria, 2003). Celecoxib, (IV), a selective COX-2 inhibitor, was used as a starting point to investigate several pharmacomodulations and subsequently to study the influence of various substituents on COX-2 and 5-LOX inhibition. While totally inactive against 5-LOX, the three title compounds exhibit different results regarding COX-2 inhibition. Indeed, in contrast to (III), (I) and (II), which are structurally closer to celecoxib, show an unexpected inactivity towards COX-2 (Barbey et al., 2002; Pommery et al., 2004). Crystal structure determination for the three compounds was carried out in order to elucidate their structural properties and to allow comparison with the previously reported structure of celecoxib (Vasu Dev, 1999), as deposited in the Cambridge Structural Database (CSD; refcode DIBBUL; Allen, 2002).

In all three crystal structures, the asymmetric unit includes two independent molecules, which differ slightly in conformation, whereas the parent compound, (IV), has only one (Fig. 1). Except for those influenced by the different nature of the moieties characteristic to each compound, the geometric parameters (bond lengths and angles) in the three studied molecules do not differ considerably from those in (IV).

Compound (I) (Fig. 2) crystallizes in space group P2₁/c. The two independent molecules are related by a non-crystallographic pseudo-twofold rotational axis (rotation of −177.70° about the b axis). Superimposition of all non-H atoms in both molecules with the quaternion transformation method (Mackay, 1984) gives a weighted (unit weight) r.m.s. fit of 0.16 Å (0.12 Å). The two vicinal phenyl rings are twisted with respect to the plane of the pyrazole ring. The extent of this deviation is not exactly the same for the two independent molecules. The C11—N1—C5—C6 and C13—C12—C11—N1 torsion angles are 39.3 (2) and 47.0 (2)°, respectively, and the C31—N21—C25—C26 and C33—C32—C31—N21 angles are −40.8 (2) and −54.7 (2)°, respectively. These orientations are quite different from that observed in celecoxib, whose two phenyl rings are almost perpendicular (the C6—C5—C3—N2 and C3—N2—C12—C17 torsion angles are 16.0 (8) and 98.8 (6)°, respectively). Weak intramolecular interactions in each residue of the asymmetric unit, involving a phenyl H atom (H7 and H27) and a sulfonyl O atom (O1 and O22, respectively), influence the conformation of the sulfonyl moiety with respect to the phenyl ring (Table 1). This kind of interaction is also found in celecoxib, between the H atom attached to atom C16 and sulfonyl atom O2. In the crystal packing (Fig. 3), cohesion is achieved by, in addition to van der Waals interactions, weak C—H···O hydrogen bonds and C—H···π interactions (Table 1 and Table 2).

Compound (II) (Fig. 4) crystallizes in space group Pca2₁. The ethyl ester chain is completely extended, with all the non-H atoms coplanar. The two residues in the asymmetric unit can be almost perfectly superimposed on one another (weighted and unit weight r.m.s. fit values of 0.065 and 0.050 Å, respectively). As observed for (I), both molecules are related by a non-crystallographic pseudo-twofold rotational axis (rotation of −179.2° about the c axis). The two vicinal phenyl rings are not perpendicular, in contrast to the situation in celecoxib (Table 3). Here again, in both asymmetric unit residues, a weak intramolecular hydrogen bond is observed, involving a phenyl H atom (H7 and H23) and one of the sulfonyl O atoms (O2 and O22; Table 4). While no classic hydrogen bond is found in the crystal packing (Fig. 5), the methyl atom (C1 and C21) of each methylsulfonyl group is involved in a weak intermolecular C—H···N interaction with the pyrazole N atom (N2 and N22) of an adjacent molecule (Table 4). Additional weak C—H···O and C—H···π contacts occur. Surprisingly, none of these intermolecular interactions involve the ethyl ester chain (Table 4 and Table 5).

Like celecoxib, compound (III) (Fig. 6) crystallizes in space group P-1. One of the residues in the asymmetric unit exhibits disorder in its morpholine moiety, as evidenced by the U_eq values. Among the three studied compounds, the two independent molecules in (III) display the most different conformations (weighted and unit weight r.m.s. fit values of 0.55 and 0.36 Å, respectively). The two vicinal phenyl rings are almost perpendicular when the two asymmetric-unit residues are superimposed. The torsion angles differ slightly from those observed for (I) and (II) (Table 6). However, both independent molecules exhibit a weak intramolecular hydrogen bond between a phenyl H atom (H7 and H33) and one of the sulfonyl O atoms (O2 and O32; Table 7). In the crystal packing (Fig. 7), several intermolecular interactions exist between symmetry-related molecules, notably C—H···O and C—H···π contacts, especially involving the morpholine moiety (Table 7 and Table 8). This additional fragment could represent an important anchoring point inside the COX-2 active site, partly explaining the higher COX-2 inhibitory potency of (III) compared with that of (I) or (II).

S2. Experimental

Crystals of (I), (II) and (III) were obtained by slow evaporation from a diethyl ether, methanol and isooctane solution, respectively.

S3. Refinement

For the three compounds, all H atoms were fixed at idealized positions, with C—H distances in the range 0.93–0.97 Å. Compound (II) crystallized in a non-centrosymmetric space group; however, owing to the absence of Friedel pairs, the absolute structure could not be determined unambiguously. In (III), the morpholine moiety of one of the molecules in the asymmetric unit is disordered. This group was refined with a split model over two positions for all atoms of the group, except N33. On the basis of CSD statistics for morpholine bond geometry, distances restraints were applied on C—C, C—N and C—O distances involving disordered atoms. Constrained refinement of the site-occupation factors led to a value of 0.620 for the major conformation.

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994) for (I), (III); CAD-4 EXPRESS (Enraf–Nonius 1994) for (II). Cell refinement: CAD-4 EXPRES for (I); CAD-4 EXPRESS for (II), (III). For all compounds, data reduction: PLATON (Spek, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: PLATON for (I), (III); PLATON (Spek, 2003) for (II). Software used to prepare material for publication: reference? for (I), (II).

Figures

	Fig. 1. : A view of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 2. : A view of the two independent molecules in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 3. : A packing diagram for (I), along the a axis, illustrating the hydrogen-bonding network.
	Fig. 4. : A view of the two independent molecules in (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 5. : A packing diagram for (II), along the b axis, illustrating the hydrogen-bonding network.
	Fig. 6. : A view of the two independent molecules in (III), with the atom-numbering scheme. Primes (') indicate the minor-site atoms. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 7. : A packing diagram for (III), illustrating the hydrogen-bonding network.

(I) 3-methyl-1-[4-(methylsulfonyl)phenyl]-5-phenyl-1H-pyrazole

Crystal data

C17H16N2O2S	F(000) = 1312
Mr = 312.39	Dx = 1.287 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.007 (1) Å	θ = 30–40°
b = 13.061 (1) Å	µ = 1.85 mm^−1
c = 24.298 (1) Å	T = 293 K
β = 112.652 (5)°	Needle, colorless
V = 3223.7 (4) Å^3	0.35 × 0.30 × 0.20 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometer	5480 reflections with I > 2σ(I)
Radiation source: long fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 71.9°, θmin = 3.9°
θ/2θ scans	h = −13→11
Absorption correction: analytical (Alcock, 1970)	k = 0→16
Tmin = 0.563, Tmax = 0.708	l = −27→29
11113 measured reflections	3 standard reflections every 200 reflections
6323 independent reflections	intensity decay: 4.2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0652P)^2 + 0.6922P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.003
6323 reflections	Δρmax = 0.33 e Å^−3
402 parameters	Δρmin = −0.30 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0048 (2)

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
C1	0.6078 (2)	0.27103 (15)	0.46200 (9)	0.0674 (5)
C10	0.16734 (18)	0.05058 (14)	0.09649 (8)	0.0640 (5)
C11	0.29134 (16)	0.05367 (12)	0.14019 (7)	0.0522 (4)
C12	0.41719 (16)	0.02082 (12)	0.13783 (7)	0.0521 (4)
C13	0.49882 (18)	−0.04831 (14)	0.17920 (8)	0.0595 (4)
C14	0.6128 (2)	−0.08314 (17)	0.17443 (10)	0.0744 (5)
C15	0.6468 (2)	−0.0497 (2)	0.12895 (12)	0.0869 (7)
C16	0.5670 (3)	0.01799 (19)	0.08743 (12)	0.0867 (7)
C17	0.4515 (2)	0.05256 (15)	0.09121 (9)	0.0674 (5)
C2	0.55376 (15)	0.15000 (12)	0.36078 (7)	0.0465 (3)
C21	1.1107 (2)	0.10766 (16)	0.45929 (8)	0.0716 (5)
C22	1.07084 (14)	0.25844 (12)	0.37443 (6)	0.0457 (3)
C23	0.95724 (16)	0.31045 (12)	0.36815 (7)	0.0494 (3)
C24	0.86933 (15)	0.33608 (12)	0.31176 (7)	0.0483 (3)
C25	0.89562 (14)	0.30840 (11)	0.26241 (6)	0.0427 (3)
C26	1.01007 (15)	0.25654 (12)	0.26882 (7)	0.0489 (3)
C27	1.09837 (15)	0.23204 (13)	0.32532 (7)	0.0505 (4)
C28	0.61091 (16)	0.34014 (13)	0.13540 (7)	0.0541 (4)
C29	0.46360 (17)	0.33466 (16)	0.10588 (10)	0.0739 (6)
C3	0.43866 (16)	0.09914 (13)	0.35421 (7)	0.0520 (4)
C30	0.69991 (17)	0.37261 (13)	0.11094 (7)	0.0543 (4)
C31	0.82223 (16)	0.36780 (12)	0.15610 (7)	0.0475 (3)
C32	0.95216 (16)	0.40003 (12)	0.15793 (7)	0.0503 (4)
C33	1.02515 (17)	0.47421 (14)	0.19799 (8)	0.0595 (4)
C34	1.1451 (2)	0.50591 (17)	0.19806 (10)	0.0776 (6)
C35	1.1943 (2)	0.4626 (2)	0.15974 (12)	0.0899 (7)
C36	1.1245 (2)	0.3891 (2)	0.12012 (11)	0.0890 (7)
C37	1.0017 (2)	0.35844 (17)	0.11817 (9)	0.0688 (5)
C4	0.34770 (16)	0.07811 (13)	0.29791 (7)	0.0519 (4)
C5	0.37174 (15)	0.10785 (11)	0.24827 (7)	0.0463 (3)
C6	0.48606 (16)	0.15999 (12)	0.25478 (7)	0.0507 (4)
C7	0.57805 (16)	0.18075 (13)	0.31128 (7)	0.0507 (4)
C8	0.08157 (18)	0.07832 (15)	0.12345 (9)	0.0674 (5)
C9	−0.0667 (2)	0.0821 (2)	0.09590 (13)	0.1001 (8)
N1	0.27573 (13)	0.08458 (10)	0.19073 (6)	0.0513 (3)
N2	0.14523 (14)	0.09971 (12)	0.18081 (7)	0.0630 (4)
N21	0.80202 (12)	0.33318 (10)	0.20478 (6)	0.0474 (3)
N22	0.67111 (12)	0.31599 (11)	0.19264 (6)	0.0535 (3)
O1	0.79096 (14)	0.20599 (17)	0.42922 (7)	0.0983 (6)
O2	0.67735 (17)	0.08180 (11)	0.46806 (6)	0.0834 (4)
O21	1.17705 (18)	0.29454 (13)	0.48832 (7)	0.1012 (6)
O22	1.30384 (13)	0.19570 (17)	0.44295 (7)	0.0997 (6)
S1	0.67233 (4)	0.17145 (3)	0.433574 (18)	0.05509 (14)
S21	1.18032 (4)	0.22062 (4)	0.446317 (17)	0.05724 (14)
H10	0.1450	0.0333	0.0567	0.077*
H13	0.4764	−0.0712	0.2103	0.071*
H14	0.6666	−0.1295	0.2022	0.089*
H15	0.7240	−0.0728	0.1261	0.104*
H16	0.5907	0.0407	0.0567	0.104*
H17	0.3969	0.0971	0.0625	0.081*
H1A	0.6638	0.2829	0.5030	0.101*
H1B	0.5212	0.2528	0.4594	0.101*
H1C	0.6028	0.3321	0.4393	0.101*
H21A	1.1672	0.0788	0.4968	0.107*
H21B	1.1003	0.0597	0.4279	0.107*
H21C	1.0262	0.1224	0.4604	0.107*
H23	0.9401	0.3281	0.4015	0.059*
H24	0.7928	0.3718	0.3069	0.058*
H26	1.0272	0.2385	0.2355	0.059*
H27	1.1761	0.1979	0.3304	0.061*
H29A	0.4293	0.3015	0.1321	0.111*
H29B	0.4391	0.2963	0.0695	0.111*
H29C	0.4282	0.4026	0.0971	0.111*
H3	0.4229	0.0793	0.3876	0.062*
H30	0.6803	0.3934	0.0718	0.065*
H33	0.9932	0.5027	0.2249	0.071*
H34	1.1925	0.5569	0.2243	0.093*
H35	1.2759	0.4833	0.1606	0.108*
H36	1.1590	0.3595	0.0945	0.107*
H37	0.9528	0.3102	0.0903	0.083*
H4	0.2702	0.0440	0.2932	0.062*
H6	0.5009	0.1809	0.2213	0.061*
H7	0.6555	0.2150	0.3161	0.061*
H9A	−0.0990	0.1132	0.1234	0.150*
H9B	−0.1009	0.0138	0.0869	0.150*
H9C	−0.0945	0.1217	0.0599	0.150*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0699 (12)	0.0599 (11)	0.0619 (11)	0.0053 (9)	0.0135 (9)	−0.0098 (8)
C10	0.0639 (10)	0.0605 (10)	0.0545 (10)	−0.0009 (8)	0.0083 (8)	0.0047 (8)
C11	0.0578 (9)	0.0463 (8)	0.0485 (8)	−0.0012 (7)	0.0160 (7)	0.0043 (6)
C12	0.0579 (9)	0.0473 (8)	0.0495 (8)	−0.0067 (7)	0.0191 (7)	−0.0066 (7)
C13	0.0619 (10)	0.0578 (10)	0.0552 (9)	0.0012 (8)	0.0186 (8)	−0.0037 (8)
C14	0.0649 (11)	0.0694 (12)	0.0815 (13)	0.0053 (9)	0.0200 (10)	−0.0114 (10)
C15	0.0732 (13)	0.0822 (15)	0.117 (2)	−0.0076 (11)	0.0498 (14)	−0.0243 (14)
C16	0.1077 (18)	0.0798 (14)	0.1000 (17)	−0.0199 (14)	0.0704 (15)	−0.0141 (13)
C17	0.0874 (13)	0.0570 (10)	0.0644 (11)	−0.0064 (9)	0.0365 (10)	−0.0011 (8)
C2	0.0462 (8)	0.0461 (8)	0.0476 (8)	0.0041 (6)	0.0187 (6)	0.0005 (6)
C21	0.0795 (13)	0.0708 (12)	0.0526 (10)	0.0055 (10)	0.0124 (9)	0.0149 (9)
C22	0.0433 (7)	0.0467 (8)	0.0409 (7)	−0.0011 (6)	0.0094 (6)	0.0028 (6)
C23	0.0526 (8)	0.0520 (8)	0.0457 (8)	0.0014 (7)	0.0213 (7)	0.0002 (6)
C24	0.0433 (7)	0.0512 (8)	0.0516 (8)	0.0072 (6)	0.0197 (6)	0.0064 (7)
C25	0.0405 (7)	0.0425 (7)	0.0427 (7)	−0.0005 (6)	0.0133 (6)	0.0064 (6)
C26	0.0515 (8)	0.0519 (8)	0.0445 (8)	0.0067 (7)	0.0198 (7)	0.0028 (6)
C27	0.0439 (8)	0.0554 (9)	0.0503 (8)	0.0097 (7)	0.0162 (6)	0.0048 (7)
C28	0.0493 (8)	0.0485 (8)	0.0518 (9)	−0.0017 (7)	0.0056 (7)	0.0007 (7)
C29	0.0497 (10)	0.0715 (12)	0.0773 (13)	−0.0062 (8)	−0.0013 (9)	0.0063 (10)
C3	0.0582 (9)	0.0527 (9)	0.0526 (8)	−0.0008 (7)	0.0295 (7)	0.0025 (7)
C30	0.0601 (9)	0.0547 (9)	0.0400 (8)	0.0030 (7)	0.0103 (7)	0.0002 (7)
C31	0.0543 (8)	0.0455 (8)	0.0419 (7)	0.0025 (6)	0.0176 (6)	0.0020 (6)
C32	0.0540 (9)	0.0513 (8)	0.0461 (8)	0.0048 (7)	0.0198 (7)	0.0119 (7)
C33	0.0579 (9)	0.0575 (10)	0.0609 (10)	0.0003 (8)	0.0205 (8)	0.0070 (8)
C34	0.0661 (12)	0.0735 (13)	0.0859 (14)	−0.0113 (10)	0.0213 (11)	0.0113 (11)
C35	0.0703 (13)	0.1008 (18)	0.1108 (19)	−0.0066 (12)	0.0482 (14)	0.0229 (15)
C36	0.0897 (16)	0.1096 (19)	0.0911 (16)	0.0073 (14)	0.0609 (14)	0.0133 (14)
C37	0.0781 (12)	0.0753 (12)	0.0632 (11)	−0.0004 (10)	0.0382 (10)	0.0031 (9)
C4	0.0491 (8)	0.0510 (9)	0.0609 (9)	−0.0054 (7)	0.0272 (7)	−0.0021 (7)
C5	0.0475 (8)	0.0415 (7)	0.0502 (8)	0.0029 (6)	0.0192 (6)	−0.0010 (6)
C6	0.0571 (9)	0.0495 (8)	0.0503 (8)	−0.0046 (7)	0.0260 (7)	0.0022 (6)
C7	0.0478 (8)	0.0526 (9)	0.0544 (9)	−0.0055 (7)	0.0228 (7)	0.0000 (7)
C8	0.0527 (10)	0.0564 (10)	0.0772 (12)	0.0023 (8)	0.0076 (9)	0.0035 (9)
C9	0.0540 (12)	0.0888 (16)	0.128 (2)	0.0053 (11)	0.0021 (12)	−0.0068 (15)
N1	0.0461 (7)	0.0509 (7)	0.0543 (7)	0.0009 (6)	0.0164 (6)	−0.0020 (6)
N2	0.0475 (7)	0.0590 (8)	0.0789 (10)	0.0034 (6)	0.0204 (7)	−0.0036 (7)
N21	0.0411 (6)	0.0523 (7)	0.0449 (7)	0.0004 (5)	0.0122 (5)	0.0087 (5)
N22	0.0409 (7)	0.0571 (8)	0.0570 (8)	−0.0024 (6)	0.0127 (6)	0.0095 (6)
O1	0.0474 (7)	0.1736 (18)	0.0709 (9)	−0.0130 (9)	0.0196 (6)	−0.0074 (10)
O2	0.1132 (12)	0.0641 (8)	0.0565 (7)	0.0205 (8)	0.0145 (7)	0.0113 (6)
O21	0.1223 (14)	0.0875 (11)	0.0567 (8)	0.0080 (10)	−0.0065 (8)	−0.0261 (8)
O22	0.0436 (7)	0.1725 (17)	0.0718 (9)	0.0156 (9)	0.0099 (6)	0.0315 (10)
S1	0.0473 (2)	0.0662 (3)	0.0482 (2)	0.00759 (17)	0.01444 (17)	0.00225 (17)
S21	0.0477 (2)	0.0696 (3)	0.0414 (2)	0.00038 (18)	0.00290 (16)	−0.00097 (17)

Geometric parameters (Å, º)

S1—O1	1.4234 (15)	S21—O21	1.4155 (16)
S1—O2	1.4284 (15)	S21—O22	1.4307 (15)
S1—C1	1.7471 (19)	S21—C21	1.746 (2)
S1—C2	1.7697 (16)	S21—C22	1.7679 (15)
N1—C11	1.365 (2)	N21—C31	1.3623 (19)
N1—N2	1.3761 (19)	N21—N22	1.3734 (17)
N1—C5	1.423 (2)	N21—C25	1.4197 (18)
N2—C8	1.326 (3)	N22—C28	1.328 (2)
C7—C6	1.383 (2)	C25—C26	1.385 (2)
C7—C2	1.388 (2)	C25—C24	1.386 (2)
C7—H7	0.9300	C22—C23	1.379 (2)
C2—C3	1.384 (2)	C22—C27	1.383 (2)
C5—C6	1.385 (2)	C27—C26	1.380 (2)
C5—C4	1.386 (2)	C27—H27	0.9300
C12—C17	1.388 (2)	C30—C31	1.372 (2)
C12—C13	1.392 (2)	C30—C28	1.393 (2)
C12—C11	1.472 (2)	C30—H30	0.9300
C3—C4	1.376 (2)	C28—C29	1.501 (2)
C3—H3	0.9300	C23—C24	1.380 (2)
C4—H4	0.9300	C23—H23	0.9300
C11—C10	1.370 (2)	C24—H24	0.9300
C8—C10	1.389 (3)	C32—C33	1.389 (2)
C8—C9	1.507 (3)	C32—C37	1.390 (2)
C13—C14	1.381 (3)	C32—C31	1.475 (2)
C13—H13	0.9300	C33—C34	1.383 (3)
C1—H1A	0.9600	C33—H33	0.9300
C1—H1B	0.9600	C26—H26	0.9300
C1—H1C	0.9600	C21—H21A	0.9600
C10—H10	0.9300	C21—H21B	0.9600
C6—H6	0.9300	C21—H21C	0.9600
C17—C16	1.385 (3)	C37—C36	1.393 (3)
C17—H17	0.9300	C37—H37	0.9300
C14—C15	1.368 (3)	C34—C35	1.367 (3)
C14—H14	0.9300	C34—H34	0.9300
C15—C16	1.374 (4)	C29—H29A	0.9600
C15—H15	0.9300	C29—H29B	0.9600
C16—H16	0.9300	C29—H29C	0.9600
C9—H9A	0.9600	C36—C35	1.367 (4)
C9—H9B	0.9600	C36—H36	0.9300
C9—H9C	0.9600	C35—H35	0.9300
O1—S1—O2	118.30 (11)	O21—S21—O22	119.01 (12)
O1—S1—C1	108.54 (11)	O21—S21—C21	108.14 (11)
O2—S1—C1	107.94 (10)	O22—S21—C21	108.12 (11)
O1—S1—C2	108.69 (8)	O21—S21—C22	108.96 (9)
O2—S1—C2	107.67 (8)	O22—S21—C22	107.95 (8)
C1—S1—C2	104.90 (8)	C21—S21—C22	103.58 (8)
C11—N1—N2	111.68 (13)	C31—N21—N22	112.10 (12)
C11—N1—C5	130.08 (13)	C31—N21—C25	129.27 (13)
N2—N1—C5	118.13 (13)	N22—N21—C25	118.52 (12)
C8—N2—N1	104.31 (15)	C28—N22—N21	104.21 (13)
C6—C7—C2	119.45 (14)	C26—C25—C24	120.95 (13)
C6—C7—H7	120.3	C26—C25—N21	120.36 (13)
C2—C7—H7	120.3	C24—C25—N21	118.68 (13)
C3—C2—C7	120.80 (15)	C23—C22—C27	121.20 (14)
C3—C2—S1	118.76 (12)	C23—C22—S21	119.41 (12)
C7—C2—S1	120.40 (12)	C27—C22—S21	119.35 (12)
C6—C5—C4	120.51 (15)	C26—C27—C22	119.74 (14)
C6—C5—N1	121.03 (14)	C26—C27—H27	120.1
C4—C5—N1	118.46 (14)	C22—C27—H27	120.1
C17—C12—C13	118.69 (17)	C31—C30—C28	106.22 (14)
C17—C12—C11	120.04 (16)	C31—C30—H30	126.9
C13—C12—C11	121.08 (15)	C28—C30—H30	126.9
C4—C3—C2	119.57 (14)	N22—C28—C30	111.71 (14)
C4—C3—H3	120.2	N22—C28—C29	120.06 (17)
C2—C3—H3	120.2	C30—C28—C29	128.18 (16)
C3—C4—C5	119.96 (15)	C22—C23—C24	119.25 (14)
C3—C4—H4	120.0	C22—C23—H23	120.4
C5—C4—H4	120.0	C24—C23—H23	120.4
N1—C11—C10	105.85 (16)	C23—C24—C25	119.72 (14)
N1—C11—C12	124.58 (14)	C23—C24—H24	120.1
C10—C11—C12	129.26 (16)	C25—C24—H24	120.1
N2—C8—C10	111.76 (16)	C33—C32—C37	118.95 (17)
N2—C8—C9	120.2 (2)	C33—C32—C31	120.84 (15)
C10—C8—C9	128.0 (2)	C37—C32—C31	120.18 (16)
C14—C13—C12	120.52 (18)	N21—C31—C30	105.76 (14)
C14—C13—H13	119.7	N21—C31—C32	123.31 (13)
C12—C13—H13	119.7	C30—C31—C32	130.72 (14)
S1—C1—H1A	109.5	C34—C33—C32	120.27 (19)
S1—C1—H1B	109.5	C34—C33—H33	119.9
H1A—C1—H1B	109.5	C32—C33—H33	119.9
S1—C1—H1C	109.5	C27—C26—C25	119.13 (14)
H1A—C1—H1C	109.5	C27—C26—H26	120.4
H1B—C1—H1C	109.5	C25—C26—H26	120.4
C11—C10—C8	106.38 (17)	S21—C21—H21A	109.5
C11—C10—H10	126.8	S21—C21—H21B	109.5
C8—C10—H10	126.8	H21A—C21—H21B	109.5
C7—C6—C5	119.70 (14)	S21—C21—H21C	109.5
C7—C6—H6	120.2	H21A—C21—H21C	109.5
C5—C6—H6	120.2	H21B—C21—H21C	109.5
C16—C17—C12	120.1 (2)	C32—C37—C36	120.0 (2)
C16—C17—H17	119.9	C32—C37—H37	120.0
C12—C17—H17	119.9	C36—C37—H37	120.0
C15—C14—C13	120.2 (2)	C35—C34—C33	120.2 (2)
C15—C14—H14	119.9	C35—C34—H34	119.9
C13—C14—H14	119.9	C33—C34—H34	119.9
C14—C15—C16	120.2 (2)	C28—C29—H29A	109.5
C14—C15—H15	119.9	C28—C29—H29B	109.5
C16—C15—H15	119.9	H29A—C29—H29B	109.5
C15—C16—C17	120.3 (2)	C28—C29—H29C	109.5
C15—C16—H16	119.9	H29A—C29—H29C	109.5
C17—C16—H16	119.9	H29B—C29—H29C	109.5
C8—C9—H9A	109.5	C35—C36—C37	120.1 (2)
C8—C9—H9B	109.5	C35—C36—H36	120.0
H9A—C9—H9B	109.5	C37—C36—H36	120.0
C8—C9—H9C	109.5	C34—C35—C36	120.5 (2)
H9A—C9—H9C	109.5	C34—C35—H35	119.8
H9B—C9—H9C	109.5	C36—C35—H35	119.8
C11—N1—N2—C8	−0.43 (19)	C31—N21—N22—C28	0.33 (18)
C5—N1—N2—C8	176.07 (15)	C25—N21—N22—C28	−176.21 (14)
C6—C7—C2—C3	−0.1 (2)	C31—N21—C25—C26	−40.8 (2)
C6—C7—C2—S1	177.71 (12)	N22—N21—C25—C26	135.02 (15)
O1—S1—C2—C3	168.73 (15)	C31—N21—C25—C24	139.89 (16)
O2—S1—C2—C3	39.46 (15)	N22—N21—C25—C24	−44.3 (2)
C1—S1—C2—C3	−75.33 (15)	O21—S21—C22—C23	−33.18 (17)
O1—S1—C2—C7	−9.17 (17)	O22—S21—C22—C23	−163.75 (15)
O2—S1—C2—C7	−138.44 (14)	C21—S21—C22—C23	81.75 (15)
C1—S1—C2—C7	106.77 (15)	O21—S21—C22—C27	149.15 (15)
C11—N1—C5—C6	39.3 (2)	O22—S21—C22—C27	18.58 (17)
N2—N1—C5—C6	−136.42 (16)	C21—S21—C22—C27	−95.91 (15)
C11—N1—C5—C4	−141.37 (17)	C23—C22—C27—C26	−1.0 (2)
N2—N1—C5—C4	42.9 (2)	S21—C22—C27—C26	176.60 (12)
C7—C2—C3—C4	0.5 (2)	N21—N22—C28—C30	−0.26 (19)
S1—C2—C3—C4	−177.38 (12)	N21—N22—C28—C29	−177.81 (15)
C2—C3—C4—C5	0.0 (2)	C31—C30—C28—N22	0.1 (2)
C6—C5—C4—C3	−0.9 (2)	C31—C30—C28—C29	177.41 (18)
N1—C5—C4—C3	179.81 (14)	C27—C22—C23—C24	0.3 (2)
N2—N1—C11—C10	0.98 (18)	S21—C22—C23—C24	−177.30 (12)
C5—N1—C11—C10	−174.98 (16)	C22—C23—C24—C25	0.7 (2)
N2—N1—C11—C12	−173.18 (15)	C26—C25—C24—C23	−1.0 (2)
C5—N1—C11—C12	10.9 (3)	N21—C25—C24—C23	178.31 (14)
C17—C12—C11—N1	−138.01 (17)	N22—N21—C31—C30	−0.27 (18)
C13—C12—C11—N1	47.0 (2)	C25—N21—C31—C30	175.80 (15)
C17—C12—C11—C10	49.2 (3)	N22—N21—C31—C32	175.01 (14)
C13—C12—C11—C10	−125.8 (2)	C25—N21—C31—C32	−8.9 (2)
N1—N2—C8—C10	−0.3 (2)	C28—C30—C31—N21	0.09 (18)
N1—N2—C8—C9	177.55 (18)	C28—C30—C31—C32	−174.70 (16)
C17—C12—C13—C14	1.1 (3)	C33—C32—C31—N21	−54.7 (2)
C11—C12—C13—C14	176.16 (16)	C37—C32—C31—N21	127.20 (18)
N1—C11—C10—C8	−1.10 (19)	C33—C32—C31—C30	119.3 (2)
C12—C11—C10—C8	172.69 (17)	C37—C32—C31—C30	−58.8 (3)
N2—C8—C10—C11	0.9 (2)	C37—C32—C33—C34	0.0 (3)
C9—C8—C10—C11	−176.7 (2)	C31—C32—C33—C34	−178.10 (16)
C2—C7—C6—C5	−0.7 (2)	C22—C27—C26—C25	0.7 (2)
C4—C5—C6—C7	1.3 (2)	C24—C25—C26—C27	0.3 (2)
N1—C5—C6—C7	−179.46 (14)	N21—C25—C26—C27	−179.00 (14)
C13—C12—C17—C16	−1.9 (3)	C33—C32—C37—C36	1.9 (3)
C11—C12—C17—C16	−177.04 (18)	C31—C32—C37—C36	−179.94 (18)
C12—C13—C14—C15	0.2 (3)	C32—C33—C34—C35	−1.7 (3)
C13—C14—C15—C16	−0.6 (3)	C32—C37—C36—C35	−2.3 (3)
C14—C15—C16—C17	−0.2 (4)	C33—C34—C35—C36	1.3 (4)
C12—C17—C16—C15	1.5 (3)	C37—C36—C35—C34	0.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O22^i	0.96	2.39	3.344 (3)	173
C7—H7···O1	0.93	2.58	2.939 (2)	104
C23—H23···O1	0.93	2.56	3.083 (3)	116
C27—H27···O22	0.93	2.55	2.921 (2)	104
C30—H30···O2^ii	0.93	2.53	3.436 (2)	165

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

(II) ethyl 1-[4-(methylsulfonyl)phenyl]-5-phenyl-1H-pyrazole-3-carboxylate

Crystal data

C19H18N2O4S	F(000) = 1552
Mr = 370.41	Dx = 1.341 Mg m^−3
Orthorhombic, Pca21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2ac	Cell parameters from 24 reflections
a = 19.479 (1) Å	θ = 40–45°
b = 5.610 (1) Å	µ = 1.80 mm^−1
c = 33.586 (3) Å	T = 293 K
V = 3670.2 (8) Å^3	Needle, colorless
Z = 8	0.42 × 0.05 × 0.04 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	2391 reflections with I > 2σ(I)
Radiation source: long fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 72.0°, θmin = 2.6°
θ/2θ scans	h = −20→24
Absorption correction: analytical (Alcock, 1970)	k = −6→0
Tmin = 0.519, Tmax = 0.932	l = 0→41
6078 measured reflections	3 standard reflections every 200 reflections
3651 independent reflections	intensity decay: 3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.049P)^2 + 0.121P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.012
3651 reflections	Δρmax = 0.18 e Å^−3
475 parameters	Δρmin = −0.18 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00046 (7)

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
C1	0.1008 (3)	0.4671 (13)	0.23797 (15)	0.097 (2)
C10	−0.0189 (2)	0.4595 (8)	0.45582 (12)	0.0426 (10)
C11	0.0310 (2)	0.6411 (8)	0.46895 (12)	0.0422 (10)
C12	0.0990 (2)	0.6349 (9)	0.45690 (14)	0.0543 (12)
C13	0.1452 (3)	0.8049 (10)	0.47048 (15)	0.0603 (13)
C14	0.1233 (3)	0.9820 (9)	0.49586 (16)	0.0635 (13)
C15	0.0566 (3)	0.9875 (10)	0.50848 (15)	0.0632 (14)
C16	0.0104 (2)	0.8166 (8)	0.49505 (13)	0.0502 (11)
C17	−0.1556 (2)	0.0180 (9)	0.45707 (14)	0.0490 (11)
C18	−0.2241 (3)	−0.2933 (10)	0.43027 (18)	0.0768 (17)
C19	−0.2257 (3)	−0.4389 (12)	0.3937 (2)	0.089 (2)
C2	0.0980 (2)	0.5326 (8)	0.31869 (13)	0.0461 (11)
C21	0.3555 (4)	0.8161 (14)	0.31983 (16)	0.101 (2)
C22	0.3447 (2)	0.9209 (8)	0.23979 (13)	0.0456 (11)
C23	0.2964 (2)	1.0886 (9)	0.22976 (13)	0.0524 (12)
C24	0.2555 (2)	1.0507 (8)	0.19670 (13)	0.0497 (11)
C25	0.2632 (2)	0.8458 (7)	0.17505 (11)	0.0399 (10)
C26	0.3103 (2)	0.6751 (8)	0.18573 (13)	0.0530 (12)
C27	0.3521 (2)	0.7111 (9)	0.21838 (14)	0.0534 (12)
C28	0.1326 (2)	0.6550 (8)	0.11237 (12)	0.0437 (10)
C29	0.1572 (2)	0.8360 (8)	0.08773 (12)	0.0451 (11)
C3	0.1094 (3)	0.3163 (9)	0.33729 (15)	0.0569 (12)
C30	0.2131 (2)	0.9300 (8)	0.10672 (12)	0.0405 (10)
C31	0.2617 (2)	1.1155 (7)	0.09382 (12)	0.0408 (10)
C32	0.3303 (2)	1.1198 (8)	0.10533 (13)	0.0474 (11)
C33	0.3737 (2)	1.2941 (9)	0.09230 (14)	0.0582 (13)
C34	0.3508 (3)	1.4710 (9)	0.06714 (15)	0.0624 (13)
C35	0.2838 (3)	1.4680 (9)	0.05466 (15)	0.0597 (13)
C36	0.2393 (2)	1.2923 (8)	0.06779 (12)	0.0491 (11)
C37	0.0747 (2)	0.4947 (10)	0.10531 (15)	0.0528 (12)
C38	0.0077 (3)	0.1781 (10)	0.13123 (16)	0.0727 (16)
C39	0.0074 (3)	0.0250 (10)	0.16705 (17)	0.0761 (16)
C4	0.0723 (2)	0.2565 (8)	0.37115 (14)	0.0538 (12)
C5	0.0237 (2)	0.4136 (8)	0.38466 (12)	0.0423 (10)
C6	0.0104 (2)	0.6272 (8)	0.36632 (14)	0.0504 (11)
C7	0.0487 (2)	0.6865 (9)	0.33249 (14)	0.0510 (11)
C8	−0.0989 (2)	0.1818 (8)	0.44939 (13)	0.0447 (10)
C9	−0.0728 (2)	0.3558 (8)	0.47539 (12)	0.0454 (11)
N1	−0.01658 (17)	0.3505 (7)	0.41944 (9)	0.0430 (9)
N2	−0.06500 (18)	0.1800 (7)	0.41477 (10)	0.0463 (9)
N21	0.21930 (17)	0.8049 (6)	0.14157 (10)	0.0418 (8)
N22	0.17038 (17)	0.6346 (6)	0.14556 (10)	0.0458 (9)
O1	0.21163 (18)	0.5010 (7)	0.27923 (14)	0.0943 (13)
O2	0.1420 (2)	0.8608 (7)	0.27151 (14)	0.1093 (16)
O21	0.46217 (16)	0.8620 (8)	0.27527 (13)	0.0934 (13)
O22	0.3948 (2)	1.2197 (7)	0.29103 (14)	0.1099 (16)
O23	0.04019 (17)	0.5020 (7)	0.07566 (11)	0.0774 (11)
O24	0.06306 (16)	0.3475 (6)	0.13552 (10)	0.0617 (9)
O3	−0.18626 (18)	0.0095 (8)	0.48787 (11)	0.0794 (12)
O4	−0.16947 (17)	−0.1189 (6)	0.42581 (10)	0.0651 (9)
S1	0.14544 (7)	0.6086 (2)	0.27617 (6)	0.0640 (4)
S21	0.39735 (6)	0.9702 (2)	0.28211 (6)	0.0635 (4)
H12	0.1138	0.5160	0.4396	0.065*
H13	0.1909	0.7991	0.4624	0.072*
H14	0.1540	1.0981	0.5044	0.076*
H15	0.0422	1.1055	0.5260	0.076*
H16	−0.0349	0.8208	0.5038	0.060*
H18A	−0.2678	−0.2135	0.4340	0.092*
H18B	−0.2155	−0.3936	0.4533	0.092*
H19A	−0.2369	−0.3395	0.3714	0.133*
H19B	−0.2596	−0.5618	0.3964	0.133*
H19C	−0.1814	−0.5102	0.3896	0.133*
H1A	0.0562	0.5377	0.2353	0.145*
H1B	0.0960	0.3008	0.2441	0.145*
H1C	0.1256	0.4847	0.2135	0.145*
H21A	0.3795	0.8392	0.3445	0.151*
H21B	0.3545	0.6492	0.3135	0.151*
H21C	0.3094	0.8745	0.3224	0.151*
H23	0.2913	1.2259	0.2450	0.063*
H24	0.2229	1.1635	0.1893	0.060*
H26	0.3141	0.5354	0.1710	0.064*
H27	0.3844	0.5974	0.2258	0.064*
H29	0.1392	0.8832	0.0633	0.054*
H3	0.1419	0.2110	0.3271	0.068*
H32	0.3469	1.0016	0.1222	0.057*
H33	0.4193	1.2935	0.1005	0.070*
H34	0.3804	1.5908	0.0587	0.075*
H35	0.2682	1.5849	0.0373	0.072*
H36	0.1940	1.2924	0.0591	0.059*
H38A	0.0146	0.0820	0.1076	0.087*
H38B	−0.0357	0.2611	0.1287	0.087*
H39A	0.0506	−0.0566	0.1692	0.114*
H39B	−0.0290	−0.0895	0.1650	0.114*
H39C	0.0005	0.1218	0.1903	0.114*
H4	0.0801	0.1133	0.3843	0.065*
H6	−0.0231	0.7297	0.3761	0.060*
H7	0.0407	0.8299	0.3194	0.061*
H9	−0.0888	0.3929	0.5007	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.131 (6)	0.116 (6)	0.042 (3)	−0.040 (5)	0.014 (3)	−0.005 (3)
C10	0.051 (2)	0.044 (3)	0.033 (2)	0.003 (2)	−0.0008 (19)	−0.0023 (19)
C11	0.051 (3)	0.041 (3)	0.034 (2)	0.003 (2)	−0.0045 (18)	0.003 (2)
C12	0.055 (3)	0.055 (3)	0.053 (3)	−0.003 (2)	−0.005 (2)	−0.005 (2)
C13	0.057 (3)	0.065 (4)	0.059 (3)	−0.009 (3)	−0.007 (2)	−0.001 (3)
C14	0.084 (4)	0.045 (3)	0.062 (3)	−0.017 (3)	−0.021 (3)	−0.001 (3)
C15	0.078 (3)	0.053 (3)	0.059 (3)	0.004 (3)	−0.017 (3)	−0.013 (3)
C16	0.057 (3)	0.047 (3)	0.046 (2)	0.003 (2)	−0.005 (2)	−0.002 (2)
C17	0.051 (2)	0.052 (3)	0.044 (2)	−0.005 (2)	0.000 (2)	−0.003 (2)
C18	0.065 (3)	0.075 (4)	0.090 (4)	−0.025 (3)	0.008 (3)	−0.009 (3)
C19	0.088 (4)	0.090 (5)	0.089 (4)	−0.024 (4)	−0.005 (3)	−0.021 (4)
C2	0.049 (2)	0.046 (3)	0.043 (2)	−0.009 (2)	0.0048 (18)	−0.004 (2)
C21	0.126 (6)	0.130 (6)	0.045 (3)	−0.031 (5)	−0.014 (3)	0.002 (4)
C22	0.049 (2)	0.047 (3)	0.041 (2)	−0.009 (2)	−0.0031 (19)	0.002 (2)
C23	0.059 (3)	0.049 (3)	0.050 (3)	−0.001 (2)	−0.004 (2)	−0.008 (2)
C24	0.052 (3)	0.047 (3)	0.049 (3)	0.008 (2)	−0.003 (2)	−0.001 (2)
C25	0.048 (2)	0.041 (2)	0.031 (2)	−0.005 (2)	0.0011 (17)	0.0060 (19)
C26	0.068 (3)	0.042 (3)	0.049 (3)	0.002 (2)	−0.006 (2)	−0.007 (2)
C27	0.055 (3)	0.048 (3)	0.057 (3)	0.007 (2)	−0.010 (2)	0.005 (2)
C28	0.043 (2)	0.053 (3)	0.035 (2)	−0.001 (2)	0.0005 (17)	−0.004 (2)
C29	0.047 (2)	0.052 (3)	0.036 (2)	0.007 (2)	0.0027 (18)	−0.001 (2)
C3	0.063 (3)	0.047 (3)	0.060 (3)	0.004 (3)	0.019 (2)	−0.011 (2)
C30	0.045 (2)	0.042 (3)	0.034 (2)	0.0034 (19)	0.0041 (17)	0.0002 (18)
C31	0.047 (2)	0.034 (2)	0.042 (2)	−0.0001 (19)	0.0064 (18)	−0.0002 (19)
C32	0.058 (3)	0.041 (3)	0.043 (2)	0.002 (2)	0.009 (2)	0.007 (2)
C33	0.058 (3)	0.061 (3)	0.056 (3)	−0.006 (3)	0.010 (2)	−0.006 (3)
C34	0.083 (4)	0.046 (3)	0.058 (3)	−0.007 (3)	0.021 (3)	0.001 (3)
C35	0.085 (4)	0.041 (3)	0.053 (3)	0.007 (3)	0.019 (3)	0.005 (2)
C36	0.051 (3)	0.048 (3)	0.048 (3)	0.008 (2)	0.011 (2)	0.007 (2)
C37	0.047 (2)	0.064 (3)	0.047 (3)	−0.004 (2)	0.004 (2)	−0.010 (3)
C38	0.056 (3)	0.079 (4)	0.083 (4)	−0.028 (3)	0.002 (3)	−0.011 (3)
C39	0.081 (4)	0.066 (4)	0.082 (4)	−0.018 (3)	0.012 (3)	−0.004 (3)
C4	0.069 (3)	0.039 (3)	0.053 (3)	0.008 (2)	0.006 (2)	0.000 (2)
C5	0.045 (2)	0.045 (3)	0.037 (2)	−0.003 (2)	0.0030 (18)	−0.002 (2)
C6	0.049 (2)	0.053 (3)	0.049 (2)	0.013 (2)	0.010 (2)	0.004 (2)
C7	0.056 (3)	0.048 (3)	0.049 (3)	0.002 (2)	0.005 (2)	0.005 (2)
C8	0.040 (2)	0.052 (3)	0.042 (2)	0.000 (2)	−0.0003 (18)	0.005 (2)
C9	0.048 (2)	0.052 (3)	0.036 (2)	−0.002 (2)	0.0018 (18)	−0.003 (2)
N1	0.051 (2)	0.044 (2)	0.0341 (18)	−0.0036 (18)	0.0007 (15)	−0.0003 (16)
N2	0.051 (2)	0.048 (2)	0.0406 (19)	−0.0050 (19)	0.0000 (16)	0.0006 (17)
N21	0.0459 (19)	0.045 (2)	0.0341 (18)	−0.0078 (17)	−0.0025 (15)	0.0047 (17)
N22	0.0477 (19)	0.049 (2)	0.0403 (19)	−0.0090 (18)	0.0063 (16)	−0.0049 (18)
O1	0.069 (2)	0.105 (3)	0.109 (3)	0.000 (2)	0.042 (2)	−0.013 (3)
O2	0.154 (4)	0.047 (2)	0.127 (4)	−0.017 (2)	0.083 (3)	0.003 (2)
O21	0.0564 (19)	0.131 (4)	0.093 (3)	0.005 (2)	−0.020 (2)	−0.002 (3)
O22	0.149 (4)	0.056 (3)	0.124 (4)	−0.015 (3)	−0.077 (3)	−0.017 (2)
O23	0.071 (2)	0.102 (3)	0.060 (2)	−0.026 (2)	−0.0172 (18)	0.007 (2)
O24	0.0587 (19)	0.066 (2)	0.061 (2)	−0.0222 (18)	−0.0060 (16)	0.0048 (18)
O3	0.078 (2)	0.106 (3)	0.054 (2)	−0.034 (2)	0.0238 (18)	−0.013 (2)
O4	0.070 (2)	0.067 (2)	0.058 (2)	−0.0243 (19)	0.0091 (16)	−0.0134 (18)
S1	0.0715 (8)	0.0568 (8)	0.0637 (8)	−0.0147 (6)	0.0288 (7)	−0.0067 (7)
S21	0.0687 (8)	0.0629 (9)	0.0588 (7)	−0.0133 (6)	−0.0195 (6)	−0.0022 (7)

Geometric parameters (Å, º)

S1—O2	1.425 (4)	S21—O21	1.420 (4)
S1—O1	1.428 (4)	S21—O22	1.433 (4)
S1—C1	1.741 (6)	S21—C21	1.736 (6)
S1—C2	1.754 (5)	S21—C22	1.774 (5)
O4—C17	1.329 (5)	O24—C37	1.328 (6)
O4—C18	1.454 (6)	O24—C38	1.444 (5)
O3—C17	1.196 (5)	O23—C37	1.202 (6)
N2—C8	1.337 (5)	N21—N22	1.356 (4)
N2—N1	1.352 (5)	N21—C30	1.370 (5)
N1—C10	1.367 (5)	N21—C25	1.431 (5)
N1—C5	1.451 (5)	N22—C28	1.340 (5)
C10—C9	1.368 (6)	C25—C24	1.369 (6)
C10—C11	1.475 (6)	C25—C26	1.375 (6)
C11—C16	1.378 (6)	C28—C29	1.395 (6)
C11—C12	1.385 (6)	C28—C37	1.463 (6)
C2—C7	1.372 (6)	C31—C36	1.392 (6)
C2—C3	1.383 (7)	C31—C32	1.392 (6)
C6—C5	1.372 (6)	C31—C30	1.471 (6)
C6—C7	1.399 (6)	C30—C29	1.367 (6)
C6—H6	0.9300	C24—C23	1.384 (6)
C8—C9	1.405 (6)	C24—H24	0.9300
C8—C17	1.459 (6)	C22—C23	1.373 (6)
C12—C13	1.388 (7)	C22—C27	1.387 (6)
C12—H12	0.9300	C32—C33	1.365 (6)
C9—H9	0.9300	C32—H32	0.9300
C16—C15	1.391 (6)	C27—C26	1.380 (6)
C16—H16	0.9300	C27—H27	0.9300
C5—C4	1.370 (6)	C29—H29	0.9300
C7—H7	0.9300	C35—C34	1.371 (7)
C15—C14	1.367 (7)	C35—C36	1.385 (6)
C15—H15	0.9300	C35—H35	0.9300
C4—C3	1.389 (6)	C26—H26	0.9300
C4—H4	0.9300	C23—H23	0.9300
C3—H3	0.9300	C34—C33	1.377 (7)
C13—C14	1.377 (7)	C34—H34	0.9300
C13—H13	0.9300	C33—H33	0.9300
C14—H14	0.9300	C36—H36	0.9300
C18—C19	1.475 (8)	C39—C38	1.478 (8)
C18—H18A	0.9700	C39—H39A	0.9600
C18—H18B	0.9700	C39—H39B	0.9600
C19—H19A	0.9600	C39—H39C	0.9600
C19—H19B	0.9600	C38—H38A	0.9700
C19—H19C	0.9600	C38—H38B	0.9700
C1—H1A	0.9600	C21—H21A	0.9600
C1—H1B	0.9600	C21—H21B	0.9600
C1—H1C	0.9600	C21—H21C	0.9600
O2—S1—O1	118.1 (3)	O21—S21—O22	118.9 (3)
O2—S1—C1	110.4 (4)	O21—S21—C21	108.8 (3)
O1—S1—C1	108.1 (3)	O22—S21—C21	108.5 (4)
O2—S1—C2	107.8 (2)	O21—S21—C22	108.5 (3)
O1—S1—C2	108.3 (3)	O22—S21—C22	107.4 (2)
C1—S1—C2	103.1 (2)	C21—S21—C22	103.7 (2)
C17—O4—C18	117.2 (4)	C37—O24—C38	117.4 (4)
C8—N2—N1	103.8 (3)	N22—N21—C30	112.5 (3)
N2—N1—C10	113.4 (3)	N22—N21—C25	117.0 (3)
N2—N1—C5	117.1 (3)	C30—N21—C25	130.0 (3)
C10—N1—C5	128.9 (4)	C28—N22—N21	104.1 (3)
N1—C10—C9	105.3 (4)	C24—C25—C26	121.3 (4)
N1—C10—C11	123.7 (4)	C24—C25—N21	119.1 (4)
C9—C10—C11	130.9 (4)	C26—C25—N21	119.5 (4)
C16—C11—C12	118.8 (4)	N22—C28—C29	111.6 (4)
C16—C11—C10	119.4 (4)	N22—C28—C37	120.4 (4)
C12—C11—C10	121.7 (4)	C29—C28—C37	128.1 (4)
C7—C2—C3	120.8 (4)	C36—C31—C32	117.6 (4)
C7—C2—S1	119.4 (4)	C36—C31—C30	119.2 (4)
C3—C2—S1	119.8 (4)	C32—C31—C30	123.2 (4)
C5—C6—C7	118.1 (4)	C29—C30—N21	105.7 (4)
C5—C6—H6	120.9	C29—C30—C31	130.3 (4)
C7—C6—H6	120.9	N21—C30—C31	123.8 (4)
N2—C8—C9	111.5 (4)	C25—C24—C23	119.5 (4)
N2—C8—C17	121.5 (4)	C25—C24—H24	120.3
C9—C8—C17	127.0 (4)	C23—C24—H24	120.3
C11—C12—C13	120.4 (5)	C23—C22—C27	121.7 (4)
C11—C12—H12	119.8	C23—C22—S21	119.1 (4)
C13—C12—H12	119.8	C27—C22—S21	119.2 (4)
C10—C9—C8	105.9 (4)	C33—C32—C31	121.2 (4)
C10—C9—H9	127.0	C33—C32—H32	119.4
C8—C9—H9	127.0	C31—C32—H32	119.4
O3—C17—O4	124.0 (4)	C26—C27—C22	118.4 (4)
O3—C17—C8	123.8 (4)	C26—C27—H27	120.8
O4—C17—C8	112.2 (4)	C22—C27—H27	120.8
C11—C16—C15	120.7 (4)	C30—C29—C28	106.1 (4)
C11—C16—H16	119.7	C30—C29—H29	126.9
C15—C16—H16	119.7	C28—C29—H29	126.9
C4—C5—C6	122.9 (4)	C34—C35—C36	120.5 (5)
C4—C5—N1	118.9 (4)	C34—C35—H35	119.7
C6—C5—N1	118.2 (4)	C36—C35—H35	119.7
C2—C7—C6	119.8 (4)	C25—C26—C27	120.0 (4)
C2—C7—H7	120.1	C25—C26—H26	120.0
C6—C7—H7	120.1	C27—C26—H26	120.0
C14—C15—C16	120.0 (5)	C22—C23—C24	119.1 (4)
C14—C15—H15	120.0	C22—C23—H23	120.4
C16—C15—H15	120.0	C24—C23—H23	120.4
C5—C4—C3	118.4 (4)	C35—C34—C33	119.1 (5)
C5—C4—H4	120.8	C35—C34—H34	120.4
C3—C4—H4	120.8	C33—C34—H34	120.4
C2—C3—C4	119.9 (4)	C32—C33—C34	120.8 (5)
C2—C3—H3	120.1	C32—C33—H33	119.6
C4—C3—H3	120.1	C34—C33—H33	119.6
C14—C13—C12	119.9 (5)	O23—C37—O24	124.0 (4)
C14—C13—H13	120.0	O23—C37—C28	123.0 (5)
C12—C13—H13	120.0	O24—C37—C28	113.0 (4)
C15—C14—C13	120.2 (5)	C35—C36—C31	120.7 (4)
C15—C14—H14	119.9	C35—C36—H36	119.6
C13—C14—H14	119.9	C31—C36—H36	119.6
O4—C18—C19	107.6 (5)	C38—C39—H39A	109.5
O4—C18—H18A	110.2	C38—C39—H39B	109.5
C19—C18—H18A	110.2	H39A—C39—H39B	109.5
O4—C18—H18B	110.2	C38—C39—H39C	109.5
C19—C18—H18B	110.2	H39A—C39—H39C	109.5
H18A—C18—H18B	108.5	H39B—C39—H39C	109.5
C18—C19—H19A	109.5	O24—C38—C39	107.7 (4)
C18—C19—H19B	109.5	O24—C38—H38A	110.2
H19A—C19—H19B	109.5	C39—C38—H38A	110.2
C18—C19—H19C	109.5	O24—C38—H38B	110.2
H19A—C19—H19C	109.5	C39—C38—H38B	110.2
H19B—C19—H19C	109.5	H38A—C38—H38B	108.5
S1—C1—H1A	109.5	S21—C21—H21A	109.5
S1—C1—H1B	109.5	S21—C21—H21B	109.5
H1A—C1—H1B	109.5	H21A—C21—H21B	109.5
S1—C1—H1C	109.5	S21—C21—H21C	109.5
H1A—C1—H1C	109.5	H21A—C21—H21C	109.5
H1B—C1—H1C	109.5	H21B—C21—H21C	109.5
C8—N2—N1—C10	0.0 (5)	C30—N21—N22—C28	−0.2 (4)
C8—N2—N1—C5	−172.4 (3)	C25—N21—N22—C28	172.8 (4)
N2—N1—C10—C9	−1.1 (5)	N22—N21—C25—C24	−108.0 (4)
C5—N1—C10—C9	170.1 (4)	C30—N21—C25—C24	63.5 (6)
N2—N1—C10—C11	176.3 (4)	N22—N21—C25—C26	69.5 (5)
C5—N1—C10—C11	−12.5 (7)	C30—N21—C25—C26	−118.9 (5)
N1—C10—C11—C16	149.6 (4)	N21—N22—C28—C29	−0.1 (4)
C9—C10—C11—C16	−33.7 (7)	N21—N22—C28—C37	178.7 (4)
N1—C10—C11—C12	−32.9 (6)	N22—N21—C30—C29	0.5 (5)
C9—C10—C11—C12	143.8 (5)	C25—N21—C30—C29	−171.4 (4)
O2—S1—C2—C7	21.7 (5)	N22—N21—C30—C31	−176.4 (4)
O1—S1—C2—C7	150.5 (4)	C25—N21—C30—C31	11.7 (7)
C1—S1—C2—C7	−95.1 (4)	C36—C31—C30—C29	28.9 (7)
O2—S1—C2—C3	−160.0 (4)	C32—C31—C30—C29	−148.9 (5)
O1—S1—C2—C3	−31.2 (5)	C36—C31—C30—N21	−155.1 (4)
C1—S1—C2—C3	83.2 (5)	C32—C31—C30—N21	27.1 (6)
N1—N2—C8—C9	1.2 (5)	C26—C25—C24—C23	0.8 (7)
N1—N2—C8—C17	−178.9 (4)	N21—C25—C24—C23	178.3 (4)
C16—C11—C12—C13	−0.9 (7)	O21—S21—C22—C23	−148.8 (4)
C10—C11—C12—C13	−178.5 (4)	O22—S21—C22—C23	−19.1 (5)
N1—C10—C9—C8	1.7 (5)	C21—S21—C22—C23	95.7 (5)
C11—C10—C9—C8	−175.4 (4)	O21—S21—C22—C27	33.1 (5)
N2—C8—C9—C10	−1.9 (5)	O22—S21—C22—C27	162.8 (4)
C17—C8—C9—C10	178.2 (4)	C21—S21—C22—C27	−82.5 (5)
C18—O4—C17—O3	−1.8 (7)	C36—C31—C32—C33	1.5 (6)
C18—O4—C17—C8	178.6 (4)	C30—C31—C32—C33	179.3 (4)
N2—C8—C17—O3	178.2 (5)	C23—C22—C27—C26	1.4 (7)
C9—C8—C17—O3	−1.9 (8)	S21—C22—C27—C26	179.5 (4)
N2—C8—C17—O4	−2.3 (6)	N21—C30—C29—C28	−0.5 (5)
C9—C8—C17—O4	177.6 (4)	C31—C30—C29—C28	176.1 (4)
C12—C11—C16—C15	1.3 (7)	N22—C28—C29—C30	0.4 (5)
C10—C11—C16—C15	178.8 (4)	C37—C28—C29—C30	−178.3 (4)
C7—C6—C5—C4	−0.5 (7)	C24—C25—C26—C27	−1.4 (7)
C7—C6—C5—N1	−179.2 (4)	N21—C25—C26—C27	−178.9 (4)
N2—N1—C5—C4	−72.7 (5)	C22—C27—C26—C25	0.3 (7)
C10—N1—C5—C4	116.4 (5)	C27—C22—C23—C24	−2.0 (7)
N2—N1—C5—C6	106.1 (5)	S21—C22—C23—C24	179.9 (4)
C10—N1—C5—C6	−64.8 (6)	C25—C24—C23—C22	0.9 (7)
C3—C2—C7—C6	1.5 (7)	C36—C35—C34—C33	1.3 (7)
S1—C2—C7—C6	179.8 (4)	C31—C32—C33—C34	−0.3 (7)
C5—C6—C7—C2	−0.1 (7)	C35—C34—C33—C32	−1.1 (7)
C11—C16—C15—C14	−0.2 (7)	C38—O24—C37—O23	3.4 (7)
C6—C5—C4—C3	−0.2 (7)	C38—O24—C37—C28	−178.7 (4)
N1—C5—C4—C3	178.5 (4)	N22—C28—C37—O23	−178.3 (5)
C7—C2—C3—C4	−2.2 (7)	C29—C28—C37—O23	0.3 (8)
S1—C2—C3—C4	179.5 (4)	N22—C28—C37—O24	3.8 (6)
C5—C4—C3—C2	1.5 (7)	C29—C28—C37—O24	−177.6 (4)
C11—C12—C13—C14	−0.5 (7)	C34—C35—C36—C31	0.0 (7)
C16—C15—C14—C13	−1.3 (8)	C32—C31—C36—C35	−1.3 (6)
C12—C13—C14—C15	1.6 (8)	C30—C31—C36—C35	−179.2 (4)
C17—O4—C18—C19	−174.5 (5)	C37—O24—C38—C39	176.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···N22	0.96	2.58	3.515 (6)	164
C7—H7···O2	0.93	2.55	2.908 (6)	103
C21—H21A···N2^i	0.96	2.60	3.545 (7)	169
C23—H23···O1^ii	0.93	2.47	3.292 (6)	147
C23—H23···O22	0.93	2.54	2.907 (6)	104

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

(III) 1-[4-(methylsulfonyl)phenyl]-3-[3-(morpholino)phenoxymethyl]-5-phenyl-1H- pyrazole

Crystal data

C27H27N3O4S	Z = 4
Mr = 489.59	F(000) = 1032
Triclinic, P1	Dx = 1.325 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 10.325 (2) Å	Cell parameters from 25 reflections
b = 13.874 (2) Å	θ = 38–42°
c = 18.094 (2) Å	µ = 1.49 mm^−1
α = 100.823 (9)°	T = 293 K
β = 104.704 (8)°	Needle, colorless
γ = 91.888 (11)°	0.40 × 0.28 × 0.24 mm
V = 2453.6 (7) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	8261 reflections with I > 2σ(I)
Radiation source: long fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 74.3°, θmin = 2.6°
θ/2θ scans	h = −12→10
Absorption correction: analytical (Alcock, 1970)	k = −17→17
Tmin = 0.587, Tmax = 0.716	l = −21→22
15978 measured reflections	3 standard reflections every 200 reflections
9997 independent reflections	intensity decay: 5%

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.168	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.085P)^2 + 0.8675P] where P = (Fo^2 + 2Fc^2)/3
9997 reflections	(Δ/σ)max = 0.001
646 parameters	Δρmax = 0.47 e Å^−3
766 restraints	Δρmin = −0.39 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)
C1	0.4313 (3)	0.25596 (18)	−0.24064 (14)	0.0639 (6)
H1A	0.3818	0.2024	−0.2806	0.096*
H1B	0.3698	0.2999	−0.2237	0.096*
H1C	0.4820	0.2306	−0.1972	0.096*
S1	0.54094 (6)	0.31973 (4)	−0.27781 (3)	0.05244 (15)
O1	0.63071 (19)	0.25199 (13)	−0.30209 (11)	0.0776 (5)
O2	0.4635 (2)	0.37016 (13)	−0.33385 (10)	0.0779 (5)
C2	0.6361 (2)	0.40977 (14)	−0.19805 (11)	0.0466 (4)
C3	0.7091 (2)	0.38190 (15)	−0.13051 (12)	0.0507 (4)
H3	0.7074	0.3160	−0.1267	0.061*
C4	0.7839 (2)	0.45327 (14)	−0.06922 (12)	0.0492 (4)
H4	0.8325	0.4356	−0.0237	0.059*
C5	0.78641 (19)	0.55119 (14)	−0.07576 (11)	0.0446 (4)
C6	0.7164 (2)	0.57815 (15)	−0.14410 (12)	0.0506 (4)
H6	0.7205	0.6438	−0.1486	0.061*
C7	0.6407 (2)	0.50724 (15)	−0.20542 (12)	0.0509 (4)
H7	0.5933	0.5249	−0.2512	0.061*
N1	0.86316 (16)	0.62534 (12)	−0.01359 (9)	0.0468 (4)
N2	0.92993 (17)	0.70156 (12)	−0.03156 (10)	0.0504 (4)
C8	0.99508 (19)	0.75569 (14)	0.03688 (12)	0.0471 (4)
C9	0.9728 (2)	0.71614 (15)	0.09895 (12)	0.0500 (4)
H9	1.0085	0.7413	0.1520	0.060*
C10	0.88785 (19)	0.63297 (14)	0.06521 (11)	0.0465 (4)
C11	0.8250 (2)	0.56538 (14)	0.10258 (11)	0.0476 (4)
C12	0.9043 (3)	0.51776 (17)	0.15553 (13)	0.0618 (5)
H12	0.9974	0.5271	0.1668	0.074*
C13	0.8453 (3)	0.4559 (2)	0.19202 (16)	0.0800 (8)
H13	0.8988	0.4236	0.2276	0.096*
C14	0.7074 (4)	0.4426 (2)	0.17527 (17)	0.0842 (9)
H14	0.6677	0.4018	0.2002	0.101*
C15	0.6287 (3)	0.4889 (2)	0.12225 (18)	0.0751 (7)
H15	0.5356	0.4786	0.1106	0.090*
C16	0.6861 (2)	0.55099 (17)	0.08565 (15)	0.0612 (5)
H16	0.6320	0.5829	0.0500	0.073*
C17	1.0808 (2)	0.84681 (15)	0.04117 (12)	0.0531 (5)
H17A	1.1301	0.8360	0.0017	0.064*
H17B	1.0259	0.9013	0.0333	0.064*
O3	1.17033 (18)	0.86680 (12)	0.11680 (9)	0.0715 (5)
C18	1.2717 (2)	0.93993 (14)	0.13405 (12)	0.0525 (5)
C19	1.3584 (3)	0.95075 (17)	0.20796 (13)	0.0620 (6)
H19	1.3436	0.9130	0.2429	0.074*
C20	1.4670 (3)	1.01936 (18)	0.22779 (15)	0.0714 (7)
H20	1.5265	1.0276	0.2771	0.086*
C21	1.4907 (2)	1.07623 (18)	0.17714 (15)	0.0673 (6)
H21	1.5654	1.1218	0.1927	0.081*
C22	1.4035 (2)	1.06602 (14)	0.10258 (12)	0.0503 (4)
C23	1.2909 (2)	0.99671 (14)	0.08225 (12)	0.0498 (4)
H23	1.2293	0.9893	0.0337	0.060*
N3	1.42877 (18)	1.11837 (13)	0.04857 (12)	0.0596 (5)
C24	1.5332 (3)	1.1972 (2)	0.07319 (18)	0.0838 (8)
H24A	1.6126	1.1751	0.1051	0.101*
H24B	1.5047	1.2517	0.1058	0.101*
C25	1.5698 (3)	1.2330 (2)	0.00947 (19)	0.0826 (8)
H25A	1.6226	1.2958	0.0312	0.099*
H25B	1.6276	1.1874	−0.0109	0.099*
O4	1.4663 (2)	1.24537 (17)	−0.05218 (14)	0.0989 (7)
C26	1.3704 (3)	1.1663 (2)	−0.07796 (18)	0.0812 (8)
H26A	1.4055	1.1137	−0.1087	0.097*
H26B	1.2922	1.1860	−0.1126	0.097*
C27	1.3254 (3)	1.1259 (3)	−0.01786 (18)	0.0863 (9)
H27A	1.2602	1.1673	−0.0010	0.104*
H27B	1.2800	1.0609	−0.0415	0.104*
C31	−0.1115 (3)	−0.1793 (2)	0.78731 (17)	0.0779 (7)
H31A	−0.1230	−0.2346	0.7448	0.117*
H31B	−0.1612	−0.1271	0.7694	0.117*
H31C	−0.1438	−0.1986	0.8281	0.117*
S31	0.05876 (5)	−0.13839 (4)	0.82311 (3)	0.05404 (15)
O31	0.1324 (2)	−0.21904 (15)	0.84274 (12)	0.0848 (6)
O32	0.0705 (2)	−0.05167 (13)	0.88235 (9)	0.0745 (5)
C32	0.10664 (19)	−0.10369 (15)	0.74394 (11)	0.0466 (4)
C33	0.1065 (2)	−0.00605 (15)	0.73708 (11)	0.0510 (4)
H33	0.0789	0.0405	0.7728	0.061*
C34	0.1479 (2)	0.02166 (14)	0.67640 (12)	0.0507 (4)
H34	0.1482	0.0870	0.6711	0.061*
C35	0.18858 (19)	−0.04863 (14)	0.62388 (11)	0.0447 (4)
C36	0.1901 (2)	−0.14649 (15)	0.63101 (12)	0.0505 (4)
H36	0.2191	−0.1928	0.5958	0.061*
C37	0.1478 (2)	−0.17406 (15)	0.69137 (12)	0.0513 (5)
H37	0.1471	−0.2395	0.6966	0.062*
N31	0.23178 (16)	−0.01802 (12)	0.56227 (9)	0.0465 (4)
N32	0.32112 (18)	0.06340 (12)	0.58138 (10)	0.0519 (4)
C38	0.3429 (2)	0.07394 (15)	0.51443 (12)	0.0511 (5)
C39	0.2686 (2)	0.00116 (16)	0.45204 (12)	0.0523 (5)
H39	0.2677	−0.0060	0.3998	0.063*
C40	0.19758 (19)	−0.05749 (14)	0.48397 (11)	0.0456 (4)
C41	0.0994 (2)	−0.14261 (14)	0.44341 (11)	0.0465 (4)
C42	−0.0179 (2)	−0.16250 (15)	0.46418 (13)	0.0515 (5)
H42	−0.0360	−0.1227	0.5072	0.062*
C43	−0.1078 (2)	−0.24159 (17)	0.42090 (16)	0.0646 (6)
H43	−0.1854	−0.2553	0.4356	0.078*
C44	−0.0833 (3)	−0.29996 (18)	0.35645 (17)	0.0749 (7)
H44	−0.1440	−0.3530	0.3277	0.090*
C45	0.0311 (3)	−0.27961 (19)	0.33477 (16)	0.0776 (7)
H45	0.0471	−0.3185	0.2907	0.093*
C46	0.1225 (3)	−0.20186 (17)	0.37783 (14)	0.0634 (6)
H46	0.2001	−0.1891	0.3629	0.076*
C47	0.4388 (2)	0.15764 (18)	0.51406 (13)	0.0596 (5)
H47A	0.4257	0.2168	0.5486	0.071*
H47B	0.5308	0.1417	0.5321	0.071*
O33	0.4139 (2)	0.17282 (14)	0.43770 (10)	0.0787 (6)
C48	0.4891 (2)	0.24647 (16)	0.42323 (12)	0.0555 (5)
C49	0.4718 (2)	0.24821 (17)	0.34530 (13)	0.0594 (5)
H49	0.4131	0.2015	0.3066	0.071*
C50	0.5434 (3)	0.32059 (18)	0.32631 (13)	0.0628 (6)
H50	0.5334	0.3216	0.2739	0.075*
C51	0.6298 (3)	0.39188 (17)	0.38213 (13)	0.0600 (5)
H51	0.6761	0.4403	0.3672	0.072*
C52	0.6473 (2)	0.39100 (15)	0.46114 (12)	0.0529 (5)
C53	0.5766 (2)	0.31620 (16)	0.48109 (12)	0.0560 (5)
H53	0.5884	0.3132	0.5333	0.067*
N33	0.7361 (2)	0.46071 (14)	0.51869 (10)	0.0680 (5)
C54	0.8085 (6)	0.5400 (4)	0.4979 (3)	0.101 (2)	0.62
H54A	0.7452	0.5855	0.4787	0.121*	0.62
H54B	0.8476	0.5121	0.4561	0.121*	0.62
C55	0.9184 (6)	0.5958 (6)	0.5660 (3)	0.118 (3)	0.62
H55A	0.9936	0.5558	0.5760	0.141*	0.62
H55B	0.9495	0.6554	0.5527	0.141*	0.62
O34	0.8735 (6)	0.6212 (6)	0.6346 (4)	0.0985 (11)	0.62
C56	0.8526 (6)	0.5303 (5)	0.6567 (4)	0.090 (2)	0.62
H56A	0.8440	0.5405	0.7097	0.108*	0.62
H56B	0.9254	0.4890	0.6523	0.108*	0.62
C57	0.7232 (6)	0.4861 (5)	0.59881 (15)	0.104 (2)	0.62
H57A	0.6930	0.4271	0.6134	0.125*	0.62
H57B	0.6553	0.5325	0.6008	0.125*	0.62
C54'	0.7348 (9)	0.5619 (3)	0.5052 (5)	0.101 (2)	0.38
H54C	0.6474	0.5853	0.5055	0.121*	0.38
H54D	0.7484	0.5619	0.4541	0.121*	0.38
C55'	0.8420 (11)	0.6313 (10)	0.5660 (6)	0.118 (3)	0.38
H55C	0.9146	0.6399	0.5421	0.141*	0.38
H55D	0.8043	0.6944	0.5734	0.141*	0.38
O34'	0.9036 (11)	0.6157 (10)	0.6420 (7)	0.0985 (11)	0.38
C56'	0.7957 (11)	0.5561 (8)	0.6502 (8)	0.090 (2)	0.38
H56C	0.7210	0.5971	0.6477	0.108*	0.38
H56D	0.8223	0.5453	0.7031	0.108*	0.38
C57'	0.7378 (16)	0.4579 (9)	0.5996 (3)	0.104 (2)	0.38
H57C	0.7919	0.4065	0.6170	0.125*	0.38
H57D	0.6472	0.4438	0.6032	0.125*	0.38

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0657 (13)	0.0639 (13)	0.0578 (12)	−0.0207 (11)	0.0171 (11)	0.0049 (10)
S1	0.0643 (3)	0.0506 (3)	0.0396 (2)	−0.0116 (2)	0.0150 (2)	0.00304 (19)
O1	0.0845 (12)	0.0720 (11)	0.0728 (11)	−0.0052 (9)	0.0371 (10)	−0.0141 (9)
O2	0.1034 (14)	0.0671 (10)	0.0494 (9)	−0.0193 (9)	−0.0033 (9)	0.0147 (7)
C2	0.0499 (10)	0.0465 (10)	0.0423 (9)	−0.0066 (8)	0.0151 (8)	0.0044 (8)
C3	0.0582 (11)	0.0416 (9)	0.0507 (10)	−0.0009 (8)	0.0133 (9)	0.0072 (8)
C4	0.0512 (10)	0.0477 (10)	0.0459 (10)	−0.0009 (8)	0.0092 (8)	0.0086 (8)
C5	0.0436 (9)	0.0470 (10)	0.0433 (9)	−0.0065 (7)	0.0160 (8)	0.0049 (7)
C6	0.0592 (11)	0.0434 (10)	0.0499 (10)	−0.0094 (8)	0.0166 (9)	0.0111 (8)
C7	0.0579 (11)	0.0508 (10)	0.0437 (10)	−0.0072 (9)	0.0124 (9)	0.0122 (8)
N1	0.0496 (9)	0.0452 (8)	0.0446 (8)	−0.0130 (7)	0.0146 (7)	0.0062 (7)
N2	0.0533 (9)	0.0481 (9)	0.0494 (9)	−0.0145 (7)	0.0156 (7)	0.0093 (7)
C8	0.0448 (10)	0.0469 (10)	0.0482 (10)	−0.0070 (8)	0.0101 (8)	0.0110 (8)
C9	0.0516 (10)	0.0496 (10)	0.0458 (10)	−0.0105 (8)	0.0109 (8)	0.0073 (8)
C10	0.0470 (10)	0.0474 (10)	0.0456 (10)	−0.0049 (8)	0.0146 (8)	0.0091 (8)
C11	0.0580 (11)	0.0411 (9)	0.0449 (10)	−0.0085 (8)	0.0218 (8)	0.0029 (7)
C12	0.0697 (14)	0.0566 (12)	0.0555 (12)	−0.0141 (10)	0.0112 (10)	0.0134 (10)
C13	0.111 (2)	0.0636 (15)	0.0633 (15)	−0.0196 (14)	0.0147 (14)	0.0224 (12)
C14	0.118 (2)	0.0683 (16)	0.0726 (16)	−0.0352 (15)	0.0450 (17)	0.0100 (13)
C15	0.0756 (16)	0.0694 (15)	0.0882 (18)	−0.0171 (12)	0.0466 (14)	0.0052 (13)
C16	0.0598 (12)	0.0579 (12)	0.0726 (14)	−0.0022 (10)	0.0315 (11)	0.0117 (11)
C17	0.0552 (11)	0.0531 (11)	0.0455 (10)	−0.0183 (9)	0.0049 (9)	0.0121 (8)
O3	0.0823 (11)	0.0694 (10)	0.0502 (8)	−0.0366 (9)	−0.0046 (8)	0.0188 (7)
C18	0.0592 (12)	0.0425 (10)	0.0475 (10)	−0.0111 (8)	0.0041 (9)	0.0050 (8)
C19	0.0753 (15)	0.0524 (12)	0.0484 (11)	−0.0060 (10)	−0.0002 (10)	0.0106 (9)
C20	0.0727 (15)	0.0640 (14)	0.0565 (13)	−0.0098 (12)	−0.0147 (11)	0.0070 (11)
C21	0.0584 (13)	0.0566 (12)	0.0681 (14)	−0.0153 (10)	−0.0098 (11)	0.0061 (11)
C22	0.0468 (10)	0.0391 (9)	0.0565 (11)	−0.0060 (8)	0.0044 (8)	0.0033 (8)
C23	0.0500 (10)	0.0438 (10)	0.0466 (10)	−0.0099 (8)	0.0006 (8)	0.0062 (8)
N3	0.0523 (10)	0.0519 (10)	0.0669 (11)	−0.0169 (8)	0.0035 (8)	0.0136 (8)
C24	0.0698 (16)	0.0873 (18)	0.0837 (18)	−0.0391 (14)	0.0096 (14)	0.0139 (15)
C25	0.0751 (17)	0.0707 (16)	0.100 (2)	−0.0258 (13)	0.0255 (15)	0.0135 (15)
O4	0.1021 (16)	0.0948 (15)	0.1017 (16)	−0.0336 (12)	0.0215 (13)	0.0391 (13)
C26	0.0862 (18)	0.0763 (17)	0.0790 (17)	−0.0217 (14)	0.0116 (14)	0.0296 (14)
C27	0.0633 (15)	0.107 (2)	0.0839 (18)	−0.0318 (15)	−0.0026 (13)	0.0440 (17)
C31	0.0654 (14)	0.0859 (18)	0.0758 (16)	−0.0270 (13)	0.0225 (13)	0.0008 (14)
S31	0.0591 (3)	0.0593 (3)	0.0432 (3)	−0.0112 (2)	0.0110 (2)	0.0154 (2)
O31	0.0991 (14)	0.0927 (13)	0.0813 (12)	0.0170 (11)	0.0302 (11)	0.0536 (11)
O32	0.0975 (13)	0.0763 (11)	0.0427 (8)	−0.0274 (9)	0.0182 (8)	0.0010 (7)
C32	0.0473 (10)	0.0508 (10)	0.0397 (9)	−0.0078 (8)	0.0066 (8)	0.0132 (8)
C33	0.0632 (12)	0.0475 (10)	0.0420 (10)	−0.0021 (9)	0.0152 (9)	0.0075 (8)
C34	0.0647 (12)	0.0408 (9)	0.0462 (10)	−0.0054 (8)	0.0140 (9)	0.0100 (8)
C35	0.0453 (9)	0.0473 (10)	0.0396 (9)	−0.0071 (8)	0.0078 (7)	0.0109 (7)
C36	0.0564 (11)	0.0455 (10)	0.0493 (10)	−0.0004 (8)	0.0148 (9)	0.0088 (8)
C37	0.0605 (12)	0.0424 (10)	0.0512 (11)	−0.0028 (8)	0.0121 (9)	0.0146 (8)
N31	0.0487 (8)	0.0463 (8)	0.0432 (8)	−0.0099 (7)	0.0120 (7)	0.0084 (6)
N32	0.0554 (9)	0.0495 (9)	0.0475 (9)	−0.0143 (7)	0.0106 (7)	0.0092 (7)
C38	0.0488 (10)	0.0539 (11)	0.0493 (10)	−0.0104 (8)	0.0126 (8)	0.0107 (9)
C39	0.0548 (11)	0.0577 (11)	0.0450 (10)	−0.0099 (9)	0.0175 (9)	0.0082 (9)
C40	0.0461 (10)	0.0464 (10)	0.0434 (9)	−0.0034 (8)	0.0130 (8)	0.0067 (8)
C41	0.0480 (10)	0.0440 (9)	0.0443 (10)	−0.0039 (8)	0.0086 (8)	0.0075 (8)
C42	0.0486 (10)	0.0513 (11)	0.0542 (11)	−0.0042 (8)	0.0108 (9)	0.0146 (9)
C43	0.0535 (12)	0.0578 (12)	0.0796 (16)	−0.0123 (10)	0.0050 (11)	0.0270 (12)
C44	0.0787 (17)	0.0497 (12)	0.0763 (16)	−0.0163 (12)	−0.0061 (13)	0.0041 (11)
C45	0.097 (2)	0.0586 (14)	0.0622 (14)	−0.0067 (13)	0.0112 (14)	−0.0095 (11)
C46	0.0697 (14)	0.0607 (13)	0.0560 (12)	−0.0057 (11)	0.0206 (11)	−0.0009 (10)
C47	0.0589 (12)	0.0649 (13)	0.0528 (11)	−0.0193 (10)	0.0128 (10)	0.0136 (10)
O33	0.0955 (13)	0.0803 (11)	0.0513 (9)	−0.0460 (10)	0.0102 (9)	0.0133 (8)
C48	0.0617 (12)	0.0531 (11)	0.0504 (11)	−0.0127 (9)	0.0145 (9)	0.0111 (9)
C49	0.0658 (13)	0.0602 (12)	0.0461 (11)	−0.0116 (10)	0.0078 (10)	0.0083 (9)
C50	0.0768 (15)	0.0663 (13)	0.0466 (11)	−0.0041 (11)	0.0154 (10)	0.0179 (10)
C51	0.0735 (14)	0.0560 (12)	0.0535 (12)	−0.0098 (10)	0.0189 (10)	0.0181 (10)
C52	0.0572 (11)	0.0497 (11)	0.0523 (11)	−0.0065 (9)	0.0152 (9)	0.0121 (9)
C53	0.0662 (13)	0.0559 (12)	0.0444 (10)	−0.0153 (10)	0.0143 (9)	0.0106 (9)
N33	0.0851 (14)	0.0610 (11)	0.0548 (10)	−0.0273 (10)	0.0181 (10)	0.0102 (9)
C54	0.115 (5)	0.108 (3)	0.069 (2)	−0.070 (3)	0.012 (3)	0.021 (2)
C55	0.133 (6)	0.124 (5)	0.078 (2)	−0.087 (5)	0.016 (3)	0.009 (3)
O34	0.115 (3)	0.0828 (15)	0.0746 (17)	−0.045 (2)	−0.003 (2)	0.0069 (12)
C56	0.096 (5)	0.096 (4)	0.061 (2)	−0.042 (3)	−0.002 (4)	0.015 (2)
C57	0.135 (3)	0.099 (4)	0.0637 (16)	−0.070 (3)	0.0256 (19)	−0.0040 (18)
C54'	0.115 (5)	0.108 (3)	0.069 (2)	−0.070 (3)	0.012 (3)	0.021 (2)
C55'	0.133 (6)	0.124 (5)	0.078 (2)	−0.087 (5)	0.016 (3)	0.009 (3)
O34'	0.115 (3)	0.0828 (15)	0.0746 (17)	−0.045 (2)	−0.003 (2)	0.0069 (12)
C56'	0.096 (5)	0.096 (4)	0.061 (2)	−0.042 (3)	−0.002 (4)	0.015 (2)
C57'	0.135 (3)	0.099 (4)	0.0637 (16)	−0.070 (3)	0.0256 (19)	−0.0040 (18)

Geometric parameters (Å, º)

C1—S1	1.750 (2)	C32—C33	1.383 (3)
C1—H1A	0.9600	C32—C37	1.387 (3)
C1—H1B	0.9600	C33—C34	1.386 (3)
C1—H1C	0.9600	C33—H33	0.9300
S1—O1	1.4299 (19)	C34—C35	1.383 (3)
S1—O2	1.4313 (19)	C34—H34	0.9300
S1—C2	1.770 (2)	C35—C36	1.388 (3)
C2—C7	1.384 (3)	C35—N31	1.428 (2)
C2—C3	1.393 (3)	C36—C37	1.385 (3)
C3—C4	1.382 (3)	C36—H36	0.9300
C3—H3	0.9300	C37—H37	0.9300
C4—C5	1.386 (3)	N31—N32	1.367 (2)
C4—H4	0.9300	N31—C40	1.369 (2)
C5—C6	1.389 (3)	N32—C38	1.320 (3)
C5—N1	1.418 (2)	C38—C39	1.401 (3)
C6—C7	1.382 (3)	C38—C47	1.504 (3)
C6—H6	0.9300	C39—C40	1.373 (3)
C7—H7	0.9300	C39—H39	0.9300
N1—C10	1.366 (2)	C40—C41	1.476 (3)
N1—N2	1.376 (2)	C41—C42	1.389 (3)
N2—C8	1.321 (3)	C41—C46	1.390 (3)
C8—C9	1.403 (3)	C42—C43	1.386 (3)
C8—C17	1.497 (3)	C42—H42	0.9300
C9—C10	1.368 (3)	C43—C44	1.374 (4)
C9—H9	0.9300	C43—H43	0.9300
C10—C11	1.476 (3)	C44—C45	1.373 (4)
C11—C12	1.378 (3)	C44—H44	0.9300
C11—C16	1.388 (3)	C45—C46	1.381 (3)
C12—C13	1.387 (3)	C45—H45	0.9300
C12—H12	0.9300	C46—H46	0.9300
C13—C14	1.378 (5)	C47—O33	1.397 (3)
C13—H13	0.9300	C47—H47A	0.9700
C14—C15	1.366 (5)	C47—H47B	0.9700
C14—H14	0.9300	O33—C48	1.366 (2)
C15—C16	1.382 (3)	C48—C49	1.381 (3)
C15—H15	0.9300	C48—C53	1.389 (3)
C16—H16	0.9300	C49—C50	1.372 (3)
C17—O3	1.415 (2)	C49—H49	0.9300
C17—H17A	0.9700	C50—C51	1.380 (3)
C17—H17B	0.9700	C50—H50	0.9300
O3—C18	1.366 (2)	C51—C52	1.397 (3)
C18—C23	1.378 (3)	C51—H51	0.9300
C18—C19	1.386 (3)	C52—N33	1.392 (3)
C19—C20	1.375 (3)	C52—C53	1.402 (3)
C19—H19	0.9300	C53—H53	0.9300
C20—C21	1.376 (4)	N33—C57	1.4673 (10)
C20—H20	0.9300	N33—C54	1.4677 (10)
C21—C22	1.398 (3)	N33—C57'	1.4685 (10)
C21—H21	0.9300	N33—C54'	1.4690 (10)
C22—N3	1.391 (3)	C54—C55	1.5091 (10)
C22—C23	1.411 (3)	C54—H54A	0.9700
C23—H23	0.9300	C54—H54B	0.9700
N3—C27	1.413 (3)	C55—O34	1.4206 (10)
N3—C24	1.433 (3)	C55—H55A	0.9700
C24—C25	1.464 (4)	C55—H55B	0.9700
C24—H24A	0.9700	O34—C56	1.4192 (10)
C24—H24B	0.9700	C56—C57	1.5009 (10)
C25—O4	1.376 (4)	C56—H56A	0.9700
C25—H25A	0.9700	C56—H56B	0.9700
C25—H25B	0.9700	C57—H57A	0.9700
O4—C26	1.380 (3)	C57—H57B	0.9700
C26—C27	1.477 (4)	C54'—C55'	1.5094 (10)
C26—H26A	0.9700	C54'—H54C	0.9700
C26—H26B	0.9700	C54'—H54D	0.9700
C27—H27A	0.9700	C55'—O34'	1.4203 (10)
C27—H27B	0.9700	C55'—H55C	0.9700
C31—S31	1.746 (3)	C55'—H55D	0.9700
C31—H31A	0.9600	O34'—C56'	1.4195 (10)
C31—H31B	0.9600	C56'—C57'	1.5006 (10)
C31—H31C	0.9600	C56'—H56C	0.9700
S31—O31	1.423 (2)	C56'—H56D	0.9700
S31—O32	1.4323 (18)	C57'—H57C	0.9700
S31—C32	1.7693 (19)	C57'—H57D	0.9700
S1—C1—H1A	109.5	C32—C33—C34	119.30 (19)
S1—C1—H1B	109.5	C32—C33—H33	120.3
H1A—C1—H1B	109.5	C34—C33—H33	120.3
S1—C1—H1C	109.5	C35—C34—C33	119.51 (18)
H1A—C1—H1C	109.5	C35—C34—H34	120.2
H1B—C1—H1C	109.5	C33—C34—H34	120.2
O1—S1—O2	118.34 (12)	C34—C35—C36	121.35 (18)
O1—S1—C1	107.69 (12)	C34—C35—N31	118.40 (17)
O2—S1—C1	108.73 (13)	C36—C35—N31	120.24 (18)
O1—S1—C2	107.89 (11)	C37—C36—C35	119.00 (19)
O2—S1—C2	107.72 (10)	C37—C36—H36	120.5
C1—S1—C2	105.80 (10)	C35—C36—H36	120.5
C7—C2—C3	120.99 (18)	C36—C37—C32	119.70 (18)
C7—C2—S1	118.76 (16)	C36—C37—H37	120.2
C3—C2—S1	120.20 (15)	C32—C37—H37	120.2
C4—C3—C2	119.27 (18)	N32—N31—C40	112.14 (15)
C4—C3—H3	120.4	N32—N31—C35	117.68 (15)
C2—C3—H3	120.4	C40—N31—C35	130.18 (16)
C3—C4—C5	119.87 (19)	C38—N32—N31	104.52 (16)
C3—C4—H4	120.1	N32—C38—C39	111.87 (17)
C5—C4—H4	120.1	N32—C38—C47	118.82 (18)
C4—C5—C6	120.55 (18)	C39—C38—C47	129.31 (19)
C4—C5—N1	120.62 (18)	C40—C39—C38	105.86 (17)
C6—C5—N1	118.81 (17)	C40—C39—H39	127.1
C7—C6—C5	119.87 (18)	C38—C39—H39	127.1
C7—C6—H6	120.1	N31—C40—C39	105.61 (17)
C5—C6—H6	120.1	N31—C40—C41	126.16 (17)
C6—C7—C2	119.41 (19)	C39—C40—C41	128.17 (18)
C6—C7—H7	120.3	C42—C41—C46	118.80 (19)
C2—C7—H7	120.3	C42—C41—C40	123.69 (18)
C10—N1—N2	111.61 (15)	C46—C41—C40	117.38 (18)
C10—N1—C5	130.04 (16)	C43—C42—C41	120.1 (2)
N2—N1—C5	118.30 (15)	C43—C42—H42	119.9
C8—N2—N1	104.44 (15)	C41—C42—H42	119.9
N2—C8—C9	111.92 (17)	C44—C43—C42	120.5 (2)
N2—C8—C17	120.19 (17)	C44—C43—H43	119.8
C9—C8—C17	127.89 (18)	C42—C43—H43	119.8
C10—C9—C8	105.69 (17)	C45—C44—C43	119.7 (2)
C10—C9—H9	127.2	C45—C44—H44	120.2
C8—C9—H9	127.2	C43—C44—H44	120.2
N1—C10—C9	106.34 (16)	C44—C45—C46	120.5 (2)
N1—C10—C11	124.37 (17)	C44—C45—H45	119.7
C9—C10—C11	129.19 (18)	C46—C45—H45	119.7
C12—C11—C16	119.80 (19)	C45—C46—C41	120.4 (2)
C12—C11—C10	120.02 (19)	C45—C46—H46	119.8
C16—C11—C10	120.2 (2)	C41—C46—H46	119.8
C11—C12—C13	120.1 (2)	O33—C47—C38	108.03 (17)
C11—C12—H12	120.0	O33—C47—H47A	110.1
C13—C12—H12	120.0	C38—C47—H47A	110.1
C14—C13—C12	119.7 (3)	O33—C47—H47B	110.1
C14—C13—H13	120.1	C38—C47—H47B	110.1
C12—C13—H13	120.1	H47A—C47—H47B	108.4
C15—C14—C13	120.3 (2)	C48—O33—C47	118.50 (17)
C15—C14—H14	119.9	O33—C48—C49	115.04 (19)
C13—C14—H14	119.9	O33—C48—C53	123.99 (19)
C14—C15—C16	120.6 (3)	C49—C48—C53	120.96 (19)
C14—C15—H15	119.7	C50—C49—C48	118.3 (2)
C16—C15—H15	119.7	C50—C49—H49	120.8
C15—C16—C11	119.5 (2)	C48—C49—H49	120.8
C15—C16—H16	120.2	C49—C50—C51	122.4 (2)
C11—C16—H16	120.2	C49—C50—H50	118.8
O3—C17—C8	105.72 (16)	C51—C50—H50	118.8
O3—C17—H17A	110.6	C50—C51—C52	119.7 (2)
C8—C17—H17A	110.6	C50—C51—H51	120.2
O3—C17—H17B	110.6	C52—C51—H51	120.2
C8—C17—H17B	110.6	N33—C52—C51	120.93 (18)
H17A—C17—H17B	108.7	N33—C52—C53	120.69 (19)
C18—O3—C17	118.46 (16)	C51—C52—C53	118.4 (2)
O3—C18—C23	123.74 (18)	C48—C53—C52	120.29 (19)
O3—C18—C19	114.38 (19)	C48—C53—H53	119.9
C23—C18—C19	121.84 (19)	C52—C53—H53	119.9
C20—C19—C18	117.6 (2)	C52—N33—C57	122.1 (3)
C20—C19—H19	121.2	C52—N33—C54	120.7 (2)
C18—C19—H19	121.2	C57—N33—C54	112.5 (4)
C19—C20—C21	122.2 (2)	C52—N33—C57'	116.1 (5)
C19—C20—H20	118.9	C54—N33—C57'	122.6 (5)
C21—C20—H20	118.9	C52—N33—C54'	115.5 (4)
C20—C21—C22	120.6 (2)	C57'—N33—C54'	111.6 (6)
C20—C21—H21	119.7	N33—C54—C55	112.6 (4)
C22—C21—H21	119.7	N33—C54—H54A	109.1
N3—C22—C21	121.93 (19)	C55—C54—H54A	109.1
N3—C22—C23	120.53 (18)	N33—C54—H54B	109.1
C21—C22—C23	117.5 (2)	C55—C54—H54B	109.1
C18—C23—C22	120.27 (19)	H54A—C54—H54B	107.8
C18—C23—H23	119.9	O34—C55—C54	111.9 (6)
C22—C23—H23	119.9	O34—C55—H55A	109.2
C22—N3—C27	120.42 (18)	C54—C55—H55A	109.2
C22—N3—C24	119.6 (2)	O34—C55—H55B	109.2
C27—N3—C24	114.8 (2)	C54—C55—H55B	109.2
N3—C24—C25	114.6 (2)	H55A—C55—H55B	107.9
N3—C24—H24A	108.6	C56—O34—C55	104.9 (7)
C25—C24—H24A	108.6	O34—C56—C57	102.5 (6)
N3—C24—H24B	108.6	O34—C56—H56A	111.3
C25—C24—H24B	108.6	C57—C56—H56A	111.3
H24A—C24—H24B	107.6	O34—C56—H56B	111.3
O4—C25—C24	117.1 (2)	C57—C56—H56B	111.3
O4—C25—H25A	108.0	H56A—C56—H56B	109.2
C24—C25—H25A	108.0	N33—C57—C56	112.7 (5)
O4—C25—H25B	108.0	N33—C57—H57A	109.0
C24—C25—H25B	108.0	C56—C57—H57A	109.0
H25A—C25—H25B	107.3	N33—C57—H57B	109.0
C25—O4—C26	112.8 (2)	C56—C57—H57B	109.0
O4—C26—C27	117.0 (3)	H57A—C57—H57B	107.8
O4—C26—H26A	108.0	N33—C54'—C55'	112.4 (7)
C27—C26—H26A	108.0	N33—C54'—H54C	109.1
O4—C26—H26B	108.0	C55'—C54'—H54C	109.1
C27—C26—H26B	108.0	N33—C54'—H54D	109.1
H26A—C26—H26B	107.3	C55'—C54'—H54D	109.1
N3—C27—C26	115.1 (2)	H54C—C54'—H54D	107.9
N3—C27—H27A	108.5	O34'—C55'—C54'	125.0 (10)
C26—C27—H27A	108.5	O34'—C55'—H55C	106.1
N3—C27—H27B	108.5	C54'—C55'—H55C	106.1
C26—C27—H27B	108.5	O34'—C55'—H55D	106.1
H27A—C27—H27B	107.5	C54'—C55'—H55D	106.1
S31—C31—H31A	109.5	H55C—C55'—H55D	106.3
S31—C31—H31B	109.5	C56'—O34'—C55'	97.6 (11)
H31A—C31—H31B	109.5	O34'—C56'—C57'	126.0 (13)
S31—C31—H31C	109.5	O34'—C56'—H56C	105.8
H31A—C31—H31C	109.5	C57'—C56'—H56C	105.8
H31B—C31—H31C	109.5	O34'—C56'—H56D	105.8
O31—S31—O32	118.48 (13)	C57'—C56'—H56D	105.8
O31—S31—C31	108.69 (14)	H56C—C56'—H56D	106.2
O32—S31—C31	107.68 (13)	N33—C57'—C56'	108.6 (9)
O31—S31—C32	107.74 (11)	N33—C57'—H57C	110.0
O32—S31—C32	107.97 (10)	C56'—C57'—H57C	110.0
C31—S31—C32	105.56 (12)	N33—C57'—H57D	110.0
C33—C32—C37	121.14 (18)	C56'—C57'—H57D	110.0
C33—C32—S31	119.29 (16)	H57C—C57'—H57D	108.4
C37—C32—S31	119.53 (15)
O1—S1—C2—C7	118.63 (18)	C33—C34—C35—N31	−179.50 (18)
O2—S1—C2—C7	−10.2 (2)	C34—C35—C36—C37	1.0 (3)
C1—S1—C2—C7	−126.33 (18)	N31—C35—C36—C37	179.91 (18)
O1—S1—C2—C3	−58.82 (19)	C35—C36—C37—C32	−0.8 (3)
O2—S1—C2—C3	172.37 (17)	C33—C32—C37—C36	0.2 (3)
C1—S1—C2—C3	56.2 (2)	S31—C32—C37—C36	−177.62 (16)
C7—C2—C3—C4	1.9 (3)	C34—C35—N31—N32	47.5 (3)
S1—C2—C3—C4	179.29 (16)	C36—C35—N31—N32	−131.4 (2)
C2—C3—C4—C5	−0.5 (3)	C34—C35—N31—C40	−132.3 (2)
C3—C4—C5—C6	−1.3 (3)	C36—C35—N31—C40	48.8 (3)
C3—C4—C5—N1	−179.71 (18)	C40—N31—N32—C38	−0.4 (2)
C4—C5—C6—C7	1.7 (3)	C35—N31—N32—C38	179.82 (18)
N1—C5—C6—C7	−179.87 (18)	N31—N32—C38—C39	0.4 (2)
C5—C6—C7—C2	−0.3 (3)	N31—N32—C38—C47	−179.60 (19)
C3—C2—C7—C6	−1.5 (3)	N32—C38—C39—C40	−0.2 (3)
S1—C2—C7—C6	−178.95 (16)	C47—C38—C39—C40	179.7 (2)
C4—C5—N1—C10	−35.7 (3)	N32—N31—C40—C39	0.2 (2)
C6—C5—N1—C10	145.9 (2)	C35—N31—C40—C39	−180.0 (2)
C4—C5—N1—N2	141.44 (19)	N32—N31—C40—C41	−177.12 (18)
C6—C5—N1—N2	−37.0 (3)	C35—N31—C40—C41	2.7 (3)
C10—N1—N2—C8	−0.2 (2)	C38—C39—C40—N31	0.0 (2)
C5—N1—N2—C8	−177.78 (17)	C38—C39—C40—C41	177.3 (2)
N1—N2—C8—C9	0.3 (2)	N31—C40—C41—C42	35.7 (3)
N1—N2—C8—C17	179.89 (18)	C39—C40—C41—C42	−141.1 (2)
N2—C8—C9—C10	−0.4 (2)	N31—C40—C41—C46	−148.6 (2)
C17—C8—C9—C10	−179.9 (2)	C39—C40—C41—C46	34.6 (3)
N2—N1—C10—C9	−0.1 (2)	C46—C41—C42—C43	1.5 (3)
C5—N1—C10—C9	177.18 (19)	C40—C41—C42—C43	177.14 (19)
N2—N1—C10—C11	176.59 (18)	C41—C42—C43—C44	−1.1 (3)
C5—N1—C10—C11	−6.2 (3)	C42—C43—C44—C45	−0.1 (4)
C8—C9—C10—N1	0.3 (2)	C43—C44—C45—C46	0.9 (4)
C8—C9—C10—C11	−176.2 (2)	C44—C45—C46—C41	−0.5 (4)
N1—C10—C11—C12	125.2 (2)	C42—C41—C46—C45	−0.7 (4)
C9—C10—C11—C12	−58.9 (3)	C40—C41—C46—C45	−176.6 (2)
N1—C10—C11—C16	−56.0 (3)	N32—C38—C47—O33	−161.5 (2)
C9—C10—C11—C16	119.9 (3)	C39—C38—C47—O33	18.6 (4)
C16—C11—C12—C13	−0.2 (3)	C38—C47—O33—C48	179.5 (2)
C10—C11—C12—C13	178.6 (2)	C47—O33—C48—C49	171.4 (2)
C11—C12—C13—C14	−0.2 (4)	C47—O33—C48—C53	−9.1 (4)
C12—C13—C14—C15	0.8 (4)	O33—C48—C49—C50	179.6 (2)
C13—C14—C15—C16	−1.1 (4)	C53—C48—C49—C50	0.0 (4)
C14—C15—C16—C11	0.6 (4)	C48—C49—C50—C51	−1.0 (4)
C12—C11—C16—C15	0.0 (3)	C49—C50—C51—C52	0.7 (4)
C10—C11—C16—C15	−178.8 (2)	C50—C51—C52—N33	178.6 (2)
N2—C8—C17—O3	−159.8 (2)	C50—C51—C52—C53	0.6 (4)
C9—C8—C17—O3	19.7 (3)	O33—C48—C53—C52	−178.3 (2)
C8—C17—O3—C18	172.4 (2)	C49—C48—C53—C52	1.2 (4)
C17—O3—C18—C23	1.0 (3)	N33—C52—C53—C48	−179.5 (2)
C17—O3—C18—C19	−176.8 (2)	C51—C52—C53—C48	−1.5 (4)
O3—C18—C19—C20	176.5 (2)	C51—C52—N33—C57	157.1 (4)
C23—C18—C19—C20	−1.2 (4)	C53—C52—N33—C57	−25.0 (5)
C18—C19—C20—C21	0.1 (4)	C51—C52—N33—C54	3.1 (5)
C19—C20—C21—C22	0.1 (4)	C53—C52—N33—C54	−179.0 (4)
C20—C21—C22—N3	−176.3 (2)	C51—C52—N33—C57'	174.9 (7)
C20—C21—C22—C23	0.8 (4)	C53—C52—N33—C57'	−7.2 (8)
O3—C18—C23—C22	−175.4 (2)	C51—C52—N33—C54'	41.4 (5)
C19—C18—C23—C22	2.2 (3)	C53—C52—N33—C54'	−140.7 (5)
N3—C22—C23—C18	175.3 (2)	C52—N33—C54—C55	−169.1 (4)
C21—C22—C23—C18	−1.9 (3)	C57—N33—C54—C55	34.6 (7)
C21—C22—N3—C27	−164.1 (3)	C57'—N33—C54—C55	19.7 (11)
C23—C22—N3—C27	18.8 (4)	C54'—N33—C54—C55	100.2 (10)
C21—C22—N3—C24	−11.0 (4)	N33—C54—C55—O34	−46.6 (8)
C23—C22—N3—C24	172.0 (2)	C54—C55—O34—C56	68.7 (6)
C22—N3—C24—C25	167.7 (3)	C55—O34—C56—C57	−75.6 (5)
C27—N3—C24—C25	−37.7 (4)	C52—N33—C57—C56	157.8 (4)
N3—C24—C25—O4	43.2 (4)	C54—N33—C57—C56	−46.3 (7)
C24—C25—O4—C26	−46.2 (4)	C57'—N33—C57—C56	84 (3)
C25—O4—C26—C27	45.1 (4)	C54'—N33—C57—C56	−77.1 (6)
C22—N3—C27—C26	−168.7 (3)	O34—C56—C57—N33	66.6 (6)
C24—N3—C27—C26	37.0 (4)	C52—N33—C54'—C55'	−174.8 (7)
O4—C26—C27—N3	−41.6 (4)	C57—N33—C54'—C55'	55.3 (8)
O31—S31—C32—C33	−148.51 (18)	C54—N33—C54'—C55'	−67.0 (10)
O32—S31—C32—C33	−19.5 (2)	C57'—N33—C54'—C55'	49.7 (11)
C31—S31—C32—C33	95.5 (2)	N33—C54'—C55'—O34'	−22.5 (17)
O31—S31—C32—C37	29.4 (2)	C54'—C55'—O34'—C56'	−27.0 (17)
O32—S31—C32—C37	158.44 (17)	C55'—O34'—C56'—C57'	61.6 (14)
C31—S31—C32—C37	−86.6 (2)	C52—N33—C57'—C56'	−159.1 (8)
C37—C32—C33—C34	0.2 (3)	C57—N33—C57'—C56'	−43.8 (18)
S31—C32—C33—C34	178.07 (16)	C54—N33—C57'—C56'	12.5 (14)
C32—C33—C34—C35	0.0 (3)	C54'—N33—C57'—C56'	−24.0 (13)
C33—C34—C35—C36	−0.6 (3)	O34'—C56'—C57'—N33	−38.0 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O2	0.93	2.50	2.887 (3)	105
C24—H24A···O31^i	0.97	2.57	3.378 (4)	141
C27—H27B···O32^ii	0.97	2.55	3.427 (4)	151
C31—H31A···O34^iii	0.96	2.53	3.489 (8)	174
C33—H33···O32	0.93	2.57	2.925 (3)	103
C46—H46···O1^iv	0.93	2.40	3.223 (4)	148

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