N-{2-[(3,5-Di-tert-butyl-4-oxo­cyclo­hexa-2,5-dien-1-yl­idene)­amino]­phenyl}-N-(5,7-di­nitro­quinolin-8-yl)-1-phenyl­methanesulfon­amide: the nature of intramolecular shortened contacts

The title compound, C₃₆H₃₅N₅O₇S, is found to exist in a non-spiro­cyclic (ring-opened) form in the crystal, although equilibrium of ring-opened and ring-closed forms (or so-called ring–chain isomerization) is possible in solution. The 4-oxo­cyclo­hexa-2,5-diene ring has a flattened sofa conformation. The N...C intramolecular separation of the atoms which would be directly bonded in a ring-closed form is quite short [2.813 (5) Å]. Topological analysis of charge density based on density-functional-theory calculations was used for consideration of shortened intramolecular contacts and indicates a strong attractive bonding interaction between these N and C atoms in the crystal structure.

S1. Comment

It is well known that electron-deficient aromatic compounds containing a tropolone moiety or its heteroatomic analogues can undergo acylotropic rearrangements (Knyazev & Drozd, 1995; Kurbatov et al., 1997). This rearrangement usually includes reversible migration of the electron-deficient aryl group and proceeds through formation of a dipolar spirocyclic Meisenheimer complex with the tropylium cation. Several structures of such dipolar Meisenheimer complexes have been established by X-ray methods (Borbulevych Antipin & Olekhnovich, 1999; Borbulevych Shishkin et al., 1999; Furmanova et al., 1980; Olekhnovich Furmanova et al., 1982). Basically, in solutions of such compounds, there is equilibrium between the ring-opened and ring-closed (Meisenheimer complex) isomers, and interrelation of these forms is determined by many factors (Olekhnovich et al., 1994). However, not only tropolone derivatives exhibit this so-called ring-chain isomerization. In particular, equilibrium of ring-opened and ring-closed forms occurs in solution for (1Z)-1-{[isopropyl(2,4,6-trinitrophenyl)amino]methylene}-4a,8a- dihydronaphthalen-2(1H)-one and a dipolar spirocyclic isomer was found in the crystal phase (Olekhnovich Mikhailov et al., 1982). Another example is the title compound, (I). According to preliminary NMR data (Borysenko et al., 1998), both ring-opened and ring-closed isomers of (I) are observed in solution (see scheme). Therefore, it is important to establish the structure of (I) in the crystal. \sch

X-ray investigation has shown that the bond lengths in (I) do not differ considerably from standard values (Allen et al., 1987). The nitro groups in (I) are not coplanar with the quinoline moiety [O2—N2—C5—C6 and O3—N3—C7—C6 torsion angles −31.4 (6) and 52.7 (5)°, respectively], which is likely be a result of the bulky substituent at atom C8.

Atom N4 has a planar conformation: the sum of the bond angles in the C10/S1/C8/N4 fragment is 359.5 (7)°. This fragment is rotated with respect to the fused-ring system and the angle between these two planes is 63.2 (1)°. The phenylmethanesulfonyl group in (I) has an ac conformation with respect to the C7—C8 bond [S1—N4—C8—C7 torsion angle −116.4 (3)°].

The C10—C15 benzene ring is rotated with respect the C8—N4 bond and the corresponding C8—N4—C10—C11 torsion angle is 45.6 (5)°. The cyclohexa-2,5-dien-1-one fragment has an sc orientation with respect to the C11—C12 bond. The C23—N5—C11—C12 torsion angle is 63.0 (5)°. Unexpectedly, the dihydrocycle C23—C28 has a flattened sofa conformation and the deviation of atom C26 from the mean-squares plane of the other ring atoms is only −0.090 (6) Å, despite the presence of two tert-butyl groups. It was shown by Shishkin (1997) that similar partly hydrogenated rings with exocyclic double bonds possess high conformational flexibility and the presence of bulky substituents often gives rise to distinct non-planar conformations of such rings. The steric strain in this fragment of (I) is confirmed by a number shortened intramolecular contacts, listed in Table 1. Nevertheless, nearly symmetrical steric interactions between the atoms of a dihydrocycle and several substituents could result in planarity of the ring (Borbulevych et al., 2000). Apparently, a similar situation occurs in (I), since the positions of the tert-butyl groups are symmetrical relative to the C23—C26 direction.

Overall, in the crystal phase, compound (I) is found to be in the ring-opened form. But, clearly, the break and formation of the N5—C8 bond is a key stage of the ring-chain isomerization of (I); the distance between these two atoms [2.813 (5) Å] is shorter than the sum of the van der Waals radii of N and C (Table 2). However, it is impossible to reach any conclusion about the nature of this interaction based only on the consideration of the distance between atoms N5 and C8. This interaction could be either a bonding or a non-bonding one.

To determine the nature of such intramolecular interactions, a topological analysis in the framework of Bader's `atoms in molecules' (AIM) theory (Bader, 1990) was applied in the present study. According to this theory, the structure of a many-electron system with a given nuclear configuration R is completely determined by a set and types of critical points of the charge density ρ(r,R) where the gradient of the charge density vanishes [\nablaρ(r) = 0]. The second derivatives of ρ(r) calculated at these points comprise a real symmetrical Hessian matrix and the eigenvalues of the Hessian determine a type of the critical point (Bader, 1990).

Critical points of the (3,-1) Or (3, 1)? type, or so-called bond critical points, which determine bonding interactions between two atoms of the molecular system, are of prime importance from the chemical standpoint. Their presence is a necessary condition for chemical bonding. It is believed that a bonding interaction occurs between two atoms if there is a line (bonding path) linking their nuclei along which the charge density has a maximum with respect to any lateral shift, and which has a minimum at the bond critical point (3,-1). Such a (3, −1) critical point in the region of the N5···C8 contact was revealed (Table 2). This indicates a strong attractive interaction between these atoms in the crystal of (I). In the AIM theory, this interaction is classified as a so-called interaction of closed shells, since the Laplacian of the charge density \nabla²ρ(r), which is determined as a sum of the eigenvalues of the Hessian, at this (3, −1) critical point is positive. Moreover, a series of other shortened attractive intramolecular contacts characterized by (3,-1) critical points has been found in (I) (Table 2). Most of them are intramolecular C—H···O or C—H···N contacts.

It is of note that the values found for ρ(r) (0.09–0.11 e ų) at the critical points for intramolecular C—H···O contacts (Table 2) are twice as large as those for intermolecular hydrogen bonds studied previously (Koch & Popelier, 1995; Coppens et al., 1999; Borbulevych et al., 1998). It is likely that the four C—H···O interactions involving atom O7 of the carbonyl group in (I) favour planarity of the C23—C28 dihydrocycle.

For long time, the van der Waals radii concept (Bondi, 1964; Zefirov & Zorky, 1989) has been a common approach for the consideration of non-bonded interactions. Moreover, it was suggested recently that mean statistical contacts (Rowland & Taylor, 1996) be used for this purpose. However, none of these approaches gives a valid conclusion about the nature of shortened contacts and, in general, attractive and repulsive interactions cannot be distinguished. On the other hand, the attractive bonding character of shortened contacts can be unambiguously established by topological analysis of the charge density, as has been demonstrated in the present study.

S2. Experimental

The procedure used for the synthesis of (I) was as follows. A mixture of the thallium salt of N-{2-[(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)amino]phenyl}-1- phenylmethanesulfonamide, (II) (0.34 g, 0.5 mmol), 8-chloro-5,7-dinitroquinoline (0.13 g, 0.5 mmol) obtained by the procedure of Khilkova et al. (1992) and pyridine (0.049 g, 0.6 mmol) in acetonitrile (10 ml) was boiled for 30 min. The ThCl precipitate was filtered out and the filtrate was concentrated by evaporation. Compound (I) was separated by a chromatographic method. Red crystals of (I) of m.p. 508 K (decomposition) were obtained by recrystallization from 2-butanol (yield 18%, 0.06 g). The ¹H NMR spectrum of (I) was recorded using a Bruker-DPX-250 spectrometer, with trimethylsulfoxide as the internal standard. Spectroscopic analysis: ¹H NMR (acetone-d6, 250 MHz, δ, p.p.m): 1.06 (s, 9H, ^tBu at C25), 1.14 (s, 9H, ^tBu at C33,), 5.17 (d, 1H, CH2, J = 13.1 Hz), 6.00 (d, 1H, CH2, J = 13.2 Hz), 5.81 (d, 1H, H24, J = 2.5 Hz), 6.27 (d, 1H, H28, J = 2.5 Hz), 6.58 (dd, 1H H15, J = 7.7 and 1.5 Hz), 7.24–7.40 (m, 5H, Ph), 7.56–7.60 (m, 2H, H13, H14), 8.15 (dd, 1H, H12, J = 11.2 and 2.7 Hz), 8.18 (dd, 1H, H2, J = 8.8 and 4.0 Hz), 8.67 (s, 1H, H6), 9.04 (dd, 1H, H3, J = 8.8 and 1.5 Hz), 9.65 (dd, 1H, H1, J = 4.0 and 1.5 Hz). Compound (II) was obtained from the reaction between N-(2-aminophenyl)-1-phenylmethanesulfonamide (3 g, 11.45 mmol) (Olekhnovich et al., 1992) and 2,6-di-tert-butylbenzo-1,4-quinone (2.52 g, 11.45 mmol) (Ley & Miller, 1956) in 2-propanol (50 ml). The mixture was boiled for 8 h and then cooled. After 12 h, the precipitate of (II) was filtered. Compound (II) was purified by a chromatographic method and then recrystallized from i-amil alcohol Not known - please clarify. Red crystals of (II) were obtained (m.p. 446 K; yield 62%, 3.3 g). The synthesis procedure for the thallium salt of (II) was as follows. Compound (II) (0.26 g, 0.6 mmol) was added to a solution of KOH (0.4 g, 0.7 mmol) in methanol (20 ml). Thallium(I) acetate (0.18 g, 0.7 mmol) in methanol (5 ml) was added to the resulting solution. The mixture was stirred for 30 min, and then the precipitate was filtered and dried in vacuuo. Violet crystals were obtained (m.p. 483 K; yield 97%, 0.36 g).

S3. Refinement

No Friedel pairs were measured in the data collection. All H atoms were located from difference Fourier syntheses. Methyl H atoms were allowed for as part of a rigid group, which was allowed to rotate but not tip or distort, with U_iso(H) = 1.5U_eq(C). The other H atoms were allowed for using a riding model, with U_iso(H) = 1.2_Ueq(C,N). The following distance constraints were applied: C—H(methylene) = 0.99, C—H(methyl) = 0.98, C—H(arom) = 0.95 and other C—H =0.95 Å. The quantum-chemical calculations for (I) were performed at the B3LYP/6–31G** level using the GAUSSIAN98 package (Frisch et al., 1998). The geometry of (I) was taken from the present X-ray data without optimization. The topological analysis of the theoretical charge-density distribution was carried out using the EXTREME program incorporated in the AIMPAC program package (Biegler-König et al., 1982).

Computing details

Data collection: P3 (Siemens, 1989); cell refinement: P3; data reduction: PROFIT (Strel'tsov & Zavodnik, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the molecule of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.

N-{2-[(3,5-Di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)amino]phenyl}- N-(5,7-dinitroquinolin-8-yl)-1-phenylmethanesulfonamide

Crystal data

C36H35N5O7S	F(000) = 1432
Mr = 681.75	Dx = 1.331 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 24 reflections
a = 12.227 (4) Å	θ = 10–11°
b = 12.936 (3) Å	µ = 0.15 mm^−1
c = 21.510 (6) Å	T = 193 K
V = 3402.1 (16) Å^3	Prism, red
Z = 4	0.40 × 0.20 × 0.20 mm

Data collection

Syntex P21/PC diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.8°
Graphite monochromator	h = 0→14
θ/2θ scans	k = 0→15
3328 measured reflections	l = 0→25
3328 independent reflections	2 standard reflections every 98 reflections
2836 reflections with I > 2σ(I)	intensity decay: 4.2%

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)] = 0.048	Hydrogen site location: difference Fourier map
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0604P)^2 + 1.2304P] where P = (Fo^2 + 2Fc^2)/3
3328 reflections	(Δ/σ)max < 0.001
448 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.36 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
S1	0.48553 (8)	0.17769 (7)	0.64517 (4)	0.0354 (2)
N1	0.7428 (3)	0.1953 (3)	0.66784 (15)	0.0444 (9)
N2	0.8247 (3)	0.5189 (4)	0.7822 (2)	0.0673 (12)
N3	0.4919 (3)	0.4845 (3)	0.66387 (16)	0.0426 (8)
N4	0.5516 (3)	0.2840 (2)	0.62202 (13)	0.0323 (7)
N5	0.7299 (2)	0.3580 (2)	0.55226 (14)	0.0342 (7)
O1	0.8775 (4)	0.4782 (4)	0.8240 (2)	0.1105 (17)
O2	0.8251 (4)	0.6112 (4)	0.7710 (2)	0.0910 (13)
O3	0.4975 (3)	0.5675 (2)	0.63801 (17)	0.0652 (9)
O4	0.4070 (2)	0.4387 (3)	0.67532 (17)	0.0592 (9)
O5	0.3725 (2)	0.1866 (2)	0.63189 (15)	0.0496 (7)
O6	0.5184 (2)	0.1607 (2)	0.70834 (11)	0.0436 (7)
O7	1.0101 (3)	0.6537 (2)	0.62182 (18)	0.0700 (10)
C1	0.8348 (3)	0.1538 (4)	0.6868 (2)	0.0508 (11)
H1	0.8525	0.0862	0.6727	0.061*
C2	0.9075 (4)	0.2032 (5)	0.7261 (2)	0.0676 (16)
H2	0.9732	0.1693	0.7380	0.081*
C3	0.8860 (4)	0.2996 (4)	0.74771 (19)	0.0559 (13)
H3	0.9356	0.3335	0.7749	0.067*
C4	0.7875 (3)	0.3485 (3)	0.72885 (18)	0.0420 (10)
C5	0.7556 (3)	0.4521 (4)	0.74318 (17)	0.0451 (11)
C6	0.6627 (3)	0.4962 (3)	0.72088 (18)	0.0419 (10)
H6	0.6451	0.5661	0.7300	0.050*
C7	0.5939 (3)	0.4356 (3)	0.68418 (17)	0.0336 (8)
C8	0.6185 (3)	0.3364 (3)	0.66595 (16)	0.0315 (8)
C9	0.7182 (3)	0.2916 (3)	0.68813 (17)	0.0379 (9)
C10	0.5325 (3)	0.3312 (3)	0.56198 (16)	0.0313 (8)
C11	0.6221 (3)	0.3732 (3)	0.53008 (16)	0.0306 (8)
C12	0.6043 (3)	0.4208 (3)	0.47207 (18)	0.0392 (9)
H12	0.6642	0.4510	0.4505	0.047*
C13	0.5009 (3)	0.4243 (3)	0.44600 (18)	0.0445 (10)
H13	0.4900	0.4555	0.4065	0.053*
C14	0.4137 (3)	0.3821 (3)	0.47790 (18)	0.0437 (10)
H14	0.3424	0.3844	0.4603	0.052*
C15	0.4297 (3)	0.3359 (3)	0.53578 (18)	0.0381 (9)
H15	0.3691	0.3074	0.5574	0.046*
C16	0.5407 (4)	0.0787 (3)	0.59685 (17)	0.0398 (9)
H16A	0.5239	0.0934	0.5527	0.048*
H16B	0.6212	0.0757	0.6017	0.048*
C17	0.4906 (4)	−0.0227 (3)	0.61572 (17)	0.0422 (10)
C18	0.5424 (5)	−0.0816 (4)	0.6612 (2)	0.0579 (13)
H18	0.6093	−0.0587	0.6790	0.070*
C19	0.4956 (6)	−0.1737 (4)	0.6803 (3)	0.078 (2)
H19	0.5320	−0.2148	0.7105	0.094*
C20	0.3996 (7)	−0.2059 (4)	0.6569 (3)	0.091 (2)
H20	0.3684	−0.2690	0.6709	0.109*
C21	0.3461 (6)	−0.1471 (5)	0.6125 (3)	0.084 (2)
H21	0.2779	−0.1695	0.5962	0.101*
C22	0.3922 (4)	−0.0561 (4)	0.5919 (2)	0.0591 (13)
H22	0.3559	−0.0161	0.5612	0.071*
C23	0.7949 (3)	0.4345 (3)	0.56411 (16)	0.0316 (8)
C24	0.9064 (3)	0.4075 (3)	0.58047 (16)	0.0338 (8)
H24	0.9265	0.3366	0.5800	0.041*
C25	0.9824 (3)	0.4771 (3)	0.59618 (16)	0.0344 (8)
C26	0.9479 (3)	0.5895 (3)	0.60042 (19)	0.0408 (10)
C27	0.8349 (3)	0.6189 (3)	0.57942 (18)	0.0383 (9)
C28	0.7651 (3)	0.5441 (3)	0.56344 (17)	0.0328 (8)
H28	0.6932	0.5628	0.5511	0.039*
C29	1.1001 (3)	0.4487 (3)	0.61219 (19)	0.0391 (9)
C30	1.1797 (3)	0.5102 (4)	0.5705 (2)	0.0502 (11)
H30A	1.2552	0.4926	0.5815	0.075*
H30B	1.1679	0.5844	0.5767	0.075*
H30C	1.1665	0.4926	0.5268	0.075*
C31	1.1243 (4)	0.4745 (5)	0.6814 (2)	0.0612 (14)
H31A	1.1992	0.4535	0.6916	0.092*
H31B	1.0728	0.4371	0.7081	0.092*
H31C	1.1162	0.5490	0.6881	0.092*
C32	1.1199 (3)	0.3323 (4)	0.6024 (2)	0.0533 (11)
H32A	1.1958	0.3155	0.6130	0.080*
H32B	1.1062	0.3145	0.5588	0.080*
H32C	1.0704	0.2927	0.6292	0.080*
C33	0.8065 (4)	0.7346 (3)	0.5778 (2)	0.0457 (10)
C34	0.8074 (4)	0.7795 (4)	0.6448 (2)	0.0645 (14)
H34A	0.7901	0.8534	0.6434	0.097*
H34B	0.8800	0.7697	0.6633	0.097*
H34C	0.7527	0.7435	0.6702	0.097*
C35	0.8875 (4)	0.7952 (4)	0.5374 (3)	0.0676 (15)
H35A	0.8622	0.8667	0.5330	0.101*
H35B	0.8922	0.7630	0.4963	0.101*
H35C	0.9598	0.7946	0.5571	0.101*
C36	0.6907 (4)	0.7510 (3)	0.5516 (2)	0.0538 (12)
H36A	0.6738	0.8251	0.5509	0.081*
H36B	0.6375	0.7151	0.5779	0.081*
H36C	0.6869	0.7233	0.5092	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0408 (5)	0.0300 (4)	0.0355 (5)	−0.0009 (4)	0.0071 (4)	−0.0004 (4)
N1	0.046 (2)	0.055 (2)	0.0329 (16)	0.0137 (17)	0.0048 (15)	0.0087 (16)
N2	0.054 (3)	0.096 (4)	0.052 (2)	−0.021 (3)	−0.008 (2)	−0.009 (3)
N3	0.038 (2)	0.0393 (19)	0.0507 (19)	0.0024 (17)	0.0025 (17)	−0.0117 (16)
N4	0.0361 (17)	0.0328 (15)	0.0280 (14)	−0.0020 (14)	0.0020 (13)	0.0035 (13)
N5	0.0321 (16)	0.0388 (18)	0.0317 (16)	−0.0027 (15)	−0.0014 (14)	0.0018 (14)
O1	0.117 (4)	0.134 (4)	0.080 (3)	−0.011 (3)	−0.058 (3)	−0.016 (3)
O2	0.087 (3)	0.090 (3)	0.096 (3)	−0.037 (3)	−0.016 (3)	−0.012 (3)
O3	0.074 (2)	0.0366 (16)	0.085 (2)	0.0103 (17)	−0.005 (2)	0.0068 (17)
O4	0.0345 (17)	0.069 (2)	0.074 (2)	0.0033 (16)	0.0016 (16)	−0.0020 (19)
O5	0.0407 (15)	0.0364 (15)	0.072 (2)	−0.0057 (12)	0.0084 (15)	0.0071 (15)
O6	0.0624 (18)	0.0384 (14)	0.0299 (13)	0.0023 (14)	0.0102 (13)	0.0001 (11)
O7	0.0423 (17)	0.0570 (19)	0.111 (3)	0.0027 (16)	−0.0236 (18)	−0.036 (2)
C1	0.043 (2)	0.067 (3)	0.042 (2)	0.019 (2)	0.007 (2)	0.018 (2)
C2	0.045 (3)	0.099 (4)	0.059 (3)	0.023 (3)	0.004 (2)	0.036 (3)
C3	0.043 (2)	0.089 (4)	0.035 (2)	0.000 (3)	−0.0060 (19)	0.016 (2)
C4	0.033 (2)	0.064 (3)	0.0290 (19)	−0.007 (2)	0.0004 (17)	0.0111 (19)
C5	0.041 (2)	0.065 (3)	0.029 (2)	−0.019 (2)	−0.0002 (18)	−0.0021 (19)
C6	0.043 (2)	0.043 (2)	0.040 (2)	−0.0084 (19)	0.0063 (19)	−0.0074 (18)
C7	0.029 (2)	0.041 (2)	0.0312 (19)	−0.0032 (17)	0.0034 (15)	−0.0004 (17)
C8	0.0310 (18)	0.0359 (19)	0.0276 (17)	−0.0017 (17)	0.0052 (15)	0.0034 (15)
C9	0.035 (2)	0.052 (2)	0.0268 (18)	0.0012 (19)	0.0039 (16)	0.0099 (17)
C10	0.0371 (19)	0.0234 (16)	0.0334 (18)	0.0031 (16)	−0.0005 (16)	−0.0005 (15)
C11	0.0324 (19)	0.0287 (17)	0.0309 (18)	−0.0016 (16)	−0.0012 (16)	−0.0030 (16)
C12	0.040 (2)	0.044 (2)	0.034 (2)	−0.0060 (19)	−0.0029 (18)	0.0076 (18)
C13	0.049 (2)	0.051 (2)	0.0342 (19)	−0.002 (2)	−0.0070 (19)	0.0038 (18)
C14	0.037 (2)	0.056 (3)	0.038 (2)	0.003 (2)	−0.0085 (18)	0.004 (2)
C15	0.034 (2)	0.043 (2)	0.037 (2)	0.0054 (19)	0.0009 (17)	−0.0004 (18)
C16	0.054 (3)	0.035 (2)	0.0299 (19)	0.0023 (19)	0.0047 (18)	−0.0028 (16)
C17	0.069 (3)	0.0300 (18)	0.0280 (18)	0.010 (2)	0.009 (2)	−0.0021 (16)
C18	0.073 (3)	0.053 (3)	0.047 (2)	0.024 (2)	0.014 (2)	0.000 (2)
C19	0.132 (6)	0.040 (3)	0.063 (3)	0.024 (4)	0.049 (4)	0.018 (2)
C20	0.145 (6)	0.031 (3)	0.098 (5)	−0.008 (4)	0.082 (5)	−0.009 (3)
C21	0.115 (5)	0.056 (3)	0.081 (4)	−0.025 (4)	0.032 (4)	−0.032 (3)
C22	0.083 (4)	0.052 (3)	0.042 (2)	−0.015 (3)	−0.004 (2)	−0.009 (2)
C23	0.0300 (19)	0.038 (2)	0.0263 (18)	−0.0014 (17)	0.0021 (15)	0.0021 (15)
C24	0.032 (2)	0.0368 (19)	0.0329 (19)	0.0021 (17)	0.0032 (16)	0.0023 (16)
C25	0.032 (2)	0.044 (2)	0.0273 (17)	0.0010 (18)	0.0000 (16)	−0.0050 (16)
C26	0.032 (2)	0.047 (2)	0.043 (2)	−0.0061 (19)	0.0008 (18)	−0.0125 (19)
C27	0.038 (2)	0.044 (2)	0.0335 (19)	0.0042 (18)	0.0017 (17)	−0.0080 (18)
C28	0.0273 (19)	0.036 (2)	0.0346 (19)	−0.0016 (16)	−0.0015 (16)	0.0013 (16)
C29	0.0272 (19)	0.048 (2)	0.042 (2)	0.0008 (18)	0.0029 (17)	−0.0030 (19)
C30	0.030 (2)	0.063 (3)	0.058 (3)	−0.006 (2)	0.002 (2)	0.001 (2)
C31	0.039 (2)	0.097 (4)	0.048 (3)	0.000 (3)	−0.009 (2)	−0.004 (3)
C32	0.032 (2)	0.058 (3)	0.069 (3)	0.006 (2)	−0.005 (2)	0.005 (2)
C33	0.053 (3)	0.033 (2)	0.051 (2)	0.0020 (19)	−0.002 (2)	−0.0072 (19)
C34	0.070 (3)	0.055 (3)	0.068 (3)	0.018 (3)	−0.016 (3)	−0.031 (3)
C35	0.072 (3)	0.045 (3)	0.086 (4)	−0.009 (3)	0.009 (3)	−0.007 (3)
C36	0.058 (3)	0.041 (2)	0.062 (3)	0.007 (2)	−0.012 (2)	−0.002 (2)

Geometric parameters (Å, º)

S1—O5	1.416 (3)	C17—C18	1.393 (6)
S1—O6	1.434 (3)	C18—C19	1.384 (8)
S1—N4	1.670 (3)	C18—H18	0.9500
S1—C16	1.782 (4)	C19—C20	1.342 (10)
N1—C1	1.312 (5)	C19—H19	0.9500
N1—C9	1.354 (5)	C20—C21	1.385 (10)
N2—O2	1.218 (6)	C20—H20	0.9500
N2—O1	1.225 (6)	C21—C22	1.379 (8)
N2—C5	1.472 (6)	C21—H21	0.9500
N3—O3	1.211 (4)	C22—H22	0.9500
N3—O4	1.221 (4)	C23—C24	1.451 (5)
N3—C7	1.465 (5)	C23—C28	1.464 (5)
N4—C8	1.423 (5)	C24—C25	1.337 (5)
N4—C10	1.448 (5)	C24—H24	0.9500
N5—C23	1.294 (5)	C25—C26	1.516 (6)
N5—C11	1.416 (5)	C25—C29	1.524 (5)
O7—C26	1.217 (5)	C26—C27	1.503 (6)
C1—C2	1.383 (7)	C27—C28	1.335 (5)
C1—H1	0.9500	C27—C33	1.537 (6)
C2—C3	1.357 (7)	C28—H28	0.9500
C2—H2	0.9500	C29—C32	1.540 (6)
C3—C4	1.419 (6)	C29—C30	1.544 (6)
C3—H3	0.9500	C29—C31	1.553 (6)
C4—C9	1.424 (6)	C30—H30A	0.9800
C4—C5	1.431 (6)	C30—H30B	0.9800
C5—C6	1.358 (6)	C30—H30C	0.9800
C6—C7	1.395 (5)	C31—H31A	0.9800
C6—H6	0.9500	C31—H31B	0.9800
C7—C8	1.375 (5)	C31—H31C	0.9800
C8—C9	1.431 (5)	C32—H32A	0.9800
C10—C15	1.378 (5)	C32—H32B	0.9800
C10—C11	1.402 (5)	C32—H32C	0.9800
C11—C12	1.408 (5)	C33—C35	1.533 (7)
C12—C13	1.385 (6)	C33—C36	1.540 (6)
C12—H12	0.9500	C33—C34	1.554 (6)
C13—C14	1.381 (6)	C34—H34A	0.9800
C13—H13	0.9500	C34—H34B	0.9800
C14—C15	1.394 (6)	C34—H34C	0.9800
C14—H14	0.9500	C35—H35A	0.9800
C15—H15	0.9500	C35—H35B	0.9800
C16—C17	1.504 (5)	C35—H35C	0.9800
C16—H16A	0.9900	C36—H36A	0.9800
C16—H16B	0.9900	C36—H36B	0.9800
C17—C22	1.377 (7)	C36—H36C	0.9800
C24···H32B	2.76	C28···H36B	2.72
C24···H32C	2.71	C28···H36C	2.77
C26···H30B	2.74	C32···H24	2.41
C26···H34B	2.82	C36···H28	2.43
C26···H35C	2.82
O5—S1—O6	118.51 (18)	C18—C19—H19	119.4
O5—S1—N4	110.17 (16)	C19—C20—C21	120.1 (5)
O6—S1—N4	105.86 (17)	C19—C20—H20	120.0
O5—S1—C16	108.1 (2)	C21—C20—H20	120.0
O6—S1—C16	109.64 (17)	C22—C21—C20	119.8 (6)
N4—S1—C16	103.57 (17)	C22—C21—H21	120.1
C1—N1—C9	117.9 (4)	C20—C21—H21	120.1
O2—N2—O1	124.3 (5)	C17—C22—C21	120.4 (5)
O2—N2—C5	117.7 (5)	C17—C22—H22	119.8
O1—N2—C5	117.9 (5)	C21—C22—H22	119.8
O3—N3—O4	124.8 (4)	N5—C23—C24	116.1 (3)
O3—N3—C7	118.2 (4)	N5—C23—C28	125.9 (3)
O4—N3—C7	117.0 (3)	C24—C23—C28	118.0 (3)
C8—N4—C10	118.9 (3)	C25—C24—C23	123.5 (4)
C8—N4—S1	118.2 (2)	C25—C24—H24	118.2
C10—N4—S1	122.4 (2)	C23—C24—H24	118.2
C23—N5—C11	122.1 (3)	C24—C25—C26	117.9 (3)
N1—C1—C2	123.5 (5)	C24—C25—C29	123.4 (4)
N1—C1—H1	118.3	C26—C25—C29	118.7 (3)
C2—C1—H1	118.3	O7—C26—C27	121.0 (4)
C3—C2—C1	120.6 (4)	O7—C26—C25	120.3 (4)
C3—C2—H2	119.7	C27—C26—C25	118.7 (3)
C1—C2—H2	119.7	C28—C27—C26	118.8 (4)
C2—C3—C4	118.5 (5)	C28—C27—C33	123.7 (4)
C2—C3—H3	120.8	C26—C27—C33	117.5 (4)
C4—C3—H3	120.8	C27—C28—C23	122.7 (4)
C3—C4—C9	116.8 (4)	C27—C28—H28	118.6
C3—C4—C5	126.0 (4)	C23—C28—H28	118.6
C9—C4—C5	117.0 (4)	C25—C29—C32	110.7 (3)
C6—C5—C4	123.1 (4)	C25—C29—C30	109.9 (3)
C6—C5—N2	115.8 (4)	C32—C29—C30	109.0 (4)
C4—C5—N2	121.1 (4)	C25—C29—C31	110.2 (3)
C5—C6—C7	117.9 (4)	C32—C29—C31	108.1 (4)
C5—C6—H6	121.1	C30—C29—C31	109.0 (4)
C7—C6—H6	121.1	C29—C30—H30A	109.5
C8—C7—C6	123.7 (4)	C29—C30—H30B	109.5
C8—C7—N3	120.3 (3)	H30A—C30—H30B	109.5
C6—C7—N3	116.0 (3)	C29—C30—H30C	109.5
C7—C8—N4	120.6 (3)	H30A—C30—H30C	109.5
C7—C8—C9	118.0 (4)	H30B—C30—H30C	109.5
N4—C8—C9	121.2 (3)	C29—C31—H31A	109.5
N1—C9—C4	122.8 (4)	C29—C31—H31B	109.5
N1—C9—C8	117.0 (4)	H31A—C31—H31B	109.5
C4—C9—C8	120.2 (4)	C29—C31—H31C	109.5
C15—C10—C11	119.7 (3)	H31A—C31—H31C	109.5
C15—C10—N4	122.0 (3)	H31B—C31—H31C	109.5
C11—C10—N4	118.3 (3)	C29—C32—H32A	109.5
C10—C11—C12	118.9 (3)	C29—C32—H32B	109.5
C10—C11—N5	120.6 (3)	H32A—C32—H32B	109.5
C12—C11—N5	120.2 (3)	C29—C32—H32C	109.5
C13—C12—C11	120.9 (4)	H32A—C32—H32C	109.5
C13—C12—H12	119.5	H32B—C32—H32C	109.5
C11—C12—H12	119.5	C35—C33—C27	111.4 (4)
C14—C13—C12	119.4 (4)	C35—C33—C36	108.4 (4)
C14—C13—H13	120.3	C27—C33—C36	110.5 (3)
C12—C13—H13	120.3	C35—C33—C34	109.3 (4)
C13—C14—C15	120.3 (4)	C27—C33—C34	110.0 (4)
C13—C14—H14	119.9	C36—C33—C34	107.2 (4)
C15—C14—H14	119.9	C33—C34—H34A	109.5
C10—C15—C14	120.8 (4)	C33—C34—H34B	109.5
C10—C15—H15	119.6	H34A—C34—H34B	109.5
C14—C15—H15	119.6	C33—C34—H34C	109.5
C17—C16—S1	108.4 (3)	H34A—C34—H34C	109.5
C17—C16—H16A	110.0	H34B—C34—H34C	109.5
S1—C16—H16A	110.0	C33—C35—H35A	109.5
C17—C16—H16B	110.0	C33—C35—H35B	109.5
S1—C16—H16B	110.0	H35A—C35—H35B	109.5
H16A—C16—H16B	108.4	C33—C35—H35C	109.5
C22—C17—C18	119.2 (4)	H35A—C35—H35C	109.5
C22—C17—C16	122.0 (4)	H35B—C35—H35C	109.5
C18—C17—C16	118.8 (4)	C33—C36—H36A	109.5
C19—C18—C17	119.4 (6)	C33—C36—H36B	109.5
C19—C18—H18	120.3	H36A—C36—H36B	109.5
C17—C18—H18	120.3	C33—C36—H36C	109.5
C20—C19—C18	121.2 (6)	H36A—C36—H36C	109.5
C20—C19—H19	119.4	H36B—C36—H36C	109.5
O5—S1—N4—C8	126.7 (3)	C23—N5—C11—C10	−124.1 (4)
O6—S1—N4—C8	−2.6 (3)	C23—N5—C11—C12	63.0 (5)
C16—S1—N4—C8	−117.9 (3)	C10—C11—C12—C13	−1.5 (6)
O5—S1—N4—C10	−45.4 (3)	N5—C11—C12—C13	171.6 (4)
O6—S1—N4—C10	−174.7 (3)	C11—C12—C13—C14	1.1 (6)
C16—S1—N4—C10	70.0 (3)	C12—C13—C14—C15	−0.2 (6)
C9—N1—C1—C2	−0.1 (6)	C11—C10—C15—C14	−0.1 (6)
N1—C1—C2—C3	0.3 (7)	N4—C10—C15—C14	179.9 (4)
C1—C2—C3—C4	−0.3 (7)	C13—C14—C15—C10	−0.3 (6)
C2—C3—C4—C9	0.0 (6)	O5—S1—C16—C17	−65.8 (3)
C2—C3—C4—C5	−175.0 (4)	O6—S1—C16—C17	64.7 (3)
C3—C4—C5—C6	176.4 (4)	N4—S1—C16—C17	177.4 (3)
C9—C4—C5—C6	1.4 (5)	S1—C16—C17—C22	86.1 (4)
C3—C4—C5—N2	−1.8 (6)	S1—C16—C17—C18	−90.2 (4)
C9—C4—C5—N2	−176.8 (4)	C22—C17—C18—C19	1.8 (6)
O2—N2—C5—C6	−31.4 (6)	C16—C17—C18—C19	178.2 (4)
O1—N2—C5—C6	148.2 (5)	C17—C18—C19—C20	−1.8 (7)
O2—N2—C5—C4	146.9 (5)	C18—C19—C20—C21	0.6 (8)
O1—N2—C5—C4	−33.5 (6)	C19—C20—C21—C22	0.6 (8)
C4—C5—C6—C7	2.4 (6)	C18—C17—C22—C21	−0.6 (6)
N2—C5—C6—C7	−179.3 (4)	C16—C17—C22—C21	−176.9 (4)
C5—C6—C7—C8	−4.6 (6)	C20—C21—C22—C17	−0.6 (7)
C5—C6—C7—N3	176.9 (3)	C11—N5—C23—C24	−173.9 (3)
O3—N3—C7—C8	−125.8 (4)	C11—N5—C23—C28	7.2 (6)
O4—N3—C7—C8	55.3 (5)	N5—C23—C24—C25	−177.5 (3)
O3—N3—C7—C6	52.7 (5)	C28—C23—C24—C25	1.5 (5)
O4—N3—C7—C6	−126.2 (4)	C23—C24—C25—C26	3.4 (5)
C6—C7—C8—N4	−171.8 (3)	C23—C24—C25—C29	−178.8 (3)
N3—C7—C8—N4	6.7 (5)	C24—C25—C26—O7	170.9 (4)
C6—C7—C8—C9	2.7 (5)	C29—C25—C26—O7	−6.9 (6)
N3—C7—C8—C9	−178.8 (3)	C24—C25—C26—C27	−7.4 (5)
C10—N4—C8—C7	56.0 (4)	C29—C25—C26—C27	174.8 (3)
S1—N4—C8—C7	−116.4 (3)	O7—C26—C27—C28	−171.9 (4)
C10—N4—C8—C9	−118.3 (4)	C25—C26—C27—C28	6.4 (6)
S1—N4—C8—C9	69.3 (4)	O7—C26—C27—C33	8.0 (6)
C1—N1—C9—C4	−0.2 (5)	C25—C26—C27—C33	−173.8 (4)
C1—N1—C9—C8	178.7 (3)	C26—C27—C28—C23	−1.5 (6)
C3—C4—C9—N1	0.2 (5)	C33—C27—C28—C23	178.7 (4)
C5—C4—C9—N1	175.7 (3)	N5—C23—C28—C27	176.3 (4)
C3—C4—C9—C8	−178.7 (3)	C24—C23—C28—C27	−2.6 (6)
C5—C4—C9—C8	−3.2 (5)	C24—C25—C29—C32	4.7 (5)
C7—C8—C9—N1	−177.7 (3)	C26—C25—C29—C32	−177.6 (4)
N4—C8—C9—N1	−3.2 (5)	C24—C25—C29—C30	125.1 (4)
C7—C8—C9—C4	1.3 (5)	C26—C25—C29—C30	−57.2 (5)
N4—C8—C9—C4	175.8 (3)	C24—C25—C29—C31	−114.8 (4)
C8—N4—C10—C15	−134.3 (4)	C26—C25—C29—C31	62.9 (5)
S1—N4—C10—C15	37.7 (5)	C28—C27—C33—C35	−124.1 (4)
C8—N4—C10—C11	45.6 (5)	C26—C27—C33—C35	56.0 (5)
S1—N4—C10—C11	−142.3 (3)	C28—C27—C33—C36	−3.6 (6)
C15—C10—C11—C12	1.0 (5)	C26—C27—C33—C36	176.6 (3)
N4—C10—C11—C12	−179.0 (3)	C28—C27—C33—C34	114.5 (5)
C15—C10—C11—N5	−172.1 (3)	C26—C27—C33—C34	−65.3 (5)
N4—C10—C11—N5	7.9 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2^i	0.95	2.59	3.480 (7)	157
C13—H13···O1^ii	0.95	2.55	3.269 (6)	133
C19—H19···O6^iii	0.95	2.45	3.218 (7)	137
C31—H31A···O4^iv	0.98	2.57	3.490 (6)	156

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