4′-(4-Chloro­phenyl)-3′'-ethyl-1′-methyl-1H-indole-3-spiro-2′-pyrrolidine-3′-spiro-5′′-[1,3]­thia­zole-2(3H),2′′(3′′H),4′′(5′′H)-trione benzene sesquisolvate

The title compound, C₂₂H₂₀ClN₃O₃S·1.5C₆H₆, was synthesized by the intermolecular [3 + 2]-cyclo­addition of azomethine yl­ide, derived from isatin and sarcosine by a de­carboxyl­ative route, and 5-(4-chloro­benzyl­idene)-3-ethyl­thia­zolidine-2,4-dione. In the mol­ecule of the title compound, an approximately planar 2-ox­indole system, a pyrrolidine ring in an envelope conformation, and a planar thia­zolidine ring are joined via two spiro-junctions. The mol­ecules in the crystal are linked by an intermolecular N—H...N hydrogen bond [N...N = 3.071 (3) Å], forming infinite chains running along the c axis. One of the solvate benzene mol­ecules occupies a special position on an inversion centre.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in solvent or counterion
• R factor = 0.057
• wR factor = 0.155
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.98

Alert level C
ABSMU01_ALERT_1_C  The ratio of given/expected absorption coefficient lies
               outside the range 0.99 <> 1.01
            Calculated value of mu =     0.237
            Value of mu given      =     0.240
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.796     0.923
            Tmin' and Tmax expected:      0.902     0.922
            RR' =      0.882
            Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.88
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT165_ALERT_3_C Nr. of Status R Flagged Non-Hydrogen Atoms .....          6
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.60 Ratio
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        C13
PLAT243_ALERT_4_C High Solvent U(eq) as Compared to Neighbors ....        C27
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        C30
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        C23
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        C26
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      33.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  14 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

Spiro-compounds represent an important class of naturally occurring substances, which in many cases exhibit interesting biological properties (Kobayashi et al., 1991; James et al., 1991). 1,3-Dipolar cycloaddition reactions are widely used for the construction of spiro-compounds (Caramella & Grunanger, 1984). In this paper, the structure of the title compound, (I), is reported. The compound was synthesized by the intermolecular [3 + 2]-cycloaddition of azomethine ylide, derived from isatin and sarcosine by a decarboxylative route, and 5-(4-chloro-benzylidene)-3-ethylthiazolidine-2,4-dione.

The molecular structure of (I) is shown in Fig. 1. The molecule involves a chain of 2-oxindole, pyrrolidine, and thiazolidine moieties, joined via two spiro-junctions. The pyrrolidine ring N2—C5—C4—C3—C6 has an envelope conformation; atom N2 is displaced by 0.618 (3) Å from the mean plane of the C5/C4/C3/C6 atoms [plane A; maximum deviation of the C4 atom is 0.031 (3) Å]. The C5/N2/C6 plane forms a dihedral angle of 135.6 (2)° with plane A, whereas the dihedral angle of the latter with the mean plane of the phenyl ring (C10–C15) is 76.7 (3)°. Both bicyclic indole system and thiazolidine ring are almost planar [maximum deviations of atoms C17 and C2 from their respective mean planes are 0.035 (3) and 0.041 (4) Å]; their planes are approximately orthogonal to the bottom plane of the pyrrolidine cycle (plane A); the dihedral angles are equal to 78.3 (2) and 88.7 (3)°, respectively. Atoms O1 and O2 are displaced from the mean plane of the thiazolidine cycle by 0.027 (2) and −0.155 (2) Å, respectively.

There is one `active' H atom in the molecule which participates in the intermolecular N3—H3···N2ⁱ hydrogen bond [symmetry code: (i) x, −y + 1/2, z − 1/2] (Table 1). This hydrogen bond links the molecules of (I) in the crystal into infinite chains running along the c axis of the crystal (Fig. 2).

S2. Experimental

A mixture of 5-(4-chlorobenzylidene)-3-ethylthiazolidine-2,4-dione (2 mmol), prepared according to Lo et al. (1958), isatin (2 mmol), and sarcosine (2 mmol) was refluxed in dioxane (30 ml) until the disappearance of the starting material (as monitored by thin-layer chromatography). When the reaction was complete, the solvent was removed in vacuo and the residue was separated by column chromatography (silica gel, petroleum ether/ethyl acetate 5:1) to give the title compound, (I). M.p. 476 K; IR (KBr): 3358.3 (–NH), 1750.2, 1718.7, 1685.9 (C═O) cm⁻¹; ¹H NMR (CDCl₃, p.p.m.): 0.87 (t, 3H, CH₃), 2.26 (s, 3H, N—CH3), 3.40–3.50 (m, 2H, –CH2), 3.61 (dd, J = 9.3, 7.8 Hz, 1H, Hc), 4.03 (dd, J = 10.2, 9.3 Hz, 1H), 4.58 (dd, J = 10.2, 7.8 Hz, 1H), 6.82–7.38 (m, 8H, ArH), 7.41 (br, 1H, –NH); ¹³C NMR (p.p.m.): 12.68, 35.18, 36.95, 51.33, 58.29, 72.12, 79.90, 110.31, 123.13, 123.22, 127.01, 128.81, 130.61, 131.46,133.69,136.16, 142.39, 169.38, 175.42, 177.50. 20 mg of (I) was dissolved in 15 ml of benzene andthe solution was kept at room temperature for 15 d. Slow evaporation of the solvent gave colorless single crystals of (I) suitable for X-ray analysis.

S3. Refinement

All H atoms were placed in calculated positions, with C—H distances ranging from 0.93 to 0.98 Å and an N—H distance of 0.86 Å. They were included in the refinement in the riding-motion approximation, with U_iso = 1.2 (1.5 for methyl) times U_eq of the carrier atom. Both solvate benzene molecules refined poorly. In the final model, the benzene molecule in the general position was included with the fixed geometry of a regular hexagon (C—C = 1.39 Å). The solvate benzene molecule in the inversion centre was represented as two-component disorder with approximately equal occupancy factors, which refined to 0.49 (3) and 0.51 (3). The bond lengths in both components of the disordered benzene were constrained to 1.39±0.01 Å.

Computing details

Data collection: Bruker SMART (Bruker,1997); cell refinement: Bruker SMART; data reduction: Bruker SAINT (Bruker,1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL (Bruker,1997); software used to prepare material for publication: Bruker SHELXTL.

Figures

	Fig. 1. The molecular structure of (I); displacement ellipsoids are drawn at the 30% probability level, H atoms have been omitted and solvate benzene molecules are not shown.
	Fig. 2. The crystal packing diagram for (I), viewed along the a axis. All H atoms, with the exception of atom H3, participating in the hydrogen bond, have been omitted. The hydrogen bonds are shown as dashed lines.

4'-(4-Chlorophenyl)-3''-ethyl-1'-methyl-1H-indole-3-spiro-2'-pyrrolidine- 3'-spiro-5''-[1,3]thiazole-2(3H),2''(3''H),4''(5''H)-trione benzene sesquisolvate

Crystal data

C22H20ClN3O3S·1.5C6H6	F(000) = 1172
Mr = 559.08	Dx = 1.266 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.132 (3) Å	Cell parameters from 886 reflections
b = 22.785 (7) Å	θ = 2.7–23.1°
c = 12.515 (4) Å	µ = 0.24 mm^−1
β = 112.477 (5)°	T = 293 K
V = 2933.2 (15) Å^3	Parallelepiped, colorless
Z = 4	0.42 × 0.40 × 0.34 mm

Data collection

Bruker SMART CCD area detector diffractometer	5070 independent reflections
Radiation source: fine-focus sealed tube	2701 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→13
Tmin = 0.796, Tmax = 0.923	k = −27→15
14461 measured reflections	l = −14→14

Refinement

Refinement on F^2	180 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.057	w = 1/[σ^2(Fo^2) + (0.084P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.155	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.27 e Å^−3
5070 reflections	Δρmin = −0.23 e Å^−3
370 parameters

Special details

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

treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	−0.11610 (11)	0.08563 (6)	−0.13037 (15)	0.1291 (6)
S1	0.47701 (9)	0.13010 (4)	−0.05396 (7)	0.0594 (3)
N1	0.6453 (3)	0.06854 (14)	0.1099 (3)	0.0637 (8)
N2	0.5755 (3)	0.25291 (12)	0.1866 (2)	0.0503 (7)
N3	0.6599 (3)	0.25950 (14)	−0.0504 (3)	0.0663 (9)
H3	0.6546	0.2754	−0.1143	0.080*
O1	0.5867 (3)	0.03034 (14)	−0.0726 (3)	0.0990 (10)
O2	0.6643 (2)	0.11726 (12)	0.2731 (2)	0.0693 (7)
O3	0.4440 (3)	0.26401 (12)	−0.07717 (19)	0.0672 (7)
C1	0.5791 (4)	0.06809 (18)	−0.0070 (4)	0.0678 (11)
C2	0.6206 (3)	0.11421 (16)	0.1690 (3)	0.0525 (9)
C3	0.5314 (3)	0.16081 (15)	0.0914 (2)	0.0467 (8)
C4	0.4222 (3)	0.17704 (15)	0.1376 (3)	0.0498 (8)
H4	0.4478	0.1589	0.2141	0.060*
C5	0.4373 (3)	0.24282 (15)	0.1574 (3)	0.0557 (9)
H5A	0.3852	0.2642	0.0882	0.067*
H5B	0.4121	0.2547	0.2203	0.067*
C6	0.6081 (3)	0.22009 (14)	0.1005 (2)	0.0460 (8)
C7	0.5563 (4)	0.25067 (16)	−0.0208 (3)	0.0538 (9)
C8	0.7316 (4)	0.01967 (19)	0.1680 (4)	0.0923 (14)
H8A	0.6943	−0.0169	0.1303	0.111*
H8B	0.7395	0.0174	0.2478	0.111*
C9	0.8621 (5)	0.0278 (3)	0.1643 (5)	0.1184 (18)
H9A	0.8550	0.0272	0.0854	0.178*
H9B	0.9185	−0.0033	0.2064	0.178*
H9C	0.8974	0.0648	0.1987	0.178*
C10	0.2874 (3)	0.15539 (16)	0.0676 (3)	0.0544 (9)
C11	0.2412 (4)	0.10599 (18)	0.1058 (4)	0.0721 (11)
H11	0.2941	0.0872	0.1734	0.086*
C12	0.1179 (4)	0.08474 (19)	0.0446 (4)	0.0854 (13)
H12	0.0880	0.0518	0.0708	0.102*
C13	0.0402 (4)	0.11219 (19)	−0.0541 (4)	0.0763 (12)
C14	0.0815 (4)	0.1606 (2)	−0.0946 (3)	0.0714 (11)
H14	0.0271	0.1791	−0.1620	0.086*
C15	0.2062 (4)	0.18181 (18)	−0.0335 (3)	0.0629 (10)
H15	0.2355	0.2144	−0.0613	0.075*
C16	0.6115 (4)	0.31501 (16)	0.1955 (3)	0.0715 (11)
H16A	0.7031	0.3185	0.2131	0.107*
H16B	0.5912	0.3330	0.2559	0.107*
H16C	0.5639	0.3342	0.1234	0.107*
C17	0.7520 (3)	0.21671 (14)	0.1265 (3)	0.0492 (8)
C18	0.7759 (4)	0.24002 (17)	0.0339 (3)	0.0584 (9)
C19	0.8984 (4)	0.2430 (2)	0.0345 (4)	0.0840 (13)
H19	0.9127	0.2579	−0.0287	0.101*
C20	1.0003 (4)	0.2236 (2)	0.1307 (4)	0.0866 (13)
H20	1.0844	0.2252	0.1320	0.104*
C21	0.9803 (4)	0.20171 (18)	0.2249 (4)	0.0724 (11)
H21	1.0503	0.1891	0.2897	0.087*
C22	0.8551 (4)	0.19856 (16)	0.2228 (3)	0.0577 (9)
H22	0.8410	0.1842	0.2866	0.069*
C23	0.0341 (7)	0.1077 (3)	0.5916 (7)	0.180 (3)
H23A	−0.0323	0.1137	0.6182	0.216*
C24	0.1618 (9)	0.1210 (3)	0.6621 (4)	0.176 (3)
H24A	0.1808	0.1359	0.7360	0.212*
C25	0.2610 (5)	0.1121 (3)	0.6223 (6)	0.166 (3)
H25A	0.3464	0.1210	0.6695	0.199*
C26	0.2326 (7)	0.0898 (3)	0.5119 (6)	0.174 (3)
H26A	0.2990	0.0838	0.4853	0.209*
C27	0.1049 (9)	0.0765 (3)	0.4413 (4)	0.243 (5)
H27A	0.0859	0.0616	0.3675	0.292*
C28	0.0057 (5)	0.0854 (3)	0.4812 (7)	0.217 (4)
H28A	−0.0798	0.0765	0.4339	0.261*
C29	0.410 (2)	−0.0334 (9)	0.4133 (18)	0.103 (6)	0.51 (3)
H29A	0.3525	−0.0567	0.3554	0.124*	0.51 (3)
C30	0.482 (3)	0.0091 (10)	0.3855 (10)	0.088 (5)	0.51 (3)
H30A	0.4683	0.0163	0.3085	0.106*	0.51 (3)
C31	0.576 (2)	0.0411 (11)	0.472 (2)	0.109 (6)	0.51 (3)
H31A	0.6293	0.0675	0.4543	0.131*	0.51 (3)
C29'	0.404 (2)	−0.0430 (10)	0.473 (3)	0.113 (6)	0.49 (3)
H29B	0.3396	−0.0714	0.4561	0.135*	0.49 (3)
C30'	0.430 (2)	−0.0158 (15)	0.3852 (11)	0.104 (6)	0.49 (3)
H30B	0.3847	−0.0266	0.3087	0.125*	0.49 (3)
C31'	0.524 (3)	0.0273 (11)	0.412 (2)	0.094 (5)	0.49 (3)
H31B	0.5401	0.0462	0.3525	0.112*	0.49 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0599 (7)	0.0985 (10)	0.1858 (14)	−0.0080 (7)	−0.0011 (8)	0.0142 (10)
S1	0.0606 (6)	0.0695 (6)	0.0469 (5)	−0.0056 (5)	0.0191 (4)	−0.0109 (5)
N1	0.0547 (19)	0.057 (2)	0.072 (2)	0.0044 (16)	0.0167 (17)	−0.0023 (17)
N2	0.0579 (18)	0.0563 (19)	0.0434 (15)	−0.0043 (15)	0.0268 (13)	−0.0077 (13)
N3	0.076 (2)	0.081 (2)	0.0568 (18)	0.0037 (18)	0.0412 (18)	0.0177 (16)
O1	0.090 (2)	0.086 (2)	0.118 (2)	−0.0016 (18)	0.0364 (18)	−0.047 (2)
O2	0.0662 (16)	0.086 (2)	0.0552 (16)	0.0067 (14)	0.0222 (13)	0.0222 (14)
O3	0.0706 (18)	0.086 (2)	0.0480 (14)	0.0125 (15)	0.0261 (14)	0.0139 (13)
C1	0.055 (2)	0.061 (3)	0.092 (3)	−0.011 (2)	0.033 (2)	−0.019 (2)
C2	0.045 (2)	0.061 (2)	0.055 (2)	−0.0047 (18)	0.0219 (18)	0.0080 (19)
C3	0.052 (2)	0.055 (2)	0.0359 (17)	−0.0016 (17)	0.0198 (15)	0.0010 (15)
C4	0.050 (2)	0.062 (2)	0.0421 (18)	0.0044 (17)	0.0220 (16)	0.0105 (16)
C5	0.064 (2)	0.064 (2)	0.0477 (19)	0.003 (2)	0.0309 (17)	−0.0018 (17)
C6	0.054 (2)	0.051 (2)	0.0376 (16)	−0.0045 (16)	0.0233 (15)	−0.0023 (15)
C7	0.065 (2)	0.057 (2)	0.050 (2)	−0.002 (2)	0.0326 (19)	−0.0014 (17)
C8	0.065 (3)	0.065 (3)	0.132 (4)	0.012 (2)	0.022 (3)	0.003 (3)
C9	0.074 (3)	0.108 (4)	0.151 (5)	0.016 (3)	0.018 (3)	−0.017 (3)
C10	0.049 (2)	0.061 (2)	0.059 (2)	0.0076 (18)	0.0272 (18)	0.0092 (19)
C11	0.050 (2)	0.069 (3)	0.093 (3)	0.007 (2)	0.023 (2)	0.028 (2)
C12	0.058 (3)	0.066 (3)	0.128 (4)	0.000 (2)	0.031 (3)	0.027 (3)
C13	0.048 (2)	0.063 (3)	0.106 (3)	0.001 (2)	0.017 (2)	0.003 (3)
C14	0.053 (2)	0.077 (3)	0.076 (3)	0.012 (2)	0.015 (2)	0.011 (2)
C15	0.059 (2)	0.070 (3)	0.060 (2)	0.002 (2)	0.024 (2)	0.0121 (19)
C16	0.095 (3)	0.057 (3)	0.074 (3)	−0.011 (2)	0.045 (2)	−0.016 (2)
C17	0.057 (2)	0.051 (2)	0.0437 (19)	−0.0049 (17)	0.0243 (18)	−0.0081 (16)
C18	0.063 (2)	0.067 (3)	0.054 (2)	−0.005 (2)	0.033 (2)	−0.0016 (19)
C19	0.077 (3)	0.111 (4)	0.085 (3)	−0.002 (3)	0.054 (3)	0.009 (3)
C20	0.063 (3)	0.110 (4)	0.100 (3)	−0.003 (3)	0.045 (3)	−0.008 (3)
C21	0.058 (3)	0.082 (3)	0.073 (3)	0.001 (2)	0.020 (2)	−0.012 (2)
C22	0.060 (2)	0.063 (2)	0.053 (2)	−0.0067 (19)	0.0247 (19)	−0.0075 (18)
C23	0.148 (7)	0.206 (9)	0.183 (9)	0.041 (6)	0.061 (6)	0.032 (7)
C24	0.179 (8)	0.190 (8)	0.171 (7)	−0.011 (7)	0.079 (7)	−0.052 (6)
C25	0.184 (8)	0.151 (6)	0.154 (7)	−0.046 (6)	0.057 (6)	−0.024 (5)
C26	0.187 (8)	0.209 (8)	0.126 (6)	0.043 (7)	0.059 (6)	0.008 (6)
C27	0.201 (10)	0.330 (13)	0.130 (7)	0.060 (10)	−0.013 (7)	−0.077 (7)
C28	0.146 (7)	0.297 (12)	0.141 (8)	0.025 (7)	−0.020 (6)	−0.033 (8)
C29	0.137 (13)	0.065 (11)	0.106 (12)	−0.016 (8)	0.045 (11)	0.006 (11)
C30	0.110 (16)	0.060 (12)	0.086 (7)	−0.019 (9)	0.028 (8)	−0.003 (7)
C31	0.133 (14)	0.102 (13)	0.070 (12)	−0.018 (9)	0.014 (11)	0.021 (11)
C29'	0.132 (14)	0.092 (12)	0.137 (18)	−0.004 (10)	0.078 (15)	0.011 (16)
C30'	0.115 (12)	0.088 (17)	0.122 (10)	−0.032 (10)	0.060 (10)	−0.004 (11)
C31'	0.101 (15)	0.087 (14)	0.101 (13)	−0.035 (10)	0.047 (12)	−0.007 (11)

Geometric parameters (Å, º)

Cl1—C13	1.742 (4)	C15—H15	0.9300
S1—C1	1.767 (4)	C16—H16A	0.9600
S1—C3	1.823 (3)	C16—H16B	0.9600
N1—C1	1.363 (5)	C16—H16C	0.9600
N1—C2	1.364 (4)	C17—C22	1.373 (5)
N1—C8	1.469 (5)	C17—C18	1.390 (4)
N2—C5	1.457 (4)	C18—C19	1.362 (5)
N2—C16	1.463 (4)	C19—C20	1.374 (6)
N2—C6	1.466 (4)	C19—H19	0.9300
N3—C7	1.354 (4)	C20—C21	1.375 (6)
N3—C18	1.391 (5)	C20—H20	0.9300
N3—H3	0.8600	C21—C22	1.385 (5)
O1—C1	1.214 (4)	C21—H21	0.9300
O2—C2	1.206 (4)	C22—H22	0.9300
O3—C7	1.216 (4)	C23—C24	1.3900
C2—C3	1.523 (5)	C23—C28	1.3900
C3—C4	1.577 (4)	C23—H23A	0.9300
C3—C6	1.578 (5)	C24—C25	1.3900
C4—C10	1.502 (5)	C24—H24A	0.9300
C4—C5	1.518 (5)	C25—C26	1.3900
C4—H4	0.9800	C25—H25A	0.9300
C5—H5A	0.9700	C26—C27	1.3900
C5—H5B	0.9700	C26—H26A	0.9300
C6—C17	1.510 (4)	C27—C28	1.3900
C6—C7	1.566 (5)	C27—H27A	0.9300
C8—C9	1.483 (6)	C28—H28A	0.9300
C8—H8A	0.9700	C29—C30	1.385 (8)
C8—H8B	0.9700	C29—C31^i	1.390 (9)
C9—H9A	0.9600	C29—H29A	0.9300
C9—H9B	0.9600	C30—C31	1.392 (9)
C9—H9C	0.9600	C30—H30A	0.9300
C10—C15	1.381 (5)	C31—C29^i	1.390 (9)
C10—C11	1.396 (5)	C31—H31A	0.9300
C11—C12	1.378 (5)	C29'—C30'	1.390 (9)
C11—H11	0.9300	C29'—C31'^i	1.398 (9)
C12—C13	1.360 (6)	C29'—H29B	0.9300
C12—H12	0.9300	C30'—C31'	1.380 (9)
C13—C14	1.366 (6)	C30'—H30B	0.9300
C14—C15	1.390 (5)	C31'—C29'^i	1.398 (9)
C14—H14	0.9300	C31'—H31B	0.9300
C1—S1—C3	92.79 (18)	C13—C14—C15	118.9 (4)
C1—N1—C2	116.7 (3)	C13—C14—H14	120.5
C1—N1—C8	120.5 (3)	C15—C14—H14	120.5
C2—N1—C8	122.6 (3)	C10—C15—C14	121.2 (4)
C5—N2—C16	113.8 (3)	C10—C15—H15	119.4
C5—N2—C6	105.6 (2)	C14—C15—H15	119.4
C16—N2—C6	114.3 (2)	N2—C16—H16A	109.5
C7—N3—C18	112.7 (3)	N2—C16—H16B	109.5
C7—N3—H3	123.7	H16A—C16—H16B	109.5
C18—N3—H3	123.7	N2—C16—H16C	109.5
O1—C1—N1	125.6 (4)	H16A—C16—H16C	109.5
O1—C1—S1	122.9 (4)	H16B—C16—H16C	109.5
N1—C1—S1	111.5 (3)	C22—C17—C18	119.0 (3)
O2—C2—N1	123.2 (3)	C22—C17—C6	131.8 (3)
O2—C2—C3	123.0 (3)	C18—C17—C6	109.1 (3)
N1—C2—C3	113.8 (3)	C19—C18—C17	121.7 (4)
C2—C3—C4	109.6 (2)	C19—C18—N3	128.7 (3)
C2—C3—C6	110.4 (3)	C17—C18—N3	109.6 (3)
C4—C3—C6	104.1 (3)	C18—C19—C20	118.6 (4)
C2—C3—S1	104.8 (2)	C18—C19—H19	120.7
C4—C3—S1	116.6 (2)	C20—C19—H19	120.7
C6—C3—S1	111.39 (19)	C19—C20—C21	121.2 (4)
C10—C4—C5	116.3 (3)	C19—C20—H20	119.4
C10—C4—C3	116.6 (3)	C21—C20—H20	119.4
C5—C4—C3	103.8 (3)	C20—C21—C22	119.6 (4)
C10—C4—H4	106.5	C20—C21—H21	120.2
C5—C4—H4	106.5	C22—C21—H21	120.2
C3—C4—H4	106.5	C17—C22—C21	119.9 (3)
N2—C5—C4	103.7 (3)	C17—C22—H22	120.0
N2—C5—H5A	111.0	C21—C22—H22	120.0
C4—C5—H5A	111.0	C24—C23—C28	120.0
N2—C5—H5B	111.0	C24—C23—H23A	120.0
C4—C5—H5B	111.0	C28—C23—H23A	120.0
H5A—C5—H5B	109.0	C25—C24—C23	120.0
N2—C6—C17	114.0 (3)	C25—C24—H24A	120.0
N2—C6—C7	112.5 (3)	C23—C24—H24A	120.0
C17—C6—C7	101.4 (2)	C26—C25—C24	120.0
N2—C6—C3	102.2 (2)	C26—C25—H25A	120.0
C17—C6—C3	118.1 (3)	C24—C25—H25A	120.0
C7—C6—C3	108.8 (3)	C25—C26—C27	120.0
O3—C7—N3	126.8 (3)	C25—C26—H26A	120.0
O3—C7—C6	126.1 (3)	C27—C26—H26A	120.0
N3—C7—C6	107.2 (3)	C28—C27—C26	120.0
N1—C8—C9	110.7 (4)	C28—C27—H27A	120.0
N1—C8—H8A	109.5	C26—C27—H27A	120.0
C9—C8—H8A	109.5	C27—C28—C23	120.0
N1—C8—H8B	109.5	C27—C28—H28A	120.0
C9—C8—H8B	109.5	C23—C28—H28A	120.0
H8A—C8—H8B	108.1	C30—C29—C31^i	120.1 (9)
C8—C9—H9A	109.5	C30—C29—H29A	120.0
C8—C9—H9B	109.5	C31^i—C29—H29A	120.0
H9A—C9—H9B	109.5	C29—C30—C31	120.2 (9)
C8—C9—H9C	109.5	C29—C30—H30A	119.9
H9A—C9—H9C	109.5	C31—C30—H30A	119.9
H9B—C9—H9C	109.5	C29^i—C31—C30	119.5 (9)
C15—C10—C11	117.9 (3)	C29^i—C31—H31A	120.3
C15—C10—C4	123.3 (3)	C30—C31—H31A	120.3
C11—C10—C4	118.8 (3)	C30'—C29'—C31'^i	119.5 (9)
C12—C11—C10	120.8 (4)	C30'—C29'—H29B	120.2
C12—C11—H11	119.6	C31'^i—C29'—H29B	120.2
C10—C11—H11	119.6	C31'—C30'—C29'	119.8 (9)
C13—C12—C11	119.7 (4)	C31'—C30'—H30B	120.1
C13—C12—H12	120.1	C29'—C30'—H30B	120.1
C11—C12—H12	120.1	C30'—C31'—C29'^i	120.7 (9)
C12—C13—C14	121.4 (4)	C30'—C31'—H31B	119.6
C12—C13—Cl1	119.6 (4)	C29'^i—C31'—H31B	119.6
C14—C13—Cl1	119.0 (3)
C2—N1—C1—O1	−178.2 (4)	N2—C6—C7—N3	123.5 (3)
C8—N1—C1—O1	−2.2 (6)	C17—C6—C7—N3	1.3 (3)
C2—N1—C1—S1	1.3 (4)	C3—C6—C7—N3	−124.0 (3)
C8—N1—C1—S1	177.3 (3)	C1—N1—C8—C9	84.4 (5)
C3—S1—C1—O1	−177.9 (3)	C2—N1—C8—C9	−99.8 (5)
C3—S1—C1—N1	2.6 (3)	C5—C4—C10—C15	44.9 (4)
C1—N1—C2—O2	173.7 (3)	C3—C4—C10—C15	−78.2 (4)
C8—N1—C2—O2	−2.3 (5)	C5—C4—C10—C11	−135.4 (3)
C1—N1—C2—C3	−5.7 (4)	C3—C4—C10—C11	101.6 (4)
C8—N1—C2—C3	178.4 (3)	C15—C10—C11—C12	−0.5 (6)
O2—C2—C3—C4	−46.6 (4)	C4—C10—C11—C12	179.7 (4)
N1—C2—C3—C4	132.8 (3)	C10—C11—C12—C13	−0.1 (7)
O2—C2—C3—C6	67.5 (4)	C11—C12—C13—C14	0.1 (7)
N1—C2—C3—C6	−113.1 (3)	C11—C12—C13—Cl1	−179.4 (3)
O2—C2—C3—S1	−172.4 (3)	C12—C13—C14—C15	0.4 (6)
N1—C2—C3—S1	6.9 (3)	Cl1—C13—C14—C15	179.9 (3)
C1—S1—C3—C2	−5.2 (2)	C11—C10—C15—C14	1.1 (5)
C1—S1—C3—C4	−126.5 (3)	C4—C10—C15—C14	−179.2 (3)
C1—S1—C3—C6	114.2 (2)	C13—C14—C15—C10	−1.0 (6)
C2—C3—C4—C10	−107.6 (3)	N2—C6—C17—C22	53.5 (5)
C6—C3—C4—C10	134.3 (3)	C7—C6—C17—C22	174.7 (4)
S1—C3—C4—C10	11.2 (4)	C3—C6—C17—C22	−66.6 (5)
C2—C3—C4—C5	123.1 (3)	N2—C6—C17—C18	−122.6 (3)
C6—C3—C4—C5	5.0 (3)	C7—C6—C17—C18	−1.4 (3)
S1—C3—C4—C5	−118.1 (3)	C3—C6—C17—C18	117.4 (3)
C16—N2—C5—C4	172.7 (3)	C22—C17—C18—C19	2.8 (6)
C6—N2—C5—C4	46.5 (3)	C6—C17—C18—C19	179.4 (4)
C10—C4—C5—N2	−159.6 (2)	C22—C17—C18—N3	−175.6 (3)
C3—C4—C5—N2	−30.2 (3)	C6—C17—C18—N3	1.0 (4)
C5—N2—C6—C17	−170.7 (3)	C7—N3—C18—C19	−178.4 (4)
C16—N2—C6—C17	63.5 (4)	C7—N3—C18—C17	−0.2 (4)
C5—N2—C6—C7	74.5 (3)	C17—C18—C19—C20	−1.4 (6)
C16—N2—C6—C7	−51.4 (4)	N3—C18—C19—C20	176.6 (4)
C5—N2—C6—C3	−42.0 (3)	C18—C19—C20—C21	−0.3 (7)
C16—N2—C6—C3	−167.9 (3)	C19—C20—C21—C22	0.7 (7)
C2—C3—C6—N2	−96.1 (3)	C18—C17—C22—C21	−2.3 (5)
C4—C3—C6—N2	21.5 (3)	C6—C17—C22—C21	−178.0 (3)
S1—C3—C6—N2	147.9 (2)	C20—C21—C22—C17	0.6 (6)
C2—C3—C6—C17	29.9 (3)	C28—C23—C24—C25	0.0
C4—C3—C6—C17	147.5 (3)	C23—C24—C25—C26	0.0
S1—C3—C6—C17	−86.1 (3)	C24—C25—C26—C27	0.0
C2—C3—C6—C7	144.7 (3)	C25—C26—C27—C28	0.0
C4—C3—C6—C7	−97.7 (3)	C26—C27—C28—C23	0.0
S1—C3—C6—C7	28.7 (3)	C24—C23—C28—C27	0.0
C18—N3—C7—O3	179.1 (4)	C31^i—C29—C30—C31	5 (4)
C18—N3—C7—C6	−0.7 (4)	C29—C30—C31—C29^i	−5 (4)
N2—C6—C7—O3	−56.3 (5)	C31'^i—C29'—C30'—C31'	−2 (5)
C17—C6—C7—O3	−178.5 (3)	C29'—C30'—C31'—C29'^i	2 (5)
C3—C6—C7—O3	56.2 (4)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N2^ii	0.86	2.39	3.071 (3)	136

Symmetry code: (ii) x, −y+1/2, z−1/2.