2-[6-(3-Chloro­phenyl)-2,4-dioxoperhydro­pyrimidin-3-yl]­ethyl morpholine-4-carbodi­thioate

In the title compound, C₁₇H₂₀ClN₃O₃S₂, the hexa­hydro­pyrimidine ring is puckered, the total puckering amplitude Q_T being 0.41 (1) Å. The morpholine ring displays orientational disorder. Molecules are linked in the crystal via N-H...O and C-H...O interactions to form infinite chains.

S1. Comment

Although there are a number of antiepileptic drugs currently available, the development of more efficient compounds with lower toxicity remains a requirement for improved antiepileptic drug treatments (Brodie, 2001). In the last decade, new anticonvulsant compounds have emerged, with substantially different structures from the classical anticonvulsant drugs, in that they contain the ureido structure (Bialer et al., 2002). For example, 3-substituted-6-arylhexahydropyrimidine-2,4-dione derivatives with a ureido structure have been reported as a new group of compounds which have been found to be active in anticonvulsant therapy (Guillon et al., 1996; Çalış & Köksal, 2001; Septio~glu et al., 2004).

It is well known that pyrimidine derivatives have various pharmacological activities, such as diuretic, antihypertensive, antiinflammatory, antiepileptic and anticancer properties (Skulnick et al., 1986; Guillon et al., 1996; Sanyal et al., 1986). In addition, numerous studies of pyrimidine derivatives have shown that these compounds have potential bacteriostatic, fungicidal and antiviral activities (Skulnick et al., 1986; Özalp et al., 2000).

In our previous studies, we have synthesized some new 3-alkyl-6-arylhexahydropyrimidine-2,4-dione derivatives and investigated their antimicrobial (Özalp et al., 2000) and anticonvulsant activities (Çalış & Köksal, 2001). At the same time, 6-arylhexahydropyrimidine-2,4-dione derivatives with a mercapto group at the 3-position were found to be protective against subcutaneous metrazole (Guillon et al., 1996).

Over the past 30 years, numerous dithiocarbamate derivatives have been synthesized and their pharmacological activities have been reported to be antibacterial, antifungal, antiviral, herbicidal, tubercolostatic and anticholinergic (Gupta & Garg, 1965; Kumar & Reddy, 1985; Chabric et al., 1956; Ramrakhyani & Shukla, 1980; Weuffen & Kewitsch, 1967; Zsolnai, 1968; Çalış et al., 1993).

These previous studies led us to synthesize several derivatives of 6-arylhexahydropyrimidine-2,4-dione with a dithiocarbamate functional group at the 3-position of the hexahydropyrimidine-2,4-dione ring. In this paper, we report the structure of one of these, the title compound, (I). \sch

In the molecule of (I), the four C—N bond distances in the hexahydropyrimidine ring show a rather wide variation [1.3405 (17)–1.4592 (17) Å; Table 1]. These distances are somewhat longer than the mean value of 1.333 Å for pyrimidines in general (Allen et al., 1987). The hexahydropyrimidine ring exhibits a puckered conformation, with puckering parameters (Cremer & Pople, 1975) q₂ = 0.4 (1) Å, q₃ = 0.2 (1) Å, Q_T = 0.41 (1) Å, ϕ = −147.42 (6)° and θ = 62.39 (5)°. This hexahydropyrimidine ring is approximately planar, the maximum deviation from the best plane being 0.26 (1) Å for C7, and the dihedral angle with the phenyl group is 86.81 (11)°.

In the crystal structure of (I), the molecules are connected via N—H···O and C—H···O interactions to form infinite spiral chains extending along the b axis (Fig. 2 and Table 2).

S2. Experimental

The potassium salt of the appropriate N,N-disubstituted dithiocarbamic acid (0.002 mol) was dissolved in methanol (25 ml) with constant stirring; 3-(2-Chloroethyl)-6-arylhexahydropyrimidine-2,4-dione (0.002 mol) was added in portions to this solution. The mixture was heated for 3 h under reflux, after which the precipitate was filtered off, the solution concentrated in vacuo, and the precipitate which formed filtered and crystallized from methanol (yield 64%; m.p. 415–416 K). Elemental analysis, calculated: C 49.33, H 4.87, N 10.15, S 15.49%; found: C 49.71, H 5.31, N 10.02, S 14.82%. Spectroscopic analysis: UV (MeOH), λ_max (log ε): 201.0 (4.48), 255.0 (3.90), 282.0 (3.94); IR (KBr, ν, cm⁻¹): 3308 (N—H), 1719–1673 (C—O), 1271 (C—S); ¹H NMR (DMSO-d₆, δ, p.p.m.): 2.10 (t, 2H, –N—CH₂), 2.80 (d, 2H, –CH₂), 3.30 (t, 2H, –CH₂S–), 3.60–4.00 (m, 8H, morpholine), 4.80 (d, 1H, –CH–), 7.20–7.40 (m, 4H, aromatic), 8.40 (s, 1H, –NH).

S3. Refinement

Atoms O21, C22, C23, N24, C25 and C26 of the morpholine moiety show positional disorder, corresponding to an approximately 180° rotation about the O21···N24 axis. The two components of this disordered ring have the usual chair conformation, with site occupancy factors of 0.5 each. The atoms of the two components are labelled with the suffix A and B, respectively. A total of 12 restraints were used in the refinement. These were associated with ensuring reasonable geometry for the two morpholine rings. The anisotropic displacement parameters of the slightly disordered morpholine O and N atoms were constrained using SHELXL EADP commands. The disordered morpholine C atoms were refined isotropically. All H atoms were positioned geometrically and refined using a riding model, with N—H = 0.86 and C—H = 0.93–0.97 Å, and with U_iso(H) = 1.2U_eq or 1.5U_eq(C,N). Please check added text relating to treatment of H atoms on N.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1997) and PARST (Nardelli, 1995).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. For clarity, only the A component of the disordered morpholine ring is shown.
	Fig. 2. A stereoview of part of the crystal structure of (I). Molecules are linked by N—H···O and C—H···O hydrogen bonds to form a spiral chain extending along the b direction (horizontal). As in Fig. 1, only the A component of the disordered morpholine ring is shown.

2-[6-(3-Chlorophenyl)-2,4-dioxoperhydropyrimidin-3-yl]ethyl morpholine-4-carbodithioate

Crystal data

C17H20ClN3O3S2	F(000) = 864
Mr = 413.93	Dx = 1.489 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5107 reflections
a = 10.2010 (12) Å	θ = 2.0–27.5°
b = 5.0606 (4) Å	µ = 0.46 mm^−1
c = 36.290 (5) Å	T = 293 K
β = 99.692 (10)°	Plate, colourless
V = 1846.6 (4) Å^3	0.50 × 0.20 × 0.02 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer	1270 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.116
Graphite monochromator	θmax = 26.0°, θmin = 2.0°
Detector resolution: 6.67 pixels mm^-1	h = −12→12
ω scans	k = −6→6
13939 measured reflections	l = −44→44
3610 independent reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0756P)^2] where P = (Fo^2 + 2Fc^2)/3
4241 reflections	(Δ/σ)max = 0.003
237 parameters	Δρmax = 0.25 e Å^−3
12 restraints	Δρmin = −0.66 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.

Some 12 restraints were used in the refinement. These were associated with the chair-form morpholine ring which was disordered over two orientations with geometry controlled by the SHELXL commands:- DFIX 1.41 0.01 O21A C22A O21A C26A O21B C22B O21B C26B DFIX 1.50 0.01 C22A C23A C25A C26A C22B C23B C25B C26B DFIX 1.46 0.01 N24A C23A N24A C25A N24B C23B N24B C25B The three DFIX distances were obtained from a survey of 353 morpholine residues in the July 2004 version of the CSD

The anisotropic displacement parameters of the slightly disordered morpholine O and N atoms were constrained with the SHELXL commands:- EADP O21A O21B EADP N24A N24B

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl3	0.88009 (6)	0.90951 (19)	0.954720 (15)	0.1002 (3)
S1	0.70143 (4)	1.04625 (9)	0.647237 (11)	0.05424 (14)
S2	0.90134 (4)	0.70364 (9)	0.617910 (12)	0.05593 (14)
O2	0.55995 (9)	0.5955 (2)	0.73200 (3)	0.0436 (2)
O4	0.95636 (11)	0.9922 (2)	0.77300 (3)	0.0529 (3)
N1	0.67375 (11)	0.4770 (2)	0.78828 (3)	0.0415 (3)
H1	0.6202	0.3470	0.7894	0.050*
N3	0.75303 (10)	0.8114 (2)	0.75390 (3)	0.0326 (2)
C2	0.65567 (12)	0.6215 (3)	0.75687 (3)	0.0353 (3)
C4	0.87680 (12)	0.8260 (2)	0.77732 (3)	0.0357 (3)
C5	0.90031 (12)	0.6139 (3)	0.80604 (4)	0.0379 (3)
H5A	0.9647	0.6770	0.8269	0.046*
H5B	0.9393	0.4630	0.7954	0.046*
C6	0.77662 (14)	0.5217 (3)	0.82082 (4)	0.0425 (3)
H6	0.7973	0.3510	0.8332	0.051*
C11	0.73705 (12)	0.7097 (3)	0.84928 (4)	0.0367 (3)
C12	0.81392 (13)	0.7219 (3)	0.88428 (4)	0.0478 (3)
H12	0.8875	0.6119	0.8902	0.057*
C13	0.78205 (14)	0.8973 (4)	0.91069 (4)	0.0532 (4)
C14	0.67551 (17)	1.0636 (4)	0.90310 (5)	0.0566 (4)
H14	0.6560	1.1825	0.9209	0.068*
C15	0.59828 (17)	1.0500 (3)	0.86840 (6)	0.0583 (4)
H15	0.5249	1.1609	0.8629	0.070*
C16	0.62646 (14)	0.8756 (3)	0.84134 (4)	0.0473 (3)
H16	0.5721	0.8691	0.8181	0.057*
C27	0.77716 (15)	0.9175 (3)	0.61088 (4)	0.0464 (3)
C28	0.75912 (14)	0.8381 (3)	0.68641 (4)	0.0413 (3)
H28A	0.7128	0.6700	0.6838	0.050*
H28B	0.8537	0.8053	0.6884	0.050*
C29	0.73048 (15)	0.9845 (3)	0.72098 (4)	0.0426 (3)
H29A	0.7878	1.1381	0.7255	0.051*
H29B	0.6390	1.0452	0.7167	0.051*
O21A	0.6463 (10)	1.292 (2)	0.5115 (3)	0.078 (2)	0.50
N24A	0.7161 (17)	0.993 (5)	0.5768 (3)	0.061 (3)	0.50
C22A	0.6017 (3)	1.3522 (6)	0.54540 (9)	0.0492 (6)*	0.50
H22A	0.6653	1.4686	0.5603	0.059*	0.50
H22B	0.5172	1.4438	0.5400	0.059*	0.50
C23A	0.5871 (3)	1.1218 (6)	0.56569 (9)	0.0498 (6)*	0.50
H23A	0.5264	1.0019	0.5505	0.060*	0.50
H23B	0.5496	1.1656	0.5878	0.060*	0.50
C25A	0.7616 (4)	0.9482 (6)	0.54117 (10)	0.0481 (7)*	0.50
H25A	0.8469	0.8586	0.5458	0.058*	0.50
H25B	0.6988	0.8337	0.5257	0.058*	0.50
C26A	0.7744 (3)	1.1789 (6)	0.52222 (9)	0.0489 (6)*	0.50
H26A	0.8141	1.1432	0.5002	0.059*	0.50
H26B	0.8317	1.3008	0.5381	0.059*	0.50
O21B	0.6208 (10)	1.238 (2)	0.5072 (3)	0.078 (2)	0.50
N24B	0.7310 (17)	1.039 (5)	0.5777 (3)	0.061 (3)	0.50
C22B	0.5417 (3)	1.2155 (6)	0.53547 (8)	0.0485 (6)*	0.50
H22C	0.4984	1.0442	0.5339	0.058*	0.50
H22D	0.4733	1.3508	0.5321	0.058*	0.50
C23B	0.6305 (3)	1.2476 (7)	0.57405 (9)	0.0495 (6)*	0.50
H23C	0.6727	1.4199	0.5759	0.059*	0.50
H23D	0.5774	1.2321	0.5938	0.059*	0.50
C25B	0.8085 (3)	1.0127 (7)	0.54752 (9)	0.0469 (7)*	0.50
H25C	0.8572	0.8471	0.5499	0.056*	0.50
H25D	0.8719	1.1565	0.5485	0.056*	0.50
C26B	0.7091 (3)	1.0196 (6)	0.50967 (9)	0.0481 (6)*	0.50
H26C	0.7591	1.0279	0.4892	0.058*	0.50
H26D	0.6578	0.8573	0.5070	0.058*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl3	0.0807 (4)	0.1683 (7)	0.0473 (3)	0.0141 (4)	−0.0014 (2)	−0.0300 (3)
S1	0.0624 (3)	0.0640 (3)	0.0370 (2)	0.01415 (17)	0.01040 (17)	0.00937 (15)
S2	0.0561 (3)	0.0635 (3)	0.0479 (2)	0.00682 (17)	0.00789 (18)	−0.00020 (17)
O2	0.0330 (4)	0.0544 (6)	0.0406 (5)	−0.0025 (4)	−0.0020 (4)	−0.0039 (4)
O4	0.0451 (5)	0.0570 (6)	0.0553 (7)	−0.0166 (5)	0.0049 (5)	−0.0051 (5)
N1	0.0448 (6)	0.0415 (6)	0.0353 (6)	−0.0137 (4)	−0.0013 (5)	0.0057 (4)
N3	0.0324 (5)	0.0384 (5)	0.0266 (5)	−0.0039 (4)	0.0037 (4)	0.0007 (4)
C2	0.0346 (6)	0.0399 (6)	0.0312 (6)	0.0038 (4)	0.0049 (5)	−0.0036 (4)
C4	0.0364 (6)	0.0389 (6)	0.0323 (6)	0.0011 (5)	0.0069 (5)	−0.0066 (4)
C5	0.0328 (6)	0.0445 (6)	0.0351 (6)	0.0055 (5)	0.0017 (5)	−0.0049 (5)
C6	0.0428 (7)	0.0450 (7)	0.0375 (7)	0.0046 (5)	0.0003 (5)	0.0080 (5)
C11	0.0329 (5)	0.0444 (6)	0.0339 (6)	−0.0062 (5)	0.0084 (5)	0.0074 (5)
C12	0.0355 (6)	0.0632 (9)	0.0453 (8)	0.0063 (6)	0.0083 (6)	−0.0048 (6)
C13	0.0398 (7)	0.0793 (11)	0.0408 (8)	−0.0024 (7)	0.0079 (6)	−0.0090 (7)
C14	0.0537 (9)	0.0636 (9)	0.0557 (9)	0.0015 (7)	0.0186 (7)	−0.0116 (7)
C15	0.0519 (9)	0.0574 (9)	0.0675 (11)	0.0159 (7)	0.0150 (8)	0.0025 (7)
C16	0.0389 (7)	0.0582 (8)	0.0442 (7)	0.0058 (6)	0.0052 (6)	0.0070 (6)
C27	0.0480 (7)	0.0549 (8)	0.0349 (7)	−0.0037 (6)	0.0029 (6)	0.0042 (5)
C28	0.0441 (7)	0.0482 (7)	0.0324 (6)	−0.0008 (5)	0.0088 (5)	0.0015 (5)
C29	0.0487 (7)	0.0429 (6)	0.0351 (7)	0.0021 (5)	0.0034 (5)	0.0035 (5)
O21A	0.092 (3)	0.092 (4)	0.0519 (19)	0.012 (3)	0.015 (2)	0.022 (2)
N24A	0.055 (3)	0.092 (6)	0.0360 (8)	0.018 (4)	0.0103 (13)	0.0107 (19)
O21B	0.092 (3)	0.092 (4)	0.0519 (19)	0.012 (3)	0.015 (2)	0.022 (2)
N24B	0.055 (3)	0.092 (6)	0.0360 (8)	0.018 (4)	0.0103 (13)	0.0107 (19)

Geometric parameters (Å, º)

Cl3—C13	1.7375 (17)	C28—H28B	0.97
S1—C27	1.7621 (16)	C29—H29A	0.97
S1—C28	1.7875 (14)	C29—H29B	0.97
S2—C27	1.6530 (16)	O21A—C22A	1.415 (8)
O2—C2	1.2201 (15)	O21A—C26A	1.420 (8)
O4—C4	1.1974 (17)	N24A—C25A	1.462 (8)
N1—C2	1.3405 (17)	N24A—C23A	1.463 (9)
N1—C6	1.4592 (17)	C22A—C23A	1.401 (4)
N1—H1	0.86	C22A—H22A	0.97
N3—C2	1.3993 (16)	C22A—H22B	0.97
N3—C4	1.4003 (15)	C23A—H23A	0.97
N3—C29	1.4680 (16)	C23A—H23B	0.97
C4—C5	1.4873 (18)	C25A—C26A	1.372 (4)
C5—C6	1.5249 (19)	C25A—H25A	0.97
C5—H5A	0.97	C25A—H25B	0.97
C5—H5B	0.97	C26A—H26A	0.97
C6—C11	1.5082 (19)	C26A—H26B	0.97
C6—H6	0.98	O21B—C22B	1.414 (8)
C11—C12	1.3773 (19)	O21B—C26B	1.419 (8)
C11—C16	1.3968 (19)	N24B—C23B	1.461 (9)
C12—C13	1.385 (2)	N24B—C25B	1.461 (8)
C12—H12	0.93	C22B—C23B	1.543 (4)
C13—C14	1.365 (2)	C22B—H22C	0.97
C14—C15	1.370 (3)	C22B—H22D	0.97
C14—H14	0.93	C23B—H23C	0.97
C15—C16	1.386 (2)	C23B—H23D	0.97
C15—H15	0.93	C25B—C26B	1.565 (4)
C16—H16	0.93	C25B—H25C	0.97
C27—N24A	1.344 (11)	C25B—H25D	0.97
C27—N24B	1.364 (10)	C26B—H26C	0.97
C28—C29	1.5271 (19)	C26B—H26D	0.97
C28—H28A	0.97
C27—S1—C28	104.50 (7)	C28—C29—H29B	109.5
C2—N1—C6	125.51 (11)	H29A—C29—H29B	108.1
C2—N1—H1	117.2	C22A—O21A—C26A	105.2 (7)
C6—N1—H1	117.2	C27—N24A—C25A	127.0 (6)
C2—N3—C4	124.65 (10)	C27—N24A—C23A	129.5 (6)
C2—N3—C29	117.18 (10)	C25A—N24A—C23A	103.4 (7)
C4—N3—C29	117.66 (10)	C23A—C22A—O21A	110.9 (5)
O2—C2—N1	123.28 (12)	C23A—C22A—H22A	109.5
O2—C2—N3	120.46 (12)	O21A—C22A—H22A	109.5
N1—C2—N3	116.26 (11)	C23A—C22A—H22B	109.5
O4—C4—N3	121.29 (12)	O21A—C22A—H22B	109.5
O4—C4—C5	124.47 (13)	H22A—C22A—H22B	108.0
N3—C4—C5	114.19 (11)	C22A—C23A—N24A	110.1 (9)
C4—C5—C6	114.96 (10)	C22A—C23A—H23A	109.6
C4—C5—H5A	108.5	N24A—C23A—H23A	109.6
C6—C5—H5A	108.5	C22A—C23A—H23B	109.6
C4—C5—H5B	108.5	N24A—C23A—H23B	109.6
C6—C5—H5B	108.5	H23A—C23A—H23B	108.1
H5A—C5—H5B	107.5	C26A—C25A—N24A	112.4 (9)
N1—C6—C11	114.39 (11)	C26A—C25A—H25A	109.1
N1—C6—C5	106.72 (11)	N24A—C25A—H25A	109.1
C11—C6—C5	112.37 (11)	C26A—C25A—H25B	109.1
N1—C6—H6	107.7	N24A—C25A—H25B	109.1
C11—C6—H6	107.7	H25A—C25A—H25B	107.8
C5—C6—H6	107.7	C25A—C26A—O21A	108.7 (6)
C12—C11—C16	118.54 (13)	C25A—C26A—H26A	110.0
C12—C11—C6	118.90 (12)	O21A—C26A—H26A	110.0
C16—C11—C6	122.55 (12)	C25A—C26A—H26B	110.0
C11—C12—C13	120.23 (14)	O21A—C26A—H26B	110.0
C11—C12—H12	119.9	H26A—C26A—H26B	108.3
C13—C12—H12	119.9	C22B—O21B—C26B	109.0 (7)
C14—C13—C12	121.81 (15)	C27—N24B—C23B	122.6 (6)
C14—C13—Cl3	118.62 (13)	C27—N24B—C25B	118.0 (6)
C12—C13—Cl3	119.56 (13)	C23B—N24B—C25B	117.3 (8)
C13—C14—C15	118.01 (15)	O21B—C22B—C23B	109.3 (5)
C13—C14—H14	121.0	O21B—C22B—H22C	109.8
C15—C14—H14	121.0	C23B—C22B—H22C	109.8
C14—C15—C16	121.83 (15)	O21B—C22B—H22D	109.8
C14—C15—H15	119.1	C23B—C22B—H22D	109.8
C16—C15—H15	119.1	H22C—C22B—H22D	108.3
C15—C16—C11	119.57 (14)	N24B—C23B—C22B	107.6 (8)
C15—C16—H16	120.2	N24B—C23B—H23C	110.2
C11—C16—H16	120.2	C22B—C23B—H23C	110.2
N24A—C27—S2	123.6 (4)	N24B—C23B—H23D	110.2
N24B—C27—S2	125.0 (3)	C22B—C23B—H23D	110.2
N24A—C27—S1	113.0 (3)	H23C—C23B—H23D	108.5
N24B—C27—S1	111.3 (4)	N24B—C25B—C26B	107.7 (7)
S2—C27—S1	123.21 (9)	N24B—C25B—H25C	110.2
C29—C28—S1	106.52 (9)	C26B—C25B—H25C	110.2
C29—C28—H28A	110.4	N24B—C25B—H25D	110.2
S1—C28—H28A	110.4	C26B—C25B—H25D	110.2
C29—C28—H28B	110.4	H25C—C25B—H25D	108.5
S1—C28—H28B	110.4	O21B—C26B—C25B	112.6 (5)
H28A—C28—H28B	108.6	O21B—C26B—H26C	109.1
N3—C29—C28	110.70 (11)	C25B—C26B—H26C	109.1
N3—C29—H29A	109.5	O21B—C26B—H26D	109.1
C28—C29—H29A	109.5	C25B—C26B—H26D	109.1
N3—C29—H29B	109.5	H26C—C26B—H26D	107.8
C6—N1—C2—O2	−171.78 (13)	C27—S1—C28—C29	163.95 (10)
C6—N1—C2—N3	7.37 (19)	C2—N3—C29—C28	−76.45 (14)
C4—N3—C2—O2	−168.17 (12)	C4—N3—C29—C28	95.72 (14)
C29—N3—C2—O2	3.40 (17)	S1—C28—C29—N3	170.24 (9)
C4—N3—C2—N1	12.65 (17)	N24B—C27—N24A—C25A	88 (3)
C29—N3—C2—N1	−175.77 (11)	S2—C27—N24A—C25A	−13 (3)
C2—N3—C4—O4	179.20 (12)	S1—C27—N24A—C25A	172.3 (18)
C29—N3—C4—O4	7.67 (18)	N24B—C27—N24A—C23A	−96 (4)
C2—N3—C4—C5	1.61 (16)	S2—C27—N24A—C23A	162.4 (16)
C29—N3—C4—C5	−169.92 (11)	S1—C27—N24A—C23A	−12 (3)
O4—C4—C5—C6	149.10 (13)	C26A—O21A—C22A—C23A	−63.7 (9)
N3—C4—C5—C6	−33.40 (15)	O21A—C22A—C23A—N24A	64.0 (10)
C2—N1—C6—C11	88.77 (17)	C27—N24A—C23A—C22A	126 (2)
C2—N1—C6—C5	−36.16 (18)	C25A—N24A—C23A—C22A	−57.4 (17)
C4—C5—C6—N1	47.59 (15)	C27—N24A—C25A—C26A	−123 (2)
C4—C5—C6—C11	−78.56 (14)	C23A—N24A—C25A—C26A	60.1 (17)
N1—C6—C11—C12	166.07 (12)	N24A—C25A—C26A—O21A	−66.0 (10)
C5—C6—C11—C12	−72.05 (16)	C22A—O21A—C26A—C25A	63.4 (9)
N1—C6—C11—C16	−15.00 (18)	N24A—C27—N24B—C23B	100 (3)
C5—C6—C11—C16	106.88 (14)	S2—C27—N24B—C23B	−173.3 (12)
C16—C11—C12—C13	−0.6 (2)	S1—C27—N24B—C23B	−1 (2)
C6—C11—C12—C13	178.36 (14)	N24A—C27—N24B—C25B	−97 (4)
C11—C12—C13—C14	−0.5 (3)	S2—C27—N24B—C25B	−10 (3)
C11—C12—C13—Cl3	179.91 (12)	S1—C27—N24B—C25B	162.7 (14)
C12—C13—C14—C15	1.0 (3)	C26B—O21B—C22B—C23B	66.7 (9)
Cl3—C13—C14—C15	−179.35 (14)	C27—N24B—C23B—C22B	−144.5 (18)
C13—C14—C15—C16	−0.5 (3)	C25B—N24B—C23B—C22B	52 (2)
C14—C15—C16—C11	−0.5 (3)	O21B—C22B—C23B—N24B	−59.7 (11)
C12—C11—C16—C15	1.1 (2)	C27—N24B—C25B—C26B	148.7 (16)
C6—C11—C16—C15	−177.85 (14)	C23B—N24B—C25B—C26B	−47 (2)
C28—S1—C27—N24A	160.8 (13)	C22B—O21B—C26B—C25B	−62.8 (9)
C28—S1—C27—N24B	173.4 (13)	N24B—C25B—C26B—O21B	50.6 (11)
C28—S1—C27—S2	−13.72 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.86	2.26	3.0598 (15)	154
C16—H16···O2^ii	0.93	2.37	3.1991 (18)	149
C5—H5B···O4^iii	0.97	2.53	3.4483 (18)	157

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