Intra­molecular hydrogen bonding in dibenzyl 2,2′-(propane-1,3-diyldiimino)bis­(cyclo­pent-1-ene-1-carbodithio­ate)

The title proligand, C₂₉H₃₄N₂S₄, exhibits two kinds of intra­molecular hydrogen bonds, N—H...S and C—H...S, described by the graph-set symbols S(6) and S(5), respectively. The structural parameters of the mol­ecule suggest a partial electron delocalization involving the nitro­gen lone pair, the cyclo­pentene ring and the carbodithio­ate group. In the crystal structure, the mol­ecules are held together mainly by C—H...π and van der Waals inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.041
• wR factor = 0.103
• Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.04 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C12
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C20
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5
PLAT480_ALERT_4_C Long H...A H-Bond Reported H14A   ..  CG3     ..       2.99 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H21A   ..  CG4     ..       3.13 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H21B   ..  CG4     ..       3.13 Ang.

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

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

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S1. Comment

The development of nitrogen and sulfurated proligands are of great relevance for bioinorganic chemistry (Holm & Solomon, 2004). Frequently, the aim has been to synthesize low molecular weight model compounds in order to gain a better understanding of the role played by metal centers on the properties of metallobiomolecules (Ibers & Holm, 1980). There are a great variety of model complexes (Mandal et al., 1997; Kim et al., 2001; Anderson et al., 1997), which involve pseudo-tetrahedral metal coordination with two N– and two S-donor atoms. From the biomimetic point of view, these molecular analogs with specific metal-coordination environments are very attractive, because of their similarity to biological systems found in nature. Among these can be mentioned those observed in (i) blue copper proteins (Gray & Solomon, 1981), (ii) carbon monoxide dehydrogenase (Diekert, 1988) and (iii) zinc finger proteins (Lipscomb & Sträter, 1996). Pioneering synthetic studies with such a family of proligands and their metal complexes were carried out by Nag & Joardar (1975, 1976) and Bereman et al. (1979, 1981). These authors focused their attention on (N₂S₂) proligands derived from 2-amino-1-cyclopentene-1-dithiocarboxylic acid. More recently, we have developed the synthesis of several ligands of the class ethyl-N,N'-alkyl-bis(2-amino-1-cyclopentenecarbodithioate) (Contreras et al., 2005) and 2,4-bis(cyclohexane)dispiro-1,2,3,4,4a,5,6,7-octahydro-(1H,3H)- quinazoline-8-carbodithioate (Contreras et al., 2001). In the present paper, the preparation of the nitrogen–sulfur tetradentate proligand benzyl-N,N'-propyl-bis(2-amino-1-cyclopentenecarbodithioate), (I), and its crystal structure are reported. This proligand has been successfully used as a chelating agent for Co^II, Ni^II, and Cu^II (Contreras, Fontal et al., 2004; Contreras, Suárez et al., 2004).

The molecule adopts pseudo-C₂ symmetry about atom C15 (Fig. 1). This molecular conformation is determined by the formation of pairs of intramolecular N—H···S and C—H···S hydrogen bonds. These interactions lead to the formation of six- and five- membered rings (see scheme), described by graph-set symbols S(6) and S(5), respectively (Bernstein et al., 1995). Details of the hydrogen-bonding geometry are given in Table 2. Each of these hydrogen-bonded rings (rings A–D) adopts a nearly planar conformation. In the six-membered rings A and B, the maximum deviation from the mean planes are 0.005 Å for C1 and 0.013 Å for C22. In the five-membered rings C and D, larger deviations are observed, viz. 0.045 Å for C1 and 0.062 Å for C22. Rings A and C are essentially coplanar, as are rings B and D, the dihedral angles between them being 3.73 (9) and 7.06 (8)°, respectively. The phenyl groups are twisted with respect to the mean plane of the hydrogen-bonded ring to which they are directly attached [dihedral angle between phenyl ring C8–C13 and ring C is 80.37 (11)°; that between phenyl ring C24–C29 and ring D is 75.32 (11)°]. The C2–C6 and C17–C21 rings adopt envelope conformations; the flap atoms C5 and C20 deviate from the respective planes by 0.168 (2) and 0.103 (2) Å.

The bond lengths in the S(6) rings have values (Table 1) typical of a conjugated system [average C—C = 1.39 Å and C—N = 1.320 Å] (Cambridge Structural Database; Version 5.25; Allen, 2002). These structural features suggest electron delocalization involving the nitrogen lone pair, the cyclopentene ring and the carbodithioate group. These distances agree with values previously reported in analogous compounds, such as methyl-N,N'-propyl-bis(2-amino-1-cylopentenecarbodithioate), methyl-N,N'-(3,6-diazaoctane)-bis(2-amino-1-cyclopentencarbodithioate), methyl-N,N'-diethylamino-bis(2-amino-1-cyclopentenecarbodithioate) (Sarkar & Gupta, 1981,1982a,b, respectively) and (R)-bis(N-phenylethyl-2-amino-1-cyclopentenemercaptomethyl)disulfide (Cea-Olivares et al., 1999). This electronic behaviour is consistent with the bathochromic shift observed in the absorption spectrum (see Experimental).

The crystal structure of (I) consists of dimers linked by self-complementary C—H···π interactions [C14···Cg3] related by an inversion centre (Fig. 2; Cg3 is the centroid of the C8–C13 phenyl ring). The other C—H···π interactions, C21···Cg4, lead to the formation, along the c axis, of ribbons built up from neighboring dimers (Fig. 3; Cg4 is the centroid of the C24–C29 phenyl ring). Finally, the stacking of adjacent ribbons is sustained by weak van der Waals interactions.

S2. Experimental

The reagents and solvents (Aldrich Chemical, Merck Co., Baker Analyzed and Eastman Co.) were used without further purification. Carbon disulfide was purified as described in the literature (Gordon & Ford, 1972). Proligand (I) was prepared by modifying the reaction conditions reported by Bordás et al. (1972), according to the method of Contreras et al. (2005). The reaction between cyclopentanone and carbon disulfide in ammonium hydroxide yielded 2-amino-1-cyclopentene-1-dithiocarboxylic acid, which was esterified with a mixture of benzyl chloride dissolved in an aqueous suspension of NaI. The product was synthesized via a Schiff base reaction with 1,3-diaminopropane. Yellow crystals, suitable for X-ray analysis, were obtained by recrystallization from toluene. Precaution: All handling and reactions must be carried out in a well ventilated fume hood and the residues properly disposed of. Analysis calculated for C₂₉H₃₂N₂S₄: C 64.88, H 6.01, N 5.22, S 23.89%; found: C 64.63, H 5.78, N 5.19, S 23.75%. Electronic spectral data, λ (cm^-1 ) (ε, M^-1 cm⁻¹): 44,050 (10,800), 31,550 (10,900), 25,690 (16,400), 25,000 (14,600). The electronic absorption spectrum shows bands in the ultraviolet region assigned as π → π* or n → π* transitions of the chromophoric groups present: –C═C– + K(benzene), C—S + B(benzene); –C═N– + –C═S–. These bands displayed a bathochromic effect. IR (cm⁻¹): 3452 (m), 1590 (s), 1485 (m), 1324 (m), 1269 (m), 950 (m), 914 (m), 702 (w). ¹H NMR spectrum shows the following results: δ 12.4 (2H, s), 7.78 (4H, d, J = 7.6 Hz), 7.27 (4H, t, J = 7.6 Hz), 7.24 (2H, d, J = 7.6 Hz), 4.52 (4H, s), 3.48 (2H, t, J = 6.4 Hz), 2.77 (2H, d, J = 7.6 Hz), 2.68 (4H, t, J = 7.4 Hz), 1.86 (4H, m), 1.80 (4H, m). The ¹³C NMR spectra show the following values: δ 202.7 (–CS₂C₇H₇), 169.8 (N—═C), 137.4, 129.3, 128.4, 127.1, 117.8, 42.9, 37.9, 33.3, 32.8, 20.6.

S3. Refinement

All H atoms bound to C atoms were included in calculated positions. The H atoms bonded to N (Table 2) were located in a Fourier difference map. All H atoms were refined using a riding model, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C,N).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXLTL-NT (Bruker, 1998); program(s) used to refine structure: SHELXLTL-NT; molecular graphics: SHELXLTL-NT and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXLTL-NT and PLATON (Spek, 2003).

Figures

	Fig. 1. Molecular structure of the title compound, showing the atom-labelling scheme and intramolecular hydrogen bonds (dashed lines). Displacement ellipsoids are drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Ball-and-stick representation, showing the centrosymmetric dimer generated by C—H···π interactions (dashed lines). [Symmetry code: (i) 1 − x, 1 − y, 2 − z.]
	Fig. 3. View of the one-dimensional ribbon along the c axis, generated by C—H···π interactions (dashed lines). [Symmetry code: (i) 1 − x, 1 − y, 2 − z; (ii) −x, 1 − y, 1 − z].

dibenzyl 2,2'-(propane-1,3-diyldiimino)bis(cyclopent-1-ene-1-carbodithioate)

Crystal data

C29H34N2S4	Z = 2
Mr = 538.82	F(000) = 572
Triclinic, P1	Dx = 1.266 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8860 (3) Å	Cell parameters from 25 reflections
b = 12.427 (3) Å	θ = 32.4–37.2°
c = 14.752 (3) Å	µ = 0.36 mm^−1
α = 90.62 (3)°	T = 298 K
β = 94.24 (3)°	Prism, yellow
γ = 101.25 (3)°	0.60 × 0.24 × 0.22 mm
V = 1413.6 (5) Å^3

Data collection

Rigaku AFC-7S diffractometer	3374 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 25.0°, θmin = 1.7°
ω–2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
Tmin = 0.861, Tmax = 0.921	l = −17→17
5320 measured reflections	3 standard reflections every 150 reflections
4986 independent reflections	intensity decay: none

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0418P)^2 + 0.4751P] where P = (Fo^2 + 2Fc^2)/3
4986 reflections	(Δ/σ)max = 0.001
316 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.19 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	0.21448 (10)	0.30419 (6)	0.96602 (5)	0.0608 (2)
S2	0.08771 (9)	0.32118 (7)	1.15285 (5)	0.0586 (2)
S3	0.06427 (10)	0.75861 (6)	0.62016 (5)	0.0618 (2)
S4	−0.29686 (10)	0.69583 (6)	0.52618 (5)	0.0595 (2)
N1	0.3263 (3)	0.54046 (19)	0.91476 (14)	0.0506 (5)
H1	0.3145	0.4711	0.9047	0.061*
N2	0.1485 (3)	0.53990 (18)	0.67601 (14)	0.0508 (5)
H2	0.1780	0.6138	0.6756	0.061*
C1	0.1804 (3)	0.3821 (2)	1.05541 (16)	0.0488 (6)
C2	0.2153 (3)	0.4956 (2)	1.06151 (16)	0.0476 (6)
C3	0.2833 (3)	0.5686 (2)	0.99481 (17)	0.0479 (6)
C4	0.2983 (4)	0.6850 (2)	1.02507 (19)	0.0587 (7)
H4A	0.2073	0.7170	0.9948	0.070*
H4B	0.4100	0.7284	1.0128	0.070*
C5	0.2791 (4)	0.6781 (3)	1.1272 (2)	0.0711 (9)
H5A	0.3918	0.6885	1.1608	0.085*
H5B	0.2181	0.7335	1.1475	0.085*
C6	0.1755 (4)	0.5638 (2)	1.14068 (18)	0.0570 (7)
H6A	0.0524	0.5642	1.1391	0.068*
H6B	0.2117	0.5352	1.1983	0.068*
C7	0.0752 (4)	0.1756 (2)	1.1360 (2)	0.0701 (9)
H7A	−0.0152	0.1365	1.1713	0.084*
H7B	0.0412	0.1566	1.0724	0.084*
C8	0.2416 (4)	0.1368 (2)	1.1621 (2)	0.0654 (8)
C9	0.3256 (4)	0.1627 (3)	1.2468 (2)	0.0704 (9)
H9	0.2789	0.2048	1.2872	0.085*
C10	0.4773 (5)	0.1281 (3)	1.2740 (3)	0.0932 (12)
H10	0.5316	0.1459	1.3318	0.112*
C11	0.5451 (6)	0.0678 (4)	1.2146 (4)	0.1239 (18)
H11	0.6485	0.0456	1.2317	0.149*
C12	0.4656 (8)	0.0385 (4)	1.1300 (4)	0.139 (2)
H12	0.5128	−0.0045	1.0907	0.166*
C13	0.3115 (6)	0.0743 (3)	1.1033 (3)	0.1067 (13)
H13	0.2569	0.0556	1.0457	0.128*
C14	0.3896 (3)	0.6170 (2)	0.84486 (17)	0.0545 (7)
H14A	0.4937	0.6672	0.8690	0.065*
H14B	0.3026	0.6598	0.8271	0.065*
C15	0.4294 (3)	0.5550 (2)	0.76260 (18)	0.0562 (7)
H15A	0.4796	0.6078	0.7193	0.067*
H15B	0.5161	0.5125	0.7816	0.067*
C16	0.2756 (3)	0.4787 (2)	0.71502 (18)	0.0549 (7)
H16A	0.3145	0.4375	0.6671	0.066*
H16B	0.2216	0.4269	0.7581	0.066*
C17	−0.0070 (3)	0.4951 (2)	0.63891 (16)	0.0459 (6)
C18	−0.1306 (3)	0.5495 (2)	0.59732 (16)	0.0472 (6)
C19	−0.2887 (3)	0.4653 (2)	0.56291 (18)	0.0542 (7)
H19A	−0.2991	0.4608	0.4970	0.065*
H19B	−0.3934	0.4841	0.5837	0.065*
C20	−0.2591 (4)	0.3572 (2)	0.6024 (2)	0.0724 (9)
H20A	−0.3304	0.3378	0.6528	0.087*
H20B	−0.2888	0.2988	0.5564	0.087*
C21	−0.0692 (4)	0.3734 (2)	0.63445 (19)	0.0556 (7)
H21A	−0.0543	0.3422	0.6938	0.067*
H21B	−0.0063	0.3392	0.5920	0.067*
C22	−0.1094 (3)	0.6619 (2)	0.58455 (16)	0.0481 (6)
C23	−0.2355 (4)	0.8398 (2)	0.4999 (2)	0.0678 (8)
H23A	−0.3360	0.8737	0.5019	0.081*
H23B	−0.1483	0.8759	0.5460	0.081*
C24	−0.1655 (4)	0.8569 (2)	0.4084 (2)	0.0624 (8)
C25	0.0087 (5)	0.8942 (2)	0.4006 (3)	0.0809 (10)
H25	0.0842	0.9105	0.4526	0.097*
C26	0.0722 (6)	0.9075 (3)	0.3144 (3)	0.0981 (13)
H26	0.1897	0.9337	0.3088	0.118*
C27	−0.0406 (7)	0.8815 (3)	0.2375 (3)	0.0972 (13)
H27	0.0015	0.8893	0.1802	0.117*
C28	−0.2103 (6)	0.8452 (3)	0.2452 (3)	0.0928 (11)
H28	−0.2855	0.8284	0.1932	0.111*
C29	−0.2743 (5)	0.8325 (3)	0.3298 (2)	0.0790 (9)
H29	−0.3923	0.8071	0.3340	0.095*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0693 (5)	0.0656 (5)	0.0475 (4)	0.0112 (4)	0.0099 (3)	−0.0007 (3)
S2	0.0560 (4)	0.0710 (5)	0.0516 (4)	0.0145 (4)	0.0156 (3)	0.0114 (4)
S3	0.0654 (5)	0.0491 (4)	0.0656 (5)	0.0012 (3)	−0.0042 (4)	0.0022 (3)
S4	0.0621 (5)	0.0551 (4)	0.0612 (5)	0.0133 (4)	−0.0021 (3)	0.0040 (4)
N1	0.0504 (13)	0.0588 (14)	0.0430 (12)	0.0101 (11)	0.0073 (10)	0.0076 (11)
N2	0.0555 (14)	0.0491 (13)	0.0481 (12)	0.0112 (11)	0.0039 (10)	0.0049 (10)
C1	0.0368 (14)	0.0698 (19)	0.0407 (14)	0.0124 (13)	0.0035 (11)	0.0054 (13)
C2	0.0401 (14)	0.0626 (18)	0.0418 (14)	0.0137 (13)	0.0042 (11)	0.0041 (13)
C3	0.0373 (14)	0.0629 (18)	0.0449 (15)	0.0144 (12)	−0.0004 (11)	0.0040 (13)
C4	0.0542 (17)	0.0627 (19)	0.0600 (18)	0.0131 (14)	0.0048 (13)	0.0040 (14)
C5	0.083 (2)	0.071 (2)	0.0605 (19)	0.0168 (18)	0.0126 (16)	−0.0063 (16)
C6	0.0537 (16)	0.073 (2)	0.0486 (16)	0.0213 (15)	0.0081 (13)	0.0017 (14)
C7	0.069 (2)	0.070 (2)	0.066 (2)	−0.0056 (16)	0.0169 (16)	0.0090 (16)
C8	0.076 (2)	0.0512 (18)	0.071 (2)	0.0090 (16)	0.0263 (17)	0.0127 (16)
C9	0.065 (2)	0.065 (2)	0.083 (2)	0.0109 (16)	0.0169 (17)	0.0146 (17)
C10	0.079 (3)	0.083 (3)	0.119 (3)	0.017 (2)	0.013 (2)	0.034 (2)
C11	0.115 (4)	0.111 (4)	0.168 (5)	0.059 (3)	0.054 (4)	0.055 (4)
C12	0.178 (6)	0.131 (4)	0.141 (5)	0.093 (4)	0.068 (4)	0.020 (4)
C13	0.150 (4)	0.092 (3)	0.092 (3)	0.047 (3)	0.039 (3)	0.008 (2)
C14	0.0511 (16)	0.0638 (18)	0.0470 (15)	0.0068 (14)	0.0045 (12)	0.0091 (13)
C15	0.0479 (16)	0.075 (2)	0.0494 (16)	0.0183 (14)	0.0115 (12)	0.0163 (14)
C16	0.0621 (17)	0.0589 (18)	0.0482 (15)	0.0205 (14)	0.0098 (13)	0.0073 (13)
C17	0.0528 (16)	0.0475 (16)	0.0361 (13)	0.0040 (13)	0.0118 (12)	0.0006 (11)
C18	0.0518 (15)	0.0489 (16)	0.0409 (14)	0.0090 (13)	0.0051 (11)	0.0009 (12)
C19	0.0563 (16)	0.0525 (17)	0.0510 (16)	0.0041 (13)	0.0048 (13)	−0.0015 (13)
C20	0.076 (2)	0.0535 (19)	0.080 (2)	−0.0016 (16)	−0.0060 (17)	0.0011 (16)
C21	0.0678 (19)	0.0470 (16)	0.0528 (16)	0.0103 (14)	0.0124 (14)	0.0022 (13)
C22	0.0525 (15)	0.0517 (17)	0.0399 (14)	0.0089 (13)	0.0062 (11)	−0.0007 (12)
C23	0.084 (2)	0.0514 (18)	0.071 (2)	0.0219 (16)	0.0021 (17)	−0.0001 (15)
C24	0.086 (2)	0.0374 (16)	0.065 (2)	0.0162 (15)	0.0050 (17)	0.0052 (14)
C25	0.100 (3)	0.0446 (18)	0.095 (3)	0.0057 (18)	0.011 (2)	0.0067 (17)
C26	0.106 (3)	0.050 (2)	0.135 (4)	−0.001 (2)	0.035 (3)	0.014 (2)
C27	0.149 (4)	0.055 (2)	0.091 (3)	0.016 (2)	0.039 (3)	0.012 (2)
C28	0.134 (4)	0.074 (3)	0.069 (2)	0.018 (2)	0.007 (2)	0.0077 (19)
C29	0.094 (3)	0.071 (2)	0.073 (2)	0.0200 (19)	0.003 (2)	0.0078 (18)

Geometric parameters (Å, º)

S1—C1	1.695 (3)	C12—H12	0.9300
S2—C1	1.771 (3)	C13—H13	0.9300
S2—C7	1.805 (3)	C14—C15	1.515 (4)
S3—C22	1.683 (3)	C14—H14A	0.9700
S4—C22	1.780 (3)	C14—H14B	0.9700
S4—C23	1.814 (3)	C15—C16	1.508 (4)
N1—C3	1.315 (3)	C15—H15A	0.9700
N1—C14	1.459 (3)	C15—H15B	0.9700
N1—H1	0.8583	C16—H16A	0.9700
N2—C17	1.320 (3)	C16—H16B	0.9700
N2—C16	1.461 (3)	C17—C18	1.400 (4)
N2—H2	0.9019	C17—C21	1.495 (4)
C1—C2	1.385 (4)	C18—C22	1.390 (4)
C2—C3	1.409 (4)	C18—C19	1.515 (4)
C2—C6	1.522 (4)	C19—C20	1.523 (4)
C3—C4	1.489 (4)	C19—H19A	0.9700
C4—C5	1.527 (4)	C19—H19B	0.9700
C4—H4A	0.9700	C20—C21	1.511 (4)
C4—H4B	0.9700	C20—H20A	0.9700
C5—C6	1.517 (4)	C20—H20B	0.9700
C5—H5A	0.9700	C21—H21A	0.9700
C5—H5B	0.9700	C21—H21B	0.9700
C6—H6A	0.9700	C23—C24	1.497 (4)
C6—H6B	0.9700	C23—H23A	0.9700
C7—C8	1.510 (4)	C23—H23B	0.9700
C7—H7A	0.9700	C24—C25	1.375 (4)
C7—H7B	0.9700	C24—C29	1.385 (4)
C8—C13	1.372 (5)	C25—C26	1.402 (5)
C8—C9	1.375 (4)	C25—H25	0.9300
C9—C10	1.382 (5)	C26—C27	1.383 (6)
C9—H9	0.9300	C26—H26	0.9300
C10—C11	1.351 (6)	C27—C28	1.341 (5)
C10—H10	0.9300	C27—H27	0.9300
C11—C12	1.367 (7)	C28—C29	1.379 (5)
C11—H11	0.9300	C28—H28	0.9300
C12—C13	1.404 (6)	C29—H29	0.9300
C1—S2—C7	105.12 (14)	H14A—C14—H14B	108.1
C22—S4—C23	105.38 (14)	C16—C15—C14	115.0 (2)
C3—N1—C14	125.1 (2)	C16—C15—H15A	108.5
C3—N1—H1	115.1	C14—C15—H15A	108.5
C14—N1—H1	119.8	C16—C15—H15B	108.5
C17—N2—C16	124.8 (2)	C14—C15—H15B	108.5
C17—N2—H2	116.6	H15A—C15—H15B	107.5
C16—N2—H2	118.5	N2—C16—C15	111.0 (2)
C2—C1—S1	126.2 (2)	N2—C16—H16A	109.4
C2—C1—S2	112.62 (19)	C15—C16—H16A	109.4
S1—C1—S2	121.15 (17)	N2—C16—H16B	109.4
C1—C2—C3	126.9 (2)	C15—C16—H16B	109.4
C1—C2—C6	125.2 (2)	H16A—C16—H16B	108.0
C3—C2—C6	107.8 (2)	N2—C17—C18	127.1 (2)
N1—C3—C2	125.8 (3)	N2—C17—C21	121.4 (2)
N1—C3—C4	122.8 (2)	C18—C17—C21	111.4 (2)
C2—C3—C4	111.4 (2)	C22—C18—C17	126.0 (2)
C3—C4—C5	103.9 (2)	C22—C18—C19	124.9 (2)
C3—C4—H4A	111.0	C17—C18—C19	108.9 (2)
C5—C4—H4A	111.0	C18—C19—C20	105.1 (2)
C3—C4—H4B	111.0	C18—C19—H19A	110.7
C5—C4—H4B	111.0	C20—C19—H19A	110.7
H4A—C4—H4B	109.0	C18—C19—H19B	110.7
C6—C5—C4	105.2 (2)	C20—C19—H19B	110.7
C6—C5—H5A	110.7	H19A—C19—H19B	108.8
C4—C5—H5A	110.7	C21—C20—C19	107.0 (2)
C6—C5—H5B	110.7	C21—C20—H20A	110.3
C4—C5—H5B	110.7	C19—C20—H20A	110.3
H5A—C5—H5B	108.8	C21—C20—H20B	110.3
C5—C6—C2	104.4 (2)	C19—C20—H20B	110.3
C5—C6—H6A	110.9	H20A—C20—H20B	108.6
C2—C6—H6A	110.9	C17—C21—C20	104.8 (2)
C5—C6—H6B	110.9	C17—C21—H21A	110.8
C2—C6—H6B	110.9	C20—C21—H21A	110.8
H6A—C6—H6B	108.9	C17—C21—H21B	110.8
C8—C7—S2	114.6 (2)	C20—C21—H21B	110.8
C8—C7—H7A	108.6	H21A—C21—H21B	108.9
S2—C7—H7A	108.6	C18—C22—S3	126.8 (2)
C8—C7—H7B	108.6	C18—C22—S4	111.27 (19)
S2—C7—H7B	108.6	S3—C22—S4	121.87 (16)
H7A—C7—H7B	107.6	C24—C23—S4	112.7 (2)
C13—C8—C9	118.4 (4)	C24—C23—H23A	109.0
C13—C8—C7	121.5 (4)	S4—C23—H23A	109.0
C9—C8—C7	120.1 (3)	C24—C23—H23B	109.0
C8—C9—C10	122.1 (3)	S4—C23—H23B	109.0
C8—C9—H9	119.0	H23A—C23—H23B	107.8
C10—C9—H9	119.0	C25—C24—C29	118.6 (3)
C11—C10—C9	118.5 (4)	C25—C24—C23	120.8 (3)
C11—C10—H10	120.7	C29—C24—C23	120.6 (3)
C9—C10—H10	120.7	C24—C25—C26	119.9 (4)
C10—C11—C12	121.8 (5)	C24—C25—H25	120.0
C10—C11—H11	119.1	C26—C25—H25	120.0
C12—C11—H11	119.1	C27—C26—C25	119.7 (4)
C11—C12—C13	119.1 (5)	C27—C26—H26	120.1
C11—C12—H12	120.4	C25—C26—H26	120.1
C13—C12—H12	120.4	C28—C27—C26	120.3 (4)
C8—C13—C12	120.1 (4)	C28—C27—H27	119.9
C8—C13—H13	120.0	C26—C27—H27	119.9
C12—C13—H13	120.0	C27—C28—C29	120.5 (4)
N1—C14—C15	110.2 (2)	C27—C28—H28	119.8
N1—C14—H14A	109.6	C29—C28—H28	119.8
C15—C14—H14A	109.6	C28—C29—C24	121.1 (4)
N1—C14—H14B	109.6	C28—C29—H29	119.5
C15—C14—H14B	109.6	C24—C29—H29	119.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1	0.86	2.29	3.018 (3)	142
N2—H2···S3	0.90	2.29	3.030 (2)	138
C7—H7B···S1	0.97	2.66	3.140 (3)	111
C23—H23B···S3	0.97	2.62	3.179 (3)	117
C14—H14A···Cg3^i	0.97	2.99	3.64 (5)	125
C21—H21A···Cg4^ii	0.97	3.13	3.58 (4)	110
C21—H21B···Cg4^ii	0.97	3.13	3.58 (4)	110

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