Hydrogen-bonded chains of rings in 1-(4-chloro­anilinometh­yl)-5-(4-chloro­phen­yl)-1,3,5-tri­azinane-2-thione and hydrogen-bonded sheets in 1-anilino­meth­yl-5-phenyl-1,3,5-tri­azinane-2-thione

In 1-(4-chloro­anilinometh­yl)-5-(4-chloro­phen­yl)-1,3,5-tri­az­in­ane-2-thione, C₁₆H₁₆Cl₂N₄S, there are two independent mol­ecules in the asymmetric unit which form inversion dimers via two weak N—H...S hydrogen bonds. The dimers are then linked into C(9)C(14) chains by a C—H...S hydrogen bond and a C—H...Cl contact. In 1-(an­il­ino­methyl)-5-phenyl-1,3,5-triazinane-2-thione, C₁₆H₁₈N₄S, mol­ecules are linked into complex sheets via a combination of N—H...S and C—H...π hydrogen bonds.

S1. Comment

Heterocyclic compounds containing the thiourea structural unit have been found to have powerful bioactivity, such as powerful ectoparasiticidal action (Enders et al., 1979), potent antidiabetic properties (Lenzen & Ahmad, 2001) and anti-HIV activity (Lam et al., 1994; Acharya et al., 2001). In addition, some of these compounds can serve as calcium channel blockers, antihypertensive agents and α-1a-antagonists (Atwal et al. 1990). Therefore, it is not surprising that the search for new methods to synthesize heterocyclic compounds starting from thiourea has received special attention. Burke and Petersen gave early reports of synthetic studies of 5-alkyl- or 4,6-dialkyl-substituted 1,3,5-triazinane-2-thiones (Burke, 1947; Petersen, 1973). In our research to develop new routes to diversely substituted 1,3,5-triazinane-2-thiones, several novel 1,5-disubstituted 1,3,5-triazinane-2-thiones have been synthesized by a one-pot three-component condensation of thiourea, aniline and formaldehyde (Zhang et al., 2008). We report here the molecular and supramolecular structures of two such compounds, namely 5-(4-chlorophenyl)-1-[(4-chlorophenylanilino)methyl]-1,3,5-triazinane-2-thione, (I), and 5-phenyl-1-[(phenylamino)methyl]-1,3,5-triazinane-2-thione, (II) (Figs. 1 and 2).

Compound (I) crystallizes with Z' = 2 in the space group P2₁ and the molecular geometries of the two independent molecules, (Ia) and (Ib) (Fig. 1), are very similar. The triazinane-2-thione rings adopt envelope conformations; atoms N1 and N5 are the flap atoms, displaced by 0.652 and 0.665 Å, respectively, from the planes of the other five atoms. The conformations of the two heterocyclic structural units and the coplanarity of the S1/C9/N2/N3/C7/C8 and S2/C24/N6/N7/C23/C25 fragments in (Ia) and (Ib) are similar to the situation found in other cyclic thiones (Zhang, Zhang et al., 2007; Pavlović et al., 2000).

The intramolecular geometries in molecules (Ia) and (Ib) present some unexpected features. Within the aryl rings, the C12—C13, C18—C19 and C17—C22 bonds are significantly shorter than those found in similar structural units [1.373 (3)–1.398 (3) Å; Zhang, Qin et al., 2007], while the C2—C3, C4—C5, C11—C12, C27—C28, C17—C18 and C20—C21 bonds all are longer than the remainder (Table 1). Within the two heterocyclic rings, the N3—C9 and N7—C24 bonds are significantly longer than the N2—C9 and N6—C24 bonds, respectively. In addition, both the N1—C4 and N5—C20 bonds are significantly longer than the N4—C11 and N8—C27 bonds. For the N1—C4 and N5—C20 bonds, these large differences in bond length are probably due to the different hybridized states between atoms N1 and N4, N5 and N8, N2 and N3 or N6 and N7. This can be confirmed by the fact that the sums of the interbond angles at atoms N1 and N5 deviate by 20 and 15°, respectively, from 360°, indicating that these two atoms have sp³ character, although they are bonded to the corresponding phenyl rings.

Interestingly, all the molecules for (Ia), (Ib) and (II) adopt cis conformations (Figs. 1 and 2); the phenyl and phenylanilinomethyl groups lie on the same sides of the heterocycle and the dihedral angles between the two aromatic rings in (Ia), (Ib) and (II) are 71.13, 67.35 and 71.89°, respectively, indicating that these benzene rings are nearly perpendicular to one another.

In (II), the heterocycle adopts an envelope conformation; atom N1 is the flap atom, displaced by 0.637 Å from the plane of the other five atoms. The C1—N1 bond is significantly longer than the C11—N4 bond (Table 1). The sum of the three angles around atom N1 is 341.61 (6)° (Table 1), which is significantly smaller than those around atoms N2, N3 or N4. These three features for (II) are similar to the situation in (I).

Within the selected asymmetric unit of (I), the two independent molecules are linked by two weak N—H···S hydrogen bonds (Fig. 1 and Table 2), forming an R₂²(8) (Bernstein et al., 1995) dimer centred at (1/6, 1/4, 1/5). Dimers of this type are further linked by two weak intermolecular interactions [a C—H···S hydrogen bond and a C—H···Cl contact (Table 2)] to form a zigzag chain (Fig. 3). Aromatic ring atom C2 and atom Cl1 in the dimeric unit at (x, y, z) act as hydrogen-bond donors and form intermolecular contacts to, respectively, thiocarbonyl atom S1 and atom H23A in the molecule at (-x, y + 1/2, -z) (Table 2), so generating by inversion a C(9)C(14) chain of R₂²(8) rings along the [010] direction (Fig. 3). Two such chains pass through each unit cell, and they are related to one another by propagation and hence parallel. There are no direction-specific interactions between the two chains.

In compound (II) (Fig. 2 and Table 3), the molecules are linked into sheets of considerable complexity by two hydrogen bonds, one of N—H···S type and one of C—H···π(arene) type (Table 4). However, the two-dimensional structure is readily analysed in terms of two relatively simple one-dimensional substructures. In the first substructure, atom N2 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom S1 in the molecule at (-x, -y, -z + 1), so generating by inversion a dimer centred at (0, 0, 1/2) and characterized by the usual R₂²(8) motif (Fig. 1) [Should this not rather refer to Fig. 4 or 5?]. The dimer can be regarded as the backone building unit, from which the first substructure is built by only one C—H···π hydrogen bond. Atom C2 in the molecule at (x, y, z), part of the dimer at (0, 0, 1/2), acts as hydrogen-bond donor to the C11–C16 ring in the molecule at (-1/2 + x, 1/2 - y, 1/2 + z), which is part of the dimer centred at (-1/2, 1/2, 1). Propagation by inversion then generates a C₂²(8) chain along (-1/4, y, 3/4) (Fig. 4). In the second substructure, atom C2 in the molecule at (x, y, z) acts as hydrogen-bond donor to the C11–C16 ring in the molecule at (x - 1/2, -y + 1/2, z + 1/2), so forming a hydrogen-bonded chain running along the [101] direction and generated by a 2₁ screw axis along [101] (Fig. 5). The combination of these two chain motifs is sufficient to link all the molecules into a two-demensional sheet parallel to [101]. Two such sheets pass through each unit cell, in the domains 0 < x < 1, 0 < z < 1 and 1 < x < 2, 1 < z < 2, and there are no direction-specific interactions between the two sheets.

Related literature

For related literature, see: Acharya et al. (2001); Atwal et al. (1990); Bernstein et al. (1995); Burke (1947); Enders et al. (1979); Lam et al. (1994); Lenzen & Ahmad (2001); Pavlović et al. (2000); Petersen (1973); Zhang et al. (2008); Zhang, Qin, Wang & Qu (2007); Zhang, Zhang, Guo & Qu (2007).

S2. Experimental

Brief details of the syntheses of the title compounds, (I) and (II), will be reported elsewhere (Zhang et al., 2008). Crystals of (I) were obtained by recrystallization from dimethyl sulfoxide. Spectroscopic analysis: ¹H NMR (DMSO, 400 MHz, δ, p.p.m.): 8.37 (s, 1H), 6.796–7.076 (m, 8H), 6.59 (t, J = 6.8 Hz, 1H), 5.20–5.19 (d, J = 6.8 Hz, 2H), 4.78 (s, 2H), 4.57 (s, 2H). Crystals of (II) were obtained by recrystallization from acetonitrile. Spectroscopic analysis: ¹H NMR (DMSO, 400 MHz, δ, p.p.m.): 8.30 (s, 1H), 7.10–6.58 (m, 10H), 6.45 (t, J = 7.2 Hz, 1H), 5.23 (d, J = 6.8 Hz, 2H), 4.79 (s, 2H), 4.57 (s, 2H).

S3. Refinement

H atoms were placed in idealized positions and allowed to ride on their respective parent atoms, with C—H = 0.98 Å and N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(C,N).

Computing details

For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The two independent molecules in compound (I), viz. (a) a type A molecule and (b) a type B molecule. [Molecules A and B are not distinguished - please clarify.] Displacement ellipsoids are drawn at the 16% [Very low?] probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II), showing the the atom-labelling scheme. Displacement ellipsoids are drawn at the 16% [Very low?] probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a C(9) C(14) chain parallel to the [010] direction. For the sake of clarity, H atoms not involved in the motif shown have been ommited. Selected atoms are labelled. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) -x, -1/2 + y, -z; (ii) -x, 1/2 + y, -z].
	Fig. 4. Part of the crystal structure of (II), showing the formation of a hydogen-bonded chain along the (-1/4, y, 3/4) direction. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Selected atoms are labelled. Dashed lines indicate hydrogen bonds. Cg is the centroid of the C11–C16 ring. [Symmetry codes: (i) -x, -y, 1 - z; (ii) -1/2 + x, 1/2 - y, 1/2 + z.]
	Fig. 5. Part of the crystal structure of (II), showing the formation of a hydrogen-bonded chain running along the [101] direction. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Selected atoms are labelled. Dashed lines indicate hydrogen bonds. Cg is the centroid of the C11–C16 ring. [Symmetry codes: (i) -1/2 + x, 1/2 - y, 1/2 + z; (ii) 1/2 + x, 1/2 - y, -1/2 + z.]

(I) 5-(4-chlorophenyl)-1-[(4-chlorophenylanilino)methyl]-1,3,5-triazinane-2-thione

Crystal data

C32H32Cl4N8S2	F(000) = 760
Mr = 734.58	Dx = 1.421 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 5.9271 (17) Å	Cell parameters from 2502 reflections
b = 16.398 (5) Å	θ = 2.3–20.4°
c = 17.864 (5) Å	µ = 0.50 mm^−1
β = 98.468 (4)°	T = 291 K
V = 1717.3 (9) Å^3	Block, yellow
Z = 2	0.38 × 0.30 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer	6252 independent reflections
Radiation source: fine-focus sealed tube	3942 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ϕ and ω scans	θmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.832, Tmax = 0.889	k = −19→19
13046 measured reflections	l = −21→21

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)] = 0.061	H-atom parameters constrained
wR(F^2) = 0.165	w = 1/[σ^2(Fo^2) + (0.0849P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
6252 reflections	Δρmax = 0.43 e Å^−3
415 parameters	Δρmin = −0.27 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (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
S1	0.3766 (2)	0.18079 (8)	0.14371 (7)	0.0568 (3)
Cl1	−0.3002 (3)	0.44557 (13)	−0.18697 (9)	0.0955 (6)
Cl2	0.0826 (4)	0.07668 (15)	−0.25984 (11)	0.1131 (7)
N1	0.4912 (8)	0.4340 (3)	0.0629 (3)	0.0659 (12)
N2	0.3528 (7)	0.3422 (3)	0.1495 (2)	0.0563 (10)
H2D	0.2424	0.3338	0.1748	0.068*
N3	0.6127 (6)	0.2920 (3)	0.0745 (2)	0.0542 (11)
N4	0.7768 (8)	0.2280 (3)	−0.0285 (3)	0.0711 (13)
H4D	0.8924	0.2502	−0.0444	0.085*
C1	−0.0625 (9)	0.4441 (4)	−0.1154 (3)	0.0681 (15)
C2	−0.0398 (11)	0.5015 (4)	−0.0594 (4)	0.0716 (16)
H2	−0.1468	0.5430	−0.0600	0.086*
C3	0.1458 (10)	0.4974 (3)	−0.0011 (4)	0.0686 (16)
H3	0.1623	0.5370	0.0366	0.082*
C4	0.3051 (9)	0.4352 (3)	0.0014 (3)	0.0577 (13)
C5	0.2854 (10)	0.3791 (4)	−0.0596 (3)	0.0659 (15)
H5	0.3953	0.3389	−0.0610	0.079*
C6	0.1015 (11)	0.3844 (4)	−0.1169 (3)	0.0765 (17)
H6	0.0882	0.3475	−0.1569	0.092*
C7	0.4206 (10)	0.4268 (3)	0.1380 (3)	0.0652 (15)
H7A	0.2935	0.4632	0.1416	0.078*
H7B	0.5458	0.4421	0.1767	0.078*
C8	0.6743 (9)	0.3775 (3)	0.0589 (3)	0.0632 (14)
H8A	0.8048	0.3936	0.0952	0.076*
H8B	0.7189	0.3803	0.0089	0.076*
C9	0.4539 (8)	0.2766 (3)	0.1225 (3)	0.0500 (12)
C10	0.7658 (9)	0.2292 (4)	0.0528 (3)	0.0635 (14)
H10A	0.7147	0.1763	0.0679	0.076*
H10B	0.9178	0.2384	0.0799	0.076*
C11	0.6103 (9)	0.1928 (3)	−0.0812 (3)	0.0601 (14)
C12	0.6426 (11)	0.1928 (4)	−0.1581 (3)	0.0791 (18)
H12	0.7701	0.2178	−0.1727	0.095*
C13	0.4859 (13)	0.1561 (5)	−0.2104 (4)	0.091 (2)
H13	0.5130	0.1531	−0.2603	0.110*
C14	0.2858 (11)	0.1229 (4)	−0.1915 (3)	0.0737 (16)
C15	0.2498 (10)	0.1243 (4)	−0.1171 (3)	0.0723 (16)
H15	0.1168	0.1023	−0.1036	0.087*
C16	0.4118 (10)	0.1583 (3)	−0.0628 (3)	0.0662 (15)
H16	0.3874	0.1581	−0.0125	0.079*
S2	−0.0579 (2)	0.33959 (9)	0.26616 (8)	0.0659 (4)
Cl3	0.5677 (4)	0.02080 (16)	0.59585 (13)	0.1272 (8)
Cl4	0.2643 (4)	0.34901 (18)	0.68867 (10)	0.1220 (8)
N5	−0.1709 (8)	0.0824 (3)	0.3362 (3)	0.0665 (12)
N6	−0.0346 (7)	0.1794 (3)	0.2543 (2)	0.0636 (12)
H6D	0.0753	0.1898	0.2293	0.076*
N7	−0.2895 (7)	0.2236 (3)	0.3309 (2)	0.0608 (11)
N8	−0.4706 (8)	0.2758 (4)	0.4348 (3)	0.0875 (16)
H8D	−0.5985	0.2591	0.4464	0.105*
C17	0.3506 (12)	0.0417 (5)	0.5201 (4)	0.0848 (19)
C18	0.3579 (12)	0.0039 (4)	0.4499 (4)	0.0852 (19)
H18	0.4768	−0.0313	0.4437	0.102*
C19	0.1902 (11)	0.0191 (4)	0.3913 (4)	0.0735 (16)
H19	0.1960	−0.0061	0.3450	0.088*
C20	0.0095 (10)	0.0715 (4)	0.3986 (3)	0.0627 (14)
C21	0.0080 (13)	0.1096 (5)	0.4688 (3)	0.088 (2)
H21	−0.1077	0.1460	0.4755	0.106*
C22	0.1792 (13)	0.0928 (5)	0.5279 (4)	0.095 (2)
H22	0.1754	0.1177	0.5744	0.114*
C23	−0.1022 (11)	0.0943 (4)	0.2609 (3)	0.0665 (16)
H23A	0.0244	0.0586	0.2549	0.080*
H23B	−0.2284	0.0814	0.2217	0.080*
C24	−0.1329 (8)	0.2417 (3)	0.2847 (3)	0.0526 (14)
C25	−0.3538 (9)	0.1374 (4)	0.3427 (3)	0.0678 (16)
H25A	−0.3986	0.1319	0.3925	0.081*
H25B	−0.4841	0.1230	0.3055	0.081*
C26	−0.4481 (10)	0.2839 (5)	0.3566 (3)	0.0793 (18)
H26A	−0.3939	0.3384	0.3479	0.095*
H26B	−0.5972	0.2776	0.3265	0.095*
C27	−0.2960 (10)	0.2936 (4)	0.4927 (3)	0.0707 (16)
C28	−0.3203 (12)	0.2705 (5)	0.5672 (3)	0.0826 (18)
H28	−0.4521	0.2441	0.5766	0.099*
C29	−0.1503 (13)	0.2869 (5)	0.6256 (4)	0.092 (2)
H29	−0.1704	0.2727	0.6746	0.111*
C30	0.0509 (12)	0.3240 (4)	0.6138 (3)	0.0811 (18)
C31	0.0752 (10)	0.3484 (4)	0.5414 (3)	0.0783 (17)
H31	0.2067	0.3757	0.5331	0.094*
C32	−0.0950 (9)	0.3326 (4)	0.4809 (3)	0.0734 (16)
H32	−0.0747	0.3480	0.4323	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0568 (7)	0.0636 (8)	0.0517 (7)	−0.0059 (6)	0.0142 (6)	0.0041 (7)
Cl1	0.0847 (11)	0.1269 (15)	0.0714 (10)	−0.0115 (11)	0.0000 (8)	0.0259 (11)
Cl2	0.1211 (17)	0.1401 (18)	0.0743 (13)	−0.0109 (13)	0.0011 (11)	−0.0234 (11)
N1	0.068 (3)	0.065 (3)	0.065 (3)	−0.007 (3)	0.012 (2)	0.008 (2)
N2	0.066 (3)	0.056 (3)	0.050 (2)	−0.003 (2)	0.018 (2)	−0.001 (2)
N3	0.042 (2)	0.068 (3)	0.054 (2)	−0.002 (2)	0.0110 (19)	0.007 (2)
N4	0.055 (3)	0.099 (4)	0.062 (3)	−0.010 (3)	0.020 (2)	−0.001 (3)
C1	0.066 (3)	0.084 (4)	0.054 (3)	0.000 (3)	0.008 (3)	0.021 (3)
C2	0.075 (4)	0.063 (4)	0.077 (4)	0.008 (3)	0.013 (3)	0.014 (3)
C3	0.083 (4)	0.052 (3)	0.072 (4)	−0.004 (3)	0.015 (3)	−0.004 (3)
C4	0.064 (3)	0.054 (3)	0.057 (3)	−0.001 (3)	0.015 (3)	0.013 (3)
C5	0.078 (4)	0.070 (4)	0.051 (3)	0.010 (3)	0.013 (3)	0.001 (3)
C6	0.092 (4)	0.083 (4)	0.055 (4)	−0.013 (4)	0.013 (3)	0.006 (3)
C7	0.074 (4)	0.068 (4)	0.053 (3)	−0.002 (3)	0.008 (3)	0.000 (3)
C8	0.063 (3)	0.065 (4)	0.063 (3)	−0.012 (3)	0.014 (3)	0.005 (3)
C9	0.045 (3)	0.059 (3)	0.045 (3)	−0.007 (2)	0.003 (2)	0.003 (2)
C10	0.051 (3)	0.089 (4)	0.051 (3)	0.003 (3)	0.011 (2)	0.007 (3)
C11	0.056 (3)	0.064 (4)	0.063 (3)	0.008 (3)	0.017 (3)	0.011 (3)
C12	0.087 (4)	0.099 (5)	0.057 (4)	−0.014 (4)	0.028 (3)	−0.005 (3)
C13	0.112 (5)	0.113 (6)	0.052 (4)	−0.001 (4)	0.023 (4)	0.001 (4)
C14	0.082 (4)	0.074 (4)	0.064 (4)	0.002 (3)	0.007 (3)	−0.003 (3)
C15	0.063 (4)	0.090 (4)	0.064 (4)	−0.006 (3)	0.009 (3)	0.000 (3)
C16	0.074 (4)	0.075 (4)	0.054 (3)	−0.003 (3)	0.022 (3)	0.001 (3)
S2	0.0646 (9)	0.0734 (9)	0.0605 (9)	0.0001 (8)	0.0118 (7)	0.0038 (8)
Cl3	0.1155 (16)	0.160 (2)	0.0972 (16)	0.0135 (15)	−0.0150 (12)	0.0239 (14)
Cl4	0.1150 (14)	0.175 (2)	0.0705 (11)	0.0108 (15)	−0.0039 (10)	−0.0220 (13)
N5	0.079 (3)	0.071 (3)	0.052 (3)	−0.009 (3)	0.016 (3)	0.002 (2)
N6	0.069 (3)	0.067 (3)	0.060 (3)	0.000 (3)	0.025 (2)	0.003 (3)
N7	0.052 (3)	0.072 (3)	0.061 (3)	0.007 (2)	0.016 (2)	−0.004 (2)
N8	0.064 (3)	0.137 (5)	0.065 (3)	−0.006 (3)	0.023 (3)	−0.010 (3)
C17	0.087 (5)	0.091 (5)	0.073 (5)	−0.003 (4)	−0.001 (4)	0.020 (4)
C18	0.092 (5)	0.085 (5)	0.081 (5)	0.019 (4)	0.020 (4)	0.016 (4)
C19	0.079 (4)	0.075 (4)	0.070 (4)	0.006 (3)	0.020 (3)	0.001 (3)
C20	0.068 (4)	0.067 (3)	0.055 (3)	−0.012 (3)	0.015 (3)	0.004 (3)
C21	0.108 (5)	0.100 (5)	0.058 (4)	0.023 (4)	0.016 (4)	−0.001 (4)
C22	0.107 (6)	0.119 (6)	0.057 (4)	0.033 (5)	0.004 (4)	−0.007 (4)
C23	0.080 (4)	0.079 (4)	0.042 (3)	0.001 (3)	0.014 (3)	−0.003 (3)
C24	0.043 (3)	0.074 (4)	0.040 (3)	0.000 (3)	0.006 (2)	0.006 (2)
C25	0.058 (4)	0.090 (5)	0.057 (4)	−0.007 (3)	0.015 (3)	0.008 (3)
C26	0.058 (3)	0.114 (5)	0.068 (4)	0.011 (3)	0.013 (3)	−0.009 (4)
C27	0.067 (4)	0.082 (4)	0.065 (4)	0.006 (3)	0.019 (3)	−0.014 (3)
C28	0.089 (4)	0.107 (5)	0.056 (4)	−0.006 (4)	0.026 (3)	0.004 (4)
C29	0.106 (5)	0.099 (5)	0.076 (5)	0.018 (4)	0.027 (4)	0.004 (4)
C30	0.086 (4)	0.100 (5)	0.055 (4)	0.013 (4)	0.005 (3)	−0.013 (3)
C31	0.078 (4)	0.093 (5)	0.066 (4)	−0.005 (4)	0.015 (3)	−0.002 (4)
C32	0.067 (4)	0.095 (4)	0.061 (4)	−0.006 (3)	0.017 (3)	−0.012 (3)

Geometric parameters (Å, º)

S1—C9	1.695 (5)	S2—C24	1.711 (5)
Cl1—C1	1.757 (6)	Cl3—C17	1.757 (7)
Cl2—C14	1.756 (6)	Cl4—C30	1.749 (6)
N1—C8	1.437 (7)	N5—C25	1.427 (7)
N1—C4	1.438 (7)	N5—C20	1.437 (7)
N1—C7	1.468 (7)	N5—C23	1.475 (6)
N2—C9	1.354 (6)	N6—C24	1.331 (6)
N2—C7	1.468 (7)	N6—C23	1.461 (7)
N2—H2D	0.8600	N6—H6D	0.8600
N3—C9	1.386 (6)	N7—C24	1.362 (6)
N3—C10	1.463 (7)	N7—C26	1.484 (7)
N3—C8	1.485 (7)	N7—C25	1.487 (8)
N4—C11	1.385 (7)	N8—C27	1.382 (7)
N4—C10	1.464 (7)	N8—C26	1.428 (7)
N4—H4D	0.8600	N8—H8D	0.8600
C1—C2	1.365 (8)	C17—C22	1.340 (9)
C1—C6	1.383 (8)	C17—C18	1.406 (10)
C2—C3	1.401 (8)	C18—C19	1.357 (8)
C2—H2	0.9300	C18—H18	0.9300
C3—C4	1.385 (8)	C19—C20	1.394 (8)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.418 (8)	C20—C21	1.403 (8)
C5—C6	1.384 (8)	C21—C22	1.380 (9)
C5—H5	0.9300	C21—H21	0.9300
C6—H6	0.9300	C22—H22	0.9300
C7—H7A	0.9700	C23—H23A	0.9700
C7—H7B	0.9700	C23—H23B	0.9700
C8—H8A	0.9700	C25—H25A	0.9700
C8—H8B	0.9700	C25—H25B	0.9700
C10—H10A	0.9700	C26—H26A	0.9700
C10—H10B	0.9700	C26—H26B	0.9700
C11—C16	1.388 (7)	C27—C32	1.395 (8)
C11—C12	1.415 (8)	C27—C28	1.412 (8)
C12—C13	1.358 (9)	C28—C29	1.366 (8)
C12—H12	0.9300	C28—H28	0.9300
C13—C14	1.391 (9)	C29—C30	1.382 (9)
C13—H13	0.9300	C29—H29	0.9300
C14—C15	1.377 (8)	C30—C31	1.381 (9)
C15—C16	1.379 (8)	C31—C32	1.390 (8)
C15—H15	0.9300	C31—H31	0.9300
C16—H16	0.9300	C32—H32	0.9300
C8—N1—C4	118.1 (5)	C25—N5—C20	120.2 (5)
C8—N1—C7	108.2 (4)	C25—N5—C23	107.8 (5)
C4—N1—C7	114.2 (4)	C20—N5—C23	116.7 (5)
C9—N2—C7	123.8 (4)	C24—N6—C23	124.0 (4)
C9—N2—H2D	118.1	C24—N6—H6D	118.0
C7—N2—H2D	118.1	C23—N6—H6D	118.0
C9—N3—C10	122.7 (4)	C24—N7—C26	124.2 (5)
C9—N3—C8	119.8 (4)	C24—N7—C25	120.4 (4)
C10—N3—C8	115.8 (4)	C26—N7—C25	113.7 (5)
C11—N4—C10	123.3 (4)	C27—N8—C26	123.0 (5)
C11—N4—H4D	118.4	C27—N8—H8D	118.5
C10—N4—H4D	118.4	C26—N8—H8D	118.5
C2—C1—C6	120.6 (6)	C22—C17—C18	119.4 (6)
C2—C1—Cl1	120.4 (5)	C22—C17—Cl3	121.5 (6)
C6—C1—Cl1	119.1 (5)	C18—C17—Cl3	119.0 (6)
C1—C2—C3	119.6 (6)	C19—C18—C17	119.5 (6)
C1—C2—H2	120.2	C19—C18—H18	120.2
C3—C2—H2	120.2	C17—C18—H18	120.2
C4—C3—C2	121.1 (6)	C18—C19—C20	121.8 (6)
C4—C3—H3	119.5	C18—C19—H19	119.1
C2—C3—H3	119.5	C20—C19—H19	119.1
C3—C4—C5	118.3 (5)	C19—C20—C21	117.7 (6)
C3—C4—N1	118.5 (5)	C19—C20—N5	119.9 (5)
C5—C4—N1	123.0 (5)	C21—C20—N5	122.4 (6)
C6—C5—C4	119.6 (5)	C22—C21—C20	119.6 (6)
C6—C5—H5	120.2	C22—C21—H21	120.2
C4—C5—H5	120.2	C20—C21—H21	120.2
C1—C6—C5	120.6 (6)	C17—C22—C21	122.0 (7)
C1—C6—H6	119.7	C17—C22—H22	119.0
C5—C6—H6	119.7	C21—C22—H22	119.0
N1—C7—N2	109.0 (4)	N6—C23—N5	108.4 (4)
N1—C7—H7A	109.9	N6—C23—H23A	110.0
N2—C7—H7A	109.9	N5—C23—H23A	110.0
N1—C7—H7B	109.9	N6—C23—H23B	110.0
N2—C7—H7B	109.9	N5—C23—H23B	110.0
H7A—C7—H7B	108.3	H23A—C23—H23B	108.4
N1—C8—N3	113.0 (4)	N6—C24—N7	117.2 (4)
N1—C8—H8A	109.0	N6—C24—S2	120.0 (4)
N3—C8—H8A	109.0	N7—C24—S2	122.8 (4)
N1—C8—H8B	109.0	N5—C25—N7	112.0 (4)
N3—C8—H8B	109.0	N5—C25—H25A	109.2
H8A—C8—H8B	107.8	N7—C25—H25A	109.2
N2—C9—N3	116.9 (4)	N5—C25—H25B	109.2
N2—C9—S1	120.5 (4)	N7—C25—H25B	109.2
N3—C9—S1	122.5 (4)	H25A—C25—H25B	107.9
N3—C10—N4	113.1 (4)	N8—C26—N7	113.3 (5)
N3—C10—H10A	109.0	N8—C26—H26A	108.9
N4—C10—H10A	109.0	N7—C26—H26A	108.9
N3—C10—H10B	109.0	N8—C26—H26B	108.9
N4—C10—H10B	109.0	N7—C26—H26B	108.9
H10A—C10—H10B	107.8	H26A—C26—H26B	107.7
N4—C11—C16	123.6 (5)	N8—C27—C32	123.0 (5)
N4—C11—C12	118.3 (5)	N8—C27—C28	118.7 (6)
C16—C11—C12	118.1 (5)	C32—C27—C28	118.3 (6)
C13—C12—C11	119.5 (5)	C29—C28—C27	120.1 (6)
C13—C12—H12	120.3	C29—C28—H28	120.0
C11—C12—H12	120.3	C27—C28—H28	120.0
C12—C13—C14	121.9 (6)	C28—C29—C30	121.7 (6)
C12—C13—H13	119.1	C28—C29—H29	119.1
C14—C13—H13	119.1	C30—C29—H29	119.1
C15—C14—C13	119.1 (6)	C31—C30—C29	118.8 (6)
C15—C14—Cl2	119.3 (5)	C31—C30—Cl4	119.0 (6)
C13—C14—Cl2	121.5 (5)	C29—C30—Cl4	122.0 (6)
C14—C15—C16	119.7 (6)	C30—C31—C32	120.6 (6)
C14—C15—H15	120.2	C30—C31—H31	119.7
C16—C15—H15	120.2	C32—C31—H31	119.7
C15—C16—C11	121.7 (5)	C31—C32—C27	120.4 (6)
C15—C16—H16	119.2	C31—C32—H32	119.8
C11—C16—H16	119.2	C27—C32—H32	119.8
C6—C1—C2—C3	−3.1 (8)	C22—C17—C18—C19	−0.6 (10)
Cl1—C1—C2—C3	177.3 (4)	Cl3—C17—C18—C19	179.5 (5)
C1—C2—C3—C4	−1.0 (8)	C17—C18—C19—C20	0.0 (10)
C2—C3—C4—C5	4.5 (8)	C18—C19—C20—C21	1.1 (9)
C2—C3—C4—N1	−179.7 (5)	C18—C19—C20—N5	−176.6 (5)
C8—N1—C4—C3	−170.4 (5)	C25—N5—C20—C19	−178.6 (5)
C7—N1—C4—C3	60.7 (6)	C23—N5—C20—C19	−45.1 (7)
C8—N1—C4—C5	5.2 (7)	C25—N5—C20—C21	3.9 (8)
C7—N1—C4—C5	−123.7 (5)	C23—N5—C20—C21	137.4 (6)
C3—C4—C5—C6	−4.1 (8)	C19—C20—C21—C22	−1.6 (10)
N1—C4—C5—C6	−179.7 (5)	N5—C20—C21—C22	176.0 (6)
C2—C1—C6—C5	3.5 (8)	C18—C17—C22—C21	0.1 (12)
Cl1—C1—C6—C5	−176.9 (4)	Cl3—C17—C22—C21	180.0 (6)
C4—C5—C6—C1	0.2 (8)	C20—C21—C22—C17	1.0 (12)
C8—N1—C7—N2	−57.7 (5)	C24—N6—C23—N5	−35.2 (7)
C4—N1—C7—N2	76.0 (6)	C25—N5—C23—N6	58.5 (6)
C9—N2—C7—N1	35.1 (6)	C20—N5—C23—N6	−80.3 (6)
C4—N1—C8—N3	−75.0 (6)	C23—N6—C24—N7	6.9 (7)
C7—N1—C8—N3	56.6 (6)	C23—N6—C24—S2	−174.0 (4)
C9—N3—C8—N1	−29.8 (7)	C26—N7—C24—N6	−167.0 (5)
C10—N3—C8—N1	164.8 (4)	C25—N7—C24—N6	−3.1 (7)
C7—N2—C9—N3	−7.3 (6)	C26—N7—C24—S2	14.0 (7)
C7—N2—C9—S1	175.7 (4)	C25—N7—C24—S2	177.8 (4)
C10—N3—C9—N2	168.0 (4)	C20—N5—C25—N7	80.1 (6)
C8—N3—C9—N2	3.7 (6)	C23—N5—C25—N7	−57.0 (6)
C10—N3—C9—S1	−15.1 (6)	C24—N7—C25—N5	29.9 (7)
C8—N3—C9—S1	−179.4 (4)	C26—N7—C25—N5	−164.7 (4)
C9—N3—C10—N4	133.4 (5)	C27—N8—C26—N7	68.6 (8)
C8—N3—C10—N4	−61.7 (6)	C24—N7—C26—N8	−137.5 (5)
C11—N4—C10—N3	−78.8 (7)	C25—N7—C26—N8	57.7 (7)
C10—N4—C11—C16	2.9 (8)	C26—N8—C27—C32	10.0 (10)
C10—N4—C11—C12	−177.9 (5)	C26—N8—C27—C28	−169.1 (6)
N4—C11—C12—C13	177.6 (6)	N8—C27—C28—C29	179.7 (6)
C16—C11—C12—C13	−3.1 (9)	C32—C27—C28—C29	0.5 (10)
C11—C12—C13—C14	4.3 (11)	C27—C28—C29—C30	−1.8 (11)
C12—C13—C14—C15	−2.7 (11)	C28—C29—C30—C31	3.0 (11)
C12—C13—C14—Cl2	179.2 (5)	C28—C29—C30—Cl4	177.3 (6)
C13—C14—C15—C16	0.0 (10)	C29—C30—C31—C32	−3.0 (10)
Cl2—C14—C15—C16	178.1 (5)	Cl4—C30—C31—C32	−177.4 (5)
C14—C15—C16—C11	1.1 (9)	C30—C31—C32—C27	1.8 (10)
N4—C11—C16—C15	179.7 (6)	N8—C27—C32—C31	−179.6 (6)
C12—C11—C16—C15	0.5 (8)	C28—C27—C32—C31	−0.5 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6D···S1	0.86	2.52	3.356 (4)	164
N2—H2D···S2	0.86	2.59	3.430 (4)	167
C2—H2···S1^i	0.93	2.93	3.743 (4)	147
C23—H23A···Cl1^ii	0.97	2.86	3.783 (7)	160

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

(II) 1-(anilinomethyl)-5-phenyl-1,3,5-triazinane-2-thione

Crystal data

C16H18N4S	Z = 4
Mr = 298.40	F(000) = 632
Mmnoclinic, P21/n	Dx = 1.266 Mg m^−3
a = 5.8564 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 15.486 (2) Å	Cell parameters from 2761 reflections
c = 17.285 (2) Å	θ = 2.4–22.8°
α = 90°	µ = 0.21 mm^−1
β = 92.660 (2)°	T = 291 K
γ = 90°	Plate, colourless
V = 1565.9 (4) Å^3	0.35 × 0.27 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2895 independent reflections
Radiation source: fine-focus sealed tube	2151 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ϕ and ω scans	θmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.931, Tmax = 0.957	k = −18→18
11424 measured reflections	l = −20→20

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0374P)^2 + 0.3074P] where P = (Fo^2 + 2Fc^2)/3
2895 reflections	(Δ/σ)max = 0.002
190 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.13 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	0.22985 (8)	0.04923 (3)	0.40760 (3)	0.06091 (17)
N1	0.4078 (3)	0.19555 (10)	0.62536 (8)	0.0560 (4)
N2	0.2185 (2)	0.08151 (9)	0.55677 (9)	0.0564 (4)
H2D	0.0937	0.0522	0.5534	0.068*
N3	0.5076 (2)	0.15073 (9)	0.49676 (8)	0.0505 (4)
N4	0.7175 (2)	0.25134 (11)	0.41977 (9)	0.0671 (5)
H4D	0.8443	0.2714	0.4394	0.081*
C1	0.2573 (3)	0.26732 (12)	0.61505 (10)	0.0526 (4)
C2	0.1013 (4)	0.28340 (14)	0.67104 (12)	0.0714 (6)
H2	0.0976	0.2473	0.7140	0.086*
C3	−0.0480 (4)	0.35158 (15)	0.66442 (14)	0.0846 (7)
H3	−0.1523	0.3609	0.7025	0.102*
C4	−0.0442 (4)	0.40607 (15)	0.60187 (15)	0.0842 (7)
H4	−0.1463	0.4520	0.5970	0.101*
C5	0.1116 (4)	0.39195 (14)	0.54692 (13)	0.0789 (6)
H5	0.1170	0.4292	0.5048	0.095*
C6	0.2615 (4)	0.32305 (12)	0.55290 (11)	0.0660 (5)
H6	0.3660	0.3142	0.5147	0.079*
C7	0.2990 (3)	0.11240 (12)	0.63295 (11)	0.0611 (5)
H7A	0.1710	0.1175	0.6663	0.073*
H7B	0.4070	0.0715	0.6563	0.073*
C8	0.3280 (3)	0.09623 (11)	0.49175 (10)	0.0500 (4)
C9	0.5885 (3)	0.18639 (13)	0.57241 (11)	0.0600 (5)
H9A	0.7054	0.1487	0.5953	0.072*
H9B	0.6575	0.2424	0.5644	0.072*
C10	0.6659 (3)	0.16269 (13)	0.43371 (12)	0.0628 (5)
H10A	0.8069	0.1320	0.4467	0.075*
H10B	0.5986	0.1375	0.3866	0.075*
C11	0.5767 (3)	0.30742 (13)	0.37660 (10)	0.0556 (5)
C12	0.6523 (4)	0.39069 (14)	0.36228 (12)	0.0684 (5)
H12	0.7944	0.4086	0.3825	0.082*
C13	0.5180 (4)	0.44710 (15)	0.31820 (13)	0.0800 (6)
H13	0.5701	0.5028	0.3091	0.096*
C14	0.3077 (4)	0.42155 (17)	0.28758 (13)	0.0814 (7)
H14	0.2185	0.4592	0.2571	0.098*
C15	0.2316 (4)	0.33993 (16)	0.30271 (11)	0.0722 (6)
H15	0.0888	0.3227	0.2826	0.087*
C16	0.3617 (3)	0.28265 (14)	0.34710 (10)	0.0602 (5)
H16	0.3060	0.2278	0.3572	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0506 (3)	0.0659 (3)	0.0662 (3)	−0.0021 (2)	0.0021 (2)	−0.0129 (2)
N1	0.0554 (9)	0.0586 (9)	0.0533 (9)	−0.0008 (7)	−0.0048 (7)	0.0016 (7)
N2	0.0481 (8)	0.0604 (10)	0.0603 (9)	−0.0071 (7)	−0.0004 (7)	0.0018 (8)
N3	0.0387 (7)	0.0554 (9)	0.0573 (9)	0.0010 (7)	0.0009 (6)	−0.0005 (7)
N4	0.0408 (8)	0.0756 (11)	0.0843 (12)	−0.0085 (8)	−0.0033 (8)	0.0129 (9)
C1	0.0562 (10)	0.0546 (11)	0.0466 (10)	−0.0046 (9)	−0.0020 (8)	−0.0044 (8)
C2	0.0842 (15)	0.0706 (14)	0.0605 (12)	0.0006 (12)	0.0162 (11)	0.0049 (10)
C3	0.0909 (17)	0.0792 (16)	0.0865 (16)	0.0073 (13)	0.0339 (13)	−0.0057 (13)
C4	0.0913 (17)	0.0668 (14)	0.0953 (17)	0.0192 (12)	0.0132 (14)	−0.0051 (13)
C5	0.1086 (18)	0.0606 (13)	0.0683 (14)	0.0173 (12)	0.0122 (13)	0.0068 (10)
C6	0.0826 (14)	0.0614 (12)	0.0549 (11)	0.0079 (11)	0.0139 (10)	0.0005 (10)
C7	0.0652 (12)	0.0601 (12)	0.0572 (11)	0.0008 (10)	−0.0035 (9)	0.0088 (9)
C8	0.0377 (9)	0.0490 (10)	0.0630 (11)	0.0074 (7)	−0.0008 (8)	0.0001 (8)
C9	0.0478 (10)	0.0632 (12)	0.0678 (12)	−0.0014 (9)	−0.0109 (9)	−0.0008 (10)
C10	0.0427 (10)	0.0678 (13)	0.0785 (13)	0.0081 (9)	0.0084 (9)	0.0011 (10)
C11	0.0479 (10)	0.0701 (13)	0.0496 (10)	0.0035 (9)	0.0095 (8)	−0.0008 (9)
C12	0.0636 (12)	0.0751 (14)	0.0669 (13)	−0.0027 (11)	0.0080 (10)	0.0003 (11)
C13	0.0957 (18)	0.0714 (14)	0.0736 (14)	0.0086 (13)	0.0126 (13)	0.0041 (12)
C14	0.0906 (17)	0.0925 (18)	0.0606 (13)	0.0291 (14)	−0.0012 (12)	0.0036 (12)
C15	0.0625 (13)	0.0984 (18)	0.0553 (12)	0.0145 (12)	−0.0022 (10)	−0.0073 (12)
C16	0.0527 (11)	0.0771 (13)	0.0509 (10)	0.0024 (10)	0.0043 (8)	−0.0035 (9)

Geometric parameters (Å, º)

S1—C8	1.7025 (18)	C5—C6	1.383 (3)
N1—C1	1.424 (2)	C5—H5	0.9300
N1—C9	1.438 (2)	C6—H6	0.9300
N1—C7	1.445 (2)	C7—H7A	0.9700
N2—C8	1.339 (2)	C7—H7B	0.9700
N2—C7	1.458 (2)	C9—H9A	0.9700
N2—H2D	0.8600	C9—H9B	0.9700
N3—C8	1.348 (2)	C10—H10A	0.9700
N3—C10	1.475 (2)	C10—H10B	0.9700
N3—C9	1.477 (2)	C11—C12	1.389 (3)
N4—C11	1.391 (2)	C11—C16	1.390 (2)
N4—C10	1.428 (2)	C12—C13	1.381 (3)
N4—H4D	0.8600	C12—H12	0.9300
C1—C6	1.379 (2)	C13—C14	1.376 (3)
C1—C2	1.384 (3)	C13—H13	0.9300
C2—C3	1.372 (3)	C14—C15	1.369 (3)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.372 (3)	C15—C16	1.379 (3)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.365 (3)	C16—H16	0.9300
C4—H4	0.9300
C1—N1—C9	117.8 (2)	H7A—C7—H7B	108.2
C1—N1—C7	115.7 (2)	N2—C8—N3	117.1 (2)
C9—N1—C7	108.1 (2)	N2—C8—S1	119.2 (1)
C8—N2—C7	123.7 (2)	N3—C8—S1	123.7 (1)
C8—N2—H2D	118.2	N1—C9—N3	112.6 (1)
C7—N2—H2D	118.2	N1—C9—H9A	109.1
C8—N3—C10	123.1 (2)	N3—C9—H9A	109.1
C8—N3—C9	120.6 (2)	N1—C9—H9B	109.1
C10—N3—C9	114.9 (1)	N3—C9—H9B	109.1
C11—N4—C10	124.5 (2)	H9A—C9—H9B	107.8
C11—N4—H4D	117.8	N4—C10—N3	113.0 (2)
C10—N4—H4D	117.8	N4—C10—H10A	109.0
C6—C1—C2	117.9 (2)	N3—C10—H10A	109.0
C6—C1—N1	123.5 (2)	N4—C10—H10B	109.0
C2—C1—N1	118.5 (2)	N3—C10—H10B	109.0
C3—C2—C1	121.3 (2)	H10A—C10—H10B	107.8
C3—C2—H2	119.4	C12—C11—C16	118.8 (2)
C1—C2—H2	119.4	C12—C11—N4	119.3 (2)
C2—C3—C4	120.3 (2)	C16—C11—N4	121.9 (2)
C2—C3—H3	119.8	C13—C12—C11	120.5 (2)
C4—C3—H3	119.8	C13—C12—H12	119.8
C5—C4—C3	119.0 (2)	C11—C12—H12	119.8
C5—C4—H4	120.5	C14—C13—C12	120.5 (2)
C3—C4—H4	120.5	C14—C13—H13	119.8
C4—C5—C6	121.0 (2)	C12—C13—H13	119.8
C4—C5—H5	119.5	C15—C14—C13	119.0 (2)
C6—C5—H5	119.5	C15—C14—H14	120.5
C1—C6—C5	120.4 (2)	C13—C14—H14	120.5
C1—C6—H6	119.8	C14—C15—C16	121.6 (2)
C5—C6—H6	119.8	C14—C15—H15	119.2
N1—C7—N2	109.6 (1)	C16—C15—H15	119.2
N1—C7—H7A	109.7	C15—C16—C11	119.6 (2)
N2—C7—H7A	109.7	C15—C16—H16	120.2
N1—C7—H7B	109.7	C11—C16—H16	120.2
N2—C7—H7B	109.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2D···S1^i	0.86	2.57	3.394 (2)	160
C2—H2···Cg^ii	0.93	2.87	3.765 (2)	163

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