Crystal structure and Hirshfeld surface analysis of 2-[(1,3-benzoxazol-2-yl)sulfan-yl]-N-(2-meth-oxy-phen-yl)acetamide.

In the title compound, C16H14N2O3S, the 1,3-benzoxazole ring system is essentially planar (r.m.s deviation = 0.004 Å) and makes a dihedral angle of 66.16 (17)° with the benzene ring of the meth-oxy-phenyl group. Two intra-molecular N-H⋯O and N-H⋯N hydrogen bonds occur, forming S(5) and S(7) ring motifs, respectively. In the crystal, pairs of C-H⋯O hydrogen bonds link the mol-ecules into inversion dimers with R 2 2(14) ring motifs, stacked along the b-axis direction. The inversion dimers are linked by C-H⋯π and π-π-stacking inter-actions [centroid-to-centroid distances = 3.631 (2) and 3.631 (2) Å], forming a three-dimensional network. Two-dimensional fingerprint plots associated with the Hirshfeld surface show that the largest contributions to the crystal packing come from H⋯H (39.3%), C⋯H/H⋯C (18.0%), O⋯H/H⋯O (15.6) and S⋯H/H⋯S (10.2%) inter-actions. © Aydin et al. 2019.

Chemical context

As a part of our ongoing research on synthesis and screening of pharmacological activities of compounds with a benzoxazole ring, which is known to produce a wide range of biological activities (Aggarwal et al., 2017 ▸; Gautam et al., 2012 ▸), we have focused on the synthesis of 3-substituted benzoxazolone-2-thione and S-substituted benzoxazole-2-thiol derivatives. It is well known that alkyl­ation of benzoxazolone-2-thione leads to the S-alkyl­ated derivatives instead of N-alkyl­ated ones (Xiang et al., 2012 ▸; Rakse et al., 2013 ▸; Yurttaş et al., 2015 ▸). In this manner, the title compound was synthesized as a member of the target S-substituted benzoxazole-2-thiol series. The title compound is listed in the literature with registry number CASRN 331966-95-1 but corresponding scientific reference data are not available.

Structural commentary

In the mol­ecular structure of the title compound (Fig. 1 ▸), the 1,3-benzoxazole ring system (N1/O1/C1–C7) is essentially planar (r.m.s deviation = 0.004 Å) and makes a dihedral angle of 66.16 (17)° with the benzene ring (C10–C15) of the meth­oxy­phenyl group. Atoms O3 and C16 deviate from the benzene ring by −0.008 (3) and 0.099 (6) Å, respectively. The torsion angle C7—S1—C8—C9 = −87.7 (3)°, S1—C8—C9— N2 = 91.6 (4)° and C8—C9—N2—C10 = −178.8 (3)°. The C7—S1 [1.740 (4) Å] and C8—S1 [1.812 (4) Å] bond lengths are comparable with those reported for three similar structures, viz. 2-[(4,6-di­amino­pyrimidin-2-yl)sulfan­yl]-N-(2-meth­yl­phen­yl)acetamide (1.763 and 1.805 Å, respectively; Subasri et al., 2014 ▸), 2-[(4,6-di­amino­pyrimidin-2-yl)sulfan­yl]-N-(2,4-di­methyl­phen­yl)acetamide [1.7650 (14) and 1.8053 (16) Å, respectively; Choudhury et al., 2017 ▸] and 2-[(4,6-di­amino­pyrimidin-2-yl)sulfan­yl]-N-(3-meth­oxy­phen­yl) acetamide [1.7721 (17) and 1.8126 (18) Å, respectively; Choudhury et al., 2017 ▸]. The two intra­molecular hydrogen bonds, N2—HN2⋯O3 and N2—HN2⋯N1, form S(5) and S(7) ring motifs, respectively (Table 1 ▸, Fig. 1 ▸).

Figure 1

The mol­ecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 30% probability level. Intra­molecular hydrogen bonds are shown as dashed lines.

Table 1

Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C10–C15 benzene ring of the meth­oxy phenyl group.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—HN2⋯O3	0.86	2.22	2.608 (4)	107
N2—HN2⋯N1	0.86	2.39	3.075 (4)	136
C8—H8A⋯N1	0.97	2.48	2.914 (5)	107
C11—H11⋯O2	0.93	2.28	2.869 (5)	121
C12—H12⋯O2i	0.93	2.52	3.378 (6)	153
C13—H13⋯Cg3ii	0.93	2.89	3.634 (5)	138

Symmetry codes: (i) ; (ii) .

Supra­molecular features

In the crystal, pairs of C—H⋯O hydrogen bonds link the mol­ecules into inversion dimers with (14) ring motifs, stacking along the b-axis direction. These dimers are linked by C—H⋯π (Table 1 ▸, Fig. 2 ▸) and π–π-stacking inter­actions [Fig. 2 ▸; distances of 3.631 (2) and 3.631 (2) Å between the centroids of the five- and opposite six-membered rings of the 1,3-benzoxazole ring system of adjacent mol­ecules], forming a three-dimensional network (Fig. 3 ▸).

Figure 2

A packing diagram of the title compound, showing the intra- and inter­molecular N—H⋯N and N—H⋯O, C—H⋯O hydrogen bonds, C—H⋯π inter­actions and π–π-stacking inter­actions (dashed lines). Symmetry code: (a) − x, 2 − y, 1 − z.

Figure 3

Packing diagram of the title compound viewed down the b axis.

Hirshfeld surface analysis

In order to explore the role of weak inter­molecular inter­actions in the crystal packing, Hirshfeld surfaces (d norm) and the related two-dimensional fingerprint plots were generated using CrystalExplorer17.5 (Spackman & Jayatilaka, 2009 ▸; Wolff et al., 2012 ▸). The three-dimensional mol­ecular Hirshfeld surfaces were generated using a high standard surface resolution over a colour scale of −0.1599 to 1.2011 a.u. for d norm (Fig. 4 ▸). The red spots in the Hirshfeld surface represent short N⋯H/H⋯N and O⋯H/H⋯O contacts. On the shape-index surface (Fig. 5 ▸), convex blue regions represent hydrogen-donor groups and concave red regions represent hydrogen-acceptor groups. In addition, concave red regions represent C—H⋯π and π–π inter­actions.

Figure 4

Hirshfeld surface mapped over d norm, showing the weak inter­molecular C—H⋯O and C—H⋯C contacts.

Figure 5

View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. Hydrogen- bond donors and acceptors are shown as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.

The bright-red spots indicate their roles as the respective donors and/or acceptors; they also appear as blue and red regions corresponding to positive and negative potentials on the Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ▸) shown in Fig. 6 ▸. The blue regions indicate the positive electrostatic potential (hydrogen-bond donors), while the red regions indicate the negative electrostatic potential (hydrogen-bond acceptors).

Figure 6

Hirshfeld surfaces for the title compound, mapped with shape-index.

The two-dimensional fingerprint plots (Fig. 7 ▸) qu­antify the contributions of each type of inter­molecular inter­action to the Hirshfeld surface (McKinnon et al., 2007 ▸). The largest contribution (39.3% of the surface) is from H⋯H contacts (Table 2 ▸), which represent van der Waals inter­actions, followed by C⋯H/H⋯C contacts involved in C—H⋯π inter­actions (18.0%). Finally, the O⋯H/H⋯O (15.6%), S⋯H/H⋯S (10.2%) and C⋯C (4.5%) contacts correspond to hydrogen bonds and π–π inter­actions, respectively. The percentage contributions to the Hirshfeld surface of the various inter­atomic contacts are given in Table 3 ▸.

Figure 7

Hirshfeld surfaces and two-dimensional fingerprints for the compound, showing (a) all inter­actions and those delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) O⋯H/H⋯O, (e) S⋯H/H⋯S and (f) C⋯O/O⋯C contacts.

Table 2

Summary of selected short inter­atomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
H5⋯O3	2.72	1 − x, 1 − y, 1 − z
S1⋯H2	3.10	x,  − y,  + z
C5⋯C1	3.38	1 − x, −y, 1 − z
H8B⋯C11	3.06	−x, 1 − y, 1 − z
H12⋯O2	2.52	−x, 2 − y, 1 − z
O2⋯H16A	2.74	x,  − y,  + z
C10⋯H13	3.04	−x, − + y,  − z
C12⋯H8A	2.82	x, 1 + y, z

Table 3

Percentage contributions of inter­atomic contacts to the Hirshfeld surface of the title compound

Contact	Percentage contribution
H⋯H	39.3
H⋯C/C⋯H	18.0
O⋯H/H⋯O	15.6
S⋯H/H⋯S	10.2
C⋯O/O⋯C	6.0
C⋯C	4.5
N⋯H/H⋯N	4.1
C⋯N/N⋯C	1.4
C⋯S/S⋯C	0.6
N⋯O/O⋯N	0.1

Database survey

Related compounds to the title compound include 2-[(4,6-di­amino­pyrimidin-2-yl)sulfan­yl]-N-(naphthalen-1-yl)acetamide (refcode JARPOK; Subasri et al., 2017 ▸), 2-[(4,6-di­amino­pyrimidin-2-yl)sulfan­yl]-N-(4-fluoro­phen­yl)acetamide (JAR­PUQ; Subasri et al., 2017 ▸), 2-[(4,6-di­amino­pyrimidin-2-yl)sulf­an­yl]-N-(2-methyl­phen­yl)acetamide (GOKWIO; Subasri et al., 2014 ▸), 2-[(4,6-di­amino­pyrimidin-2-yl)sulfan­yl]-N-(2,4-di­methyl­phen­yl)acetamide (JAXFIA; Choudhury et al., 2017 ▸), 2-[(4,6-di­amino­pyrimidin-2-yl)sulfan­yl]-N-(3-meth­oxy­phen­yl) acetamide (refcode: JAXFOG; Choudhury et al., 2017 ▸) and 2-[(2-amino­phen­yl)sulfan­yl]-N-(4-meth­oxy­phen­yl)acetamide (PAXTEP; Murtaza et al., 2012 ▸).

In the crystals of JARPOK and JARPUQ, mol­ecules are linked by pairs of N—H⋯N hydrogen bonds, forming inversion dimers with (8) ring motifs. In the crystal of JARPOK, the dimers are linked by bifurcated N—H⋯(O,O) and C—H⋯O hydrogen bonds, forming layers parallel to (100). In the crystal of JARPUQ, the dimers are linked by N—H⋯O hydrogen bonds, also forming layers parallel to (100). The layers are linked by C—H⋯F hydrogen bonds, forming a three-dimensional architecture.

In the crystal of GOKWIO, mol­ecules are linked via pairs of N—H⋯N hydrogen bonds, forming inversion dimers with an (8) ring motif. The dimers are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming sheets parallel to (100).

In the crystals of JAXFIA and JAXFOG, a pair of N—H⋯N hydrogen bonds links the mol­ecules, forming inversion dimers with (8) ring motifs. In JAXFIA, the dimers are linked by N—H⋯O and C—H⋯O hydrogen bonds, enclosing (14), (11) and (7) ring motifs, forming layers parallel to the (100) plane. There is also an N—H⋯π inter­action present within the layer. In JAXFOG, the inversion dimers are linked by N—H⋯O hydrogen bonds enclosing an (18) ring motif. The presence of N—H⋯O and C—H⋯O hydrogen bonds generate an (6) ring motif. The combination of these various hydrogen bonds results in the formation of layers parallel to the (11) plane.

In the crystal of PAXTEP, mol­ecules are consolidated in the form of polymeric chains along [010] as a result of N—H⋯O hydrogen bonds, which generate (18) and (22) loops. The polymeric chains are inter­linked through C—H⋯O inter­action and complete (8) ring motifs.

Synthesis and crystallization

The starting materials, 2-mercaptobenzoxazole and α-chloro-N-(o-meth­oxy­phen­yl)acetamide, were synthesized according to literature methods (Maske et al., 2012 ▸; Ren et al., 2015 ▸). For the synthesis of the title compound, 2-mercaptobenzoxazole (1 eq) and α-chloro-N-(o-meth­oxy­phen­yl) acetamide (1 eq) were heated in acetone under reflux for 1.5 h in the presence of K2CO3 (1 eq). The reaction mixture was then cooled to room temperature and cold water was added until precipitation was complete. The precipitate was filtered, washed with cold water and dried. The crude product was crystallized from methanol (yield 31%); m.p. 370 K.

1H NMR (DMSO-d 6, 400 MHz) δ 3.82 (3H, s, OCH3), δ 4.42 (2H, s, CH2), δ 6.89 (1H, m, Ar-H), δ 7.03–7.10 (2H, m, Ar-H), δ 7.31–7.38 (2H, m, Ar-H), δ 7.62–7.68 (2H, m, Ar-H), δ 7.97 (1H, d, J = 8.4 Hz, Ar-H), δ 9.65 (1H, s, NH) p.p.m. IR v max cm−1: 3295 (NH), 1675 (amide I), 1534 (amide II); MS (ESI) m/z (intensity %): 315.32 (26) [M+H]+ 192.27 (100).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. All H atoms were positioned with idealized geometry and refined as riding: N—H = 0.86 Å, C—H = 0.93–0.97 Å with U iso(H) = 1.5U eq(C) for methyl H atoms and U iso(H) = 1.2U eq(C, N) for all other H atoms. Thirty one outliers (13 1 3), ( 1 1), (8 3 12), ( 5 15), (0 3 18), (5 0 14), (14 2 5), ( 0 14), ( 4 17), (14 3 1), ( 3 5), (1 8 4), (1 4 15), (10 5 2), ( 7 8), ( 0 10), (14 2 1), ( 1 1), ( 3 12), ( 2 7), (4 1 17), (11 0 10), (15 1 2), (3 4 14), (10 2 6), ( 0 18), ( 3 18), ( 6 11), ( 5 2), (10 1 9), (4 1 2) were omitted in the final cycles of refinement.

Table 4

Experimental details

Crystal data
Chemical formula	C16H14N2O3S
M r	314.35
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	296
a, b, c (Å)	13.6670 (13), 6.8704 (6), 16.7220 (16)
β (°)	108.020 (4)
V (Å3)	1493.1 (2)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.23
Crystal size (mm)	0.10 × 0.07 × 0.06
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 ▸)
T min, T max	0.654, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	23464, 3019, 2241
R int	0.092
(sin θ/λ)max (Å−1)	0.627
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.092, 0.169, 1.10
No. of reflections	3019
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.25, −0.31

Computer programs: APEX2 and SAINT (Bruker, 2007 ▸), SHELXT2014/5 (Sheldrick, 2015a ▸), SHELXL2018/1 (Sheldrick, 2015b ▸), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019012908/rz5264sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019012908/rz5264Isup2.hkl

CCDC reference: 1954699

Additional supporting information: crystallographic information; 3D view; checkCIF report

C16H14N2O3S	F(000) = 656
Mr = 314.35	Dx = 1.398 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.6670 (13) Å	Cell parameters from 6692 reflections
b = 6.8704 (6) Å	θ = 3.2–26.3°
c = 16.7220 (16) Å	µ = 0.23 mm−1
β = 108.020 (4)°	T = 296 K
V = 1493.1 (2) Å3	Block, colourless
Z = 4	0.10 × 0.07 × 0.06 mm

Bruker APEXII CCD diffractometer	2241 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.092
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θmax = 26.5°, θmin = 3.1°
Tmin = 0.654, Tmax = 0.745	h = −17→17
23464 measured reflections	k = −8→8
3019 independent reflections	l = −20→20

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.092	H-atom parameters constrained
wR(F2) = 0.169	w = 1/[σ2(Fo2) + (0.0406P)2 + 3.9251P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
3019 reflections	Δρmax = 0.25 e Å−3
200 parameters	Δρmin = −0.31 e Å−3

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

	x	y	z	Uiso*/Ueq
C1	0.4055 (3)	0.2452 (5)	0.4388 (2)	0.0301 (9)
C2	0.4121 (3)	0.1973 (6)	0.3599 (3)	0.0437 (11)
H2	0.353578	0.186794	0.313350	0.052*
C3	0.5089 (4)	0.1660 (7)	0.3535 (3)	0.0507 (12)
H3	0.515664	0.134545	0.301349	0.061*
C4	0.5962 (4)	0.1801 (6)	0.4223 (3)	0.0515 (13)
H4	0.660182	0.158127	0.415281	0.062*
C5	0.5910 (3)	0.2258 (6)	0.5012 (3)	0.0460 (11)
H5	0.649354	0.234724	0.547961	0.055*
C6	0.4940 (3)	0.2573 (5)	0.5059 (3)	0.0330 (9)
C7	0.3608 (3)	0.3093 (5)	0.5452 (2)	0.0304 (9)
C8	0.1670 (3)	0.3513 (7)	0.5515 (3)	0.0401 (10)
H8A	0.160668	0.258715	0.506432	0.048*
H8B	0.122257	0.308919	0.583244	0.048*
C9	0.1330 (3)	0.5503 (6)	0.5143 (2)	0.0368 (10)
C10	0.1249 (3)	0.7568 (6)	0.3915 (2)	0.0272 (8)
C11	0.0683 (3)	0.9111 (6)	0.4077 (2)	0.0364 (10)
H11	0.044048	0.906129	0.453818	0.044*
C12	0.0479 (3)	1.0720 (7)	0.3557 (3)	0.0438 (11)
H12	0.008978	1.173897	0.366520	0.053*
C13	0.0844 (3)	1.0826 (7)	0.2882 (3)	0.0443 (11)
H13	0.070946	1.191980	0.253773	0.053*
C14	0.1411 (3)	0.9312 (7)	0.2714 (2)	0.0380 (10)
H14	0.165837	0.938978	0.225560	0.046*
C15	0.1615 (3)	0.7687 (6)	0.3217 (2)	0.0290 (9)
C16	0.2621 (5)	0.6219 (9)	0.2449 (3)	0.078 (2)
H16A	0.209173	0.634567	0.191795	0.118*
H16B	0.301214	0.505956	0.244719	0.118*
H16C	0.306739	0.733112	0.253872	0.118*
N1	0.3202 (2)	0.2815 (5)	0.46627 (18)	0.0309 (7)
N2	0.1476 (2)	0.5848 (5)	0.43945 (19)	0.0302 (7)
HN2	0.173630	0.491051	0.418615	0.036*
O1	0.4653 (2)	0.3005 (4)	0.57658 (16)	0.0363 (7)
O2	0.0961 (3)	0.6653 (6)	0.55175 (19)	0.0687 (11)
O3	0.2163 (2)	0.6103 (4)	0.31065 (17)	0.0467 (8)
S1	0.29895 (9)	0.35394 (17)	0.62002 (6)	0.0420 (3)

	U11	U22	U33	U12	U13	U23
C1	0.036 (2)	0.0217 (18)	0.032 (2)	0.0038 (16)	0.0093 (17)	0.0053 (16)
C2	0.047 (3)	0.045 (3)	0.039 (2)	0.002 (2)	0.013 (2)	0.000 (2)
C3	0.059 (3)	0.046 (3)	0.058 (3)	0.006 (2)	0.033 (3)	0.001 (2)
C4	0.044 (3)	0.036 (2)	0.085 (4)	0.005 (2)	0.035 (3)	0.009 (2)
C5	0.032 (2)	0.035 (2)	0.066 (3)	−0.0031 (19)	0.007 (2)	0.009 (2)
C6	0.038 (2)	0.0217 (19)	0.039 (2)	−0.0024 (17)	0.0112 (18)	0.0046 (17)
C7	0.036 (2)	0.024 (2)	0.029 (2)	0.0016 (16)	0.0067 (17)	0.0061 (16)
C8	0.041 (2)	0.052 (3)	0.034 (2)	−0.009 (2)	0.0208 (19)	0.000 (2)
C9	0.036 (2)	0.053 (3)	0.026 (2)	−0.001 (2)	0.0156 (18)	−0.0053 (19)
C10	0.0190 (18)	0.040 (2)	0.0195 (18)	−0.0011 (16)	0.0007 (15)	−0.0058 (16)
C11	0.027 (2)	0.050 (3)	0.030 (2)	0.0069 (19)	0.0060 (17)	−0.0084 (19)
C12	0.035 (2)	0.049 (3)	0.040 (3)	0.017 (2)	0.002 (2)	−0.010 (2)
C13	0.043 (3)	0.044 (3)	0.038 (2)	0.012 (2)	0.000 (2)	0.005 (2)
C14	0.034 (2)	0.055 (3)	0.022 (2)	0.004 (2)	0.0055 (17)	0.0048 (19)
C15	0.0247 (19)	0.040 (2)	0.0224 (18)	0.0045 (17)	0.0067 (15)	−0.0009 (17)
C16	0.117 (5)	0.081 (4)	0.066 (4)	0.054 (4)	0.071 (4)	0.027 (3)
N1	0.0325 (18)	0.0342 (18)	0.0236 (17)	0.0008 (14)	0.0055 (14)	−0.0010 (14)
N2	0.0334 (18)	0.0369 (18)	0.0261 (16)	0.0024 (14)	0.0177 (14)	−0.0058 (14)
O1	0.0348 (16)	0.0358 (15)	0.0311 (15)	−0.0026 (13)	−0.0002 (12)	0.0042 (12)
O2	0.101 (3)	0.082 (3)	0.0401 (19)	0.035 (2)	0.046 (2)	0.0056 (18)
O3	0.062 (2)	0.0517 (19)	0.0380 (17)	0.0240 (16)	0.0333 (15)	0.0094 (14)
S1	0.0516 (7)	0.0517 (7)	0.0226 (5)	0.0004 (6)	0.0114 (5)	0.0050 (5)

C1—C6	1.375 (6)	C9—O2	1.211 (5)
C1—C2	1.389 (5)	C9—N2	1.348 (5)
C1—N1	1.401 (5)	C10—C11	1.388 (5)
C2—C3	1.377 (6)	C10—C15	1.406 (5)
C2—H2	0.9300	C10—N2	1.408 (5)
C3—C4	1.382 (7)	C11—C12	1.381 (6)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.379 (7)	C12—C13	1.370 (6)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.370 (6)	C13—C14	1.377 (6)
C5—H5	0.9300	C13—H13	0.9300
C6—O1	1.388 (5)	C14—C15	1.374 (6)
C7—N1	1.278 (5)	C14—H14	0.9300
C7—O1	1.362 (5)	C15—O3	1.366 (4)
C7—S1	1.740 (4)	C16—O3	1.426 (5)
C8—C9	1.514 (6)	C16—H16A	0.9600
C8—S1	1.812 (4)	C16—H16B	0.9600
C8—H8A	0.9700	C16—H16C	0.9600
C8—H8B	0.9700	N2—HN2	0.8600
C6—C1—C2	119.4 (4)	C11—C10—N2	124.6 (3)
C6—C1—N1	109.4 (3)	C15—C10—N2	116.7 (3)
C2—C1—N1	131.2 (4)	C12—C11—C10	120.4 (4)
C3—C2—C1	117.2 (4)	C12—C11—H11	119.8
C3—C2—H2	121.4	C10—C11—H11	119.8
C1—C2—H2	121.4	C13—C12—C11	120.4 (4)
C2—C3—C4	121.8 (4)	C13—C12—H12	119.8
C2—C3—H3	119.1	C11—C12—H12	119.8
C4—C3—H3	119.1	C12—C13—C14	120.0 (4)
C5—C4—C3	121.8 (4)	C12—C13—H13	120.0
C5—C4—H4	119.1	C14—C13—H13	120.0
C3—C4—H4	119.1	C15—C14—C13	120.6 (4)
C6—C5—C4	115.3 (4)	C15—C14—H14	119.7
C6—C5—H5	122.3	C13—C14—H14	119.7
C4—C5—H5	122.3	O3—C15—C14	125.4 (3)
C5—C6—C1	124.5 (4)	O3—C15—C10	114.6 (3)
C5—C6—O1	128.0 (4)	C14—C15—C10	120.0 (4)
C1—C6—O1	107.4 (3)	O3—C16—H16A	109.5
N1—C7—O1	117.4 (3)	O3—C16—H16B	109.5
N1—C7—S1	128.1 (3)	H16A—C16—H16B	109.5
O1—C7—S1	114.5 (3)	O3—C16—H16C	109.5
C9—C8—S1	111.7 (3)	H16A—C16—H16C	109.5
C9—C8—H8A	109.3	H16B—C16—H16C	109.5
S1—C8—H8A	109.3	C7—N1—C1	103.1 (3)
C9—C8—H8B	109.3	C9—N2—C10	127.4 (3)
S1—C8—H8B	109.3	C9—N2—HN2	116.3
H8A—C8—H8B	107.9	C10—N2—HN2	116.3
O2—C9—N2	124.7 (4)	C7—O1—C6	102.7 (3)
O2—C9—C8	120.1 (4)	C15—O3—C16	116.7 (3)
N2—C9—C8	115.2 (3)	C7—S1—C8	98.82 (18)
C11—C10—C15	118.7 (4)
C6—C1—C2—C3	−0.6 (6)	N2—C10—C15—O3	−1.0 (5)
N1—C1—C2—C3	−178.6 (4)	C11—C10—C15—C14	0.2 (5)
C1—C2—C3—C4	0.4 (7)	N2—C10—C15—C14	179.1 (3)
C2—C3—C4—C5	0.1 (7)	O1—C7—N1—C1	1.2 (4)
C3—C4—C5—C6	−0.5 (6)	S1—C7—N1—C1	−177.6 (3)
C4—C5—C6—C1	0.3 (6)	C6—C1—N1—C7	−0.9 (4)
C4—C5—C6—O1	178.3 (4)	C2—C1—N1—C7	177.2 (4)
C2—C1—C6—C5	0.3 (6)	O2—C9—N2—C10	0.9 (7)
N1—C1—C6—C5	178.7 (4)	C8—C9—N2—C10	−178.8 (3)
C2—C1—C6—O1	−178.1 (3)	C11—C10—N2—C9	−10.6 (6)
N1—C1—C6—O1	0.3 (4)	C15—C10—N2—C9	170.5 (4)
S1—C8—C9—O2	−88.1 (5)	N1—C7—O1—C6	−1.1 (4)
S1—C8—C9—N2	91.6 (4)	S1—C7—O1—C6	177.9 (2)
C15—C10—C11—C12	0.5 (6)	C5—C6—O1—C7	−177.9 (4)
N2—C10—C11—C12	−178.3 (4)	C1—C6—O1—C7	0.4 (4)
C10—C11—C12—C13	−1.0 (6)	C14—C15—O3—C16	4.8 (6)
C11—C12—C13—C14	0.7 (7)	C10—C15—O3—C16	−175.1 (4)
C12—C13—C14—C15	0.1 (6)	N1—C7—S1—C8	−0.8 (4)
C13—C14—C15—O3	179.7 (4)	O1—C7—S1—C8	−179.7 (3)
C13—C14—C15—C10	−0.5 (6)	C9—C8—S1—C7	−87.7 (3)
C11—C10—C15—O3	−180.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN2···O3	0.86	2.22	2.608 (4)	107
N2—HN2···N1	0.86	2.39	3.075 (4)	136
C8—H8A···N1	0.97	2.48	2.914 (5)	107
C11—H11···O2	0.93	2.28	2.869 (5)	121
C12—H12···O2i	0.93	2.52	3.378 (6)	153
C13—H13···Cg3ii	0.93	2.89	3.634 (5)	138