1,3-Dibenzoylimidazolidine-2-thione and 1,3-dibenzo­yl-3,4,5,6-tetra­hydro­pyrimidine-2(1H)-thione

The title compounds, 1,3-dibenzo­ylimidazolidine-2-thione, C₁₇H₁₄N₂O₂S, (I), and 1,3-dibenzo­yl-3,4,5,6-tetra­hydro­pyrimidine-2(1H)-thione, C₁₈H₁₆N₂O₂S, (II), were obtained from the reactions of imidazolidine-2-thione and 1,4,5,6-tetra­hydro­pyrimidine-2-thiol, respectively, with benzoyl chloride. Compounds (I) and (II) contain, respectively, imidazolidinethione [C=S = 1.6509 (14) Å] and ­pyrimidinethione [C=S = 1.6918 (19) Å] moieties bonded to two benzoyl rings. The mol­ecules of (I) exhibit C₂ symmetry, the C=S bond lying along the twofold rotation axis, while the mol­ecules of (II) have mirror symmetry (C_s). The imida­zolidine ring in (I) is essentially planar, while the pyrimidine ring in (II) adopts a boat conformation. Mol­ecules of (I) are linked by weak inter­molecular C-H...O inter­actions, while mol­ecules of (II) are held together by van der Waals inter­actions.

S1. Comment

Heterocyclic thioamides usually occurring in their thioketo form are referred to as `thiones'. Heterocyclic thiones have a wide range of applications as analytical reagents, as metal corrosion inhibitors and in the pharmaceutical field (Hussain et al., 1990). These compounds are of particular interest in coordination chemistry because they display both hard and soft donor sites. In many instances, heterocyclic thiones behave as polyfunctional ligands with monodentate, chelating and bridging coordination modes and form a wide range transition metal complexes, many of which have important chemical and biological properties (Raper, 1985, 1994, 1996, 1997; Akrivos, 2001). Furthermore, metal complexes of heterocyclic thiones exhibit interesting anticarcinogenic properties (Reedijk, 1992; van Boom & Reedijk, 1993; Barnham et al., 1994) and are used in the treatment of rheumatoid arthritis (Haynes & Whitehouse, 1989). Such complexes? are also used as models to understand the electronic and structural properties of the active sites in metalloenzymes (Casella et al., 1988; Gullotti, et al., 1989) and metal–DNA interactions (Tran Qui & Bagieu, 1990). In the course of synthesizing new ligands suitable for coordination chemistry, we prepared two new heterocyclic thiones, namely 1,3-dibenzoyl-4,5-dihydro-1H-imidazole-2-thione, C₁₇H₁₄N₂O₂S, (I), and 1,3-dibenzoyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, C₁₈H₁₆N₂O₂S, (II), from the reactions of 4,5-dihydroimidazole-2(3H)-thione and 1,4,5,6-tetrahydropyrimidine-2-thiol, respectively, with benzoyl chloride.

Views of the molecules of (I) and (II), including the atom-numbering schemes, are shown in Figs. 1 and 2. Selected bond distances and angles are listed in Tables 1 and 2. Each compound exhibits a soft thione S donor and three hard donor sites (a carbonyl O and two N atoms) and seems to act as a chelating or a bridging ligand. These compounds are also interesting building blocks for generating coordination polymers upon metal complexation. Both (I) and (II) consist of thioimidazole and thiopyrimidine moieties bonded to two benzoyl rings. The thio substituents exist in the thione form. The C—S bond lengths in (I) and (II) are consistent with a double bond and are similar to those in other reported heterocyclic thione derivatives containing thioimidazole and thiopyrimidine cycles (Ozbey et al., 1991; Akkurt et al., 1992, 2000; Cox et al., 1996; Liu et al., 2003; Ozcelik et al., 2004; Brito et al., 2004). The C8—N1 bond distances in both compounds are intermediate between standard single C—N (1.47 Å) and double C═N (1.28 Å) bonds, being significantly shorter than the C9—N1 bonds, because atom C8 is in an sp² hybridized state, while atom C9 is sp³. The remaining bond lengths in both compounds show no unusual values.

The molecules of (I) show C₂ symmetry, and the C8—S1 bond lies on the twofold rotation axis, while the molecules of (II) have mirror symmetry (C_s), with atoms S1, C8, C10, H10A and H10B situated on the mirror plane. The five-membered imidazole ring in (I) is essentially planar, with maximum deviations from the mean plane of −0.1418 (8) and 0.1397 (8) Å for atoms N1 and C9ⁱ [symmetry code: (i) 1 − x, 2 − y, z], respectively. The six-membered pyrimidine ring in (II) adopts a half-boat conformation, in which atoms C8 and C10 are displaced from the mean plane by 0.0387 (10) and 0.2561 (13) Å. The benzoyl rings in (I) make dihedral angles of 76.55 (3) and 79.85 (3)° with the mean plane of the imidazole ring. The dihedral angles between the two planar benzoyl fragments are 75.92 (3)° in (I) and 61.08 (4)° in (II). A non-planar disposition of the three rings in both compounds has been observed in other reported heterocyclic thione derivatives with similar fragments (Ozbey et al., 1991; Cox et al., 1996; Akkurt et al., 2000; Ozcelik et al., 2004).

The packing of the molecules in (I) and (II) is shown in Figs. 3 and 4. The molecules of (I) are linked by means of weak intermolecular C—H···O interactions (Table 1). Although there are no π···π stacking interactions in (II), the molecules are approximately paired, the two phenyl rings overlapping, forming channels running parallel to the a axis as shown in Fig 4. Examination of the structures with PLATON (Spek, 2003) indicates that there are no solvent-accesible voids in (I) and (II).

S2. Experimental

Triethylamine (TEA, 2.02 g, 20 mmol) was added to a solution of 4,5-dihydroimidazole-2(3H)-thione (1.02 g, 10 mmol) dissolved in THF (100 ml) with stirring on an ice bath for 30 min. Benzoyl chloride (2.81 g, 20 mmol) was added to the reaction mixture dropwise and it was refluxed for 4 h. The resulting solution was evaporated under vacuum to half the volume and then poured into ice water to precipitate. The residue was filtered off and single crystals of (I) suitable for X-ray measurements were obtained by crystallization from acetone. The procedure and molar quantities of the reactants for the preparation of (II) were the same as for (I), with 1,4,5,6-tetrahydropyrimidine-2-thiole replacing 4,5-dihydroimidazole-2(3H)-thione.

S3. Refinement

All H atoms were refined with a riding model [C—H = 0.95 and 0.99 Å, and U_iso(H) = 1.2 U_eq(C)].

Computing details

For both compounds, data collection: COLLECT (Bruker, 2002); cell refinement: EVALCCD (Bruker, 2002); data reduction: EVALCCD; program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecule of (I), showing the atom-labelling scheme (40% probability displacement ellipsoids).
	Fig. 2. The molecule of (II), showing the atom-labelling scheme (40% probability displacement ellipsoids).
	Fig. 3. A packing diagram of (I), viewed along the b axis.
	Fig. 4. A packing diagram of (II), viewed along the a axis.

(I) 1,3-Dibenzoyl-4,5-dihydro-1H-imidazole-2(3H)-thione

Crystal data

C17H14N2O2S	F(000) = 324
Mr = 310.36	Dx = 1.429 Mg m^−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 128 reflections
a = 11.8543 (8) Å	θ = 6.0–20.0°
b = 5.7221 (2) Å	µ = 0.23 mm^−1
c = 10.6312 (6) Å	T = 100 K
V = 721.13 (7) Å^3	Prism, yellow
Z = 2	0.37 × 0.16 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer	1864 independent reflections
Radiation source: fine-focus sealed tube	1772 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 9 pixels mm^-1	θmax = 28.7°, θmin = 3.4°
ϕ and ω scans with 2.0° and 80 s per frame	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2002)	k = −7→7
Tmin = 0.925, Tmax = 0.967	l = −14→14
21502 measured reflections

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)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.0278P)^2 + 0.1874P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
1864 reflections	Δρmax = 0.26 e Å^−3
101 parameters	Δρmin = −0.19 e Å^−3
1 restraint	Absolute structure: Flack (1983), 757 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (6)

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	0.5000	1.0000	0.68869 (3)	0.01560 (10)
O1	0.35542 (8)	0.50573 (19)	0.94793 (8)	0.02187 (19)
N1	0.43482 (8)	0.86246 (17)	0.92143 (9)	0.0134 (2)
C1	0.22621 (9)	0.93431 (19)	0.76869 (11)	0.0141 (2)
H1A	0.2426	1.0572	0.8259	0.017*
C2	0.14397 (9)	0.9638 (2)	0.67731 (11)	0.0158 (2)
H2A	0.1023	1.1054	0.6733	0.019*
C3	0.12244 (10)	0.7855 (2)	0.59125 (12)	0.0165 (2)
H3A	0.0667	0.8068	0.5281	0.020*
C4	0.18194 (11)	0.5772 (2)	0.59733 (12)	0.0173 (2)
H4A	0.1678	0.4572	0.5376	0.021*
C5	0.26257 (10)	0.54389 (19)	0.69133 (11)	0.0159 (2)
H5A	0.3021	0.3999	0.6973	0.019*
C6	0.28466 (9)	0.7233 (2)	0.77616 (11)	0.0131 (2)
C7	0.36160 (10)	0.6815 (2)	0.88443 (11)	0.0144 (2)
C8	0.5000	1.0000	0.84393 (13)	0.0121 (3)
C9	0.47107 (10)	0.8805 (2)	1.05407 (11)	0.0157 (2)
H9A	0.5243	0.7541	1.0768	0.019*
H9B	0.4058	0.8772	1.1122	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01409 (17)	0.02380 (19)	0.00891 (16)	−0.00350 (16)	0.000	0.000
O1	0.0273 (4)	0.0177 (4)	0.0206 (4)	−0.0021 (4)	−0.0026 (3)	0.0066 (4)
N1	0.0143 (5)	0.0162 (5)	0.0096 (4)	0.0004 (4)	0.0001 (4)	0.0014 (4)
C1	0.0124 (5)	0.0145 (5)	0.0153 (5)	−0.0006 (4)	0.0034 (4)	−0.0019 (4)
C2	0.0124 (5)	0.0155 (6)	0.0196 (5)	0.0010 (4)	0.0015 (4)	−0.0003 (5)
C3	0.0121 (5)	0.0203 (6)	0.0172 (6)	−0.0026 (4)	−0.0001 (4)	0.0004 (5)
C4	0.0173 (5)	0.0173 (5)	0.0174 (5)	−0.0044 (4)	0.0018 (4)	−0.0036 (5)
C5	0.0168 (5)	0.0127 (5)	0.0182 (5)	−0.0001 (4)	0.0031 (4)	0.0006 (5)
C6	0.0118 (5)	0.0146 (5)	0.0131 (5)	−0.0017 (4)	0.0020 (4)	0.0014 (4)
C7	0.0138 (5)	0.0144 (5)	0.0151 (5)	0.0018 (4)	0.0030 (4)	−0.0006 (4)
C8	0.0103 (6)	0.0139 (6)	0.0121 (5)	0.0028 (6)	0.000	0.000
C9	0.0199 (6)	0.0181 (6)	0.0092 (5)	0.0013 (5)	−0.0003 (4)	0.0007 (4)

Geometric parameters (Å, º)

N1—C7	1.4073 (15)	C3—C4	1.3864 (17)
N1—C8	1.3766 (13)	C3—H3A	0.9500
N1—C9	1.4777 (15)	C4—C5	1.3959 (17)
O1—C7	1.2135 (16)	C4—H4A	0.9500
S1—C8	1.6504 (14)	C5—C6	1.3915 (16)
C1—C2	1.3866 (16)	C5—H5A	0.9500
C1—C6	1.3942 (15)	C6—C7	1.4879 (17)
C1—H1A	0.9500	C9—C9^i	1.530 (2)
C2—C3	1.3940 (17)	C9—H9A	0.9900
C2—H2A	0.9500	C9—H9B	0.9900
C7—N1—C9	119.83 (9)	C4—C5—H5A	120.3
C8—N1—C7	126.84 (10)	C5—C6—C1	120.56 (11)
C8—N1—C9	111.59 (9)	C5—C6—C7	119.87 (10)
C2—C1—C6	119.64 (11)	C1—C6—C7	119.21 (10)
C2—C1—H1A	120.2	O1—C7—N1	119.45 (11)
C6—C1—H1A	120.2	O1—C7—C6	121.78 (11)
C1—C2—C3	119.97 (11)	N1—C7—C6	118.42 (10)
C1—C2—H2A	120.0	N1^i—C8—N1	106.48 (13)
C3—C2—H2A	120.0	N1^i—C8—S1	126.76 (6)
C4—C3—C2	120.36 (11)	N1—C8—S1	126.76 (6)
C4—C3—H3A	119.8	N1—C9—C9^i	101.11 (6)
C2—C3—H3A	119.8	N1—C9—H9A	111.5
C3—C4—C5	119.93 (11)	C9^i—C9—H9A	111.5
C3—C4—H4A	120.0	N1—C9—H9B	111.5
C5—C4—H4A	120.0	C9^i—C9—H9B	111.5
C6—C5—C4	119.49 (10)	H9A—C9—H9B	109.4
C6—C5—H5A	120.3
C6—C1—C2—C3	−1.87 (17)	C9—N1—C7—C6	151.18 (10)
C1—C2—C3—C4	0.76 (17)	C5—C6—C7—O1	−44.62 (17)
C2—C3—C4—C5	1.07 (18)	C1—C6—C7—O1	128.55 (12)
C3—C4—C5—C6	−1.76 (18)	C5—C6—C7—N1	142.26 (11)
C4—C5—C6—C1	0.65 (17)	C1—C6—C7—N1	−44.56 (15)
C4—C5—C6—C7	173.73 (11)	C7—N1—C8—N1^i	−174.60 (13)
C2—C1—C6—C5	1.17 (17)	C9—N1—C8—N1^i	−9.82 (6)
C2—C1—C6—C7	−171.95 (10)	C7—N1—C8—S1	5.40 (13)
C8—N1—C7—O1	141.55 (10)	C9—N1—C8—S1	170.18 (6)
C9—N1—C7—O1	−22.10 (17)	C8—N1—C9—C9^i	23.99 (13)
C8—N1—C7—C6	−45.17 (15)	C7—N1—C9—C9^i	−170.02 (11)

Symmetry code: (i) −x+1, −y+2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1^ii	0.99	2.47	3.2231 (16)	132

Symmetry code: (ii) −x+1, −y+1, z.

(II) 1,3-Dibenzoyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione

Crystal data

C18H16N2O2S	F(000) = 680
Mr = 324.39	Dx = 1.382 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 150 reflections
a = 8.6803 (6) Å	θ = 6.0–20.0°
b = 21.946 (1) Å	µ = 0.22 mm^−1
c = 8.1845 (9) Å	T = 100 K
V = 1559.1 (2) Å^3	Irregular, colorless
Z = 4	0.23 × 0.23 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer	2051 independent reflections
Radiation source: fine-focus sealed tube	1707 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 9 pixels mm^-1	θmax = 28.7°, θmin = 3.4°
ϕ and ω scans with 1.4° and 126 s per frame	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2002)	k = −24→29
Tmin = 0.941, Tmax = 0.972	l = −11→11
22525 measured 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0438P)^2 + 0.7208P] where P = (Fo^2 + 2Fc^2)/3
2051 reflections	(Δ/σ)max = 0.001
109 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.28 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	0.03972 (5)	0.7500	0.05041 (6)	0.01700 (13)
O1	0.18277 (15)	0.61397 (5)	−0.15616 (13)	0.0334 (3)
N1	0.30041 (13)	0.69748 (5)	−0.04365 (13)	0.0183 (2)
C1	0.27306 (16)	0.63935 (7)	0.26952 (17)	0.0211 (3)
H1A	0.3281	0.6765	0.2588	0.025*
C2	0.26144 (18)	0.61116 (8)	0.42084 (18)	0.0302 (4)
H2A	0.3088	0.6291	0.5138	0.036*
C3	0.1815 (2)	0.55730 (8)	0.4367 (2)	0.0378 (4)
H3A	0.1729	0.5385	0.5408	0.045*
C4	0.1137 (2)	0.53055 (8)	0.3019 (2)	0.0398 (5)
H4A	0.0598	0.4931	0.3135	0.048*
C5	0.12401 (18)	0.55813 (7)	0.1492 (2)	0.0274 (3)
H5A	0.0771	0.5398	0.0566	0.033*
C6	0.20375 (15)	0.61295 (6)	0.13345 (16)	0.0177 (3)
C7	0.21906 (16)	0.63974 (6)	−0.03214 (16)	0.0192 (3)
C8	0.2246 (2)	0.7500	−0.0151 (2)	0.0157 (4)
C9	0.45417 (16)	0.69417 (7)	−0.12014 (19)	0.0257 (3)
H9A	0.4435	0.6920	−0.2404	0.031*
H9B	0.5085	0.6571	−0.0825	0.031*
C10	0.5456 (2)	0.7500	−0.0738 (3)	0.0266 (5)
H10A	0.6457	0.7500	−0.1317	0.032*
H10B	0.5659	0.7500	0.0452	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0152 (2)	0.0180 (2)	0.0179 (2)	0.000	0.00326 (17)	0.000
O1	0.0498 (7)	0.0282 (6)	0.0221 (6)	0.0020 (5)	−0.0116 (5)	−0.0064 (4)
N1	0.0172 (5)	0.0197 (6)	0.0179 (5)	0.0024 (4)	0.0043 (4)	0.0013 (4)
C1	0.0194 (6)	0.0248 (7)	0.0191 (6)	0.0018 (5)	−0.0006 (5)	0.0012 (5)
C2	0.0272 (8)	0.0447 (10)	0.0188 (7)	0.0115 (7)	0.0016 (6)	0.0061 (7)
C3	0.0376 (9)	0.0412 (10)	0.0345 (9)	0.0170 (8)	0.0159 (7)	0.0198 (8)
C4	0.0354 (9)	0.0226 (8)	0.0614 (12)	0.0027 (7)	0.0191 (8)	0.0148 (8)
C5	0.0239 (7)	0.0187 (7)	0.0398 (9)	0.0006 (6)	0.0026 (6)	−0.0020 (6)
C6	0.0152 (6)	0.0170 (6)	0.0209 (6)	0.0038 (5)	0.0005 (5)	0.0009 (5)
C7	0.0210 (6)	0.0168 (6)	0.0197 (6)	0.0043 (5)	−0.0035 (5)	−0.0017 (5)
C8	0.0176 (8)	0.0190 (9)	0.0104 (8)	0.000	0.0006 (7)	0.000
C9	0.0190 (7)	0.0310 (8)	0.0271 (7)	0.0061 (6)	0.0066 (6)	−0.0019 (6)
C10	0.0159 (9)	0.0409 (12)	0.0231 (10)	0.000	0.0017 (8)	0.000

Geometric parameters (Å, º)

N1—C7	1.4537 (18)	C3—H3A	0.9500
N1—C8	1.3478 (15)	C4—C5	1.391 (2)
N1—C9	1.4760 (17)	C4—H4A	0.9500
O1—C7	1.2039 (17)	C5—C6	1.394 (2)
S1—C8	1.6918 (19)	C5—H5A	0.9500
C1—C2	1.388 (2)	C6—C7	1.4832 (19)
C1—C6	1.3920 (19)	C9—C10	1.5082 (19)
C1—H1A	0.9500	C9—H9A	0.9900
C2—C3	1.377 (3)	C9—H9B	0.9900
C2—H2A	0.9500	C10—H10A	0.9900
C3—C4	1.381 (3)	C10—H10B	0.9900
C7—N1—C9	115.08 (11)	C1—C6—C7	121.82 (13)
C8—N1—C7	119.80 (12)	C5—C6—C7	118.11 (13)
C8—N1—C9	123.87 (12)	O1—C7—N1	118.82 (13)
C2—C1—C6	119.79 (14)	O1—C7—C6	124.10 (13)
C2—C1—H1A	120.1	N1—C7—C6	116.63 (11)
C6—C1—H1A	120.1	N1^i—C8—N1	117.56 (16)
C3—C2—C1	120.21 (16)	N1—C8—S1	121.21 (8)
C3—C2—H2A	119.9	N1—C9—C10	109.21 (13)
C1—C2—H2A	119.9	N1—C9—H9A	109.8
C2—C3—C4	120.30 (15)	C10—C9—H9A	109.8
C2—C3—H3A	119.8	N1—C9—H9B	109.8
C4—C3—H3A	119.8	C10—C9—H9B	109.8
C3—C4—C5	120.32 (15)	H9A—C9—H9B	108.3
C3—C4—H4A	119.8	C9—C10—C9^i	108.66 (17)
C5—C4—H4A	119.8	C9—C10—H10A	110.0
C4—C5—C6	119.38 (15)	C9^i—C10—H10A	110.0
C4—C5—H5A	120.3	C9—C10—H10B	110.0
C6—C5—H5A	120.3	C9^i—C10—H10B	110.0
C1—C6—C5	119.98 (13)	H10A—C10—H10B	108.3
C6—C1—C2—C3	−0.1 (2)	C1—C6—C7—O1	167.71 (14)
C1—C2—C3—C4	0.7 (2)	C5—C6—C7—O1	−8.9 (2)
C2—C3—C4—C5	−0.8 (2)	C1—C6—C7—N1	−4.47 (19)
C3—C4—C5—C6	0.2 (2)	C5—C6—C7—N1	178.89 (12)
C2—C1—C6—C5	−0.5 (2)	C7—N1—C8—N1^i	−173.28 (10)
C2—C1—C6—C7	−177.07 (13)	C9—N1—C8—N1^i	−6.7 (2)
C4—C5—C6—C1	0.5 (2)	C7—N1—C8—S1	5.5 (2)
C4—C5—C6—C7	177.16 (13)	C9—N1—C8—S1	172.02 (11)
C8—N1—C7—O1	103.75 (17)	C8—N1—C9—C10	32.02 (19)
C9—N1—C7—O1	−63.95 (17)	C7—N1—C9—C10	−160.84 (12)
C8—N1—C7—C6	−83.64 (16)	N1—C9—C10—C9^i	−54.9 (2)
C9—N1—C7—C6	108.66 (13)

Symmetry code: (i) x, −y+3/2, z.