4-Methyl-2-[N-(3,4-methyl­ene­dioxy­benzyl­idene)hydrazino]­thia­zole and its reduction product, 4-methyl-2-[N-(3,4-methyl­ene­dioxybenzyl­idene)hydrazono]-4,5-di­hydro­thia­zole

The crystal structures of 4-methyl-2-[N-(3,4-methyl­ene­dioxybenzyl­idene)hydrazino]­thia­zole, C₁₂H₁₁N₃O₂S, and its reduction product 4-methyl-2-[N-(3,4-methyl­ene­dioxybenzyl­idene)hydrazono]-4,5-di­hydro­thia­zole, C₁₂H₁₃N₃O₂S, have been determined and compared. In the reduction product, the tautomer observed bears an H atom on the exocyclic N atom. Both compounds form hydrogen-bonded dimers over centers of inversion.

S1. Comment

Reduction of N-(3,4-methylenedioxy) benzylidene hydrazino methylthiazole (1) has been reported to lead to the corresponding benzyl analogue (2) (Mazzone et al., 1992; Pignatello et al., 1994; Cambria et al., 1996; Gritsch et al., 2001). Determination of the crystal structures of both compounds has been undertaken in order to clarify the mechanism of reduction of (1). The structural evidence given in this work demonstrates that the product of the reaction is the (2 b) isomer. The crystal structure further establishes that the tautomeric form of this product is the one with an H on the endocyclic N3 nitrogen.

Both compounds adopt an extended conformation (Fig. 1) with torsion angles N3—C4—N6—N7 [-177.53 (14) and 176.72 (19)° for (1) and (2) respectively], C4—N6—N7—C8 [179.46 (15) and 171.73 (18)°], and N6—N7—C8—C9 [179.9 (2) and 177.6 (2)°] close to 180°. A similar anti E conformation is observed for related substituted thiazol-2-yl hydrazines in solution as demonstrated by NMR data and ab initio calculations in water (Wouters et al., 2001).

For the fully oxidized molecule (1), analysis of the bond lengths and angles confirm an sp2 hybridation of all C and N atoms of the benzylidene hydrazino thiazole fragment. The C1—C2 [1.345 (3) Å], C2—N3 [1.394 (2) Å], N3—C4 [1.3071 (19) Å], C4—N6 [1.356 (2) Å], N6—N7 [1.3714 (18) Å], and N7—C8 (1.276 (2) Å) bond lengths are intermediate between C—C or C—N single and double bonds. The alternation of shorter and longer bonds further confirms electron delocalization along the whole molecule.

In the reduced product (2), C1 and C2 adopt a (sp3) tetrahedral geometry as demonstrated by the C2—C1—S5 [107.37 (15)°] and C1—C2—N3 [104.93 (18)°] valence angles. The C1—C2 bond [1.533 (3) Å] is significantly longer that the corresponding bond in molecule (1). In (2), the C4—N3 bond [1.339 (3) Å] is also longer than the C4—N6 bond [1.294 (3) Å]. The opposite is observed in (1). Analysis of the geometry therefore strongly suggests that the structure of the reduction product of (1) is the (2 b) isomer and not (2a).

Unambiguous localization from the difference Fourier map of an hydrogen on endocyclic N3 nitrogen in (2) establishes the tautomeric preference of the reduction product. Recent results obtained by energy calculations at the HF/6–31 G(d) and MP2/6–31 G(d) levels confirm the stability of the endocyclic N3 tautomeric form (Wouters et al., 2001).

In compound (2), the hydrogen on endocyclic nitrogen N3 is involved in an H bond connecting N3 to N6 [N3···N6 = 3.005 (2) Å, Table 1]. As a consequence of this H bond, molecules form interesting dimers in the crystal packing as illustrated in the ORTEP plot (Fig. 1).

A similar dimeric assembly is observed in the crystal structure of compound (1). The same nitrogen atoms are involved in the stabilization via H bond. In contrast to structure (2), the H donor in (1) is the exocyclic nitrogen N6 [N6···N3 = 3.048 (2) Å, Table 1].

S2. Experimental

Description of the synthesis of the title compounds is given in Mazzone et al. (1992), Pignatello et al. (1994) and Cambria et al. (1996).

S3. Refinement

H atoms on N3 or N6 were located at the end of the refinement by Fourier difference synthesis. Once located, they were refined using the riding model method.

Computing details

Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I); SHELXS97 (Sheldrick, 1990) for (IIb). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: PLATON (Spek, 1990).

Figures

Fig. 1. View of the dimers formed in the crystal structures of (a) compound (1) and (b) compound (2). Displacement ellipsoids for non-H atoms are drawn at the 50% probability level and the atom-numbering scheme is given.

(I)

Crystal data

C12H11N3O2S	F(000) = 544
Mr = 261.31	Dx = 1.447 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 6.219 (1) Å	θ = 35–45°
b = 12.163 (2) Å	µ = 2.40 mm^−1
c = 15.855 (1) Å	T = 293 K
β = 91.13 (1)°	Plate, yellow
V = 1199.1 (3) Å^3	0.6 × 0.4 × 0.09 mm
Z = 4

Data collection

Enraf Nonius CAD 4 diffractometer	2066 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
Graphite monochromator	θmax = 71.9°, θmin = 4.6°
θ/2θ scans	h = 0→7
Absorption correction: analytical North et al. (1968)	k = −11→14
Tmin = 0.393, Tmax = 0.805	l = −19→19
3882 measured reflections	3 standard reflections every 60 min
2356 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.038	Calculated w = 1/[σ^2(Fo^2) + (0.0521P)^2 + 0.2929P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.106	(Δ/σ)max = 0.001
S = 1.09	Δρmax = 0.23 e Å^−3
2356 reflections	Δρmin = −0.28 e Å^−3
164 parameters

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	Uiso*/Ueq
S5	0.79678 (8)	0.14782 (4)	0.29729 (3)	0.0618 (2)
O12	−0.09986 (19)	0.39953 (11)	0.40256 (8)	0.0611 (4)
O14	−0.26993 (19)	0.41203 (10)	0.53016 (9)	0.0581 (4)
N3	1.0512 (2)	0.01641 (11)	0.37999 (8)	0.0455 (4)
N6	0.7658 (2)	0.08673 (11)	0.45879 (9)	0.0479 (4)
N7	0.5847 (2)	0.15092 (11)	0.45379 (9)	0.0458 (4)
C0	1.3144 (3)	−0.04372 (19)	0.27277 (14)	0.0727 (8)
C1	1.0092 (3)	0.08857 (18)	0.24570 (11)	0.0627 (7)
C2	1.1240 (3)	0.02250 (15)	0.29753 (11)	0.0518 (5)
C4	0.8793 (2)	0.07730 (13)	0.38701 (10)	0.0429 (5)
C8	0.4753 (3)	0.15987 (13)	0.52066 (11)	0.0464 (5)
C9	0.2798 (2)	0.22569 (13)	0.52381 (10)	0.0429 (5)
C10	0.1948 (2)	0.27923 (13)	0.45198 (10)	0.0449 (5)
C11	0.0113 (2)	0.33899 (13)	0.46195 (11)	0.0443 (5)
C13	−0.2898 (3)	0.43654 (16)	0.44252 (13)	0.0568 (6)
C15	−0.0907 (2)	0.34695 (13)	0.53856 (11)	0.0458 (5)
C16	−0.0125 (3)	0.29586 (14)	0.60916 (11)	0.0508 (5)
C17	0.1753 (3)	0.23447 (14)	0.60032 (11)	0.0484 (5)
H0A	1.34333	−0.03118	0.21431	0.1091*
H0B	1.28525	−0.12034	0.28153	0.1091*
H0C	1.43715	−0.02228	0.30655	0.1091*
H1	1.04029	0.10075	0.18933	0.0753*
H6	0.80514	0.05435	0.50478	0.0575*
H8	0.52195	0.12312	0.56909	0.0558*
H10	0.26074	0.27416	0.39999	0.0539*
H13A	−0.30716	0.51511	0.43438	0.0682*
H13B	−0.41484	0.39973	0.41829	0.0682*
H16	−0.08072	0.30160	0.66064	0.0610*
H17	0.23261	0.19814	0.64722	0.0581*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S5	0.0541 (3)	0.0811 (4)	0.0499 (3)	0.0050 (2)	−0.0033 (2)	0.0081 (2)
O12	0.0469 (7)	0.0730 (8)	0.0638 (8)	0.0118 (6)	0.0103 (6)	0.0139 (6)
O14	0.0409 (6)	0.0627 (8)	0.0710 (8)	0.0090 (5)	0.0116 (6)	−0.0015 (6)
N3	0.0426 (7)	0.0479 (7)	0.0463 (7)	−0.0012 (6)	0.0102 (5)	−0.0017 (6)
N6	0.0401 (7)	0.0547 (8)	0.0493 (7)	0.0078 (6)	0.0081 (6)	0.0041 (6)
N7	0.0347 (7)	0.0474 (7)	0.0553 (8)	0.0013 (5)	0.0038 (6)	−0.0011 (6)
C0	0.0717 (13)	0.0837 (14)	0.0640 (12)	0.0061 (11)	0.0307 (10)	−0.0048 (11)
C1	0.0608 (11)	0.0839 (14)	0.0436 (9)	−0.0082 (10)	0.0068 (8)	0.0002 (9)
C2	0.0488 (9)	0.0598 (10)	0.0472 (9)	−0.0080 (8)	0.0123 (7)	−0.0056 (8)
C4	0.0377 (8)	0.0455 (8)	0.0456 (8)	−0.0066 (6)	0.0032 (6)	−0.0027 (6)
C8	0.0381 (8)	0.0487 (9)	0.0526 (9)	0.0003 (7)	0.0030 (7)	−0.0016 (7)
C9	0.0336 (7)	0.0427 (8)	0.0526 (9)	−0.0050 (6)	0.0052 (6)	−0.0047 (6)
C10	0.0365 (8)	0.0492 (9)	0.0494 (8)	−0.0046 (6)	0.0088 (6)	−0.0022 (7)
C11	0.0348 (8)	0.0446 (8)	0.0537 (9)	−0.0051 (6)	0.0042 (7)	0.0006 (7)
C13	0.0357 (8)	0.0593 (10)	0.0755 (12)	0.0019 (7)	0.0031 (8)	0.0002 (9)
C15	0.0323 (7)	0.0453 (8)	0.0600 (10)	−0.0044 (6)	0.0091 (7)	−0.0078 (7)
C16	0.0452 (9)	0.0579 (10)	0.0499 (9)	−0.0024 (7)	0.0124 (7)	−0.0068 (8)
C17	0.0439 (9)	0.0525 (9)	0.0490 (8)	−0.0015 (7)	0.0034 (7)	−0.0028 (7)

Geometric parameters (Å, º)

S5—C4	1.7303 (17)	C8—C9	1.457 (2)
S5—C1	1.725 (2)	C9—C10	1.406 (2)
O12—C11	1.372 (2)	C9—C17	1.392 (2)
O12—C13	1.424 (2)	C10—C11	1.3648 (19)
O14—C13	1.424 (3)	C11—C15	1.385 (2)
O14—C15	1.3715 (18)	C15—C16	1.362 (2)
N3—C4	1.3071 (19)	C16—C17	1.396 (3)
N3—C2	1.394 (2)	C1—H1	0.9300
N6—N7	1.3714 (18)	C8—H8	0.9300
N6—C4	1.356 (2)	C10—H10	0.9299
N7—C8	1.276 (2)	C13—H13A	0.9701
N6—H6	0.8600	C13—H13B	0.9700
C0—C2	1.491 (3)	C16—H16	0.9299
C1—C2	1.345 (3)	C17—H17	0.9299
C1—S5—C4	88.01 (8)	C10—C11—C15	122.50 (15)
C11—O12—C13	105.99 (13)	O12—C13—O14	108.12 (14)
C13—O14—C15	105.68 (14)	O14—C15—C16	128.29 (16)
C2—N3—C4	109.33 (14)	O14—C15—C11	109.92 (14)
N7—N6—C4	116.11 (13)	C11—C15—C16	121.79 (14)
N6—N7—C8	116.83 (14)	C15—C16—C17	116.59 (16)
C4—N6—H6	121.93	C9—C17—C16	122.33 (16)
N7—N6—H6	121.96	S5—C1—H1	124.38
S5—C1—C2	111.24 (14)	C2—C1—H1	124.38
N3—C2—C1	115.26 (16)	N7—C8—H8	118.84
N3—C2—C0	119.51 (16)	C9—C8—H8	118.86
C0—C2—C1	125.23 (17)	C9—C10—H10	121.46
S5—C4—N6	119.82 (11)	C11—C10—H10	121.49
S5—C4—N3	116.15 (12)	O12—C13—H13A	110.08
N3—C4—N6	124.03 (14)	O12—C13—H13B	110.08
N7—C8—C9	122.30 (15)	O14—C13—H13A	110.08
C8—C9—C17	118.44 (15)	O14—C13—H13B	110.08
C10—C9—C17	119.73 (13)	H13A—C13—H13B	108.41
C8—C9—C10	121.82 (14)	C15—C16—H16	121.70
C9—C10—C11	117.05 (14)	C17—C16—H16	121.70
O12—C11—C15	109.35 (12)	C9—C17—H17	118.84
O12—C11—C10	128.15 (15)	C16—C17—H17	118.83
C1—S5—C4—N6	−178.59 (14)	S5—C1—C2—N3	−0.5 (2)
C4—S5—C1—C2	−0.19 (15)	S5—C1—C2—C0	178.26 (16)
C1—S5—C4—N3	0.96 (14)	N7—C8—C9—C10	3.0 (2)
C11—O12—C13—O14	9.60 (18)	N7—C8—C9—C17	−177.43 (16)
C13—O12—C11—C10	174.33 (16)	C10—C9—C17—C16	−0.5 (2)
C13—O12—C11—C15	−6.17 (17)	C8—C9—C17—C16	179.90 (18)
C15—O14—C13—O12	−9.36 (17)	C8—C9—C10—C11	−179.83 (14)
C13—O14—C15—C16	−175.03 (17)	C17—C9—C10—C11	0.6 (2)
C13—O14—C15—C11	5.61 (17)	C9—C10—C11—C15	−0.6 (2)
C4—N3—C2—C1	1.2 (2)	C9—C10—C11—O12	178.85 (15)
C2—N3—C4—S5	−1.39 (17)	O12—C11—C15—C16	−179.05 (15)
C2—N3—C4—N6	178.13 (15)	O12—C11—C15—O14	0.36 (17)
C4—N3—C2—C0	−177.65 (16)	C10—C11—C15—C16	0.5 (2)
N7—N6—C4—S5	1.98 (19)	C10—C11—C15—O14	179.88 (18)
N7—N6—C4—N3	−177.53 (14)	C11—C15—C16—C17	−0.3 (2)
C4—N6—N7—C8	179.46 (15)	O14—C15—C16—C17	−179.63 (15)
N6—N7—C8—C9	179.9 (2)	C15—C16—C17—C9	0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···N3^i	0.86	2.19	3.048 (2)	172

Symmetry code: (i) −x+2, −y, −z+1.

(IIb)

Crystal data

C12H13N3O2S	F(000) = 552
Mr = 263.32	Dx = 1.344 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 14.738 (1) Å	θ = 35–45°
b = 5.750 (1) Å	µ = 2.21 mm^−1
c = 15.898 (1) Å	T = 293 K
β = 105.02 (1)°	Prism, yellow
V = 1301.2 (3) Å^3	0.6 × 0.4 × 0.21 mm
Z = 4

Data collection

Enraf Nonius CAD 4 diffractometer	2333 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 71.9°, θmin = 3.1°
θ/2θ scans	h = −18→17
Absorption correction: analytical North et al. (1968)	k = −7→5
Tmin = 0.336, Tmax = 0.660	l = 0→19
3758 measured reflections	3 standard reflections every 60 min
2540 independent reflections	intensity decay: 1%

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)] = 0.042	H-atom parameters not refined
wR(F^2) = 0.135	Calculated w = 1/[σ^2(Fo^2) + (0.0703P)^2 + 0.3517P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
2540 reflections	Δρmax = 0.30 e Å^−3
167 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0035 (5)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	Uiso*/Ueq
C0	−0.19889 (19)	0.2577 (7)	0.0887 (2)	0.1012 (11)
H0A	−0.2273	0.1440	0.0457	0.152*
H0B	−0.2469	0.3537	0.1015	0.152*
H0C	−0.1648	0.1803	0.1408	0.152*
C1	−0.08248 (17)	0.5943 (5)	0.11810 (16)	0.0692 (6)
H1A	−0.1205	0.6380	0.1571	0.074 (7)*
H1B	−0.0718	0.7317	0.0866	0.092 (9)*
C2	−0.13261 (16)	0.4067 (5)	0.05427 (16)	0.0672 (6)
H2	−0.1673	0.4809	0.0000	0.085 (9)*
N3	−0.05820 (12)	0.2663 (3)	0.03746 (12)	0.0596 (5)
H3	−0.0687	0.1533	−0.0003	0.050*
C4	0.02269 (13)	0.2579 (4)	0.09979 (12)	0.0495 (4)
S5	0.02832 (4)	0.47341 (10)	0.17933 (3)	0.0597 (2)
N6	0.08724 (11)	0.1051 (3)	0.10000 (11)	0.0548 (4)
N7	0.16639 (11)	0.1413 (3)	0.16895 (10)	0.0514 (4)
C8	0.22709 (13)	−0.0193 (3)	0.17883 (13)	0.0506 (4)
H8	0.2158	−0.1543	0.1389	0.050*
C9	0.31637 (13)	−0.0098 (3)	0.24518 (12)	0.0458 (4)
C10	0.33979 (13)	0.1817 (3)	0.30242 (12)	0.0475 (4)
H10	0.2984	0.3049	0.3005	0.057*
C11	0.42579 (13)	0.1774 (3)	0.36064 (11)	0.0469 (4)
O12	0.46423 (10)	0.3403 (3)	0.42296 (10)	0.0628 (4)
C13	0.55967 (15)	0.2700 (4)	0.45742 (14)	0.0612 (5)
H13A	0.6013	0.3749	0.4376	0.073*
H13B	0.5758	0.2741	0.5206	0.073*
O14	0.56982 (11)	0.0399 (3)	0.42813 (10)	0.0639 (4)
C15	0.48911 (13)	−0.0032 (3)	0.36400 (12)	0.0485 (4)
C16	0.46836 (14)	−0.1908 (4)	0.31048 (12)	0.0522 (5)
H16	0.5107	−0.3123	0.3134	0.063*
C17	0.38013 (13)	−0.1920 (3)	0.25082 (12)	0.0501 (4)
H17	0.3633	−0.3185	0.2136	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C0	0.0680 (15)	0.128 (3)	0.112 (2)	−0.0048 (17)	0.0307 (16)	−0.036 (2)
C1	0.0724 (13)	0.0618 (13)	0.0698 (14)	0.0151 (11)	0.0118 (11)	−0.0135 (12)
C2	0.0606 (12)	0.0721 (14)	0.0626 (12)	0.0180 (11)	0.0046 (10)	−0.0121 (11)
N3	0.0522 (9)	0.0648 (10)	0.0561 (9)	0.0057 (8)	0.0039 (7)	−0.0207 (8)
C4	0.0517 (9)	0.0518 (10)	0.0446 (9)	−0.0034 (8)	0.0121 (8)	−0.0083 (8)
S5	0.0721 (4)	0.0556 (3)	0.0467 (3)	0.0055 (2)	0.0065 (2)	−0.0135 (2)
N6	0.0482 (8)	0.0623 (10)	0.0503 (9)	0.0018 (7)	0.0062 (7)	−0.0169 (8)
N7	0.0485 (8)	0.0574 (9)	0.0459 (8)	−0.0021 (7)	0.0078 (6)	−0.0106 (7)
C8	0.0520 (10)	0.0534 (10)	0.0478 (10)	−0.0019 (8)	0.0152 (8)	−0.0099 (8)
C9	0.0503 (9)	0.0478 (9)	0.0426 (9)	−0.0016 (7)	0.0177 (7)	−0.0013 (7)
C10	0.0499 (9)	0.0455 (9)	0.0488 (9)	0.0019 (7)	0.0157 (7)	−0.0025 (8)
C11	0.0543 (9)	0.0465 (9)	0.0414 (9)	−0.0034 (8)	0.0151 (7)	0.0007 (7)
O12	0.0641 (8)	0.0574 (9)	0.0595 (8)	−0.0015 (7)	0.0025 (7)	−0.0105 (7)
C13	0.0597 (11)	0.0718 (14)	0.0477 (10)	−0.0055 (10)	0.0058 (9)	0.0014 (10)
O14	0.0588 (8)	0.0718 (10)	0.0537 (8)	0.0068 (7)	0.0014 (6)	0.0044 (7)
C15	0.0517 (10)	0.0545 (10)	0.0399 (9)	0.0029 (8)	0.0132 (7)	0.0094 (8)
C16	0.0610 (11)	0.0530 (11)	0.0461 (9)	0.0121 (8)	0.0202 (8)	0.0074 (8)
C17	0.0613 (11)	0.0479 (10)	0.0447 (9)	0.0027 (8)	0.0203 (8)	−0.0020 (8)

Geometric parameters (Å, º)

C0—C2	1.504 (4)	C8—H8	0.9890
C0—H0A	0.9600	C9—C17	1.395 (3)
C0—H0B	0.9600	C9—C10	1.413 (3)
C0—H0C	0.9600	C10—C11	1.362 (3)
C1—C2	1.533 (3)	C10—H10	0.9300
C1—S5	1.809 (2)	C11—O12	1.375 (2)
C1—H1A	0.9700	C11—C15	1.388 (3)
C1—H1B	0.9700	O12—C13	1.429 (3)
C2—N3	1.441 (3)	C13—O14	1.424 (3)
C2—H2	0.9800	C13—H13A	0.9700
N3—C4	1.339 (3)	C13—H13B	0.9700
N3—H3	0.8707	O14—C15	1.374 (2)
C4—N6	1.294 (3)	C15—C16	1.359 (3)
C4—S5	1.7569 (19)	C16—C17	1.397 (3)
N6—N7	1.394 (2)	C16—H16	0.9300
N7—C8	1.267 (3)	C17—H17	0.9300
C8—C9	1.459 (3)
C2—C0—H0A	109.5	N7—C8—H8	119.8
C2—C0—H0B	109.5	C9—C8—H8	117.6
H0A—C0—H0B	109.5	C17—C9—C10	119.73 (18)
C2—C0—H0C	109.5	C17—C9—C8	118.99 (17)
H0A—C0—H0C	109.5	C10—C9—C8	121.28 (17)
H0B—C0—H0C	109.5	C11—C10—C9	116.90 (17)
C2—C1—S5	107.37 (16)	C11—C10—H10	121.5
C2—C1—H1A	110.2	C9—C10—H10	121.5
S5—C1—H1A	110.2	C10—C11—O12	127.91 (17)
C2—C1—H1B	110.2	C10—C11—C15	122.53 (18)
S5—C1—H1B	110.2	O12—C11—C15	109.56 (16)
H1A—C1—H1B	108.5	C11—O12—C13	105.32 (16)
N3—C2—C0	110.2 (2)	O14—C13—O12	108.30 (17)
N3—C2—C1	104.93 (18)	O14—C13—H13A	110.0
C0—C2—C1	114.0 (2)	O12—C13—H13A	110.0
N3—C2—H2	109.2	O14—C13—H13B	110.0
C0—C2—H2	109.2	O12—C13—H13B	110.0
C1—C2—H2	109.2	H13A—C13—H13B	108.4
C4—N3—C2	117.19 (17)	C15—O14—C13	105.43 (15)
C4—N3—H3	116.7	C16—C15—O14	128.22 (18)
C2—N3—H3	122.5	C16—C15—C11	122.00 (18)
N6—C4—N3	122.62 (17)	O14—C15—C11	109.77 (17)
N6—C4—S5	125.39 (14)	C15—C16—C17	116.59 (18)
N3—C4—S5	111.99 (15)	C15—C16—H16	121.7
C4—S5—C1	90.92 (10)	C17—C16—H16	121.7
C4—N6—N7	111.45 (16)	C9—C17—C16	122.22 (18)
C8—N7—N6	114.15 (16)	C9—C17—H17	118.9
N7—C8—C9	122.54 (17)	C16—C17—H17	118.9
S5—C1—C2—N3	−27.7 (3)	C9—C10—C11—O12	−179.43 (17)
S5—C1—C2—C0	92.9 (2)	C9—C10—C11—C15	0.8 (3)
C0—C2—N3—C4	−96.2 (3)	C10—C11—O12—C13	−171.82 (19)
C1—C2—N3—C4	26.9 (3)	C15—C11—O12—C13	7.9 (2)
C2—N3—C4—N6	166.1 (2)	C11—O12—C13—O14	−12.6 (2)
C2—N3—C4—S5	−13.1 (3)	O12—C13—O14—C15	12.4 (2)
N6—C4—S5—C1	176.1 (2)	C13—O14—C15—C16	173.63 (19)
N3—C4—S5—C1	−4.62 (18)	C13—O14—C15—C11	−7.5 (2)
C2—C1—S5—C4	19.02 (19)	C10—C11—C15—C16	−1.6 (3)
N3—C4—N6—N7	176.72 (19)	O12—C11—C15—C16	178.65 (17)
S5—C4—N6—N7	−4.1 (3)	C10—C11—C15—O14	179.45 (17)
C4—N6—N7—C8	171.73 (18)	O12—C11—C15—O14	−0.3 (2)
N6—N7—C8—C9	177.58 (17)	O14—C15—C16—C17	179.53 (18)
N7—C8—C9—C17	−178.90 (18)	C11—C15—C16—C17	0.8 (3)
N7—C8—C9—C10	0.0 (3)	C10—C9—C17—C16	−1.4 (3)
C17—C9—C10—C11	0.6 (3)	C8—C9—C17—C16	177.57 (17)
C8—C9—C10—C11	−178.33 (17)	C15—C16—C17—C9	0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N6^i	0.87	2.139	3.005 (2)	174.6

Symmetry code: (i) −x, −y, −z.