Ethyl 4-(4-cyano-phen-yl)-6-methyl-2-thioxo-1,2,3,4-tetra-hydro-pyrimidine-5-carboxyl-ate.

The asymmetric unit of the title compound, C(15)H(15)N(3)O(2)S, contains two independent mol-ecules corresponding to the R and S enanti-omers. The dihydro-pyrimidinone rings adopt a flattened boat conformation. One of the ethyl groups is disordered over two orientations with occupancy factors of 0.700 (7) and 0.300 (7). In the crystal structure, mol-ecules are linked by inter-molecular N-H⋯O hydrogen-bonding inter-actions into one-dimensional chains along the c-axis direction. The chains are further connected by N-H⋯S hydrogen bonds, forming a three-dimensional network.

Related literature

For the synthesis and the pharmaceutical applications of pyrimidinones, see: Atwal (1990 ▶); Steele et al. (1998 ▶); Manjula et al. (2004 ▶); Matsuda & Hirao (1965 ▶).

Experimental

Crystal data

C15H15N3O2S

M = 301.37

Triclinic,

a = 9.2938 (19) Å

b = 13.277 (3) Å

c = 14.512 (3) Å

α = 101.247 (17)°

β = 108.442 (13)°

γ = 107.89 (3)°

V = 1529.6 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 291 K

0.50 × 0.48 × 0.47 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.898, T max = 0.904

13899 measured reflections

5958 independent reflections

4590 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.151

S = 1.06

5958 reflections

386 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.30 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024520/rz2341sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024520/rz2341Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H15N3O2S	Z = 4
Mr = 301.37	F(000) = 632
Triclinic, P1	Dx = 1.309 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2938 (19) Å	Cell parameters from 4203 reflections
b = 13.277 (3) Å	θ = 2.4–27.5°
c = 14.512 (3) Å	µ = 0.22 mm−1
α = 101.247 (17)°	T = 291 K
β = 108.442 (13)°	Block, yellow
γ = 107.89 (3)°	0.50 × 0.48 × 0.47 mm
V = 1529.6 (7) Å3

Rigaku SCXmini diffractometer	5958 independent reflections
Radiation source: fine-focus sealed tube	4590 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 13.6612 pixels mm-1	θmax = 26.0°, θmin = 2.4°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
Tmin = 0.898, Tmax = 0.904	l = −17→17
13899 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0841P)2 + 0.2227P] where P = (Fo2 + 2Fc2)/3
5958 reflections	(Δ/σ)max < 0.001
386 parameters	Δρmax = 0.32 e Å−3
2 restraints	Δρmin = −0.30 e Å−3

Experimental. 1H-NMR (d4-Methanol) δ (p.p.m.): 7.73 (d, 2H, J = 8 Hz), 7.50 (d, 2H, J = 8 Hz), 5.40 (s, 1H), 4.11 (q, 2H, J = 7 Hz), 2.37 (s, 3H), 1.19(t, 3H, J = 7 Hz). 13 C-NMR (d4-Methanol) δ(p.p.m.): 13.08 (–CH2—CH3), 16.33 (–CH3), 54.66 (C*), 60.03 (–CH2—CH3), 100.73 (C—C=O), 111.32 (C—CN), 118.08 (–CN), 127.46, 132.29 (CH in phenyl), 145.42 (C in phenyl), 148.56 (CH3—C—NH–), 165.53 (C=O), 175.35 (C=S).

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.2143 (2)	−0.01219 (17)	0.21806 (15)	0.0419 (4)
C2	0.2370 (2)	0.03499 (16)	0.06791 (14)	0.0398 (4)
C3	0.2591 (3)	−0.0104 (2)	−0.02697 (17)	0.0561 (6)
H3A	0.2465	0.0359	−0.0696	0.084*
H3B	0.1776	−0.0852	−0.0639	0.084*
H3C	0.3675	−0.0110	−0.0084	0.084*
C4	0.2051 (2)	0.12633 (16)	0.09358 (13)	0.0374 (4)
C5	0.1790 (3)	0.19201 (18)	0.02444 (15)	0.0454 (5)
C6	0.1450 (8)	0.3589 (6)	0.0092 (7)	0.082 (2)	0.700 (7)
H6A	0.0435	0.3271	−0.0523	0.098*	0.700 (7)
H6B	0.2375	0.3768	−0.0108	0.098*	0.700 (7)
C7	0.1533 (8)	0.4606 (4)	0.0772 (5)	0.1006 (17)	0.700 (7)
H7A	0.1462	0.5134	0.0410	0.151*	0.700 (7)
H7B	0.2560	0.4930	0.1366	0.151*	0.700 (7)
H7C	0.0632	0.4415	0.0983	0.151*	0.700 (7)
C8	0.2021 (2)	0.16692 (16)	0.19771 (13)	0.0368 (4)
H8A	0.1093	0.1899	0.1884	0.044*
C9	0.3609 (2)	0.26699 (16)	0.27233 (14)	0.0387 (4)
C10	0.5112 (3)	0.25592 (17)	0.30151 (16)	0.0474 (5)
H10A	0.5152	0.1881	0.2735	0.057*
C11	0.6553 (3)	0.34466 (18)	0.37184 (17)	0.0510 (5)
H11A	0.7548	0.3357	0.3922	0.061*
C12	0.6507 (3)	0.44634 (17)	0.41161 (15)	0.0461 (5)
C13	0.8014 (3)	0.53885 (19)	0.48441 (17)	0.0554 (6)
C14	0.5017 (3)	0.45957 (19)	0.38096 (17)	0.0554 (6)
H14A	0.4989	0.5286	0.4064	0.067*
C15	0.3576 (3)	0.36968 (18)	0.31243 (16)	0.0495 (5)
H15A	0.2578	0.3782	0.2931	0.059*
C16	0.5233 (3)	0.77227 (17)	0.18205 (15)	0.0451 (5)
C17	0.5666 (3)	0.77320 (17)	0.35679 (15)	0.0436 (5)
C18	0.4795 (3)	0.7769 (2)	0.42837 (19)	0.0603 (6)
H18A	0.5549	0.7901	0.4967	0.091*
H18B	0.3873	0.7069	0.4060	0.091*
H18C	0.4408	0.8362	0.4280	0.091*
C19	0.7254 (2)	0.78795 (16)	0.38041 (14)	0.0384 (4)
C20	0.8419 (3)	0.82399 (17)	0.48790 (15)	0.0439 (5)
C21	1.1249 (3)	0.9003 (2)	0.60221 (18)	0.0630 (6)
H21A	1.1071	0.8446	0.6364	0.076*
H21B	1.1211	0.9669	0.6412	0.076*
C22	1.2875 (3)	0.9271 (3)	0.5945 (3)	0.0823 (9)
H22A	1.3741	0.9563	0.6621	0.123*
H22B	1.3032	0.9818	0.5601	0.123*
H22C	1.2900	0.8604	0.5562	0.123*
C23	0.7893 (2)	0.77481 (16)	0.29625 (14)	0.0382 (4)
H23A	0.9001	0.8337	0.3216	0.046*
C24	0.8018 (2)	0.66181 (16)	0.26707 (14)	0.0381 (4)
C25	0.9496 (3)	0.65221 (18)	0.31451 (17)	0.0488 (5)
H25A	1.0406	0.7151	0.3626	0.059*
C26	0.9640 (3)	0.5505 (2)	0.29138 (18)	0.0556 (6)
H26A	1.0641	0.5455	0.3238	0.067*
C27	0.8294 (3)	0.45617 (18)	0.21999 (16)	0.0504 (5)
C28	0.6818 (3)	0.4646 (2)	0.17110 (18)	0.0591 (6)
H28A	0.5913	0.4017	0.1226	0.071*
C29	0.6684 (3)	0.56674 (19)	0.19433 (17)	0.0538 (5)
H29A	0.5687	0.5718	0.1608	0.065*
C30	0.8447 (4)	0.3498 (2)	0.20089 (19)	0.0659 (7)
C6'	0.070 (2)	0.3356 (16)	−0.0032 (18)	0.082 (2)	0.300 (7)
H6'A	0.0324	0.2960	−0.0756	0.098*	0.300 (7)
H6'B	−0.0202	0.3477	0.0105	0.098*	0.300 (7)
C7'	0.2159 (17)	0.4385 (11)	0.0334 (12)	0.1006 (17)	0.300 (7)
H7'A	0.1932	0.4860	−0.0063	0.151*	0.300 (7)
H7'B	0.3057	0.4212	0.0264	0.151*	0.300 (7)
H7'C	0.2453	0.4762	0.1043	0.151*	0.300 (7)
N1	0.2529 (2)	−0.02691 (14)	0.13483 (13)	0.0448 (4)
H1A	0.2896	−0.0779	0.1228	0.054*
N2	0.1754 (2)	0.07505 (14)	0.24092 (12)	0.0416 (4)
H2A	0.1310	0.0779	0.2846	0.050*
N3	0.9225 (3)	0.60999 (18)	0.54293 (17)	0.0738 (6)
N4	0.4650 (2)	0.75428 (16)	0.25562 (13)	0.0516 (4)
H4A	0.3600	0.7300	0.2385	0.062*
N5	0.6813 (2)	0.79053 (14)	0.20621 (12)	0.0441 (4)
H5A	0.7242	0.8135	0.1658	0.053*
N6	0.8613 (4)	0.2675 (2)	0.1898 (2)	0.0943 (9)
O1	0.1803 (2)	0.17349 (17)	−0.06000 (12)	0.0695 (5)
O2	0.1501 (3)	0.27880 (16)	0.06545 (13)	0.0776 (6)
O3	0.8045 (2)	0.82617 (18)	0.56068 (12)	0.0720 (5)
O4	0.99902 (18)	0.85749 (13)	0.49825 (11)	0.0513 (4)
S1	0.21451 (8)	−0.10085 (6)	0.28636 (5)	0.0632 (2)
S2	0.39778 (8)	0.77075 (5)	0.06890 (4)	0.0592 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0376 (10)	0.0473 (11)	0.0412 (10)	0.0142 (8)	0.0170 (9)	0.0176 (9)
C2	0.0396 (10)	0.0435 (10)	0.0339 (9)	0.0131 (8)	0.0160 (8)	0.0111 (8)
C3	0.0722 (15)	0.0587 (13)	0.0437 (11)	0.0300 (12)	0.0304 (11)	0.0110 (10)
C4	0.0373 (9)	0.0438 (10)	0.0305 (9)	0.0142 (8)	0.0148 (8)	0.0124 (8)
C5	0.0460 (11)	0.0568 (12)	0.0369 (10)	0.0220 (9)	0.0173 (9)	0.0190 (9)
C6	0.119 (6)	0.075 (4)	0.075 (3)	0.057 (5)	0.035 (5)	0.048 (3)
C7	0.114 (4)	0.074 (3)	0.136 (5)	0.051 (3)	0.050 (3)	0.055 (3)
C8	0.0386 (10)	0.0442 (10)	0.0329 (9)	0.0192 (8)	0.0169 (8)	0.0148 (8)
C9	0.0448 (10)	0.0440 (10)	0.0309 (9)	0.0189 (9)	0.0181 (8)	0.0131 (8)
C10	0.0467 (11)	0.0404 (10)	0.0530 (12)	0.0197 (9)	0.0173 (10)	0.0116 (9)
C11	0.0435 (11)	0.0491 (12)	0.0551 (13)	0.0174 (10)	0.0147 (10)	0.0161 (10)
C12	0.0517 (12)	0.0451 (11)	0.0353 (10)	0.0122 (9)	0.0166 (9)	0.0130 (8)
C13	0.0643 (14)	0.0469 (12)	0.0485 (12)	0.0175 (11)	0.0198 (12)	0.0145 (10)
C14	0.0690 (15)	0.0440 (12)	0.0513 (12)	0.0263 (11)	0.0225 (11)	0.0079 (9)
C15	0.0513 (12)	0.0517 (12)	0.0448 (11)	0.0264 (10)	0.0163 (10)	0.0094 (9)
C16	0.0611 (13)	0.0422 (11)	0.0392 (10)	0.0269 (10)	0.0216 (10)	0.0157 (8)
C17	0.0533 (12)	0.0497 (11)	0.0409 (10)	0.0265 (9)	0.0260 (9)	0.0204 (9)
C18	0.0621 (14)	0.0887 (18)	0.0607 (14)	0.0418 (13)	0.0427 (12)	0.0379 (13)
C19	0.0518 (11)	0.0390 (10)	0.0373 (10)	0.0246 (9)	0.0247 (9)	0.0166 (8)
C20	0.0581 (12)	0.0448 (11)	0.0386 (10)	0.0285 (10)	0.0237 (10)	0.0138 (8)
C21	0.0676 (15)	0.0553 (14)	0.0467 (12)	0.0228 (12)	0.0068 (11)	0.0058 (10)
C22	0.0594 (16)	0.0692 (17)	0.095 (2)	0.0237 (13)	0.0063 (15)	0.0221 (15)
C23	0.0468 (10)	0.0412 (10)	0.0361 (9)	0.0211 (8)	0.0222 (8)	0.0168 (8)
C24	0.0490 (11)	0.0434 (10)	0.0343 (9)	0.0236 (9)	0.0247 (9)	0.0161 (8)
C25	0.0502 (12)	0.0504 (12)	0.0488 (12)	0.0250 (10)	0.0195 (10)	0.0152 (9)
C26	0.0582 (13)	0.0606 (14)	0.0585 (13)	0.0369 (12)	0.0233 (11)	0.0197 (11)
C27	0.0710 (14)	0.0501 (12)	0.0446 (11)	0.0367 (11)	0.0286 (11)	0.0159 (9)
C28	0.0675 (15)	0.0488 (13)	0.0532 (13)	0.0262 (11)	0.0187 (12)	0.0043 (10)
C29	0.0532 (12)	0.0535 (12)	0.0537 (13)	0.0290 (10)	0.0160 (11)	0.0114 (10)
C30	0.0886 (18)	0.0633 (15)	0.0518 (13)	0.0462 (14)	0.0248 (13)	0.0111 (11)
C6'	0.119 (6)	0.075 (4)	0.075 (3)	0.057 (5)	0.035 (5)	0.048 (3)
C7'	0.114 (4)	0.074 (3)	0.136 (5)	0.051 (3)	0.050 (3)	0.055 (3)
N1	0.0559 (10)	0.0441 (9)	0.0463 (9)	0.0253 (8)	0.0274 (8)	0.0189 (7)
N2	0.0458 (9)	0.0482 (9)	0.0372 (8)	0.0181 (8)	0.0237 (7)	0.0162 (7)
N3	0.0695 (14)	0.0556 (12)	0.0631 (13)	0.0094 (11)	0.0093 (12)	0.0049 (10)
N4	0.0486 (10)	0.0679 (12)	0.0459 (10)	0.0265 (9)	0.0219 (8)	0.0240 (9)
N5	0.0591 (10)	0.0524 (10)	0.0398 (9)	0.0317 (8)	0.0288 (8)	0.0238 (8)
N6	0.134 (2)	0.0732 (16)	0.0725 (15)	0.0687 (17)	0.0222 (16)	0.0050 (12)
O1	0.0948 (13)	0.1007 (14)	0.0499 (9)	0.0593 (11)	0.0437 (9)	0.0432 (9)
O2	0.1407 (18)	0.0738 (12)	0.0546 (10)	0.0714 (13)	0.0467 (11)	0.0369 (9)
O3	0.0800 (12)	0.1160 (15)	0.0370 (8)	0.0530 (11)	0.0314 (8)	0.0239 (9)
O4	0.0519 (9)	0.0556 (9)	0.0404 (8)	0.0189 (7)	0.0153 (7)	0.0122 (6)
S1	0.0743 (4)	0.0735 (4)	0.0747 (4)	0.0400 (3)	0.0448 (4)	0.0500 (4)
S2	0.0743 (4)	0.0698 (4)	0.0399 (3)	0.0421 (3)	0.0167 (3)	0.0196 (3)

C1—N2	1.329 (3)	C18—H18A	0.9600
C1—N1	1.361 (2)	C18—H18B	0.9600
C1—S1	1.680 (2)	C18—H18C	0.9600
C2—C4	1.346 (3)	C19—C20	1.469 (3)
C2—N1	1.391 (3)	C19—C23	1.521 (2)
C2—C3	1.494 (3)	C20—O3	1.210 (2)
C3—H3A	0.9600	C20—O4	1.337 (3)
C3—H3B	0.9600	C21—O4	1.452 (3)
C3—H3C	0.9600	C21—C22	1.489 (4)
C4—C5	1.464 (3)	C21—H21A	0.9700
C4—C8	1.514 (2)	C21—H21B	0.9700
C5—O1	1.206 (2)	C22—H22A	0.9600
C5—O2	1.333 (3)	C22—H22B	0.9600
C6—O2	1.464 (8)	C22—H22C	0.9600
C6—C7	1.473 (9)	C23—N5	1.471 (2)
C6—H6A	0.9700	C23—C24	1.528 (3)
C6—H6B	0.9700	C23—H23A	0.9800
C7—H7A	0.9600	C24—C25	1.386 (3)
C7—H7B	0.9600	C24—C29	1.391 (3)
C7—H7C	0.9600	C25—C26	1.385 (3)
C8—N2	1.467 (2)	C25—H25A	0.9300
C8—C9	1.529 (3)	C26—C27	1.385 (3)
C8—H8A	0.9800	C26—H26A	0.9300
C9—C15	1.388 (3)	C27—C28	1.381 (3)
C9—C10	1.389 (3)	C27—C30	1.445 (3)
C10—C11	1.386 (3)	C28—C29	1.385 (3)
C10—H10A	0.9300	C28—H28A	0.9300
C11—C12	1.380 (3)	C29—H29A	0.9300
C11—H11A	0.9300	C30—N6	1.137 (3)
C12—C14	1.391 (3)	C6'—C7'	1.453 (16)
C12—C13	1.445 (3)	C6'—O2	1.51 (2)
C13—N3	1.144 (3)	C6'—H6'A	0.9700
C14—C15	1.386 (3)	C6'—H6'B	0.9700
C14—H14A	0.9300	C7'—H7'A	0.9600
C15—H15A	0.9300	C7'—H7'B	0.9600
C16—N5	1.327 (3)	C7'—H7'C	0.9600
C16—N4	1.370 (3)	N1—H1A	0.8600
C16—S2	1.679 (2)	N2—H2A	0.8600
C17—C19	1.345 (3)	N4—H4A	0.8600
C17—N4	1.394 (3)	N5—H5A	0.8600
C17—C18	1.508 (3)
N2—C1—N1	116.14 (17)	C20—C19—C23	118.95 (17)
N2—C1—S1	122.57 (15)	O3—C20—O4	122.34 (19)
N1—C1—S1	121.29 (16)	O3—C20—C19	125.4 (2)
C4—C2—N1	118.89 (17)	O4—C20—C19	112.29 (16)
C4—C2—C3	127.33 (19)	O4—C21—C22	107.1 (2)
N1—C2—C3	113.77 (18)	O4—C21—H21A	110.3
C2—C3—H3A	109.5	C22—C21—H21A	110.3
C2—C3—H3B	109.5	O4—C21—H21B	110.3
H3A—C3—H3B	109.5	C22—C21—H21B	110.3
C2—C3—H3C	109.5	H21A—C21—H21B	108.5
H3A—C3—H3C	109.5	C21—C22—H22A	109.5
H3B—C3—H3C	109.5	C21—C22—H22B	109.5
C2—C4—C5	121.66 (17)	H22A—C22—H22B	109.5
C2—C4—C8	120.44 (17)	C21—C22—H22C	109.5
C5—C4—C8	117.85 (17)	H22A—C22—H22C	109.5
O1—C5—O2	121.6 (2)	H22B—C22—H22C	109.5
O1—C5—C4	126.9 (2)	N5—C23—C19	109.13 (15)
O2—C5—C4	111.51 (17)	N5—C23—C24	110.81 (15)
O2—C6—C7	108.0 (6)	C19—C23—C24	112.27 (15)
O2—C6—H6A	110.1	N5—C23—H23A	108.2
C7—C6—H6A	110.1	C19—C23—H23A	108.2
O2—C6—H6B	110.1	C24—C23—H23A	108.2
C7—C6—H6B	110.1	C25—C24—C29	118.28 (19)
H6A—C6—H6B	108.4	C25—C24—C23	119.63 (18)
C6—C7—H7A	109.5	C29—C24—C23	122.09 (18)
C6—C7—H7B	109.5	C26—C25—C24	121.0 (2)
H7A—C7—H7B	109.5	C26—C25—H25A	119.5
C6—C7—H7C	109.5	C24—C25—H25A	119.5
H7A—C7—H7C	109.5	C25—C26—C27	120.0 (2)
H7B—C7—H7C	109.5	C25—C26—H26A	120.0
N2—C8—C4	109.60 (15)	C27—C26—H26A	120.0
N2—C8—C9	109.97 (15)	C28—C27—C26	119.6 (2)
C4—C8—C9	112.24 (15)	C28—C27—C30	121.2 (2)
N2—C8—H8A	108.3	C26—C27—C30	119.1 (2)
C4—C8—H8A	108.3	C27—C28—C29	120.0 (2)
C9—C8—H8A	108.3	C27—C28—H28A	120.0
C15—C9—C10	118.92 (18)	C29—C28—H28A	120.0
C15—C9—C8	120.95 (17)	C28—C29—C24	121.0 (2)
C10—C9—C8	120.14 (17)	C28—C29—H29A	119.5
C11—C10—C9	120.83 (19)	C24—C29—H29A	119.5
C11—C10—H10A	119.6	N6—C30—C27	177.3 (3)
C9—C10—H10A	119.6	C7'—C6'—O2	95.9 (11)
C12—C11—C10	119.8 (2)	C7'—C6'—H6'A	112.6
C12—C11—H11A	120.1	O2—C6'—H6'A	112.6
C10—C11—H11A	120.1	C7'—C6'—H6'B	112.6
C11—C12—C14	119.99 (19)	O2—C6'—H6'B	112.6
C11—C12—C13	119.6 (2)	H6'A—C6'—H6'B	110.1
C14—C12—C13	120.4 (2)	C6'—C7'—H7'A	109.5
N3—C13—C12	178.1 (3)	C6'—C7'—H7'B	109.5
C15—C14—C12	119.8 (2)	H7'A—C7'—H7'B	109.5
C15—C14—H14A	120.1	C6'—C7'—H7'C	109.5
C12—C14—H14A	120.1	H7'A—C7'—H7'C	109.5
C14—C15—C9	120.6 (2)	H7'B—C7'—H7'C	109.5
C14—C15—H15A	119.7	C1—N1—C2	124.43 (17)
C9—C15—H15A	119.7	C1—N1—H1A	117.8
N5—C16—N4	116.15 (18)	C2—N1—H1A	117.8
N5—C16—S2	123.41 (16)	C1—N2—C8	125.33 (15)
N4—C16—S2	120.44 (17)	C1—N2—H2A	117.3
C19—C17—N4	119.20 (17)	C8—N2—H2A	117.3
C19—C17—C18	127.79 (19)	C16—N4—C17	123.55 (18)
N4—C17—C18	113.00 (18)	C16—N4—H4A	118.2
C17—C18—H18A	109.5	C17—N4—H4A	118.2
C17—C18—H18B	109.5	C16—N5—C23	125.58 (16)
H18A—C18—H18B	109.5	C16—N5—H5A	117.2
C17—C18—H18C	109.5	C23—N5—H5A	117.2
H18A—C18—H18C	109.5	C5—O2—C6	116.0 (4)
H18B—C18—H18C	109.5	C5—O2—C6'	119.6 (10)
C17—C19—C20	120.67 (17)	C20—O4—C21	116.71 (17)
C17—C19—C23	120.26 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S2i	0.86	2.60	3.4612 (19)	174
N2—H2A···O3ii	0.86	2.14	2.843 (2)	138
N5—H5A···O1iii	0.86	2.01	2.852 (2)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S2i	0.86	2.60	3.4612 (19)	174
N2—H2A⋯O3ii	0.86	2.14	2.843 (2)	138
N5—H5A⋯O1iii	0.86	2.01	2.852 (2)	165

Symmetry codes: (i) ; (ii) ; (iii) .