A concise synthesis of a highly substituted 6-(1H-benzimidazol-1-yl)-5-nitroso­pyrimidin-2-amine: synthetic sequence and the mol­ecular and supra­molecular structures of one product and two inter­mediates

A concise and efficient synthesis of 6-benzimidazolyl-5-nitrosopyrimidines has been developed using Schiff base-type inter­mediates derived from N⁴-(2-amino­phen­yl)-6-meth­oxy-5-nitro­sopyrimidine-2,4-di­amine. 6-Meth­oxy-N⁴-{2-[(4-methyl­benzyl­idene)amino]­phen­yl}-5-nitro­sopyrimidine-2,4-di­amine, (I), and N⁴-{2-[(eth­oxy­methyl­idene)amino]­phen­yl}-6-meth­oxy-5-nitro­sopyrimidine-2,4-di­amine, (III), both crystallize from dimethyl sulfoxide solution as the 1:1 solvates C₁₉H₁₈N₆O₂·C₂H₆OS, (Ia), and C₁₄H₁₆N₆O₃·C₂H₆OS, (IIIa), respectively. The inter­atomic distances in these inter­mediates indicate significant electronic polarization within the substituted pyrimidine system. In each of (Ia) and (IIIa), inter­molecular N—H...O hydrogen bonds generate centrosymmetric four-mol­ecule aggregates. Oxidative ring closure of inter­mediate (I), effected using ammonium hexa­nitratocerate(IV), produced 4-meth­oxy-6-[2-(4-methyl­phenyl-1H-benzimidazol-1-yl]-5-nitrosopyrimidin-2-amine, C₁₉H₁₆N₆O₂, (II) [Cobo et al. (2018). Private communication (CCDC 1830889). CCDC, Cambridge, England], where the extent of electronic polarization is much less than in (Ia) and (IIIa). A combination of N—H...N and C—H...O hydrogen bonds links the mol­ecules of (II) into complex sheets.

Computing details

For both structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

6-Methoxy-N⁴-{2-[(4-methylbenzylidene)amino]phenyl}-5-nitrosopyrimidine-2,4-diamine dimethyl sulfoxide monosolvate (I)

Crystal data

C19H18N6O2·C2H6OS	F(000) = 928
Mr = 440.52	Dx = 1.372 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.801 (5) Å	Cell parameters from 4914 reflections
b = 17.301 (8) Å	θ = 2.1–27.6°
c = 11.777 (7) Å	µ = 0.19 mm^−1
β = 104.28 (2)°	T = 100 K
V = 2132.7 (19) Å^3	Block, green
Z = 4	0.22 × 0.22 × 0.17 mm

Data collection

Bruker D8 Venture diffractometer	4914 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3658 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.066
φ and ω scans	θmax = 27.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −13→14
Tmin = 0.818, Tmax = 0.969	k = −22→22
20005 measured reflections	l = −15→15

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0366P)^2 + 0.9653P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
4914 reflections	Δρmax = 0.44 e Å^−3
293 parameters	Δρmin = −0.41 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
N1	0.63176 (14)	0.44867 (8)	0.44069 (13)	0.0120 (3)
C2	0.70798 (17)	0.49327 (9)	0.39280 (16)	0.0119 (4)
N3	0.67939 (14)	0.52579 (8)	0.28358 (13)	0.0126 (3)
C4	0.56203 (17)	0.51537 (9)	0.22182 (15)	0.0124 (4)
C5	0.46824 (17)	0.47089 (10)	0.26155 (15)	0.0124 (4)
C6	0.51361 (17)	0.43704 (9)	0.37651 (15)	0.0113 (4)
N21	0.82477 (15)	0.50708 (9)	0.45704 (15)	0.0140 (3)
H21A	0.879 (2)	0.5321 (11)	0.4269 (18)	0.017*
H21B	0.8523 (19)	0.4849 (11)	0.5261 (19)	0.017*
O41	0.52485 (12)	0.54582 (7)	0.11541 (11)	0.0164 (3)
C41	0.62018 (18)	0.58875 (11)	0.07361 (17)	0.0204 (4)
H41C	0.6879	0.5535	0.0639	0.031*
H41A	0.6570	0.6290	0.1306	0.031*
H41B	0.5801	0.6128	−0.0019	0.031*
N51	0.34929 (15)	0.46832 (9)	0.18987 (14)	0.0172 (3)
O51	0.26510 (12)	0.42777 (7)	0.22353 (12)	0.0199 (3)
N61	0.43163 (15)	0.39245 (8)	0.41667 (13)	0.0115 (3)
H61	0.359 (2)	0.3896 (11)	0.3682 (18)	0.014*
C61	0.44691 (17)	0.35231 (9)	0.52304 (15)	0.0113 (4)
C62	0.34263 (17)	0.30489 (10)	0.53073 (16)	0.0129 (4)
C63	0.34837 (18)	0.26217 (10)	0.63204 (17)	0.0164 (4)
H63	0.2799	0.2287	0.6361	0.020*
C64	0.45325 (18)	0.26823 (10)	0.72687 (17)	0.0172 (4)
H64	0.4566	0.2394	0.7962	0.021*
C65	0.55336 (18)	0.31665 (10)	0.71999 (16)	0.0153 (4)
H65	0.6243	0.3217	0.7858	0.018*
C66	0.55184 (17)	0.35804 (10)	0.61841 (16)	0.0136 (4)
H66	0.6221	0.3900	0.6143	0.016*
N62	0.23880 (14)	0.30157 (8)	0.43151 (13)	0.0142 (3)
C77	0.12606 (17)	0.31075 (9)	0.44571 (16)	0.0132 (4)
H77	0.1149	0.3187	0.5224	0.016*
C71	0.01410 (17)	0.30927 (9)	0.34622 (16)	0.0122 (4)
C72	0.02521 (18)	0.28960 (10)	0.23395 (16)	0.0148 (4)
H72	0.1061	0.2753	0.2223	0.018*
C73	−0.08009 (18)	0.29075 (10)	0.14038 (17)	0.0165 (4)
H73	−0.0709	0.2772	0.0647	0.020*
C74	−0.20049 (18)	0.31150 (10)	0.15462 (17)	0.0155 (4)
C75	−0.21199 (17)	0.32966 (10)	0.26681 (16)	0.0149 (4)
H75	−0.2934	0.3428	0.2784	0.018*
C76	−0.10657 (17)	0.32890 (9)	0.36166 (16)	0.0132 (4)
H76	−0.1161	0.3417	0.4375	0.016*
C78	−0.31356 (19)	0.31587 (11)	0.05064 (18)	0.0230 (4)
H78A	−0.3157	0.3667	0.0136	0.034*
H78C	−0.3923	0.3081	0.0764	0.034*
H78B	−0.3064	0.2756	−0.0059	0.034*
S21	0.97174 (4)	0.59113 (2)	0.22222 (4)	0.01328 (11)
O21	1.01515 (12)	0.57943 (7)	0.35309 (11)	0.0185 (3)
C21	0.94880 (19)	0.49656 (10)	0.15963 (19)	0.0211 (4)
H21C	1.0290	0.4675	0.1826	0.032*
H21D	0.9225	0.5007	0.0740	0.032*
H21E	0.8824	0.4697	0.1879	0.032*
C22	1.11243 (18)	0.61524 (10)	0.17569 (18)	0.0189 (4)
H22C	1.1459	0.6649	0.2100	0.028*
H22D	1.0915	0.6191	0.0900	0.028*
H22E	1.1770	0.5749	0.2015	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0118 (8)	0.0123 (7)	0.0124 (8)	−0.0001 (6)	0.0038 (6)	0.0005 (6)
C2	0.0131 (9)	0.0100 (8)	0.0134 (9)	0.0006 (7)	0.0045 (8)	−0.0013 (7)
N3	0.0130 (8)	0.0134 (7)	0.0121 (8)	0.0014 (6)	0.0046 (6)	0.0005 (6)
C4	0.0149 (9)	0.0123 (8)	0.0110 (9)	0.0041 (7)	0.0052 (8)	0.0004 (6)
C5	0.0132 (9)	0.0131 (8)	0.0112 (9)	0.0018 (7)	0.0034 (7)	−0.0007 (7)
C6	0.0140 (9)	0.0088 (7)	0.0123 (9)	0.0005 (7)	0.0052 (7)	−0.0026 (6)
N21	0.0124 (8)	0.0175 (8)	0.0126 (8)	−0.0027 (6)	0.0043 (7)	0.0023 (6)
O41	0.0154 (7)	0.0218 (7)	0.0122 (7)	−0.0003 (5)	0.0038 (6)	0.0047 (5)
C41	0.0174 (10)	0.0288 (10)	0.0163 (10)	0.0004 (8)	0.0063 (8)	0.0088 (8)
N51	0.0145 (8)	0.0209 (8)	0.0164 (9)	0.0003 (6)	0.0041 (7)	0.0001 (6)
O51	0.0117 (7)	0.0268 (7)	0.0205 (8)	−0.0032 (5)	0.0026 (6)	0.0020 (6)
N61	0.0093 (7)	0.0140 (7)	0.0106 (8)	−0.0007 (6)	0.0014 (6)	−0.0001 (6)
C61	0.0122 (9)	0.0103 (8)	0.0126 (9)	0.0027 (6)	0.0053 (7)	−0.0002 (6)
C62	0.0113 (9)	0.0138 (8)	0.0145 (10)	0.0003 (7)	0.0045 (8)	−0.0020 (7)
C63	0.0143 (9)	0.0154 (8)	0.0211 (11)	−0.0015 (7)	0.0075 (8)	0.0016 (7)
C64	0.0166 (10)	0.0194 (9)	0.0169 (10)	0.0022 (8)	0.0066 (8)	0.0057 (7)
C65	0.0139 (9)	0.0192 (9)	0.0121 (10)	0.0024 (7)	0.0020 (8)	0.0000 (7)
C66	0.0118 (9)	0.0135 (8)	0.0164 (10)	−0.0008 (7)	0.0053 (8)	−0.0014 (7)
N62	0.0111 (8)	0.0152 (7)	0.0159 (9)	−0.0031 (6)	0.0025 (7)	−0.0007 (6)
C77	0.0157 (9)	0.0105 (8)	0.0149 (10)	−0.0019 (7)	0.0064 (8)	0.0007 (7)
C71	0.0113 (9)	0.0088 (8)	0.0160 (10)	−0.0015 (6)	0.0028 (8)	0.0013 (6)
C72	0.0140 (9)	0.0142 (8)	0.0179 (10)	−0.0015 (7)	0.0072 (8)	−0.0004 (7)
C73	0.0213 (10)	0.0158 (9)	0.0134 (10)	−0.0024 (7)	0.0066 (8)	−0.0016 (7)
C74	0.0161 (10)	0.0116 (8)	0.0176 (10)	−0.0006 (7)	0.0019 (8)	0.0033 (7)
C75	0.0111 (9)	0.0118 (8)	0.0221 (11)	0.0009 (7)	0.0048 (8)	0.0017 (7)
C76	0.0153 (9)	0.0099 (8)	0.0155 (10)	−0.0004 (7)	0.0059 (8)	0.0007 (7)
C78	0.0203 (11)	0.0265 (10)	0.0194 (11)	−0.0011 (8)	−0.0002 (9)	0.0049 (8)
S21	0.0120 (2)	0.0138 (2)	0.0145 (2)	−0.00037 (17)	0.00398 (18)	0.00120 (17)
O21	0.0175 (7)	0.0238 (7)	0.0143 (7)	−0.0023 (5)	0.0039 (6)	0.0032 (5)
C21	0.0210 (11)	0.0156 (9)	0.0283 (12)	−0.0048 (8)	0.0091 (9)	−0.0044 (8)
C22	0.0184 (10)	0.0154 (9)	0.0259 (11)	−0.0016 (7)	0.0111 (9)	0.0022 (7)

Geometric parameters (Å, º)

N1—C6	1.328 (2)	C65—H65	0.9500
N1—C2	1.349 (2)	C66—H66	0.9500
C2—N21	1.323 (2)	N62—C77	1.279 (2)
C2—N3	1.368 (2)	C77—C71	1.462 (3)
N3—C4	1.309 (2)	C77—H77	0.9500
C4—O41	1.327 (2)	C71—C72	1.399 (3)
C4—C5	1.439 (2)	C71—C76	1.401 (3)
C5—N51	1.353 (2)	C72—C73	1.375 (3)
C5—C6	1.445 (3)	C72—H72	0.9500
C6—N61	1.345 (2)	C73—C74	1.399 (3)
N21—H21A	0.87 (2)	C73—H73	0.9500
N21—H21B	0.88 (2)	C74—C75	1.393 (3)
O41—C41	1.451 (2)	C74—C78	1.503 (3)
C41—H41C	0.9800	C75—C76	1.384 (3)
C41—H41A	0.9800	C75—H75	0.9500
C41—H41B	0.9800	C76—H76	0.9500
N51—O51	1.286 (2)	C78—H78A	0.9800
N61—C61	1.406 (2)	C78—H78C	0.9800
N61—H61	0.85 (2)	C78—H78B	0.9800
C61—C66	1.389 (3)	S21—O21	1.5100 (16)
C61—C62	1.414 (2)	S21—C21	1.7865 (19)
C62—C63	1.392 (3)	S21—C22	1.787 (2)
C62—N62	1.407 (2)	C21—H21C	0.9800
C63—C64	1.385 (3)	C21—H21D	0.9800
C63—H63	0.9500	C21—H21E	0.9800
C64—C65	1.386 (3)	C22—H22C	0.9800
C64—H64	0.9500	C22—H22D	0.9800
C65—C66	1.391 (3)	C22—H22E	0.9800
C6—N1—C2	116.64 (15)	C65—C66—H66	120.2
N21—C2—N1	117.28 (17)	C77—N62—C62	118.41 (16)
N21—C2—N3	115.21 (16)	N62—C77—C71	121.26 (17)
N1—C2—N3	127.51 (17)	N62—C77—H77	119.4
C4—N3—C2	115.41 (15)	C71—C77—H77	119.4
N3—C4—O41	119.74 (16)	C72—C71—C76	118.75 (17)
N3—C4—C5	123.76 (16)	C72—C71—C77	121.00 (17)
O41—C4—C5	116.49 (16)	C76—C71—C77	120.25 (17)
N51—C5—C4	116.80 (16)	C73—C72—C71	120.48 (17)
N51—C5—C6	128.44 (16)	C73—C72—H72	119.8
C4—C5—C6	114.71 (16)	C71—C72—H72	119.8
N1—C6—N61	120.67 (16)	C72—C73—C74	121.16 (18)
N1—C6—C5	121.86 (16)	C72—C73—H73	119.4
N61—C6—C5	117.47 (16)	C74—C73—H73	119.4
C2—N21—H21A	119.9 (14)	C75—C74—C73	118.34 (17)
C2—N21—H21B	120.4 (13)	C75—C74—C78	121.12 (17)
H21A—N21—H21B	119.0 (19)	C73—C74—C78	120.52 (18)
C4—O41—C41	116.68 (14)	C76—C75—C74	121.00 (17)
O41—C41—H41C	109.5	C76—C75—H75	119.5
O41—C41—H41A	109.5	C74—C75—H75	119.5
H41C—C41—H41A	109.5	C75—C76—C71	120.25 (17)
O41—C41—H41B	109.5	C75—C76—H76	119.9
H41C—C41—H41B	109.5	C71—C76—H76	119.9
H41A—C41—H41B	109.5	C74—C78—H78A	109.5
O51—N51—C5	117.41 (15)	C74—C78—H78C	109.5
C6—N61—C61	130.83 (16)	H78A—C78—H78C	109.5
C6—N61—H61	111.9 (13)	C74—C78—H78B	109.5
C61—N61—H61	117.2 (13)	H78A—C78—H78B	109.5
C66—C61—N61	125.34 (16)	H78C—C78—H78B	109.5
C66—C61—C62	119.58 (16)	O21—S21—C21	105.95 (9)
N61—C61—C62	115.04 (16)	O21—S21—C22	105.72 (9)
C63—C62—N62	123.24 (16)	C21—S21—C22	97.42 (9)
C63—C62—C61	119.68 (17)	S21—C21—H21C	109.5
N62—C62—C61	117.04 (16)	S21—C21—H21D	109.5
C64—C63—C62	120.38 (17)	H21C—C21—H21D	109.5
C64—C63—H63	119.8	S21—C21—H21E	109.5
C62—C63—H63	119.8	H21C—C21—H21E	109.5
C63—C64—C65	119.57 (17)	H21D—C21—H21E	109.5
C63—C64—H64	120.2	S21—C22—H22C	109.5
C65—C64—H64	120.2	S21—C22—H22D	109.5
C64—C65—C66	121.17 (18)	H22C—C22—H22D	109.5
C64—C65—H65	119.4	S21—C22—H22E	109.5
C66—C65—H65	119.4	H22C—C22—H22E	109.5
C61—C66—C65	119.54 (17)	H22D—C22—H22E	109.5
C61—C66—H66	120.2
C6—N1—C2—N21	178.19 (15)	N61—C61—C62—C63	179.51 (16)
C6—N1—C2—N3	−2.7 (2)	C66—C61—C62—N62	179.76 (15)
N21—C2—N3—C4	−176.88 (15)	N61—C61—C62—N62	1.8 (2)
N1—C2—N3—C4	4.0 (2)	N62—C62—C63—C64	−179.81 (16)
C2—N3—C4—O41	178.97 (14)	C61—C62—C63—C64	2.6 (3)
C2—N3—C4—C5	−2.1 (2)	C62—C63—C64—C65	−0.6 (3)
N3—C4—C5—N51	177.09 (16)	C63—C64—C65—C66	−1.5 (3)
O41—C4—C5—N51	−3.9 (2)	N61—C61—C66—C65	178.21 (16)
N3—C4—C5—C6	−0.6 (2)	C62—C61—C66—C65	0.4 (3)
O41—C4—C5—C6	178.40 (14)	C64—C65—C66—C61	1.6 (3)
C2—N1—C6—N61	179.07 (15)	C63—C62—N62—C77	50.9 (2)
C2—N1—C6—C5	−0.5 (2)	C61—C62—N62—C77	−131.48 (17)
N51—C5—C6—N1	−175.36 (16)	C62—N62—C77—C71	178.98 (14)
C4—C5—C6—N1	2.0 (2)	N62—C77—C71—C72	6.9 (2)
N51—C5—C6—N61	5.0 (3)	N62—C77—C71—C76	−172.06 (16)
C4—C5—C6—N61	−177.63 (14)	C76—C71—C72—C73	1.0 (2)
N3—C4—O41—C41	0.8 (2)	C77—C71—C72—C73	−177.95 (15)
C5—C4—O41—C41	−178.20 (15)	C71—C72—C73—C74	0.0 (3)
C4—C5—N51—O51	178.94 (15)	C72—C73—C74—C75	−1.2 (3)
C6—C5—N51—O51	−3.8 (3)	C72—C73—C74—C78	177.29 (16)
N1—C6—N61—C61	0.5 (3)	C73—C74—C75—C76	1.4 (2)
C5—C6—N61—C61	−179.90 (16)	C78—C74—C75—C76	−177.11 (16)
C6—N61—C61—C66	7.8 (3)	C74—C75—C76—C71	−0.4 (2)
C6—N61—C61—C62	−174.29 (16)	C72—C71—C76—C75	−0.8 (2)
C66—C61—C62—C63	−2.5 (2)	C77—C71—C76—C75	178.13 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21A···O21	0.87 (2)	2.05 (2)	2.922 (3)	173.7 (19)
N21—H21B···O21^i	0.88 (2)	2.08 (2)	2.885 (3)	152.1 (19)
N61—H61···O51	0.85 (2)	1.88 (2)	2.601 (3)	142.4 (19)

Symmetry code: (i) −x+2, −y+1, −z+1.

N⁴-{2-[(Ethoxymethylidene)amino]phenyl}-6-methoxy-5-nitrosopyrimidine-2,4-diamine dimethyl sulfoxide monosolvate (III)

Crystal data

C14H16N6O3·C2H6OS	F(000) = 832
Mr = 394.46	Dx = 1.363 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.8498 (11) Å	Cell parameters from 4608 reflections
b = 17.2238 (15) Å	θ = 2.3–27.9°
c = 11.3806 (11) Å	µ = 0.20 mm^−1
β = 115.351 (3)°	T = 100 K
V = 1921.9 (3) Å^3	Block, brown
Z = 4	0.20 × 0.17 × 0.13 mm

Data collection

Bruker D8 Venture diffractometer	4606 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3808 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.066
φ and ω scans	θmax = 27.9°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −14→14
Tmin = 0.935, Tmax = 0.974	k = −22→22
51879 measured reflections	l = −14→14

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0343P)^2 + 1.3229P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
4606 reflections	Δρmax = 0.35 e Å^−3
257 parameters	Δρmin = −0.38 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
N1	0.62364 (12)	0.45133 (7)	0.43599 (11)	0.0132 (2)
C2	0.68864 (15)	0.49854 (8)	0.38650 (13)	0.0134 (3)
N3	0.63374 (12)	0.53671 (7)	0.26896 (12)	0.0134 (2)
C4	0.50414 (15)	0.52505 (8)	0.19766 (13)	0.0124 (3)
C5	0.42094 (14)	0.47440 (8)	0.23492 (14)	0.0124 (3)
C6	0.49167 (14)	0.43866 (8)	0.36181 (13)	0.0116 (3)
N21	0.82050 (13)	0.51041 (8)	0.45783 (13)	0.0181 (3)
H21A	0.8645 (19)	0.5371 (11)	0.4248 (18)	0.022*
H21B	0.8638 (19)	0.4833 (11)	0.5284 (19)	0.022*
O41	0.44084 (10)	0.56004 (6)	0.08289 (10)	0.0156 (2)
C41	0.52208 (16)	0.61220 (9)	0.04430 (15)	0.0181 (3)
H41A	0.5663	0.6508	0.1128	0.027*
H41B	0.4630	0.6386	−0.0366	0.027*
H41C	0.5918	0.5824	0.0307	0.027*
N51	0.29003 (13)	0.46569 (7)	0.14913 (12)	0.0163 (3)
O51	0.21437 (11)	0.42050 (6)	0.18101 (11)	0.0194 (2)
N61	0.41891 (13)	0.39107 (7)	0.40144 (12)	0.0124 (2)
H61	0.3344 (19)	0.3865 (10)	0.3433 (17)	0.015*
C61	0.45849 (15)	0.34729 (8)	0.51643 (13)	0.0124 (3)
C62	0.35674 (15)	0.29664 (8)	0.51885 (14)	0.0146 (3)
C63	0.38502 (17)	0.25081 (9)	0.62812 (15)	0.0189 (3)
H63	0.3172	0.2166	0.6302	0.023*
C64	0.51191 (17)	0.25470 (9)	0.73433 (15)	0.0204 (3)
H64	0.5308	0.2231	0.8085	0.024*
C65	0.61052 (17)	0.30466 (9)	0.73158 (15)	0.0198 (3)
H65	0.6969	0.3072	0.8044	0.024*
C66	0.58482 (15)	0.35135 (8)	0.62337 (14)	0.0154 (3)
H66	0.6531	0.3857	0.6227	0.018*
N62	0.23363 (13)	0.29167 (7)	0.40440 (12)	0.0164 (3)
C67	0.12132 (17)	0.29543 (9)	0.41230 (16)	0.0206 (3)
H67	0.1223	0.3044	0.4951	0.025*
O67	0.00062 (11)	0.28728 (7)	0.30906 (11)	0.0233 (3)
C68	0.00766 (16)	0.27278 (9)	0.18557 (15)	0.0195 (3)
H68A	0.0664	0.2272	0.1935	0.023*
H68B	0.0468	0.3184	0.1607	0.023*
C69	−0.13509 (17)	0.25776 (10)	0.08446 (17)	0.0275 (4)
H69A	−0.1728	0.2126	0.1101	0.041*
H69B	−0.1334	0.2476	0.0005	0.041*
H69C	−0.1921	0.3033	0.0770	0.041*
S21	0.89988 (4)	0.57171 (2)	0.18998 (3)	0.01387 (9)
O21	0.97955 (11)	0.57988 (6)	0.33640 (10)	0.0180 (2)
C21	0.88050 (17)	0.46953 (9)	0.15983 (15)	0.0195 (3)
H21C	0.9705	0.4448	0.1956	0.029*
H21D	0.8345	0.4602	0.0659	0.029*
H21E	0.8258	0.4475	0.2015	0.029*
C22	1.01965 (16)	0.59012 (9)	0.12422 (15)	0.0192 (3)
H22A	1.0980	0.5553	0.1650	0.029*
H22B	1.0505	0.6441	0.1414	0.029*
H22C	0.9762	0.5810	0.0302	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0145 (6)	0.0141 (6)	0.0125 (6)	−0.0005 (5)	0.0071 (5)	0.0011 (5)
C2	0.0148 (7)	0.0140 (6)	0.0127 (7)	−0.0001 (5)	0.0072 (6)	−0.0008 (5)
N3	0.0141 (6)	0.0145 (6)	0.0134 (6)	−0.0002 (5)	0.0076 (5)	0.0016 (5)
C4	0.0158 (7)	0.0107 (6)	0.0129 (6)	0.0025 (5)	0.0084 (6)	0.0010 (5)
C5	0.0133 (7)	0.0116 (6)	0.0135 (7)	0.0020 (5)	0.0068 (6)	−0.0002 (5)
C6	0.0142 (7)	0.0091 (6)	0.0135 (6)	0.0017 (5)	0.0079 (5)	−0.0012 (5)
N21	0.0135 (6)	0.0261 (7)	0.0137 (6)	−0.0038 (5)	0.0049 (5)	0.0056 (5)
O41	0.0151 (5)	0.0167 (5)	0.0152 (5)	−0.0004 (4)	0.0068 (4)	0.0065 (4)
C41	0.0191 (8)	0.0197 (7)	0.0177 (7)	−0.0007 (6)	0.0099 (6)	0.0073 (6)
N51	0.0147 (6)	0.0161 (6)	0.0189 (6)	0.0003 (5)	0.0079 (5)	0.0034 (5)
O51	0.0137 (5)	0.0217 (6)	0.0229 (6)	−0.0020 (4)	0.0078 (4)	0.0066 (4)
N61	0.0125 (6)	0.0128 (6)	0.0132 (6)	0.0008 (5)	0.0066 (5)	0.0016 (5)
C61	0.0180 (7)	0.0103 (6)	0.0123 (7)	0.0021 (5)	0.0098 (6)	0.0003 (5)
C62	0.0196 (7)	0.0113 (6)	0.0159 (7)	−0.0004 (5)	0.0107 (6)	−0.0018 (5)
C63	0.0275 (8)	0.0136 (7)	0.0205 (8)	−0.0033 (6)	0.0151 (7)	0.0003 (6)
C64	0.0307 (9)	0.0168 (7)	0.0164 (7)	0.0017 (6)	0.0128 (7)	0.0044 (6)
C65	0.0218 (8)	0.0228 (8)	0.0148 (7)	0.0030 (6)	0.0079 (6)	0.0036 (6)
C66	0.0179 (7)	0.0155 (7)	0.0157 (7)	0.0012 (5)	0.0100 (6)	0.0019 (5)
N62	0.0201 (7)	0.0123 (6)	0.0180 (6)	−0.0040 (5)	0.0094 (5)	−0.0001 (5)
C67	0.0234 (8)	0.0205 (8)	0.0209 (8)	−0.0058 (6)	0.0124 (7)	−0.0011 (6)
O67	0.0189 (6)	0.0295 (6)	0.0234 (6)	−0.0061 (5)	0.0110 (5)	−0.0007 (5)
C68	0.0214 (8)	0.0174 (7)	0.0198 (8)	−0.0038 (6)	0.0091 (6)	0.0015 (6)
C69	0.0233 (9)	0.0284 (9)	0.0258 (9)	−0.0049 (7)	0.0057 (7)	0.0030 (7)
S21	0.01340 (17)	0.01437 (17)	0.01379 (17)	0.00099 (13)	0.00578 (14)	0.00251 (13)
O21	0.0193 (5)	0.0197 (5)	0.0136 (5)	−0.0035 (4)	0.0058 (4)	0.0016 (4)
C21	0.0228 (8)	0.0141 (7)	0.0204 (8)	−0.0020 (6)	0.0081 (7)	−0.0003 (6)
C22	0.0196 (8)	0.0210 (7)	0.0208 (8)	−0.0004 (6)	0.0122 (6)	0.0022 (6)

Geometric parameters (Å, º)

N1—C6	1.3324 (18)	C64—C65	1.384 (2)
N1—C2	1.3476 (18)	C64—H64	0.9500
C2—N21	1.3240 (19)	C65—C66	1.395 (2)
C2—N3	1.3762 (18)	C65—H65	0.9500
N3—C4	1.3034 (19)	C66—H66	0.9500
C4—O41	1.3315 (17)	N62—C67	1.261 (2)
C4—C5	1.4434 (19)	C67—O67	1.341 (2)
C5—N51	1.3437 (19)	C67—H67	0.9500
C5—C6	1.4506 (19)	O67—C68	1.4613 (19)
C6—N61	1.3429 (18)	C68—C69	1.505 (2)
N21—H21A	0.86 (2)	C68—H68A	0.9900
N21—H21B	0.87 (2)	C68—H68B	0.9900
O41—C41	1.4520 (17)	C69—H69A	0.9800
C41—H41A	0.9800	C69—H69B	0.9800
C41—H41B	0.9800	C69—H69C	0.9800
C41—H41C	0.9800	S21—O21	1.5200 (11)
N51—O51	1.2909 (16)	S21—C22	1.7839 (15)
N61—C61	1.4087 (18)	S21—C21	1.7883 (15)
N61—H61	0.874 (18)	C21—H21C	0.9800
C61—C66	1.392 (2)	C21—H21D	0.9800
C61—C62	1.417 (2)	C21—H21E	0.9800
C62—C63	1.392 (2)	C22—H22A	0.9800
C62—N62	1.414 (2)	C22—H22B	0.9800
C63—C64	1.391 (2)	C22—H22C	0.9800
C63—H63	0.9500
C6—N1—C2	116.53 (12)	C63—C64—H64	120.1
N21—C2—N1	117.28 (13)	C64—C65—C66	120.94 (15)
N21—C2—N3	115.25 (13)	C64—C65—H65	119.5
N1—C2—N3	127.47 (13)	C66—C65—H65	119.5
C4—N3—C2	115.73 (12)	C61—C66—C65	119.52 (14)
N3—C4—O41	120.45 (13)	C61—C66—H66	120.2
N3—C4—C5	123.64 (13)	C65—C66—H66	120.2
O41—C4—C5	115.91 (13)	C67—N62—C62	119.46 (13)
N51—C5—C4	116.96 (13)	N62—C67—O67	122.90 (14)
N51—C5—C6	128.32 (13)	N62—C67—H67	118.6
C4—C5—C6	114.71 (12)	O67—C67—H67	118.6
N1—C6—N61	120.93 (13)	C67—O67—C68	115.28 (12)
N1—C6—C5	121.89 (12)	O67—C68—C69	107.72 (13)
N61—C6—C5	117.18 (13)	O67—C68—H68A	110.2
C2—N21—H21A	118.2 (13)	C69—C68—H68A	110.2
C2—N21—H21B	119.8 (12)	O67—C68—H68B	110.2
H21A—N21—H21B	120.6 (18)	C69—C68—H68B	110.2
C4—O41—C41	116.86 (11)	H68A—C68—H68B	108.5
O41—C41—H41A	109.5	C68—C69—H69A	109.5
O41—C41—H41B	109.5	C68—C69—H69B	109.5
H41A—C41—H41B	109.5	H69A—C69—H69B	109.5
O41—C41—H41C	109.5	C68—C69—H69C	109.5
H41A—C41—H41C	109.5	H69A—C69—H69C	109.5
H41B—C41—H41C	109.5	H69B—C69—H69C	109.5
O51—N51—C5	117.68 (12)	O21—S21—C22	105.61 (7)
C6—N61—C61	130.50 (13)	O21—S21—C21	105.44 (7)
C6—N61—H61	112.2 (11)	C22—S21—C21	98.13 (7)
C61—N61—H61	117.3 (11)	S21—C21—H21C	109.5
C66—C61—N61	125.45 (13)	S21—C21—H21D	109.5
C66—C61—C62	119.86 (13)	H21C—C21—H21D	109.5
N61—C61—C62	114.68 (13)	S21—C21—H21E	109.5
C63—C62—N62	123.29 (13)	H21C—C21—H21E	109.5
C63—C62—C61	119.42 (14)	H21D—C21—H21E	109.5
N62—C62—C61	117.14 (13)	S21—C22—H22A	109.5
C64—C63—C62	120.43 (14)	S21—C22—H22B	109.5
C64—C63—H63	119.8	H22A—C22—H22B	109.5
C62—C63—H63	119.8	S21—C22—H22C	109.5
C65—C64—C63	119.82 (14)	H22A—C22—H22C	109.5
C65—C64—H64	120.1	H22B—C22—H22C	109.5
C6—N1—C2—N21	−178.60 (13)	N1—C6—N61—C61	−0.6 (2)
C6—N1—C2—N3	1.5 (2)	C5—C6—N61—C61	178.58 (13)
N21—C2—N3—C4	179.62 (13)	C6—N61—C61—C66	7.5 (2)
N1—C2—N3—C4	−0.5 (2)	C6—N61—C61—C62	−173.40 (13)
C2—N3—C4—O41	179.17 (12)	C66—C61—C62—C63	−0.7 (2)
C2—N3—C4—C5	−1.4 (2)	N61—C61—C62—C63	−179.83 (13)
N3—C4—C5—N51	−177.41 (13)	C66—C61—C62—N62	−176.28 (12)
O41—C4—C5—N51	2.03 (19)	N61—C61—C62—N62	4.55 (18)
N3—C4—C5—C6	2.1 (2)	N62—C62—C63—C64	175.50 (14)
O41—C4—C5—C6	−178.47 (12)	C61—C62—C63—C64	0.2 (2)
C2—N1—C6—N61	178.48 (12)	C62—C63—C64—C65	0.2 (2)
C2—N1—C6—C5	−0.65 (19)	C63—C64—C65—C66	−0.1 (2)
N51—C5—C6—N1	178.46 (14)	N61—C61—C66—C65	179.82 (13)
C4—C5—C6—N1	−0.97 (19)	C62—C61—C66—C65	0.8 (2)
N51—C5—C6—N61	−0.7 (2)	C64—C65—C66—C61	−0.4 (2)
C4—C5—C6—N61	179.87 (12)	C63—C62—N62—C67	51.4 (2)
N3—C4—O41—C41	−1.46 (19)	C61—C62—N62—C67	−133.18 (15)
C5—C4—O41—C41	179.08 (12)	C62—N62—C67—O67	−176.57 (13)
C4—C5—N51—O51	179.92 (12)	N62—C67—O67—C68	0.6 (2)
C6—C5—N51—O51	0.5 (2)	C67—O67—C68—C69	174.70 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21A···O21	0.86 (2)	2.05 (2)	2.8916 (19)	168.7 (18)
N21—H21B···O21^i	0.87 (2)	2.05 (2)	2.8737 (18)	157 (2)
N61—H61···O51	0.88 (2)	1.841 (18)	2.5899 (18)	142.4 (18)

Symmetry code: (i) −x+2, −y+1, −z+1.