Eth­yl 5-amino-3-(4,6-dimethyl­pyrimidin-2-ylamino)-1-meth­yl-1H-pyrazole-4-carboxyl­ate and eth­yl 5-amino-3-(4,6-dimethyl­pyrimidin-2-ylamino)-1-(2-nitro­phenyl­sulfon­yl)-1H-pyrazole-4-carboxyl­ate

The mol­ecular structures of eth­yl 5-amino-3-(4,6-dimethyl­pyrimidin-2-ylamino)-1-meth­yl-1H-pyrazole-4-carboxyl­ate, C₁₃H₁₈N₆O₂, (I), and eth­yl 5-amino-3-(4,6-dimethyl­pyrimidin-2-ylamino)-1-(2-nitro­phenyl­sulfon­yl)-1H-pyrazole-4-carboxyl­­ate, C₁₈H₁₉N₇O₆S, (II), have been determined. There are two intra­molecular N—H...O bonds and one inter­molecular N—H...O hydrogen bond in (I). The rings formed by the N—H...O hydrogen bonds are almost planar. In (II), three intra­molecular N—H...O hydrogen bonds exist.

S1. Comment

Many pyrazoles and pyrimidines show fungicidal or herbicidal activities (Malhotra et al., 1997; Takao et al., 1994; Ohvchi & Okada, 1998; Kleschick et al., 1992). Some of these kinds of compounds, such as flumetsulam, metosulam and pyrazosulfuron, have been commercialized as agrochemicals. The pyrazole and pyrimidine derivatives have also been investigated extensively in pharmacological applications (Kees et al., 1996; Lesyk et al., 1998). In order to discover further biologically active pyrazole and pyrimidine compounds, a series of novel pyrimidinylaminopyrazole derivatives were designed and synthesized. Some of them showed high fungicidal or herbicidal activity. It has been reported that the position of the acid H atom on a pyrazole ring is not stationary. For example, for 3{5}-substituted pyrazoles, the position of the acid H atom could be correlated with the Hammett σ_m parameter of the 3{5}-substituent. Substituents with positive σ_m values prefer the 3-positon, while those with negative σ_m adopt the 5-position (Lopez et al., 1993; Malcolm et al., 1996). It is possible that the substitution reaction occurs at the two endocyclic N atoms simultaneously, and thus a pair of isomers could be obtained. For instance, when the 4-position substitutents are cyano and ethoxycarbonyl groups, respectively, the ratios of isomer (III) to isomer (IV) are 100:83 and 100:1.13 (Ren et al., 2004). When ethyl 3-(4,6-dimethylpyrimidin-2-ylamino)-5-amino-1H-pyrazole- 4-carboxylate was reacted with methyl iodide and 2-nitrobenzenesulfonyl chloride, only one primary product was obtained in each case, which was found by X-ray determination to be (I) and (II), respectively (Figs. 1 and 2). According to Fig. 2, the nitro group in the ortho-position is twisted by 48.07 (13)° from the plane of the phenyl ring. This tilting of the nitro group avoids unfavourable steric contacts with atom O1 (Jeyakanthan et al., 1999). Similarly, the interplanar angle between the phenyl ring F' and the pyrazole ring A' is 77.08 (9)°. The molecular structure of (II) is stabilized by three N—H···O-type intramolecular hydrogen bonds (Table 4). Rings A', B', C' and D' are not coplanar; the dihedral angles between the the planes of rings B', C' and D' and the palne of the pyrazole ring A' are 2.4 (5), 1.7 (6) and 4.4 (5)°, respectively. The molecular structure of (I) is stabilized by two intramolecular N—H···O hydrogen bonds and one intermolecular N—H···O hydrogen bond (Table 2). The hydrogen bonds of the molecular structure of (I) are longer than the corresponding bonds of (II), but rings A, B and C are almost coplanar. For (I) and (II), the dihedral angles between the pyrimidine ring and the pyrazole ring are 7.9 (2) and 14.1 (1)°, respectively.

S2. Experimental

Ethyl 3-(4,6-dimethylpyrimidin-2-ylamino)-5-amino-1H-pyrazole-4-carboxylate (0.69 g, 2.5 mmol) and anhydrous kalium carbonate (0.41 g, 3 mmol) were mixed in acetone (30 ml) and kept in ice-cold conditions. A solution of 2-nitrobenzene-1-sulfonyl chloride (0.66 g, 3 mmol) in acetone (5 ml) was added dropwise with stirring for 10 min. The mixture was stirred at room temperature overnight, and then the solvent was evaporated to dryness in a vacuum. The residue was washed with water. The resulting pale-yellow precipitate was filtered off and recrystallized from ethanol, and well shaped crystals of (II) were obtained. Compound (I) was synthesized using the same procedure, except that dimethyl sulfate was used as a starting material, and the product was purified by silica column chromatography (eluant ethyl acetate/petroleum ether 1:5) and recrystallized from ethanol. Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.

S3. Refinement

H atoms attached to C atoms were included in calculated positions and treated as riding atoms using SHELXL97 default parameters [C—H = 0.93, 0.96 or 0.97 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C). For (I), the H atoms of atoms N3 and N6 were located from difference Fourier maps and refined isotropically, with the N—H distance restrained to 0.86 (1) Å. For (II), the H atoms of atoms N3 and N4 were located from difference Fourier maps and refined isotropically with the N—H distance restrained to 0.87 (1).

Computing details

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at 50% probability level.
	Fig. 2. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at 50% probability level.
	Fig. 3. A packing diagram of (I), showing the intermolecular hydrogen bonds as dashed lines. [Symmetry code: (A) 2 − x, 1/2 + y, 1/2 − z.]

(I) Ethyl 5-amino-3-(4,6-dimethylpyrimidin-2-ylamino)-1-methyl-1H- pyrazole-4-carboxylate

Crystal data

C13H18N6O2	Dx = 1.261 Mg m^−3
Mr = 290.33	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 825 reflections
a = 7.5466 (15) Å	θ = 2.4–25.5°
b = 9.042 (2) Å	µ = 0.09 mm^−1
c = 22.412 (8) Å	T = 293 K
V = 1529.3 (7) Å^3	Prism, yellow
Z = 4	0.38 × 0.30 × 0.20 mm
F(000) = 616

Data collection

Bruker Smart 1000 CCD area detector diffractometer	1629 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.048
Graphite monochromator	θmax = 26.5°, θmin = 2.4°
ϕ and ω scans	h = −5→9
7861 measured reflections	k = −11→11
1836 independent reflections	l = −28→22

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0529P)^2 + 0.2041P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
1836 reflections	Δρmax = 0.17 e Å^−3
204 parameters	Δρmin = −0.13 e Å^−3
3 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (2)

Special details

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
N1	1.1476 (3)	0.0360 (2)	0.14949 (8)	0.0443 (5)
N2	0.9392 (3)	−0.0621 (2)	0.07917 (9)	0.0510 (5)
N3	0.8989 (3)	0.1682 (2)	0.11810 (8)	0.0444 (5)
H3	0.801 (2)	0.168 (3)	0.0981 (10)	0.053*
N4	1.0657 (2)	0.3276 (2)	0.18130 (8)	0.0416 (4)
N5	1.0323 (3)	0.4665 (2)	0.20579 (8)	0.0418 (4)
N6	0.8102 (3)	0.6522 (3)	0.20842 (10)	0.0528 (6)
H6A	0.840 (4)	0.678 (3)	0.2439 (6)	0.063*
H6B	0.7034 (19)	0.672 (3)	0.1975 (11)	0.063*
O1	0.5761 (2)	0.30987 (19)	0.09362 (7)	0.0466 (4)
O2	0.5227 (2)	0.5323 (2)	0.13480 (9)	0.0638 (5)
C1	1.2426 (3)	−0.0891 (3)	0.14458 (11)	0.0483 (6)
C2	1.1893 (4)	−0.2033 (3)	0.10863 (11)	0.0557 (7)
H2	1.2557	−0.2897	0.1059	0.067*
C3	1.0336 (4)	−0.1864 (3)	0.07637 (11)	0.0558 (7)
C4	1.0024 (3)	0.0425 (3)	0.11612 (9)	0.0391 (5)
C5	0.9224 (3)	0.2980 (2)	0.14997 (9)	0.0361 (5)
C6	0.7943 (3)	0.4123 (3)	0.15343 (9)	0.0386 (5)
C7	0.8723 (3)	0.5186 (3)	0.19083 (9)	0.0396 (5)
C8	0.6205 (3)	0.4271 (3)	0.12755 (10)	0.0415 (5)
C9	0.4022 (3)	0.3112 (3)	0.06501 (12)	0.0554 (7)
H9A	0.3898	0.3977	0.0398	0.066*
H9B	0.3090	0.3127	0.0948	0.066*
C10	0.3915 (4)	0.1735 (3)	0.02862 (11)	0.0615 (7)
H10A	0.4766	0.1782	−0.0032	0.092*
H10B	0.2746	0.1643	0.0122	0.092*
H10C	0.4164	0.0895	0.0534	0.092*
C11	1.4110 (4)	−0.0949 (4)	0.17995 (16)	0.0745 (9)
H11A	1.4533	0.0038	0.1868	0.112*
H11B	1.4986	−0.1498	0.1582	0.112*
H11C	1.3891	−0.1425	0.2175	0.112*
C12	0.9660 (6)	−0.3055 (4)	0.03575 (16)	0.0945 (12)
H12A	0.8399	−0.3141	0.0401	0.142*
H12B	1.0208	−0.3979	0.0460	0.142*
H12C	0.9941	−0.2809	−0.0048	0.142*
C13	1.1718 (3)	0.5367 (3)	0.23903 (11)	0.0508 (6)
H13A	1.1445	0.6396	0.2442	0.076*
H13B	1.2815	0.5270	0.2177	0.076*
H13C	1.1825	0.4904	0.2774	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0425 (10)	0.0417 (10)	0.0485 (9)	0.0101 (9)	−0.0048 (8)	−0.0047 (9)
N2	0.0598 (12)	0.0428 (11)	0.0503 (10)	0.0072 (10)	−0.0097 (10)	−0.0087 (9)
N3	0.0455 (10)	0.0396 (10)	0.0481 (10)	0.0110 (9)	−0.0131 (9)	−0.0077 (9)
N4	0.0399 (9)	0.0376 (10)	0.0473 (10)	0.0077 (9)	−0.0062 (8)	−0.0038 (9)
N5	0.0407 (10)	0.0383 (10)	0.0465 (9)	0.0058 (9)	−0.0066 (8)	−0.0046 (9)
N6	0.0534 (12)	0.0457 (12)	0.0593 (12)	0.0161 (10)	−0.0136 (10)	−0.0129 (11)
O1	0.0377 (8)	0.0501 (10)	0.0522 (9)	0.0099 (8)	−0.0099 (7)	−0.0109 (8)
O2	0.0513 (10)	0.0586 (11)	0.0815 (12)	0.0239 (10)	−0.0181 (9)	−0.0221 (10)
C1	0.0482 (13)	0.0443 (13)	0.0524 (13)	0.0129 (12)	0.0007 (11)	−0.0010 (11)
C2	0.0676 (16)	0.0391 (13)	0.0602 (14)	0.0181 (13)	0.0014 (13)	−0.0042 (12)
C3	0.0743 (17)	0.0391 (13)	0.0539 (13)	0.0060 (13)	−0.0018 (14)	−0.0076 (11)
C4	0.0439 (11)	0.0345 (10)	0.0388 (10)	0.0045 (10)	0.0000 (9)	−0.0006 (9)
C5	0.0386 (10)	0.0345 (11)	0.0352 (9)	0.0055 (9)	−0.0013 (8)	0.0009 (8)
C6	0.0411 (11)	0.0377 (11)	0.0371 (10)	0.0056 (10)	−0.0031 (9)	−0.0020 (9)
C7	0.0413 (11)	0.0384 (12)	0.0391 (10)	0.0070 (10)	−0.0022 (10)	0.0001 (9)
C8	0.0392 (11)	0.0425 (12)	0.0428 (11)	0.0083 (10)	−0.0037 (10)	−0.0035 (10)
C9	0.0371 (12)	0.0680 (17)	0.0611 (14)	0.0053 (13)	−0.0127 (11)	−0.0087 (14)
C10	0.0573 (15)	0.0725 (19)	0.0546 (14)	−0.0059 (15)	−0.0089 (12)	−0.0082 (14)
C11	0.0651 (18)	0.0646 (18)	0.094 (2)	0.0301 (16)	−0.0218 (17)	−0.0122 (18)
C12	0.123 (3)	0.0550 (19)	0.105 (2)	0.015 (2)	−0.035 (2)	−0.0359 (18)
C13	0.0418 (12)	0.0513 (14)	0.0594 (13)	−0.0018 (12)	−0.0070 (11)	−0.0098 (13)

Geometric parameters (Å, º)

N1—C4	1.328 (3)	C2—H2	0.9300
N1—C1	1.343 (3)	C3—C12	1.500 (4)
N2—C3	1.332 (3)	C5—C6	1.417 (3)
N2—C4	1.344 (3)	C6—C7	1.404 (3)
N3—C4	1.379 (3)	C6—C8	1.440 (3)
N3—C5	1.386 (3)	C9—C10	1.490 (4)
N3—H3	0.865 (10)	C9—H9A	0.9700
N4—C5	1.317 (3)	C9—H9B	0.9700
N4—N5	1.394 (3)	C10—H10A	0.9600
N5—C7	1.339 (3)	C10—H10B	0.9600
N5—C13	1.437 (3)	C10—H10C	0.9600
N6—C7	1.355 (3)	C11—H11A	0.9600
N6—H6A	0.860 (10)	C11—H11B	0.9600
N6—H6B	0.860 (10)	C11—H11C	0.9600
O1—C8	1.347 (3)	C12—H12A	0.9600
O1—C9	1.461 (3)	C12—H12B	0.9600
O2—C8	1.215 (3)	C12—H12C	0.9600
C1—C2	1.370 (4)	C13—H13A	0.9600
C1—C11	1.499 (4)	C13—H13B	0.9600
C2—C3	1.389 (4)	C13—H13C	0.9600
C4—N1—C1	115.6 (2)	O2—C8—O1	122.7 (2)
C3—N2—C4	115.7 (2)	O2—C8—C6	124.9 (2)
C4—N3—C5	129.94 (18)	O1—C8—C6	112.38 (19)
C4—N3—H3	117.6 (19)	O1—C9—C10	106.4 (2)
C5—N3—H3	112.4 (18)	O1—C9—H9A	110.4
C5—N4—N5	104.14 (17)	C10—C9—H9A	110.4
C7—N5—N4	112.42 (18)	O1—C9—H9B	110.4
C7—N5—C13	129.4 (2)	C10—C9—H9B	110.4
N4—N5—C13	118.03 (19)	H9A—C9—H9B	108.6
C7—N6—H6A	115 (2)	C9—C10—H10A	109.5
C7—N6—H6B	115 (2)	C9—C10—H10B	109.5
H6A—N6—H6B	117 (3)	H10A—C10—H10B	109.5
C8—O1—C9	117.70 (18)	C9—C10—H10C	109.5
N1—C1—C2	121.8 (2)	H10A—C10—H10C	109.5
N1—C1—C11	116.0 (2)	H10B—C10—H10C	109.5
C2—C1—C11	122.2 (2)	C1—C11—H11A	109.5
C1—C2—C3	118.1 (2)	C1—C11—H11B	109.5
C1—C2—H2	120.9	H11A—C11—H11B	109.5
C3—C2—H2	120.9	C1—C11—H11C	109.5
N2—C3—C2	121.4 (2)	H11A—C11—H11C	109.5
N2—C3—C12	116.9 (3)	H11B—C11—H11C	109.5
C2—C3—C12	121.7 (3)	C3—C12—H12A	109.5
N1—C4—N2	127.4 (2)	C3—C12—H12B	109.5
N1—C4—N3	119.1 (2)	H12A—C12—H12B	109.5
N2—C4—N3	113.49 (19)	C3—C12—H12C	109.5
N4—C5—N3	123.49 (19)	H12A—C12—H12C	109.5
N4—C5—C6	112.53 (19)	H12B—C12—H12C	109.5
N3—C5—C6	123.96 (19)	N5—C13—H13A	109.5
C7—C6—C5	104.20 (19)	N5—C13—H13B	109.5
C7—C6—C8	124.0 (2)	H13A—C13—H13B	109.5
C5—C6—C8	131.8 (2)	N5—C13—H13C	109.5
N5—C7—N6	123.6 (2)	H13A—C13—H13C	109.5
N5—C7—C6	106.69 (19)	H13B—C13—H13C	109.5
N6—C7—C6	129.7 (2)
C5—N4—N5—C7	1.2 (2)	N4—C5—C6—C7	−0.1 (3)
C5—N4—N5—C13	−174.9 (2)	N3—C5—C6—C7	178.8 (2)
C4—N1—C1—C2	−1.7 (3)	N4—C5—C6—C8	−179.3 (2)
C4—N1—C1—C11	177.4 (2)	N3—C5—C6—C8	−0.3 (4)
N1—C1—C2—C3	0.6 (4)	N4—N5—C7—N6	−179.0 (2)
C11—C1—C2—C3	−178.4 (3)	C13—N5—C7—N6	−3.5 (4)
C4—N2—C3—C2	−1.7 (4)	N4—N5—C7—C6	−1.3 (2)
C4—N2—C3—C12	179.7 (3)	C13—N5—C7—C6	174.2 (2)
C1—C2—C3—N2	1.2 (4)	C5—C6—C7—N5	0.9 (2)
C1—C2—C3—C12	179.7 (3)	C8—C6—C7—N5	−179.9 (2)
C1—N1—C4—N2	1.2 (3)	C5—C6—C7—N6	178.4 (2)
C1—N1—C4—N3	−179.2 (2)	C8—C6—C7—N6	−2.4 (4)
C3—N2—C4—N1	0.5 (4)	C9—O1—C8—O2	−0.3 (3)
C3—N2—C4—N3	−179.1 (2)	C9—O1—C8—C6	179.7 (2)
C5—N3—C4—N1	1.3 (4)	C7—C6—C8—O2	0.3 (4)
C5—N3—C4—N2	−179.1 (2)	C5—C6—C8—O2	179.3 (2)
N5—N4—C5—N3	−179.54 (19)	C7—C6—C8—O1	−179.7 (2)
N5—N4—C5—C6	−0.6 (2)	C5—C6—C8—O1	−0.8 (3)
C4—N3—C5—N4	6.7 (4)	C8—O1—C9—C10	177.5 (2)
C4—N3—C5—C6	−172.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1	0.87 (1)	2.13 (2)	2.806 (2)	135 (2)
N6—H6A···N4^i	0.86 (1)	2.27 (2)	3.082 (3)	158 (3)
N6—H6B···O2	0.86 (1)	2.33 (2)	2.933 (3)	128 (3)

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

(II) 5-amino-3-(4,6-dimethylpyrimidin-2-ylamino)-1-(2-nitrophenylsulfonyl)-1H- pyrazole-4-carboxylate

Crystal data

C18H19N7O6S	F(000) = 960
Mr = 461.46	Dx = 1.471 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.536 (2) Å	Cell parameters from 965 reflections
b = 13.715 (3) Å	θ = 2.9–25.0°
c = 14.443 (3) Å	µ = 0.21 mm^−1
β = 93.570 (8)°	T = 293 K
V = 2083.1 (7) Å^3	Prism, yellow
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection

Bruker Smart 1000 CCD area detector diffractometer	4118 independent reflections
Radiation source: fine-focus sealed tube	2700 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 26.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→13
Tmin = 0.920, Tmax = 0.960	k = −17→15
9353 measured reflections	l = −17→17

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.064P)^2 + 0.3838P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4118 reflections	Δρmax = 0.28 e Å^−3
299 parameters	Δρmin = −0.28 e Å^−3
3 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0039 (7)

Special details

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	0.57284 (6)	0.12638 (5)	0.22549 (5)	0.0438 (2)
N1	0.69234 (18)	0.05903 (14)	0.26817 (14)	0.0425 (5)
N2	0.78835 (19)	0.10974 (14)	0.32040 (14)	0.0430 (5)
N3	0.6384 (2)	−0.10196 (16)	0.21611 (17)	0.0499 (6)
H3A	0.575 (2)	−0.0796 (19)	0.1806 (17)	0.060*
H3B	0.664 (3)	−0.1613 (10)	0.215 (2)	0.060*
N4	0.98180 (19)	0.05405 (15)	0.39663 (16)	0.0474 (6)
H4A	1.025 (2)	0.0004 (12)	0.4048 (19)	0.057*
N5	0.9867 (2)	0.22207 (15)	0.40477 (14)	0.0445 (5)
N6	1.16411 (19)	0.12307 (16)	0.45559 (15)	0.0497 (6)
N7	0.6725 (3)	0.11561 (18)	0.02380 (18)	0.0617 (7)
O1	0.49884 (15)	0.06442 (13)	0.16489 (13)	0.0533 (5)
O2	0.51682 (18)	0.17169 (15)	0.30025 (14)	0.0630 (6)
O3	1.00872 (17)	−0.14395 (13)	0.36592 (14)	0.0579 (5)
O4	0.84198 (16)	−0.22107 (12)	0.29616 (12)	0.0469 (5)
O5	0.7269 (3)	0.04895 (16)	0.06355 (17)	0.0845 (8)
O6	0.6219 (3)	0.11078 (19)	−0.05265 (18)	0.1118 (11)
C1	0.7172 (2)	−0.03886 (17)	0.26109 (16)	0.0366 (6)
C2	0.8317 (2)	−0.05307 (17)	0.31064 (16)	0.0369 (6)
C3	0.8694 (2)	0.04090 (17)	0.34392 (16)	0.0374 (6)
C4	1.0454 (2)	0.13825 (18)	0.41982 (17)	0.0408 (6)
C5	1.0572 (3)	0.30159 (19)	0.42412 (18)	0.0499 (7)
C6	1.1811 (3)	0.2942 (2)	0.45954 (19)	0.0575 (8)
H6	1.2296	0.3498	0.4724	0.069*
C7	1.2319 (3)	0.2031 (2)	0.47556 (19)	0.0544 (7)
C8	0.9927 (3)	0.3963 (2)	0.4053 (3)	0.0748 (10)
H8A	0.9428	0.3927	0.3475	0.112*
H8B	1.0553	0.4469	0.4019	0.112*
H8C	0.9382	0.4107	0.4544	0.112*
C9	1.3653 (3)	0.1879 (3)	0.5150 (3)	0.0807 (11)
H9A	1.3683	0.1316	0.5544	0.121*
H9B	1.3925	0.2442	0.5504	0.121*
H9C	1.4205	0.1783	0.4654	0.121*
C10	0.9035 (2)	−0.14145 (17)	0.32715 (17)	0.0401 (6)
C11	0.9102 (3)	−0.31255 (17)	0.31087 (19)	0.0485 (7)
H11A	0.9441	−0.3175	0.3747	0.058*
H11B	0.9801	−0.3166	0.2704	0.058*
C12	0.8169 (3)	−0.3917 (2)	0.2893 (2)	0.0674 (9)
H12A	0.7532	−0.3911	0.3340	0.101*
H12B	0.8599	−0.4534	0.2915	0.101*
H12C	0.7773	−0.3818	0.2283	0.101*
C13	0.6420 (2)	0.21922 (17)	0.16187 (18)	0.0403 (6)
C14	0.6728 (2)	0.20987 (18)	0.07062 (19)	0.0437 (6)
C15	0.7072 (3)	0.2879 (2)	0.0193 (2)	0.0562 (8)
H15	0.7267	0.2798	−0.0422	0.067*
C16	0.7128 (3)	0.3781 (2)	0.0594 (3)	0.0672 (9)
H16	0.7360	0.4319	0.0251	0.081*
C17	0.6846 (3)	0.3895 (2)	0.1487 (3)	0.0685 (9)
H17	0.6897	0.4511	0.1755	0.082*
C18	0.6484 (3)	0.3110 (2)	0.2007 (2)	0.0556 (8)
H18	0.6283	0.3200	0.2619	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0326 (3)	0.0495 (4)	0.0487 (4)	0.0019 (3)	−0.0029 (3)	−0.0044 (3)
N1	0.0396 (11)	0.0392 (11)	0.0468 (13)	−0.0028 (9)	−0.0129 (10)	−0.0011 (10)
N2	0.0420 (12)	0.0386 (11)	0.0466 (13)	−0.0062 (9)	−0.0117 (10)	−0.0036 (10)
N3	0.0478 (13)	0.0405 (12)	0.0594 (15)	−0.0054 (11)	−0.0131 (11)	−0.0063 (12)
N4	0.0412 (12)	0.0415 (12)	0.0568 (14)	−0.0058 (10)	−0.0177 (11)	0.0041 (11)
N5	0.0466 (12)	0.0467 (13)	0.0397 (13)	−0.0099 (10)	−0.0006 (10)	−0.0022 (10)
N6	0.0386 (12)	0.0656 (15)	0.0439 (13)	−0.0117 (11)	−0.0044 (10)	−0.0008 (11)
N7	0.0812 (18)	0.0550 (16)	0.0496 (16)	0.0070 (13)	0.0089 (14)	−0.0024 (13)
O1	0.0359 (9)	0.0564 (11)	0.0654 (13)	−0.0043 (8)	−0.0147 (9)	−0.0069 (10)
O2	0.0536 (12)	0.0782 (14)	0.0584 (13)	0.0090 (10)	0.0146 (10)	−0.0128 (11)
O3	0.0434 (11)	0.0542 (11)	0.0741 (14)	0.0031 (9)	−0.0126 (10)	−0.0024 (10)
O4	0.0511 (11)	0.0380 (9)	0.0502 (11)	0.0036 (8)	−0.0078 (9)	−0.0019 (8)
O5	0.116 (2)	0.0569 (13)	0.0825 (17)	0.0343 (13)	0.0214 (15)	0.0006 (13)
O6	0.187 (3)	0.0845 (18)	0.0593 (16)	−0.0117 (18)	−0.0240 (18)	−0.0163 (14)
C1	0.0363 (12)	0.0388 (13)	0.0347 (14)	−0.0065 (11)	0.0023 (10)	−0.0011 (11)
C2	0.0357 (12)	0.0393 (13)	0.0355 (13)	−0.0039 (10)	0.0000 (10)	−0.0004 (11)
C3	0.0374 (13)	0.0399 (13)	0.0346 (13)	−0.0066 (11)	−0.0012 (10)	0.0043 (11)
C4	0.0398 (13)	0.0480 (15)	0.0340 (14)	−0.0096 (12)	−0.0032 (11)	0.0004 (12)
C5	0.0623 (18)	0.0510 (16)	0.0374 (15)	−0.0165 (14)	0.0112 (13)	−0.0056 (13)
C6	0.0574 (18)	0.069 (2)	0.0470 (17)	−0.0342 (16)	0.0098 (14)	−0.0132 (15)
C7	0.0439 (15)	0.080 (2)	0.0395 (16)	−0.0207 (15)	0.0032 (12)	−0.0086 (15)
C8	0.090 (2)	0.0479 (18)	0.087 (3)	−0.0164 (16)	0.014 (2)	−0.0126 (17)
C9	0.0417 (17)	0.124 (3)	0.075 (2)	−0.0263 (19)	−0.0085 (15)	−0.008 (2)
C10	0.0426 (14)	0.0418 (14)	0.0359 (14)	−0.0037 (11)	0.0027 (11)	−0.0020 (11)
C11	0.0579 (17)	0.0429 (14)	0.0444 (15)	0.0092 (12)	0.0018 (13)	0.0005 (13)
C12	0.080 (2)	0.0433 (16)	0.078 (2)	−0.0008 (15)	−0.0019 (18)	0.0000 (15)
C13	0.0321 (12)	0.0410 (13)	0.0462 (16)	0.0060 (10)	−0.0093 (11)	−0.0011 (12)
C14	0.0380 (13)	0.0438 (15)	0.0482 (17)	0.0038 (11)	−0.0053 (12)	−0.0016 (12)
C15	0.0470 (16)	0.0587 (18)	0.0622 (19)	−0.0011 (13)	−0.0021 (14)	0.0121 (15)
C16	0.0528 (18)	0.0546 (19)	0.093 (3)	−0.0110 (14)	−0.0093 (17)	0.0148 (19)
C17	0.063 (2)	0.0428 (17)	0.097 (3)	−0.0074 (14)	−0.0130 (19)	−0.0106 (18)
C18	0.0525 (17)	0.0508 (17)	0.0620 (19)	0.0052 (13)	−0.0091 (14)	−0.0147 (15)

Geometric parameters (Å, º)

S1—O2	1.407 (2)	C5—C8	1.484 (4)
S1—O1	1.4182 (17)	C6—C7	1.373 (4)
S1—N1	1.650 (2)	C6—H6	0.9300
S1—C13	1.755 (3)	C7—C9	1.498 (4)
N1—C1	1.373 (3)	C8—H8A	0.9600
N1—N2	1.408 (2)	C8—H8B	0.9600
N2—C3	1.304 (3)	C8—H8C	0.9600
N3—C1	1.339 (3)	C9—H9A	0.9600
N3—H3A	0.874 (10)	C9—H9B	0.9600
N3—H3B	0.860 (10)	C9—H9C	0.9600
N4—C4	1.366 (3)	C11—C12	1.484 (4)
N4—C3	1.380 (3)	C11—H11A	0.9700
N4—H4A	0.869 (10)	C11—H11B	0.9700
N5—C4	1.317 (3)	C12—H12A	0.9600
N5—C5	1.339 (3)	C12—H12B	0.9600
N6—C7	1.331 (3)	C12—H12C	0.9600
N6—C4	1.340 (3)	C13—C18	1.378 (3)
N7—O6	1.198 (3)	C13—C14	1.383 (4)
N7—O5	1.205 (3)	C14—C15	1.364 (4)
N7—C14	1.459 (3)	C15—C16	1.366 (4)
O3—C10	1.211 (3)	C15—H15	0.9300
O4—C10	1.333 (3)	C16—C17	1.350 (5)
O4—C11	1.455 (3)	C16—H16	0.9300
C1—C2	1.378 (3)	C17—C18	1.381 (4)
C2—C3	1.423 (3)	C17—H17	0.9300
C2—C10	1.441 (3)	C18—H18	0.9300
C5—C6	1.376 (4)
O2—S1—O1	119.83 (12)	C5—C8—H8B	109.5
O2—S1—N1	107.90 (12)	H8A—C8—H8B	109.5
O1—S1—N1	105.81 (10)	C5—C8—H8C	109.5
O2—S1—C13	106.81 (13)	H8A—C8—H8C	109.5
O1—S1—C13	110.00 (12)	H8B—C8—H8C	109.5
N1—S1—C13	105.64 (11)	C7—C9—H9A	109.5
C1—N1—N2	112.89 (18)	C7—C9—H9B	109.5
C1—N1—S1	131.64 (16)	H9A—C9—H9B	109.5
N2—N1—S1	115.46 (15)	C7—C9—H9C	109.5
C3—N2—N1	102.64 (18)	H9A—C9—H9C	109.5
C1—N3—H3A	119.2 (19)	H9B—C9—H9C	109.5
C1—N3—H3B	115.7 (19)	O3—C10—O4	123.0 (2)
H3A—N3—H3B	124 (3)	O3—C10—C2	123.8 (2)
C4—N4—C3	129.6 (2)	O4—C10—C2	113.2 (2)
C4—N4—H4A	116.0 (18)	O4—C11—C12	106.6 (2)
C3—N4—H4A	112.9 (18)	O4—C11—H11A	110.4
C4—N5—C5	115.3 (2)	C12—C11—H11A	110.4
C7—N6—C4	115.5 (2)	O4—C11—H11B	110.4
O6—N7—O5	124.6 (3)	C12—C11—H11B	110.4
O6—N7—C14	117.7 (3)	H11A—C11—H11B	108.6
O5—N7—C14	117.7 (2)	C11—C12—H12A	109.5
C10—O4—C11	115.60 (19)	C11—C12—H12B	109.5
N3—C1—N1	123.5 (2)	H12A—C12—H12B	109.5
N3—C1—C2	131.1 (2)	C11—C12—H12C	109.5
N1—C1—C2	105.34 (19)	H12A—C12—H12C	109.5
C1—C2—C3	105.3 (2)	H12B—C12—H12C	109.5
C1—C2—C10	129.7 (2)	C18—C13—C14	117.7 (2)
C3—C2—C10	125.0 (2)	C18—C13—S1	117.4 (2)
N2—C3—N4	125.1 (2)	C14—C13—S1	124.16 (19)
N2—C3—C2	113.8 (2)	C15—C14—C13	122.1 (3)
N4—C3—C2	121.1 (2)	C15—C14—N7	115.9 (3)
N5—C4—N6	128.1 (2)	C13—C14—N7	122.0 (2)
N5—C4—N4	118.6 (2)	C14—C15—C16	119.1 (3)
N6—C4—N4	113.3 (2)	C14—C15—H15	120.5
N5—C5—C6	121.2 (3)	C16—C15—H15	120.5
N5—C5—C8	115.7 (3)	C17—C16—C15	120.2 (3)
C6—C5—C8	123.1 (3)	C17—C16—H16	119.9
C7—C6—C5	118.7 (3)	C15—C16—H16	119.9
C7—C6—H6	120.6	C16—C17—C18	121.0 (3)
C5—C6—H6	120.6	C16—C17—H17	119.5
N6—C7—C6	121.0 (2)	C18—C17—H17	119.5
N6—C7—C9	116.5 (3)	C13—C18—C17	119.9 (3)
C6—C7—C9	122.5 (3)	C13—C18—H18	120.0
C5—C8—H8A	109.5	C17—C18—H18	120.0
O2—S1—N1—C1	121.9 (2)	C8—C5—C6—C7	179.2 (3)
O1—S1—N1—C1	−7.5 (3)	C4—N6—C7—C6	−0.2 (4)
C13—S1—N1—C1	−124.1 (2)	C4—N6—C7—C9	−179.6 (2)
O2—S1—N1—N2	−59.2 (2)	C5—C6—C7—N6	1.4 (4)
O1—S1—N1—N2	171.39 (17)	C5—C6—C7—C9	−179.3 (3)
C13—S1—N1—N2	54.7 (2)	C11—O4—C10—O3	−0.7 (4)
C1—N1—N2—C3	−0.1 (3)	C11—O4—C10—C2	179.9 (2)
S1—N1—N2—C3	−179.19 (17)	C1—C2—C10—O3	173.9 (3)
N2—N1—C1—N3	178.8 (2)	C3—C2—C10—O3	−5.5 (4)
S1—N1—C1—N3	−2.3 (4)	C1—C2—C10—O4	−6.7 (4)
N2—N1—C1—C2	0.6 (3)	C3—C2—C10—O4	173.9 (2)
S1—N1—C1—C2	179.5 (2)	C10—O4—C11—C12	168.9 (2)
N3—C1—C2—C3	−178.8 (3)	O2—S1—C13—C18	9.9 (2)
N1—C1—C2—C3	−0.8 (3)	O1—S1—C13—C18	141.41 (19)
N3—C1—C2—C10	1.7 (5)	N1—S1—C13—C18	−104.8 (2)
N1—C1—C2—C10	179.7 (2)	O2—S1—C13—C14	−160.0 (2)
N1—N2—C3—N4	−180.0 (2)	O1—S1—C13—C14	−28.5 (2)
N1—N2—C3—C2	−0.4 (3)	N1—S1—C13—C14	85.3 (2)
C4—N4—C3—N2	−14.2 (4)	C18—C13—C14—C15	−0.7 (4)
C4—N4—C3—C2	166.3 (2)	S1—C13—C14—C15	169.2 (2)
C1—C2—C3—N2	0.8 (3)	C18—C13—C14—N7	178.3 (2)
C10—C2—C3—N2	−179.7 (2)	S1—C13—C14—N7	−11.8 (3)
C1—C2—C3—N4	−179.6 (2)	O6—N7—C14—C15	−47.1 (4)
C10—C2—C3—N4	−0.1 (4)	O5—N7—C14—C15	130.5 (3)
C5—N5—C4—N6	3.2 (4)	O6—N7—C14—C13	133.9 (3)
C5—N5—C4—N4	−176.3 (2)	O5—N7—C14—C13	−48.6 (4)
C7—N6—C4—N5	−2.3 (4)	C13—C14—C15—C16	0.7 (4)
C7—N6—C4—N4	177.2 (2)	N7—C14—C15—C16	−178.4 (2)
C3—N4—C4—N5	12.5 (4)	C14—C15—C16—C17	0.1 (4)
C3—N4—C4—N6	−167.0 (3)	C15—C16—C17—C18	−0.8 (5)
C4—N5—C5—C6	−1.7 (4)	C14—C13—C18—C17	−0.1 (4)
C4—N5—C5—C8	178.7 (3)	S1—C13—C18—C17	−170.7 (2)
N5—C5—C6—C7	−0.4 (4)	C16—C17—C18—C13	0.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.87 (1)	2.14 (2)	2.789 (3)	131 (2)
N3—H3B···O4	0.86 (1)	2.30 (2)	2.881 (3)	125 (2)
N4—H4A···O3	0.87 (1)	2.06 (2)	2.769 (3)	138 (2)