rac-6-Hy-droxy-4-(4-nitro-phen-yl)-5-(2-thienyl-carbon-yl)-6-(trifluoro-meth-yl)-3,4,5,6-tetra-hydro-pyrimidin-2(1H)-one monohydrate.

The title compound, C(16)H(12)F(3)N(3)O(5)S·H(2)O, was prepared by reaction of 4-nitro-benzaldehyde, 4,4,4-trifluoro-1-(thio-phen-2-yl)butane-1,3-dione and urea. The asymmetric unit contains two independent mol-ecules, with essentially identical geom-etries and conformations. The dihydro-pyrimidine rings adopt a half-chair conformation. The dihedral angles between the benzene ring and the thio-phene ring are 54.82 (8) and 58.72 (8)° in the two mol-ecules. The mol-ecular conformation of one of the mol-ecules is stabilized by two intra-molecular O-H⋯O hydrogen bonds, generating an S(6) ring. The crystal structure is stabilized by inter-molecular O-H⋯O and N-H⋯O hydrogen bonds.

Related literature

For the bioactivity of dihydro­pyrimidines, see: Brier et al. (2004 ▶); Cochran et al. (2005 ▶); Moran et al. (2007 ▶); Zorkun et al. (2006 ▶). For the bioactivity of organofluorine compounds, see: Hermann et al. (2003 ▶); Ulrich (2004 ▶).

Experimental

Crystal data

C16H12F3N3O5S·H2O

M = 433.36

Orthorhombic,

a = 14.1640 (13) Å

b = 9.136 (1) Å

c = 27.459 (3) Å

V = 3553.3 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.26 mm−1

T = 113 K

0.24 × 0.20 × 0.18 mm

Data collection

Rigaku Saturn724 CCD diffractometer

Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2009 ▶) T min = 0.941, T max = 0.956

34133 measured reflections

7861 independent reflections

7466 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.091

S = 1.05

7861 reflections

563 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.37 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: Flack (1983 ▶), 3539 Friedel pairs

Flack parameter: −0.01 (5)

Data collection: CrystalClear-SM Expert (Rigaku, 2009 ▶); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2009 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810041589/fj2348sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041589/fj2348Isup2.hkl

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

C16H12F3N3O5S·H2O	F(000) = 1776
Mr = 433.36	Dx = 1.620 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2c -2n	Cell parameters from 9674 reflections
a = 14.1640 (13) Å	θ = 1.6–27.9°
b = 9.136 (1) Å	µ = 0.26 mm−1
c = 27.459 (3) Å	T = 113 K
V = 3553.3 (6) Å3	Prism, colorless
Z = 8	0.24 × 0.20 × 0.18 mm

Rigaku Saturn724 CCD diffractometer	7861 independent reflections
Radiation source: rotating anode	7466 reflections with I > 2σ(I)
multilayer	Rint = 0.031
Detector resolution: 14.222 pixels mm-1	θmax = 27.9°, θmin = 1.5°
ω scans	h = −18→18
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2009)	k = −12→11
Tmin = 0.941, Tmax = 0.956	l = −35→36
34133 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091	w = 1/[σ2(Fo2) + (0.0567P)2] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
7861 reflections	Δρmax = 0.37 e Å−3
563 parameters	Δρmin = −0.27 e Å−3
1 restraint	Absolute structure: Flack (1983), 3539 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.01 (5)

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
S1	0.60772 (5)	−0.35697 (6)	0.08791 (3)	0.03689 (15)
F1	0.37968 (10)	−0.23469 (13)	0.00751 (6)	0.0331 (3)
F2	0.27429 (8)	−0.07998 (14)	−0.01598 (5)	0.0274 (3)
F3	0.35284 (9)	−0.04033 (14)	0.04972 (5)	0.0292 (3)
O1	0.45567 (10)	−0.08713 (15)	−0.06818 (5)	0.0212 (3)
O2	0.43350 (10)	0.36232 (14)	−0.06593 (5)	0.0211 (3)
O3	0.59480 (11)	−0.23377 (16)	−0.01125 (6)	0.0282 (3)
O4	0.89623 (12)	0.33821 (17)	0.13355 (6)	0.0335 (4)
O5	0.96906 (14)	0.1399 (2)	0.11251 (7)	0.0467 (5)
N1	0.40188 (13)	0.13684 (17)	−0.03407 (6)	0.0180 (3)
N2	0.55597 (13)	0.2246 (2)	−0.04098 (7)	0.0203 (4)
N3	0.90201 (14)	0.22519 (19)	0.10965 (7)	0.0249 (4)
C1	0.43619 (13)	−0.01001 (19)	−0.02507 (7)	0.0165 (4)
C2	0.46358 (14)	0.2445 (2)	−0.04839 (7)	0.0183 (4)
C3	0.60082 (14)	0.0912 (2)	−0.02294 (7)	0.0173 (4)
H3	0.6249	0.0323	−0.0510	0.021*
C4	0.52713 (14)	0.00176 (19)	0.00539 (7)	0.0172 (4)
H4A	0.5117	0.0564	0.0359	0.021*
C5	0.68228 (15)	0.1286 (2)	0.01111 (7)	0.0182 (4)
C6	0.67296 (15)	0.2434 (2)	0.04432 (8)	0.0216 (4)
H6A	0.6169	0.3005	0.0445	0.026*
C7	0.74425 (16)	0.2748 (2)	0.07696 (7)	0.0214 (4)
H7	0.7383	0.3535	0.0994	0.026*
C8	0.82467 (15)	0.1886 (2)	0.07617 (7)	0.0205 (4)
C9	0.83640 (15)	0.0731 (2)	0.04422 (8)	0.0226 (4)
H9	0.8922	0.0154	0.0447	0.027*
C10	0.76357 (14)	0.0438 (2)	0.01115 (7)	0.0202 (4)
H10	0.7698	−0.0346	−0.0114	0.024*
C11	0.35973 (15)	−0.0915 (2)	0.00413 (7)	0.0203 (4)
C12	0.56951 (15)	−0.1468 (2)	0.01993 (8)	0.0206 (4)
C13	0.57782 (15)	−0.1808 (2)	0.07158 (8)	0.0217 (4)
C14	0.56852 (15)	−0.0877 (2)	0.11324 (7)	0.0241 (4)
H14	0.5543	0.0139	0.1124	0.029*
C15	0.58417 (19)	−0.1726 (3)	0.15664 (9)	0.0361 (6)
H15	0.5803	−0.1326	0.1885	0.043*
C16	0.60494 (19)	−0.3148 (3)	0.14778 (10)	0.0407 (7)
H16	0.6168	−0.3842	0.1728	0.049*
S2	0.87505 (5)	0.87073 (6)	0.23286 (2)	0.03609 (15)
F4	0.62278 (9)	0.54205 (14)	0.26486 (4)	0.0278 (3)
F5	0.64890 (10)	0.73570 (13)	0.30749 (6)	0.0319 (3)
F6	0.54339 (9)	0.57986 (14)	0.33042 (5)	0.0261 (3)
O6	0.72494 (11)	0.58706 (15)	0.38319 (5)	0.0206 (3)
O7	0.70213 (11)	0.13746 (14)	0.38037 (5)	0.0213 (3)
O8	0.86907 (11)	0.72990 (16)	0.32953 (6)	0.0253 (3)
O9	1.16517 (13)	0.15713 (17)	0.18214 (6)	0.0363 (4)
O10	1.23927 (14)	0.3536 (2)	0.20196 (8)	0.0558 (6)
N4	0.67149 (13)	0.36304 (16)	0.34850 (6)	0.0174 (3)
N5	0.82537 (13)	0.27411 (19)	0.35508 (7)	0.0201 (4)
N6	1.17126 (14)	0.2717 (2)	0.20498 (7)	0.0264 (4)
C17	0.70562 (14)	0.5113 (2)	0.34018 (7)	0.0181 (4)
C18	0.73277 (14)	0.2537 (2)	0.36261 (7)	0.0172 (4)
C19	0.87044 (14)	0.4083 (2)	0.33745 (7)	0.0194 (4)
H19	0.8951	0.4658	0.3657	0.023*
C20	0.79665 (14)	0.49985 (19)	0.30975 (7)	0.0173 (4)
H20	0.7814	0.4485	0.2786	0.021*
C21	0.62941 (15)	0.5919 (2)	0.31056 (8)	0.0208 (4)
C22	0.95101 (14)	0.37086 (19)	0.30321 (7)	0.0173 (4)
C23	0.94011 (15)	0.2601 (2)	0.26815 (8)	0.0222 (4)
H23	0.8829	0.2060	0.2669	0.027*
C24	1.01085 (15)	0.2290 (2)	0.23565 (7)	0.0218 (4)
H24	1.0034	0.1537	0.2121	0.026*
C25	1.09372 (15)	0.3103 (2)	0.23800 (7)	0.0205 (4)
C26	1.10671 (16)	0.4235 (2)	0.27159 (8)	0.0236 (4)
H26	1.1635	0.4789	0.2720	0.028*
C27	1.03457 (14)	0.4527 (2)	0.30426 (8)	0.0211 (4)
H27	1.0419	0.5287	0.3275	0.025*
C28	0.83971 (14)	0.6501 (2)	0.29737 (7)	0.0190 (4)
C29	0.84472 (15)	0.6933 (2)	0.24656 (8)	0.0210 (4)
C30	0.82926 (16)	0.6111 (2)	0.20372 (8)	0.0251 (4)
H30	0.8130	0.5102	0.2032	0.030*
C31	0.84114 (19)	0.6988 (3)	0.16187 (9)	0.0356 (6)
H31	0.8340	0.6624	0.1297	0.043*
C32	0.8636 (2)	0.8396 (3)	0.17194 (10)	0.0391 (6)
H32	0.8720	0.9128	0.1478	0.047*
O11	0.98547 (11)	0.12871 (16)	0.40001 (6)	0.0222 (3)
O12	0.78322 (11)	0.87168 (16)	0.41523 (6)	0.0219 (3)
H12A	0.785 (2)	0.818 (3)	0.3900 (11)	0.043 (8)*
H12B	0.777 (2)	0.950 (4)	0.4040 (12)	0.058 (10)*
H1	0.3382 (17)	0.146 (2)	−0.0483 (9)	0.020 (6)*
H2	0.5907 (17)	0.283 (3)	−0.0528 (9)	0.022 (6)*
H5	0.859 (2)	0.209 (3)	0.3656 (10)	0.035 (7)*
H4	0.615 (2)	0.362 (3)	0.3582 (9)	0.028 (7)*
H6	0.6766 (19)	0.603 (3)	0.3989 (10)	0.029 (7)*
H1A	0.399 (3)	−0.106 (4)	−0.0845 (14)	0.073 (11)*
H11A	0.9996 (19)	0.051 (3)	0.4119 (10)	0.034 (8)*
H11B	0.982 (2)	0.188 (3)	0.4227 (11)	0.042 (8)*

	U11	U22	U33	U12	U13	U23
S1	0.0438 (4)	0.0252 (3)	0.0416 (4)	0.0070 (2)	−0.0030 (3)	0.0096 (2)
F1	0.0316 (8)	0.0147 (6)	0.0531 (9)	−0.0018 (5)	0.0029 (7)	0.0088 (6)
F2	0.0176 (6)	0.0335 (7)	0.0311 (7)	−0.0052 (5)	−0.0027 (5)	0.0088 (5)
F3	0.0302 (7)	0.0358 (7)	0.0216 (6)	−0.0038 (5)	0.0023 (6)	0.0011 (5)
O1	0.0194 (8)	0.0232 (7)	0.0210 (7)	0.0013 (6)	−0.0034 (6)	−0.0063 (6)
O2	0.0199 (8)	0.0173 (6)	0.0261 (7)	−0.0003 (5)	−0.0042 (6)	0.0053 (5)
O3	0.0308 (9)	0.0224 (7)	0.0313 (8)	0.0083 (6)	−0.0068 (7)	−0.0071 (6)
O4	0.0384 (10)	0.0298 (8)	0.0322 (9)	−0.0065 (7)	−0.0105 (8)	−0.0042 (7)
O5	0.0321 (11)	0.0551 (11)	0.0528 (12)	0.0129 (8)	−0.0214 (9)	−0.0176 (10)
N1	0.0175 (9)	0.0135 (8)	0.0230 (8)	0.0008 (6)	−0.0030 (7)	0.0024 (6)
N2	0.0158 (9)	0.0194 (8)	0.0256 (9)	−0.0023 (7)	−0.0031 (7)	0.0076 (7)
N3	0.0253 (10)	0.0276 (9)	0.0219 (9)	−0.0060 (7)	−0.0058 (8)	0.0032 (7)
C1	0.0171 (10)	0.0132 (8)	0.0192 (9)	−0.0001 (7)	−0.0034 (8)	−0.0014 (7)
C2	0.0183 (10)	0.0200 (9)	0.0167 (9)	−0.0010 (8)	0.0011 (8)	0.0017 (7)
C3	0.0160 (10)	0.0163 (8)	0.0196 (9)	0.0014 (7)	−0.0007 (8)	0.0005 (7)
C4	0.0180 (10)	0.0138 (8)	0.0199 (9)	0.0017 (7)	−0.0020 (8)	−0.0001 (7)
C5	0.0181 (10)	0.0180 (9)	0.0185 (9)	−0.0018 (7)	−0.0011 (8)	0.0031 (7)
C6	0.0189 (11)	0.0213 (9)	0.0246 (10)	0.0016 (8)	−0.0020 (8)	−0.0015 (8)
C7	0.0236 (11)	0.0203 (9)	0.0204 (10)	−0.0017 (8)	−0.0001 (8)	−0.0035 (8)
C8	0.0198 (11)	0.0237 (9)	0.0180 (9)	−0.0054 (8)	−0.0038 (8)	0.0039 (7)
C9	0.0201 (11)	0.0214 (9)	0.0265 (10)	0.0001 (8)	−0.0010 (8)	−0.0006 (8)
C10	0.0199 (11)	0.0184 (9)	0.0222 (10)	0.0010 (8)	−0.0027 (8)	−0.0009 (8)
C11	0.0209 (11)	0.0185 (9)	0.0216 (10)	0.0010 (7)	−0.0022 (8)	0.0017 (7)
C12	0.0154 (10)	0.0169 (9)	0.0296 (11)	−0.0006 (7)	−0.0048 (9)	0.0002 (8)
C13	0.0184 (11)	0.0163 (9)	0.0303 (10)	−0.0008 (8)	−0.0060 (9)	0.0055 (7)
C14	0.0208 (11)	0.0311 (10)	0.0205 (10)	0.0064 (8)	−0.0012 (8)	0.0112 (8)
C15	0.0361 (15)	0.0453 (14)	0.0269 (12)	0.0058 (11)	−0.0007 (11)	0.0050 (10)
C16	0.0357 (15)	0.0459 (16)	0.0405 (15)	0.0049 (12)	−0.0027 (12)	0.0243 (12)
S2	0.0525 (4)	0.0218 (2)	0.0340 (3)	−0.0066 (2)	0.0044 (3)	0.0062 (2)
F4	0.0294 (7)	0.0327 (7)	0.0213 (6)	0.0030 (5)	−0.0034 (5)	0.0000 (5)
F5	0.0323 (7)	0.0156 (5)	0.0478 (8)	0.0023 (5)	−0.0039 (7)	0.0052 (6)
F6	0.0173 (6)	0.0315 (6)	0.0296 (6)	0.0051 (5)	0.0031 (5)	0.0058 (5)
O6	0.0196 (8)	0.0229 (7)	0.0193 (7)	−0.0004 (6)	0.0025 (6)	−0.0042 (6)
O7	0.0226 (8)	0.0160 (7)	0.0253 (7)	0.0012 (5)	0.0047 (6)	0.0047 (5)
O8	0.0287 (9)	0.0236 (7)	0.0236 (7)	−0.0073 (6)	0.0028 (6)	−0.0041 (6)
O9	0.0433 (11)	0.0295 (8)	0.0361 (9)	0.0045 (7)	0.0192 (8)	−0.0046 (7)
O10	0.0339 (11)	0.0690 (14)	0.0646 (14)	−0.0199 (10)	0.0273 (10)	−0.0271 (11)
N4	0.0145 (9)	0.0147 (7)	0.0231 (9)	0.0011 (6)	0.0033 (7)	0.0030 (6)
N5	0.0184 (9)	0.0171 (8)	0.0247 (9)	0.0038 (7)	0.0033 (7)	0.0054 (7)
N6	0.0239 (10)	0.0317 (9)	0.0238 (9)	0.0025 (8)	0.0045 (8)	0.0008 (8)
C17	0.0184 (11)	0.0150 (8)	0.0210 (10)	−0.0004 (7)	0.0017 (8)	−0.0002 (7)
C18	0.0185 (10)	0.0163 (8)	0.0167 (9)	0.0006 (8)	0.0032 (8)	0.0000 (7)
C19	0.0202 (11)	0.0184 (9)	0.0196 (9)	0.0012 (8)	0.0037 (8)	0.0016 (7)
C20	0.0181 (10)	0.0153 (8)	0.0185 (9)	0.0002 (7)	0.0015 (8)	−0.0015 (7)
C21	0.0232 (11)	0.0168 (9)	0.0225 (10)	0.0002 (7)	0.0017 (8)	0.0005 (7)
C22	0.0179 (10)	0.0165 (9)	0.0174 (9)	0.0027 (7)	0.0032 (8)	0.0014 (7)
C23	0.0201 (11)	0.0199 (9)	0.0266 (11)	−0.0033 (8)	0.0001 (9)	−0.0031 (8)
C24	0.0222 (11)	0.0210 (9)	0.0222 (10)	0.0015 (8)	−0.0004 (9)	−0.0023 (8)
C25	0.0198 (11)	0.0215 (9)	0.0203 (9)	0.0048 (8)	0.0043 (8)	0.0029 (8)
C26	0.0185 (11)	0.0259 (10)	0.0264 (11)	−0.0031 (8)	0.0033 (9)	0.0021 (8)
C27	0.0220 (11)	0.0198 (9)	0.0215 (9)	−0.0002 (8)	−0.0009 (9)	−0.0017 (8)
C28	0.0177 (10)	0.0167 (9)	0.0226 (10)	0.0001 (7)	0.0031 (8)	0.0005 (7)
C29	0.0180 (11)	0.0192 (9)	0.0258 (10)	−0.0012 (8)	0.0022 (8)	0.0009 (8)
C30	0.0264 (12)	0.0282 (10)	0.0208 (10)	−0.0069 (8)	0.0033 (9)	−0.0006 (8)
C31	0.0333 (15)	0.0496 (15)	0.0238 (11)	−0.0044 (11)	0.0023 (10)	0.0034 (10)
C32	0.0449 (16)	0.0382 (13)	0.0342 (13)	−0.0031 (11)	0.0040 (12)	0.0150 (11)
O11	0.0262 (9)	0.0159 (7)	0.0245 (8)	0.0022 (6)	0.0001 (6)	−0.0019 (6)
O12	0.0239 (8)	0.0178 (7)	0.0242 (8)	0.0026 (6)	0.0004 (6)	−0.0026 (6)

S1—C16	1.689 (3)	F4—C21	1.338 (2)
S1—C13	1.724 (2)	F5—C21	1.345 (2)
F1—C11	1.341 (2)	F6—C21	1.339 (2)
F2—C11	1.334 (2)	O6—C17	1.396 (2)
F3—C11	1.340 (2)	O6—H6	0.82 (3)
O1—C1	1.405 (2)	O7—C18	1.247 (2)
O1—H1A	0.93 (4)	O8—C28	1.218 (2)
O2—C2	1.254 (2)	O9—N6	1.224 (2)
O3—C12	1.222 (3)	O10—N6	1.222 (3)
O4—N3	1.226 (2)	N4—C18	1.379 (2)
O5—N3	1.231 (3)	N4—C17	1.456 (2)
N1—C2	1.373 (2)	N4—H4	0.84 (3)
N1—C1	1.448 (2)	N5—C18	1.341 (3)
N1—H1	0.99 (2)	N5—C19	1.465 (2)
N2—C2	1.337 (3)	N5—H5	0.82 (3)
N2—C3	1.462 (2)	N6—C25	1.467 (3)
N2—H2	0.80 (3)	C17—C21	1.539 (3)
N3—C8	1.469 (3)	C17—C20	1.540 (3)
C1—C4	1.540 (3)	C19—C22	1.518 (3)
C1—C11	1.540 (3)	C19—C20	1.539 (3)
C3—C5	1.524 (3)	C19—H19	1.0000
C3—C4	1.537 (3)	C20—C28	1.540 (3)
C3—H3	1.0000	C20—H20	1.0000
C4—C12	1.537 (3)	C22—C27	1.400 (3)
C4—H4A	1.0000	C22—C23	1.405 (3)
C5—C10	1.388 (3)	C23—C24	1.372 (3)
C5—C6	1.396 (3)	C23—H23	0.9500
C6—C7	1.380 (3)	C24—C25	1.391 (3)
C6—H6A	0.9500	C24—H24	0.9500
C7—C8	1.385 (3)	C25—C26	1.398 (3)
C7—H7	0.9500	C26—C27	1.386 (3)
C8—C9	1.382 (3)	C26—H26	0.9500
C9—C10	1.400 (3)	C27—H27	0.9500
C9—H9	0.9500	C28—C29	1.452 (3)
C10—H10	0.9500	C29—C30	1.413 (3)
C12—C13	1.457 (3)	C30—C31	1.411 (3)
C13—C14	1.432 (3)	C30—H30	0.9500
C14—C15	1.439 (3)	C31—C32	1.354 (4)
C14—H14	0.9500	C31—H31	0.9500
C15—C16	1.355 (4)	C32—H32	0.9500
C15—H15	0.9500	O11—H11A	0.81 (3)
C16—H16	0.9500	O11—H11B	0.83 (3)
S2—C32	1.705 (3)	O12—H12A	0.85 (3)
S2—C29	1.719 (2)	O12—H12B	0.79 (3)
C16—S1—C13	91.98 (12)	C17—O6—H6	111.8 (18)
C1—O1—H1A	109 (2)	C18—N4—C17	120.59 (17)
C2—N1—C1	119.93 (17)	C18—N4—H4	120.1 (17)
C2—N1—H1	114.3 (13)	C17—N4—H4	111.9 (16)
C1—N1—H1	116.7 (13)	C18—N5—C19	126.40 (17)
C2—N2—C3	126.19 (17)	C18—N5—H5	115 (2)
C2—N2—H2	116.9 (18)	C19—N5—H5	118 (2)
C3—N2—H2	115.4 (18)	O10—N6—O9	122.99 (19)
O4—N3—O5	123.40 (19)	O10—N6—C25	118.99 (18)
O4—N3—C8	118.49 (19)	O9—N6—C25	118.01 (18)
O5—N3—C8	118.10 (18)	O6—C17—N4	113.17 (16)
O1—C1—N1	112.75 (16)	O6—C17—C21	110.32 (15)
O1—C1—C4	109.18 (15)	N4—C17—C21	107.17 (16)
N1—C1—C4	107.98 (14)	O6—C17—C20	109.18 (16)
O1—C1—C11	109.54 (15)	N4—C17—C20	107.44 (15)
N1—C1—C11	107.52 (16)	C21—C17—C20	109.46 (16)
C4—C1—C11	109.84 (16)	O7—C18—N5	121.27 (18)
O2—C2—N2	120.51 (18)	O7—C18—N4	120.53 (18)
O2—C2—N1	120.57 (18)	N5—C18—N4	118.16 (17)
N2—C2—N1	118.82 (18)	N5—C19—C22	110.10 (16)
N2—C3—C5	110.45 (16)	N5—C19—C20	108.79 (16)
N2—C3—C4	108.65 (16)	C22—C19—C20	109.09 (16)
C5—C3—C4	108.86 (16)	N5—C19—H19	109.6
N2—C3—H3	109.6	C22—C19—H19	109.6
C5—C3—H3	109.6	C20—C19—H19	109.6
C4—C3—H3	109.6	C19—C20—C28	108.92 (16)
C3—C4—C12	109.60 (16)	C19—C20—C17	109.72 (15)
C3—C4—C1	109.30 (15)	C28—C20—C17	113.00 (15)
C12—C4—C1	113.97 (15)	C19—C20—H20	108.4
C3—C4—H4A	107.9	C28—C20—H20	108.4
C12—C4—H4A	107.9	C17—C20—H20	108.4
C1—C4—H4A	107.9	F4—C21—F6	106.85 (17)
C10—C5—C6	119.84 (19)	F4—C21—F5	106.75 (16)
C10—C5—C3	120.19 (17)	F6—C21—F5	107.02 (16)
C6—C5—C3	119.87 (18)	F4—C21—C17	112.44 (16)
C7—C6—C5	120.74 (19)	F6—C21—C17	112.55 (16)
C7—C6—H6A	119.6	F5—C21—C17	110.88 (16)
C5—C6—H6A	119.6	C27—C22—C23	119.43 (18)
C6—C7—C8	118.24 (18)	C27—C22—C19	120.17 (17)
C6—C7—H7	120.9	C23—C22—C19	120.28 (18)
C8—C7—H7	120.9	C24—C23—C22	120.99 (19)
C9—C8—C7	122.89 (19)	C24—C23—H23	119.5
C9—C8—N3	118.78 (19)	C22—C23—H23	119.5
C7—C8—N3	118.29 (18)	C23—C24—C25	118.40 (19)
C8—C9—C10	117.99 (19)	C23—C24—H24	120.8
C8—C9—H9	121.0	C25—C24—H24	120.8
C10—C9—H9	121.0	C24—C25—C26	122.47 (19)
C5—C10—C9	120.30 (18)	C24—C25—N6	118.35 (18)
C5—C10—H10	119.9	C26—C25—N6	119.15 (19)
C9—C10—H10	119.9	C27—C26—C25	118.2 (2)
F2—C11—F3	107.04 (16)	C27—C26—H26	120.9
F2—C11—F1	107.27 (16)	C25—C26—H26	120.9
F3—C11—F1	106.93 (16)	C26—C27—C22	120.49 (19)
F2—C11—C1	112.58 (16)	C26—C27—H27	119.8
F3—C11—C1	111.65 (16)	C22—C27—H27	119.8
F1—C11—C1	111.06 (16)	O8—C28—C29	121.14 (18)
O3—C12—C13	121.33 (19)	O8—C28—C20	120.58 (18)
O3—C12—C4	120.45 (19)	C29—C28—C20	118.28 (17)
C13—C12—C4	118.22 (18)	C30—C29—C28	130.41 (18)
C14—C13—C12	130.08 (18)	C30—C29—S2	110.97 (16)
C14—C13—S1	111.70 (15)	C28—C29—S2	118.61 (15)
C12—C13—S1	118.18 (16)	C31—C30—C29	110.97 (19)
C13—C14—C15	109.10 (19)	C31—C30—H30	124.5
C13—C14—H14	125.4	C29—C30—H30	124.5
C15—C14—H14	125.4	C32—C31—C30	113.7 (2)
C16—C15—C14	113.7 (2)	C32—C31—H31	123.2
C16—C15—H15	123.2	C30—C31—H31	123.2
C14—C15—H15	123.2	C31—C32—S2	112.42 (19)
C15—C16—S1	113.50 (19)	C31—C32—H32	123.8
C15—C16—H16	123.3	S2—C32—H32	123.8
S1—C16—H16	123.3	H11A—O11—H11B	107 (3)
C32—S2—C29	91.93 (12)	H12A—O12—H12B	102 (3)
C2—N1—C1—O1	−75.5 (2)	C18—N4—C17—O6	−75.2 (2)
C2—N1—C1—C4	45.2 (2)	C18—N4—C17—C21	162.97 (17)
C2—N1—C1—C11	163.65 (17)	C18—N4—C17—C20	45.4 (2)
C3—N2—C2—O2	−177.07 (18)	C19—N5—C18—O7	−175.88 (19)
C3—N2—C2—N1	6.4 (3)	C19—N5—C18—N4	6.5 (3)
C1—N1—C2—O2	165.12 (18)	C17—N4—C18—O7	163.48 (18)
C1—N1—C2—N2	−18.3 (3)	C17—N4—C18—N5	−18.9 (3)
C2—N2—C3—C5	−142.2 (2)	C18—N5—C19—C22	−142.0 (2)
C2—N2—C3—C4	−22.9 (3)	C18—N5—C19—C20	−22.5 (3)
N2—C3—C4—C12	173.84 (16)	N5—C19—C20—C28	172.20 (16)
C5—C3—C4—C12	−65.8 (2)	C22—C19—C20—C28	−67.68 (19)
N2—C3—C4—C1	48.3 (2)	N5—C19—C20—C17	48.0 (2)
C5—C3—C4—C1	168.61 (15)	C22—C19—C20—C17	168.15 (15)
O1—C1—C4—C3	63.20 (18)	O6—C17—C20—C19	63.79 (19)
N1—C1—C4—C3	−59.71 (19)	N4—C17—C20—C19	−59.30 (19)
C11—C1—C4—C3	−176.67 (15)	C21—C17—C20—C19	−175.35 (15)
O1—C1—C4—C12	−59.8 (2)	O6—C17—C20—C28	−58.0 (2)
N1—C1—C4—C12	177.29 (17)	N4—C17—C20—C28	178.94 (16)
C11—C1—C4—C12	60.3 (2)	C21—C17—C20—C28	62.9 (2)
N2—C3—C5—C10	−143.50 (19)	O6—C17—C21—F4	166.64 (15)
C4—C3—C5—C10	97.3 (2)	N4—C17—C21—F4	−69.8 (2)
N2—C3—C5—C6	40.2 (2)	C20—C17—C21—F4	46.5 (2)
C4—C3—C5—C6	−79.0 (2)	O6—C17—C21—F6	−72.6 (2)
C10—C5—C6—C7	0.8 (3)	N4—C17—C21—F6	51.0 (2)
C3—C5—C6—C7	177.05 (18)	C20—C17—C21—F6	167.20 (15)
C5—C6—C7—C8	−0.6 (3)	O6—C17—C21—F5	47.2 (2)
C6—C7—C8—C9	0.0 (3)	N4—C17—C21—F5	170.82 (16)
C6—C7—C8—N3	177.81 (18)	C20—C17—C21—F5	−73.0 (2)
O4—N3—C8—C9	170.99 (19)	N5—C19—C22—C27	−141.55 (19)
O5—N3—C8—C9	−9.6 (3)	C20—C19—C22—C27	99.1 (2)
O4—N3—C8—C7	−6.9 (3)	N5—C19—C22—C23	42.6 (2)
O5—N3—C8—C7	172.6 (2)	C20—C19—C22—C23	−76.8 (2)
C7—C8—C9—C10	0.4 (3)	C27—C22—C23—C24	1.4 (3)
N3—C8—C9—C10	−177.31 (18)	C19—C22—C23—C24	177.32 (18)
C6—C5—C10—C9	−0.2 (3)	C22—C23—C24—C25	−0.4 (3)
C3—C5—C10—C9	−176.53 (18)	C23—C24—C25—C26	−1.1 (3)
C8—C9—C10—C5	−0.3 (3)	C23—C24—C25—N6	176.76 (18)
O1—C1—C11—F2	−72.7 (2)	O10—N6—C25—C24	170.3 (2)
N1—C1—C11—F2	50.2 (2)	O9—N6—C25—C24	−10.7 (3)
C4—C1—C11—F2	167.44 (15)	O10—N6—C25—C26	−11.8 (3)
O1—C1—C11—F3	166.91 (15)	O9—N6—C25—C26	167.2 (2)
N1—C1—C11—F3	−70.3 (2)	C24—C25—C26—C27	1.4 (3)
C4—C1—C11—F3	47.0 (2)	N6—C25—C26—C27	−176.41 (19)
O1—C1—C11—F1	47.7 (2)	C25—C26—C27—C22	−0.3 (3)
N1—C1—C11—F1	170.49 (16)	C23—C22—C27—C26	−1.1 (3)
C4—C1—C11—F1	−72.3 (2)	C19—C22—C27—C26	−176.98 (19)
C3—C4—C12—O3	−62.2 (2)	C19—C20—C28—O8	−58.2 (2)
C1—C4—C12—O3	60.6 (3)	C17—C20—C28—O8	64.0 (2)
C3—C4—C12—C13	118.2 (2)	C19—C20—C28—C29	121.5 (2)
C1—C4—C12—C13	−118.9 (2)	C17—C20—C28—C29	−116.3 (2)
O3—C12—C13—C14	167.7 (2)	O8—C28—C29—C30	168.8 (2)
C4—C12—C13—C14	−12.8 (3)	C20—C28—C29—C30	−10.9 (3)
O3—C12—C13—S1	−9.5 (3)	O8—C28—C29—S2	−10.4 (3)
C4—C12—C13—S1	170.01 (15)	C20—C28—C29—S2	169.89 (14)
C16—S1—C13—C14	1.81 (19)	C32—S2—C29—C30	1.98 (19)
C16—S1—C13—C12	179.52 (18)	C32—S2—C29—C28	−178.64 (19)
C12—C13—C14—C15	−179.3 (2)	C28—C29—C30—C31	179.5 (2)
S1—C13—C14—C15	−1.9 (2)	S2—C29—C30—C31	−1.3 (2)
C13—C14—C15—C16	1.1 (3)	C29—C30—C31—C32	−0.4 (3)
C14—C15—C16—S1	0.2 (3)	C30—C31—C32—S2	1.9 (3)
C13—S1—C16—C15	−1.2 (2)	C29—S2—C32—C31	−2.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12A···O6	0.85 (3)	2.28 (3)	2.867 (2)	126 (2)
O12—H12A···O8	0.85 (3)	2.20 (3)	2.949 (2)	147 (3)
O12—H12B···O7i	0.79 (3)	2.11 (3)	2.852 (2)	156 (3)
N1—H1···O12ii	0.99 (2)	2.00 (2)	2.969 (2)	168.5 (19)
N2—H2···O12iii	0.80 (3)	2.15 (3)	2.905 (2)	159 (2)
N5—H5···O11	0.82 (3)	2.15 (3)	2.903 (2)	153 (3)
N4—H4···O11iv	0.84 (3)	2.17 (3)	2.991 (2)	166 (2)
O6—H6···O2v	0.82 (3)	1.86 (3)	2.684 (2)	179 (3)
O1—H1A···O7vi	0.93 (4)	1.76 (4)	2.684 (2)	175 (4)
O11—H11A···O2vii	0.81 (3)	2.06 (3)	2.849 (2)	166 (3)
O11—H11B···O3viii	0.83 (3)	2.23 (3)	2.968 (2)	148 (3)
O11—H11B···O1viii	0.83 (3)	2.25 (3)	2.863 (2)	131 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H12A⋯O6	0.85 (3)	2.28 (3)	2.867 (2)	126 (2)
O12—H12A⋯O8	0.85 (3)	2.20 (3)	2.949 (2)	147 (3)
O12—H12B⋯O7i	0.79 (3)	2.11 (3)	2.852 (2)	156 (3)
N1—H1⋯O12ii	0.99 (2)	2.00 (2)	2.969 (2)	168.5 (19)
N2—H2⋯O12iii	0.80 (3)	2.15 (3)	2.905 (2)	159 (2)
N5—H5⋯O11	0.82 (3)	2.15 (3)	2.903 (2)	153 (3)
N4—H4⋯O11iv	0.84 (3)	2.17 (3)	2.991 (2)	166 (2)
O6—H6⋯O2v	0.82 (3)	1.86 (3)	2.684 (2)	179 (3)
O1—H1A⋯O7vi	0.93 (4)	1.76 (4)	2.684 (2)	175 (4)
O11—H11A⋯O2vii	0.81 (3)	2.06 (3)	2.849 (2)	166 (3)
O11—H11B⋯O3viii	0.83 (3)	2.23 (3)	2.968 (2)	148 (3)
O11—H11B⋯O1viii	0.83 (3)	2.25 (3)	2.863 (2)	131 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .