organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 11| November 2010| Pages o2932-o2933

rac-6-Hy­dr­oxy-4-(4-nitro­phen­yl)-5-(2-thienyl­carbon­yl)-6-(tri­fluoro­meth­yl)-3,4,5,6-tetra­hydro­pyrimidin-2(1H)-one monohydrate

aCollege of Chemistry and Chemical Engineering, Xuchang University, Xuchang, Henan Province, 461000, People's Republic of China
*Correspondence e-mail: xcuwaller@163.com

(Received 29 September 2010; accepted 15 October 2010; online 23 October 2010)

The title compound, C16H12F3N3O5S·H2O, was prepared by reaction of 4-nitro­benzaldehyde, 4,4,4-trifluoro-1-(thio­phen-2-yl)butane-1,3-dione and urea. The asymmetric unit contains two independent mol­ecules, with essentially identical geom­etries and conformations. The dihydro­pyrimidine rings adopt a half-chair conformation. The dihedral angles between the benzene ring and the thio­phene ring are 54.82 (8) and 58.72 (8)° in the two mol­ecules. The mol­ecular conformation of one of the mol­ecules is stabilized by two intra­molecular O—H⋯O hydrogen bonds, generating an S(6) ring. The crystal structure is stabilized by inter­molecular O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For the bioactivity of dihydro­pyrimidines, see: Brier et al. (2004[Brier, S., Lemaire, D., DeBonis, S., Forest, E. & Kozielski, F. (2004). Biochem. 43, 13072-13082.]); Cochran et al. (2005[Cochran, J. C., Gatial, J. E., Kapoor, T. M. & Gilbert, S. P. (2005). J. Biol. Chem. 280, 12658-12667.]); Moran et al. (2007[Moran, M. M., Fanger, C., Chong, J. A., McNamara, C., Zhen, X. G. & Mandel-Brehm, J. (2007). WO Patent No. 2 007 073 505.]); Zorkun et al. (2006[Zorkun, I. S., Sarac, S., Celebi, S. & Erol, K. (2006). Bioorg. Med. Chem. 14, 8582-8589.]). For the bioactivity of organofluorine compounds, see: Hermann et al. (2003[Hermann, B., Erwin, H. & Hansjorg, K. (2003). US patent No. 2 003 176 284.]); Ulrich (2004[Ulrich, H. (2004). US Patent No. 2 004 033 897.]).

[Scheme 1]

Experimental

Crystal data
  • C16H12F3N3O5S·H2O

  • Mr = 433.36

  • Orthorhombic, P n a 21

  • 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[Rigaku (2009). CrystalClear-SM Expert and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]) Tmin = 0.941, Tmax = 0.956

  • 34133 measured reflections

  • 7861 independent reflections

  • 7466 reflections with I > 2σ(I)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 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[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 3539 Friedel pairs

  • Flack parameter: −0.01 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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) x, y+1, z; (ii) [-x+1, -y+1, z-{\script{1\over 2}}]; (iii) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]; (iv) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]; (v) [-x+1, -y+1, z+{\script{1\over 2}}]; (vi) [-x+1, -y, z-{\script{1\over 2}}]; (vii) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z+{\script{1\over 2}}]; (viii) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: CrystalClear-SM Expert (Rigaku, 2009[Rigaku (2009). CrystalClear-SM Expert and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: CrystalStructure (Rigaku, 2009[Rigaku (2009). CrystalClear-SM Expert and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); software used to prepare material for publication: CrystalStructure.

Supporting information


Comment top

Dihydropyrimidine (DHPM) derivatives can be used as potential calcium channel blockers (Zorkun et al., 2006), inhibitors of mitotic kinesin Eg5 for treating cancer (Cochran et al., 2005; Brier et al., 2004) and as TRPA1 modulators for treating pain (Moran et al., 2007). In addition, compounds that contain fluorine have special bioactivity, e.g. flumioxazin is a widely used herbicide (Hermann et al., 2003; Ulrich, 2004). This led us to focus our attention on the synthesis and bioactivity of these important fused perfluoroalkylated heterocyclic compounds. During the synthesis of DHPM derivatives, the title compound, an intermediate C16H14F3N3O6S (I) was isolated and the structure confirmed by X-ray diffraction, in order to elucidate the reaction mechanism.

The title compound crystallizes with two independent molecules in the asymmetric unit. In the structure of the title molecule, the dihydropyrimidine ring adopts a half-chair conformation. The molecular conformation of one of the molecules is stabilized by two intramolecular O—H···O hydrogen bond, generating an S(6) ring. The crystal structure is stabilized by nine intermolecular hydrogen bonds (six O—H···O and three N—H···O) (Table 1). The dihedral angles between the pyridine ring and the thiophene ring are 54.82 (8)° and 58.72 (8)° in the two molecules.

Related literature top

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 top

The title compound was synthesized refluxing for 3 h a stirred solution of 4-nitrobenzaldehyde (0.30 g, 2 mmol), 4,4,4-trifluoro-1- (thiophen-2-yl)butane-1,3-dione (0.51 g, 2.3 mmol) and urea (0.18 g, 3 mmol) in 3 ml of anhydrous ethanol, the reaction catalyzed by sulfamic acid (0.06 g). The solvent was evaporated in vacuo and the residue was washed with water. The title compound was recrystallized from 50% aqueous ethanol and single crystals of (I) were obtained by slow evaporation.

Refinement top

Hydrogen atoms involved in hydrogen-bonding inetractions were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were placed in calculated positions, with C—H(aromatic) = 0.95 Å and C—H(aliphatic) = 1.00 Å, and treated as riding, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: CrystalClear-SM Expert (Rigaku, 2009); data reduction: CrystalClear-SM Expert (Rigaku, 2009); 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 (Rigaku, 2009).

Figures top
[Figure 1] Fig. 1. Molecular configuration and atom numbering scheme for (I), with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. The packing diagram of the title compound. Intermolecular hydrogen bonds are shown as dashed line.
rac-6-Hydroxy-4-(4-nitrophenyl)-5-(2-thienylcarbonyl)-6- (trifluoromethyl)-3,4,5,6-tetrahydropyrimidin-2(1H)-one monohydrate top
Crystal data top
C16H12F3N3O5S·H2OF(000) = 1776
Mr = 433.36Dx = 1.620 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2c -2nCell parameters from 9674 reflections
a = 14.1640 (13) Åθ = 1.6–27.9°
b = 9.136 (1) ŵ = 0.26 mm1
c = 27.459 (3) ÅT = 113 K
V = 3553.3 (6) Å3Prism, colorless
Z = 80.24 × 0.20 × 0.18 mm
Data collection top
Rigaku Saturn724 CCD
diffractometer
7861 independent reflections
Radiation source: rotating anode7466 reflections with I > 2σ(I)
Multilayer monochromatorRint = 0.031
Detector resolution: 14.222 pixels mm-1θmax = 27.9°, θmin = 1.5°
ω scansh = 1818
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2009)
k = 1211
Tmin = 0.941, Tmax = 0.956l = 3536
34133 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H 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 reflectionsΔρmax = 0.37 e Å3
563 parametersΔρmin = 0.27 e Å3
1 restraintAbsolute structure: Flack (1983), 3539 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.01 (5)
Crystal data top
C16H12F3N3O5S·H2OV = 3553.3 (6) Å3
Mr = 433.36Z = 8
Orthorhombic, Pna21Mo Kα radiation
a = 14.1640 (13) ŵ = 0.26 mm1
b = 9.136 (1) ÅT = 113 K
c = 27.459 (3) Å0.24 × 0.20 × 0.18 mm
Data collection top
Rigaku Saturn724 CCD
diffractometer
7861 independent reflections
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2009)
7466 reflections with I > 2σ(I)
Tmin = 0.941, Tmax = 0.956Rint = 0.031
34133 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091Δρmax = 0.37 e Å3
S = 1.05Δρmin = 0.27 e Å3
7861 reflectionsAbsolute structure: Flack (1983), 3539 Friedel pairs
563 parametersAbsolute structure parameter: 0.01 (5)
1 restraint
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.60772 (5)0.35697 (6)0.08791 (3)0.03689 (15)
F10.37968 (10)0.23469 (13)0.00751 (6)0.0331 (3)
F20.27429 (8)0.07998 (14)0.01598 (5)0.0274 (3)
F30.35284 (9)0.04033 (14)0.04972 (5)0.0292 (3)
O10.45567 (10)0.08713 (15)0.06818 (5)0.0212 (3)
O20.43350 (10)0.36232 (14)0.06593 (5)0.0211 (3)
O30.59480 (11)0.23377 (16)0.01125 (6)0.0282 (3)
O40.89623 (12)0.33821 (17)0.13355 (6)0.0335 (4)
O50.96906 (14)0.1399 (2)0.11251 (7)0.0467 (5)
N10.40188 (13)0.13684 (17)0.03407 (6)0.0180 (3)
N20.55597 (13)0.2246 (2)0.04098 (7)0.0203 (4)
N30.90201 (14)0.22519 (19)0.10965 (7)0.0249 (4)
C10.43619 (13)0.01001 (19)0.02507 (7)0.0165 (4)
C20.46358 (14)0.2445 (2)0.04839 (7)0.0183 (4)
C30.60082 (14)0.0912 (2)0.02294 (7)0.0173 (4)
H30.62490.03230.05100.021*
C40.52713 (14)0.00176 (19)0.00539 (7)0.0172 (4)
H4A0.51170.05640.03590.021*
C50.68228 (15)0.1286 (2)0.01111 (7)0.0182 (4)
C60.67296 (15)0.2434 (2)0.04432 (8)0.0216 (4)
H6A0.61690.30050.04450.026*
C70.74425 (16)0.2748 (2)0.07696 (7)0.0214 (4)
H70.73830.35350.09940.026*
C80.82467 (15)0.1886 (2)0.07617 (7)0.0205 (4)
C90.83640 (15)0.0731 (2)0.04422 (8)0.0226 (4)
H90.89220.01540.04470.027*
C100.76357 (14)0.0438 (2)0.01115 (7)0.0202 (4)
H100.76980.03460.01140.024*
C110.35973 (15)0.0915 (2)0.00413 (7)0.0203 (4)
C120.56951 (15)0.1468 (2)0.01993 (8)0.0206 (4)
C130.57782 (15)0.1808 (2)0.07158 (8)0.0217 (4)
C140.56852 (15)0.0877 (2)0.11324 (7)0.0241 (4)
H140.55430.01390.11240.029*
C150.58417 (19)0.1726 (3)0.15664 (9)0.0361 (6)
H150.58030.13260.18850.043*
C160.60494 (19)0.3148 (3)0.14778 (10)0.0407 (7)
H160.61680.38420.17280.049*
S20.87505 (5)0.87073 (6)0.23286 (2)0.03609 (15)
F40.62278 (9)0.54205 (14)0.26486 (4)0.0278 (3)
F50.64890 (10)0.73570 (13)0.30749 (6)0.0319 (3)
F60.54339 (9)0.57986 (14)0.33042 (5)0.0261 (3)
O60.72494 (11)0.58706 (15)0.38319 (5)0.0206 (3)
O70.70213 (11)0.13746 (14)0.38037 (5)0.0213 (3)
O80.86907 (11)0.72990 (16)0.32953 (6)0.0253 (3)
O91.16517 (13)0.15713 (17)0.18214 (6)0.0363 (4)
O101.23927 (14)0.3536 (2)0.20196 (8)0.0558 (6)
N40.67149 (13)0.36304 (16)0.34850 (6)0.0174 (3)
N50.82537 (13)0.27411 (19)0.35508 (7)0.0201 (4)
N61.17126 (14)0.2717 (2)0.20498 (7)0.0264 (4)
C170.70562 (14)0.5113 (2)0.34018 (7)0.0181 (4)
C180.73277 (14)0.2537 (2)0.36261 (7)0.0172 (4)
C190.87044 (14)0.4083 (2)0.33745 (7)0.0194 (4)
H190.89510.46580.36570.023*
C200.79665 (14)0.49985 (19)0.30975 (7)0.0173 (4)
H200.78140.44850.27860.021*
C210.62941 (15)0.5919 (2)0.31056 (8)0.0208 (4)
C220.95101 (14)0.37086 (19)0.30321 (7)0.0173 (4)
C230.94011 (15)0.2601 (2)0.26815 (8)0.0222 (4)
H230.88290.20600.26690.027*
C241.01085 (15)0.2290 (2)0.23565 (7)0.0218 (4)
H241.00340.15370.21210.026*
C251.09372 (15)0.3103 (2)0.23800 (7)0.0205 (4)
C261.10671 (16)0.4235 (2)0.27159 (8)0.0236 (4)
H261.16350.47890.27200.028*
C271.03457 (14)0.4527 (2)0.30426 (8)0.0211 (4)
H271.04190.52870.32750.025*
C280.83971 (14)0.6501 (2)0.29737 (7)0.0190 (4)
C290.84472 (15)0.6933 (2)0.24656 (8)0.0210 (4)
C300.82926 (16)0.6111 (2)0.20372 (8)0.0251 (4)
H300.81300.51020.20320.030*
C310.84114 (19)0.6988 (3)0.16187 (9)0.0356 (6)
H310.83400.66240.12970.043*
C320.8636 (2)0.8396 (3)0.17194 (10)0.0391 (6)
H320.87200.91280.14780.047*
O110.98547 (11)0.12871 (16)0.40001 (6)0.0222 (3)
O120.78322 (11)0.87168 (16)0.41523 (6)0.0219 (3)
H12A0.785 (2)0.818 (3)0.3900 (11)0.043 (8)*
H12B0.777 (2)0.950 (4)0.4040 (12)0.058 (10)*
H10.3382 (17)0.146 (2)0.0483 (9)0.020 (6)*
H20.5907 (17)0.283 (3)0.0528 (9)0.022 (6)*
H50.859 (2)0.209 (3)0.3656 (10)0.035 (7)*
H40.615 (2)0.362 (3)0.3582 (9)0.028 (7)*
H60.6766 (19)0.603 (3)0.3989 (10)0.029 (7)*
H1A0.399 (3)0.106 (4)0.0845 (14)0.073 (11)*
H11A0.9996 (19)0.051 (3)0.4119 (10)0.034 (8)*
H11B0.982 (2)0.188 (3)0.4227 (11)0.042 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0438 (4)0.0252 (3)0.0416 (4)0.0070 (2)0.0030 (3)0.0096 (2)
F10.0316 (8)0.0147 (6)0.0531 (9)0.0018 (5)0.0029 (7)0.0088 (6)
F20.0176 (6)0.0335 (7)0.0311 (7)0.0052 (5)0.0027 (5)0.0088 (5)
F30.0302 (7)0.0358 (7)0.0216 (6)0.0038 (5)0.0023 (6)0.0011 (5)
O10.0194 (8)0.0232 (7)0.0210 (7)0.0013 (6)0.0034 (6)0.0063 (6)
O20.0199 (8)0.0173 (6)0.0261 (7)0.0003 (5)0.0042 (6)0.0053 (5)
O30.0308 (9)0.0224 (7)0.0313 (8)0.0083 (6)0.0068 (7)0.0071 (6)
O40.0384 (10)0.0298 (8)0.0322 (9)0.0065 (7)0.0105 (8)0.0042 (7)
O50.0321 (11)0.0551 (11)0.0528 (12)0.0129 (8)0.0214 (9)0.0176 (10)
N10.0175 (9)0.0135 (8)0.0230 (8)0.0008 (6)0.0030 (7)0.0024 (6)
N20.0158 (9)0.0194 (8)0.0256 (9)0.0023 (7)0.0031 (7)0.0076 (7)
N30.0253 (10)0.0276 (9)0.0219 (9)0.0060 (7)0.0058 (8)0.0032 (7)
C10.0171 (10)0.0132 (8)0.0192 (9)0.0001 (7)0.0034 (8)0.0014 (7)
C20.0183 (10)0.0200 (9)0.0167 (9)0.0010 (8)0.0011 (8)0.0017 (7)
C30.0160 (10)0.0163 (8)0.0196 (9)0.0014 (7)0.0007 (8)0.0005 (7)
C40.0180 (10)0.0138 (8)0.0199 (9)0.0017 (7)0.0020 (8)0.0001 (7)
C50.0181 (10)0.0180 (9)0.0185 (9)0.0018 (7)0.0011 (8)0.0031 (7)
C60.0189 (11)0.0213 (9)0.0246 (10)0.0016 (8)0.0020 (8)0.0015 (8)
C70.0236 (11)0.0203 (9)0.0204 (10)0.0017 (8)0.0001 (8)0.0035 (8)
C80.0198 (11)0.0237 (9)0.0180 (9)0.0054 (8)0.0038 (8)0.0039 (7)
C90.0201 (11)0.0214 (9)0.0265 (10)0.0001 (8)0.0010 (8)0.0006 (8)
C100.0199 (11)0.0184 (9)0.0222 (10)0.0010 (8)0.0027 (8)0.0009 (8)
C110.0209 (11)0.0185 (9)0.0216 (10)0.0010 (7)0.0022 (8)0.0017 (7)
C120.0154 (10)0.0169 (9)0.0296 (11)0.0006 (7)0.0048 (9)0.0002 (8)
C130.0184 (11)0.0163 (9)0.0303 (10)0.0008 (8)0.0060 (9)0.0055 (7)
C140.0208 (11)0.0311 (10)0.0205 (10)0.0064 (8)0.0012 (8)0.0112 (8)
C150.0361 (15)0.0453 (14)0.0269 (12)0.0058 (11)0.0007 (11)0.0050 (10)
C160.0357 (15)0.0459 (16)0.0405 (15)0.0049 (12)0.0027 (12)0.0243 (12)
S20.0525 (4)0.0218 (2)0.0340 (3)0.0066 (2)0.0044 (3)0.0062 (2)
F40.0294 (7)0.0327 (7)0.0213 (6)0.0030 (5)0.0034 (5)0.0000 (5)
F50.0323 (7)0.0156 (5)0.0478 (8)0.0023 (5)0.0039 (7)0.0052 (6)
F60.0173 (6)0.0315 (6)0.0296 (6)0.0051 (5)0.0031 (5)0.0058 (5)
O60.0196 (8)0.0229 (7)0.0193 (7)0.0004 (6)0.0025 (6)0.0042 (6)
O70.0226 (8)0.0160 (7)0.0253 (7)0.0012 (5)0.0047 (6)0.0047 (5)
O80.0287 (9)0.0236 (7)0.0236 (7)0.0073 (6)0.0028 (6)0.0041 (6)
O90.0433 (11)0.0295 (8)0.0361 (9)0.0045 (7)0.0192 (8)0.0046 (7)
O100.0339 (11)0.0690 (14)0.0646 (14)0.0199 (10)0.0273 (10)0.0271 (11)
N40.0145 (9)0.0147 (7)0.0231 (9)0.0011 (6)0.0033 (7)0.0030 (6)
N50.0184 (9)0.0171 (8)0.0247 (9)0.0038 (7)0.0033 (7)0.0054 (7)
N60.0239 (10)0.0317 (9)0.0238 (9)0.0025 (8)0.0045 (8)0.0008 (8)
C170.0184 (11)0.0150 (8)0.0210 (10)0.0004 (7)0.0017 (8)0.0002 (7)
C180.0185 (10)0.0163 (8)0.0167 (9)0.0006 (8)0.0032 (8)0.0000 (7)
C190.0202 (11)0.0184 (9)0.0196 (9)0.0012 (8)0.0037 (8)0.0016 (7)
C200.0181 (10)0.0153 (8)0.0185 (9)0.0002 (7)0.0015 (8)0.0015 (7)
C210.0232 (11)0.0168 (9)0.0225 (10)0.0002 (7)0.0017 (8)0.0005 (7)
C220.0179 (10)0.0165 (9)0.0174 (9)0.0027 (7)0.0032 (8)0.0014 (7)
C230.0201 (11)0.0199 (9)0.0266 (11)0.0033 (8)0.0001 (9)0.0031 (8)
C240.0222 (11)0.0210 (9)0.0222 (10)0.0015 (8)0.0004 (9)0.0023 (8)
C250.0198 (11)0.0215 (9)0.0203 (9)0.0048 (8)0.0043 (8)0.0029 (8)
C260.0185 (11)0.0259 (10)0.0264 (11)0.0031 (8)0.0033 (9)0.0021 (8)
C270.0220 (11)0.0198 (9)0.0215 (9)0.0002 (8)0.0009 (9)0.0017 (8)
C280.0177 (10)0.0167 (9)0.0226 (10)0.0001 (7)0.0031 (8)0.0005 (7)
C290.0180 (11)0.0192 (9)0.0258 (10)0.0012 (8)0.0022 (8)0.0009 (8)
C300.0264 (12)0.0282 (10)0.0208 (10)0.0069 (8)0.0033 (9)0.0006 (8)
C310.0333 (15)0.0496 (15)0.0238 (11)0.0044 (11)0.0023 (10)0.0034 (10)
C320.0449 (16)0.0382 (13)0.0342 (13)0.0031 (11)0.0040 (12)0.0150 (11)
O110.0262 (9)0.0159 (7)0.0245 (8)0.0022 (6)0.0001 (6)0.0019 (6)
O120.0239 (8)0.0178 (7)0.0242 (8)0.0026 (6)0.0004 (6)0.0026 (6)
Geometric parameters (Å, º) top
S1—C161.689 (3)F4—C211.338 (2)
S1—C131.724 (2)F5—C211.345 (2)
F1—C111.341 (2)F6—C211.339 (2)
F2—C111.334 (2)O6—C171.396 (2)
F3—C111.340 (2)O6—H60.82 (3)
O1—C11.405 (2)O7—C181.247 (2)
O1—H1A0.93 (4)O8—C281.218 (2)
O2—C21.254 (2)O9—N61.224 (2)
O3—C121.222 (3)O10—N61.222 (3)
O4—N31.226 (2)N4—C181.379 (2)
O5—N31.231 (3)N4—C171.456 (2)
N1—C21.373 (2)N4—H40.84 (3)
N1—C11.448 (2)N5—C181.341 (3)
N1—H10.99 (2)N5—C191.465 (2)
N2—C21.337 (3)N5—H50.82 (3)
N2—C31.462 (2)N6—C251.467 (3)
N2—H20.80 (3)C17—C211.539 (3)
N3—C81.469 (3)C17—C201.540 (3)
C1—C41.540 (3)C19—C221.518 (3)
C1—C111.540 (3)C19—C201.539 (3)
C3—C51.524 (3)C19—H191.0000
C3—C41.537 (3)C20—C281.540 (3)
C3—H31.0000C20—H201.0000
C4—C121.537 (3)C22—C271.400 (3)
C4—H4A1.0000C22—C231.405 (3)
C5—C101.388 (3)C23—C241.372 (3)
C5—C61.396 (3)C23—H230.9500
C6—C71.380 (3)C24—C251.391 (3)
C6—H6A0.9500C24—H240.9500
C7—C81.385 (3)C25—C261.398 (3)
C7—H70.9500C26—C271.386 (3)
C8—C91.382 (3)C26—H260.9500
C9—C101.400 (3)C27—H270.9500
C9—H90.9500C28—C291.452 (3)
C10—H100.9500C29—C301.413 (3)
C12—C131.457 (3)C30—C311.411 (3)
C13—C141.432 (3)C30—H300.9500
C14—C151.439 (3)C31—C321.354 (4)
C14—H140.9500C31—H310.9500
C15—C161.355 (4)C32—H320.9500
C15—H150.9500O11—H11A0.81 (3)
C16—H160.9500O11—H11B0.83 (3)
S2—C321.705 (3)O12—H12A0.85 (3)
S2—C291.719 (2)O12—H12B0.79 (3)
C16—S1—C1391.98 (12)C17—O6—H6111.8 (18)
C1—O1—H1A109 (2)C18—N4—C17120.59 (17)
C2—N1—C1119.93 (17)C18—N4—H4120.1 (17)
C2—N1—H1114.3 (13)C17—N4—H4111.9 (16)
C1—N1—H1116.7 (13)C18—N5—C19126.40 (17)
C2—N2—C3126.19 (17)C18—N5—H5115 (2)
C2—N2—H2116.9 (18)C19—N5—H5118 (2)
C3—N2—H2115.4 (18)O10—N6—O9122.99 (19)
O4—N3—O5123.40 (19)O10—N6—C25118.99 (18)
O4—N3—C8118.49 (19)O9—N6—C25118.01 (18)
O5—N3—C8118.10 (18)O6—C17—N4113.17 (16)
O1—C1—N1112.75 (16)O6—C17—C21110.32 (15)
O1—C1—C4109.18 (15)N4—C17—C21107.17 (16)
N1—C1—C4107.98 (14)O6—C17—C20109.18 (16)
O1—C1—C11109.54 (15)N4—C17—C20107.44 (15)
N1—C1—C11107.52 (16)C21—C17—C20109.46 (16)
C4—C1—C11109.84 (16)O7—C18—N5121.27 (18)
O2—C2—N2120.51 (18)O7—C18—N4120.53 (18)
O2—C2—N1120.57 (18)N5—C18—N4118.16 (17)
N2—C2—N1118.82 (18)N5—C19—C22110.10 (16)
N2—C3—C5110.45 (16)N5—C19—C20108.79 (16)
N2—C3—C4108.65 (16)C22—C19—C20109.09 (16)
C5—C3—C4108.86 (16)N5—C19—H19109.6
N2—C3—H3109.6C22—C19—H19109.6
C5—C3—H3109.6C20—C19—H19109.6
C4—C3—H3109.6C19—C20—C28108.92 (16)
C3—C4—C12109.60 (16)C19—C20—C17109.72 (15)
C3—C4—C1109.30 (15)C28—C20—C17113.00 (15)
C12—C4—C1113.97 (15)C19—C20—H20108.4
C3—C4—H4A107.9C28—C20—H20108.4
C12—C4—H4A107.9C17—C20—H20108.4
C1—C4—H4A107.9F4—C21—F6106.85 (17)
C10—C5—C6119.84 (19)F4—C21—F5106.75 (16)
C10—C5—C3120.19 (17)F6—C21—F5107.02 (16)
C6—C5—C3119.87 (18)F4—C21—C17112.44 (16)
C7—C6—C5120.74 (19)F6—C21—C17112.55 (16)
C7—C6—H6A119.6F5—C21—C17110.88 (16)
C5—C6—H6A119.6C27—C22—C23119.43 (18)
C6—C7—C8118.24 (18)C27—C22—C19120.17 (17)
C6—C7—H7120.9C23—C22—C19120.28 (18)
C8—C7—H7120.9C24—C23—C22120.99 (19)
C9—C8—C7122.89 (19)C24—C23—H23119.5
C9—C8—N3118.78 (19)C22—C23—H23119.5
C7—C8—N3118.29 (18)C23—C24—C25118.40 (19)
C8—C9—C10117.99 (19)C23—C24—H24120.8
C8—C9—H9121.0C25—C24—H24120.8
C10—C9—H9121.0C24—C25—C26122.47 (19)
C5—C10—C9120.30 (18)C24—C25—N6118.35 (18)
C5—C10—H10119.9C26—C25—N6119.15 (19)
C9—C10—H10119.9C27—C26—C25118.2 (2)
F2—C11—F3107.04 (16)C27—C26—H26120.9
F2—C11—F1107.27 (16)C25—C26—H26120.9
F3—C11—F1106.93 (16)C26—C27—C22120.49 (19)
F2—C11—C1112.58 (16)C26—C27—H27119.8
F3—C11—C1111.65 (16)C22—C27—H27119.8
F1—C11—C1111.06 (16)O8—C28—C29121.14 (18)
O3—C12—C13121.33 (19)O8—C28—C20120.58 (18)
O3—C12—C4120.45 (19)C29—C28—C20118.28 (17)
C13—C12—C4118.22 (18)C30—C29—C28130.41 (18)
C14—C13—C12130.08 (18)C30—C29—S2110.97 (16)
C14—C13—S1111.70 (15)C28—C29—S2118.61 (15)
C12—C13—S1118.18 (16)C31—C30—C29110.97 (19)
C13—C14—C15109.10 (19)C31—C30—H30124.5
C13—C14—H14125.4C29—C30—H30124.5
C15—C14—H14125.4C32—C31—C30113.7 (2)
C16—C15—C14113.7 (2)C32—C31—H31123.2
C16—C15—H15123.2C30—C31—H31123.2
C14—C15—H15123.2C31—C32—S2112.42 (19)
C15—C16—S1113.50 (19)C31—C32—H32123.8
C15—C16—H16123.3S2—C32—H32123.8
S1—C16—H16123.3H11A—O11—H11B107 (3)
C32—S2—C2991.93 (12)H12A—O12—H12B102 (3)
C2—N1—C1—O175.5 (2)C18—N4—C17—O675.2 (2)
C2—N1—C1—C445.2 (2)C18—N4—C17—C21162.97 (17)
C2—N1—C1—C11163.65 (17)C18—N4—C17—C2045.4 (2)
C3—N2—C2—O2177.07 (18)C19—N5—C18—O7175.88 (19)
C3—N2—C2—N16.4 (3)C19—N5—C18—N46.5 (3)
C1—N1—C2—O2165.12 (18)C17—N4—C18—O7163.48 (18)
C1—N1—C2—N218.3 (3)C17—N4—C18—N518.9 (3)
C2—N2—C3—C5142.2 (2)C18—N5—C19—C22142.0 (2)
C2—N2—C3—C422.9 (3)C18—N5—C19—C2022.5 (3)
N2—C3—C4—C12173.84 (16)N5—C19—C20—C28172.20 (16)
C5—C3—C4—C1265.8 (2)C22—C19—C20—C2867.68 (19)
N2—C3—C4—C148.3 (2)N5—C19—C20—C1748.0 (2)
C5—C3—C4—C1168.61 (15)C22—C19—C20—C17168.15 (15)
O1—C1—C4—C363.20 (18)O6—C17—C20—C1963.79 (19)
N1—C1—C4—C359.71 (19)N4—C17—C20—C1959.30 (19)
C11—C1—C4—C3176.67 (15)C21—C17—C20—C19175.35 (15)
O1—C1—C4—C1259.8 (2)O6—C17—C20—C2858.0 (2)
N1—C1—C4—C12177.29 (17)N4—C17—C20—C28178.94 (16)
C11—C1—C4—C1260.3 (2)C21—C17—C20—C2862.9 (2)
N2—C3—C5—C10143.50 (19)O6—C17—C21—F4166.64 (15)
C4—C3—C5—C1097.3 (2)N4—C17—C21—F469.8 (2)
N2—C3—C5—C640.2 (2)C20—C17—C21—F446.5 (2)
C4—C3—C5—C679.0 (2)O6—C17—C21—F672.6 (2)
C10—C5—C6—C70.8 (3)N4—C17—C21—F651.0 (2)
C3—C5—C6—C7177.05 (18)C20—C17—C21—F6167.20 (15)
C5—C6—C7—C80.6 (3)O6—C17—C21—F547.2 (2)
C6—C7—C8—C90.0 (3)N4—C17—C21—F5170.82 (16)
C6—C7—C8—N3177.81 (18)C20—C17—C21—F573.0 (2)
O4—N3—C8—C9170.99 (19)N5—C19—C22—C27141.55 (19)
O5—N3—C8—C99.6 (3)C20—C19—C22—C2799.1 (2)
O4—N3—C8—C76.9 (3)N5—C19—C22—C2342.6 (2)
O5—N3—C8—C7172.6 (2)C20—C19—C22—C2376.8 (2)
C7—C8—C9—C100.4 (3)C27—C22—C23—C241.4 (3)
N3—C8—C9—C10177.31 (18)C19—C22—C23—C24177.32 (18)
C6—C5—C10—C90.2 (3)C22—C23—C24—C250.4 (3)
C3—C5—C10—C9176.53 (18)C23—C24—C25—C261.1 (3)
C8—C9—C10—C50.3 (3)C23—C24—C25—N6176.76 (18)
O1—C1—C11—F272.7 (2)O10—N6—C25—C24170.3 (2)
N1—C1—C11—F250.2 (2)O9—N6—C25—C2410.7 (3)
C4—C1—C11—F2167.44 (15)O10—N6—C25—C2611.8 (3)
O1—C1—C11—F3166.91 (15)O9—N6—C25—C26167.2 (2)
N1—C1—C11—F370.3 (2)C24—C25—C26—C271.4 (3)
C4—C1—C11—F347.0 (2)N6—C25—C26—C27176.41 (19)
O1—C1—C11—F147.7 (2)C25—C26—C27—C220.3 (3)
N1—C1—C11—F1170.49 (16)C23—C22—C27—C261.1 (3)
C4—C1—C11—F172.3 (2)C19—C22—C27—C26176.98 (19)
C3—C4—C12—O362.2 (2)C19—C20—C28—O858.2 (2)
C1—C4—C12—O360.6 (3)C17—C20—C28—O864.0 (2)
C3—C4—C12—C13118.2 (2)C19—C20—C28—C29121.5 (2)
C1—C4—C12—C13118.9 (2)C17—C20—C28—C29116.3 (2)
O3—C12—C13—C14167.7 (2)O8—C28—C29—C30168.8 (2)
C4—C12—C13—C1412.8 (3)C20—C28—C29—C3010.9 (3)
O3—C12—C13—S19.5 (3)O8—C28—C29—S210.4 (3)
C4—C12—C13—S1170.01 (15)C20—C28—C29—S2169.89 (14)
C16—S1—C13—C141.81 (19)C32—S2—C29—C301.98 (19)
C16—S1—C13—C12179.52 (18)C32—S2—C29—C28178.64 (19)
C12—C13—C14—C15179.3 (2)C28—C29—C30—C31179.5 (2)
S1—C13—C14—C151.9 (2)S2—C29—C30—C311.3 (2)
C13—C14—C15—C161.1 (3)C29—C30—C31—C320.4 (3)
C14—C15—C16—S10.2 (3)C30—C31—C32—S21.9 (3)
C13—S1—C16—C151.2 (2)C29—S2—C32—C312.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12A···O60.85 (3)2.28 (3)2.867 (2)126 (2)
O12—H12A···O80.85 (3)2.20 (3)2.949 (2)147 (3)
O12—H12B···O7i0.79 (3)2.11 (3)2.852 (2)156 (3)
N1—H1···O12ii0.99 (2)2.00 (2)2.969 (2)168.5 (19)
N2—H2···O12iii0.80 (3)2.15 (3)2.905 (2)159 (2)
N5—H5···O110.82 (3)2.15 (3)2.903 (2)153 (3)
N4—H4···O11iv0.84 (3)2.17 (3)2.991 (2)166 (2)
O6—H6···O2v0.82 (3)1.86 (3)2.684 (2)179 (3)
O1—H1A···O7vi0.93 (4)1.76 (4)2.684 (2)175 (4)
O11—H11A···O2vii0.81 (3)2.06 (3)2.849 (2)166 (3)
O11—H11B···O3viii0.83 (3)2.23 (3)2.968 (2)148 (3)
O11—H11B···O1viii0.83 (3)2.25 (3)2.863 (2)131 (3)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z1/2; (iii) x+3/2, y1/2, z1/2; (iv) x1/2, y+1/2, z; (v) x+1, y+1, z+1/2; (vi) x+1, y, z1/2; (vii) x+3/2, y1/2, z+1/2; (viii) x+3/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC16H12F3N3O5S·H2O
Mr433.36
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)113
a, b, c (Å)14.1640 (13), 9.136 (1), 27.459 (3)
V3)3553.3 (6)
Z8
Radiation typeMo Kα
µ (mm1)0.26
Crystal size (mm)0.24 × 0.20 × 0.18
Data collection
DiffractometerRigaku Saturn724 CCD
diffractometer
Absorption correctionMulti-scan
(CrystalClear-SM Expert; Rigaku, 2009)
Tmin, Tmax0.941, 0.956
No. of measured, independent and
observed [I > 2σ(I)] reflections
34133, 7861, 7466
Rint0.031
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.091, 1.05
No. of reflections7861
No. of parameters563
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.37, 0.27
Absolute structureFlack (1983), 3539 Friedel pairs
Absolute structure parameter0.01 (5)

Computer programs: CrystalClear-SM Expert (Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12A···O60.85 (3)2.28 (3)2.867 (2)126 (2)
O12—H12A···O80.85 (3)2.20 (3)2.949 (2)147 (3)
O12—H12B···O7i0.79 (3)2.11 (3)2.852 (2)156 (3)
N1—H1···O12ii0.99 (2)2.00 (2)2.969 (2)168.5 (19)
N2—H2···O12iii0.80 (3)2.15 (3)2.905 (2)159 (2)
N5—H5···O110.82 (3)2.15 (3)2.903 (2)153 (3)
N4—H4···O11iv0.84 (3)2.17 (3)2.991 (2)166 (2)
O6—H6···O2v0.82 (3)1.86 (3)2.684 (2)179 (3)
O1—H1A···O7vi0.93 (4)1.76 (4)2.684 (2)175 (4)
O11—H11A···O2vii0.81 (3)2.06 (3)2.849 (2)166 (3)
O11—H11B···O3viii0.83 (3)2.23 (3)2.968 (2)148 (3)
O11—H11B···O1viii0.83 (3)2.25 (3)2.863 (2)131 (3)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z1/2; (iii) x+3/2, y1/2, z1/2; (iv) x1/2, y+1/2, z; (v) x+1, y+1, z+1/2; (vi) x+1, y, z1/2; (vii) x+3/2, y1/2, z+1/2; (viii) x+3/2, y+1/2, z+1/2.
 

Acknowledgements

This work was supported by the Natural Science Foundation of Henan Province, China (grant No. 082300420110) and the Natural Science Foundation of Henan Province Education Department, China (grant No. 2007150036).

References

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COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 11| November 2010| Pages o2932-o2933
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