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organic compounds
2-[3,5-Bis(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]-4,6-bis(4-fluorophenyl)pyrimidine
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, and cDepartment of Chemistry, P. A. College of Engineering, Nadupadavu, Mangalore 574 153, India
*Correspondence e-mail: hkfun@usm.my
In the title compound, C31H20F4N4, the pyrazole ring adopts an and forms a dihedral angle of 9.91 (6)° with the adjacent pyrimidine ring. The pyrimidine ring forms dihedral angles of 9.23 (6) and 2.16 (5)° with its adjacent fluoro-substituted benzene rings, whereas these angles are 88.22 (6) and 9.66 (6)° for the pyrazole ring and its adjacent benzene rings. In the crystal, molecules are linked by C—H⋯F hydrogen bonds into ribbons along [01-1]. The crystal packing is further stabilized by C—H⋯π and by π–π interactions, with centroid–centroid distances of 3.7428 (7) and 3.7630 (6) Å.
Related literature
For related literature, see: Calabresi et al. (1975); El-Hashash et al. (1993
); Huang & Huang (2002
); Marquez & Russ (2002
); Townsend & Drach (2002
). For related structures and background to various derivatives of 4,4′-difluorochalcone, see: Fun et al. (2010a
,b
, 2011
, 2012
). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986
). For ring conformations and ring puckering analysis, see: Cremer & Pople (1975
). For reference bond lengths, see: Allen et al. (1987
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009
); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008
); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009
).
Supporting information
10.1107/S1600536812006976/fj2517sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812006976/fj2517Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812006976/fj2517Isup3.cml
A mixture of 4,4'-difluoro chalcone (2.44 g, 0.01 mol) and amino guanidine hydrochloride (0.065 g, 0.005 mol) in 25 ml e thanol was refluxed for 24 h in the presence of sodium ethoxide (2 ml). The reaction mixture was cooled to room temperature and refrigerated overnight. The solid product obtained was filtered and recrystallized from ethanol to get a yellow powder. The single crystals were grown from MDC by slow evaporation method and the yield of the compound was 49% (m.p.: 548 K).
All H atoms were positioned geometrically (C—H = 0.93, 0.97 or 0.98 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).C31H20F4N4 | Z = 2 |
Mr = 524.51 | F(000) = 540 |
Triclinic, P1 | Dx = 1.489 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1020 (1) Å | Cell parameters from 9041 reflections |
b = 10.1106 (1) Å | θ = 2.6–32.2° |
c = 12.3886 (1) Å | µ = 0.11 mm−1 |
α = 104.719 (1)° | T = 100 K |
β = 98.275 (1)° | Block, orange |
γ = 102.167 (1)° | 0.38 × 0.26 × 0.12 mm |
V = 1169.94 (2) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 8234 independent reflections |
Radiation source: fine-focus sealed tube | 6443 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ and ω scans | θmax = 32.3°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −15→15 |
Tmin = 0.959, Tmax = 0.987 | k = −15→15 |
30262 measured reflections | l = −18→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.069P)2 + 0.3191P] where P = (Fo2 + 2Fc2)/3 |
8234 reflections | (Δ/σ)max < 0.001 |
352 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C31H20F4N4 | γ = 102.167 (1)° |
Mr = 524.51 | V = 1169.94 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.1020 (1) Å | Mo Kα radiation |
b = 10.1106 (1) Å | µ = 0.11 mm−1 |
c = 12.3886 (1) Å | T = 100 K |
α = 104.719 (1)° | 0.38 × 0.26 × 0.12 mm |
β = 98.275 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 8234 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 6443 reflections with I > 2σ(I) |
Tmin = 0.959, Tmax = 0.987 | Rint = 0.029 |
30262 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.47 e Å−3 |
8234 reflections | Δρmin = −0.23 e Å−3 |
352 parameters |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K. |
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 | ||
F1 | 0.89250 (10) | 0.66229 (9) | 0.65306 (6) | 0.0382 (2) | |
F2 | 0.46323 (8) | 0.14504 (8) | −0.40779 (6) | 0.02907 (17) | |
F3 | 0.41746 (8) | 1.23828 (8) | 0.34142 (7) | 0.02823 (17) | |
F4 | 0.85454 (8) | 1.31912 (8) | −0.39439 (6) | 0.02724 (17) | |
N1 | 0.80575 (9) | 0.81293 (10) | 0.19025 (7) | 0.01531 (16) | |
N2 | 0.73090 (9) | 0.71218 (9) | −0.01349 (8) | 0.01557 (16) | |
N3 | 0.82490 (10) | 0.95255 (9) | 0.07072 (7) | 0.01658 (17) | |
N4 | 0.81772 (9) | 0.97309 (10) | −0.03568 (7) | 0.01557 (17) | |
C1 | 0.79155 (15) | 0.54528 (13) | 0.34519 (10) | 0.0270 (3) | |
H1A | 0.7638 | 0.4614 | 0.2856 | 0.032* | |
C2 | 0.82258 (16) | 0.54050 (14) | 0.45700 (11) | 0.0333 (3) | |
H2A | 0.8166 | 0.4545 | 0.4728 | 0.040* | |
C3 | 0.86230 (14) | 0.66581 (14) | 0.54355 (10) | 0.0255 (2) | |
C4 | 0.87484 (13) | 0.79565 (13) | 0.52391 (10) | 0.0235 (2) | |
H4A | 0.9030 | 0.8790 | 0.5841 | 0.028* | |
C5 | 0.84417 (12) | 0.79855 (12) | 0.41174 (10) | 0.0210 (2) | |
H5A | 0.8523 | 0.8852 | 0.3969 | 0.025* | |
C6 | 0.80148 (11) | 0.67431 (11) | 0.32098 (9) | 0.01634 (19) | |
C7 | 0.77219 (10) | 0.68237 (11) | 0.20211 (9) | 0.01509 (18) | |
C8 | 0.78434 (10) | 0.81953 (11) | 0.08231 (9) | 0.01468 (18) | |
C9 | 0.69487 (10) | 0.58258 (11) | −0.00015 (9) | 0.01464 (18) | |
C10 | 0.71525 (11) | 0.56267 (11) | 0.10790 (9) | 0.01625 (19) | |
H10A | 0.6917 | 0.4727 | 0.1169 | 0.019* | |
C11 | 0.63204 (10) | 0.46548 (11) | −0.10704 (9) | 0.01510 (18) | |
C12 | 0.61879 (12) | 0.49503 (12) | −0.21201 (9) | 0.0189 (2) | |
H12A | 0.6493 | 0.5878 | −0.2137 | 0.023* | |
C13 | 0.56065 (13) | 0.38780 (13) | −0.31367 (10) | 0.0220 (2) | |
H13A | 0.5510 | 0.4078 | −0.3832 | 0.026* | |
C14 | 0.51758 (12) | 0.25068 (12) | −0.30883 (10) | 0.0210 (2) | |
C15 | 0.52830 (12) | 0.21662 (12) | −0.20708 (10) | 0.0204 (2) | |
H15A | 0.4980 | 0.1235 | −0.2063 | 0.025* | |
C16 | 0.58535 (11) | 0.32499 (12) | −0.10650 (9) | 0.0180 (2) | |
H16A | 0.5928 | 0.3041 | −0.0373 | 0.022* | |
C17 | 0.86637 (11) | 1.08631 (11) | 0.16485 (8) | 0.01558 (18) | |
H17A | 0.9378 | 1.0824 | 0.2256 | 0.019* | |
C18 | 0.92757 (11) | 1.19104 (11) | 0.10206 (9) | 0.01707 (19) | |
H18A | 0.8960 | 1.2766 | 0.1209 | 0.020* | |
H18B | 1.0280 | 1.2159 | 0.1198 | 0.020* | |
C19 | 0.87065 (10) | 1.10600 (11) | −0.02133 (9) | 0.01479 (18) | |
C20 | 0.74267 (11) | 1.12033 (11) | 0.21187 (9) | 0.01539 (18) | |
C21 | 0.74268 (11) | 1.14552 (12) | 0.32750 (9) | 0.0183 (2) | |
H21A | 0.8178 | 1.1375 | 0.3762 | 0.022* | |
C22 | 0.63167 (12) | 1.18269 (12) | 0.37163 (9) | 0.0207 (2) | |
H22A | 0.6310 | 1.1975 | 0.4487 | 0.025* | |
C23 | 0.52321 (11) | 1.19689 (12) | 0.29813 (10) | 0.0206 (2) | |
C24 | 0.51718 (12) | 1.17086 (12) | 0.18210 (10) | 0.0211 (2) | |
H24A | 0.4418 | 1.1796 | 0.1342 | 0.025* | |
C25 | 0.62721 (11) | 1.13136 (12) | 0.13951 (9) | 0.0185 (2) | |
H25A | 0.6247 | 1.1118 | 0.0616 | 0.022* | |
C26 | 0.87168 (10) | 1.16138 (11) | −0.11947 (9) | 0.01481 (18) | |
C27 | 0.92096 (11) | 1.30626 (11) | −0.10361 (9) | 0.01704 (19) | |
H27A | 0.9579 | 1.3672 | −0.0303 | 0.020* | |
C28 | 0.91544 (12) | 1.36053 (12) | −0.19632 (10) | 0.0193 (2) | |
H28A | 0.9478 | 1.4570 | −0.1860 | 0.023* | |
C29 | 0.86081 (11) | 1.26735 (12) | −0.30369 (9) | 0.0193 (2) | |
C30 | 0.81118 (12) | 1.12320 (12) | −0.32338 (9) | 0.0197 (2) | |
H30A | 0.7745 | 1.0632 | −0.3971 | 0.024* | |
C31 | 0.81755 (11) | 1.07049 (12) | −0.23047 (9) | 0.01756 (19) | |
H31A | 0.7856 | 0.9737 | −0.2419 | 0.021* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0612 (6) | 0.0311 (4) | 0.0157 (3) | 0.0003 (4) | −0.0045 (3) | 0.0118 (3) |
F2 | 0.0366 (4) | 0.0216 (4) | 0.0209 (3) | 0.0025 (3) | 0.0030 (3) | −0.0020 (3) |
F3 | 0.0246 (3) | 0.0301 (4) | 0.0304 (4) | 0.0098 (3) | 0.0107 (3) | 0.0046 (3) |
F4 | 0.0355 (4) | 0.0302 (4) | 0.0214 (3) | 0.0086 (3) | 0.0041 (3) | 0.0180 (3) |
N1 | 0.0177 (4) | 0.0148 (4) | 0.0152 (4) | 0.0044 (3) | 0.0035 (3) | 0.0072 (3) |
N2 | 0.0183 (4) | 0.0132 (4) | 0.0158 (4) | 0.0036 (3) | 0.0034 (3) | 0.0059 (3) |
N3 | 0.0254 (4) | 0.0127 (4) | 0.0124 (4) | 0.0038 (3) | 0.0040 (3) | 0.0057 (3) |
N4 | 0.0196 (4) | 0.0151 (4) | 0.0140 (4) | 0.0047 (3) | 0.0043 (3) | 0.0071 (3) |
C1 | 0.0418 (7) | 0.0163 (5) | 0.0174 (5) | −0.0014 (5) | −0.0033 (5) | 0.0078 (4) |
C2 | 0.0533 (8) | 0.0191 (6) | 0.0211 (5) | −0.0027 (5) | −0.0061 (5) | 0.0120 (5) |
C3 | 0.0329 (6) | 0.0258 (6) | 0.0155 (5) | 0.0014 (5) | −0.0011 (4) | 0.0105 (4) |
C4 | 0.0335 (6) | 0.0210 (5) | 0.0158 (5) | 0.0087 (5) | 0.0019 (4) | 0.0052 (4) |
C5 | 0.0294 (5) | 0.0178 (5) | 0.0173 (5) | 0.0081 (4) | 0.0037 (4) | 0.0071 (4) |
C6 | 0.0180 (4) | 0.0165 (5) | 0.0152 (4) | 0.0032 (4) | 0.0021 (3) | 0.0076 (4) |
C7 | 0.0158 (4) | 0.0154 (5) | 0.0161 (4) | 0.0046 (3) | 0.0035 (3) | 0.0078 (4) |
C8 | 0.0164 (4) | 0.0135 (4) | 0.0159 (4) | 0.0041 (3) | 0.0038 (3) | 0.0068 (4) |
C9 | 0.0143 (4) | 0.0142 (4) | 0.0168 (4) | 0.0042 (3) | 0.0031 (3) | 0.0064 (4) |
C10 | 0.0184 (4) | 0.0141 (4) | 0.0170 (4) | 0.0031 (4) | 0.0024 (4) | 0.0073 (4) |
C11 | 0.0161 (4) | 0.0138 (4) | 0.0162 (4) | 0.0045 (3) | 0.0034 (3) | 0.0053 (4) |
C12 | 0.0237 (5) | 0.0164 (5) | 0.0175 (5) | 0.0055 (4) | 0.0041 (4) | 0.0066 (4) |
C13 | 0.0277 (5) | 0.0209 (5) | 0.0169 (5) | 0.0066 (4) | 0.0037 (4) | 0.0051 (4) |
C14 | 0.0212 (5) | 0.0186 (5) | 0.0196 (5) | 0.0046 (4) | 0.0034 (4) | 0.0004 (4) |
C15 | 0.0209 (5) | 0.0153 (5) | 0.0248 (5) | 0.0035 (4) | 0.0055 (4) | 0.0060 (4) |
C16 | 0.0188 (4) | 0.0159 (5) | 0.0205 (5) | 0.0045 (4) | 0.0043 (4) | 0.0070 (4) |
C17 | 0.0194 (4) | 0.0132 (4) | 0.0129 (4) | 0.0024 (4) | 0.0016 (3) | 0.0042 (3) |
C18 | 0.0210 (5) | 0.0141 (4) | 0.0149 (4) | 0.0014 (4) | 0.0030 (4) | 0.0052 (4) |
C19 | 0.0169 (4) | 0.0140 (4) | 0.0142 (4) | 0.0033 (3) | 0.0033 (3) | 0.0060 (4) |
C20 | 0.0187 (4) | 0.0121 (4) | 0.0142 (4) | 0.0017 (3) | 0.0020 (3) | 0.0046 (3) |
C21 | 0.0213 (5) | 0.0188 (5) | 0.0143 (4) | 0.0041 (4) | 0.0025 (4) | 0.0052 (4) |
C22 | 0.0243 (5) | 0.0201 (5) | 0.0165 (5) | 0.0044 (4) | 0.0054 (4) | 0.0040 (4) |
C23 | 0.0197 (5) | 0.0167 (5) | 0.0245 (5) | 0.0040 (4) | 0.0065 (4) | 0.0042 (4) |
C24 | 0.0198 (5) | 0.0212 (5) | 0.0212 (5) | 0.0050 (4) | 0.0012 (4) | 0.0064 (4) |
C25 | 0.0220 (5) | 0.0181 (5) | 0.0145 (4) | 0.0037 (4) | 0.0020 (4) | 0.0056 (4) |
C26 | 0.0161 (4) | 0.0142 (4) | 0.0156 (4) | 0.0038 (3) | 0.0038 (3) | 0.0069 (4) |
C27 | 0.0193 (4) | 0.0156 (5) | 0.0172 (4) | 0.0035 (4) | 0.0037 (4) | 0.0073 (4) |
C28 | 0.0220 (5) | 0.0169 (5) | 0.0215 (5) | 0.0042 (4) | 0.0053 (4) | 0.0104 (4) |
C29 | 0.0208 (5) | 0.0235 (5) | 0.0188 (5) | 0.0076 (4) | 0.0046 (4) | 0.0138 (4) |
C30 | 0.0238 (5) | 0.0208 (5) | 0.0152 (4) | 0.0057 (4) | 0.0030 (4) | 0.0070 (4) |
C31 | 0.0209 (5) | 0.0158 (5) | 0.0164 (4) | 0.0040 (4) | 0.0038 (4) | 0.0061 (4) |
F1—C3 | 1.3582 (12) | C13—H13A | 0.9300 |
F2—C14 | 1.3561 (13) | C14—C15 | 1.3844 (16) |
F3—C23 | 1.3577 (13) | C15—C16 | 1.3852 (16) |
F4—C29 | 1.3538 (11) | C15—H15A | 0.9300 |
N1—C7 | 1.3429 (13) | C16—H16A | 0.9300 |
N1—C8 | 1.3445 (12) | C17—C20 | 1.5193 (15) |
N2—C8 | 1.3386 (14) | C17—C18 | 1.5458 (14) |
N2—C9 | 1.3428 (13) | C17—H17A | 0.9800 |
N3—C8 | 1.3712 (13) | C18—C19 | 1.5090 (14) |
N3—N4 | 1.3798 (11) | C18—H18A | 0.9700 |
N3—C17 | 1.4777 (14) | C18—H18B | 0.9700 |
N4—C19 | 1.2929 (13) | C19—C26 | 1.4625 (13) |
C1—C2 | 1.3909 (16) | C20—C21 | 1.3897 (14) |
C1—C6 | 1.3980 (15) | C20—C25 | 1.4076 (14) |
C1—H1A | 0.9300 | C21—C22 | 1.3955 (16) |
C2—C3 | 1.3738 (19) | C21—H21A | 0.9300 |
C2—H2A | 0.9300 | C22—C23 | 1.3769 (16) |
C3—C4 | 1.3784 (17) | C22—H22A | 0.9300 |
C4—C5 | 1.3886 (15) | C23—C24 | 1.3839 (16) |
C4—H4A | 0.9300 | C24—C25 | 1.3864 (16) |
C5—C6 | 1.3938 (16) | C24—H24A | 0.9300 |
C5—H5A | 0.9300 | C25—H25A | 0.9300 |
C6—C7 | 1.4861 (14) | C26—C27 | 1.3966 (14) |
C7—C10 | 1.3975 (15) | C26—C31 | 1.4015 (15) |
C9—C10 | 1.3964 (13) | C27—C28 | 1.3921 (14) |
C9—C11 | 1.4842 (15) | C27—H27A | 0.9300 |
C10—H10A | 0.9300 | C28—C29 | 1.3763 (16) |
C11—C12 | 1.4008 (14) | C28—H28A | 0.9300 |
C11—C16 | 1.4013 (14) | C29—C30 | 1.3824 (16) |
C12—C13 | 1.3898 (16) | C30—C31 | 1.3848 (14) |
C12—H12A | 0.9300 | C30—H30A | 0.9300 |
C13—C14 | 1.3822 (16) | C31—H31A | 0.9300 |
C7—N1—C8 | 115.54 (9) | C11—C16—H16A | 119.4 |
C8—N2—C9 | 116.12 (9) | N3—C17—C20 | 111.40 (8) |
C8—N3—N4 | 121.04 (9) | N3—C17—C18 | 100.36 (8) |
C8—N3—C17 | 125.56 (8) | C20—C17—C18 | 112.75 (8) |
N4—N3—C17 | 113.14 (8) | N3—C17—H17A | 110.6 |
C19—N4—N3 | 107.85 (8) | C20—C17—H17A | 110.6 |
C2—C1—C6 | 121.00 (11) | C18—C17—H17A | 110.6 |
C2—C1—H1A | 119.5 | C19—C18—C17 | 101.79 (8) |
C6—C1—H1A | 119.5 | C19—C18—H18A | 111.4 |
C3—C2—C1 | 118.41 (11) | C17—C18—H18A | 111.4 |
C3—C2—H2A | 120.8 | C19—C18—H18B | 111.4 |
C1—C2—H2A | 120.8 | C17—C18—H18B | 111.4 |
F1—C3—C2 | 118.88 (10) | H18A—C18—H18B | 109.3 |
F1—C3—C4 | 118.40 (11) | N4—C19—C26 | 120.47 (9) |
C2—C3—C4 | 122.71 (10) | N4—C19—C18 | 113.62 (8) |
C3—C4—C5 | 118.12 (11) | C26—C19—C18 | 125.90 (9) |
C3—C4—H4A | 120.9 | C21—C20—C25 | 118.57 (10) |
C5—C4—H4A | 120.9 | C21—C20—C17 | 120.88 (9) |
C4—C5—C6 | 121.40 (10) | C25—C20—C17 | 120.52 (9) |
C4—C5—H5A | 119.3 | C20—C21—C22 | 120.97 (10) |
C6—C5—H5A | 119.3 | C20—C21—H21A | 119.5 |
C5—C6—C1 | 118.34 (10) | C22—C21—H21A | 119.5 |
C5—C6—C7 | 119.64 (9) | C23—C22—C21 | 118.33 (10) |
C1—C6—C7 | 121.99 (10) | C23—C22—H22A | 120.8 |
N1—C7—C10 | 121.61 (9) | C21—C22—H22A | 120.8 |
N1—C7—C6 | 115.61 (9) | F3—C23—C22 | 118.54 (10) |
C10—C7—C6 | 122.78 (9) | F3—C23—C24 | 118.54 (10) |
N2—C8—N1 | 127.67 (9) | C22—C23—C24 | 122.93 (11) |
N2—C8—N3 | 117.20 (9) | C23—C24—C25 | 117.86 (10) |
N1—C8—N3 | 115.12 (9) | C23—C24—H24A | 121.1 |
N2—C9—C10 | 121.18 (10) | C25—C24—H24A | 121.1 |
N2—C9—C11 | 115.31 (9) | C24—C25—C20 | 121.28 (10) |
C10—C9—C11 | 123.50 (9) | C24—C25—H25A | 119.4 |
C9—C10—C7 | 117.85 (9) | C20—C25—H25A | 119.4 |
C9—C10—H10A | 121.1 | C27—C26—C31 | 119.09 (9) |
C7—C10—H10A | 121.1 | C27—C26—C19 | 120.48 (9) |
C12—C11—C16 | 118.56 (10) | C31—C26—C19 | 120.37 (9) |
C12—C11—C9 | 119.53 (9) | C28—C27—C26 | 120.75 (10) |
C16—C11—C9 | 121.91 (9) | C28—C27—H27A | 119.6 |
C13—C12—C11 | 120.98 (10) | C26—C27—H27A | 119.6 |
C13—C12—H12A | 119.5 | C29—C28—C27 | 118.12 (10) |
C11—C12—H12A | 119.5 | C29—C28—H28A | 120.9 |
C14—C13—C12 | 118.31 (10) | C27—C28—H28A | 120.9 |
C14—C13—H13A | 120.8 | F4—C29—C28 | 118.58 (10) |
C12—C13—H13A | 120.8 | F4—C29—C30 | 118.33 (10) |
F2—C14—C13 | 118.70 (10) | C28—C29—C30 | 123.09 (10) |
F2—C14—C15 | 118.61 (10) | C29—C30—C31 | 118.24 (10) |
C13—C14—C15 | 122.68 (11) | C29—C30—H30A | 120.9 |
C14—C15—C16 | 118.22 (10) | C31—C30—H30A | 120.9 |
C14—C15—H15A | 120.9 | C30—C31—C26 | 120.72 (10) |
C16—C15—H15A | 120.9 | C30—C31—H31A | 119.6 |
C15—C16—C11 | 121.23 (10) | C26—C31—H31A | 119.6 |
C15—C16—H16A | 119.4 | ||
C8—N3—N4—C19 | −175.75 (9) | C13—C14—C15—C16 | −0.36 (17) |
C17—N3—N4—C19 | 9.72 (12) | C14—C15—C16—C11 | −0.41 (16) |
C6—C1—C2—C3 | 0.5 (2) | C12—C11—C16—C15 | 0.57 (16) |
C1—C2—C3—F1 | 179.84 (13) | C9—C11—C16—C15 | −179.29 (10) |
C1—C2—C3—C4 | −1.1 (2) | C8—N3—C17—C20 | −71.63 (12) |
F1—C3—C4—C5 | 179.83 (11) | N4—N3—C17—C20 | 102.61 (9) |
C2—C3—C4—C5 | 0.8 (2) | C8—N3—C17—C18 | 168.78 (10) |
C3—C4—C5—C6 | 0.17 (19) | N4—N3—C17—C18 | −16.98 (11) |
C4—C5—C6—C1 | −0.74 (18) | N3—C17—C18—C19 | 16.42 (10) |
C4—C5—C6—C7 | −178.88 (10) | C20—C17—C18—C19 | −102.19 (10) |
C2—C1—C6—C5 | 0.4 (2) | N3—N4—C19—C26 | −177.14 (9) |
C2—C1—C6—C7 | 178.49 (12) | N3—N4—C19—C18 | 2.85 (12) |
C8—N1—C7—C10 | −1.71 (14) | C17—C18—C19—N4 | −13.07 (12) |
C8—N1—C7—C6 | 177.45 (9) | C17—C18—C19—C26 | 166.92 (10) |
C5—C6—C7—N1 | 7.77 (14) | N3—C17—C20—C21 | 125.54 (10) |
C1—C6—C7—N1 | −170.30 (11) | C18—C17—C20—C21 | −122.51 (10) |
C5—C6—C7—C10 | −173.07 (10) | N3—C17—C20—C25 | −56.48 (12) |
C1—C6—C7—C10 | 8.86 (17) | C18—C17—C20—C25 | 55.47 (13) |
C9—N2—C8—N1 | −0.24 (16) | C25—C20—C21—C22 | −0.77 (16) |
C9—N2—C8—N3 | 178.53 (9) | C17—C20—C21—C22 | 177.25 (10) |
C7—N1—C8—N2 | 1.70 (15) | C20—C21—C22—C23 | −1.41 (17) |
C7—N1—C8—N3 | −177.10 (9) | C21—C22—C23—F3 | −177.53 (10) |
N4—N3—C8—N2 | −3.49 (14) | C21—C22—C23—C24 | 2.47 (18) |
C17—N3—C8—N2 | 170.33 (9) | F3—C23—C24—C25 | 178.77 (10) |
N4—N3—C8—N1 | 175.44 (9) | C22—C23—C24—C25 | −1.23 (18) |
C17—N3—C8—N1 | −10.74 (15) | C23—C24—C25—C20 | −1.09 (17) |
C8—N2—C9—C10 | −1.20 (14) | C21—C20—C25—C24 | 2.06 (16) |
C8—N2—C9—C11 | 178.28 (9) | C17—C20—C25—C24 | −175.97 (10) |
N2—C9—C10—C7 | 1.11 (15) | N4—C19—C26—C27 | 175.99 (10) |
C11—C9—C10—C7 | −178.34 (9) | C18—C19—C26—C27 | −4.00 (16) |
N1—C7—C10—C9 | 0.45 (15) | N4—C19—C26—C31 | −1.19 (15) |
C6—C7—C10—C9 | −178.66 (9) | C18—C19—C26—C31 | 178.82 (10) |
N2—C9—C11—C12 | 2.11 (14) | C31—C26—C27—C28 | 0.63 (16) |
C10—C9—C11—C12 | −178.42 (10) | C19—C26—C27—C28 | −176.58 (10) |
N2—C9—C11—C16 | −178.03 (9) | C26—C27—C28—C29 | −0.32 (16) |
C10—C9—C11—C16 | 1.44 (16) | C27—C28—C29—F4 | 179.78 (10) |
C16—C11—C12—C13 | 0.02 (16) | C27—C28—C29—C30 | 0.15 (17) |
C9—C11—C12—C13 | 179.89 (10) | F4—C29—C30—C31 | −179.93 (10) |
C11—C12—C13—C14 | −0.74 (17) | C28—C29—C30—C31 | −0.31 (17) |
C12—C13—C14—F2 | −178.73 (10) | C29—C30—C31—C26 | 0.62 (16) |
C12—C13—C14—C15 | 0.93 (18) | C27—C26—C31—C30 | −0.79 (16) |
F2—C14—C15—C16 | 179.29 (10) | C19—C26—C31—C30 | 176.43 (10) |
Cg5 is the centroid of the C20–C25 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···F4i | 0.93 | 2.43 | 3.2759 (16) | 151 |
C31—H31A···F3ii | 0.93 | 2.53 | 3.3208 (14) | 143 |
C1—H1A···Cg5iii | 0.93 | 2.98 | 3.7144 (14) | 137 |
C15—H15A···Cg5iv | 0.93 | 2.74 | 3.6459 (13) | 166 |
Symmetry codes: (i) x, y−1, z+1; (ii) −x+1, −y+2, −z; (iii) x, y−1, z; (iv) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C31H20F4N4 |
Mr | 524.51 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 10.1020 (1), 10.1106 (1), 12.3886 (1) |
α, β, γ (°) | 104.719 (1), 98.275 (1), 102.167 (1) |
V (Å3) | 1169.94 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.38 × 0.26 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.959, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30262, 8234, 6443 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.751 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.132, 1.04 |
No. of reflections | 8234 |
No. of parameters | 352 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.23 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
Cg5 is the centroid of the C20–C25 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···F4i | 0.9300 | 2.4300 | 3.2759 (16) | 151.00 |
C31—H31A···F3ii | 0.9300 | 2.5300 | 3.3208 (14) | 143.00 |
C1—H1A···Cg5iii | 0.9300 | 2.98 | 3.7144 (14) | 137 |
C15—H15A···Cg5iv | 0.9300 | 2.74 | 3.6459 (13) | 166 |
Symmetry codes: (i) x, y−1, z+1; (ii) −x+1, −y+2, −z; (iii) x, y−1, z; (iv) −x+1, −y+1, −z. |
Footnotes
‡Thomson Reuters ResearcherID: A-3561-2009.
Acknowledgements
HKF and TSC thank the Universiti Sains Malaysia (USM) for a Research University Grant (No. 1001/PFIZIK/811160). TSC thanks the Malaysian Government and USM for the award of the post of Research Officer under the Research University Grant No. 1001/PSKBP/8630013. BN thanks the UGC for financial assistance through SAP and BSR one-time grant for the purchase of chemicals. SS thanks Mangalore University for the research facilities.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The importance of pyrimidines and analogous compounds in pharmaceutical and biological fields is well known (Townsend & Drach, 2002). Some substituted pyrimidines and their derivatives have been reported to possess antimicrobial and antifungal activities (El-Hashash et al., 1993). It has incidental antiviral activity against herpes and vaccinia infections (Calabresi et al., 1975). With the development of clinically useful pyrimidine-based antitumor (Huang & Huang, 2002) and antiviral (Marquez & Russ, 2002) drugs, there has been noticeable interest in synthetic manipulations of pyrimidines. In view of the biological importance of pyrimidines and in continuation of our work on synthesis of various derivatives of 4,4'-difluoro chalcone (Fun et al., 2010a,b;2011;2012), the title compound is prepared and its crystal structure is reported.
The molecular structure of the title compound is shown in Fig. 1. The pyrazole ring (N3/N4/C17–C19) adopts an envelope conformation [puckering parameters Q = 0.1757 (11) Å and ϕ = 135.8 (4)° (Cremer & Pople, 1975)] and forms a dihedral angle of 9.91 (6)° with the adjacent pyrimidine ring (N1/N2/C7–C10) (maximum deviation = 0.011 (1) Å at atom N1). The pyrimidine ring forms dihedral angles of 9.23 (6) and 2.16 (5)° with its adjacent fluoro-substituted benzene rings (C1–C6 & C11–C16, respectively), whereas for pyrazole ring these angles are 88.22 (6) and 9.66 (6)° (C20–C25 & C26–C31, respectively). In the crystal packing, the molecules are linked by intermolecular C—H···F hydrogen bonds into ribbons along [01–1]. The crystal packing is further stabilized by C–H···π interactions (Table 1), involving Cg5 which is the centroid of C20–C25 ring. π–π interactions are also observed with Cg2···Cg4 = 3.7428 (7) Å (symmetry code = 1-X,1-Y,-Z) and Cg2···Cg6 = 3.7630 (6) Å (symmetry code = 2-X,2-Y,-Z), where Cg2, Cg4 and Cg6 are the centroids of N1/N2/C7–C10, C11–C16 and C26–C31 rings, respectively.