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In the current study, the crystal structure of 1-(3-nitrophenyl)-2,2,2-trifluoro­ethanone (A1) and (E)-4-((4-fluorophenyl) diazenyl)phenol (A2) has been analyzed for the characterization of the presence of a `unique' and `rare' intermolecular C(sp3/sp2)—F...O contact, which has been observed to play a significant role in the crystal packing. Theoretical charge-density calculations have been performed to study the nature and strength associated with the existence of this intermolecular F...O contact, wherein the F atom is attached to an sp3-hybridized C atom in the case of A1 and to an sp2 hybridized carbon in the case of A2. The crystal packing of the former contains two `electronically different' Csp3—F...O contacts which are present across and in between the layers of molecules. In the latter case, it is characterized by the presence of a very `short' (2.708 Å) and `highly directional' (168° at ∠C4—F1...O1 and 174° at ∠C10—O1...F1) Csp2—F...O contact. According to the Cambridge Structural Database (CSD) study, it is a rare example in molecular crystals. Topological features of F...O contacts in the solid state were compared with the gas-phase models. The two-dimensional and three-dimensional static deformation density obtained from theoretical multipole modeling confirm the presence of a charge depleted region on the F atoms. Minimization of the electrostatic repulsion between like charges are observed through subtle arrangements in the electronic environment in two of the short intermolecular F...O contacts. These contacts were investigated using inputs from pair energy decomposition analysis, Bader's quantum theory of atoms in molecules (QTAIM), Hirshfeld surface analysis, delocalization index, reduced density gradient (RDG) plot, electrostatic potential surface and distributed atomic polarizability. The intermolecular energy decomposition (PIXEL) and RDG–NCI (non-covalent interaction) analysis of the F...O contacts establish the interaction to be dispersive in nature. The mutual polarization of an O atom by fluorine and vice versa provides real physical insights into the role of atomic polarizability in interacting atoms in molecules in crystals.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520616017492/ao5019sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520616017492/ao5019Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520616017492/ao5019sup3.pdf
Supporting figures and tables

CCDC reference: 1477385

Computing details top

Program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014).

(I) top
Crystal data top
C12H9FN2OF(000) = 448
Mr = 216.21Dx = 1.446 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.7681 (7) ÅCell parameters from 1894 reflections
b = 10.5358 (7) Åθ = 2.4–27.0°
c = 10.5740 (8) ŵ = 0.11 mm1
β = 114.134 (4)°T = 100 K
V = 993.10 (13) Å3Plate, yellow
Z = 40.20 × 0.10 × 0.03 mm
Data collection top
Bruker APEX-II CCD
diffractometer
1385 reflections with I > 2σ(I)
φ and ω scansRint = 0.058
Absorption correction: multi-scan
SADABS
θmax = 27.1°, θmin = 2.4°
Tmin = 0.609, Tmax = 0.746h = 1112
6854 measured reflectionsk = 1313
2194 independent reflectionsl = 139
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.161 w = 1/[σ2(Fo2) + (0.0489P)2 + 0.217P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
2194 reflectionsΔρmax = 0.42 e Å3
146 parametersΔρmin = 0.26 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.97315 (17)0.21736 (14)0.40883 (15)0.0294 (4)
H10.95870.18830.33040.044*
F10.19694 (14)1.04951 (13)0.44854 (14)0.0348 (4)
N10.5729 (2)0.65103 (17)0.46831 (19)0.0266 (5)
N20.5703 (2)0.60640 (18)0.35838 (19)0.0297 (5)
C40.2860 (2)0.95074 (19)0.4487 (2)0.0207 (5)
C50.2679 (2)0.8957 (2)0.3242 (2)0.0217 (5)
H50.19270.92580.23970.026*
C60.3599 (2)0.7970 (2)0.3240 (2)0.0230 (5)
H60.34950.75880.23920.028*
C10.4696 (2)0.7530 (2)0.4505 (2)0.0229 (5)
C70.6750 (2)0.5049 (2)0.3782 (2)0.0246 (5)
C80.7878 (3)0.4709 (2)0.5063 (2)0.0299 (6)
H80.79680.51470.58780.036*
C90.8857 (2)0.3738 (2)0.5146 (2)0.0287 (6)
H90.96150.35010.60180.034*
C100.8731 (2)0.3107 (2)0.3946 (2)0.0230 (5)
C30.3918 (2)0.9082 (2)0.5743 (2)0.0247 (5)
H30.40130.94640.65890.030*
C20.4825 (2)0.8092 (2)0.5734 (2)0.0248 (5)
H20.55580.77860.65870.030*
C120.6636 (3)0.4416 (2)0.2595 (2)0.0273 (5)
H120.58810.46530.17220.033*
C110.7613 (2)0.3442 (2)0.2674 (2)0.0259 (5)
H110.75200.30020.18590.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0341 (9)0.0270 (9)0.0210 (8)0.0159 (7)0.0051 (7)0.0044 (7)
F10.0325 (7)0.0335 (8)0.0347 (8)0.0111 (6)0.0100 (6)0.0055 (6)
N10.0289 (10)0.0258 (11)0.0266 (10)0.0043 (8)0.0129 (8)0.0034 (8)
N20.0352 (11)0.0302 (11)0.0243 (10)0.0039 (9)0.0127 (8)0.0018 (8)
C40.0175 (10)0.0174 (11)0.0278 (11)0.0024 (9)0.0098 (9)0.0011 (9)
C50.0213 (10)0.0218 (12)0.0204 (10)0.0004 (9)0.0068 (8)0.0013 (9)
C60.0244 (11)0.0219 (12)0.0251 (11)0.0028 (9)0.0126 (9)0.0050 (9)
C10.0198 (10)0.0165 (11)0.0321 (12)0.0015 (9)0.0102 (9)0.0017 (9)
C70.0258 (11)0.0180 (11)0.0334 (12)0.0025 (10)0.0155 (10)0.0041 (9)
C80.0348 (13)0.0288 (13)0.0311 (12)0.0012 (11)0.0184 (10)0.0078 (10)
C90.0282 (12)0.0320 (13)0.0224 (11)0.0028 (10)0.0068 (9)0.0037 (10)
C100.0256 (11)0.0175 (11)0.0269 (11)0.0034 (9)0.0116 (9)0.0011 (9)
C30.0236 (11)0.0286 (13)0.0209 (11)0.0004 (10)0.0080 (9)0.0019 (9)
C20.0224 (11)0.0252 (12)0.0233 (11)0.0036 (9)0.0059 (9)0.0047 (9)
C120.0301 (12)0.0279 (13)0.0240 (11)0.0063 (10)0.0112 (9)0.0055 (9)
C110.0286 (12)0.0255 (12)0.0228 (11)0.0042 (10)0.0097 (9)0.0002 (9)
Geometric parameters (Å, º) top
O1—C101.351 (2)C7—C121.385 (3)
O1—H10.8400C7—C81.399 (3)
F1—C41.356 (2)C8—C91.378 (3)
N1—N21.245 (3)C8—H80.9500
N1—C11.432 (3)C9—C101.393 (3)
N2—C71.435 (3)C9—H90.9500
C4—C51.382 (3)C10—C111.387 (3)
C4—C31.382 (3)C3—C21.371 (3)
C5—C61.375 (3)C3—H30.9500
C5—H50.9500C2—H20.9500
C6—C11.407 (3)C12—C111.380 (3)
C6—H60.9500C12—H120.9500
C1—C21.386 (3)C11—H110.9500
C10—O1—H1109.5C7—C8—H8119.9
N2—N1—C1114.60 (19)C8—C9—C10119.7 (2)
N1—N2—C7113.85 (18)C8—C9—H9120.2
F1—C4—C5119.25 (18)C10—C9—H9120.2
F1—C4—C3118.48 (19)O1—C10—C11122.7 (2)
C5—C4—C3122.26 (19)O1—C10—C9117.09 (19)
C6—C5—C4119.31 (19)C11—C10—C9120.2 (2)
C6—C5—H5120.3C2—C3—C4118.1 (2)
C4—C5—H5120.3C2—C3—H3121.0
C5—C6—C1119.5 (2)C4—C3—H3121.0
C5—C6—H6120.3C3—C2—C1121.4 (2)
C1—C6—H6120.3C3—C2—H2119.3
C2—C1—C6119.5 (2)C1—C2—H2119.3
C2—C1—N1114.09 (18)C11—C12—C7120.4 (2)
C6—C1—N1126.42 (19)C11—C12—H12119.8
C12—C7—C8119.6 (2)C7—C12—H12119.8
C12—C7—N2116.01 (19)C12—C11—C10119.9 (2)
C8—C7—N2124.4 (2)C12—C11—H11120.1
C9—C8—C7120.2 (2)C10—C11—H11120.1
C9—C8—H8119.9
C1—N1—N2—C7179.63 (16)C8—C9—C10—O1179.3 (2)
F1—C4—C5—C6178.89 (18)C8—C9—C10—C110.8 (3)
C3—C4—C5—C61.5 (3)F1—C4—C3—C2179.27 (19)
C4—C5—C6—C10.7 (3)C5—C4—C3—C21.1 (3)
C5—C6—C1—C20.4 (3)C4—C3—C2—C10.1 (3)
C5—C6—C1—N1179.44 (19)C6—C1—C2—C30.8 (3)
N2—N1—C1—C2174.6 (2)N1—C1—C2—C3179.95 (19)
N2—N1—C1—C66.3 (3)C8—C7—C12—C110.9 (3)
N1—N2—C7—C12172.2 (2)N2—C7—C12—C11178.7 (2)
N1—N2—C7—C810.1 (3)C7—C12—C11—C100.9 (3)
C12—C7—C8—C90.8 (3)O1—C10—C11—C12179.2 (2)
N2—C7—C8—C9178.4 (2)C9—C10—C11—C120.9 (3)
C7—C8—C9—C100.7 (3)
 

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