research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 5| May 2016| Pages 716-719

Crystal structure and Hirshfeld surface analysis of (E)-3-(2-chloro-6-fluoro­phen­yl)-1-(3-fluoro-4-meth­­oxy­phen­yl)prop-2-en-1-one

CROSSMARK_Color_square_no_text.svg

aSchool of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
*Correspondence e-mail: arazaki@usm.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 13 April 2016; accepted 18 April 2016; online 22 April 2016)

In the title chalcone derivative, C16H11ClF2O2, the enone group adopts an E conformation. The dihedral angle between the benzene rings is 0.47 (9)° and an intra­molecular C—H⋯F hydrogen bond closes an S(6) ring. In the crystal, mol­ecules are linked into a three-dimensional network by C—H⋯O hydrogen bonds and aromatic ππ stacking inter­actions are also observed [centroid–centroid separation = 3.5629 (18) Å]. The inter­molecular inter­actions in the crystal structure were qu­anti­fied and analysed using Hirshfeld surface analysis.

1. Chemical context

Chalcone derivatives possess a wide range of biological properties such as anti­bacterial (Jarag et al., 2011[Jarag, K. J., Pinjari, D. V., Pandit, A. B. & Shankarling, G. S. (2011). Ultrason. Sonochem. 18, 617-623.]), anti-inflammatory (Mukherjee et al., 2001[Mukherjee, S., Kumar, V., Prasad, A. K., Raj, H. G., Bracke, M. E., Olsen, C. E., Jain, S. C. & Parmar, V. S. (2001). Bioorg. Med. Chem. 9, 337-345.]) and anti-oxidant (Arty et al., 2000[Arty, I. S., Timmerman, H., Samhoedi, M., Sastrohamidjojo, Sugiyanto & van der Goot, H. (2000). Eur. J. Med. Chem. 35, 449-457.]) activities. As part of our ongoing studies on chalcone derivatives, we hereby report the synthesis and crystal structure of the title compound, (I)[link].

[Scheme 1]

2. Structural commentary

The mol­ecular structure of (I)[link] is shown in Fig. 1[link]. The enone moiety (O1/C7–C9) adopts an E-conformation with respect to C7=C8 bond. The mol­ecule is slightly twisted at the C9—-C10 bond with a C8—C9—C10—C15 torsion angle of −2.2 (4)° and a maximum deviation of 0.193 (16) Å for atom O1. The dihedral angle between the terminal benzene rings (C1–C6 and C10–C15) is 0.47 (9)°. The least-squares plane through the enone moiety (O1/C7–C9) makes dihedral angles of 2.87 (14) and 3.33 (14)° with the C1–C6 and C10–C15 benzene rings, respectively. An intra­molecular C8—H8A⋯F1 hydrogen bond (Table 1[link]) is observed, generating an S(6) ring motif. The bond lengths and angles are comparable with the equivalent data for previously reported structures; (Razak et al., 2009[Razak, I. A., Fun, H.-K., Ngaini, Z., Rahman, N. I. A. & Hussain, H. (2009). Acta Cryst. E65, o1439-o1440.]; Harrison et al., 2006a[Harrison, W. T. A., Yathirajan, H. S., Anilkumar, H. G., Sarojini, B. K. & Narayana, B. (2006a). Acta Cryst. E62, o3251-o3253.]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2A⋯O1i 0.93 2.50 3.391 (4) 162
C3—H3A⋯O2ii 0.93 2.52 3.441 (4) 171
C8—H8A⋯F1 0.93 2.21 2.842 (4) 124
Symmetry codes: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (ii) [x-{\script{3\over 2}}, y+{\script{1\over 2}}, z].
[Figure 1]
Figure 1
The structure of the title compound, showing 50% probability displacement ellipsoids. The intra­molecular C—H⋯F hydrogen bond is shown as a dashed line.

3. Supra­molecular features

In the crystal, mol­ecules are linked into a three-dimensional network via C2—H2A⋯O1 (x − [{1\over 2}], −y + [{3\over 2}], z + [{1\over 2}]) and C3—H3A⋯O2 (x − [{3\over 2}], y + [{1\over 2}], z) hydrogen bonds (Table 1[link]), as shown in Fig. 2[link]. The crystal structure also features ππ inter­actions [Cg1⋯Cg2 (−1 + x, y, z), centroid-to-centroid distance = 3.5629 (18) Å, where Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively].

[Figure 2]
Figure 2
The packing in (I)[link] showing C—H⋯O and ππ inter­actions as dashed lines.

4. Analysis of the Hirshfeld Surfaces

Crystal Explorer 3.1(Wolff et al., 2012[Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). Crystal Explorer. University of Western Australia.]) was used to analyse the close contacts in the crystal of (I)[link], which can be summarized with fingerprint plots mapped over dnorm, electrostatic potential, shape index and curvedness. The electrostatic potentials were calculated using TONTO (Spackman et al., 2008[Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377-388.]; Jayatilaka et al., 2005[Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). TONTO. https://hirshfeldsurface.net/]) integrated within Crystal Explorer. The electrostatic potentials were mapped on Hirshfeld surfaces using the STO-3G basis set at Hartree–Fock level theory over a range ±0.03 au.

The strong C—H⋯O inter­actions are visualized as bright-red spots between the respective donor and acceptor atoms on the Hirshfeld surfaces mapped over dnorm (Fig. 3[link]a) with neighbouring mol­ecules connected by C2—H2A⋯O1 and C3—H3A⋯O2 hydrogen bonds. This finding is corroborated by Hirshfeld surfaces mapped over the electrostatic potential (Fig. 3[link]b) showing the negative potential around the oxygen atoms as light-red clouds and the positive potential around hydrogen atoms as light-blue clouds.

[Figure 3]
Figure 3
(a) dnorm mapped on Hirshfeld surfaces for visualizing the inter­molecular inter­actions of the title chalcone compound. (b) Hirshfeld surfaces mapped over the electrostatic potential. Dotted lines (green) represent hydrogen bonds.

Significant inter­molecular inter­actions are plotted in Fig. 4[link]: the H⋯H inter­actions appear as the largest region of the fingerprint plot with a high concentration in the middle region, shown in light blue, at de = di ∼1.4 Å (Fig. 4[link]a) with overall Hirshfeld surfaces of 27.5%. The contribution from the O⋯H/H⋯O contacts, corresponding to C—H⋯O inter­actions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond inter­action having almost the same de + di ∼2.3 Å (Fig. 4[link]b).

[Figure 4]
Figure 4
Fingerprint plots for the title chalcone compound, broken down into contributions from specific pairs of atom types. For each plot, the grey shadow is an outline of the complete fingerprint plot. Surfaces to the right highlight the relevant surface patches associated with the specific contacts, with dnorm mapped in the same manner as Fig. 3[link]a.

The C⋯C contacts, which refer to π–·π stacking inter­actions, contribute 13.7% of the Hirshfeld surfaces. This appears as a distinct triangle at around de = di ∼1.8 Å (Fig. 4[link]c). The presence of the ππ stacking inter­actions is also indicated by the appearance of red and blue triangles on the shape-indexed surfaces, identified with black arrows in Fig. 5[link], and in the flat regions on the Hirshfeld surfaces mapped over curvedness in Fig. 6[link].

[Figure 5]
Figure 5
Hirshfeld surfaces mapped over the shape index of the title chalcone compound.
[Figure 6]
Figure 6
Hirshfeld surfaces mapped over curvedness of the title chalcone compound.

5. Synthesis and crystallization

A mixture of 3-fluoro-4-meth­oxy­aceto­phenone (0.1 mol, 0.08 g) and 2-chloro-6-fluoro­benzaldehyde (0.1 mol, 0.08 g) was dissolved in methanol (20 ml). A catalytic amount of NaOH (5 ml, 20%) was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 5–6 h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50 ml) and the resulting crude solid was collected by filtration. Brownish blocks of (I)[link] were grown from an acetone solution by slow evaporation.

6. Refinement details

Crystal data collection and structure refinement details are summarized in Table 2[link]. All H atoms were positioned geometrically (C—H = 0.93 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C). In the final refinement, the most disagreeable reflection (020) was omitted.

Table 2
Experimental details

Crystal data
Chemical formula C16H11ClF2O2
Mr 308.70
Crystal system, space group Monoclinic, Cc
Temperature (K) 294
a, b, c (Å) 9.0832 (13), 11.1072 (13), 13.9564 (17)
β (°) 102.027 (3)
V3) 1377.1 (3)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.30
Crystal size (mm) 0.45 × 0.17 × 0.13
 
Data collection
Diffractometer Bruker SMART APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.791, 0.889
No. of measured, independent and observed [I > 2σ(I)] reflections 14473, 4003, 3111
Rint 0.031
(sin θ/λ)max−1) 0.705
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.116, 1.05
No. of reflections 4003
No. of parameters 191
No. of restraints 2
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.20, −0.27
Absolute structure Flack x determined using 1298 quotients [(I+)−(I)]/[(I+)+(I)] Parsons et al. (2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])
Absolute structure parameter 0.08 (2)
Computer programs: APEX2 and SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXTL (Sheldrick 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Chemical context top

Chalcone derivatives possesses a wide range of biological properties such as anti­bacterial (Jarag et al., 2011), anti-inflammatory (Mukherjee et al., 2001) and anti-oxidant (Arty et al., 2000) activities. As part of our ongoing studies on chalcone derivatives, we hereby report the synthesis and crystal structure of the title compound, (I).

Structural commentary top

The molecular structure of (I) is shown in Fig.1. The enone moiety (O1/C7–C9) adopts an E-conformation with respect to C7C8 bond. The molecule is slightly twisted at the C9—-C10 bond with a C8—C9—C10—C15 torsion angle of –2.2 (4)° and a maximum deviation of 0.193 (16) Å for atom O1. The dihedral angle between the terminal benzene rings (C1–C6 and C10–C15) is 0.47 (9)°. The least-squares plane through the enone moiety (O1/C7–C9) makes dihedral angles of 2.87 (14) and 3.33 (14)° with the C1–C6 and C10–C15 benzene rings, respectively. An intra­molecular C8—H8A···F1 hydrogen bond (Table 1) is observed, generating an S(6) ring motif. The bond lengths and angles are comparable with the equivalent data for previously reported structures; (Razak et al., 2009; Harrison et al., 2006a).

Supra­molecular features top

In the extended structure of (I), the molecules are linked into a three-dimensional network via C2—H2A···O1 (x - 1/2, -y + 3/2, z + 1/2) and C3—H3A···O2 (x - 3/2, y + 1/2, z) hydrogen bonds (Table 1), as shown in Fig. 2. The crystal structure also features ππ inter­actions [Cg1···Cg2 (-1 + x, y, z), centroid-to-centroid distance = 3.5629 (18) Å, where Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively].

Analysis of the Hirshfeld Surfaces top

Crystal Explorer 3.1(Wolff et al., 2012) was used to analyse the close contacts in the crystal of (I), which can be summarized with fingerprint plots mapped over dnorm, electrostatic potential, shape index and curvedness. The electrostatic potentials were calculated using TONTO (Spackman et al., 2008; Jayatilaka et al., 2005) integrated within Crystal Explorer. The electrostatic potentials were mapped on Hirshfeld surfaces using the STO-3G basis set at Hartree–Fock level theory over a range ±0.03 au.

The strong C—H···O inter­actions are visualized as bright-red spots between the respective donor and acceptor atoms on the Hirshfeld surfaces mapped over dnorm (Fig. 3a) with neighbouring molecules connected by C2—H2A···O1 and C3—H3A···O2 hydrogen bonds. This finding is corroborated by Hirshfeld surfaces mapped over the electrostatic potential (Fig. 3b) showing the negative potential around the oxygen atoms as light-red clouds and the positive potential around hydrogen atoms as light-blue clouds.

Significant inter­molecular inter­actions are plotted in Fig. 4: the H···H inter­actions appear as the largest region of the fingerprint plot with a high concentration in the middle region, shown in light blue, at de = di ~1.4 Å (Fig. 4a) with overall Hirshfeld surfaces of 27.5%. The contribution from the O···H/H···O contacts, corresponding to C—H···O inter­actions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond inter­action having almost the same de + di ~2.3 Å (Fig. 4b).

The C···C contacts, which refer to π–·π stacking inter­actions, contribute 13.7% of the Hirshfeld surfaces. This appears as a distinct triangle at around de = di ~1.8 Å (Fig. 4c). The presence of the ππ stacking inter­actions is also indicated by the appearance of red and blue triangles on the shape-indexed surfaces, identified with black arrows in Fig. 5, and in the flat regions on the Hirshfeld surfaces mapped over curvedness in Fig. 6.

Synthesis and crystallization top

A mixture of 3-fluoro-4-meth­oxy­aceto­phenone (0.1 mol, 0.08 g) and 2-chloro-6-fluoro­benzaldehyde (0.1 mol, 0.08 g) was dissolved in methanol (20 ml). A catalytic amount of NaOH (5 ml, 20%) was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 5–6 h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50 ml) and the resulting crude solid was collected by filtration. Brownish blocks of (I) were grown from acetone solution by slow evaporation.

Refinement details top

Crystal data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically (C—H = 0.93 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C). In the final refinement, the most disagreeable reflection (020) was omitted.

Structure description top

Chalcone derivatives possesses a wide range of biological properties such as anti­bacterial (Jarag et al., 2011), anti-inflammatory (Mukherjee et al., 2001) and anti-oxidant (Arty et al., 2000) activities. As part of our ongoing studies on chalcone derivatives, we hereby report the synthesis and crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig.1. The enone moiety (O1/C7–C9) adopts an E-conformation with respect to C7C8 bond. The molecule is slightly twisted at the C9—-C10 bond with a C8—C9—C10—C15 torsion angle of –2.2 (4)° and a maximum deviation of 0.193 (16) Å for atom O1. The dihedral angle between the terminal benzene rings (C1–C6 and C10–C15) is 0.47 (9)°. The least-squares plane through the enone moiety (O1/C7–C9) makes dihedral angles of 2.87 (14) and 3.33 (14)° with the C1–C6 and C10–C15 benzene rings, respectively. An intra­molecular C8—H8A···F1 hydrogen bond (Table 1) is observed, generating an S(6) ring motif. The bond lengths and angles are comparable with the equivalent data for previously reported structures; (Razak et al., 2009; Harrison et al., 2006a).

In the extended structure of (I), the molecules are linked into a three-dimensional network via C2—H2A···O1 (x - 1/2, -y + 3/2, z + 1/2) and C3—H3A···O2 (x - 3/2, y + 1/2, z) hydrogen bonds (Table 1), as shown in Fig. 2. The crystal structure also features ππ inter­actions [Cg1···Cg2 (-1 + x, y, z), centroid-to-centroid distance = 3.5629 (18) Å, where Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively].

Crystal Explorer 3.1(Wolff et al., 2012) was used to analyse the close contacts in the crystal of (I), which can be summarized with fingerprint plots mapped over dnorm, electrostatic potential, shape index and curvedness. The electrostatic potentials were calculated using TONTO (Spackman et al., 2008; Jayatilaka et al., 2005) integrated within Crystal Explorer. The electrostatic potentials were mapped on Hirshfeld surfaces using the STO-3G basis set at Hartree–Fock level theory over a range ±0.03 au.

The strong C—H···O inter­actions are visualized as bright-red spots between the respective donor and acceptor atoms on the Hirshfeld surfaces mapped over dnorm (Fig. 3a) with neighbouring molecules connected by C2—H2A···O1 and C3—H3A···O2 hydrogen bonds. This finding is corroborated by Hirshfeld surfaces mapped over the electrostatic potential (Fig. 3b) showing the negative potential around the oxygen atoms as light-red clouds and the positive potential around hydrogen atoms as light-blue clouds.

Significant inter­molecular inter­actions are plotted in Fig. 4: the H···H inter­actions appear as the largest region of the fingerprint plot with a high concentration in the middle region, shown in light blue, at de = di ~1.4 Å (Fig. 4a) with overall Hirshfeld surfaces of 27.5%. The contribution from the O···H/H···O contacts, corresponding to C—H···O inter­actions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond inter­action having almost the same de + di ~2.3 Å (Fig. 4b).

The C···C contacts, which refer to π–·π stacking inter­actions, contribute 13.7% of the Hirshfeld surfaces. This appears as a distinct triangle at around de = di ~1.8 Å (Fig. 4c). The presence of the ππ stacking inter­actions is also indicated by the appearance of red and blue triangles on the shape-indexed surfaces, identified with black arrows in Fig. 5, and in the flat regions on the Hirshfeld surfaces mapped over curvedness in Fig. 6.

Synthesis and crystallization top

A mixture of 3-fluoro-4-meth­oxy­aceto­phenone (0.1 mol, 0.08 g) and 2-chloro-6-fluoro­benzaldehyde (0.1 mol, 0.08 g) was dissolved in methanol (20 ml). A catalytic amount of NaOH (5 ml, 20%) was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 5–6 h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50 ml) and the resulting crude solid was collected by filtration. Brownish blocks of (I) were grown from acetone solution by slow evaporation.

Refinement details top

Crystal data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically (C—H = 0.93 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C). In the final refinement, the most disagreeable reflection (020) was omitted.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids. The intramolecular C—H···F hydrogen bond is shown as a dashed line.
[Figure 2] Fig. 2. The packing in (I) showing C—H···O and ππ interactions as dashed lines.
[Figure 3] Fig. 3. (a) dnorm mapped on Hirshfeld surfaces for visualizing the intermolecular interactions of the title chalcone compound. (b) Hirshfeld surfaces mapped over the electrostatic potential. Dotted lines (green) represent hydrogen bonds.
[Figure 4] Fig. 4. Fingerprint plots for the title chalcone compound, broken down into contributions from specific pairs of atom types. For each plot, the grey shadow is an outline of the complete fingerprint plot. Surfaces to the right highlight the relevant surface patches associated with the specific contacts, with dnorm mapped in the same manner as Fig. 3a.
[Figure 5] Fig. 5. Hirshfeld surfaces mapped over the shape index of the title chalcone compound.
[Figure 6] Fig. 6. Hirshfeld surfaces mapped over curvedness of the title chalcone compound.
(E)-3- (2-Chloro-6-fluorophenyl)-1-(3-fluoro-4-methoxyphenyl)prop-2-en-1-one top
Crystal data top
C16H11ClF2O2F(000) = 632
Mr = 308.70Dx = 1.489 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 9.0832 (13) ÅCell parameters from 4692 reflections
b = 11.1072 (13) Åθ = 2.9–28.9°
c = 13.9564 (17) ŵ = 0.30 mm1
β = 102.027 (3)°T = 294 K
V = 1377.1 (3) Å3Block, brown
Z = 40.45 × 0.17 × 0.13 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
4003 independent reflections
Radiation source: fine-focus sealed tube3111 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
φ and ω scansθmax = 30.1°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 1212
Tmin = 0.791, Tmax = 0.889k = 1515
14473 measured reflectionsl = 1919
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.039 w = 1/[σ2(Fo2) + (0.0664P)2 + 0.0639P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.116(Δ/σ)max < 0.001
S = 1.05Δρmax = 0.20 e Å3
4003 reflectionsΔρmin = 0.27 e Å3
191 parametersAbsolute structure: Flack x determined using 1298 quotients [(I+)-(I-)]/[(I+)+(I-)] Parsons et al. (2013)
2 restraintsAbsolute structure parameter: 0.08 (2)
Crystal data top
C16H11ClF2O2V = 1377.1 (3) Å3
Mr = 308.70Z = 4
Monoclinic, CcMo Kα radiation
a = 9.0832 (13) ŵ = 0.30 mm1
b = 11.1072 (13) ÅT = 294 K
c = 13.9564 (17) Å0.45 × 0.17 × 0.13 mm
β = 102.027 (3)°
Data collection top
Bruker SMART APEXII CCD
diffractometer
4003 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
3111 reflections with I > 2σ(I)
Tmin = 0.791, Tmax = 0.889Rint = 0.031
14473 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.116Δρmax = 0.20 e Å3
S = 1.05Δρmin = 0.27 e Å3
4003 reflectionsAbsolute structure: Flack x determined using 1298 quotients [(I+)-(I-)]/[(I+)+(I-)] Parsons et al. (2013)
191 parametersAbsolute structure parameter: 0.08 (2)
2 restraints
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
Cl10.01382 (11)0.90043 (10)0.28908 (7)0.0766 (3)
F10.2567 (2)0.7732 (2)0.63725 (14)0.0679 (6)
F21.0123 (2)0.5464 (2)0.42338 (15)0.0676 (5)
O10.5069 (4)0.7363 (3)0.3366 (2)0.0864 (9)
O21.0692 (2)0.5000 (2)0.61111 (18)0.0654 (6)
C10.1380 (3)0.8232 (3)0.5705 (2)0.0473 (6)
C20.0177 (4)0.8618 (3)0.6081 (2)0.0558 (7)
H2A0.01810.85380.67450.067*
C30.1020 (3)0.9121 (3)0.5458 (3)0.0555 (7)
H3A0.18440.93910.56980.067*
C40.1017 (3)0.9231 (3)0.4480 (3)0.0533 (7)
H4A0.18370.95730.40570.064*
C50.0209 (3)0.8832 (2)0.4124 (2)0.0447 (6)
C60.1479 (3)0.8313 (2)0.47289 (19)0.0409 (5)
C70.2772 (3)0.7932 (3)0.4327 (2)0.0480 (6)
H7A0.26700.80340.36550.058*
C80.4052 (4)0.7467 (3)0.4783 (2)0.0527 (6)
H8A0.42150.73210.54530.063*
C90.5248 (3)0.7170 (3)0.4236 (2)0.0501 (6)
C100.6672 (3)0.6632 (2)0.4787 (2)0.0428 (6)
C110.7762 (3)0.6300 (3)0.4255 (2)0.0458 (6)
H11A0.75980.64330.35830.055*
C120.9060 (3)0.5780 (2)0.4739 (2)0.0463 (6)
C130.9367 (3)0.5544 (3)0.5741 (2)0.0478 (6)
C140.8298 (3)0.5889 (3)0.6265 (2)0.0505 (6)
H14A0.84710.57620.69380.061*
C150.6969 (3)0.6426 (3)0.5783 (2)0.0480 (6)
H15A0.62590.66530.61420.058*
C161.1014 (5)0.4726 (5)0.7133 (3)0.0857 (13)
H16A1.19720.43290.73040.129*
H16B1.02450.42060.72780.129*
H16C1.10410.54570.75020.129*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0769 (5)0.1065 (7)0.0450 (4)0.0182 (5)0.0090 (3)0.0033 (4)
F10.0590 (11)0.0974 (14)0.0482 (10)0.0220 (9)0.0137 (8)0.0121 (10)
F20.0564 (9)0.0931 (14)0.0632 (11)0.0103 (9)0.0350 (9)0.0092 (10)
O10.0880 (18)0.125 (2)0.0543 (14)0.0458 (17)0.0320 (13)0.0164 (15)
O20.0398 (10)0.1009 (18)0.0566 (13)0.0060 (11)0.0124 (9)0.0102 (12)
C10.0477 (13)0.0491 (14)0.0478 (14)0.0008 (11)0.0161 (11)0.0033 (12)
C20.0601 (17)0.0623 (17)0.0529 (16)0.0056 (14)0.0297 (14)0.0028 (14)
C30.0464 (14)0.0587 (16)0.0685 (19)0.0037 (12)0.0281 (13)0.0069 (14)
C40.0398 (13)0.0518 (15)0.068 (2)0.0015 (11)0.0099 (12)0.0036 (14)
C50.0441 (13)0.0465 (14)0.0436 (13)0.0029 (11)0.0098 (11)0.0027 (10)
C60.0421 (12)0.0388 (12)0.0435 (13)0.0024 (9)0.0130 (10)0.0011 (10)
C70.0517 (14)0.0520 (15)0.0441 (14)0.0054 (12)0.0189 (11)0.0010 (11)
C80.0542 (15)0.0589 (16)0.0501 (15)0.0084 (13)0.0225 (12)0.0005 (13)
C90.0540 (14)0.0515 (14)0.0510 (15)0.0076 (12)0.0247 (12)0.0003 (12)
C100.0471 (13)0.0385 (12)0.0490 (14)0.0052 (10)0.0242 (11)0.0053 (10)
C110.0503 (14)0.0491 (14)0.0437 (13)0.0043 (11)0.0229 (11)0.0057 (11)
C120.0426 (12)0.0540 (15)0.0491 (14)0.0051 (11)0.0246 (11)0.0112 (12)
C130.0365 (12)0.0564 (15)0.0527 (15)0.0066 (11)0.0147 (11)0.0110 (12)
C140.0449 (13)0.0684 (18)0.0418 (14)0.0043 (12)0.0174 (11)0.0068 (13)
C150.0446 (12)0.0583 (15)0.0473 (14)0.0024 (11)0.0236 (11)0.0070 (12)
C160.0552 (19)0.142 (4)0.057 (2)0.014 (2)0.0050 (16)0.002 (2)
Geometric parameters (Å, º) top
Cl1—C51.720 (3)C7—H7A0.9300
F1—C11.386 (3)C8—C91.489 (4)
F2—C121.354 (3)C8—H8A0.9300
O1—C91.209 (4)C9—C101.485 (4)
O2—C131.349 (4)C10—C151.379 (4)
O2—C161.427 (5)C10—C111.405 (3)
C1—C21.376 (4)C11—C121.359 (4)
C1—C61.387 (4)C11—H11A0.9300
C2—C31.363 (5)C12—C131.393 (4)
C2—H2A0.9300C13—C141.386 (4)
C3—C41.371 (5)C14—C151.389 (4)
C3—H3A0.9300C14—H14A0.9300
C4—C51.383 (4)C15—H15A0.9300
C4—H4A0.9300C16—H16A0.9600
C5—C61.403 (4)C16—H16B0.9600
C6—C71.466 (3)C16—H16C0.9600
C7—C81.309 (4)
C13—O2—C16117.3 (3)O1—C9—C8121.0 (3)
C2—C1—F1115.9 (3)C10—C9—C8118.2 (3)
C2—C1—C6125.0 (3)C15—C10—C11118.5 (3)
F1—C1—C6119.1 (2)C15—C10—C9123.7 (2)
C3—C2—C1118.4 (3)C11—C10—C9117.7 (2)
C3—C2—H2A120.8C12—C11—C10118.9 (3)
C1—C2—H2A120.8C12—C11—H11A120.6
C2—C3—C4120.3 (3)C10—C11—H11A120.6
C2—C3—H3A119.8F2—C12—C11119.4 (3)
C4—C3—H3A119.8F2—C12—C13117.3 (3)
C3—C4—C5119.9 (3)C11—C12—C13123.3 (2)
C3—C4—H4A120.1O2—C13—C14126.0 (3)
C5—C4—H4A120.1O2—C13—C12116.4 (2)
C4—C5—C6122.5 (3)C14—C13—C12117.6 (3)
C4—C5—Cl1117.3 (2)C13—C14—C15119.8 (3)
C6—C5—Cl1120.1 (2)C13—C14—H14A120.1
C1—C6—C5113.8 (2)C15—C14—H14A120.1
C1—C6—C7125.3 (3)C10—C15—C14121.9 (2)
C5—C6—C7120.9 (2)C10—C15—H15A119.1
C8—C7—C6129.1 (3)C14—C15—H15A119.1
C8—C7—H7A115.5O2—C16—H16A109.5
C6—C7—H7A115.5O2—C16—H16B109.5
C7—C8—C9120.5 (3)H16A—C16—H16B109.5
C7—C8—H8A119.7O2—C16—H16C109.5
C9—C8—H8A119.7H16A—C16—H16C109.5
O1—C9—C10120.8 (3)H16B—C16—H16C109.5
F1—C1—C2—C3179.8 (3)O1—C9—C10—C15177.8 (3)
C6—C1—C2—C30.1 (5)C8—C9—C10—C152.2 (4)
C1—C2—C3—C40.2 (5)O1—C9—C10—C113.2 (4)
C2—C3—C4—C50.1 (5)C8—C9—C10—C11176.9 (3)
C3—C4—C5—C60.3 (4)C15—C10—C11—C120.5 (4)
C3—C4—C5—Cl1179.8 (2)C9—C10—C11—C12178.5 (2)
C2—C1—C6—C50.4 (4)C10—C11—C12—F2179.6 (2)
F1—C1—C6—C5179.9 (2)C10—C11—C12—C130.7 (4)
C2—C1—C6—C7178.4 (3)C16—O2—C13—C141.7 (5)
F1—C1—C6—C71.3 (4)C16—O2—C13—C12178.6 (3)
C4—C5—C6—C10.5 (4)F2—C12—C13—O21.1 (4)
Cl1—C5—C6—C1180.0 (2)C11—C12—C13—O2178.6 (3)
C4—C5—C6—C7178.3 (3)F2—C12—C13—C14178.7 (2)
Cl1—C5—C6—C71.2 (3)C11—C12—C13—C141.7 (4)
C1—C6—C7—C80.7 (5)O2—C13—C14—C15179.0 (3)
C5—C6—C7—C8178.0 (3)C12—C13—C14—C151.3 (4)
C6—C7—C8—C9178.2 (3)C11—C10—C15—C140.9 (4)
C7—C8—C9—O10.8 (5)C9—C10—C15—C14178.2 (3)
C7—C8—C9—C10179.3 (3)C13—C14—C15—C100.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1i0.932.503.391 (4)162
C3—H3A···O2ii0.932.523.441 (4)171
C8—H8A···F10.932.212.842 (4)124
Symmetry codes: (i) x1/2, y+3/2, z+1/2; (ii) x3/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1i0.932.503.391 (4)162
C3—H3A···O2ii0.932.523.441 (4)171
C8—H8A···F10.932.212.842 (4)124
Symmetry codes: (i) x1/2, y+3/2, z+1/2; (ii) x3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC16H11ClF2O2
Mr308.70
Crystal system, space groupMonoclinic, Cc
Temperature (K)294
a, b, c (Å)9.0832 (13), 11.1072 (13), 13.9564 (17)
β (°) 102.027 (3)
V3)1377.1 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.45 × 0.17 × 0.13
Data collection
DiffractometerBruker SMART APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.791, 0.889
No. of measured, independent and
observed [I > 2σ(I)] reflections
14473, 4003, 3111
Rint0.031
(sin θ/λ)max1)0.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.116, 1.05
No. of reflections4003
No. of parameters191
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.27
Absolute structureFlack x determined using 1298 quotients [(I+)-(I-)]/[(I+)+(I-)] Parsons et al. (2013)
Absolute structure parameter0.08 (2)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick 2008), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

 

Footnotes

Thomson Reuters ResearcherID: F-9119-2012.

§Thomson Reuters ResearcherID: A-5599-2009.

Acknowledgements

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the research facilities and Research University Grant No. 1001/PFIZIK/811238 to conduct this work. NCK thanks Malaysian Government for a MyBrain15 (MyPhD) scholarship.

References

First citationArty, I. S., Timmerman, H., Samhoedi, M., Sastrohamidjojo, Sugiyanto & van der Goot, H. (2000). Eur. J. Med. Chem. 35, 449–457.  Google Scholar
First citationBruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHarrison, W. T. A., Yathirajan, H. S., Anilkumar, H. G., Sarojini, B. K. & Narayana, B. (2006a). Acta Cryst. E62, o3251–o3253.  CSD CrossRef IUCr Journals Google Scholar
First citationJarag, K. J., Pinjari, D. V., Pandit, A. B. & Shankarling, G. S. (2011). Ultrason. Sonochem. 18, 617–623.  CrossRef CAS PubMed Google Scholar
First citationJayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). TONTO. https://hirshfeldsurface.net/  Google Scholar
First citationMukherjee, S., Kumar, V., Prasad, A. K., Raj, H. G., Bracke, M. E., Olsen, C. E., Jain, S. C. & Parmar, V. S. (2001). Bioorg. Med. Chem. 9, 337–345.  Web of Science CrossRef PubMed CAS Google Scholar
First citationParsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationRazak, I. A., Fun, H.-K., Ngaini, Z., Rahman, N. I. A. & Hussain, H. (2009). Acta Cryst. E65, o1439–o1440.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSpackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388.  CAS Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). Crystal Explorer. University of Western Australia.  Google Scholar

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Volume 72| Part 5| May 2016| Pages 716-719
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