organic compounds
2-(4-Fluorobenzylidene)propanedinitrile: monoclinic polymorph
aChemistry Department, Faculty of Science, King Khalid University, Abha 61413, PO Box 9004, Saudi Arabia, bChemistry Department, Faculty of Science, Al-Azhar University, Nasr City, Cairo 11884, Egypt, cPharmaceutical Chemistry Department, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, dDrug Exploration & Development Chair (DEDC), College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, eApplied Organic Chemistry Department, National Research Center, Dokki 12622, Cairo, Egypt, fDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and gChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: edward.tiekink@gmail.com
The title compound, C10H5FN2, is a monoclinic (P21/c) polymorph of the previously reported triclinic (P-1) form [Antipin et al. (2003). J. Mol. Struct. 650, 1–20]. The 13 non-H atoms in the title polymorph are almost coplanar (r.m.s. deviation = 0.020 Å); a small twist between the fluorobenzene and dinitrile groups [C—C—C—C torsion angle = 175.49 (16)°] is evident in the triclinic polymorph. In the crystal, C—H⋯N interactions lead to supramolecular layers parallel to (-101); these are connected by C—F⋯π interactions.
Related literature
For background to the chemistry and biological activity of 4H-pyran derivatives, see: El-Agrody et al. (2011); Sabry et al. (2011). For the structure of the triclinic polymorph, see: Antipin et al. (2003); Ng & Tiekink (2013).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2011); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536813006235/hb7051sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813006235/hb7051Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813006235/hb7051Isup3.cml
A solution of 6-bromo-1-naphthol (0.01 mol) in EtOH (30 ml) was treated with 4-fluoro-1-(2,2-dicyanovinyl)benzene (0.01 mol) and piperidine (0.5 ml). The reaction mixture was heated until complete precipitation occurred (reaction time: 60 min). The solid product which formed was collected by filtration and recrystallized from ethanol to give the title compound, i.e. unreacted 4-fluoro-1-(2,2-dicyanovinyl)benzene, as both triclinic (Ng & Tiekink, 2013) and monoclinic (I) polymorphs. Both crystal forms have the appearance of yellow prisms.
The C-bound H atoms were geometrically placed (C–H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C10H5FN2 | F(000) = 352 |
Mr = 172.16 | Dx = 1.342 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1835 reflections |
a = 9.1491 (9) Å | θ = 3.1–27.5° |
b = 12.7961 (14) Å | µ = 0.10 mm−1 |
c = 7.5828 (11) Å | T = 295 K |
β = 106.317 (13)° | Prism, yellow |
V = 851.98 (18) Å3 | 0.35 × 0.15 × 0.05 mm |
Z = 4 |
Agilent SuperNova Dual diffractometer with an Atlas detector | 1957 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 1149 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.045 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.6°, θmin = 3.2° |
ω scan | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −16→14 |
Tmin = 0.892, Tmax = 1.000 | l = −9→9 |
7732 measured reflections |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.190 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0742P)2 + 0.0917P] where P = (Fo2 + 2Fc2)/3 |
1957 reflections | (Δ/σ)max < 0.001 |
118 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C10H5FN2 | V = 851.98 (18) Å3 |
Mr = 172.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.1491 (9) Å | µ = 0.10 mm−1 |
b = 12.7961 (14) Å | T = 295 K |
c = 7.5828 (11) Å | 0.35 × 0.15 × 0.05 mm |
β = 106.317 (13)° |
Agilent SuperNova Dual diffractometer with an Atlas detector | 1957 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 1149 reflections with I > 2σ(I) |
Tmin = 0.892, Tmax = 1.000 | Rint = 0.045 |
7732 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.190 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.15 e Å−3 |
1957 reflections | Δρmin = −0.18 e Å−3 |
118 parameters |
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 | 0.35050 (15) | 0.22275 (14) | 0.1895 (2) | 0.0959 (6) | |
N1 | 1.2165 (3) | 0.47627 (19) | 0.9490 (4) | 0.1097 (9) | |
N2 | 1.0706 (2) | 0.15887 (19) | 0.8205 (3) | 0.0900 (8) | |
C1 | 0.7452 (2) | 0.34429 (17) | 0.5304 (3) | 0.0566 (6) | |
C2 | 0.6299 (3) | 0.4089 (2) | 0.4263 (3) | 0.0704 (7) | |
H2 | 0.6434 | 0.4809 | 0.4340 | 0.084* | |
C3 | 0.4968 (3) | 0.3689 (2) | 0.3126 (3) | 0.0775 (7) | |
H3 | 0.4209 | 0.4129 | 0.2442 | 0.093* | |
C4 | 0.4797 (2) | 0.2624 (2) | 0.3035 (3) | 0.0685 (7) | |
C5 | 0.5886 (2) | 0.1964 (2) | 0.4027 (3) | 0.0651 (6) | |
H5 | 0.5733 | 0.1245 | 0.3937 | 0.078* | |
C6 | 0.7208 (2) | 0.23631 (18) | 0.5158 (3) | 0.0606 (6) | |
H6 | 0.7952 | 0.1911 | 0.5836 | 0.073* | |
C7 | 0.8788 (2) | 0.39364 (18) | 0.6487 (3) | 0.0627 (6) | |
H7 | 0.8763 | 0.4663 | 0.6451 | 0.075* | |
C8 | 1.0061 (2) | 0.35367 (18) | 0.7630 (3) | 0.0611 (6) | |
C9 | 1.1232 (3) | 0.4227 (2) | 0.8665 (3) | 0.0773 (7) | |
C10 | 1.0398 (2) | 0.2445 (2) | 0.7927 (3) | 0.0648 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0668 (9) | 0.1132 (15) | 0.0951 (11) | −0.0038 (8) | 0.0019 (8) | −0.0117 (9) |
N1 | 0.1033 (16) | 0.0584 (16) | 0.131 (2) | −0.0124 (13) | −0.0271 (14) | 0.0014 (13) |
N2 | 0.0849 (14) | 0.0549 (15) | 0.1148 (19) | 0.0018 (11) | 0.0028 (12) | 0.0019 (12) |
C1 | 0.0644 (12) | 0.0469 (14) | 0.0582 (12) | 0.0029 (9) | 0.0169 (9) | 0.0002 (9) |
C2 | 0.0809 (15) | 0.0528 (15) | 0.0747 (14) | 0.0089 (11) | 0.0174 (12) | 0.0037 (11) |
C3 | 0.0714 (14) | 0.080 (2) | 0.0734 (15) | 0.0198 (13) | 0.0088 (11) | 0.0048 (13) |
C4 | 0.0595 (13) | 0.080 (2) | 0.0642 (14) | −0.0006 (11) | 0.0139 (10) | −0.0066 (11) |
C5 | 0.0686 (13) | 0.0576 (15) | 0.0684 (13) | −0.0032 (11) | 0.0179 (11) | −0.0039 (10) |
C6 | 0.0639 (12) | 0.0516 (14) | 0.0632 (12) | 0.0033 (10) | 0.0125 (10) | 0.0013 (9) |
C7 | 0.0760 (14) | 0.0398 (13) | 0.0702 (13) | 0.0018 (10) | 0.0174 (11) | 0.0001 (9) |
C8 | 0.0681 (12) | 0.0434 (14) | 0.0686 (13) | −0.0041 (10) | 0.0141 (10) | −0.0015 (9) |
C9 | 0.0803 (15) | 0.0485 (16) | 0.0899 (17) | −0.0003 (12) | 0.0024 (13) | 0.0028 (12) |
C10 | 0.0638 (13) | 0.0487 (15) | 0.0766 (14) | −0.0028 (11) | 0.0113 (10) | −0.0037 (11) |
F1—C4 | 1.352 (3) | C3—H3 | 0.9300 |
N1—C9 | 1.135 (3) | C4—C5 | 1.361 (3) |
N2—C10 | 1.136 (3) | C5—C6 | 1.370 (3) |
C1—C6 | 1.399 (3) | C5—H5 | 0.9300 |
C1—C2 | 1.396 (3) | C6—H6 | 0.9300 |
C1—C7 | 1.443 (3) | C7—C8 | 1.342 (3) |
C2—C3 | 1.378 (3) | C7—H7 | 0.9300 |
C2—H2 | 0.9300 | C8—C10 | 1.435 (3) |
C3—C4 | 1.372 (3) | C8—C9 | 1.440 (3) |
C6—C1—C2 | 117.5 (2) | C4—C5—H5 | 120.2 |
C6—C1—C7 | 124.74 (19) | C6—C5—H5 | 120.2 |
C2—C1—C7 | 117.8 (2) | C5—C6—C1 | 120.7 (2) |
C3—C2—C1 | 121.9 (3) | C5—C6—H6 | 119.6 |
C3—C2—H2 | 119.0 | C1—C6—H6 | 119.6 |
C1—C2—H2 | 119.0 | C8—C7—C1 | 131.6 (2) |
C4—C3—C2 | 118.0 (2) | C8—C7—H7 | 114.2 |
C4—C3—H3 | 121.0 | C1—C7—H7 | 114.2 |
C2—C3—H3 | 121.0 | C7—C8—C10 | 125.6 (2) |
F1—C4—C5 | 119.5 (3) | C7—C8—C9 | 119.7 (2) |
F1—C4—C3 | 118.2 (2) | C10—C8—C9 | 114.7 (2) |
C5—C4—C3 | 122.3 (2) | N1—C9—C8 | 179.3 (3) |
C4—C5—C6 | 119.7 (2) | N2—C10—C8 | 177.8 (2) |
C6—C1—C2—C3 | −0.2 (3) | C4—C5—C6—C1 | 0.0 (3) |
C7—C1—C2—C3 | −178.55 (19) | C2—C1—C6—C5 | 0.2 (3) |
C1—C2—C3—C4 | −0.1 (4) | C7—C1—C6—C5 | 178.50 (19) |
C2—C3—C4—F1 | −178.78 (19) | C6—C1—C7—C8 | 1.7 (4) |
C2—C3—C4—C5 | 0.3 (4) | C2—C1—C7—C8 | −180.0 (2) |
F1—C4—C5—C6 | 178.84 (19) | C1—C7—C8—C10 | 0.8 (4) |
C3—C4—C5—C6 | −0.2 (4) | C1—C7—C8—C9 | −179.9 (2) |
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N1i | 0.93 | 2.61 | 3.478 (4) | 155 |
C7—H7···N2ii | 0.93 | 2.51 | 3.424 (3) | 167 |
C4—F1···Cg1iii | 1.35 (1) | 3.59 (1) | 3.573 (2) | 79 (1) |
Symmetry codes: (i) x−1, y, z−1; (ii) −x+2, y+1/2, −z+3/2; (iii) x, −y−1/2, z−3/2. |
Experimental details
Crystal data | |
Chemical formula | C10H5FN2 |
Mr | 172.16 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 9.1491 (9), 12.7961 (14), 7.5828 (11) |
β (°) | 106.317 (13) |
V (Å3) | 851.98 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.35 × 0.15 × 0.05 |
Data collection | |
Diffractometer | Agilent SuperNova Dual diffractometer with an Atlas detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.892, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7732, 1957, 1149 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.190, 1.09 |
No. of reflections | 1957 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.18 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N1i | 0.93 | 2.61 | 3.478 (4) | 155 |
C7—H7···N2ii | 0.93 | 2.51 | 3.424 (3) | 167 |
C4—F1···Cg1iii | 1.352 (3) | 3.5852 (18) | 3.573 (2) | 78.60 (11) |
Symmetry codes: (i) x−1, y, z−1; (ii) −x+2, y+1/2, −z+3/2; (iii) x, −y−1/2, z−3/2. |
Footnotes
‡Additional correspondence author, e-mail: aamr1963@yahoo.com.
Acknowledgements
The authors extend their appreciation to the Deanship of Scientific Research at King Saud University for funding this work through the research group project No. RGP-VPP-099. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/12).
References
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In continuation of a program on the chemistry of 4H-pyran derivatives (El-Agrody et al., 2011; Sabry et al., 2011), the title compound was isolated from a failed reaction, see Experimental, as a monoclinic polymorph (P21/c) of the previously reported triclinic (P1) form (Antipin et al., 2003). In fact, both forms were characterized from the same reaction product (Ng & Tiekink, 2013).
In (I), Fig. 1, the 13 non-hydrogen atoms are almost co-planar with a r.m.s. deviation of 0.020 Å, and with maximum deviations of 0.028 (2) Å for the C5 atom and -0.028 (2) Å for C2. This contrasts the small twist found in the triclinic form (r.m.s. deviation = 0.062 Å) as seen in the C2—C1—C7—C8 torsion angle of 175.49 (16)° (Ng & Tiekink, 2013), which compares to -180.0 (2)° in (I); this difference is emphasized in the overlay diagram shown in Fig. 2.
In the crystal, supramolecular layers mediated by C—H···N interactions are formed parallel to (1 0 1), Fig. 2 and Table 1, and these are connected into a three-dimensional array by C—F···π contacts, Fig. 4 and Table 1. This pattern of interactions is in stark contrast to that in the triclinic polymorph whereby C—H···N interactions, involving one N atom only, lead to supramolecular chains which are connected into double chains by weak π—π contacts (Ng & Tiekink, 2013).