2-(4-Fluoro­benzyl­idene)propane­dinitrile: monoclinic polymorph

El-Agrody, A.M.; Al-Omar, M.A.; Amr, A.E.-G.E.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536813006235

organic compounds

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Volume 69| Part 4| April 2013| Page o515

doi:10.1107/S1600536813006235

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2-(4-Fluorobenzylidene)propanedinitrile: monoclinic polymorph

Ahmed M. El-Agrody,^a,^b Mohamed A. Al-Omar,^c,^d Abd El-Galil E. Amr,^d,^e ‡ Seik Weng Ng ^f,^g and Edward R. T. Tiekink ^f ^*

^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

(Received 4 March 2013; accepted 4 March 2013; online 9 March 2013)

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

C₁₀H₅FN₂
M_r = 172.16
Monoclinic, P 2₁ /c
a = 9.1491 (9) Å
b = 12.7961 (14) Å
c = 7.5828 (11) Å
β = 106.317 (13)°
V = 851.98 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.35 × 0.15 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.892, T_max = 1.000
7732 measured reflections
1957 independent reflections
1149 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.190
S = 1.09
1957 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y-{\script{1\over 2}}, z-{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813006235/hb7051sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813006235/hb7051Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813006235/hb7051Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: 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).

Figures top

	Fig. 1. The molecular structures of (I) showing displacement ellipsoids at the 35% probability level.
	Fig. 2. Overlay diagram of (I) (red) with the triclinic form (blue). The molecules are overlaid so that the benzene rings are superimposed.
	Fig. 3. A view of the supramolecular layer parallel to (1 0 1) in (I) sustained by C—H···N interactions, shown as blue dashed lines.
	Fig. 4. A view in projection down the b axis of the crystal packing in (I). The C—H···N and C—F···π interactions are shown as blue and purple dashed lines, respectively.

2-(4-Fluorobenzylidene)propanedinitrile top

Crystal data top

C₁₀H₅FN₂	F(000) = 352
M_r = 172.16	D_x = 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

Data collection top

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	R_int = 0.045
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 3.2°
ω scan	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −16→14
T_min = 0.892, T_max = 1.000	l = −9→9
7732 measured reflections

Refinement top

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(F_o²) + (0.0742P)² + 0.0917P] where P = (F_o² + 2F_c²)/3
1957 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₀H₅FN₂	V = 851.98 (18) Å³
M_r = 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)°

Data collection top

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)
T_min = 0.892, T_max = 1.000	R_int = 0.045
7732 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.190	H-atom parameters constrained
S = 1.09	Δρ_max = 0.15 e Å⁻³
1957 reflections	Δρ_min = −0.18 e Å⁻³
118 parameters

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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.892, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7732, 1957, 1149
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Antipin, M. Yu., Nesterov, V. N., Jiang, S., Borbulevych, O. Ya., Sammeth, D. M., Sevostianova, E. V. & Timofeeva, T. V. (2003). J. Mol. Struct. 650, 1–20. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
El-Agrody, A. M., Sabry, N. M. & Motlaq, S. S. (2011). J. Chem. Res. 35, 77–83. CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gans, J. & Shalloway, D. (2001). J. Mol. Graph. Model. 19, 557–559. Web of Science CrossRef PubMed CAS Google Scholar
Ng, S. W. & Tiekink, E. R. T. (2013). Private communication (deposition number 926904). CCDC, Cambridge, England. Google Scholar
Sabry, N. M., Mohamed, H. M., Khattab, E. S. A. E. H., Motlaq, S. S. & El-Agrody, A. M. (2011). Eur. J. Med. Chem. 46, 765–772. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536813006235

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