N,N′-[4,4′-Methyl­enebis(4,1-phenyl­ene)]bis­(2,6-difluoro­benzamide)

Al-Dajani, M.T.M.; Talaat, J.; Mohamed, N.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536811024524

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1832

doi:10.1107/S1600536811024524

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N,N′-[4,4′-Methylenebis(4,1-phenylene)]bis(2,6-difluorobenzamide)

Mohammad T. M. Al-Dajani,^a Jamal Talaat,^b Nornisah Mohamed,^a Madhukar Hemamalini ^c and Hoong-Kun Fun ^c ^*‡

^aSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bVirginia Commonwealth University, Chemistry School, USA, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 21 June 2011; accepted 22 June 2011; online 30 June 2011)

The complete molecule of the title compound, C₂₇H₁₈F₄N₂O₂, is generated by crystallographic twofold symmetry, with one C atom lying on the rotation axis. The dihedral angle between fluoro-substituted phenyl ring and the adjacent benzene ring is 10.37 (5)°. In the crystal, molecules are connected by N—H⋯O and C—H⋯F hydrogen bonds, resulting in supramolecular chains propagating along the c direction.

Related literature

For applications of benzamide derivatives, see: Ashwood et al. (1990 ); Kees et al. (1989 ); Ragavan et al. (2010 ); Carmellino et al. (1994 ); Rauko et al. (2001 ). For a related structure, see: Cronin et al. (2000 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₂₇H₁₈F₄N₂O₂
M_r = 478.43
Monoclinic, C 2/c
a = 42.0478 (10) Å
b = 5.2980 (1) Å
c = 9.5643 (2) Å
β = 92.522 (2)°
V = 2128.57 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.48 × 0.38 × 0.05 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.946, T_max = 0.994
26445 measured reflections
3871 independent reflections
3172 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.114
S = 1.06
3871 reflections
163 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1ⁱ	0.841 (15)	2.078 (15)	2.8811 (11)	159.4 (14)
C9—H9A⋯F1ⁱⁱ	0.95	2.41	3.2318 (11)	145
Symmetry codes: (i) $[x, -y+2, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+2, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811024524/hb5924sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024524/hb5924Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811024524/hb5924Isup3.cml

checkCIF report

Comment top

A number of benzamide derivatives were reported to possess anti-hypertensive (Ashwood et al., 1990), anti-diabetic (Kees et al., 1989), anti-bacterial (Ragavan et al., 2010), anti-fungal (Carmellino et al., 1994) and anti-cancer (Rauko et al., 2001) activities. As a part of our study on the synthesis of new fluorine- containing compounds with possible biological activities, we report here the crystal structure of the title compound, (I).

The asymmetric unit of the title compound, (Fig. 1), consists of a half molecule of N,N'-(4,4'-methylenebis(4,1-phenylene))bis (2,6-difluorobenzamide), which has a twofold symmetry and it adopts an E, E conformation. The dihedral angle between fluoro- substituted phenyl (C1–C6) rings and benzene (C8–13) ring is 10.37 (5)°. All bond lengths and angles are comparable to values observed in a closely related benzamide structure (Cronin et al., 2000).

In the crystal structure (Fig. 2), the adjacent molecules are connected via N1—H1N1..O1 and C9—H9A···F1 (Table 1) hydrogen bonds forming one-dimensional supramolecular chains along the c-axis.

Related literature top

For applications of benzamide derivatives, see: Ashwood et al. (1990); Kees et al. (1989); Ragavan et al. (2010); Carmellino et al. (1994); Rauko et al. (2001). For a related structure, see: Cronin et al. (2000). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

In a round bottom flask, 25ml of tetrahydrofuran (THF) was mixed with 4,4'-diaminodiphenylmethane (0.01 mol,2 g) with stirring. Drops of 2,6-Difluorobenzylchloride (0.02 mol, 3.4 g ) which was dissolved in THF was then added. The mixture was refluxed for 30 min and the yellow precipitate formed was filtered and washed with alkaline water, then with toluene and further washed with dilute hydrochloric acid. The precipate was dissolved in methanol at room temperature yielding colourless plates of (I).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids.
	Fig. 2. A view of a one-dimensional supramolecular chain along the c-axis

N-{4-[4-(2,6-difluorobenzamido)benzyl]phenyl}-2,6-difluorobenzamide top

Crystal data top

C₂₇H₁₈F₄N₂O₂	F(000) = 984
M_r = 478.43	D_x = 1.493 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8910 reflections
a = 42.0478 (10) Å	θ = 2.9–32.5°
b = 5.2980 (1) Å	µ = 0.12 mm⁻¹
c = 9.5643 (2) Å	T = 100 K
β = 92.522 (2)°	Plate, colourless
V = 2128.57 (8) Å³	0.48 × 0.38 × 0.05 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD diffractometer	3871 independent reflections
Radiation source: fine-focus sealed tube	3172 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 32.6°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −63→63
T_min = 0.946, T_max = 0.994	k = −7→7
26445 measured reflections	l = −14→14

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0569P)² + 1.3081P] where P = (F_o² + 2F_c²)/3
3871 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₇H₁₈F₄N₂O₂	V = 2128.57 (8) Å³
M_r = 478.43	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 42.0478 (10) Å	µ = 0.12 mm⁻¹
b = 5.2980 (1) Å	T = 100 K
c = 9.5643 (2) Å	0.48 × 0.38 × 0.05 mm
β = 92.522 (2)°

Data collection top

Bruker APEXII DUO CCD diffractometer	3871 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3172 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.994	R_int = 0.031
26445 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.43 e Å⁻³
3871 reflections	Δρ_min = −0.21 e Å⁻³
163 parameters

Special details top

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 s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.131371 (14)	0.52803 (12)	0.04350 (6)	0.02016 (14)
F2	0.201443 (15)	1.06377 (13)	0.30050 (7)	0.02303 (15)
O1	0.136883 (18)	0.97437 (15)	0.36217 (7)	0.02009 (16)
N1	0.113987 (19)	1.00956 (16)	0.14156 (8)	0.01541 (16)
C1	0.16118 (2)	0.60034 (18)	0.08307 (9)	0.01554 (17)
C2	0.18629 (3)	0.4631 (2)	0.03344 (10)	0.01989 (19)
H2A	0.1826	0.3219	−0.0264	0.024*
C3	0.21695 (2)	0.5379 (2)	0.07365 (11)	0.0223 (2)
H3A	0.2346	0.4482	0.0398	0.027*
C4	0.22225 (2)	0.7422 (2)	0.16280 (11)	0.0207 (2)
H4A	0.2433	0.7941	0.1895	0.025*
C5	0.19617 (2)	0.86802 (19)	0.21155 (10)	0.01656 (18)
C6	0.16482 (2)	0.80494 (17)	0.17353 (9)	0.01396 (16)
C7	0.13715 (2)	0.93935 (17)	0.23513 (9)	0.01430 (17)
C8	0.08569 (2)	1.13880 (18)	0.17534 (9)	0.01475 (17)
C9	0.08638 (2)	1.33660 (19)	0.27115 (10)	0.01791 (18)
H9A	0.1058	1.3826	0.3189	0.021*
C10	0.05852 (2)	1.46660 (19)	0.29678 (10)	0.01816 (18)
H10A	0.0591	1.6004	0.3630	0.022*
C11	0.02971 (2)	1.40427 (18)	0.22709 (10)	0.01674 (18)
C12	0.02942 (2)	1.20383 (19)	0.13243 (11)	0.01962 (19)
H12A	0.0100	1.1570	0.0852	0.024*
C13	0.05708 (2)	1.07101 (19)	0.10588 (10)	0.01794 (18)
H13A	0.0565	0.9352	0.0409	0.022*
C14	0.0000	1.5573 (3)	0.2500	0.0213 (3)
H14A	−0.0040	1.6645	0.1702	0.026*
H1N1	0.1173 (3)	0.984 (3)	0.0566 (16)	0.023 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0186 (3)	0.0209 (3)	0.0208 (3)	−0.0022 (2)	−0.0022 (2)	−0.0022 (2)
F2	0.0207 (3)	0.0257 (3)	0.0225 (3)	−0.0035 (2)	−0.0013 (2)	−0.0072 (2)
O1	0.0220 (3)	0.0272 (4)	0.0112 (3)	0.0051 (3)	0.0022 (2)	0.0005 (3)
N1	0.0144 (3)	0.0210 (4)	0.0110 (3)	0.0032 (3)	0.0022 (3)	−0.0003 (3)
C1	0.0159 (4)	0.0180 (4)	0.0127 (4)	0.0003 (3)	0.0000 (3)	0.0020 (3)
C2	0.0249 (5)	0.0197 (5)	0.0151 (4)	0.0056 (4)	0.0019 (3)	−0.0017 (3)
C3	0.0201 (4)	0.0269 (5)	0.0202 (4)	0.0078 (4)	0.0043 (4)	0.0006 (4)
C4	0.0148 (4)	0.0268 (5)	0.0205 (4)	0.0026 (3)	0.0012 (3)	0.0017 (4)
C5	0.0168 (4)	0.0189 (4)	0.0139 (4)	−0.0001 (3)	−0.0001 (3)	−0.0001 (3)
C6	0.0146 (4)	0.0161 (4)	0.0112 (3)	0.0008 (3)	0.0011 (3)	0.0009 (3)
C7	0.0150 (4)	0.0151 (4)	0.0130 (4)	0.0003 (3)	0.0022 (3)	0.0010 (3)
C8	0.0137 (4)	0.0176 (4)	0.0132 (4)	0.0012 (3)	0.0024 (3)	0.0011 (3)
C9	0.0151 (4)	0.0220 (4)	0.0166 (4)	0.0002 (3)	0.0003 (3)	−0.0031 (3)
C10	0.0166 (4)	0.0194 (4)	0.0186 (4)	0.0005 (3)	0.0023 (3)	−0.0036 (3)
C11	0.0139 (4)	0.0158 (4)	0.0208 (4)	0.0000 (3)	0.0042 (3)	0.0014 (3)
C12	0.0145 (4)	0.0198 (4)	0.0244 (5)	−0.0008 (3)	−0.0001 (3)	−0.0023 (4)
C13	0.0166 (4)	0.0185 (4)	0.0187 (4)	0.0000 (3)	0.0004 (3)	−0.0032 (3)
C14	0.0140 (6)	0.0159 (6)	0.0343 (8)	0.000	0.0044 (5)	0.000

Geometric parameters (Å, º) top

F1—C1	1.3489 (11)	C6—C7	1.5058 (13)
F2—C5	1.3534 (11)	C8—C9	1.3916 (13)
O1—C7	1.2297 (11)	C8—C13	1.3954 (13)
N1—C7	1.3459 (12)	C9—C10	1.3901 (13)
N1—C8	1.4222 (12)	C9—H9A	0.9500
N1—H1N1	0.842 (15)	C10—C11	1.3963 (13)
C1—C2	1.3828 (13)	C10—H10A	0.9500
C1—C6	1.3911 (13)	C11—C12	1.3952 (14)
C2—C3	1.3870 (15)	C11—C14	1.5131 (12)
C2—H2A	0.9500	C12—C13	1.3922 (13)
C3—C4	1.3899 (15)	C12—H12A	0.9500
C3—H3A	0.9500	C13—H13A	0.9500
C4—C5	1.3815 (13)	C14—C11ⁱ	1.5131 (12)
C4—H4A	0.9500	C14—H14A	0.9601
C5—C6	1.3929 (12)

C7—N1—C8	124.77 (8)	N1—C7—C6	114.80 (8)
C7—N1—H1N1	116.8 (10)	C9—C8—C13	119.99 (9)
C8—N1—H1N1	118.2 (10)	C9—C8—N1	121.25 (8)
F1—C1—C2	117.93 (9)	C13—C8—N1	118.70 (8)
F1—C1—C6	118.10 (8)	C10—C9—C8	119.73 (9)
C2—C1—C6	123.96 (9)	C10—C9—H9A	120.1
C1—C2—C3	117.96 (9)	C8—C9—H9A	120.1
C1—C2—H2A	121.0	C9—C10—C11	121.26 (9)
C3—C2—H2A	121.0	C9—C10—H10A	119.4
C2—C3—C4	120.98 (9)	C11—C10—H10A	119.4
C2—C3—H3A	119.5	C12—C11—C10	118.18 (9)
C4—C3—H3A	119.5	C12—C11—C14	121.20 (8)
C5—C4—C3	118.33 (9)	C10—C11—C14	120.57 (8)
C5—C4—H4A	120.8	C13—C12—C11	121.31 (9)
C3—C4—H4A	120.8	C13—C12—H12A	119.3
F2—C5—C4	118.12 (8)	C11—C12—H12A	119.3
F2—C5—C6	118.35 (8)	C12—C13—C8	119.51 (9)
C4—C5—C6	123.53 (9)	C12—C13—H13A	120.2
C1—C6—C5	115.22 (8)	C8—C13—H13A	120.2
C1—C6—C7	123.11 (8)	C11—C14—C11ⁱ	115.22 (11)
C5—C6—C7	121.53 (8)	C11—C14—H14A	108.5
O1—C7—N1	125.27 (9)	C11ⁱ—C14—H14A	108.4
O1—C7—C6	119.92 (8)

F1—C1—C2—C3	179.76 (9)	C5—C6—C7—O1	−46.84 (13)
C6—C1—C2—C3	−1.62 (15)	C1—C6—C7—N1	−50.49 (12)
C1—C2—C3—C4	0.95 (16)	C5—C6—C7—N1	133.95 (9)
C2—C3—C4—C5	0.57 (16)	C7—N1—C8—C9	42.34 (14)
C3—C4—C5—F2	178.73 (9)	C7—N1—C8—C13	−140.39 (10)
C3—C4—C5—C6	−1.60 (15)	C13—C8—C9—C10	−0.27 (15)
F1—C1—C6—C5	179.29 (8)	N1—C8—C9—C10	176.96 (9)
C2—C1—C6—C5	0.68 (14)	C8—C9—C10—C11	−0.61 (15)
F1—C1—C6—C7	3.47 (13)	C9—C10—C11—C12	1.22 (15)
C2—C1—C6—C7	−175.14 (9)	C9—C10—C11—C14	−176.46 (9)
F2—C5—C6—C1	−179.35 (8)	C10—C11—C12—C13	−0.98 (15)
C4—C5—C6—C1	0.98 (14)	C14—C11—C12—C13	176.68 (9)
F2—C5—C6—C7	−3.46 (13)	C11—C12—C13—C8	0.14 (15)
C4—C5—C6—C7	176.87 (9)	C9—C8—C13—C12	0.50 (15)
C8—N1—C7—O1	0.91 (16)	N1—C8—C13—C12	−176.80 (9)
C8—N1—C7—C6	−179.94 (8)	C12—C11—C14—C11ⁱ	47.96 (8)
C1—C6—C7—O1	128.72 (10)	C10—C11—C14—C11ⁱ	−134.43 (10)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱⁱ	0.841 (15)	2.078 (15)	2.8811 (11)	159.4 (14)
C9—H9A···F1ⁱⁱⁱ	0.95	2.41	3.2318 (11)	145

Symmetry codes: (ii) x, −y+2, z−1/2; (iii) x, −y+2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₇H₁₈F₄N₂O₂
M_r	478.43
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	42.0478 (10), 5.2980 (1), 9.5643 (2)
β (°)	92.522 (2)
V (Å³)	2128.57 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.48 × 0.38 × 0.05

Data collection
Diffractometer	Bruker APEXII DUO CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.946, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	26445, 3871, 3172
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.114, 1.06
No. of reflections	3871
No. of parameters	163
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.21

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.841 (15)	2.078 (15)	2.8811 (11)	159.4 (14)
C9—H9A···F1ⁱⁱ	0.95	2.41	3.2318 (11)	145

Symmetry codes: (i) x, −y+2, z−1/2; (ii) x, −y+2, z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

NM gratefully acknowledges funding from Universiti Sains Malaysia under the University Research Grant (No. 1001/PFARMASI/821142). HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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