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Acta Cryst. (2009). E65, o1556    [ doi:10.1107/S1600536809021874 ]

N,N'-(Biphenyl-2,2'-diyl)bis(furan-2-carboxamide)

C. H. Kee, N. F. Thomas, A. Ariffin, K. Awang and S. W. Ng

Abstract top

The title molecule, C22H16N2O4, is a 2,2'-disubstituted biphenyl whose phenylene rings are rotated by 66.5 (1)° so as to avoid repulsion by the substituents. Only one of the two amide -NH- fragments engages in hydrogen bonding, and this interacts with the amido -C(=O)- acceptor of an inversion-related molecule to generate a hydrogen-bonded dimer.

Related literature top

The Heck reaction produces the desired stilbene along with a symmetrical biaryl owing to homocoupling of the aryl halide reactant. For the synthesis of stilbene carboxamides synthesized by using radical cations in a modified Heck reaction; see: Thomas et al. (2008).

Experimental top

N-(2-Iodophenyl)furan-2-carboxamide (1.51 g, 4.81 mmol) was dissolved in DMF (30 ml) under a nitrogen atmosphere. The solution was heated to 393 K. Palladium acetate (0.01 g, 0.05 mmol) was added followed by triethylamine (2.4 ml, 0.2 mol) and 4-methoxystyrene (0.83 g, 6.16 mmol). The mixture was heated for 48 h. The solution was cooled and then mixed with saturated sodium chloride. The organic compound was extracted with ethylacetate. The ethylacetate solution was dried with sodium sulfate. The solvent was evaporated and the product purified by column chromatography (0.12 g, 10% yield). Single crystals were obtained by recrystallization from hexane/chloroform.

Refinement top

Carbon-bound H atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding model approximation with U(H) set to 1.2Ueq(C). The nitrogen-bound H atoms were located in a difference Fourier map, and were refined with a restraint of N–H 0.88±0.01 Å

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C22H16N2O4 at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radiius.
[Figure 2] Fig. 2. Hydrogen-bonded dimer in the crystal structure of (I). Red dashed lines represent N-H···O hydrogen bonds.
N,N'-(Biphenyl-2,2'-diyl)bis(furan-2-carboxamide) top
Crystal data top
C22H16N2O4Z = 2
Mr = 372.37F(000) = 388
Triclinic, P1Dx = 1.431 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.1784 (2) ÅCell parameters from 3508 reflections
b = 10.1399 (2) Åθ = 2.6–28.3°
c = 11.1475 (2) ŵ = 0.10 mm−1
α = 99.938 (1)°T = 100 K
β = 107.521 (1)°Block, colorless
γ = 92.439 (1)°0.30 × 0.25 × 0.20 mm
V = 863.92 (3) Å3
Data collection top
Bruker SMART APEX
diffractometer		3349 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.015
graphiteθmax = 27.5°, θmin = 2.0°
ω scansh = −10→10
6080 measured reflectionsk = −12→13
3836 independent reflectionsl = −14→14
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0627P)2 + 0.3539P]
where P = (Fo2 + 2Fc2)/3
3836 reflections(Δ/σ)max = 0.001
261 parametersΔρmax = 0.33 e Å−3
2 restraintsΔρmin = −0.27 e Å−3
Crystal data top
C22H16N2O4γ = 92.439 (1)°
Mr = 372.37V = 863.92 (3) Å3
Triclinic, P1Z = 2
a = 8.1784 (2) ÅMo Kα radiation
b = 10.1399 (2) ŵ = 0.10 mm−1
c = 11.1475 (2) ÅT = 100 K
α = 99.938 (1)°0.30 × 0.25 × 0.20 mm
β = 107.521 (1)°
Data collection top
Bruker SMART APEX
diffractometer		3349 reflections with I > 2σ(I)
6080 measured reflectionsRint = 0.015
3836 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.111Δρmax = 0.33 e Å−3
S = 1.03Δρmin = −0.27 e Å−3
3836 reflectionsAbsolute structure: ?
261 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.37952 (12)0.28756 (9)0.22024 (9)0.0174 (2)
O20.32912 (12)0.61791 (9)0.36569 (9)0.0186 (2)
O30.42615 (12)0.02447 (10)0.82668 (9)0.0213 (2)
O40.80281 (12)0.23741 (9)0.86550 (9)0.0191 (2)
N10.29107 (14)0.41257 (11)0.42005 (10)0.0156 (2)
H10.295 (2)0.3271 (10)0.3921 (17)0.028 (5)*
N20.47787 (14)0.16551 (11)0.70037 (10)0.0148 (2)
H20.5491 (17)0.2298 (13)0.6951 (15)0.016 (4)*
C10.40891 (17)0.24580 (13)0.10565 (13)0.0190 (3)
H1a0.43040.15700.07490.023*
C20.40293 (17)0.34894 (14)0.04255 (13)0.0190 (3)
H2a0.41800.3456−0.03910.023*
C30.36958 (16)0.46370 (13)0.12235 (12)0.0173 (3)
H30.35810.55170.10440.021*
C40.35755 (16)0.42216 (12)0.22885 (12)0.0155 (3)
C50.32496 (16)0.49452 (12)0.34438 (12)0.0145 (2)
C60.24862 (16)0.44495 (13)0.53444 (12)0.0144 (2)
C70.23946 (17)0.57726 (13)0.59222 (12)0.0169 (3)
H70.26030.65010.55370.020*
C80.19978 (17)0.60133 (13)0.70591 (12)0.0182 (3)
H80.19500.69130.74550.022*
C90.16695 (17)0.49624 (14)0.76291 (12)0.0192 (3)
H90.13860.51380.84040.023*
C100.17609 (17)0.36502 (13)0.70536 (12)0.0174 (3)
H100.15390.29280.74430.021*
C110.21726 (16)0.33732 (12)0.59167 (12)0.0142 (2)
C120.21741 (16)0.19410 (12)0.53056 (12)0.0142 (3)
C130.08880 (17)0.13778 (13)0.41514 (12)0.0164 (3)
H130.00940.19370.37310.020*
C140.07515 (17)0.00244 (13)0.36117 (12)0.0182 (3)
H14−0.0121−0.03370.28250.022*
C150.18976 (17)−0.08003 (13)0.42285 (12)0.0178 (3)
H150.1790−0.17340.38770.021*
C160.31983 (16)−0.02613 (13)0.53571 (12)0.0161 (3)
H160.3991−0.08260.57700.019*
C170.33501 (16)0.11065 (12)0.58905 (12)0.0141 (2)
C180.52125 (16)0.10827 (12)0.80562 (12)0.0150 (3)
C190.69553 (16)0.15138 (12)0.89706 (12)0.0155 (3)
C200.77797 (18)0.11564 (13)1.01001 (13)0.0195 (3)
H200.73190.05771.05290.023*
C210.94791 (18)0.18268 (15)1.05134 (13)0.0226 (3)
H211.03800.17791.12720.027*
C220.95558 (18)0.25413 (15)0.96175 (13)0.0226 (3)
H221.05460.30900.96520.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0214 (5)0.0138 (4)0.0181 (4)0.0017 (4)0.0076 (4)0.0032 (3)
O20.0226 (5)0.0136 (4)0.0217 (5)0.0018 (4)0.0085 (4)0.0058 (4)
O30.0197 (5)0.0241 (5)0.0206 (5)−0.0031 (4)0.0051 (4)0.0095 (4)
O40.0162 (5)0.0212 (5)0.0196 (5)−0.0015 (4)0.0041 (4)0.0065 (4)
N10.0211 (6)0.0113 (5)0.0162 (5)0.0023 (4)0.0082 (4)0.0031 (4)
N20.0136 (5)0.0140 (5)0.0169 (5)−0.0005 (4)0.0037 (4)0.0057 (4)
C10.0176 (6)0.0193 (6)0.0187 (6)−0.0010 (5)0.0066 (5)−0.0011 (5)
C20.0166 (6)0.0231 (6)0.0170 (6)−0.0003 (5)0.0058 (5)0.0029 (5)
C30.0160 (6)0.0178 (6)0.0185 (6)0.0005 (5)0.0056 (5)0.0050 (5)
C40.0143 (6)0.0132 (6)0.0185 (6)0.0005 (5)0.0036 (5)0.0044 (5)
C50.0124 (5)0.0151 (6)0.0158 (6)0.0013 (4)0.0031 (5)0.0050 (5)
C60.0132 (6)0.0158 (6)0.0140 (6)0.0022 (4)0.0031 (5)0.0039 (5)
C70.0176 (6)0.0147 (6)0.0177 (6)0.0030 (5)0.0038 (5)0.0044 (5)
C80.0182 (6)0.0163 (6)0.0176 (6)0.0056 (5)0.0026 (5)0.0012 (5)
C90.0198 (6)0.0230 (7)0.0143 (6)0.0049 (5)0.0048 (5)0.0031 (5)
C100.0178 (6)0.0192 (6)0.0157 (6)0.0015 (5)0.0044 (5)0.0060 (5)
C110.0120 (6)0.0143 (6)0.0148 (6)0.0019 (4)0.0016 (5)0.0037 (4)
C120.0153 (6)0.0140 (6)0.0150 (6)−0.0001 (5)0.0063 (5)0.0047 (5)
C130.0178 (6)0.0162 (6)0.0154 (6)0.0026 (5)0.0044 (5)0.0053 (5)
C140.0194 (6)0.0181 (6)0.0153 (6)−0.0015 (5)0.0040 (5)0.0018 (5)
C150.0211 (6)0.0139 (6)0.0193 (6)−0.0002 (5)0.0089 (5)0.0018 (5)
C160.0157 (6)0.0146 (6)0.0202 (6)0.0034 (5)0.0078 (5)0.0053 (5)
C170.0141 (6)0.0156 (6)0.0137 (6)0.0000 (5)0.0057 (5)0.0040 (4)
C180.0154 (6)0.0147 (6)0.0156 (6)0.0032 (5)0.0055 (5)0.0032 (5)
C190.0163 (6)0.0147 (6)0.0166 (6)0.0018 (5)0.0064 (5)0.0036 (5)
C200.0205 (7)0.0206 (6)0.0171 (6)0.0020 (5)0.0049 (5)0.0049 (5)
C210.0183 (7)0.0283 (7)0.0178 (6)0.0018 (5)0.0017 (5)0.0023 (5)
C220.0152 (6)0.0277 (7)0.0219 (7)−0.0026 (5)0.0032 (5)0.0024 (5)
Geometric parameters (Å, °) top
O1—C11.3695 (16)C8—H80.9500
O1—C41.3749 (15)C9—C101.3893 (18)
O2—C51.2295 (15)C9—H90.9500
O3—C181.2267 (16)C10—C111.3931 (18)
O4—C221.3613 (16)C10—H100.9500
O4—C191.3716 (15)C11—C121.4941 (17)
N1—C51.3572 (16)C12—C171.3957 (18)
N1—C61.4093 (16)C12—C131.4030 (17)
N1—H10.875 (9)C13—C141.3853 (17)
N2—C181.3569 (16)C13—H130.9500
N2—C171.4311 (16)C14—C151.3884 (19)
N2—H20.877 (9)C14—H140.9500
C1—C21.3521 (19)C15—C161.3858 (18)
C1—H1a0.9500C15—H150.9500
C2—C31.4267 (19)C16—C171.3961 (17)
C2—H2a0.9500C16—H160.9500
C3—C41.3550 (18)C18—C191.4765 (18)
C3—H30.9500C19—C201.3559 (18)
C4—C51.4715 (18)C20—C211.4255 (19)
C6—C71.3999 (17)C20—H200.9500
C6—C111.4067 (17)C21—C221.345 (2)
C7—C81.3851 (18)C21—H210.9500
C7—H70.9500C22—H220.9500
C8—C91.3869 (19)
C1—O1—C4106.32 (10)C11—C10—H10119.4
C22—O4—C19105.90 (10)C10—C11—C6118.87 (12)
C5—N1—C6129.64 (11)C10—C11—C12119.07 (11)
C5—N1—H1114.1 (12)C6—C11—C12121.97 (11)
C6—N1—H1116.3 (12)C17—C12—C13118.24 (11)
C18—N2—C17122.19 (10)C17—C12—C11122.04 (11)
C18—N2—H2118.8 (10)C13—C12—C11119.58 (11)
C17—N2—H2118.2 (10)C14—C13—C12121.42 (12)
C2—C1—O1110.34 (11)C14—C13—H13119.3
C2—C1—H1a124.8C12—C13—H13119.3
O1—C1—H1a124.8C13—C14—C15119.56 (12)
C1—C2—C3106.73 (12)C13—C14—H14120.2
C1—C2—H2a126.6C15—C14—H14120.2
C3—C2—H2a126.6C16—C15—C14120.02 (12)
C4—C3—C2106.31 (12)C16—C15—H15120.0
C4—C3—H3126.8C14—C15—H15120.0
C2—C3—H3126.8C15—C16—C17120.36 (12)
C3—C4—O1110.30 (11)C15—C16—H16119.8
C3—C4—C5131.50 (12)C17—C16—H16119.8
O1—C4—C5118.19 (11)C12—C17—C16120.35 (11)
O2—C5—N1125.53 (12)C12—C17—N2120.43 (11)
O2—C5—C4120.77 (11)C16—C17—N2119.14 (11)
N1—C5—C4113.70 (11)O3—C18—N2124.03 (12)
C7—C6—C11120.02 (11)O3—C18—C19119.98 (12)
C7—C6—N1122.95 (11)N2—C18—C19115.98 (11)
C11—C6—N1117.03 (11)C20—C19—O4110.52 (11)
C8—C7—C6119.61 (12)C20—C19—C18131.14 (12)
C8—C7—H7120.2O4—C19—C18118.26 (11)
C6—C7—H7120.2C19—C20—C21106.02 (12)
C9—C8—C7121.07 (12)C19—C20—H20127.0
C9—C8—H8119.5C21—C20—H20127.0
C7—C8—H8119.5C22—C21—C20106.47 (12)
C8—C9—C10119.20 (12)C22—C21—H21126.8
C8—C9—H9120.4C20—C21—H21126.8
C10—C9—H9120.4C21—C22—O4111.09 (12)
C9—C10—C11121.23 (12)C21—C22—H22124.5
C9—C10—H10119.4O4—C22—H22124.5
C4—O1—C1—C2−1.04 (14)C10—C11—C12—C13109.90 (14)
O1—C1—C2—C30.66 (15)C6—C11—C12—C13−66.72 (16)
C1—C2—C3—C40.00 (14)C17—C12—C13—C141.43 (19)
C2—C3—C4—O1−0.65 (14)C11—C12—C13—C14−174.25 (11)
C2—C3—C4—C5179.98 (13)C12—C13—C14—C150.66 (19)
C1—O1—C4—C31.04 (14)C13—C14—C15—C16−1.8 (2)
C1—O1—C4—C5−179.49 (11)C14—C15—C16—C170.93 (19)
C6—N1—C5—O22.2 (2)C13—C12—C17—C16−2.34 (18)
C6—N1—C5—C4−177.63 (12)C11—C12—C17—C16173.22 (11)
C3—C4—C5—O2−11.2 (2)C13—C12—C17—N2174.26 (11)
O1—C4—C5—O2169.42 (11)C11—C12—C17—N2−10.18 (18)
C3—C4—C5—N1168.56 (13)C15—C16—C17—C121.20 (18)
O1—C4—C5—N1−10.77 (16)C15—C16—C17—N2−175.44 (11)
C5—N1—C6—C7−1.9 (2)C18—N2—C17—C12133.43 (13)
C5—N1—C6—C11178.99 (12)C18—N2—C17—C16−49.93 (17)
C11—C6—C7—C80.14 (19)C17—N2—C18—O3−15.7 (2)
N1—C6—C7—C8−178.89 (12)C17—N2—C18—C19163.63 (11)
C6—C7—C8—C9−0.7 (2)C22—O4—C19—C200.32 (15)
C7—C8—C9—C100.7 (2)C22—O4—C19—C18−176.70 (11)
C8—C9—C10—C11−0.1 (2)O3—C18—C19—C20−1.2 (2)
C9—C10—C11—C6−0.48 (19)N2—C18—C19—C20179.49 (13)
C9—C10—C11—C12−177.20 (12)O3—C18—C19—O4175.11 (11)
C7—C6—C11—C100.46 (18)N2—C18—C19—O4−4.22 (17)
N1—C6—C11—C10179.55 (11)O4—C19—C20—C21−0.45 (15)
C7—C6—C11—C12177.08 (11)C18—C19—C20—C21176.06 (13)
N1—C6—C11—C12−3.83 (18)C19—C20—C21—C220.40 (16)
C10—C11—C12—C17−65.60 (16)C20—C21—C22—O4−0.22 (16)
C6—C11—C12—C17117.78 (14)C19—O4—C22—C21−0.05 (15)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.88 (1)2.12 (1)2.970 (1)165 (1)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.88 (1)2.12 (1)2.970 (1)165 (1)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

We thank the Malaysia Toray Science Foundation for supporting this study. CHK thanks MOSTI for an NSF scholarship.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Thomas, N. F., Kee, C.-H., Ariffin, A., Awang, K., Weber, J.-F. F., Lim, C.-G., Mukhtar, M. R. & Abdul Hadi, A. H. (2008). Heterocycles, 75, 1097–1108.

Westrip, S. P. (2009). publCIF. In preparation.