Acta Cryst.(2004). E60, o631±o633 DOI: 10.1107/S1600536804006245 Gordana PavlovicÂet al. C11H9NO2
o631
organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
2-Furancarboxanilide
Gordana PavlovicÂ,a* Vesna TralicÂ-KulenovicÂaand Zora PopovicÂb
aFaculty of Textile Technology, University of
Zagreb, Pierottijeva 6, HR-10000 Zagreb, Croatia, andbDepartment of Chemistry,
Laboratory of General and Inorganic Chemistry, Faculty of Science, University of Zagreb, Zvonimirova 8, HR-10000 Zagreb, Croatia
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 296 K
Mean(C±C) = 0.002 AÊ Rfactor = 0.050 wRfactor = 0.130
Data-to-parameter ratio = 14.5
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
In the title compound, N-phenylfuran-2-carboxamide, C11H9NO2, the C O group is antiin relation to the amide NH group. The phenyl ring is twisted by 147.67 (14)about the
C(phenyl)ÐN bond with respect to the planar 2-furamide fragment. The amide H atom is the donor in a bifurcated hydrogen bond involving an intramolecular NÐH O [2.682 (2) AÊ] interaction with the furan O atom and an intermolecular NÐH O hydrogen bond [3.084 (2) AÊ] with the amide O atom. According to the graph-set assignment, the intramolecular hydrogen-bond pattern is of theS(5) type. The intermolecular NÐH O hydrogen bond links the molecules into in®niteC(4) chains along theaaxis.
Comment
The title compound, (I), ®rst prepared by Baum (1904), has now been investigated by X-ray single-crystal diffraction.
Compound (I) was prepared as part of our study of aryl-substituted benzothiazole derivatives. These compounds exhibit complex biological activity, such as anti-infective, antifungal, anthelmintic or antitumor activities (TralicÂ-KulenovicÂet al., 1993; RacaneÂet al., 2001). The thionation of the corresponding N-arylfuramides leads to N -arylthiofur-amides, which are precursors in the synthesis of 2-(2- or 3-furyl)benzothiazoles by oxidative cyclization (FisÏer-JakicÂet al., 1980). 2-Furancarboxanilide is known for its antifungal activity. A survey of the Cambridge Structural Database (Version 5.25, November 2003; Allen, 2002) reveals only two structures of 2-furancarboxamides,N -(4,6-dimethylpyridine-2-yl)(furan-2-yl)carboxamide, (II) (Rodieret al., 1991), andN -(2-chloroethyl)-2-furamide, (III) (GalesÏicÂet al., 1987).
The molecule of (I) is not planar: the dihedral angle between the phenyl and furan rings is 32.30 (9). The planarity
of the 2-furancarboxamide moiety is preserved by the presence of a strong intramolecular NÐH O hydrogen bond between the amide N atom and the furan O atom, thus forming a ®ve-membered chelate ring (Fig. 1 and Table 2). A corresponding intramolecular hydrogen bond is formed in (II) [N O 2.668 (2) AÊ and 108 (2)] and in (III) [N O
2.727 (4) AÊ and 110 (4)].
organic papers
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Gordana PavlovicÂet al. C11H9NO2 Acta Cryst.(2004). E60, o631±o633The C5ÐN bond length of 1.350 (2) AÊ shows remarkable -electron delocalization within the planar 2-furamide moiety. On the other hand, the C6ÐN bond, with a length of 1.416 (2) AÊ, can be regarded as a single bond. The analogous CÐN bond lengths in (II) are 1.360 (2) and 1.403 (2) AÊ, respectively, and 1.337 (6) and 1.437 (6) AÊ, respectively, in (III). The O1ÐC1 and O1ÐC4 bonds are 1.368 (2) and 1.361 (2) AÊ, respectively, which corresponds to an average OÐCsp2distance of 1.368 AÊ (Allenet al., 1987). The C1 C2 bond [1.347 (2) AÊ] within the furan ring is within the expected range, while the C3 C4 bond [1.328 (2) AÊ] is slightly shorter using a 3criterion (1.341 AÊ; Allenet al., 1987). Other bond distances in both the furan and the phenyl rings are consistent with expected values (Allenet al., 1987).
The dihedral angle between the furan and pyridine rings in (II) is 6.6 (3), in contrast with the analogous dihedral angle in
(I), between the furan and phenyl rings, of 32.30 (9). The
additional CÐH O intramolecular hydrogen bond [C O 2.927 (2) AÊ and 120 (2)] between the pyridine C atom and the
keto O atom contributes to the planarity of (II). Similar intramolecular hydrogen bonding is not found in the structure of (I). Although the C11 O2 distance is 2.953 (2) AÊ, the H11 O2 distance is 2.504 (1) AÊ and the C11ÐH11 O2 angle is only 109.9 (1). Therefore, it is obvious that atom H11
is not directed towards the O2 electron lone pair, explaining the twisted molecular conformation of (I).
Molecules of (I) are joined by NÐH1N O2i [symmetry code: (i) xÿ1
2, y, 12ÿz] intermolecular hydrogen bonds [N O 3.084 (2) AÊ and 161 (2)] into in®nite chains running
parallel to theaaxis (Table 2). The pattern is speci®ed asC(4) chains. A similar packing mode is found in the structure of
(III) [NÐH O 2.872 (5) AÊ and 150 (4)], where
inter-molecular hydrogen bonding connects the molecules into in®niteC(4) chains along thebaxis, while in the structure of (II), the molecules form pairs through weak CÐH O hydrogen bonds [C O 3.316 (2) AÊ and 149 (2)].
Experimental
Compound (I) was prepared according to the procedure of Baum (1904). Single crystals were obtained by evaporation of an ethanol solution.
Crystal data
C11H9NO2
Mr= 187.19
Orthorhombic,Pbca a= 8.699 (2) AÊ
b= 12.983 (2) AÊ
c= 16.712 (2) AÊ
V= 1887.4 (5) AÊ3
Z= 8
Dx= 1.318 Mg mÿ3
MoKradiation Cell parameters from 5046
re¯ections
= 15±27 = 0.09 mmÿ1
T= 296 (2) K Prism, colourless 0.640.510.42 mm
Data collection
Oxford Diffraction Xcalibur2 diffractometer with Sapphire 3 CCD detector
'and!scans
Absorption correction: none 32 112 measured re¯ections 1903 independent re¯ections
1758 re¯ections withI> 2(I)
Rint= 0.049
max= 26.5
h=ÿ10!10
k=ÿ16!16
l=ÿ20!20
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.050
wR(F2) = 0.130
S= 1.19 1903 re¯ections 131 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.0753P)2
+ 0.0157P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.15 e AÊÿ3
min=ÿ0.14 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
O1ÐC4 1.361 (2) O1ÐC1 1.368 (2) O2ÐC5 1.232 (2) NÐC5 1.349 (2) NÐC6 1.416 (2)
C1ÐC2 1.347 (2) C1ÐC5 1.474 (2) C2ÐC3 1.416 (3) C3ÐC4 1.328 (2)
C5ÐNÐC6 126.6 (2)
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
NÐH1N O1 0.85 (2) 2.28 (2) 2.682 (2) 109 (2) NÐH1N O2i 0.85 (2) 2.27 (2) 3.084 (2) 161 (2)
Symmetry code: (i)xÿ12;y;1 2ÿz.
H atoms bonded to the phenyl and furan C atoms were introduced at calculated positions and re®ned using a riding model [Uiso(H) =
1.2Ueq(C) and CÐH = 0.93 AÊ]. The H atom on the amide N atom was
found in a difference Fourier electron-density map and re®ned freely. Data collection: CrysAlisCCD (Oxford Diffraction, 2003); cell re®nement:CrysAlisRED(Oxford Diffraction, 2003); data reduction:
Figure 2
A view of the crystal structure of (I), showing in®nite C(4) chains extending along theaaxis. Hydrogen bonds are indicated by dashed lines. O atoms are shown as solid circles, C atoms as open circles and N atoms as shaded circles.
Figure 1
CrysAlisRED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON98 (Spek, 1998); software used to prepare material for publication:SHELXL97.
This research was supported by the Ministry of Science and Technology of the Republic of Croatia (Grant Nos. 0119633 and 0125005).
References
Allen, F. H. (2002).Acta Cryst.B58, 380±388.
Allen, F. H., Kennard, O., Watson, D. G., Brammer L. & Orpen, A. G. (1987).
J. Chem. Soc. Perkin Trans.2, pp. S1±S19.
Baum, E. (1904).Chem. Ber.37, 2949.
FisÏer-JakicÂ, L., Karaman, B. & JakopcÏicÂ, K. (1980).Croat. Chem. Acta,53, 69± 79.
GalesÏicÂ, N., KovacÏevicÂ, K., Vlahov A. & GalesÏicÂ, M. (1987).Acta Cryst.C43, 2350±2353.
Oxford Diffraction (2003).CrysAlisCCDandCrysAlisRED. Versions 1.170. Oxford Diffraction Ltd, Abingdon, Oxford, England.
RacaneÂ, L., TralicÂ-KulenovicÂ, V., FisÏer-JakicÂ, L., Boykin, D. W. & Karminski-Zamola, G. (2001).Heterocycles,55, 2085±2098.
Rodier, P. N., Cense, J. M., Robert, J.-M. & Le Baut G. (1991).Acta Cryst.C47, 2688±2690.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Spek, A. L. (1998). PLATON98for Windows. University of Utrecht, The Netherlands.
TralicÂ-KulenovicÂ, V., FisÏer-JakicÂ, L. & LazarevicÂ, Z. (1993).Spectrosc. Lett.26, 1771±1784.
Acta Cryst.(2004). E60, o631±o633 Gordana PavlovicÂet al. C11H9NO2
o633
supporting information
sup-1 Acta Cryst. (2004). E60, o631–o633
supporting information
Acta Cryst. (2004). E60, o631–o633 [https://doi.org/10.1107/S1600536804006245]
2-Furancarboxanilide
Gordana Pavlovi
ć
, Vesna Trali
ć
-Kulenovi
ć
and Zora Popovi
ć
N-phenylfuran-2-carboxamide
Crystal data
C11H9NO2 Mr = 187.19
Orthorhombic, Pbca
Hall symbol: -P 2ac 2ab
a = 8.699 (2) Å
b = 12.983 (2) Å
c = 16.712 (2) Å
V = 1887.4 (5) Å3 Z = 8
F(000) = 784
Dx = 1.318 Mg m−3 Melting point = 396–397 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 5046 reflections
θ = 15–27°
µ = 0.09 mm−1 T = 296 K Prism, colourless 0.64 × 0.51 × 0.42 mm
Data collection
Oxford Diffraction Xcalibur2
diffractometer with Sapphire 3 CCD detector Radiation source: fine-focus sealed tube Graphite parallel monochromator
φ and ω scans
32112 measured reflections 1903 independent reflections
1758 reflections with I > 2σ(I)
Rint = 0.049
θmax = 26.5°, θmin = 4.6° h = −10→10
k = −16→16
l = −20→20
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.050 wR(F2) = 0.130 S = 1.19 1903 reflections 131 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: geom & difmap H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(F
o2) + (0.0753P)2 + 0.0157P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.15 e Å−3 Δρmin = −0.14 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.01579 (12) 0.23504 (9) 0.17519 (6) 0.0489 (3)
O2 0.39457 (12) 0.13439 (10) 0.16041 (7) 0.0551 (4)
N 0.20672 (15) 0.10881 (10) 0.25433 (7) 0.0425 (3)
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sup-2 Acta Cryst. (2004). E60, o631–o633
C1 0.15826 (16) 0.21861 (11) 0.14299 (9) 0.0399 (4)
C2 0.17223 (19) 0.27172 (14) 0.07415 (10) 0.0527 (4)
H2 0.2577 0.2735 0.0407 0.063*
C3 0.0314 (2) 0.32436 (14) 0.06263 (10) 0.0570 (5)
H3 0.0063 0.3674 0.0201 0.068*
C4 −0.0578 (2) 0.30038 (13) 0.12434 (10) 0.0538 (4)
H4 −0.1573 0.3249 0.1318 0.065*
C5 0.26397 (17) 0.14961 (11) 0.18630 (8) 0.0402 (4)
C6 0.28327 (16) 0.04057 (11) 0.30710 (9) 0.0397 (4)
C7 0.24840 (18) 0.04681 (12) 0.38803 (9) 0.0483 (4)
H7 0.1769 0.0949 0.4058 0.058*
C8 0.3190 (2) −0.01771 (15) 0.44211 (11) 0.0577 (5)
H8 0.2948 −0.0133 0.4962 0.069*
C9 0.4255 (2) −0.08887 (14) 0.41620 (11) 0.0609 (5)
H9 0.4746 −0.1316 0.4528 0.073*
C10 0.4590 (2) −0.09649 (14) 0.33579 (11) 0.0577 (5)
H10 0.5302 −0.1450 0.3184 0.069*
C11 0.38778 (18) −0.03252 (12) 0.28042 (11) 0.0492 (4)
H11 0.4098 −0.0386 0.2262 0.059*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.0375 (6) 0.0579 (7) 0.0513 (7) 0.0089 (5) 0.0039 (4) 0.0106 (5) O2 0.0359 (6) 0.0736 (8) 0.0558 (7) 0.0095 (5) 0.0076 (5) 0.0099 (5) N 0.0312 (7) 0.0512 (8) 0.0451 (7) 0.0068 (5) 0.0030 (5) 0.0046 (5) C1 0.0317 (7) 0.0449 (8) 0.0432 (8) −0.0011 (6) −0.0006 (6) −0.0030 (6) C2 0.0443 (9) 0.0667 (10) 0.0472 (9) 0.0021 (7) 0.0051 (7) 0.0093 (7) C3 0.0541 (10) 0.0638 (11) 0.0530 (9) 0.0072 (8) −0.0018 (8) 0.0150 (8) C4 0.0428 (9) 0.0583 (10) 0.0604 (10) 0.0114 (7) −0.0027 (7) 0.0098 (8) C5 0.0341 (8) 0.0446 (8) 0.0418 (7) 0.0004 (6) −0.0012 (6) −0.0026 (6) C6 0.0326 (7) 0.0420 (7) 0.0444 (8) −0.0023 (6) −0.0028 (6) 0.0012 (6) C7 0.0449 (8) 0.0531 (9) 0.0470 (9) −0.0009 (7) −0.0029 (6) −0.0039 (7) C8 0.0570 (10) 0.0687 (11) 0.0475 (9) −0.0080 (9) −0.0104 (7) 0.0038 (8) C9 0.0514 (10) 0.0630 (11) 0.0684 (11) −0.0034 (8) −0.0202 (9) 0.0165 (9) C10 0.0447 (9) 0.0517 (9) 0.0767 (12) 0.0085 (8) −0.0040 (8) 0.0064 (8) C11 0.0443 (8) 0.0493 (8) 0.0540 (9) 0.0053 (7) 0.0017 (7) 0.0010 (7)
Geometric parameters (Å, º)
O1—C4 1.361 (2) C4—H4 0.9300
O1—C1 1.368 (2) C6—C11 1.388 (2)
O2—C5 1.232 (2) C6—C7 1.388 (2)
N—C5 1.349 (2) C7—C8 1.377 (2)
N—C6 1.416 (2) C7—H7 0.9300
N—H1N 0.85 (2) C8—C9 1.378 (3)
C1—C2 1.347 (2) C8—H8 0.9300
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sup-3 Acta Cryst. (2004). E60, o631–o633
C2—C3 1.416 (3) C9—H9 0.9300
C2—H2 0.9300 C10—C11 1.389 (2)
C3—C4 1.328 (2) C10—H10 0.9300
C3—H3 0.9300 C11—H11 0.9300
C4—O1—C1 106.14 (12) C11—C6—C7 119.74 (15)
C5—N—C6 126.6 (2) C11—C6—N 122.38 (14)
C5—N—H1N 118.4 (12) C7—C6—N 117.87 (13)
C6—N—H1N 114.9 (12) C8—C7—C6 120.43 (16)
C2—C1—O1 109.75 (13) C8—C7—H7 119.8
C2—C1—C5 132.42 (14) C6—C7—H7 119.8
O1—C1—C5 117.83 (12) C7—C8—C9 120.09 (16)
C1—C2—C3 106.58 (14) C7—C8—H8 120.0
C1—C2—H2 126.7 C9—C8—H8 120.0
C3—C2—H2 126.7 C8—C9—C10 119.77 (16)
C4—C3—C2 106.68 (14) C8—C9—H9 120.1
C4—C3—H3 126.7 C10—C9—H9 120.1
C2—C3—H3 126.7 C9—C10—C11 120.80 (17)
C3—C4—O1 110.85 (14) C9—C10—H10 119.6
C3—C4—H4 124.6 C11—C10—H10 119.6
O1—C4—H4 124.6 C6—C11—C10 119.14 (16)
O2—C5—N 124.98 (14) C6—C11—H11 120.4
O2—C5—C1 120.04 (13) C10—C11—H11 120.4
N—C5—C1 114.97 (13)
C4—O1—C1—C2 −0.28 (17) O1—C1—C5—N 0.40 (19)
C4—O1—C1—C5 −179.91 (13) C5—N—C6—C11 −33.7 (2)
O1—C1—C2—C3 0.13 (18) C5—N—C6—C7 147.67 (14)
C5—C1—C2—C3 179.69 (16) C11—C6—C7—C8 1.2 (2)
C1—C2—C3—C4 0.1 (2) N—C6—C7—C8 179.86 (14)
C2—C3—C4—O1 −0.3 (2) C6—C7—C8—C9 0.3 (2)
C1—O1—C4—C3 0.33 (19) C7—C8—C9—C10 −1.2 (3)
C6—N—C5—O2 −1.2 (2) C8—C9—C10—C11 0.6 (3)
C6—N—C5—C1 −179.99 (13) C7—C6—C11—C10 −1.8 (2)
C2—C1—C5—O2 2.0 (3) N—C6—C11—C10 179.67 (14)
O1—C1—C5—O2 −178.42 (13) C9—C10—C11—C6 0.8 (3)
C2—C1—C5—N −179.13 (16)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N—H1N···O1 0.85 (2) 2.28 (2) 2.682 (2) 109 (2)
N—H1N···O2i 0.85 (2) 2.27 (2) 3.084 (2) 161 (2)
