(E)-2-(2-Nitro­ethen­yl)furan

Valerga, P.; Puerta, M.C.; Rodríguez Negrín, Z.; Castañedo Cancio, N.; Palma Lovillo, M.

doi:10.1107/S160053680902861X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1979

doi:10.1107/S160053680902861X

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(E)-2-(2-Nitroethenyl)furan

Pedro Valerga,^a ^* M. Carmen Puerta,^a Zenaida Rodríguez Negrín,^b Nilo Castañedo Cancio ^b and Miguel Palma Lovillo ^c

^aDepartamento de Ciencia de los Materiales e Ingeniería Metalúrgica, Facultad de Ciencias, Campus Universitario del Río San Pedro, Puerto Real 11510, Spain, ^bCentro de Bioactivos Químicos, Universidad Central Marta Abreu de Las, Villas, Cuba, and ^cDepartamento de Química Analítica, Facultad de Ciencias, Campus Universitario del Río San Pedro, Puerto Real 11510, Spain
^*Correspondence e-mail: pedro.valerga@uca.es

(Received 10 July 2009; accepted 20 July 2009; online 25 July 2009)

The title compound, C₆H₅NO₃, was synthesized via condensation of furfural with nitromethane in the presence of isobutylamine. The compound crystallizes exclusively as the E isomer. The angle between the mean planes of the furan ring and the nitroalkenyl group is 1.3 (2)°.

Related literature

For general background, see: Wang et al. (2009 ); An et al. (2007 ); Rastogi et al. (2006 ); Rao et al. (2005 ); Negrín et al. (2002 , 2003 ); Vallejosa et al. (2005 ). For related structures, see: Martínez-Bescos et al. (2008 ); Novoa-de-Armas et al. (1997 ); Pomes et al. (1995 ).

Experimental

Crystal data

C₆H₅NO₃
M_r = 139.11
Monoclinic, P 2₁ /n
a = 9.0374 (18) Å
b = 5.2012 (10) Å
c = 13.027 (3) Å
β = 97.58 (3)°
V = 607.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 100 K
0.47 × 0.17 × 0.14 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.916, T_max = 0.980
4852 measured reflections
1387 independent reflections
1317 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.107
S = 1.06
1387 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680902861X/fj2237sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680902861X/fj2237Isup2.hkl

checkCIF report

Comment top

Among the biological properties of (nitro-alkenyl)-furan compounds our interest is focused in their antibacterial and antifungal activities. In spite of the importance of the structure to explain physical and chemical properties, there are not reports on the structures of the more simple compounds in this family. We start with this study a series of structural reports about them. The structure of title compound, showing trans or E configuration, is shown in Fig. 1. Ring aromaticity is extended to the alkenyl group being C1—C5 bond length, 1.430 (2), significatively shorter than a single C—C bond. Alkenyl sp² carbons mantain coplanarity with furan ring as shown by an angle of 1.3 (2)° between ring plane and C5—C6—N1 plane. Crystal packing does not show hydrogen bonds nor N···π intermolecular interactions (Fig. 2).

Related literature top

For general background, see: Wang et al. (2009); An et al. (2007); Rastogi et al. (2006); Rao et al. (2005); Vallejosa et al.(2005); Negrín et al. (2002, 2003). For related structures, see: Martínez-Bescos et al. (2008); Novoa-de-Armas et al. (1997); Pomes et al. (1995).

Experimental top

2-(2-Nitro-ethenyl)-furan, also called G-0, was obtained by a variation of Knoevenagel's method: condensation of an aldehyde with substances containing an active α-hydrogen in the presence of a base (ammonia or amines) as catalyst. The Centro de Bioactivos Químicos (Cuba) has already patented this modified method using furfural, an aromatic compound from acid hydrolisis of sugar cane residuals (straw, sawdust, etc.) and nitromethane in the presence of isobutylamine. A yellow crystalline solid was obtained with purity higher than 98%, melting point 74.5°, scarcely soluble in water and very soluble in nitromethane, carbon tetrachloride, petroleum ether and ethanol.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP representation of the molecular structure of the title compound showing the atom labelling scheme (thermal ellipsoid probability 50%).
	Fig. 2. Packing diagram of the title compound.

(E)-2-(2-Nitroethenyl)furan top

Crystal data top

C₆H₅NO₃	F(000) = 288
M_r = 139.11	D_x = 1.522 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2396 reflections
a = 9.0374 (18) Å	θ = 2.6–27.5°
b = 5.2012 (10) Å	µ = 0.13 mm⁻¹
c = 13.027 (3) Å	T = 100 K
β = 97.58 (3)°	Prism, yellow
V = 607.0 (2) Å³	0.47 × 0.17 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1387 independent reflections
Radiation source: fine-focus sealed tube	1317 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
1700 ω scan frames (0.3°, 10)	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −11→11
T_min = 0.916, T_max = 0.980	k = −6→6
4852 measured reflections	l = −16→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	0 constraints
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0569P)² + 0.266P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1387 reflections	Δρ_max = 0.25 e Å⁻³
91 parameters	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₆H₅NO₃	V = 607.0 (2) Å³
M_r = 139.11	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.0374 (18) Å	µ = 0.13 mm⁻¹
b = 5.2012 (10) Å	T = 100 K
c = 13.027 (3) Å	0.47 × 0.17 × 0.14 mm
β = 97.58 (3)°

Data collection top

Bruker SMART APEX diffractometer	1387 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1317 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.980	R_int = 0.023
4852 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	Δρ_max = 0.25 e Å⁻³
1387 reflections	Δρ_min = −0.28 e Å⁻³
91 parameters

Special details top

Experimental. Refinement of F² against unique set of 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 > 2sigma(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.

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 unique set of 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
O1	0.67495 (10)	0.19614 (17)	0.08110 (7)	0.0206 (2)
O2	0.15283 (11)	0.49888 (19)	0.10417 (8)	0.0290 (3)
O3	0.16242 (10)	0.13012 (19)	0.18291 (7)	0.0254 (3)
N1	0.21943 (12)	0.3007 (2)	0.13567 (8)	0.0205 (3)
C1	0.59854 (14)	0.0119 (2)	0.12894 (9)	0.0182 (3)
C2	0.68866 (14)	−0.1941 (2)	0.15531 (9)	0.0202 (3)
H2	0.6627	−0.3465	0.1890	0.024*
C3	0.82904 (14)	−0.1370 (3)	0.12270 (10)	0.0221 (3)
H3	0.9152	−0.2435	0.1300	0.027*
C4	0.81535 (14)	0.0996 (3)	0.07909 (10)	0.0227 (3)
H4	0.8930	0.1870	0.0508	0.027*
C5	0.44755 (13)	0.0618 (2)	0.14455 (9)	0.0185 (3)
H5	0.3974	−0.0667	0.1787	0.022*
C6	0.37162 (14)	0.2755 (3)	0.11477 (10)	0.0197 (3)
H6	0.4172	0.4090	0.0803	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0179 (4)	0.0200 (5)	0.0243 (5)	0.0009 (3)	0.0046 (3)	0.0019 (3)
O2	0.0269 (5)	0.0301 (5)	0.0303 (5)	0.0112 (4)	0.0053 (4)	0.0047 (4)
O3	0.0206 (5)	0.0269 (5)	0.0299 (5)	−0.0014 (4)	0.0074 (4)	0.0019 (4)
N1	0.0189 (5)	0.0244 (6)	0.0182 (5)	0.0026 (4)	0.0023 (4)	−0.0017 (4)
C1	0.0199 (6)	0.0185 (6)	0.0163 (6)	−0.0013 (4)	0.0027 (4)	−0.0017 (4)
C2	0.0221 (6)	0.0199 (6)	0.0186 (6)	0.0006 (5)	0.0019 (5)	−0.0010 (5)
C3	0.0201 (6)	0.0256 (6)	0.0204 (6)	0.0042 (5)	0.0016 (5)	−0.0025 (5)
C4	0.0164 (6)	0.0279 (7)	0.0242 (6)	0.0007 (5)	0.0040 (5)	−0.0011 (5)
C5	0.0185 (6)	0.0212 (6)	0.0159 (6)	−0.0021 (5)	0.0028 (4)	−0.0023 (4)
C6	0.0170 (6)	0.0236 (6)	0.0194 (6)	0.0002 (5)	0.0052 (4)	−0.0013 (5)

Geometric parameters (Å, º) top

O1—C4	1.3680 (15)	C2—H2	0.9500
O1—C1	1.3772 (15)	C3—C4	1.3544 (19)
O2—N1	1.2361 (14)	C3—H3	0.9500
O3—N1	1.2309 (15)	C4—H4	0.9500
N1—C6	1.4428 (16)	C5—C6	1.3366 (18)
C1—C2	1.3623 (17)	C5—H5	0.9500
C1—C5	1.4296 (17)	C6—H6	0.9500
C2—C3	1.4214 (18)

C4—O1—C1	105.97 (10)	C4—C3—H3	126.9
O3—N1—O2	123.33 (11)	C2—C3—H3	126.9
O3—N1—C6	120.08 (11)	C3—C4—O1	111.04 (12)
O2—N1—C6	116.59 (11)	C3—C4—H4	124.5
C2—C1—O1	110.03 (11)	O1—C4—H4	124.5
C2—C1—C5	131.07 (12)	C6—C5—C1	124.94 (12)
O1—C1—C5	118.89 (11)	C6—C5—H5	117.5
C1—C2—C3	106.73 (11)	C1—C5—H5	117.5
C1—C2—H2	126.6	C5—C6—N1	119.11 (12)
C3—C2—H2	126.6	C5—C6—H6	120.4
C4—C3—C2	106.23 (11)	N1—C6—H6	120.4

C4—O1—C1—C2	−0.39 (13)	C1—O1—C4—C3	0.54 (14)
C4—O1—C1—C5	178.58 (10)	C2—C1—C5—C6	179.68 (13)
O1—C1—C2—C3	0.12 (14)	O1—C1—C5—C6	0.96 (18)
C5—C1—C2—C3	−178.69 (12)	C1—C5—C6—N1	−179.91 (11)
C1—C2—C3—C4	0.21 (14)	O3—N1—C6—C5	2.03 (17)
C2—C3—C4—O1	−0.47 (14)	O2—N1—C6—C5	−178.15 (11)

Experimental details

Crystal data
Chemical formula	C₆H₅NO₃
M_r	139.11
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.0374 (18), 5.2012 (10), 13.027 (3)
β (°)	97.58 (3)
V (Å³)	607.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.47 × 0.17 × 0.14

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.916, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	4852, 1387, 1317
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.107, 1.06
No. of reflections	1387
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.28

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Acknowledgements

We thank the SCCYT (Universidad de Cádiz) for the X-ray data collection and the Consejería de Innovación, Ciencia y Empresa de la Junta de Andalucía, for financial support. ZRN thanks the AUIP and Aula Iberoamericana for the stay at UCA.

References

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