N-Nitro-1H-pyrrole-2-carboxamide

Liu, L.; He, C.; Li, Z.; Li, C.; Zhang, X.; Zhang, S.

doi:10.1107/S1600536811002455

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o479

doi:10.1107/S1600536811002455

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N-Nitro-1H-pyrrole-2-carboxamide

Long Liu,^a Chunlin He,^b Zengxi Li,^a ^* Chunshan Li,^b Xiangping Zhang ^b and Suojiang Zhang ^b

^aGraduate University of the Chinese Academy of Sciences, Beijing 100049, People's Republic of China, and ^bState Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, People's Republic of China
^*Correspondence e-mail: zxli@home.ipe.ac.cn(Zengxi_Li), csli@home.ipe.ac.cn(Chunshan_Li)

(Received 31 December 2010; accepted 18 January 2011; online 22 January 2011)

In the title compound, C₅H₅N₃O₃, the nitro group is twisted with respect to the amide group, with C—N—N—O torsion angles of 29.0 (2) and −153.66 (14)°. In the crystal, molecules are linked through intermolecular N—H⋯O and C—H⋯O hydrogen bonds, forming supramolecular chains along the a axis. These chains stack in parallel and form distinct layer motifs in the (001) plane.

Related literature

For applications of pyrrole derivatives as antimicrobials, see: Mohamed et al. (2009 ). For the structures of similar pyrrole derivatives, see: Zeng et al. (2007 , 2010 ); Wang et al. (2010 ); Ferreira et al. (2002 ). For the synthesis of N,N′-dinitrourea (DNU), see: Goede et al. (2001 ).

Experimental

Crystal data

C₅H₅N₃O₃
M_r = 155.12
Orthorhombic, P b c a
a = 9.988 (3) Å
b = 6.4547 (17) Å
c = 19.184 (6) Å
V = 1236.8 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 133 K
0.47 × 0.43 × 0.20 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
8849 measured reflections
1402 independent reflections
1214 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.106
S = 1.00
1402 reflections
108 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3ⁱ	0.88 (3)	2.21 (3)	3.001 (2)	150 (2)
N2—H2N⋯O1ⁱⁱ	0.88 (2)	2.11 (2)	2.982 (2)	171.5 (19)
C3—H3⋯O1ⁱⁱ	0.95	2.39	3.269 (2)	154
C3—H3⋯O2ⁱⁱ	0.95	2.48	3.245 (2)	138
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002455/fj2382sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002455/fj2382Isup2.hkl

checkCIF report

Comment top

Pyrrole derivatives play an important role in heterocyclic chemistry due to their intrinsic biological activities as antimicrobial agents (Mohamed et al., 2009). The structures of these compounds have been reported extensively, such as 2,3,5-substituted pyrrole derivatives (Ferreira et al., 2002), 1-Benzyl-N-methyl-1H-pyrrole-2-carboxamide (Zeng et al., 2010), 2-(4,5-dibromo-1H-pyrrole-2-carboxamido) propionate (Zeng et al., 2007) and Tetraethyl 1,1'-(ethane-1,2-diyl)bis(2,5- dimethyl-1H-pyrrole-3,4-dicarboxylate) (Wang et al., 2010).

The bond length of N2—C5 for the title compound (1.404 (2) Å) is about 0.07 Å longer than compound 1-Benzyl-N-methyl-1H-pyrrole-2-carboxamide (1.334 (3) Å) (Zeng et al., 2010) (Fig. 1). The unit is nearly co-planar with the twist happens at nitro group (C5—N2—N3—O2 = 29.0 (2), C5—N2—N3—O3 = -153.66 (14)), the maximum deviation of other torsions is C3—C4—C5—N2 = -8.6 (3)°.

In the crystal structure (Fig. 2), molecules are connected through N1—H1N···O3, N2—H2N···O1, C3—H3···O1, C3—H3···O3 (Table 1) hydrogen bonds to form one-dimensional supramolecular chains along the a axis. These supramolecular chains stack in parallel and form distinct layer motif in (0 0 1) plane.

Related literature top

For applications of pyrrole derivatives as antimicrobials, see: Mohamed et al. (2009). For the structures of similar pyrrole derivatives, see: Zeng et al. (2007, 2010); Wang et al. (2010); Ferreira et al. (2002). For the synthesis of N,N'-dinitrourea (DNU), see: Goede et al. (2001).

Experimental top

Pyrrole (0.67 g, 0.01 mol) was added to a solution of N,N'-dinitrourea (DNU) (1.5 g, 0.01 mol) dissolved in acetonitrile (10 ml), stirred at room temperature for 24 h, the crude compound was obtained after acetonitrile was evaporated. Then the products were dissoved in ethyl acetate, colourless crystals suitable for X-ray crystal diffraction were obtained by slow evaporation of the solution at room temperature. DNU was synthesized according to the literautre (Goede et al., 2001).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 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, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot of C₅H₅N₃O₃ at the 50% probability level; Hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded layer structure.

N-Nitro-1H-pyrrole-2-carboxamide top

Crystal data top

C₅H₅N₃O₃	F(000) = 640
M_r = 155.12	D_x = 1.666 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3166 reflections
a = 9.988 (3) Å	θ = 3.2–27.5°
b = 6.4547 (17) Å	µ = 0.14 mm⁻¹
c = 19.184 (6) Å	T = 133 K
V = 1236.8 (6) Å³	Platelet, colourless
Z = 8	0.47 × 0.43 × 0.20 mm

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	1214 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.034
Graphite monochromator	θ_max = 27.5°, θ_min = 3.9°
Detector resolution: 28.5714 pixels mm^-1	h = −12→12
ϕ and ω scans	k = −8→8
8849 measured reflections	l = −24→24
1402 independent 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0596P)² + 0.536P] where P = (F_o² + 2F_c²)/3
1402 reflections	(Δ/σ)_max < 0.001
108 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₅H₅N₃O₃	V = 1236.8 (6) Å³
M_r = 155.12	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.988 (3) Å	µ = 0.14 mm⁻¹
b = 6.4547 (17) Å	T = 133 K
c = 19.184 (6) Å	0.47 × 0.43 × 0.20 mm

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	1214 reflections with I > 2σ(I)
8849 measured reflections	R_int = 0.034
1402 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.34 e Å⁻³
1402 reflections	Δρ_min = −0.15 e Å⁻³
108 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
O1	0.17512 (12)	0.34028 (18)	0.50500 (5)	0.0219 (3)
O2	0.27334 (11)	0.3909 (2)	0.37665 (6)	0.0256 (3)
O3	0.45611 (12)	0.21230 (19)	0.36431 (6)	0.0255 (3)
N1	0.25340 (14)	0.3489 (2)	0.64493 (7)	0.0207 (3)
N2	0.39562 (13)	0.3045 (2)	0.47037 (7)	0.0182 (3)
N3	0.37143 (13)	0.3012 (2)	0.39910 (7)	0.0178 (3)
C1	0.31849 (18)	0.3310 (3)	0.70652 (8)	0.0235 (4)
H1	0.2800	0.3496	0.7514	0.028*
C2	0.44956 (17)	0.2815 (3)	0.69312 (8)	0.0240 (4)
H2	0.5173	0.2581	0.7270	0.029*
C3	0.46594 (16)	0.2715 (2)	0.62056 (8)	0.0198 (4)
H3	0.5464	0.2417	0.5962	0.024*
C4	0.34176 (15)	0.3137 (2)	0.59132 (8)	0.0160 (3)
C5	0.29335 (15)	0.3204 (2)	0.52027 (8)	0.0158 (3)
H1N	0.169 (3)	0.380 (4)	0.6375 (12)	0.049 (7)*
H2N	0.474 (2)	0.250 (3)	0.4794 (11)	0.032 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0140 (6)	0.0339 (7)	0.0177 (5)	−0.0002 (5)	−0.0004 (4)	0.0003 (5)
O2	0.0181 (6)	0.0398 (7)	0.0188 (6)	0.0049 (5)	−0.0022 (4)	0.0071 (5)
O3	0.0198 (6)	0.0381 (7)	0.0187 (6)	0.0050 (5)	0.0027 (5)	−0.0052 (5)
N1	0.0164 (7)	0.0276 (7)	0.0180 (6)	0.0021 (6)	0.0007 (5)	0.0002 (6)
N2	0.0132 (6)	0.0281 (7)	0.0133 (6)	0.0016 (5)	−0.0022 (5)	0.0011 (5)
N3	0.0153 (6)	0.0241 (7)	0.0141 (6)	−0.0022 (5)	0.0004 (5)	0.0013 (5)
C1	0.0273 (9)	0.0286 (9)	0.0145 (7)	−0.0002 (7)	0.0011 (6)	0.0000 (6)
C2	0.0223 (8)	0.0315 (9)	0.0183 (8)	−0.0013 (7)	−0.0053 (6)	0.0015 (6)
C3	0.0146 (7)	0.0257 (8)	0.0191 (8)	−0.0008 (6)	−0.0001 (6)	0.0010 (6)
C4	0.0147 (7)	0.0176 (7)	0.0158 (7)	−0.0013 (6)	0.0003 (6)	−0.0001 (5)
C5	0.0148 (7)	0.0164 (7)	0.0163 (7)	−0.0011 (6)	−0.0002 (5)	−0.0002 (6)

Geometric parameters (Å, º) top

O1—C5	1.2234 (19)	N2—H2N	0.88 (2)
O2—N3	1.2167 (17)	C1—C2	1.372 (2)
O3—N3	1.2206 (17)	C1—H1	0.9500
N1—C1	1.354 (2)	C2—C3	1.403 (2)
N1—C4	1.374 (2)	C2—H2	0.9500
N1—H1N	0.88 (3)	C3—C4	1.388 (2)
N2—N3	1.3886 (18)	C3—H3	0.9500
N2—C5	1.404 (2)	C4—C5	1.447 (2)

C1—N1—C4	109.32 (14)	C1—C2—C3	107.93 (15)
C1—N1—H1N	128.4 (16)	C1—C2—H2	126.0
C4—N1—H1N	122.3 (16)	C3—C2—H2	126.0
N3—N2—C5	123.09 (13)	C4—C3—C2	106.72 (14)
N3—N2—H2N	110.2 (14)	C4—C3—H3	126.6
C5—N2—H2N	123.1 (14)	C2—C3—H3	126.6
O2—N3—O3	126.02 (14)	N1—C4—C3	107.68 (13)
O2—N3—N2	118.77 (13)	N1—C4—C5	119.04 (14)
O3—N3—N2	115.15 (13)	C3—C4—C5	133.25 (14)
N1—C1—C2	108.33 (14)	O1—C5—N2	123.14 (14)
N1—C1—H1	125.8	O1—C5—C4	123.46 (14)
C2—C1—H1	125.8	N2—C5—C4	113.39 (13)

C5—N2—N3—O2	29.0 (2)	C2—C3—C4—C5	−177.88 (16)
C5—N2—N3—O3	−153.66 (14)	N3—N2—C5—O1	−2.7 (2)
C4—N1—C1—C2	−0.71 (19)	N3—N2—C5—C4	177.98 (13)
N1—C1—C2—C3	0.9 (2)	N1—C4—C5—O1	−5.8 (2)
C1—C2—C3—C4	−0.67 (19)	C3—C4—C5—O1	172.13 (17)
C1—N1—C4—C3	0.28 (18)	N1—C4—C5—N2	173.46 (13)
C1—N1—C4—C5	178.72 (14)	C3—C4—C5—N2	−8.6 (3)
C2—C3—C4—N1	0.24 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.88 (3)	2.21 (3)	3.001 (2)	150 (2)
N2—H2N···O1ⁱⁱ	0.88 (2)	2.11 (2)	2.982 (2)	171.5 (19)
C3—H3···O1ⁱⁱ	0.95	2.39	3.269 (2)	154
C3—H3···O2ⁱⁱ	0.95	2.48	3.245 (2)	138

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

Experimental details

Crystal data
Chemical formula	C₅H₅N₃O₃
M_r	155.12
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	133
a, b, c (Å)	9.988 (3), 6.4547 (17), 19.184 (6)
V (Å³)	1236.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.47 × 0.43 × 0.20

Data collection
Diffractometer	Rigaku AFC10/Saturn724+ diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8849, 1402, 1214
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.106, 1.00
No. of reflections	1402
No. of parameters	108
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.15

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.88 (3)	2.21 (3)	3.001 (2)	150 (2)
N2—H2N···O1ⁱⁱ	0.88 (2)	2.11 (2)	2.982 (2)	171.5 (19)
C3—H3···O1ⁱⁱ	0.95	2.39	3.269 (2)	154
C3—H3···O2ⁱⁱ	0.95	2.48	3.245 (2)	138

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

Acknowledgements

We thank the National Natural Science Foundation of China (grant No. 21076221) and the National Defence Science and Technology Innovation Fund of the Chinese Academy of Sciences (grant No. CXJJ-11-M52).

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