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ISSN: 2056-9890

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

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[Mohamed, M. S., EL-Domany, R. A. & EL-Hameed, R. H. (2009). Acta Pharm. 59, 145-158.]). For the structures of similar pyrrole derivatives, see: Zeng et al. (2007[Zeng, X.-C., Zeng, J., Li, X. & Ling, X. (2007). Acta Cryst. E63, o3424.], 2010[Zeng, X. C., Li, K. P., Hu, F. & Zheng, L. (2010). Acta Cryst. E66, o2051.]); Wang et al. (2010[Wang, S.-F., Li, C. & Chen, S. (2010). Acta Cryst. E66, o3047.]); Ferreira et al. (2002[Ferreira, P. M. T., Maia, H. L. L. & Monteiro, L. S. (2002). Tetrahedron Lett. 43, 4491-4493.]). For the synthesis of N,N′-dinitro­urea (DNU), see: Goede et al. (2001[Goede, P., Wingborg, N., Bergman, H. & Latypov, N. V. (2001). Propellant Explos. Pyrotech. 26, 17-20.]).

[Scheme 1]

Experimental

Crystal data
  • C5H5N3O3

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.34 e Å−3

  • Δρmin = −0.15 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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).

Refinement top

The hydrogen atoms bonded to N1 and N2 were located from a difference Fourier maps and refined isotropically with N—H = 0.88 (3) Å and 0.88 (2) Å respectively. The remaining hydrogen atoms were geometrically positioned (all C—H = 0.9500 Å).

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
[Figure 1] Fig. 1. Thermal ellipsoid plot of C5H5N3O3 at the 50% probability level; Hydrogen atoms are drawn as spheres of arbitrary radius.
[Figure 2] Fig. 2. Hydrogen-bonded layer structure.
N-Nitro-1H-pyrrole-2-carboxamide top
Crystal data top
C5H5N3O3F(000) = 640
Mr = 155.12Dx = 1.666 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3166 reflections
a = 9.988 (3) Åθ = 3.2–27.5°
b = 6.4547 (17) ŵ = 0.14 mm1
c = 19.184 (6) ÅT = 133 K
V = 1236.8 (6) Å3Platelet, colourless
Z = 80.47 × 0.43 × 0.20 mm
Data collection top
Rigaku AFC10/Saturn724+
diffractometer
1214 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.034
Graphite monochromatorθmax = 27.5°, θmin = 3.9°
Detector resolution: 28.5714 pixels mm-1h = 1212
ϕ and ω scansk = 88
8849 measured reflectionsl = 2424
1402 independent reflections
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0596P)2 + 0.536P]
where P = (Fo2 + 2Fc2)/3
1402 reflections(Δ/σ)max < 0.001
108 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C5H5N3O3V = 1236.8 (6) Å3
Mr = 155.12Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.988 (3) ŵ = 0.14 mm1
b = 6.4547 (17) ÅT = 133 K
c = 19.184 (6) Å0.47 × 0.43 × 0.20 mm
Data collection top
Rigaku AFC10/Saturn724+
diffractometer
1214 reflections with I > 2σ(I)
8849 measured reflectionsRint = 0.034
1402 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.34 e Å3
1402 reflectionsΔρmin = 0.15 e Å3
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
xyzUiso*/Ueq
O10.17512 (12)0.34028 (18)0.50500 (5)0.0219 (3)
O20.27334 (11)0.3909 (2)0.37665 (6)0.0256 (3)
O30.45611 (12)0.21230 (19)0.36431 (6)0.0255 (3)
N10.25340 (14)0.3489 (2)0.64493 (7)0.0207 (3)
N20.39562 (13)0.3045 (2)0.47037 (7)0.0182 (3)
N30.37143 (13)0.3012 (2)0.39910 (7)0.0178 (3)
C10.31849 (18)0.3310 (3)0.70652 (8)0.0235 (4)
H10.28000.34960.75140.028*
C20.44956 (17)0.2815 (3)0.69312 (8)0.0240 (4)
H20.51730.25810.72700.029*
C30.46594 (16)0.2715 (2)0.62056 (8)0.0198 (4)
H30.54640.24170.59620.024*
C40.34176 (15)0.3137 (2)0.59132 (8)0.0160 (3)
C50.29335 (15)0.3204 (2)0.52027 (8)0.0158 (3)
H1N0.169 (3)0.380 (4)0.6375 (12)0.049 (7)*
H2N0.474 (2)0.250 (3)0.4794 (11)0.032 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0140 (6)0.0339 (7)0.0177 (5)0.0002 (5)0.0004 (4)0.0003 (5)
O20.0181 (6)0.0398 (7)0.0188 (6)0.0049 (5)0.0022 (4)0.0071 (5)
O30.0198 (6)0.0381 (7)0.0187 (6)0.0050 (5)0.0027 (5)0.0052 (5)
N10.0164 (7)0.0276 (7)0.0180 (6)0.0021 (6)0.0007 (5)0.0002 (6)
N20.0132 (6)0.0281 (7)0.0133 (6)0.0016 (5)0.0022 (5)0.0011 (5)
N30.0153 (6)0.0241 (7)0.0141 (6)0.0022 (5)0.0004 (5)0.0013 (5)
C10.0273 (9)0.0286 (9)0.0145 (7)0.0002 (7)0.0011 (6)0.0000 (6)
C20.0223 (8)0.0315 (9)0.0183 (8)0.0013 (7)0.0053 (6)0.0015 (6)
C30.0146 (7)0.0257 (8)0.0191 (8)0.0008 (6)0.0001 (6)0.0010 (6)
C40.0147 (7)0.0176 (7)0.0158 (7)0.0013 (6)0.0003 (6)0.0001 (5)
C50.0148 (7)0.0164 (7)0.0163 (7)0.0011 (6)0.0002 (5)0.0002 (6)
Geometric parameters (Å, º) top
O1—C51.2234 (19)N2—H2N0.88 (2)
O2—N31.2167 (17)C1—C21.372 (2)
O3—N31.2206 (17)C1—H10.9500
N1—C11.354 (2)C2—C31.403 (2)
N1—C41.374 (2)C2—H20.9500
N1—H1N0.88 (3)C3—C41.388 (2)
N2—N31.3886 (18)C3—H30.9500
N2—C51.404 (2)C4—C51.447 (2)
C1—N1—C4109.32 (14)C1—C2—C3107.93 (15)
C1—N1—H1N128.4 (16)C1—C2—H2126.0
C4—N1—H1N122.3 (16)C3—C2—H2126.0
N3—N2—C5123.09 (13)C4—C3—C2106.72 (14)
N3—N2—H2N110.2 (14)C4—C3—H3126.6
C5—N2—H2N123.1 (14)C2—C3—H3126.6
O2—N3—O3126.02 (14)N1—C4—C3107.68 (13)
O2—N3—N2118.77 (13)N1—C4—C5119.04 (14)
O3—N3—N2115.15 (13)C3—C4—C5133.25 (14)
N1—C1—C2108.33 (14)O1—C5—N2123.14 (14)
N1—C1—H1125.8O1—C5—C4123.46 (14)
C2—C1—H1125.8N2—C5—C4113.39 (13)
C5—N2—N3—O229.0 (2)C2—C3—C4—C5177.88 (16)
C5—N2—N3—O3153.66 (14)N3—N2—C5—O12.7 (2)
C4—N1—C1—C20.71 (19)N3—N2—C5—C4177.98 (13)
N1—C1—C2—C30.9 (2)N1—C4—C5—O15.8 (2)
C1—C2—C3—C40.67 (19)C3—C4—C5—O1172.13 (17)
C1—N1—C4—C30.28 (18)N1—C4—C5—N2173.46 (13)
C1—N1—C4—C5178.72 (14)C3—C4—C5—N28.6 (3)
C2—C3—C4—N10.24 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O3i0.88 (3)2.21 (3)3.001 (2)150 (2)
N2—H2N···O1ii0.88 (2)2.11 (2)2.982 (2)171.5 (19)
C3—H3···O1ii0.952.393.269 (2)154
C3—H3···O2ii0.952.483.245 (2)138
Symmetry codes: (i) x1/2, y+1/2, z+1; (ii) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC5H5N3O3
Mr155.12
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)133
a, b, c (Å)9.988 (3), 6.4547 (17), 19.184 (6)
V3)1236.8 (6)
Z8
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.47 × 0.43 × 0.20
Data collection
DiffractometerRigaku AFC10/Saturn724+
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8849, 1402, 1214
Rint0.034
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.106, 1.00
No. of reflections1402
No. of parameters108
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1N···O3i0.88 (3)2.21 (3)3.001 (2)150 (2)
N2—H2N···O1ii0.88 (2)2.11 (2)2.982 (2)171.5 (19)
C3—H3···O1ii0.952.393.269 (2)154
C3—H3···O2ii0.952.483.245 (2)138
Symmetry codes: (i) x1/2, 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).

References

First citationBarbour, L. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationFerreira, P. M. T., Maia, H. L. L. & Monteiro, L. S. (2002). Tetrahedron Lett. 43, 4491–4493.  Web of Science CrossRef CAS Google Scholar
First citationGoede, P., Wingborg, N., Bergman, H. & Latypov, N. V. (2001). Propellant Explos. Pyrotech. 26, 17–20.  Web of Science CrossRef CAS Google Scholar
First citationMohamed, M. S., EL-Domany, R. A. & EL-Hameed, R. H. (2009). Acta Pharm. 59, 145–158.  Web of Science CrossRef PubMed CAS Google Scholar
First citationRigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWang, S.-F., Li, C. & Chen, S. (2010). Acta Cryst. E66, o3047.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZeng, X. C., Li, K. P., Hu, F. & Zheng, L. (2010). Acta Cryst. E66, o2051.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationZeng, X.-C., Zeng, J., Li, X. & Ling, X. (2007). Acta Cryst. E63, o3424.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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