1H-Pyrrole-2-carbohydrazide

Wang, L.; Liu, X.; Yang, C.; Zhao, S.; Li, K.

doi:10.1107/S1600536811002650

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o493

doi:10.1107/S1600536811002650

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1H-Pyrrole-2-carbohydrazide

Lina Wang,^a Xiangrong Liu,^a ^* Chun Yang,^a Shunsheng Zhao ^a and Kanshe Li ^a

^aCollege of Chemistry and Chemical Engineering, Xi'an University of Science & Technology, Xi'an 710054, People's Republic of China
^*Correspondence e-mail: xkchemistry@yahoo.com.cn

(Received 7 January 2011; accepted 19 January 2011; online 26 January 2011)

The title compound, C₅H₇N₃O, was obtained by the reaction of ethyl 1H-pyrrol-2-carboxylate and hydrazide hydrate. In the crystal, molecules are linked via intermolecular N—H⋯N and N—H⋯O hydrogen bonds, forming a supramolecular grid.

Related literature

For background to pyrrole derivatives and their biological activity, see: Joshi et al. (2008 ); Demirayak et al. (1999 ); Halazy & Magnus (1984 ); Bijev (2006 ); Sbardella et al. (2004 ).

Experimental

Crystal data

C₅H₇N₃O
M_r = 125.14
Orthorhombic, P b c a
a = 9.9789 (16) Å
b = 8.5633 (14) Å
c = 13.657 (2) Å
V = 1167.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.31 × 0.28 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.968, T_max = 0.983
5327 measured reflections
1043 independent reflections
758 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.146
S = 1.04
1043 reflections
90 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3ⁱ	0.86	2.15	2.996 (2)	169
N2—H2⋯O1ⁱⁱ	0.86	2.06	2.8422 (19)	151
N3—H3B⋯O1ⁱⁱⁱ	0.91 (3)	2.12 (3)	3.023 (3)	168 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) -x+1, -y+1, -z+1.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002650/fy2001sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002650/fy2001Isup2.hkl

checkCIF report

Comment top

Pyrrole is one of the most ubiquitous heterocycles in the plant and animal kingdom because of its participation as a subunit of chlorophyll in plant cells and hemin and vitamin B12 in animal cells (Joshi et al., 2008). Pyrrole and its derivatives have shown to possess biological activities such as antibacterial (Demirayak et al., 1999), antitumor (Halazy et al., 1984), analgesics, antitubercular (Bijev, 2006), anti-inflammatory, and antiallergic (Sbardella et al., 2004). Several macromolecular antibiotics having pyrrole structure were isolated from biological sources and their activities were defined.

The molecular structure for 2-pyrrole hydrazide is shown in Fig. 1. The crystal structure is stabilized by N1—H1···N3, N2—H2···O1 and N3—H3B···O1 hydrogen bonds, as shown in Fig. 2 and Table 1.

In addition, as shown in Fig.3, the packing diagram of the title compound looks like the wave viewed down the a axis.

Related literature top

For background to pyrrole derivatives and their biological activity, see: Joshi et al. (2008); Demirayak et al. (1999); Halazy et al. (1984); Bijev (2006); Sbardella et al. (2004).

Experimental top

To a 25 mL round-bottomed flask equipped with a magnetic stirrer, 0.5 mL of hydrazine hydrate (80% in water) and 0.1392 g of 1H-pyrrol-2-carboxlic acid ethyl ester (1 mmol) were added. Then the temperature of the mixture was elevated to 70°C for 45 min and the mixture was cooled to room temperature. The formed suspension was filtered off, washed with Et₂O, and recrystallized from absolute ethyl alcohol. 0.113 g of the hydrazide was obtained with a yield of 90%.

Computing details top

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

Figures top

	Fig. 1. The molecular structure for 2-pyrrole hydrazide, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. View of the hydrogen bonds for 2-pyrrole hydrazide, H atoms not involved in hydrogen bonding have been omitted.
	Fig. 3. The packing for 2-pyrrole hydrazide, viewed down the a axis.

1H-Pyrrole-2-carbohydrazide top

Crystal data top

C₅H₇N₃O	D_x = 1.424 Mg m⁻³
M_r = 125.14	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 990 reflections
a = 9.9789 (16) Å	θ = 3.0–22.4°
b = 8.5633 (14) Å	µ = 0.11 mm⁻¹
c = 13.657 (2) Å	T = 296 K
V = 1167.0 (3) Å³	Block, colourless
Z = 8	0.31 × 0.28 × 0.16 mm
F(000) = 528

Data collection top

Bruker APEXII CCD diffractometer	1043 independent reflections
Radiation source: fine-focus sealed tube	758 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 25.1°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −11→11
T_min = 0.968, T_max = 0.983	k = −6→10
5327 measured reflections	l = −16→16

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) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0957P)²] where P = (F_o² + 2F_c²)/3
1043 reflections	(Δ/σ)_max < 0.001
90 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₅H₇N₃O	V = 1167.0 (3) Å³
M_r = 125.14	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.9789 (16) Å	µ = 0.11 mm⁻¹
b = 8.5633 (14) Å	T = 296 K
c = 13.657 (2) Å	0.31 × 0.28 × 0.16 mm

Data collection top

Bruker APEXII CCD diffractometer	1043 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	758 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.983	R_int = 0.031
5327 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.16 e Å⁻³
1043 reflections	Δρ_min = −0.21 e Å⁻³
90 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
N1	0.55417 (12)	0.04787 (18)	0.64606 (11)	0.0469 (5)
H1	0.6352	0.0752	0.6332	0.056*
N2	0.34109 (14)	0.28224 (17)	0.48978 (11)	0.0495 (5)
H2	0.2667	0.2414	0.5087	0.059*
N3	0.33807 (16)	0.3955 (2)	0.41573 (15)	0.0551 (5)
O1	0.56366 (11)	0.29286 (15)	0.50912 (10)	0.0538 (5)
C1	0.5178 (2)	−0.0654 (2)	0.71020 (14)	0.0523 (5)
H1A	0.5761	−0.1266	0.7470	0.063*
C2	0.3816 (2)	−0.0744 (2)	0.71164 (14)	0.0544 (6)
H2A	0.3304	−0.1421	0.7495	0.065*
C3	0.33310 (17)	0.0371 (2)	0.64571 (14)	0.0510 (6)
H3	0.2435	0.0573	0.6318	0.061*
C4	0.44238 (15)	0.1116 (2)	0.60516 (13)	0.0418 (5)
C5	0.45432 (16)	0.2352 (2)	0.53214 (13)	0.0423 (5)
H3A	0.394 (3)	0.359 (3)	0.3665 (19)	0.086 (8)*
H3B	0.380 (3)	0.483 (3)	0.4387 (19)	0.095 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0320 (8)	0.0562 (10)	0.0526 (10)	−0.0009 (7)	0.0010 (6)	0.0026 (8)
N2	0.0285 (8)	0.0569 (10)	0.0631 (10)	−0.0010 (6)	0.0003 (6)	0.0119 (8)
N3	0.0383 (10)	0.0595 (12)	0.0674 (12)	−0.0003 (8)	−0.0021 (8)	0.0121 (10)
O1	0.0304 (8)	0.0574 (9)	0.0737 (10)	−0.0019 (5)	0.0016 (6)	0.0054 (7)
C1	0.0483 (11)	0.0604 (12)	0.0481 (11)	0.0021 (9)	−0.0002 (8)	0.0056 (10)
C2	0.0455 (12)	0.0631 (13)	0.0545 (12)	−0.0060 (9)	0.0063 (9)	0.0041 (10)
C3	0.0357 (10)	0.0618 (12)	0.0554 (12)	−0.0037 (9)	0.0001 (8)	−0.0008 (10)
C4	0.0336 (9)	0.0469 (11)	0.0447 (10)	−0.0001 (7)	−0.0003 (7)	−0.0048 (8)
C5	0.0319 (10)	0.0452 (10)	0.0497 (11)	0.0003 (8)	0.0005 (7)	−0.0091 (9)

Geometric parameters (Å, º) top

N1—C1	1.356 (2)	O1—C5	1.2380 (18)
N1—C4	1.362 (2)	C1—C2	1.361 (3)
N1—H1	0.8600	C1—H1A	0.9300
N2—C5	1.332 (2)	C2—C3	1.399 (3)
N2—N3	1.402 (2)	C2—H2A	0.9300
N2—H2	0.8600	C3—C4	1.380 (2)
N3—H3A	0.93 (3)	C3—H3	0.9300
N3—H3B	0.91 (3)	C4—C5	1.459 (3)

C1—N1—C4	109.41 (15)	C1—C2—C3	107.33 (17)
C1—N1—H1	125.3	C1—C2—H2A	126.3
C4—N1—H1	125.3	C3—C2—H2A	126.3
C5—N2—N3	122.74 (15)	C4—C3—C2	107.48 (16)
C5—N2—H2	118.6	C4—C3—H3	126.3
N3—N2—H2	118.6	C2—C3—H3	126.3
N2—N3—H3A	106.1 (15)	N1—C4—C3	107.30 (17)
N2—N3—H3B	108.1 (17)	N1—C4—C5	120.28 (14)
H3A—N3—H3B	104 (2)	C3—C4—C5	132.42 (15)
N1—C1—C2	108.47 (17)	O1—C5—N2	121.13 (18)
N1—C1—H1A	125.8	O1—C5—C4	122.32 (15)
C2—C1—H1A	125.8	N2—C5—C4	116.54 (15)

C4—N1—C1—C2	−0.5 (2)	N3—N2—C5—O1	1.6 (3)
N1—C1—C2—C3	0.2 (2)	N3—N2—C5—C4	−177.42 (17)
C1—C2—C3—C4	0.2 (2)	N1—C4—C5—O1	−4.4 (3)
C1—N1—C4—C3	0.6 (2)	C3—C4—C5—O1	175.93 (18)
C1—N1—C4—C5	−179.09 (15)	N1—C4—C5—N2	174.58 (16)
C2—C3—C4—N1	−0.5 (2)	C3—C4—C5—N2	−5.1 (3)
C2—C3—C4—C5	179.19 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.86	2.15	2.996 (2)	169
N2—H2···O1ⁱⁱ	0.86	2.06	2.8422 (19)	151
N3—H3B···O1ⁱⁱⁱ	0.91 (3)	2.12 (3)	3.023 (3)	168 (2)

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

Experimental details

Crystal data
Chemical formula	C₅H₇N₃O
M_r	125.14
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	9.9789 (16), 8.5633 (14), 13.657 (2)
V (Å³)	1167.0 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.31 × 0.28 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.968, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	5327, 1043, 758
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.146, 1.04
No. of reflections	1043
No. of parameters	90
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.21

Computer programs: APEX2 (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.86	2.15	2.996 (2)	169
N2—H2···O1ⁱⁱ	0.86	2.06	2.8422 (19)	151
N3—H3B···O1ⁱⁱⁱ	0.91 (3)	2.12 (3)	3.023 (3)	168 (2)

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

Acknowledgements

This project was supported by the National Natural Science Foundation (No. 21073139) and the Scientific Research Program Funded by Shaanxi Provincial Education Commission (No. 07 J K317).

References

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