Crystal structure of (E)-N′-benzyl­idene-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide

Wang, Z.; Zhou, C.; Yan, L.; Wang, J.

doi:10.1107/S1600536814018054

organic compounds

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doi:10.1107/S1600536814018054

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Crystal structure of (E)-N′-benzylidene-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide

Zhijun Wang,^a Chengyong Zhou,^a Lei Yan ^a and Jinglin Wang ^a ^*

^aDepartment of Chemistry, Changzhi University, Changzhi, Shanxi 046011, People's Republic of China
^*Correspondence e-mail: jlwangczu@163.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 30 July 2014; accepted 6 August 2014; online 13 August 2014)

In the title compound, C₁₃H₁₂N₄O₃, the dihedral angle between the planes of the pyrrole and benzene rings is 7.47 (1)°. In the crystal, molecules are arranged in sheets lying parallel to (101). Neighbouring sheets are linked by N—H⋯O hydrogen bonds, weak π–π [centroid–centroid distance between the pyrrole rings = 3.765 (11) Å] and C—H⋯π interactions, forming a three-dimensional structure.

Keywords: crystal structure; pyrrole-2-carbohydrazide; aroylhydrazones; hydrogen bonding; π–π interactions.

CCDC reference: 1018158

1. Related literature

For applications and structures of aroylhydrazones, see: Krishnamoorthy et al. (2012 ); Raja et al. (2012 ); Wang et al. (2014 ). For similar structures, see: Wang et al. (2011 , 2014). For π–π interactions, see: Janiak (2000 ).

2. Experimental

2.1. Crystal data

C₁₃H₁₂N₄O₃
M_r = 272.27
Monoclinic, P 2₁ /c
a = 13.030 (3) Å
b = 11.900 (3) Å
c = 8.331 (2) Å
β = 95.409 (3)°
V = 1285.92 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.32 × 0.20 × 0.17 mm

2.2. Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.968, T_max = 0.983
6283 measured reflections
2248 independent reflections
1382 reflections with I > 2σ(I)
R_int = 0.043

2.3. Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.135
S = 1.03
2248 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.13	2.942 (2)	158
C6—H6B⋯Cgⁱ	0.96	2.70	3.590 (3)	154
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); 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 and DIAMOND (Brandenburg, 2005 ).

Supporting information

CCDC reference: 1018158

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814018054/bt6990sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814018054/bt6990Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814018054/bt6990Isup3.cml

checkCIF report

Comment top

Hydrazones and analogous compounds have attracted attention from researchers due to their well known chelating capability and structural flexibility (Krishnamoorthy, et al., 2012; Raja, et al., 2012). In our lab, a series of asymmetric N-heterocyclic substituted hydrazones and their metal complexes were obtained and characterized (Wang et al., 2011). The interactions of these compounds with CT-DNA and pBR322 DNA has been explored (Wang et al., 2014). The present work is an extension of our earlier studies.

In the title compound (Fig. 1) the phenyl and pyrrolyl ring are linked by an acyl-hydrazone moiety. The dihedral angle between the phenyl and pyrrolyl rings is 7.47 (1)°.

As shown in Figure 2, molecules of the title compound form sheet parallel to the (101) plane.

The neighbouring sheets are linked by N–H···O hydrogen bonds, weak π···π interactions between pyrrolyl rings and C–H···π interactions (Figure 3). These interactions result in the formation of a three-dimensional network (Fig. 4).

Related literature top

For applications and structures of aroylhydrazones, see: Krishnamoorthy et al. (2012); Raja et al. (2012); Wang et al. (2014). For similar structures, see: Wang et al. (2011, 2014). For π–π interactions, see: Janiak (2000).

Experimental top

The precursor 1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide was synthesized according to literature procedures (Wang et al., 2011). Similar to the synthesis of (E)-1-methyl-4-nitro-N'-(pyridin-2-ylmethylene)-1H-pyrrole-2-carbohydrazide, the reaction of the precursor and benzaldehyde in a 1:1 molar ratio gave the title compound as a yellowish powder in 80% yield. Anal. Calc. (%) for C₁₃H₁₂N₄O₃: C 57.35, H 4.44, N 20.58; found: C 57.31, H 4.51, N 20.55. The powder of the title compound was dissolved in N,N-dimethyl formamide and the yellow crystals were collected after slow evaporation at room temperature for about two weeks.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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) and DIAMOND (Brandenburg, 2005).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radius.
	Fig. 2. Molecules of the title compound forming planes parallel to the (101) plane.
	Fig. 3. The intermolecular N–H···O hydrogen bonds (black dotted lines), π···π and C–H···π interactions (pink dotted lines) between adjacent sheets (H atoms not involved in hydrogen bonds have been omitted for clarity, all distances in Å).
	Fig. 4. Packing of the title compound viewed along the b axis.

(E)-N'-Benzylidene-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide top

Crystal data top

C₁₃H₁₂N₄O₃	F(000) = 568
M_r = 272.27	D_x = 1.406 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1529 reflections
a = 13.030 (3) Å	θ = 2.3–24.0°
b = 11.900 (3) Å	µ = 0.10 mm⁻¹
c = 8.331 (2) Å	T = 298 K
β = 95.409 (3)°	Block, yellow
V = 1285.92 (17) Å³	0.32 × 0.20 × 0.17 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	2248 independent reflections
Radiation source: fine-focus sealed tube	1382 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
phi and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→15
T_min = 0.968, T_max = 0.983	k = −14→14
6283 measured reflections	l = −9→9

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0571P)² + 0.2921P] where P = (F_o² + 2F_c²)/3
2248 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₃H₁₂N₄O₃	V = 1285.92 (17) Å³
M_r = 272.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.030 (3) Å	µ = 0.10 mm⁻¹
b = 11.900 (3) Å	T = 298 K
c = 8.331 (2) Å	0.32 × 0.20 × 0.17 mm
β = 95.409 (3)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2248 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1382 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.983	R_int = 0.043
6283 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.03	Δρ_max = 0.19 e Å⁻³
2248 reflections	Δρ_min = −0.18 e Å⁻³
182 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	0.80415 (15)	0.34342 (17)	0.4275 (2)	0.0409 (5)
N2	0.74919 (15)	0.27603 (17)	0.5233 (2)	0.0435 (6)
H2	0.7314	0.3006	0.6138	0.052*
N3	0.64881 (15)	−0.00154 (17)	0.5892 (2)	0.0436 (6)
N4	0.45223 (18)	0.0771 (3)	0.8358 (3)	0.0618 (7)
O1	0.75036 (14)	0.12934 (15)	0.3497 (2)	0.0540 (5)
O2	0.41349 (15)	−0.0109 (2)	0.8783 (2)	0.0804 (7)
O3	0.42286 (18)	0.1703 (2)	0.8735 (3)	0.0916 (8)
C1	0.72375 (18)	0.1713 (2)	0.4734 (3)	0.0397 (6)
C2	0.65549 (18)	0.1145 (2)	0.5783 (3)	0.0386 (6)
C3	0.58369 (18)	0.1601 (2)	0.6690 (3)	0.0441 (7)
H3	0.5704	0.2361	0.6829	0.053*
C4	0.53470 (19)	0.0704 (2)	0.7359 (3)	0.0469 (7)
C5	0.57607 (19)	−0.0277 (2)	0.6867 (3)	0.0502 (7)
H5	0.5572	−0.0998	0.7156	0.060*
C6	0.7129 (2)	−0.0846 (2)	0.5155 (3)	0.0560 (8)
H6A	0.6865	−0.1586	0.5319	0.084*
H6B	0.7825	−0.0796	0.5644	0.084*
H6C	0.7117	−0.0700	0.4020	0.084*
C7	0.81171 (19)	0.4454 (2)	0.4711 (3)	0.0419 (6)
H7	0.7786	0.4697	0.5589	0.050*
C8	0.87158 (18)	0.5250 (2)	0.3853 (3)	0.0388 (6)
C9	0.93840 (19)	0.4903 (2)	0.2762 (3)	0.0467 (7)
H9	0.9426	0.4143	0.2512	0.056*
C10	0.9988 (2)	0.5662 (2)	0.2040 (3)	0.0530 (8)
H10	1.0445	0.5413	0.1324	0.064*
C11	0.9919 (2)	0.6776 (3)	0.2370 (3)	0.0604 (8)
H11	1.0330	0.7290	0.1885	0.072*
C12	0.9246 (3)	0.7139 (2)	0.3416 (4)	0.0724 (10)
H12	0.9186	0.7903	0.3620	0.087*
C13	0.8655 (2)	0.6380 (2)	0.4170 (3)	0.0587 (8)
H13	0.8210	0.6635	0.4901	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0444 (12)	0.0449 (13)	0.0346 (12)	−0.0062 (10)	0.0097 (10)	0.0028 (10)
N2	0.0533 (13)	0.0436 (12)	0.0362 (13)	−0.0105 (10)	0.0172 (10)	−0.0027 (10)
N3	0.0437 (13)	0.0442 (13)	0.0428 (13)	−0.0056 (10)	0.0024 (10)	0.0019 (11)
N4	0.0421 (14)	0.096 (2)	0.0474 (15)	−0.0117 (15)	0.0069 (12)	0.0073 (16)
O1	0.0735 (13)	0.0526 (11)	0.0388 (11)	−0.0083 (10)	0.0211 (10)	−0.0081 (9)
O2	0.0547 (13)	0.1207 (19)	0.0668 (15)	−0.0377 (13)	0.0107 (11)	0.0153 (14)
O3	0.0764 (17)	0.112 (2)	0.0932 (19)	0.0082 (15)	0.0433 (14)	−0.0026 (17)
C1	0.0425 (15)	0.0449 (16)	0.0319 (15)	−0.0037 (12)	0.0039 (12)	0.0031 (13)
C2	0.0400 (14)	0.0439 (15)	0.0316 (14)	−0.0057 (12)	0.0009 (11)	0.0038 (12)
C3	0.0436 (15)	0.0507 (16)	0.0385 (16)	−0.0035 (13)	0.0065 (13)	0.0029 (13)
C4	0.0354 (14)	0.0679 (19)	0.0379 (16)	−0.0091 (14)	0.0054 (12)	0.0040 (14)
C5	0.0473 (17)	0.0566 (18)	0.0455 (17)	−0.0171 (14)	−0.0013 (14)	0.0101 (14)
C6	0.0604 (19)	0.0455 (16)	0.061 (2)	0.0004 (14)	0.0017 (15)	−0.0036 (14)
C7	0.0439 (15)	0.0466 (16)	0.0367 (15)	0.0009 (13)	0.0115 (12)	−0.0018 (13)
C8	0.0417 (14)	0.0402 (15)	0.0343 (15)	−0.0041 (11)	0.0023 (12)	0.0002 (12)
C9	0.0474 (16)	0.0388 (15)	0.0552 (17)	0.0036 (12)	0.0116 (14)	0.0038 (13)
C10	0.0493 (16)	0.0574 (19)	0.0547 (19)	−0.0070 (14)	0.0177 (14)	0.0038 (15)
C11	0.075 (2)	0.0553 (19)	0.0521 (19)	−0.0224 (16)	0.0116 (16)	0.0043 (15)
C12	0.110 (3)	0.0413 (17)	0.069 (2)	−0.0147 (18)	0.025 (2)	−0.0071 (16)
C13	0.078 (2)	0.0486 (18)	0.0523 (19)	−0.0055 (15)	0.0238 (16)	−0.0101 (15)

Geometric parameters (Å, º) top

N1—C7	1.268 (3)	C6—H6A	0.9600
N1—N2	1.379 (3)	C6—H6B	0.9600
N2—C1	1.346 (3)	C6—H6C	0.9600
N2—H2	0.8600	C7—C8	1.456 (3)
N3—C5	1.342 (3)	C7—H7	0.9300
N3—C2	1.386 (3)	C8—C13	1.374 (3)
N3—C6	1.466 (3)	C8—C9	1.380 (3)
N4—O3	1.224 (3)	C9—C10	1.374 (3)
N4—O2	1.230 (3)	C9—H9	0.9300
N4—C4	1.422 (3)	C10—C11	1.359 (4)
O1—C1	1.224 (3)	C10—H10	0.9300
C1—C2	1.469 (3)	C11—C12	1.363 (4)
C2—C3	1.369 (3)	C11—H11	0.9300
C3—C4	1.387 (3)	C12—C13	1.376 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.365 (4)	C13—H13	0.9300
C5—H5	0.9300

C7—N1—N2	114.9 (2)	N3—C6—H6B	109.5
C1—N2—N1	119.1 (2)	H6A—C6—H6B	109.5
C1—N2—H2	120.5	N3—C6—H6C	109.5
N1—N2—H2	120.5	H6A—C6—H6C	109.5
C5—N3—C2	108.8 (2)	H6B—C6—H6C	109.5
C5—N3—C6	124.1 (2)	N1—C7—C8	120.8 (2)
C2—N3—C6	127.0 (2)	N1—C7—H7	119.6
O3—N4—O2	123.5 (3)	C8—C7—H7	119.6
O3—N4—C4	118.2 (3)	C13—C8—C9	118.1 (2)
O2—N4—C4	118.3 (3)	C13—C8—C7	119.9 (2)
O1—C1—N2	123.8 (2)	C9—C8—C7	121.9 (2)
O1—C1—C2	123.3 (2)	C10—C9—C8	121.0 (2)
N2—C1—C2	112.8 (2)	C10—C9—H9	119.5
C3—C2—N3	108.0 (2)	C8—C9—H9	119.5
C3—C2—C1	129.0 (2)	C11—C10—C9	120.1 (3)
N3—C2—C1	122.8 (2)	C11—C10—H10	119.9
C2—C3—C4	106.3 (2)	C9—C10—H10	119.9
C2—C3—H3	126.8	C10—C11—C12	119.8 (3)
C4—C3—H3	126.8	C10—C11—H11	120.1
C5—C4—C3	109.1 (2)	C12—C11—H11	120.1
C5—C4—N4	124.4 (3)	C11—C12—C13	120.4 (3)
C3—C4—N4	126.4 (3)	C11—C12—H12	119.8
N3—C5—C4	107.8 (2)	C13—C12—H12	119.8
N3—C5—H5	126.1	C8—C13—C12	120.6 (3)
C4—C5—H5	126.1	C8—C13—H13	119.7
N3—C6—H6A	109.5	C12—C13—H13	119.7

C7—N1—N2—C1	170.0 (2)	O3—N4—C4—C3	−3.2 (4)
N1—N2—C1—O1	3.3 (4)	O2—N4—C4—C3	176.1 (3)
N1—N2—C1—C2	−173.4 (2)	C2—N3—C5—C4	1.1 (3)
C5—N3—C2—C3	−1.1 (3)	C6—N3—C5—C4	178.1 (2)
C6—N3—C2—C3	−178.0 (2)	C3—C4—C5—N3	−0.7 (3)
C5—N3—C2—C1	−176.4 (2)	N4—C4—C5—N3	177.4 (2)
C6—N3—C2—C1	6.7 (4)	N2—N1—C7—C8	177.2 (2)
O1—C1—C2—C3	−146.8 (3)	N1—C7—C8—C13	169.5 (3)
N2—C1—C2—C3	29.9 (4)	N1—C7—C8—C9	−13.1 (4)
O1—C1—C2—N3	27.4 (4)	C13—C8—C9—C10	1.4 (4)
N2—C1—C2—N3	−155.9 (2)	C7—C8—C9—C10	−176.0 (2)
N3—C2—C3—C4	0.7 (3)	C8—C9—C10—C11	−1.3 (4)
C1—C2—C3—C4	175.6 (2)	C9—C10—C11—C12	−0.2 (5)
C2—C3—C4—C5	0.0 (3)	C10—C11—C12—C13	1.7 (5)
C2—C3—C4—N4	−178.1 (2)	C9—C8—C13—C12	0.0 (4)
O3—N4—C4—C5	179.0 (3)	C7—C8—C13—C12	177.5 (3)
O2—N4—C4—C5	−1.7 (4)	C11—C12—C13—C8	−1.6 (5)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C8–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.13	2.942 (2)	158
C6—H6B···Cgⁱ	0.96	2.70	3.590 (3)	154

Symmetry code: (i) x, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C8–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.13	2.942 (2)	158
C6—H6B···Cgⁱ	0.96	2.70	3.590 (3)	154

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

The authors thank the National Natural Science Foundation of the People's Republic of China (grant No. 21201024), the Natural Science Foundation of Shanxi Province (grant No. 2012021009-1) and the National-level College Students' Innovative Training Plan Program of the People's Republic of China (grant No. 201410122004).

References

Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Janiak, C. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3896. Web of Science CrossRef Google Scholar
Krishnamoorthy, P., Sathyadevi, P., Butorac, R. R., Cowley, A. H., Bhuvanesh, N. S. P. & Dharmaraj, N. (2012). Dalton Trans. 41, 4423–4436. Web of Science CSD CrossRef CAS PubMed Google Scholar
Raja, D. S., Bhuvanesh, N. S. P. & Natarajan, K. (2012). Dalton Trans. 41, 4365–4377. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, J., Liu, B. & Yang, B. (2011). CrystEngComm, 13, 7086–7097. CAS Google Scholar
Wang, J., Zhao, Y. & Yang, B. (2014). Inorg. Chim. Acta, 409, 484–496. Web of Science CSD CrossRef CAS Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (E)-N′-benzyl­­idene-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of (E)-N′-benzylidene-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide