organic compounds
(E)-N′-(2-Chlorobenzylidene)-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide
aDepartment of Chemistry, Changzhi University, Changzhi, Shanxi 046011, People's Republic of China
*Correspondence e-mail: jlwangczu@163.com
In the title compound, C13H11ClN4O3, the phenyl and pyrrolyl ring are linked by an acyl–hydrazone (R2C=N—N—CO—R) group, forming a slightly bent molecule: the dihedral angle subtended by the the phenyl and pyrrolyl rings is 8.46 (12)°. In the crystal, the three-dimensional supramolecular structure is assembled by N—H⋯O hydrogen bonding. Molecular sheets are formed parallel to (101) in a herringbone arrangement by weak van der Waals interactions; weak π–π [centroid–centroid phenyl–phenyl and pyrrolyl–pyrrolyl distances of 3.7816 (3) and 3.8946 (2) Å, respectively] interactions occur between neighbouring sheets.
CCDC reference: 977773
Related literature
For applications and structures of aroylhydrazones, see: Raja et al. (2012); Wang et al. (2014).
Experimental
Crystal data
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Data collection: SMART (Bruker, 1999); cell 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: DIAMOND (Brandenburg, 1999) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009) and SHELXTL.
Supporting information
CCDC reference: 977773
https://doi.org/10.1107/S1600536813034119/ff2124sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813034119/ff2124Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813034119/ff2124Isup3.cml
Single crystals of the title compound were obtained accidentally in the attempted synthesis of a Ni complex. (E)-N'-(2-hydroxybenzylidene)-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide (L) was synthesized according to literature procedures (Wang et al., 2014). Sodium methoxide (250 µL, 3%, g/V) was added to solution of L (0.50 mmol, 0.144 g) in 15 ml MeOH and was heated to reflux. NiCl2·6H2O (0.50 mmol, 0.119 g) was then added to the refluxing mixture and further refluxed for 2 h. The reaction mixture was cooled and was allowed to stir at room temperature overnight. The mixture was filtered and washed with methanol. The L—Ni complex is not achieved as predicted. However, orange single crystals of the title compound suitable for X-ray analysis were obtained after several days from the mother liquor by slow evaporation.
H atoms attached to C atoms are placed in geometrically idealized position, with N–H=0.86 Å, C–H=0.93 and 0.96 Å, for CH and CH3 groups, respectively, and with Uiso(H) = k × Ueq(parent C-atom), where k = 1.5 for CH3 H-atoms and =1.2 for other H-atoms.
A great number of aroylhydrazones (AH) have triggered wide interest because of their diverse spectra of biological and pharmaceutical properties (Raja, et al., 2012). In our lab, the AH compound (E)-N'-(2-hydroxybenzylidene)-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide (L) and its transition metal complexes were obtained and characterized. The interaction of these compounds with CT-DNA and pBR322 DNA has been explored (Wang, et al., 2014). The present report is an extension of our earlier studies in this area.
In the title compound (Fig. 1), C13H11ClN4O3, the phenyl and pyrrolyl ring are linked by acyl-hydrazone (R2C=N–N–CO–R) to form a slightly bent molecule. The dihedral angle between the phenyl (C8—C13) and pyrrolyl rings (C2—C5, N1) is 8.46 (12)°.
As shown in Figure 2, the herringbone molecular sheet of the title compound is formed by weak van-der-Waals interactions along (101) plane.
The three-dimensional supramolecular structure (Fig. 3) is assembled by N3–H3···O1i hydrogen bonding (pink dotted lines) and weak Cg1···Cg1ii (Cg1 is the centroid of the phenyl ring) and Cg2···Cg2iii (Cg2 is the centroid of the pyrrolyl ring) interactions (black dotted lines) between the neighbouring molecular sheets [symmetry code: (i) x, 3/2 - y, 1/2 + z; (ii)1 - x, 2 - y, 2 – z; (iii) - x, 1 - y, 2 - z]. The data of hydrogen-bond geometry are given in Table 1.
For applications and structures of aroylhydrazones, see: Raja et al. (2012); Wang et al. (2014).
Data collection: SMART (Bruker, 1999); cell
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: DIAMOND (Brandenburg, 1999) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009) and SHELXTL (Sheldrick, 2008).C13H11ClN4O3 | F(000) = 632 |
Mr = 306.71 | Dx = 1.464 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.7649 (13) Å | Cell parameters from 1539 reflections |
b = 12.4993 (11) Å | θ = 3.0–25.2° |
c = 8.1263 (10) Å | µ = 0.29 mm−1 |
β = 95.523 (1)° | T = 298 K |
V = 1391.7 (2) Å3 | Block, yellow |
Z = 4 | 0.30 × 0.20 × 0.16 mm |
Bruker SMART 1000 CCD diffractometer | 2452 independent reflections |
Radiation source: fine-focus sealed tube | 1435 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
phi and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −15→16 |
Tmin = 0.918, Tmax = 0.955 | k = −14→14 |
6871 measured reflections | l = −6→9 |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0787P)2] where P = (Fo2 + 2Fc2)/3 |
2452 reflections | (Δ/σ)max = 0.001 |
191 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C13H11ClN4O3 | V = 1391.7 (2) Å3 |
Mr = 306.71 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.7649 (13) Å | µ = 0.29 mm−1 |
b = 12.4993 (11) Å | T = 298 K |
c = 8.1263 (10) Å | 0.30 × 0.20 × 0.16 mm |
β = 95.523 (1)° |
Bruker SMART 1000 CCD diffractometer | 2452 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1435 reflections with I > 2σ(I) |
Tmin = 0.918, Tmax = 0.955 | Rint = 0.071 |
6871 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.23 e Å−3 |
2452 reflections | Δρmin = −0.33 e Å−3 |
191 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.29032 (9) | 1.16858 (8) | 1.00653 (18) | 0.1044 (6) | |
N1 | 0.14340 (19) | 0.51021 (19) | 1.0868 (3) | 0.0508 (7) | |
N2 | −0.0430 (2) | 0.5940 (3) | 1.3388 (4) | 0.0712 (9) | |
N3 | 0.24317 (19) | 0.7725 (2) | 1.0085 (3) | 0.0512 (8) | |
H3 | 0.2231 | 0.7996 | 1.0964 | 0.061* | |
N4 | 0.30201 (18) | 0.83156 (19) | 0.9133 (3) | 0.0470 (7) | |
O1 | 0.24317 (17) | 0.62828 (16) | 0.8366 (3) | 0.0587 (7) | |
O2 | −0.0656 (2) | 0.6852 (3) | 1.3780 (4) | 0.1057 (12) | |
O3 | −0.08399 (19) | 0.5122 (3) | 1.3789 (3) | 0.0907 (9) | |
C1 | 0.2175 (2) | 0.6716 (2) | 0.9618 (4) | 0.0465 (8) | |
C2 | 0.1506 (2) | 0.6203 (2) | 1.0708 (4) | 0.0451 (8) | |
C3 | 0.0829 (2) | 0.6674 (3) | 1.1612 (4) | 0.0514 (8) | |
H3A | 0.0711 | 0.7403 | 1.1715 | 0.062* | |
C4 | 0.0352 (2) | 0.5839 (3) | 1.2344 (4) | 0.0561 (9) | |
C5 | 0.0737 (2) | 0.4884 (3) | 1.1897 (4) | 0.0573 (9) | |
H5 | 0.0554 | 0.4209 | 1.2235 | 0.069* | |
C6 | 0.2046 (3) | 0.4285 (3) | 1.0169 (5) | 0.0659 (10) | |
H6A | 0.2708 | 0.4362 | 1.0642 | 0.099* | |
H6B | 0.2017 | 0.4376 | 0.8992 | 0.099* | |
H6C | 0.1810 | 0.3586 | 1.0416 | 0.099* | |
C7 | 0.3117 (2) | 0.9297 (2) | 0.9548 (4) | 0.0483 (8) | |
H7 | 0.2764 | 0.9569 | 1.0373 | 0.058* | |
C8 | 0.3779 (2) | 1.0000 (2) | 0.8743 (4) | 0.0467 (8) | |
C9 | 0.3778 (2) | 1.1102 (2) | 0.8944 (4) | 0.0571 (9) | |
C10 | 0.4438 (3) | 1.1761 (3) | 0.8256 (5) | 0.0698 (11) | |
H10 | 0.4413 | 1.2498 | 0.8406 | 0.084* | |
C11 | 0.5133 (3) | 1.1319 (3) | 0.7348 (5) | 0.0698 (11) | |
H11 | 0.5587 | 1.1756 | 0.6900 | 0.084* | |
C12 | 0.5154 (3) | 1.0231 (3) | 0.7108 (5) | 0.0659 (10) | |
H12 | 0.5620 | 0.9933 | 0.6491 | 0.079* | |
C13 | 0.4481 (2) | 0.9577 (3) | 0.7784 (4) | 0.0568 (9) | |
H13 | 0.4497 | 0.8843 | 0.7598 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1002 (9) | 0.0517 (6) | 0.1730 (14) | 0.0028 (6) | 0.0731 (9) | −0.0179 (7) |
N1 | 0.0553 (16) | 0.0427 (14) | 0.0560 (18) | −0.0065 (13) | 0.0130 (13) | 0.0045 (13) |
N2 | 0.057 (2) | 0.102 (3) | 0.057 (2) | −0.019 (2) | 0.0189 (16) | 0.0023 (19) |
N3 | 0.0646 (18) | 0.0459 (15) | 0.0477 (17) | −0.0109 (13) | 0.0286 (14) | −0.0042 (12) |
N4 | 0.0549 (16) | 0.0436 (15) | 0.0455 (16) | −0.0057 (13) | 0.0199 (13) | 0.0025 (11) |
O1 | 0.0821 (17) | 0.0499 (12) | 0.0490 (14) | −0.0105 (12) | 0.0310 (12) | −0.0064 (11) |
O2 | 0.088 (2) | 0.121 (3) | 0.117 (3) | −0.010 (2) | 0.056 (2) | −0.027 (2) |
O3 | 0.0637 (17) | 0.134 (3) | 0.077 (2) | −0.0337 (18) | 0.0193 (14) | 0.0198 (18) |
C1 | 0.053 (2) | 0.0444 (17) | 0.045 (2) | −0.0027 (15) | 0.0197 (15) | 0.0023 (14) |
C2 | 0.0476 (18) | 0.0425 (16) | 0.047 (2) | −0.0063 (14) | 0.0123 (15) | −0.0010 (14) |
C3 | 0.0496 (19) | 0.0530 (18) | 0.054 (2) | −0.0032 (16) | 0.0153 (16) | −0.0007 (16) |
C4 | 0.0516 (19) | 0.069 (2) | 0.050 (2) | −0.0095 (18) | 0.0160 (16) | 0.0016 (17) |
C5 | 0.059 (2) | 0.059 (2) | 0.055 (2) | −0.0168 (18) | 0.0113 (17) | 0.0151 (17) |
C6 | 0.075 (3) | 0.0447 (18) | 0.079 (3) | 0.0036 (18) | 0.014 (2) | 0.0010 (18) |
C7 | 0.0515 (19) | 0.0442 (18) | 0.053 (2) | −0.0001 (15) | 0.0227 (16) | −0.0005 (15) |
C8 | 0.0473 (18) | 0.0431 (16) | 0.052 (2) | −0.0039 (15) | 0.0150 (15) | 0.0006 (14) |
C9 | 0.056 (2) | 0.0442 (18) | 0.074 (3) | −0.0032 (16) | 0.0199 (18) | 0.0008 (17) |
C10 | 0.068 (2) | 0.0459 (19) | 0.098 (3) | −0.0110 (18) | 0.021 (2) | 0.0092 (19) |
C11 | 0.061 (2) | 0.076 (3) | 0.074 (3) | −0.013 (2) | 0.016 (2) | 0.018 (2) |
C12 | 0.063 (2) | 0.075 (3) | 0.064 (3) | −0.002 (2) | 0.0284 (19) | 0.003 (2) |
C13 | 0.064 (2) | 0.0502 (19) | 0.059 (2) | −0.0029 (17) | 0.0220 (18) | 0.0008 (16) |
Cl1—C9 | 1.739 (3) | C5—H5 | 0.9300 |
N1—C5 | 1.359 (4) | C6—H6A | 0.9600 |
N1—C2 | 1.387 (4) | C6—H6B | 0.9600 |
N1—C6 | 1.472 (4) | C6—H6C | 0.9600 |
N2—O3 | 1.227 (4) | C7—C8 | 1.465 (4) |
N2—O2 | 1.232 (4) | C7—H7 | 0.9300 |
N2—C4 | 1.439 (4) | C8—C9 | 1.387 (4) |
N3—C1 | 1.354 (4) | C8—C13 | 1.402 (4) |
N3—N4 | 1.386 (3) | C9—C10 | 1.383 (5) |
N3—H3 | 0.8600 | C10—C11 | 1.379 (5) |
N4—C7 | 1.276 (4) | C10—H10 | 0.9300 |
O1—C1 | 1.234 (3) | C11—C12 | 1.374 (5) |
C1—C2 | 1.483 (4) | C11—H11 | 0.9300 |
C2—C3 | 1.374 (4) | C12—C13 | 1.388 (4) |
C3—C4 | 1.397 (4) | C12—H12 | 0.9300 |
C3—H3A | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.369 (5) | ||
C5—N1—C2 | 108.5 (3) | N1—C6—H6B | 109.5 |
C5—N1—C6 | 124.2 (3) | H6A—C6—H6B | 109.5 |
C2—N1—C6 | 127.1 (2) | N1—C6—H6C | 109.5 |
O3—N2—O2 | 124.7 (3) | H6A—C6—H6C | 109.5 |
O3—N2—C4 | 118.2 (4) | H6B—C6—H6C | 109.5 |
O2—N2—C4 | 117.1 (3) | N4—C7—C8 | 120.8 (3) |
C1—N3—N4 | 119.4 (2) | N4—C7—H7 | 119.6 |
C1—N3—H3 | 120.3 | C8—C7—H7 | 119.6 |
N4—N3—H3 | 120.3 | C9—C8—C13 | 116.7 (3) |
C7—N4—N3 | 114.6 (2) | C9—C8—C7 | 122.4 (3) |
O1—C1—N3 | 123.5 (3) | C13—C8—C7 | 120.9 (3) |
O1—C1—C2 | 123.1 (3) | C10—C9—C8 | 122.4 (3) |
N3—C1—C2 | 113.3 (3) | C10—C9—Cl1 | 118.5 (3) |
C3—C2—N1 | 108.5 (3) | C8—C9—Cl1 | 119.1 (2) |
C3—C2—C1 | 128.8 (3) | C11—C10—C9 | 119.6 (3) |
N1—C2—C1 | 122.6 (3) | C11—C10—H10 | 120.2 |
C2—C3—C4 | 106.1 (3) | C9—C10—H10 | 120.2 |
C2—C3—H3A | 126.9 | C12—C11—C10 | 119.8 (3) |
C4—C3—H3A | 126.9 | C12—C11—H11 | 120.1 |
C5—C4—C3 | 109.2 (3) | C10—C11—H11 | 120.1 |
C5—C4—N2 | 124.3 (3) | C11—C12—C13 | 120.2 (3) |
C3—C4—N2 | 126.4 (3) | C11—C12—H12 | 119.9 |
N1—C5—C4 | 107.6 (3) | C13—C12—H12 | 119.9 |
N1—C5—H5 | 126.2 | C12—C13—C8 | 121.3 (3) |
C4—C5—H5 | 126.2 | C12—C13—H13 | 119.4 |
N1—C6—H6A | 109.5 | C8—C13—H13 | 119.4 |
C1—N3—N4—C7 | 171.3 (3) | C2—N1—C5—C4 | 1.7 (4) |
N4—N3—C1—O1 | −0.5 (5) | C6—N1—C5—C4 | 177.5 (3) |
N4—N3—C1—C2 | −177.2 (3) | C3—C4—C5—N1 | −1.2 (4) |
C5—N1—C2—C3 | −1.6 (4) | N2—C4—C5—N1 | 178.0 (3) |
C6—N1—C2—C3 | −177.2 (3) | N3—N4—C7—C8 | 175.1 (3) |
C5—N1—C2—C1 | −177.7 (3) | N4—C7—C8—C9 | 168.3 (3) |
C6—N1—C2—C1 | 6.7 (5) | N4—C7—C8—C13 | −14.7 (5) |
O1—C1—C2—C3 | −147.4 (4) | C13—C8—C9—C10 | −0.6 (6) |
N3—C1—C2—C3 | 29.3 (5) | C7—C8—C9—C10 | 176.4 (4) |
O1—C1—C2—N1 | 27.9 (5) | C13—C8—C9—Cl1 | 178.0 (3) |
N3—C1—C2—N1 | −155.5 (3) | C7—C8—C9—Cl1 | −4.9 (5) |
N1—C2—C3—C4 | 0.8 (4) | C8—C9—C10—C11 | −0.7 (6) |
C1—C2—C3—C4 | 176.6 (3) | Cl1—C9—C10—C11 | −179.4 (3) |
C2—C3—C4—C5 | 0.3 (4) | C9—C10—C11—C12 | 1.2 (6) |
C2—C3—C4—N2 | −178.9 (3) | C10—C11—C12—C13 | −0.4 (6) |
O3—N2—C4—C5 | −6.7 (6) | C11—C12—C13—C8 | −1.0 (6) |
O2—N2—C4—C5 | 175.1 (4) | C9—C8—C13—C12 | 1.5 (5) |
O3—N2—C4—C3 | 172.3 (3) | C7—C8—C13—C12 | −175.6 (3) |
O2—N2—C4—C3 | −5.9 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1i | 0.86 | 2.14 | 2.941 (3) | 154 |
Symmetry code: (i) x, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1i | 0.860 | 2.144 | 2.941 (3) | 154.03 |
Symmetry code: (i) x, −y+3/2, z+1/2. |
Acknowledgements
This work was supported by the National-level College Students' Innovative Training Plan Program of the People's Republic of China (grant No. 201310122001) and the Scientific Research Foundation for PhDs of Changzhi University.
References
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A great number of aroylhydrazones (AH) have triggered wide interest because of their diverse spectra of biological and pharmaceutical properties (Raja, et al., 2012). In our lab, the AH compound (E)-N'-(2-hydroxybenzylidene)-1-methyl-4-nitro-1H-pyrrole-2-carbohydrazide (L) and its transition metal complexes were obtained and characterized. The interaction of these compounds with CT-DNA and pBR322 DNA has been explored (Wang, et al., 2014). The present report is an extension of our earlier studies in this area.
In the title compound (Fig. 1), C13H11ClN4O3, the phenyl and pyrrolyl ring are linked by acyl-hydrazone (R2C=N–N–CO–R) to form a slightly bent molecule. The dihedral angle between the phenyl (C8—C13) and pyrrolyl rings (C2—C5, N1) is 8.46 (12)°.
As shown in Figure 2, the herringbone molecular sheet of the title compound is formed by weak van-der-Waals interactions along (101) plane.
The three-dimensional supramolecular structure (Fig. 3) is assembled by N3–H3···O1i hydrogen bonding (pink dotted lines) and weak Cg1···Cg1ii (Cg1 is the centroid of the phenyl ring) and Cg2···Cg2iii (Cg2 is the centroid of the pyrrolyl ring) interactions (black dotted lines) between the neighbouring molecular sheets [symmetry code: (i) x, 3/2 - y, 1/2 + z; (ii)1 - x, 2 - y, 2 – z; (iii) - x, 1 - y, 2 - z]. The data of hydrogen-bond geometry are given in Table 1.