organic compounds
2-{[(Dimethylamino)methylidene]amino}-5-nitrobenzonitrile
aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and bPCSIR Labortories Complex, Karachi, Shahrah-e-Dr. Salmuzzaman Siddiqui, Karachi 75280, Pakistan
*Correspondence e-mail: dr.sammer.yousuf@gmail.com
The title molecule, C10H10N4O2, is almost planar and adopts an E configuration of the azomethine [C=N = 1.298 (2) Å] double bond. The benzene ring is attached to an essentially planar (r.m.s. deviation = 0.0226 Å) amidine moiety (N=CN/Me2), the dihedral angle between the two mean planes being 18.42 (11)°. The cyano group lies in the plane of the benzene ring [the C and N atoms deviating by 0.030 (3) and 0.040 (3) Å, respectively], while the nitro group makes a dihedral angle 5.8 (3)° with the benzene ring. There are two distinct intermolecular hydrogen bonds, C—H⋯O and C—H⋯N, that stabilize the the former interactions result in centrosymmetric dimers about inversion centers resulting in ten-membered rings, while the later give rise to chains of molecules running parallel to the b axis.
Related literature
For the biological activity of amidine derivatives, see: Sienkiewich et al. (2005); Sasaki et al. (1997). For a related structure, see: Cizak et al. (1989).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); 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, PARST (Nardelli, 1995) and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536812048866/pv2610sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812048866/pv2610Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812048866/pv2610Isup3.cml
5-Nitroanthranilonitrile (45.8 mmol, 7.47 g) was suspended in N,N-dimethylformamide dimethylacetal (137.4 mmol, 16.5 ml) and the mixture was allow to refluxed for 1.5 h. The progress of the reaction was monitored by thin layer
After the completion of the reaction, the resulting mixture was cooled to room temperature and refrigerated overnight to obtain yellow crystals. The crystals were filtered, washed with diethyl ether to afford the pure compound (9.4 g, 94% yield). Single-crystal suitable for X-ray diffraction studies were grown from ethanol. All chemicals were purchased by Sigma Aldrich Germany.The H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 0.96 Å, for aryl and methyl H-atoms, respectively. The Uiso(H) were allowed at 1.5Ueq(C methyl) or 1.2Ueq(C aryl). A rotating group model was applied to the methyl groups.
The compounds having amidine group (–N═CHNR2) in their structures are known to have a wide range of pharmacological properties such as anti-HIV (Sasaki et al., 1997) and anticancer (Sienkiewich et al., 2005). The title compound is also an amidine derivatived we have synthesized in order to evaluate its biological potential and determined its that is reported here.
In the title compound (Fig. 1) the benzene ring (C1–C6) is attached with an essentially planar amidine moiety (N3/N4/C8–C10) with r.m.s.d 0.0226 Å; the dihedral angle between the two mean planes being 18.42 (11)°. The atoms C7 and N1 of the cyano group lie in the plane of the benzene ring with deviations 0.030 (3) and 0.040 (3) Å, respectively. The nitro group (N2/O1/O2) makes a dihedral angle 5.8 (3) ° with the benzene ring. The bond distances and angles in the title compound agree very well with the corresponding bond distances and angles reported in a closely related compound (Cizak et al., 1989).
There are two distinct intermolecular hydrogen bonds, C1—H1A···O1 and C8—H8A···N1 that stabilize the
(Table 2 and Fig. 2). The former interactions result in centrosymmetric dimers about inversion centers resulting in 10-membered rings, while the later give rise to chains of molecules running parallel to the b-axis.For the biological activity of amidine derivatives, see: Sienkiewich et al. (2005); Sasaki et al. (1997). For a related structure, see: Cizak et al. (1989).
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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), PARST (Nardelli, 1995) and PLATON (Spek, 2009).C10H10N4O2 | F(000) = 456 |
Mr = 218.22 | Dx = 1.355 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1456 reflections |
a = 7.6496 (11) Å | θ = 2.5–26.3° |
b = 13.0693 (19) Å | µ = 0.10 mm−1 |
c = 11.1617 (17) Å | T = 273 K |
β = 106.475 (3)° | Block, yellow |
V = 1070.1 (3) Å3 | 0.25 × 0.24 × 0.09 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 1976 independent reflections |
Radiation source: fine-focus sealed tube | 1427 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scan | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→6 |
Tmin = 0.976, Tmax = 0.991 | k = −15→15 |
6194 measured reflections | l = −13→13 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0727P)2 + 0.0566P] where P = (Fo2 + 2Fc2)/3 |
1976 reflections | (Δ/σ)max < 0.001 |
147 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C10H10N4O2 | V = 1070.1 (3) Å3 |
Mr = 218.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6496 (11) Å | µ = 0.10 mm−1 |
b = 13.0693 (19) Å | T = 273 K |
c = 11.1617 (17) Å | 0.25 × 0.24 × 0.09 mm |
β = 106.475 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 1976 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1427 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.991 | Rint = 0.025 |
6194 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.18 e Å−3 |
1976 reflections | Δρmin = −0.16 e Å−3 |
147 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 | ||
O1 | 1.0056 (2) | 0.13577 (12) | 1.04462 (17) | 0.0870 (6) | |
O2 | 0.8695 (2) | 0.25597 (13) | 1.11451 (17) | 0.0883 (6) | |
N1 | 0.4989 (2) | −0.15217 (12) | 0.71893 (17) | 0.0660 (5) | |
N2 | 0.8674 (2) | 0.18015 (13) | 1.04982 (17) | 0.0619 (5) | |
N3 | 0.1940 (2) | 0.02940 (11) | 0.75738 (14) | 0.0482 (4) | |
N4 | −0.1087 (2) | 0.05091 (12) | 0.65346 (15) | 0.0543 (5) | |
C1 | 0.6835 (3) | 0.05189 (13) | 0.91041 (16) | 0.0463 (5) | |
H1A | 0.7889 | 0.0151 | 0.9140 | 0.056* | |
C2 | 0.6912 (3) | 0.14214 (13) | 0.97521 (17) | 0.0459 (5) | |
C3 | 0.5357 (3) | 0.19632 (13) | 0.97190 (17) | 0.0488 (5) | |
H3B | 0.5439 | 0.2565 | 1.0176 | 0.059* | |
C4 | 0.3696 (3) | 0.16215 (13) | 0.90195 (17) | 0.0501 (5) | |
H4A | 0.2657 | 0.1994 | 0.9011 | 0.060* | |
C5 | 0.3520 (2) | 0.07166 (12) | 0.83108 (16) | 0.0426 (4) | |
C6 | 0.5146 (3) | 0.01730 (12) | 0.83973 (16) | 0.0421 (4) | |
C7 | 0.5035 (3) | −0.07743 (14) | 0.77211 (17) | 0.0490 (5) | |
C8 | 0.0485 (3) | 0.08563 (14) | 0.72313 (16) | 0.0481 (5) | |
H8A | 0.0558 | 0.1535 | 0.7491 | 0.058* | |
C9 | −0.2656 (3) | 0.11779 (17) | 0.6087 (2) | 0.0711 (7) | |
H9A | −0.2429 | 0.1815 | 0.6533 | 0.107* | |
H9B | −0.3713 | 0.0857 | 0.6223 | 0.107* | |
H9C | −0.2861 | 0.1303 | 0.5210 | 0.107* | |
C10 | −0.1270 (3) | −0.05486 (17) | 0.6095 (2) | 0.0753 (7) | |
H10A | −0.0086 | −0.0858 | 0.6275 | 0.113* | |
H10B | −0.1837 | −0.0560 | 0.5209 | 0.113* | |
H10C | −0.2008 | −0.0923 | 0.6510 | 0.113* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0470 (10) | 0.0792 (11) | 0.1247 (15) | 0.0011 (8) | 0.0079 (10) | −0.0227 (9) |
O2 | 0.0709 (12) | 0.0766 (11) | 0.1064 (13) | −0.0137 (8) | 0.0075 (10) | −0.0416 (9) |
N1 | 0.0732 (13) | 0.0482 (10) | 0.0718 (11) | 0.0013 (8) | 0.0125 (10) | −0.0114 (8) |
N2 | 0.0528 (12) | 0.0526 (10) | 0.0734 (12) | −0.0048 (8) | 0.0068 (9) | −0.0053 (8) |
N3 | 0.0436 (10) | 0.0425 (8) | 0.0543 (9) | 0.0004 (7) | 0.0070 (8) | −0.0005 (6) |
N4 | 0.0458 (11) | 0.0553 (10) | 0.0566 (10) | 0.0019 (7) | 0.0059 (8) | 0.0004 (7) |
C1 | 0.0453 (12) | 0.0409 (9) | 0.0520 (11) | 0.0044 (8) | 0.0127 (9) | 0.0026 (7) |
C2 | 0.0456 (12) | 0.0400 (9) | 0.0493 (10) | −0.0033 (8) | 0.0087 (9) | 0.0021 (7) |
C3 | 0.0559 (13) | 0.0358 (9) | 0.0518 (11) | 0.0005 (8) | 0.0103 (9) | −0.0021 (7) |
C4 | 0.0491 (12) | 0.0407 (10) | 0.0577 (11) | 0.0074 (8) | 0.0103 (10) | −0.0007 (8) |
C5 | 0.0457 (11) | 0.0373 (9) | 0.0432 (10) | 0.0000 (8) | 0.0100 (8) | 0.0063 (7) |
C6 | 0.0472 (12) | 0.0342 (8) | 0.0438 (9) | 0.0003 (7) | 0.0109 (8) | 0.0035 (7) |
C7 | 0.0506 (12) | 0.0420 (10) | 0.0514 (10) | 0.0023 (8) | 0.0098 (9) | 0.0022 (8) |
C8 | 0.0520 (13) | 0.0441 (10) | 0.0449 (10) | 0.0007 (8) | 0.0083 (9) | 0.0033 (7) |
C9 | 0.0523 (14) | 0.0767 (15) | 0.0736 (14) | 0.0061 (11) | 0.0004 (11) | 0.0162 (11) |
C10 | 0.0629 (16) | 0.0674 (14) | 0.0909 (17) | −0.0132 (11) | 0.0141 (13) | −0.0176 (12) |
O1—N2 | 1.222 (2) | C3—C4 | 1.364 (3) |
O2—N2 | 1.224 (2) | C3—H3B | 0.9300 |
N1—C7 | 1.138 (2) | C4—C5 | 1.408 (2) |
N2—C2 | 1.456 (2) | C4—H4A | 0.9300 |
N3—C8 | 1.298 (2) | C5—C6 | 1.412 (2) |
N3—C5 | 1.371 (2) | C6—C7 | 1.440 (2) |
N4—C8 | 1.314 (2) | C8—H8A | 0.9300 |
N4—C9 | 1.454 (2) | C9—H9A | 0.9600 |
N4—C10 | 1.460 (2) | C9—H9B | 0.9600 |
C1—C2 | 1.376 (2) | C9—H9C | 0.9600 |
C1—C6 | 1.385 (2) | C10—H10A | 0.9600 |
C1—H1A | 0.9300 | C10—H10B | 0.9600 |
C2—C3 | 1.375 (3) | C10—H10C | 0.9600 |
O1—N2—O2 | 123.09 (18) | C4—C5—C6 | 116.26 (16) |
O1—N2—C2 | 118.95 (17) | C1—C6—C5 | 122.42 (16) |
O2—N2—C2 | 117.96 (17) | C1—C6—C7 | 119.09 (16) |
C8—N3—C5 | 119.04 (15) | C5—C6—C7 | 118.50 (16) |
C8—N4—C9 | 121.57 (17) | N1—C7—C6 | 178.4 (2) |
C8—N4—C10 | 120.69 (17) | N3—C8—N4 | 122.92 (17) |
C9—N4—C10 | 117.54 (17) | N3—C8—H8A | 118.5 |
C2—C1—C6 | 118.24 (17) | N4—C8—H8A | 118.5 |
C2—C1—H1A | 120.9 | N4—C9—H9A | 109.5 |
C6—C1—H1A | 120.9 | N4—C9—H9B | 109.5 |
C3—C2—C1 | 121.29 (17) | H9A—C9—H9B | 109.5 |
C3—C2—N2 | 119.53 (16) | N4—C9—H9C | 109.5 |
C1—C2—N2 | 119.18 (17) | H9A—C9—H9C | 109.5 |
C4—C3—C2 | 120.32 (17) | H9B—C9—H9C | 109.5 |
C4—C3—H3B | 119.8 | N4—C10—H10A | 109.5 |
C2—C3—H3B | 119.8 | N4—C10—H10B | 109.5 |
C3—C4—C5 | 121.44 (17) | H10A—C10—H10B | 109.5 |
C3—C4—H4A | 119.3 | N4—C10—H10C | 109.5 |
C5—C4—H4A | 119.3 | H10A—C10—H10C | 109.5 |
N3—C5—C4 | 127.10 (17) | H10B—C10—H10C | 109.5 |
N3—C5—C6 | 116.62 (15) | ||
C6—C1—C2—C3 | 0.9 (3) | C3—C4—C5—N3 | −179.98 (17) |
C6—C1—C2—N2 | −179.79 (16) | C3—C4—C5—C6 | 1.8 (3) |
O1—N2—C2—C3 | −174.48 (18) | C2—C1—C6—C5 | 0.7 (3) |
O2—N2—C2—C3 | 5.1 (3) | C2—C1—C6—C7 | −179.46 (16) |
O1—N2—C2—C1 | 6.2 (3) | N3—C5—C6—C1 | 179.62 (15) |
O2—N2—C2—C1 | −174.19 (18) | C4—C5—C6—C1 | −2.0 (3) |
C1—C2—C3—C4 | −1.1 (3) | N3—C5—C6—C7 | −0.2 (2) |
N2—C2—C3—C4 | 179.63 (17) | C4—C5—C6—C7 | 178.12 (16) |
C2—C3—C4—C5 | −0.4 (3) | C5—N3—C8—N4 | −179.43 (17) |
C8—N3—C5—C4 | 17.3 (3) | C9—N4—C8—N3 | −175.20 (18) |
C8—N3—C5—C6 | −164.50 (16) | C10—N4—C8—N3 | −0.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O1i | 0.93 | 2.48 | 3.354 (3) | 156 |
C8—H8A···N1ii | 0.93 | 2.61 | 3.525 (2) | 166 |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1/2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C10H10N4O2 |
Mr | 218.22 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 7.6496 (11), 13.0693 (19), 11.1617 (17) |
β (°) | 106.475 (3) |
V (Å3) | 1070.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.25 × 0.24 × 0.09 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.976, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6194, 1976, 1427 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.134, 1.04 |
No. of reflections | 1976 |
No. of parameters | 147 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.16 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O1i | 0.9300 | 2.4800 | 3.354 (3) | 156.00 |
C8—H8A···N1ii | 0.9300 | 2.6100 | 3.525 (2) | 166.00 |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1/2, y+1/2, −z+3/2. |
Acknowledgements
The authors are thankful to the Higher Education Commission (HEC) Pakistan (Project No. 20–2073) and the Pakistan Academy of Sciences (PAS) for their financial support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The compounds having amidine group (–N═CHNR2) in their structures are known to have a wide range of pharmacological properties such as anti-HIV (Sasaki et al., 1997) and anticancer (Sienkiewich et al., 2005). The title compound is also an amidine derivatived we have synthesized in order to evaluate its biological potential and determined its crystal structure that is reported here.
In the title compound (Fig. 1) the benzene ring (C1–C6) is attached with an essentially planar amidine moiety (N3/N4/C8–C10) with r.m.s.d 0.0226 Å; the dihedral angle between the two mean planes being 18.42 (11)°. The atoms C7 and N1 of the cyano group lie in the plane of the benzene ring with deviations 0.030 (3) and 0.040 (3) Å, respectively. The nitro group (N2/O1/O2) makes a dihedral angle 5.8 (3) ° with the benzene ring. The bond distances and angles in the title compound agree very well with the corresponding bond distances and angles reported in a closely related compound (Cizak et al., 1989).
There are two distinct intermolecular hydrogen bonds, C1—H1A···O1 and C8—H8A···N1 that stabilize the crystal structure (Table 2 and Fig. 2). The former interactions result in centrosymmetric dimers about inversion centers resulting in 10-membered rings, while the later give rise to chains of molecules running parallel to the b-axis.