Literature DB >> 21754082

Methyl 2-[2-(2,6-dichloro-4-nitro-anilino)-3,5-dinitro-phen-yl]acetate.

Muhammad Ilyas Tariq, Muhammad Jameel, M Nawaz Tahir, Toqir Ali, Muhammad Rizwan.   

Abstract

In the title compound, C(15)H(10)Cl(2)N(4)O(8), the methyl-acetate and dichloro-anilinic groups are oriented at dihedral angles of 57.73 (8) and 62.44 (4)°, respectively to the dinitro-sustituted benzene ring. S(5) and S(7) rings are formed due to intra-molecular N-H⋯Cl and N-H⋯O hydrogen bonds, respectively. In the crystal, N-H⋯O hydrogen bonds link the mol-ecules into C(8) chains along the a axis. Further C-H⋯O and N-H⋯O hydrogen bonds link these chains in pairs, forming a polymeric network.

Entities:  

Year:  2011        PMID： 21754082      PMCID： PMC3100048          DOI： 10.1107/S1600536811007720

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

The title compound is the nitration product of diclofenac [systematic name 2-(2-(2,6-dichloro­phenyl­amino)­phen­yl)acetic acid] potassium, a non-steroidal anti-inflammatory drug (NSAID) and an anti-cancer agent. For nitro-substituted NSAIDs, see: Kashfi et al., (2002 ▶). For their anti-fungal properties, see: Afghahi et al. (1975 ▶); Gershon et al., (1971 ▶). For related structures, see: Castellari & Ottani (1997 ▶); Nawaz et al. (2007 ▶, 2008 ▶); Saleem et al., (2008 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶); Etter (1990 ▶); Etter et al. (1990 ▶).

Experimental

Crystal data

C15H10Cl2N4O8 M = 445.17 Monoclinic, a = 8.9527 (5) Å b = 9.5121 (5) Å c = 20.897 (1) Å β = 94.543 (1)° V = 1773.98 (16) Å3 Z = 4 Mo Kα radiation μ = 0.42 mm−1 T = 296 K 0.30 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.897, T max = 0.922 12379 measured reflections 3203 independent reflections 2621 reflections with I > 2σ(I) R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.034 wR(F 2) = 0.087 S = 1.05 3203 reflections 263 parameters H-atom parameters constrained Δρmax = 0.20 e Å−3 Δρmin = −0.21 e Å−3 Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811007720/dn2660sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007720/dn2660Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C15H10Cl2N4O8F(000) = 904
Mr = 445.17Dx = 1.667 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2621 reflections
a = 8.9527 (5) Åθ = 2.4–25.2°
b = 9.5121 (5) ŵ = 0.42 mm−1
c = 20.897 (1) ÅT = 296 K
β = 94.543 (1)°Prism, yellow
V = 1773.98 (16) Å30.30 × 0.22 × 0.20 mm
Z = 4
Bruker Kappa APEXII CCD diffractometer3203 independent reflections
Radiation source: fine-focus sealed tube2621 reflections with I > 2σ(I)
graphiteRint = 0.024
Detector resolution: 8.10 pixels mm-1θmax = 25.2°, θmin = 2.4°
ω scansh = −10→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −11→10
Tmin = 0.897, Tmax = 0.922l = −22→25
12379 measured reflections
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0389P)2 + 0.6501P] where P = (Fo2 + 2Fc2)/3
3203 reflections(Δ/σ)max = 0.001
263 parametersΔρmax = 0.20 e Å−3
0 restraintsΔρmin = −0.21 e Å−3
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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.
xyzUiso*/Ueq
Cl11.08890 (6)0.09167 (6)0.11740 (2)0.0457 (2)
Cl20.70818 (6)0.50170 (6)0.02516 (3)0.0510 (2)
O10.98208 (16)0.41699 (17)0.33608 (6)0.0511 (5)
O20.95143 (18)0.24847 (18)0.26208 (7)0.0584 (6)
O30.26958 (18)0.4702 (2)0.25979 (8)0.0771 (7)
O40.17334 (16)0.40470 (18)0.16740 (8)0.0596 (6)
O50.4754 (2)0.1723 (2)0.02287 (9)0.0864 (8)
O60.68940 (18)0.09329 (18)0.06051 (8)0.0640 (6)
O71.1745 (2)0.1899 (2)−0.12328 (8)0.0830 (8)
O80.9727 (2)0.2898 (2)−0.16374 (8)0.0793 (7)
N10.28053 (19)0.4219 (2)0.20692 (8)0.0464 (6)
N20.5835 (2)0.1715 (2)0.06248 (8)0.0493 (6)
N30.85497 (16)0.30502 (18)0.12926 (7)0.0364 (5)
N41.0551 (3)0.2455 (2)−0.11838 (9)0.0558 (7)
C11.0795 (3)0.3245 (3)0.37513 (11)0.0741 (10)
C20.9253 (2)0.3648 (2)0.28064 (9)0.0394 (6)
C30.8298 (2)0.4690 (2)0.24288 (9)0.0386 (6)
C40.6961 (2)0.4044 (2)0.20505 (8)0.0324 (6)
C50.5548 (2)0.4308 (2)0.22451 (8)0.0359 (6)
C60.4294 (2)0.3837 (2)0.18818 (9)0.0370 (6)
C70.4395 (2)0.3036 (2)0.13420 (9)0.0390 (6)
C80.5803 (2)0.2706 (2)0.11649 (8)0.0355 (6)
C90.7113 (2)0.3240 (2)0.14891 (8)0.0323 (6)
C100.89884 (18)0.29106 (19)0.06728 (8)0.0311 (6)
C111.0138 (2)0.1965 (2)0.05521 (8)0.0335 (6)
C121.0680 (2)0.1815 (2)−0.00449 (9)0.0390 (6)
C131.0017 (2)0.2607 (2)−0.05380 (9)0.0401 (6)
C140.8891 (2)0.3552 (2)−0.04567 (9)0.0405 (6)
C150.8406 (2)0.3721 (2)0.01525 (9)0.0349 (6)
H1A1.160580.294280.350990.1113*
H1B1.023770.244120.387490.1113*
H1C1.119020.373780.412850.1113*
H30.925900.301510.159480.0437*
H3A0.890710.517250.213420.0463*
H3B0.794420.538560.272060.0463*
H50.544290.480460.262220.0431*
H70.353870.272460.110240.0468*
H121.146250.12025−0.011010.0467*
H140.846300.40681−0.080210.0486*
U11U22U33U12U13U23
Cl10.0452 (3)0.0477 (3)0.0442 (3)0.0062 (2)0.0037 (2)0.0042 (2)
Cl20.0435 (3)0.0509 (3)0.0595 (3)0.0093 (3)0.0095 (2)0.0098 (3)
O10.0441 (8)0.0722 (11)0.0363 (7)0.0005 (8)−0.0018 (6)−0.0081 (7)
O20.0741 (11)0.0503 (10)0.0485 (8)0.0103 (9)−0.0089 (8)−0.0039 (8)
O30.0464 (9)0.1287 (17)0.0585 (10)0.0024 (10)0.0180 (8)−0.0339 (11)
O40.0325 (8)0.0785 (12)0.0673 (10)0.0005 (8)0.0002 (8)−0.0077 (9)
O50.0771 (13)0.1165 (18)0.0626 (11)0.0001 (12)−0.0136 (10)−0.0434 (11)
O60.0528 (10)0.0583 (11)0.0839 (12)−0.0101 (9)0.0249 (9)−0.0285 (9)
O70.0786 (13)0.1118 (17)0.0639 (11)0.0109 (12)0.0382 (10)−0.0111 (11)
O80.1126 (15)0.0877 (14)0.0393 (9)0.0031 (12)0.0171 (10)0.0061 (9)
N10.0326 (9)0.0602 (12)0.0473 (10)−0.0025 (9)0.0089 (8)−0.0034 (9)
N20.0468 (11)0.0589 (12)0.0435 (10)−0.0166 (10)0.0120 (9)−0.0141 (9)
N30.0262 (8)0.0550 (11)0.0281 (7)0.0000 (8)0.0027 (6)−0.0051 (7)
N40.0721 (14)0.0566 (12)0.0411 (10)−0.0122 (11)0.0205 (10)−0.0053 (9)
C10.0701 (17)0.106 (2)0.0435 (12)0.0062 (16)−0.0119 (12)0.0126 (14)
C20.0332 (10)0.0520 (14)0.0332 (9)−0.0056 (10)0.0042 (8)−0.0031 (9)
C30.0344 (10)0.0408 (12)0.0402 (10)−0.0034 (9)0.0005 (8)−0.0073 (9)
C40.0311 (9)0.0352 (11)0.0307 (9)−0.0019 (8)0.0019 (7)0.0002 (8)
C50.0366 (10)0.0416 (12)0.0301 (9)−0.0008 (9)0.0058 (8)−0.0036 (8)
C60.0296 (10)0.0465 (12)0.0360 (9)−0.0010 (9)0.0088 (8)0.0014 (9)
C70.0296 (10)0.0503 (13)0.0369 (10)−0.0091 (9)0.0024 (8)−0.0027 (9)
C80.0365 (10)0.0392 (11)0.0312 (9)−0.0067 (9)0.0056 (8)−0.0054 (8)
C90.0302 (9)0.0364 (11)0.0307 (9)−0.0017 (8)0.0057 (7)0.0017 (8)
C100.0251 (9)0.0366 (11)0.0318 (9)−0.0075 (8)0.0038 (7)−0.0047 (8)
C110.0308 (9)0.0350 (11)0.0347 (9)−0.0049 (8)0.0031 (8)−0.0017 (8)
C120.0364 (10)0.0391 (12)0.0428 (10)−0.0043 (9)0.0121 (8)−0.0066 (9)
C130.0447 (11)0.0428 (12)0.0343 (10)−0.0128 (10)0.0127 (9)−0.0050 (9)
C140.0434 (11)0.0449 (12)0.0330 (9)−0.0114 (10)0.0015 (8)0.0038 (9)
C150.0293 (9)0.0364 (11)0.0391 (10)−0.0059 (8)0.0032 (8)−0.0012 (8)
Cl1—C111.7312 (18)C4—C91.416 (2)
Cl2—C151.7341 (19)C5—C61.379 (3)
O1—C11.445 (3)C6—C71.370 (3)
O1—C21.324 (2)C7—C81.378 (3)
O2—C21.202 (3)C8—C91.402 (3)
O3—N11.208 (2)C10—C151.399 (3)
O4—N11.226 (2)C10—C111.405 (3)
O5—N21.223 (3)C11—C121.381 (3)
O6—N21.208 (2)C12—C131.373 (3)
O7—N41.204 (3)C13—C141.371 (3)
O8—N41.229 (3)C14—C151.387 (3)
N1—C61.464 (2)C1—H1A0.9600
N2—C81.473 (3)C1—H1B0.9600
N3—C91.393 (2)C1—H1C0.9600
N3—C101.389 (2)C3—H3A0.9700
N4—C131.474 (3)C3—H3B0.9700
N3—H30.8600C5—H50.9300
C2—C31.493 (3)C7—H70.9300
C3—C41.512 (3)C12—H120.9300
C4—C51.382 (3)C14—H140.9300
Cl1···O4i3.2255 (18)N3···Cl23.0833 (17)
Cl1···N32.9408 (17)N3···O22.891 (2)
Cl1···N4ii3.457 (2)N3···O4i3.049 (2)
Cl1···O3iii3.0019 (18)N3···O62.825 (2)
Cl2···C83.1830 (19)N3···N22.988 (2)
Cl2···N33.0833 (17)N3···C23.227 (2)
Cl2···C93.0877 (19)N4···Cl1ii3.457 (2)
Cl2···N23.443 (2)N3···H3A2.6800
Cl2···C13iv3.4592 (19)C1···O3i3.358 (3)
Cl1···H32.6600C1···O5xi3.295 (3)
Cl1···H7i2.9400C1···C14xi3.552 (3)
Cl1···H5iii3.0600C2···O3i3.303 (2)
O1···O3i3.174 (2)C2···O4i3.392 (2)
O1···O6v3.219 (2)C2···N33.227 (2)
O1···O7vi3.116 (2)C2···O7vi3.171 (3)
O2···N32.891 (2)C3···O8iv3.404 (3)
O2···C93.150 (2)C5···O8vi3.266 (3)
O2···C5iii3.036 (3)C5···O2v3.036 (3)
O3···Cl1v3.0019 (18)C8···C153.409 (3)
O3···O1vii3.174 (2)C8···Cl23.1830 (19)
O3···C2vii3.303 (2)C9···O23.150 (2)
O3···C1vii3.358 (3)C9···Cl23.0877 (19)
O4···Cl1vii3.2255 (18)C10···O4i3.282 (2)
O4···O8viii3.185 (3)C10···N23.038 (2)
O4···C11vii3.306 (2)C10···O62.652 (2)
O4···C10vii3.282 (2)C11···O63.076 (2)
O4···N3vii3.049 (2)C11···O4i3.306 (2)
O4···C2vii3.392 (2)C13···Cl2iv3.4592 (19)
O5···C1ix3.295 (3)C14···C1ix3.552 (3)
O6···C102.652 (2)C14···C15iv3.570 (3)
O6···N32.825 (2)C15···O63.157 (3)
O6···O1iii3.219 (2)C15···C83.409 (3)
O6···C113.076 (2)C15···C14iv3.570 (3)
O6···C153.157 (3)C15···N23.205 (3)
O6···O7ii3.195 (3)C2···H32.6000
O7···O1x3.116 (2)C3···H32.5600
O7···C2x3.171 (3)H1A···O22.5700
O7···O6ii3.195 (3)H1A···O3i2.7700
O8···C5x3.266 (3)H1B···O22.6500
O8···C3iv3.404 (3)H1C···O5xi2.7600
O8···O4viii3.185 (3)H3···Cl12.6600
O2···H1B2.6500H3···O22.2000
O2···H1A2.5700H3···O4i2.4200
O2···H5iii2.6000H3···C22.6000
O2···H32.2000H3···C32.5600
O3···H52.4600H3···H3A2.3700
O3···H1Avii2.7700H3A···N32.6800
O4···H72.4300H3A···H32.3700
O4···H14viii2.5500H3A···O8iv2.4800
O4···H3vii2.4200H3B···H52.3000
O5···H1Cix2.7600H5···O32.4600
O5···H72.4000H5···H3B2.3000
O6···H12ii2.7600H5···Cl1v3.0600
O7···H122.4700H5···O2v2.6000
O8···H142.4200H7···Cl1vii2.9400
O8···H3Aiv2.4800H7···O42.4300
N2···Cl23.443 (2)H7···O52.4000
N2···N32.988 (2)H12···O72.4700
N2···C103.038 (2)H12···O6ii2.7600
N2···C153.205 (3)H14···O82.4200
N3···Cl12.9408 (17)H14···O4viii2.5500
C1—O1—C2116.01 (17)N3—C10—C15123.80 (16)
O3—N1—O4123.43 (18)N3—C10—C11119.60 (15)
O3—N1—C6118.72 (17)Cl1—C11—C10118.72 (13)
O4—N1—C6117.84 (16)Cl1—C11—C12118.37 (14)
O5—N2—O6124.19 (19)C10—C11—C12122.90 (16)
O5—N2—C8116.90 (18)C11—C12—C13117.34 (17)
O6—N2—C8118.89 (17)C12—C13—C14123.03 (18)
C9—N3—C10128.55 (14)N4—C13—C12118.75 (17)
O7—N4—O8124.6 (2)N4—C13—C14118.21 (17)
O7—N4—C13118.38 (19)C13—C14—C15118.46 (17)
O8—N4—C13117.0 (2)C10—C15—C14121.67 (17)
C9—N3—H3116.00Cl2—C15—C10121.00 (14)
C10—N3—H3116.00Cl2—C15—C14117.31 (14)
O1—C2—O2123.82 (18)O1—C1—H1A109.00
O2—C2—C3123.97 (17)O1—C1—H1B109.00
O1—C2—C3112.18 (16)O1—C1—H1C109.00
C2—C3—C4113.77 (16)H1A—C1—H1B109.00
C3—C4—C9121.92 (16)H1A—C1—H1C109.00
C5—C4—C9119.48 (16)H1B—C1—H1C109.00
C3—C4—C5118.53 (16)C2—C3—H3A109.00
C4—C5—C6120.21 (16)C2—C3—H3B109.00
N1—C6—C7118.62 (16)C4—C3—H3A109.00
N1—C6—C5119.38 (16)C4—C3—H3B109.00
C5—C6—C7122.00 (17)H3A—C3—H3B108.00
C6—C7—C8117.99 (17)C4—C5—H5120.00
N2—C8—C9122.40 (16)C6—C5—H5120.00
N2—C8—C7115.18 (16)C6—C7—H7121.00
C7—C8—C9122.39 (17)C8—C7—H7121.00
N3—C9—C8124.56 (16)C11—C12—H12121.00
N3—C9—C4117.77 (16)C13—C12—H12121.00
C4—C9—C8117.67 (16)C13—C14—H14121.00
C11—C10—C15116.51 (15)C15—C14—H14121.00
C1—O1—C2—O2−0.5 (3)C5—C4—C9—C8−2.0 (3)
C1—O1—C2—C3−178.39 (17)C4—C5—C6—N1−175.34 (17)
O3—N1—C6—C5−14.0 (3)C4—C5—C6—C73.6 (3)
O3—N1—C6—C7166.96 (19)N1—C6—C7—C8178.84 (17)
O4—N1—C6—C5164.98 (19)C5—C6—C7—C8−0.1 (3)
O4—N1—C6—C7−14.0 (3)C6—C7—C8—N2173.43 (17)
O5—N2—C8—C729.3 (3)C6—C7—C8—C9−4.6 (3)
O5—N2—C8—C9−152.72 (19)N2—C8—C9—N38.6 (3)
O6—N2—C8—C7−149.23 (19)N2—C8—C9—C4−172.25 (17)
O6—N2—C8—C928.8 (3)C7—C8—C9—N3−173.48 (18)
C10—N3—C9—C4−147.95 (19)C7—C8—C9—C45.6 (3)
C10—N3—C9—C831.2 (3)N3—C10—C11—Cl14.2 (2)
C9—N3—C10—C11−141.91 (19)N3—C10—C11—C12−177.02 (17)
C9—N3—C10—C1541.7 (3)C15—C10—C11—Cl1−179.21 (14)
O7—N4—C13—C12−16.4 (3)C15—C10—C11—C12−0.4 (3)
O7—N4—C13—C14162.6 (2)N3—C10—C15—Cl21.3 (3)
O8—N4—C13—C12162.84 (19)N3—C10—C15—C14179.35 (17)
O8—N4—C13—C14−18.1 (3)C11—C10—C15—Cl2−175.21 (14)
O1—C2—C3—C4−144.61 (16)C11—C10—C15—C142.9 (3)
O2—C2—C3—C437.5 (3)Cl1—C11—C12—C13176.86 (14)
C2—C3—C4—C5109.8 (2)C10—C11—C12—C13−2.0 (3)
C2—C3—C4—C9−73.4 (2)C11—C12—C13—N4−178.98 (18)
C3—C4—C5—C6174.51 (17)C11—C12—C13—C142.0 (3)
C9—C4—C5—C6−2.4 (3)N4—C13—C14—C15−178.66 (18)
C3—C4—C9—N30.3 (3)C12—C13—C14—C150.4 (3)
C3—C4—C9—C8−178.85 (17)C13—C14—C15—Cl2175.25 (14)
C5—C4—C9—N3177.16 (17)C13—C14—C15—C10−2.9 (3)
D—H···AD—HH···AD···AD—H···A
N3—H3···Cl10.862.662.9408 (17)100
N3—H3···O20.862.202.891 (2)138
N3—H3···O4i0.862.423.049 (2)131
C3—H3A···O8iv0.972.483.404 (3)160
C14—H14···O4viii0.932.553.431 (3)158
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N3—H3⋯Cl10.862.662.9408 (17)100
N3—H3⋯O20.862.202.891 (2)138
N3—H3⋯O4i0.862.423.049 (2)131
C3—H3A⋯O8ii0.972.483.404 (3)160
C14—H14⋯O4iii0.932.553.431 (3)158

Symmetry codes: (i) ; (ii) ; (iii) .

  8 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  Graph-set analysis of hydrogen-bond patterns in organic crystals.

Authors:  M C Etter; J C MacDonald; J Bernstein
Journal:  Acta Crystallogr B       Date:  1990-04-01

3.  Nitric oxide-donating nonsteroidal anti-inflammatory drugs inhibit the growth of various cultured human cancer cells: evidence of a tissue type-independent effect.

Authors:  Khosrow Kashfi; Yassir Rayyan; Leon L Qiao; Jennie L Williams; Jie Chen; Piero Del Soldato; Frank Traganos; Basil Rigas; Yassir Ryann
Journal:  J Pharmacol Exp Ther       Date:  2002-12       Impact factor: 4.030

4.  Antifungal activity of substituted nitrobenzenes and anilines.

Authors:  H Gershon; M W McNeil; R Parmegiani; P K Godfrey
Journal:  Appl Microbiol       Date:  1971-09

5.  Synthesis and antibacterial and antifungal activities of 5-nitro-2-furfurylidene polyhalophenoxyacethydrazides VIII.

Authors:  F Afghahi; S Yazdany; I Lalezari
Journal:  J Pharm Sci       Date:  1975-05       Impact factor: 3.534

6.  Methyl 2-[2-(2,6-dichloro-anilino)-phenyl]-acetate.

Authors:  Rashid Saleem; Ghulam Shabir; Muhammad Hanif; Ghulam Qadeer; Wai-Yeung Wong
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2008-11-20

7.  Isopropyl 2-[2-(2,6-dichloro-anilino)phen-yl]acetate.

Authors:  Hamid Nawaz; M Khawar Rauf; Masahiro Ebihara; Amin Badshah
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2007-12-21

8.  Structure validation in chemical crystallography.

Authors:  Anthony L Spek
Journal:  Acta Crystallogr D Biol Crystallogr       Date:  2009-01-20
  8 in total

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