





Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809052520/tk2591sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536809052520/tk2591Isup2.hkl |
CCDC reference: 766842
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean
(C-C) = 0.002 Å
- R factor = 0.028
- wR factor = 0.079
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C14 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.24 PLAT431_ALERT_2_C Short Inter HL..A Contact Cl3 .. O6 .. 3.13 Ang. PLAT431_ALERT_2_C Short Inter HL..A Contact Cl4 .. O1 .. 3.05 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The solution of maleic anhydride (0.025 mol) in toluene (25 ml) was treated drop-wise with the solution of 2,4,5-trichloroaniline (0.025 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was warmed with stirring for over 30 min and set aside for an additional 30 min at room temperature for completion of the reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 2,4,5-trichloroaniline. The resultant solid N-(2,4,5-trichlorophenyl)maleamic acid was filtered under suction and washed thoroughly with water to remove the unreacted maleic anhydride and maleic acid. It was recrystallized to constant melting point from ethanol. The purity of the compound was checked by elemental analysis and characterized by its infrared spectra. Colourless single crystals used in X-ray diffraction studies were grown in an ethanol solution by slow evaporation at room temperature.
H atoms were visible in difference maps. In the final cycles of refinement, the amido-H atoms were refined freely, while the C,O-bound H atoms were placed in calculated positions and refined using the riding model with C–H = 0.93Å and O–H = 0.82 Å. The Uiso(H) values were set at 1.2Ueq(C,O).
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).
C10H6Cl3NO3 | F(000) = 1184 |
Mr = 294.51 | Dx = 1.68 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 30027 reflections |
a = 10.8979 (2) Å | θ = 1.8–29.5° |
b = 11.0225 (2) Å | µ = 0.78 mm−1 |
c = 19.4739 (3) Å | T = 295 K |
β = 95.4761 (9)° | Block, colourless |
V = 2328.57 (7) Å3 | 0.34 × 0.25 × 0.22 mm |
Z = 8 |
Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector | 4424 independent reflections |
Graphite monochromator | 3825 reflections with I > 2σ(I) |
Detector resolution: 10.434 pixels mm-1 | Rint = 0.022 |
ω scans | θmax = 25.7°, θmin = 1.9° |
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009) | h = −13→13 |
Tmin = 0.794, Tmax = 0.852 | k = −13→13 |
49446 measured reflections | l = −23→23 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0464P)2 + 0.5233P] where P = (Fo2 + 2Fc2)/3 |
4424 reflections | (Δ/σ)max = 0.001 |
315 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C10H6Cl3NO3 | V = 2328.57 (7) Å3 |
Mr = 294.51 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.8979 (2) Å | µ = 0.78 mm−1 |
b = 11.0225 (2) Å | T = 295 K |
c = 19.4739 (3) Å | 0.34 × 0.25 × 0.22 mm |
β = 95.4761 (9)° |
Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector | 4424 independent reflections |
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009) | 3825 reflections with I > 2σ(I) |
Tmin = 0.794, Tmax = 0.852 | Rint = 0.022 |
49446 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.28 e Å−3 |
4424 reflections | Δρmin = −0.32 e Å−3 |
315 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 | ||
C1 | 0.44390 (14) | 0.49367 (14) | 0.63260 (8) | 0.0359 (3) | |
C2 | 0.49027 (16) | 0.44723 (15) | 0.70185 (8) | 0.0435 (4) | |
H2 | 0.5531 | 0.4921 | 0.7254 | 0.052* | |
C3 | 0.45354 (16) | 0.34984 (16) | 0.73449 (8) | 0.0437 (4) | |
H3 | 0.4945 | 0.3395 | 0.7782 | 0.052* | |
C4 | 0.36034 (14) | 0.25383 (14) | 0.71553 (8) | 0.0353 (3) | |
C5 | 0.47664 (14) | 0.65859 (13) | 0.55063 (8) | 0.0338 (3) | |
C6 | 0.55197 (15) | 0.75667 (14) | 0.53696 (8) | 0.0390 (4) | |
C7 | 0.52840 (17) | 0.82580 (15) | 0.47808 (9) | 0.0447 (4) | |
H7 | 0.5787 | 0.8917 | 0.4705 | 0.054* | |
C8 | 0.43056 (16) | 0.79770 (15) | 0.43042 (8) | 0.0418 (4) | |
C9 | 0.35753 (15) | 0.69853 (15) | 0.44191 (8) | 0.0385 (4) | |
C10 | 0.37961 (15) | 0.63019 (14) | 0.50161 (8) | 0.0374 (3) | |
H10 | 0.3289 | 0.5645 | 0.5090 | 0.045* | |
N1 | 0.50133 (13) | 0.59440 (12) | 0.61283 (7) | 0.0364 (3) | |
H1N | 0.5504 (19) | 0.6210 (18) | 0.6398 (10) | 0.047 (6)* | |
O1 | 0.36099 (12) | 0.44379 (11) | 0.59559 (6) | 0.0524 (3) | |
O2 | 0.29633 (10) | 0.25568 (10) | 0.65501 (6) | 0.0440 (3) | |
H2A | 0.3156 | 0.3154 | 0.6334 | 0.053* | |
O3 | 0.34614 (11) | 0.17281 (10) | 0.75610 (6) | 0.0439 (3) | |
Cl1 | 0.67690 (5) | 0.79432 (5) | 0.59434 (2) | 0.06029 (15) | |
Cl2 | 0.40225 (5) | 0.88690 (4) | 0.35759 (3) | 0.06031 (15) | |
Cl3 | 0.23559 (4) | 0.65766 (5) | 0.38355 (2) | 0.05600 (14) | |
C11 | −0.01578 (14) | 0.08037 (14) | 0.62405 (8) | 0.0356 (3) | |
C12 | 0.05760 (15) | 0.08711 (15) | 0.69170 (8) | 0.0405 (4) | |
H12 | 0.1200 | 0.1450 | 0.6953 | 0.049* | |
C13 | 0.04666 (15) | 0.02176 (16) | 0.74809 (8) | 0.0429 (4) | |
H13 | 0.1058 | 0.0398 | 0.7843 | 0.051* | |
C14 | −0.04107 (16) | −0.07430 (17) | 0.76485 (9) | 0.0468 (4) | |
C15 | −0.04415 (14) | 0.19115 (14) | 0.51309 (7) | 0.0348 (3) | |
C16 | −0.00319 (16) | 0.29029 (15) | 0.47665 (8) | 0.0393 (4) | |
C17 | −0.05759 (17) | 0.32085 (16) | 0.41215 (8) | 0.0450 (4) | |
H17 | −0.0298 | 0.3880 | 0.3892 | 0.054* | |
C18 | −0.15340 (16) | 0.25164 (15) | 0.38159 (8) | 0.0410 (4) | |
C19 | −0.19375 (15) | 0.15206 (15) | 0.41656 (8) | 0.0374 (3) | |
C20 | −0.14062 (15) | 0.12225 (14) | 0.48168 (8) | 0.0380 (4) | |
H20 | −0.1696 | 0.0557 | 0.5046 | 0.046* | |
N2 | 0.01228 (14) | 0.16733 (13) | 0.57959 (7) | 0.0393 (3) | |
H2N | 0.0613 (18) | 0.2172 (17) | 0.5962 (9) | 0.044 (5)* | |
O4 | −0.09307 (13) | 0.00116 (12) | 0.60847 (6) | 0.0572 (4) | |
O5 | −0.12126 (16) | −0.11735 (15) | 0.71730 (7) | 0.0818 (5) | |
H5A | −0.1146 | −0.0818 | 0.6808 | 0.098* | |
O6 | −0.03687 (14) | −0.11161 (13) | 0.82354 (7) | 0.0629 (4) | |
Cl4 | 0.11807 (5) | 0.37788 (4) | 0.51289 (2) | 0.05662 (14) | |
Cl5 | −0.22020 (5) | 0.29035 (5) | 0.30038 (2) | 0.06325 (15) | |
Cl6 | −0.31341 (4) | 0.06298 (4) | 0.38018 (2) | 0.05475 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0387 (8) | 0.0346 (8) | 0.0336 (8) | −0.0062 (6) | −0.0006 (6) | −0.0020 (6) |
C2 | 0.0481 (10) | 0.0433 (9) | 0.0364 (8) | −0.0128 (7) | −0.0103 (7) | −0.0004 (7) |
C3 | 0.0486 (10) | 0.0459 (9) | 0.0335 (8) | −0.0075 (8) | −0.0123 (7) | 0.0040 (7) |
C4 | 0.0341 (8) | 0.0345 (8) | 0.0363 (8) | 0.0035 (6) | −0.0014 (6) | 0.0018 (7) |
C5 | 0.0366 (8) | 0.0325 (8) | 0.0326 (7) | −0.0023 (6) | 0.0044 (6) | −0.0035 (6) |
C6 | 0.0420 (9) | 0.0372 (8) | 0.0376 (8) | −0.0096 (7) | 0.0035 (7) | −0.0066 (7) |
C7 | 0.0546 (10) | 0.0372 (9) | 0.0435 (9) | −0.0113 (7) | 0.0107 (8) | −0.0004 (7) |
C8 | 0.0498 (10) | 0.0393 (9) | 0.0372 (8) | 0.0034 (7) | 0.0095 (7) | 0.0047 (7) |
C9 | 0.0371 (8) | 0.0426 (9) | 0.0354 (8) | 0.0011 (7) | 0.0007 (7) | −0.0016 (7) |
C10 | 0.0367 (8) | 0.0378 (8) | 0.0373 (8) | −0.0074 (7) | 0.0012 (7) | 0.0012 (7) |
N1 | 0.0387 (7) | 0.0359 (7) | 0.0331 (7) | −0.0101 (6) | −0.0049 (6) | −0.0018 (6) |
O1 | 0.0594 (8) | 0.0510 (7) | 0.0427 (6) | −0.0255 (6) | −0.0165 (6) | 0.0126 (5) |
O2 | 0.0467 (7) | 0.0429 (6) | 0.0398 (6) | −0.0156 (5) | −0.0099 (5) | 0.0095 (5) |
O3 | 0.0487 (7) | 0.0372 (6) | 0.0441 (6) | −0.0003 (5) | −0.0035 (5) | 0.0105 (5) |
Cl1 | 0.0609 (3) | 0.0657 (3) | 0.0520 (3) | −0.0323 (2) | −0.0066 (2) | −0.0027 (2) |
Cl2 | 0.0741 (3) | 0.0548 (3) | 0.0516 (3) | 0.0010 (2) | 0.0036 (2) | 0.0191 (2) |
Cl3 | 0.0502 (3) | 0.0696 (3) | 0.0451 (2) | −0.0060 (2) | −0.01197 (19) | 0.0054 (2) |
C11 | 0.0355 (8) | 0.0389 (8) | 0.0320 (8) | −0.0030 (7) | 0.0002 (6) | 0.0020 (6) |
C12 | 0.0358 (8) | 0.0466 (9) | 0.0377 (8) | −0.0102 (7) | −0.0041 (7) | 0.0043 (7) |
C13 | 0.0402 (9) | 0.0516 (10) | 0.0347 (8) | −0.0073 (7) | −0.0081 (7) | 0.0046 (7) |
C14 | 0.0491 (10) | 0.0495 (10) | 0.0403 (9) | −0.0074 (8) | −0.0043 (8) | 0.0098 (8) |
C15 | 0.0392 (8) | 0.0366 (8) | 0.0278 (7) | −0.0015 (6) | −0.0002 (6) | −0.0009 (6) |
C16 | 0.0424 (9) | 0.0405 (9) | 0.0341 (8) | −0.0096 (7) | −0.0008 (7) | −0.0007 (7) |
C17 | 0.0541 (10) | 0.0454 (9) | 0.0346 (8) | −0.0102 (8) | −0.0006 (7) | 0.0069 (7) |
C18 | 0.0465 (9) | 0.0473 (9) | 0.0282 (7) | −0.0003 (7) | −0.0024 (7) | 0.0022 (7) |
C19 | 0.0386 (8) | 0.0404 (9) | 0.0325 (8) | −0.0033 (7) | −0.0006 (6) | −0.0039 (6) |
C20 | 0.0419 (9) | 0.0375 (8) | 0.0339 (8) | −0.0056 (7) | 0.0006 (7) | 0.0010 (6) |
N2 | 0.0435 (8) | 0.0411 (8) | 0.0316 (7) | −0.0117 (6) | −0.0057 (6) | 0.0031 (6) |
O4 | 0.0698 (8) | 0.0597 (8) | 0.0385 (6) | −0.0307 (7) | −0.0139 (6) | 0.0111 (6) |
O5 | 0.0967 (12) | 0.0929 (12) | 0.0499 (8) | −0.0596 (10) | −0.0235 (8) | 0.0280 (8) |
O6 | 0.0715 (9) | 0.0722 (9) | 0.0433 (7) | −0.0173 (7) | −0.0040 (6) | 0.0210 (6) |
Cl4 | 0.0632 (3) | 0.0586 (3) | 0.0450 (2) | −0.0288 (2) | −0.0107 (2) | 0.0078 (2) |
Cl5 | 0.0709 (3) | 0.0774 (3) | 0.0373 (2) | −0.0156 (3) | −0.0160 (2) | 0.0162 (2) |
Cl6 | 0.0557 (3) | 0.0606 (3) | 0.0443 (2) | −0.0203 (2) | −0.0140 (2) | 0.0024 (2) |
C1—O1 | 1.2304 (18) | C11—O4 | 1.2309 (19) |
C1—N1 | 1.349 (2) | C11—N2 | 1.346 (2) |
C1—C2 | 1.485 (2) | C11—C12 | 1.476 (2) |
C2—C3 | 1.329 (2) | C12—C13 | 1.328 (2) |
C2—H2 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.489 (2) | C13—C14 | 1.484 (2) |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—O3 | 1.2121 (18) | C14—O6 | 1.211 (2) |
C4—O2 | 1.3111 (18) | C14—O5 | 1.301 (2) |
C5—C10 | 1.391 (2) | C15—C20 | 1.390 (2) |
C5—C6 | 1.398 (2) | C15—C16 | 1.399 (2) |
C5—N1 | 1.406 (2) | C15—N2 | 1.404 (2) |
C6—C7 | 1.380 (2) | C16—C17 | 1.379 (2) |
C6—Cl1 | 1.7274 (16) | C16—Cl4 | 1.7315 (16) |
C7—C8 | 1.380 (3) | C17—C18 | 1.381 (2) |
C7—H7 | 0.9300 | C17—H17 | 0.9300 |
C8—C9 | 1.383 (2) | C18—C19 | 1.385 (2) |
C8—Cl2 | 1.7292 (16) | C18—Cl5 | 1.7301 (16) |
C9—C10 | 1.387 (2) | C19—C20 | 1.382 (2) |
C9—Cl3 | 1.7240 (16) | C19—Cl6 | 1.7292 (16) |
C10—H10 | 0.9300 | C20—H20 | 0.9300 |
N1—H1N | 0.77 (2) | N2—H2N | 0.81 (2) |
O2—H2A | 0.8200 | O5—H5A | 0.8200 |
O1—C1—N1 | 122.38 (14) | O4—C11—N2 | 122.58 (14) |
O1—C1—C2 | 123.03 (14) | O4—C11—C12 | 123.73 (14) |
N1—C1—C2 | 114.58 (13) | N2—C11—C12 | 113.65 (14) |
C3—C2—C1 | 128.39 (15) | C13—C12—C11 | 128.82 (15) |
C3—C2—H2 | 115.8 | C13—C12—H12 | 115.6 |
C1—C2—H2 | 115.8 | C11—C12—H12 | 115.6 |
C2—C3—C4 | 133.25 (15) | C12—C13—C14 | 132.80 (15) |
C2—C3—H3 | 113.4 | C12—C13—H13 | 113.6 |
C4—C3—H3 | 113.4 | C14—C13—H13 | 113.6 |
O3—C4—O2 | 120.49 (14) | O6—C14—O5 | 120.67 (16) |
O3—C4—C3 | 119.25 (14) | O6—C14—C13 | 118.86 (16) |
O2—C4—C3 | 120.25 (13) | O5—C14—C13 | 120.47 (15) |
C10—C5—C6 | 117.71 (14) | C20—C15—C16 | 117.90 (14) |
C10—C5—N1 | 123.25 (14) | C20—C15—N2 | 123.35 (14) |
C6—C5—N1 | 119.04 (14) | C16—C15—N2 | 118.74 (14) |
C7—C6—C5 | 121.26 (15) | C17—C16—C15 | 121.51 (15) |
C7—C6—Cl1 | 118.52 (13) | C17—C16—Cl4 | 118.70 (13) |
C5—C6—Cl1 | 120.22 (12) | C15—C16—Cl4 | 119.79 (12) |
C6—C7—C8 | 120.35 (15) | C16—C17—C18 | 119.95 (15) |
C6—C7—H7 | 119.8 | C16—C17—H17 | 120.0 |
C8—C7—H7 | 119.8 | C18—C17—H17 | 120.0 |
C7—C8—C9 | 119.22 (15) | C17—C18—C19 | 119.22 (14) |
C7—C8—Cl2 | 119.33 (13) | C17—C18—Cl5 | 119.50 (13) |
C9—C8—Cl2 | 121.46 (13) | C19—C18—Cl5 | 121.28 (13) |
C8—C9—C10 | 120.56 (15) | C20—C19—C18 | 120.96 (15) |
C8—C9—Cl3 | 121.27 (13) | C20—C19—Cl6 | 118.32 (12) |
C10—C9—Cl3 | 118.16 (13) | C18—C19—Cl6 | 120.72 (12) |
C9—C10—C5 | 120.85 (14) | C19—C20—C15 | 120.44 (15) |
C9—C10—H10 | 119.6 | C19—C20—H20 | 119.8 |
C5—C10—H10 | 119.6 | C15—C20—H20 | 119.8 |
C1—N1—C5 | 127.17 (14) | C11—N2—C15 | 128.30 (14) |
C1—N1—H1N | 115.5 (15) | C11—N2—H2N | 114.0 (13) |
C5—N1—H1N | 117.3 (15) | C15—N2—H2N | 117.0 (13) |
C4—O2—H2A | 109.5 | C14—O5—H5A | 109.5 |
O1—C1—C2—C3 | 0.1 (3) | O4—C11—C12—C13 | −7.6 (3) |
N1—C1—C2—C3 | −178.97 (18) | N2—C11—C12—C13 | 174.36 (18) |
C1—C2—C3—C4 | 1.6 (3) | C11—C12—C13—C14 | −2.5 (3) |
C2—C3—C4—O3 | 179.39 (19) | C12—C13—C14—O6 | −173.1 (2) |
C2—C3—C4—O2 | 0.8 (3) | C12—C13—C14—O5 | 6.7 (3) |
C10—C5—C6—C7 | 2.3 (2) | C20—C15—C16—C17 | 1.2 (2) |
N1—C5—C6—C7 | −177.16 (15) | N2—C15—C16—C17 | −177.78 (16) |
C10—C5—C6—Cl1 | −178.08 (12) | C20—C15—C16—Cl4 | −179.11 (13) |
N1—C5—C6—Cl1 | 2.4 (2) | N2—C15—C16—Cl4 | 1.9 (2) |
C5—C6—C7—C8 | −1.3 (3) | C15—C16—C17—C18 | −1.2 (3) |
Cl1—C6—C7—C8 | 179.06 (13) | Cl4—C16—C17—C18 | 179.12 (14) |
C6—C7—C8—C9 | −0.9 (3) | C16—C17—C18—C19 | 0.1 (3) |
C6—C7—C8—Cl2 | 179.30 (13) | C16—C17—C18—Cl5 | −179.56 (14) |
C7—C8—C9—C10 | 2.0 (2) | C17—C18—C19—C20 | 0.8 (3) |
Cl2—C8—C9—C10 | −178.14 (13) | Cl5—C18—C19—C20 | −179.46 (13) |
C7—C8—C9—Cl3 | −178.97 (13) | C17—C18—C19—Cl6 | 180.00 (14) |
Cl2—C8—C9—Cl3 | 0.9 (2) | Cl5—C18—C19—Cl6 | −0.3 (2) |
C8—C9—C10—C5 | −1.0 (2) | C18—C19—C20—C15 | −0.8 (3) |
Cl3—C9—C10—C5 | 179.95 (12) | Cl6—C19—C20—C15 | −179.99 (12) |
C6—C5—C10—C9 | −1.1 (2) | C16—C15—C20—C19 | −0.2 (2) |
N1—C5—C10—C9 | 178.32 (15) | N2—C15—C20—C19 | 178.71 (15) |
O1—C1—N1—C5 | 1.4 (3) | O4—C11—N2—C15 | 5.9 (3) |
C2—C1—N1—C5 | −179.53 (15) | C12—C11—N2—C15 | −176.01 (16) |
C10—C5—N1—C1 | 5.1 (3) | C20—C15—N2—C11 | −1.6 (3) |
C6—C5—N1—C1 | −175.47 (15) | C16—C15—N2—C11 | 177.28 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1 | 0.82 | 1.69 | 2.5080 (15) | 175 |
O5—H5A···O4 | 0.82 | 1.72 | 2.5332 (17) | 175 |
N1—H1N···O3i | 0.77 (2) | 2.30 (2) | 3.0356 (18) | 161.2 (19) |
N2—H2N···O6ii | 0.81 (2) | 2.481 (19) | 3.0775 (19) | 131.3 (16) |
N1—H1N···Cl1 | 0.77 (2) | 2.56 (2) | 2.9628 (14) | 114.2 (17) |
N2—H2N···Cl4 | 0.81 (2) | 2.519 (18) | 2.9476 (14) | 114.3 (15) |
C2—H2···O3i | 0.93 | 2.29 | 3.123 (2) | 149 |
C12—H12···O2 | 0.93 | 2.47 | 3.330 (2) | 154 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C10H6Cl3NO3 |
Mr | 294.51 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 10.8979 (2), 11.0225 (2), 19.4739 (3) |
β (°) | 95.4761 (9) |
V (Å3) | 2328.57 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.78 |
Crystal size (mm) | 0.34 × 0.25 × 0.22 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector |
Absorption correction | Analytical (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.794, 0.852 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 49446, 4424, 3825 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.079, 1.06 |
No. of reflections | 4424 |
No. of parameters | 315 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.32 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1 | 0.82 | 1.69 | 2.5080 (15) | 175 |
O5—H5A···O4 | 0.82 | 1.72 | 2.5332 (17) | 175 |
N1—H1N···O3i | 0.77 (2) | 2.30 (2) | 3.0356 (18) | 161.2 (19) |
N2—H2N···O6ii | 0.81 (2) | 2.481 (19) | 3.0775 (19) | 131.3 (16) |
N1—H1N···Cl1 | 0.77 (2) | 2.56 (2) | 2.9628 (14) | 114.2 (17) |
N2—H2N···Cl4 | 0.81 (2) | 2.519 (18) | 2.9476 (14) | 114.3 (15) |
C2—H2···O3i | 0.93 | 2.29 | 3.123 (2) | 149 |
C12—H12···O2 | 0.93 | 2.47 | 3.330 (2) | 154 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2. |
C–Cl···O | Cl···O | C–Cl···O |
C9–Cl3···O6iii | 3.1267 (15) | 158.99 (6) |
C16–Cl4···O1 | 3.0523 (12) | 159.62 (7) |
Symmetry code: (iii) x, -y+1/2, z-1/2. |
In the present work, as a part of studying the effect of ring- and side-chain substitutions on the crystal structures of biologically significant amides (Gowda et al., 2009, 2010; Shakuntala et al., 2009; Prasad et al., 2002), the crystal structure of N-(2,4,5-trichlorophenyl)-maleamic acid (I) has been determined. The asymmetric unit of (I) contains two independent molecules (Fig. 1).
The conformations of the N—H and C=O bonds in the amide segment of the structure are anti to each other, and the amide-O atom and the carbonyl-O atom of the acid segment are also anti to each other. Further, the amide-O atom is anti to the H atom attached to the adjacent C atom, while the carbonyl-O atom is syn to the H atom attached to its adjacent C atom (Fig.1). In the structure, a rare anti conformation of the C=O and O—H bonds of the acid group has been observed, similar to that observed in N-phenylmaleamic acid (Lo & Ng, 2009), N-(2,5-dichlorophenyl)maleamic acid (Shakuntala et al., 2009), N-(3,5-dichlorophenyl)maleamic acid (Gowda et al., 2010) and N-(2,4,6-dimethylphenyl)maleamic acid (Gowda et al., 2009). Further, the conformation of the N—H bond is syn to the 2-Cl in the phenyl ring, while it is anti to the 5-Cl in the ring. Each maleamic unit includes a short intramolecular hydrogen O—H···O bond (Table 1). The bond lengths of C2–C3 and C12–C13 (i.e. 1.329 (2) and 1.328 (2) Å) clearly indicate double bond character.
In both the molecules, the dihedral angle between the amido group –NHCO– and the tri-substituted phenyl ring is 6.1 (3)°. The two N—H···O hydrogen bonds have quite different geometry, as seen in the N—H···O angles (Table 1). Remarkably small N2—H2N···O6ii angle of 131.3 (16)° can be attributed to the competing effect of the neighbouring C9—Cl3···O6iii halogen bond. The angle Cl3···O6iii···H2N =78.24 (6)° is close to 90° and can be interpreted within the concept of orthogonality of halogen and hydrogen bonds (Voth et al., 2009). The N1—H1N···O3i hydrogen bond with the angle of 161.2 (19)° is much less influenced by the near C6—Cl1···O3i halogen bond, which is weaker as indicated by the Cl1···O3i contact of 3.2372 (13) A. [Symmetry codes: (i) -x + 1, y + 1/2, -z + 3/2; (ii) -x, y + 1/2, -z + 3/2; (iii) x, -y + 1/2, z - 1/2.]
In the crystal of (I), the intermolecular N–H···O hydrogen bonds link the molecules, which self-associate, into infinite chains running along the b axis. These chains are connected through relatively short Cl···O contacts: Cl4···O1 =3.0523 (12), Cl3···O6(iii) =3.1267 (15) Å. [Symmetry codes: (iii) x, -y + 1/2, z - 1/2].(iii) x, -y + 1/2, z - 1/2] as well as C–H···O contacts to consolidate the crystal packing. Fig. 2 outlines part of the crystal structure of (I) with the N–H···O hydrogen bonding and Cl···O contacts highlighted. The data for the C–Cl···O halogen bonds are in agreement with others (Kubicki, 2004; Fourmigué, 2009).