organic compounds
4-Methylanilinium trichloroacetate
aDepartment of Physics, Presidency College, Chennai 600 005, India, bDepartment of Physics, Panimalar Engineering College, Chennai 600 123, India, and cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
*Correspondence e-mail: mohan66@hotmail.com, chakkaravarthi_2005@yahoo.com
The 7H10N+·C2Cl3O2−, consists of two cations and two anions. In the crystal, N—H⋯O hydrogen bonds link the components into [100] chains incorporating R23(10) loops and weak π–π stacking [centroid-to-centroid distance = 3.865 (2) Å] is also observed.
of the title molecular salt, CKeywords: molecular salt; crystal structure; hydrogen bonding.
CCDC reference: 1590296
Structure description
We herewith report the synthesis and the et al., 2014; Benali-Cherif et al., 2009; Kalaiyarasi et al., 2017).
of the title molecular salt. Its geometric parameters agree well with those for reported similar structures (BabuThe ) comprises a pair of 4-methylanilinium cations and trichloroacetate anions. The dihedral angle between the benzene rings of the cations is 6.32 (1)°. Within the chosen N1—H1A⋯O4, N1—H1C⋯O2, N2—H2B⋯O3 and N2—H2C⋯O2 hydrogen bonds link the components, thereby generating an (10) loop and when symmetry-generated N2—H2A⋯O4ii, N1—H1B⋯O1i and N2—H2C⋯O2 hydrogen bonds are considered, another (10) loop is generated (Fig. 2, Table 1). The overall result is a supramolecular chain propagating along the a-axis direction (Fig. 3). The packing is further consolidated by weak π–π interactions [Cg1⋯Cg2 = 3.865 (2) Å; Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively].
of the title compound (Fig. 1Synthesis and crystallization
p-Toluidine (1.33 g) and trichloroacetic acid (1.48 g) were taken in a 1:1 ratio and dissolved in water at room temperature and the solution was stirred for 6 h. It was filtered and kept for slow evaporation and colourless blocks were obtained after four weeks.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1590296
https://doi.org/10.1107/S2414314617017679/hb4190sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617017679/hb4190Isup2.hkl
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXT2016/6 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016/6 (Sheldrick, 2015b) and PLATON (Spek, 2009).C7H10N+·C2Cl3O2− | Z = 4 |
Mr = 270.53 | F(000) = 552 |
Triclinic, P1 | Dx = 1.508 Mg m−3 |
a = 6.7395 (2) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 11.3491 (3) Å | Cell parameters from 9965 reflections |
c = 16.1078 (5) Å | θ = 2.8–70.5° |
α = 75.681 (2)° | µ = 6.82 mm−1 |
β = 88.031 (2)° | T = 295 K |
γ = 86.856 (2)° | Block, colourless |
V = 1191.69 (6) Å3 | 0.26 × 0.22 × 0.18 mm |
Bruker APEXII CCD diffractometer | 3713 reflections with I > 2σ(I) |
ω and φ scans | Rint = 0.066 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | θmax = 72.5°, θmin = 2.8° |
Tmin = 0.386, Tmax = 0.754 | h = −8→8 |
37675 measured reflections | k = −14→13 |
4685 independent reflections | l = −19→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters constrained |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0459P)2 + 1.3481P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
4685 reflections | Δρmax = 0.45 e Å−3 |
275 parameters | Δρmin = −0.48 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0236 (4) | 0.8176 (3) | 0.3452 (2) | 0.0550 (8) | |
C2 | 0.0345 (5) | 0.7010 (4) | 0.3974 (2) | 0.0626 (9) | |
H2 | 0.032750 | 0.690668 | 0.456533 | 0.075* | |
C3 | 0.0480 (5) | 0.5996 (3) | 0.36460 (19) | 0.0560 (8) | |
H3 | 0.054310 | 0.521988 | 0.401045 | 0.067* | |
C4 | 0.0519 (4) | 0.6150 (3) | 0.27675 (17) | 0.0412 (6) | |
C5 | 0.0444 (4) | 0.7297 (3) | 0.22276 (18) | 0.0464 (7) | |
H5 | 0.049155 | 0.739887 | 0.163650 | 0.056* | |
C6 | 0.0297 (4) | 0.8296 (3) | 0.2575 (2) | 0.0538 (8) | |
H6 | 0.023774 | 0.907162 | 0.220901 | 0.065* | |
C7 | 0.0015 (7) | 0.9265 (4) | 0.3818 (3) | 0.0829 (12) | |
H7A | −0.045476 | 0.995783 | 0.338455 | 0.124* | |
H7B | 0.127876 | 0.942503 | 0.401343 | 0.124* | |
H7C | −0.092142 | 0.911241 | 0.429039 | 0.124* | |
C8 | 0.5084 (5) | 0.9077 (3) | 0.2121 (2) | 0.0620 (9) | |
C9 | 0.5367 (4) | 0.7938 (3) | 0.2677 (2) | 0.0579 (9) | |
H9 | 0.542346 | 0.787788 | 0.326206 | 0.069* | |
C10 | 0.5568 (4) | 0.6891 (3) | 0.2385 (2) | 0.0506 (7) | |
H10 | 0.577655 | 0.613701 | 0.276898 | 0.061* | |
C11 | 0.5456 (4) | 0.6972 (3) | 0.15239 (19) | 0.0482 (7) | |
C12 | 0.5148 (6) | 0.8089 (3) | 0.0954 (2) | 0.0672 (10) | |
H12 | 0.506275 | 0.814448 | 0.037024 | 0.081* | |
C13 | 0.4969 (6) | 0.9119 (4) | 0.1260 (3) | 0.0755 (11) | |
H13 | 0.476311 | 0.987076 | 0.087357 | 0.091* | |
C14 | 0.4872 (7) | 1.0201 (4) | 0.2444 (3) | 0.0934 (14) | |
H14A | 0.584074 | 1.076280 | 0.216207 | 0.140* | |
H14B | 0.507760 | 0.999367 | 0.305112 | 0.140* | |
H14C | 0.356226 | 1.056932 | 0.232833 | 0.140* | |
C15 | 0.4706 (4) | 0.2780 (3) | 0.40294 (18) | 0.0430 (6) | |
C16 | 0.5665 (4) | 0.3595 (3) | 0.32056 (17) | 0.0395 (6) | |
C17 | −0.0049 (4) | 0.7259 (3) | −0.07151 (18) | 0.0441 (6) | |
C18 | 0.0910 (4) | 0.6342 (3) | 0.00763 (17) | 0.0399 (6) | |
N1 | 0.0600 (3) | 0.5075 (2) | 0.24171 (15) | 0.0443 (6) | |
H1A | 0.048514 | 0.530754 | 0.185045 | 0.066* | |
H1B | −0.039197 | 0.460317 | 0.264266 | 0.066* | |
H1C | 0.175484 | 0.466167 | 0.254491 | 0.066* | |
N2 | 0.5668 (3) | 0.5879 (2) | 0.12006 (16) | 0.0503 (6) | |
H2A | 0.686813 | 0.583562 | 0.095871 | 0.076* | |
H2B | 0.474359 | 0.590779 | 0.081347 | 0.076* | |
H2C | 0.552053 | 0.522479 | 0.163241 | 0.076* | |
O1 | 0.7457 (3) | 0.3714 (3) | 0.32515 (15) | 0.0670 (7) | |
O2 | 0.4537 (3) | 0.40509 (19) | 0.26125 (12) | 0.0499 (5) | |
O3 | 0.2719 (3) | 0.6182 (2) | 0.00216 (16) | 0.0661 (7) | |
O4 | −0.0249 (3) | 0.59187 (19) | 0.06740 (12) | 0.0466 (5) | |
Cl1 | 0.45338 (17) | 0.36565 (11) | 0.47998 (6) | 0.0839 (3) | |
Cl2 | 0.6160 (2) | 0.14573 (9) | 0.44281 (9) | 0.1000 (4) | |
Cl3 | 0.22772 (14) | 0.23875 (9) | 0.38605 (6) | 0.0722 (3) | |
Cl4 | −0.25288 (12) | 0.69394 (8) | −0.08705 (5) | 0.0618 (2) | |
Cl5 | 0.12882 (16) | 0.72723 (10) | −0.16713 (5) | 0.0763 (3) | |
Cl6 | −0.00309 (17) | 0.87155 (8) | −0.04977 (7) | 0.0793 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0387 (15) | 0.067 (2) | 0.060 (2) | −0.0023 (14) | 0.0021 (14) | −0.0174 (17) |
C2 | 0.065 (2) | 0.079 (2) | 0.0420 (17) | 0.0003 (18) | 0.0085 (15) | −0.0140 (17) |
C3 | 0.0583 (19) | 0.064 (2) | 0.0375 (15) | 0.0028 (16) | 0.0036 (14) | 0.0015 (14) |
C4 | 0.0248 (12) | 0.0574 (17) | 0.0375 (14) | −0.0010 (11) | 0.0005 (10) | −0.0046 (12) |
C5 | 0.0349 (14) | 0.0619 (19) | 0.0368 (14) | −0.0077 (13) | −0.0016 (11) | −0.0001 (13) |
C6 | 0.0408 (16) | 0.0560 (19) | 0.0592 (19) | −0.0052 (14) | −0.0050 (14) | −0.0028 (15) |
C7 | 0.087 (3) | 0.080 (3) | 0.086 (3) | 0.001 (2) | −0.002 (2) | −0.031 (2) |
C8 | 0.0458 (18) | 0.060 (2) | 0.073 (2) | −0.0049 (15) | 0.0028 (16) | −0.0038 (18) |
C9 | 0.0386 (16) | 0.075 (2) | 0.0522 (18) | −0.0080 (15) | −0.0074 (13) | 0.0011 (17) |
C10 | 0.0324 (14) | 0.0570 (19) | 0.0515 (17) | −0.0041 (13) | −0.0056 (12) | 0.0085 (14) |
C11 | 0.0260 (13) | 0.0595 (19) | 0.0473 (16) | −0.0008 (12) | 0.0054 (11) | 0.0083 (14) |
C12 | 0.074 (2) | 0.064 (2) | 0.0483 (19) | 0.0094 (18) | 0.0103 (17) | 0.0124 (16) |
C13 | 0.083 (3) | 0.061 (2) | 0.063 (2) | 0.0072 (19) | 0.0108 (19) | 0.0175 (18) |
C14 | 0.094 (3) | 0.076 (3) | 0.107 (4) | −0.003 (2) | −0.002 (3) | −0.017 (3) |
C15 | 0.0493 (16) | 0.0399 (15) | 0.0378 (14) | −0.0077 (12) | 0.0016 (12) | −0.0048 (12) |
C16 | 0.0388 (14) | 0.0420 (15) | 0.0363 (14) | −0.0039 (11) | 0.0059 (11) | −0.0072 (12) |
C17 | 0.0481 (16) | 0.0450 (16) | 0.0368 (14) | −0.0029 (13) | 0.0008 (12) | −0.0053 (12) |
C18 | 0.0392 (14) | 0.0414 (15) | 0.0382 (14) | −0.0044 (11) | −0.0047 (11) | −0.0070 (12) |
N1 | 0.0317 (11) | 0.0589 (15) | 0.0370 (12) | −0.0013 (10) | 0.0004 (9) | −0.0024 (11) |
N2 | 0.0333 (12) | 0.0605 (16) | 0.0456 (14) | 0.0021 (11) | 0.0035 (10) | 0.0076 (12) |
O1 | 0.0368 (11) | 0.0967 (19) | 0.0588 (14) | −0.0150 (12) | 0.0041 (10) | −0.0004 (13) |
O2 | 0.0431 (11) | 0.0593 (13) | 0.0380 (10) | −0.0017 (9) | 0.0012 (9) | 0.0056 (9) |
O3 | 0.0335 (11) | 0.0805 (17) | 0.0731 (15) | −0.0048 (11) | −0.0063 (10) | 0.0039 (13) |
O4 | 0.0440 (11) | 0.0584 (12) | 0.0314 (10) | 0.0035 (9) | 0.0008 (8) | −0.0014 (9) |
Cl1 | 0.0997 (8) | 0.1091 (8) | 0.0561 (5) | −0.0204 (6) | 0.0153 (5) | −0.0441 (5) |
Cl2 | 0.1093 (9) | 0.0528 (5) | 0.1176 (9) | 0.0153 (5) | −0.0250 (7) | 0.0163 (6) |
Cl3 | 0.0624 (5) | 0.0783 (6) | 0.0699 (6) | −0.0369 (4) | 0.0035 (4) | −0.0006 (4) |
Cl4 | 0.0522 (4) | 0.0709 (5) | 0.0558 (5) | 0.0019 (4) | −0.0188 (4) | −0.0020 (4) |
Cl5 | 0.0892 (7) | 0.0884 (7) | 0.0452 (4) | −0.0131 (5) | 0.0221 (4) | −0.0065 (4) |
Cl6 | 0.1087 (8) | 0.0431 (4) | 0.0869 (7) | 0.0003 (5) | −0.0135 (6) | −0.0166 (4) |
C1—C2 | 1.381 (5) | C12—C13 | 1.375 (6) |
C1—C6 | 1.385 (5) | C12—H12 | 0.9300 |
C1—C7 | 1.494 (5) | C13—H13 | 0.9300 |
C2—C3 | 1.378 (5) | C14—H14A | 0.9600 |
C2—H2 | 0.9300 | C14—H14B | 0.9600 |
C3—C4 | 1.382 (4) | C14—H14C | 0.9600 |
C3—H3 | 0.9300 | C15—C16 | 1.560 (4) |
C4—C5 | 1.375 (4) | C15—Cl2 | 1.741 (3) |
C4—N1 | 1.463 (4) | C15—Cl3 | 1.767 (3) |
C5—C6 | 1.380 (5) | C15—Cl1 | 1.770 (3) |
C5—H5 | 0.9300 | C16—O1 | 1.230 (3) |
C6—H6 | 0.9300 | C16—O2 | 1.233 (3) |
C7—H7A | 0.9600 | C17—C18 | 1.566 (4) |
C7—H7B | 0.9600 | C17—Cl5 | 1.755 (3) |
C7—H7C | 0.9600 | C17—Cl4 | 1.769 (3) |
C8—C13 | 1.380 (6) | C17—Cl6 | 1.773 (3) |
C8—C9 | 1.386 (5) | C18—O3 | 1.226 (3) |
C8—C14 | 1.491 (6) | C18—O4 | 1.236 (3) |
C9—C10 | 1.381 (5) | N1—H1A | 0.8900 |
C9—H9 | 0.9300 | N1—H1B | 0.8900 |
C10—C11 | 1.372 (4) | N1—H1C | 0.8900 |
C10—H10 | 0.9300 | N2—H2A | 0.8900 |
C11—C12 | 1.379 (4) | N2—H2B | 0.8900 |
C11—N2 | 1.458 (4) | N2—H2C | 0.8900 |
C2—C1—C6 | 117.4 (3) | C12—C13—C8 | 122.3 (3) |
C2—C1—C7 | 121.3 (3) | C12—C13—H13 | 118.8 |
C6—C1—C7 | 121.3 (3) | C8—C13—H13 | 118.8 |
C3—C2—C1 | 122.0 (3) | C8—C14—H14A | 109.5 |
C3—C2—H2 | 119.0 | C8—C14—H14B | 109.5 |
C1—C2—H2 | 119.0 | H14A—C14—H14B | 109.5 |
C2—C3—C4 | 119.0 (3) | C8—C14—H14C | 109.5 |
C2—C3—H3 | 120.5 | H14A—C14—H14C | 109.5 |
C4—C3—H3 | 120.5 | H14B—C14—H14C | 109.5 |
C5—C4—C3 | 120.6 (3) | C16—C15—Cl2 | 111.6 (2) |
C5—C4—N1 | 120.2 (3) | C16—C15—Cl3 | 112.51 (19) |
C3—C4—N1 | 119.2 (3) | Cl2—C15—Cl3 | 109.27 (16) |
C4—C5—C6 | 119.1 (3) | C16—C15—Cl1 | 106.45 (19) |
C4—C5—H5 | 120.4 | Cl2—C15—Cl1 | 109.14 (16) |
C6—C5—H5 | 120.4 | Cl3—C15—Cl1 | 107.67 (16) |
C5—C6—C1 | 121.9 (3) | O1—C16—O2 | 129.0 (3) |
C5—C6—H6 | 119.1 | O1—C16—C15 | 114.4 (2) |
C1—C6—H6 | 119.1 | O2—C16—C15 | 116.5 (2) |
C1—C7—H7A | 109.5 | C18—C17—Cl5 | 112.3 (2) |
C1—C7—H7B | 109.5 | C18—C17—Cl4 | 112.67 (19) |
H7A—C7—H7B | 109.5 | Cl5—C17—Cl4 | 107.38 (16) |
C1—C7—H7C | 109.5 | C18—C17—Cl6 | 106.09 (19) |
H7A—C7—H7C | 109.5 | Cl5—C17—Cl6 | 109.53 (16) |
H7B—C7—H7C | 109.5 | Cl4—C17—Cl6 | 108.85 (16) |
C13—C8—C9 | 117.1 (4) | O3—C18—O4 | 129.5 (3) |
C13—C8—C14 | 121.7 (4) | O3—C18—C17 | 114.8 (2) |
C9—C8—C14 | 121.2 (4) | O4—C18—C17 | 115.6 (2) |
C10—C9—C8 | 121.8 (3) | C4—N1—H1A | 109.5 |
C10—C9—H9 | 119.1 | C4—N1—H1B | 109.5 |
C8—C9—H9 | 119.1 | H1A—N1—H1B | 109.5 |
C11—C10—C9 | 119.4 (3) | C4—N1—H1C | 109.5 |
C11—C10—H10 | 120.3 | H1A—N1—H1C | 109.5 |
C9—C10—H10 | 120.3 | H1B—N1—H1C | 109.5 |
C10—C11—C12 | 120.4 (3) | C11—N2—H2A | 109.5 |
C10—C11—N2 | 120.4 (3) | C11—N2—H2B | 109.5 |
C12—C11—N2 | 119.2 (3) | H2A—N2—H2B | 109.5 |
C13—C12—C11 | 119.1 (4) | C11—N2—H2C | 109.5 |
C13—C12—H12 | 120.5 | H2A—N2—H2C | 109.5 |
C11—C12—H12 | 120.5 | H2B—N2—H2C | 109.5 |
C6—C1—C2—C3 | −1.0 (5) | N2—C11—C12—C13 | −179.4 (3) |
C7—C1—C2—C3 | 177.7 (3) | C11—C12—C13—C8 | −0.1 (6) |
C1—C2—C3—C4 | 0.4 (5) | C9—C8—C13—C12 | −0.8 (6) |
C2—C3—C4—C5 | 0.6 (5) | C14—C8—C13—C12 | −179.6 (4) |
C2—C3—C4—N1 | −178.1 (3) | Cl2—C15—C16—O1 | −44.8 (3) |
C3—C4—C5—C6 | −1.0 (4) | Cl3—C15—C16—O1 | −168.1 (2) |
N1—C4—C5—C6 | 177.7 (2) | Cl1—C15—C16—O1 | 74.2 (3) |
C4—C5—C6—C1 | 0.4 (4) | Cl2—C15—C16—O2 | 136.9 (2) |
C2—C1—C6—C5 | 0.6 (5) | Cl3—C15—C16—O2 | 13.6 (3) |
C7—C1—C6—C5 | −178.1 (3) | Cl1—C15—C16—O2 | −104.1 (3) |
C13—C8—C9—C10 | 1.3 (5) | Cl5—C17—C18—O3 | 29.9 (3) |
C14—C8—C9—C10 | −179.9 (3) | Cl4—C17—C18—O3 | 151.3 (2) |
C8—C9—C10—C11 | −1.0 (4) | Cl6—C17—C18—O3 | −89.7 (3) |
C9—C10—C11—C12 | 0.0 (4) | Cl5—C17—C18—O4 | −152.5 (2) |
C9—C10—C11—N2 | 179.9 (2) | Cl4—C17—C18—O4 | −31.1 (3) |
C10—C11—C12—C13 | 0.5 (5) | Cl6—C17—C18—O4 | 87.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4 | 0.89 | 1.92 | 2.801 (3) | 169 |
N1—H1B···O1i | 0.89 | 1.91 | 2.796 (3) | 172 |
N1—H1C···O2 | 0.89 | 1.96 | 2.834 (3) | 167 |
N2—H2A···O4ii | 0.89 | 1.98 | 2.851 (3) | 165 |
N2—H2B···O3 | 0.89 | 1.86 | 2.745 (3) | 172 |
N2—H2C···O2 | 0.89 | 1.92 | 2.789 (3) | 164 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Acknowledgements
The authors acknowledge the SAIF, IIT, Madras for the data collection.
References
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