Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051124/sj2370sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051124/sj2370Isup2.hkl |
CCDC reference: 667399
The title compound was prepared according to the method described by Odabaşoğlu & Büyükgüngör (2007c), using 3-(trifluoromethyl)aniline and 4,5-dichlorophthalic acid as starting materials (yield 95%; m.p. 465–466 K). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol–water (1:1) solution at room temperature.
All H atoms bound to C and N were refined freely with isotropic displacement parameters. The O-bound H atom was was refined using the riding model approximation with d(C—O) = 0.82 and Uiso(H) = 1.5Ueq(O)]
Secondary interactions are proposed to be important in the biological activities of molecules involved in biochemical processes in the living cell. Molecular interactions find their origin in the dispersion, polarization, electrostatic, charge transfer and exchange forces (Rigby et al., 1986; Buckingham, 1993). There is considerable current interest in the preparation of compounds constructed from two molecular networks as they provide a source of novel materials with highly anisotropic electrical, optical and magnetic properties (Mas-Torrent et al., 2003; Setifi et al., 2002; Bryce & Petty, 1995; Peng et al., 1998; Rombaut et al., 2001; Bredas et al., 1994).
We have been interested in hydrogen-bonding systems formed by organic amines and carboxylic acids (Odabaşoğlu & Büyükgüngör, 2007a,b,c; 2006a,b; Odabaşoğlu et al., 2003; Yeşilel et al., 2006). The present work is part of a structural study of compounds of organic ammonium systems with hydrogen and halogen-bond donors and we report here the molecular and supramolecular structure of (I) (Fig. 1).
The C2–C7 ring and O1—C1—O2 and O3—C8—O4 planes are approximately coplanar with the dihedral angles between C2–C7 ring and O—C—O planes of 0.96 (2)° and 5.38 (1)°, respectively. The C1—C2 and C8—C7 bonds are approximately equal. This suggests some delocalization between the C2–C7 ring and the –COO- and –COOH groups that form an intramolecular hydrogen bond. Furthermore, these bonds, together with the C8—O3 and C8—O4 lengths indicate delocalization of the negative charge over the O3, C8 and O4 atoms. In the 4,5-dichlorohydrogenphthalate anion, the O1 and O4 distance is 2.3908 (17) Å and this distance is approximately 0.65 Å less than the sum of the van der Waals radii (3.04 Å) due to the presence of a strong intramolecular hydrogen bond in the anion (Table 1). The dihedral angle between the planes of the aromatic rings in the cation and anion is 34.86 (1)°.
Intramolecular O—H···O and C—H···F hydrogen bonds generate edge-fused [S(7)R44(24)S(7)R22(10)S(7)R44(24)S(7)] motifs (Etter, 1990) (Fig. 2). The ions are linked to each other by C—H···O hydrogen bonds chain along the z-axis (Fig. 3). This chain and other hydrogen bonds form [R32(6)R12(4)S(7)R12(4)R44(18)R55(24) R44(18)R12(4)R12(4)S(7)R12(4)R32(6)] motifs (Fig. 4).
For general background, see: Rigby et al. (1986); Buckingham (1993); Mas-Torrent et al. (2003); Setifi et al. (2002); Bryce & Petty (1995); Peng et al. (1998); Rombaut et al. (2001); Bredas et al. (1994); Etter (1990). For related structures, see: Odabaşoğlu & Büyükgüngör (2007a,b,c, 2006a,b); Odabaşoğlu et al. (2003); Yeşilel et al. (2006).
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C7H7F3N+·C8H3Cl2O4− | F(000) = 800 |
Mr = 396.14 | Dx = 1.672 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 28359 reflections |
a = 15.0048 (7) Å | θ = 2.0–28.0° |
b = 14.5270 (9) Å | µ = 0.47 mm−1 |
c = 7.3292 (3) Å | T = 296 K |
β = 99.887 (4)° | Prism, colourless |
V = 1573.85 (14) Å3 | 0.58 × 0.45 × 0.25 mm |
Z = 4 |
Stoe IPDS 2 diffractometer | 3740 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 2826 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.032 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.9°, θmin = 2.0° |
ω scans | h = −19→19 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −19→19 |
Tmin = 0.776, Tmax = 0.895 | l = −9→9 |
28359 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0517P)2 + 0.1939P] where P = (Fo2 + 2Fc2)/3 |
3740 reflections | (Δ/σ)max < 0.001 |
262 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C7H7F3N+·C8H3Cl2O4− | V = 1573.85 (14) Å3 |
Mr = 396.14 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.0048 (7) Å | µ = 0.47 mm−1 |
b = 14.5270 (9) Å | T = 296 K |
c = 7.3292 (3) Å | 0.58 × 0.45 × 0.25 mm |
β = 99.887 (4)° |
Stoe IPDS 2 diffractometer | 3740 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 2826 reflections with I > 2σ(I) |
Tmin = 0.776, Tmax = 0.895 | Rint = 0.032 |
28359 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.21 e Å−3 |
3740 reflections | Δρmin = −0.27 e Å−3 |
262 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 | ||
C8 | 1.03044 (10) | 0.23067 (10) | 0.5787 (2) | 0.0418 (3) | |
C7 | 0.93692 (9) | 0.26142 (9) | 0.6066 (2) | 0.0379 (3) | |
C6 | 0.92664 (11) | 0.35648 (10) | 0.6057 (2) | 0.0466 (4) | |
C5 | 0.84683 (11) | 0.39823 (10) | 0.6262 (2) | 0.0492 (4) | |
C4 | 0.77395 (11) | 0.34493 (11) | 0.6513 (2) | 0.0478 (4) | |
C3 | 0.78183 (11) | 0.25045 (11) | 0.6524 (2) | 0.0444 (3) | |
C2 | 0.86192 (9) | 0.20676 (9) | 0.6303 (2) | 0.0378 (3) | |
C1 | 0.85570 (10) | 0.10270 (10) | 0.6377 (2) | 0.0438 (3) | |
C9 | 0.51139 (13) | 0.12618 (18) | 0.6703 (3) | 0.0723 (6) | |
C10 | 0.42647 (11) | 0.17517 (13) | 0.5905 (2) | 0.0517 (4) | |
C11 | 0.42547 (12) | 0.26998 (14) | 0.5840 (3) | 0.0574 (4) | |
C12 | 0.34774 (12) | 0.31557 (13) | 0.5041 (3) | 0.0557 (4) | |
C13 | 0.27120 (11) | 0.26640 (11) | 0.4323 (3) | 0.0475 (4) | |
C14 | 0.27297 (10) | 0.17171 (10) | 0.4429 (2) | 0.0413 (3) | |
C15 | 0.34971 (11) | 0.12457 (12) | 0.5200 (2) | 0.0466 (4) | |
N1 | 0.19072 (9) | 0.12074 (10) | 0.3714 (2) | 0.0460 (3) | |
O3 | 1.08795 (8) | 0.28955 (8) | 0.5704 (2) | 0.0615 (3) | |
O4 | 1.04647 (8) | 0.14594 (8) | 0.5608 (2) | 0.0614 (4) | |
O2 | 0.78483 (8) | 0.06732 (8) | 0.6604 (2) | 0.0600 (3) | |
O1 | 0.92388 (9) | 0.05241 (8) | 0.6222 (2) | 0.0709 (4) | |
H1 | 0.9667 | 0.0853 | 0.6089 | 0.106* | |
F1 | 0.56882 (9) | 0.17904 (13) | 0.7817 (3) | 0.1085 (6) | |
F2 | 0.55617 (10) | 0.09759 (15) | 0.5410 (3) | 0.1219 (7) | |
F3 | 0.49697 (10) | 0.05389 (11) | 0.7687 (3) | 0.1119 (6) | |
Cl1 | 0.84144 (4) | 0.51638 (3) | 0.62076 (9) | 0.0786 (2) | |
Cl2 | 0.67383 (3) | 0.39467 (4) | 0.68542 (9) | 0.07518 (19) | |
H1A | 0.1623 (15) | 0.1449 (15) | 0.267 (3) | 0.066 (6)* | |
H1B | 0.1476 (16) | 0.1275 (16) | 0.451 (3) | 0.071 (6)* | |
H1C | 0.2018 (13) | 0.0619 (15) | 0.355 (3) | 0.057 (5)* | |
H6 | 0.9769 (14) | 0.3918 (13) | 0.588 (3) | 0.056 (5)* | |
H3 | 0.7311 (13) | 0.2155 (13) | 0.670 (3) | 0.055 (5)* | |
H11 | 0.4770 (15) | 0.3036 (14) | 0.637 (3) | 0.063 (6)* | |
H12 | 0.3451 (14) | 0.3819 (15) | 0.495 (3) | 0.068 (6)* | |
H13 | 0.2163 (14) | 0.2967 (13) | 0.373 (3) | 0.060 (5)* | |
H15 | 0.3498 (13) | 0.0592 (14) | 0.524 (3) | 0.056 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C8 | 0.0378 (7) | 0.0417 (7) | 0.0445 (9) | −0.0005 (6) | 0.0035 (6) | 0.0002 (6) |
C7 | 0.0376 (7) | 0.0334 (6) | 0.0406 (8) | 0.0016 (5) | 0.0010 (6) | −0.0012 (6) |
C6 | 0.0444 (8) | 0.0349 (7) | 0.0579 (10) | −0.0024 (6) | 0.0014 (7) | −0.0004 (7) |
C5 | 0.0525 (9) | 0.0321 (7) | 0.0582 (10) | 0.0059 (6) | −0.0039 (7) | −0.0068 (7) |
C4 | 0.0421 (8) | 0.0443 (8) | 0.0538 (10) | 0.0093 (6) | −0.0007 (7) | −0.0096 (7) |
C3 | 0.0392 (7) | 0.0417 (8) | 0.0511 (9) | 0.0003 (6) | 0.0042 (6) | −0.0063 (7) |
C2 | 0.0376 (7) | 0.0333 (7) | 0.0407 (8) | 0.0010 (5) | 0.0021 (6) | −0.0024 (6) |
C1 | 0.0429 (8) | 0.0339 (7) | 0.0535 (9) | −0.0007 (6) | 0.0050 (6) | −0.0018 (6) |
C9 | 0.0433 (9) | 0.0919 (16) | 0.0801 (15) | 0.0032 (10) | 0.0062 (9) | 0.0066 (12) |
C10 | 0.0404 (8) | 0.0640 (10) | 0.0521 (10) | −0.0006 (7) | 0.0115 (7) | 0.0016 (8) |
C11 | 0.0471 (9) | 0.0653 (11) | 0.0615 (12) | −0.0156 (8) | 0.0144 (8) | −0.0071 (9) |
C12 | 0.0563 (10) | 0.0439 (9) | 0.0700 (12) | −0.0097 (7) | 0.0196 (9) | −0.0047 (8) |
C13 | 0.0458 (8) | 0.0388 (8) | 0.0601 (11) | 0.0005 (6) | 0.0155 (7) | 0.0015 (7) |
C14 | 0.0379 (7) | 0.0389 (7) | 0.0493 (9) | −0.0023 (6) | 0.0136 (6) | −0.0007 (6) |
C15 | 0.0409 (8) | 0.0442 (8) | 0.0562 (10) | 0.0030 (6) | 0.0127 (7) | 0.0034 (7) |
N1 | 0.0370 (7) | 0.0354 (7) | 0.0658 (10) | 0.0003 (5) | 0.0095 (7) | 0.0004 (6) |
O3 | 0.0456 (6) | 0.0535 (7) | 0.0879 (10) | −0.0113 (5) | 0.0187 (6) | −0.0086 (6) |
O4 | 0.0463 (6) | 0.0402 (6) | 0.1027 (11) | 0.0069 (5) | 0.0264 (7) | 0.0044 (6) |
O2 | 0.0459 (6) | 0.0378 (6) | 0.0974 (10) | −0.0050 (5) | 0.0154 (6) | −0.0002 (6) |
O1 | 0.0536 (7) | 0.0325 (6) | 0.1329 (13) | 0.0017 (5) | 0.0339 (8) | 0.0008 (7) |
F1 | 0.0599 (8) | 0.1288 (13) | 0.1226 (13) | −0.0077 (8) | −0.0243 (8) | 0.0022 (10) |
F2 | 0.0727 (9) | 0.1784 (18) | 0.1183 (13) | 0.0540 (10) | 0.0266 (9) | −0.0015 (12) |
F3 | 0.0657 (8) | 0.1102 (12) | 0.1504 (15) | 0.0109 (8) | −0.0083 (8) | 0.0569 (11) |
Cl1 | 0.0804 (3) | 0.0313 (2) | 0.1167 (5) | 0.0096 (2) | −0.0044 (3) | −0.0089 (2) |
Cl2 | 0.0498 (2) | 0.0661 (3) | 0.1078 (4) | 0.0182 (2) | 0.0082 (2) | −0.0247 (3) |
C8—O3 | 1.2239 (19) | C9—F1 | 1.326 (3) |
C8—O4 | 1.2653 (19) | C9—C10 | 1.489 (3) |
C8—C7 | 1.520 (2) | C10—C11 | 1.378 (3) |
C7—C6 | 1.389 (2) | C10—C15 | 1.389 (2) |
C7—C2 | 1.412 (2) | C11—C12 | 1.381 (3) |
C6—C5 | 1.374 (2) | C11—H11 | 0.94 (2) |
C6—H6 | 0.94 (2) | C12—C13 | 1.378 (2) |
C5—C4 | 1.378 (2) | C12—H12 | 0.97 (2) |
C5—Cl1 | 1.7184 (15) | C13—C14 | 1.378 (2) |
C4—C3 | 1.377 (2) | C13—H13 | 0.97 (2) |
C4—Cl2 | 1.7235 (16) | C14—C15 | 1.375 (2) |
C3—C2 | 1.393 (2) | C14—N1 | 1.4574 (19) |
C3—H3 | 0.94 (2) | C15—H15 | 0.95 (2) |
C2—C1 | 1.5161 (19) | N1—H1A | 0.88 (2) |
C1—O2 | 1.2180 (19) | N1—H1B | 0.95 (3) |
C1—O1 | 1.2781 (19) | N1—H1C | 0.88 (2) |
C9—F3 | 1.313 (3) | O1—H1 | 0.8200 |
C9—F2 | 1.319 (3) | ||
O3—C8—O4 | 121.76 (14) | F2—C9—C10 | 112.05 (19) |
O3—C8—C7 | 118.47 (13) | F1—C9—C10 | 112.8 (2) |
O4—C8—C7 | 119.75 (13) | C11—C10—C15 | 120.84 (16) |
C6—C7—C2 | 118.00 (13) | C11—C10—C9 | 119.66 (17) |
C6—C7—C8 | 113.31 (13) | C15—C10—C9 | 119.49 (17) |
C2—C7—C8 | 128.69 (12) | C10—C11—C12 | 119.82 (16) |
C5—C6—C7 | 122.44 (15) | C10—C11—H11 | 120.1 (12) |
C5—C6—H6 | 120.7 (12) | C12—C11—H11 | 120.1 (12) |
C7—C6—H6 | 116.9 (12) | C13—C12—C11 | 120.08 (17) |
C6—C5—C4 | 119.56 (14) | C13—C12—H12 | 118.0 (13) |
C6—C5—Cl1 | 118.49 (13) | C11—C12—H12 | 121.9 (13) |
C4—C5—Cl1 | 121.95 (13) | C14—C13—C12 | 119.30 (16) |
C3—C4—C5 | 119.44 (14) | C14—C13—H13 | 119.0 (11) |
C3—C4—Cl2 | 119.53 (13) | C12—C13—H13 | 121.7 (11) |
C5—C4—Cl2 | 121.02 (12) | C15—C14—C13 | 121.80 (15) |
C4—C3—C2 | 121.88 (15) | C15—C14—N1 | 119.50 (14) |
C4—C3—H3 | 117.9 (11) | C13—C14—N1 | 118.69 (14) |
C2—C3—H3 | 120.2 (11) | C14—C15—C10 | 118.14 (15) |
C3—C2—C7 | 118.67 (13) | C14—C15—H15 | 120.5 (12) |
C3—C2—C1 | 112.98 (13) | C10—C15—H15 | 121.3 (12) |
C7—C2—C1 | 128.35 (13) | C14—N1—H1A | 111.4 (14) |
O2—C1—O1 | 120.13 (14) | C14—N1—H1B | 110.6 (14) |
O2—C1—C2 | 119.09 (14) | H1A—N1—H1B | 102 (2) |
O1—C1—C2 | 120.77 (14) | C14—N1—H1C | 111.9 (13) |
F3—C9—F2 | 107.2 (2) | H1A—N1—H1C | 110.1 (19) |
F3—C9—F1 | 106.0 (2) | H1B—N1—H1C | 110.2 (19) |
F2—C9—F1 | 105.51 (19) | C1—O1—H1 | 109.5 |
F3—C9—C10 | 112.80 (17) | ||
O3—C8—C7—C6 | 4.5 (2) | C3—C2—C1—O2 | 0.3 (2) |
O4—C8—C7—C6 | −173.96 (15) | C7—C2—C1—O2 | 179.50 (16) |
O3—C8—C7—C2 | −176.27 (16) | C3—C2—C1—O1 | −179.04 (16) |
O4—C8—C7—C2 | 5.2 (3) | C7—C2—C1—O1 | 0.2 (3) |
C2—C7—C6—C5 | −0.2 (3) | F3—C9—C10—C11 | 141.3 (2) |
C8—C7—C6—C5 | 179.10 (15) | F2—C9—C10—C11 | −97.7 (3) |
C7—C6—C5—C4 | 0.9 (3) | F1—C9—C10—C11 | 21.2 (3) |
C7—C6—C5—Cl1 | −179.42 (13) | F3—C9—C10—C15 | −40.1 (3) |
C6—C5—C4—C3 | −1.0 (3) | F2—C9—C10—C15 | 81.0 (3) |
Cl1—C5—C4—C3 | 179.28 (14) | F1—C9—C10—C15 | −160.16 (19) |
C6—C5—C4—Cl2 | 177.78 (14) | C15—C10—C11—C12 | −0.9 (3) |
Cl1—C5—C4—Cl2 | −1.9 (2) | C9—C10—C11—C12 | 177.70 (19) |
C5—C4—C3—C2 | 0.5 (3) | C10—C11—C12—C13 | 0.5 (3) |
Cl2—C4—C3—C2 | −178.33 (13) | C11—C12—C13—C14 | 0.6 (3) |
C4—C3—C2—C7 | 0.2 (2) | C12—C13—C14—C15 | −1.3 (3) |
C4—C3—C2—C1 | 179.50 (15) | C12—C13—C14—N1 | 178.19 (16) |
C6—C7—C2—C3 | −0.4 (2) | C13—C14—C15—C10 | 0.8 (3) |
C8—C7—C2—C3 | −179.51 (15) | N1—C14—C15—C10 | −178.66 (16) |
C6—C7—C2—C1 | −179.54 (15) | C11—C10—C15—C14 | 0.3 (3) |
C8—C7—C2—C1 | 1.3 (3) | C9—C10—C15—C14 | −178.33 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3i | 0.88 (2) | 1.92 (2) | 2.788 (2) | 169 (2) |
N1—H1B···O3ii | 0.95 (3) | 2.72 (2) | 3.360 (2) | 125.8 (17) |
N1—H1B···O4ii | 0.95 (3) | 1.86 (3) | 2.789 (2) | 168 (2) |
N1—H1C···O2iii | 0.88 (2) | 1.89 (2) | 2.7717 (18) | 173.2 (19) |
N1—H1C···O1iii | 0.88 (2) | 2.54 (2) | 3.0518 (18) | 117.8 (15) |
O1—H1···O4 | 0.82 | 1.57 | 2.3908 (17) | 174 |
C3—H3···F1 | 0.94 (2) | 2.75 (2) | 3.637 (2) | 157.2 (15) |
C15—H15···F2iii | 0.95 (2) | 2.76 (2) | 3.582 (2) | 144.7 (15) |
C13—H13···O3i | 0.97 (2) | 2.95 (2) | 3.571 (2) | 122.7 (14) |
C13—H13···O3ii | 0.97 (2) | 2.60 (2) | 3.107 (2) | 112.5 (14) |
C13—H13···Cl1iv | 0.97 (2) | 2.85 (2) | 3.5693 (17) | 131.4 (14) |
Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x−1, y, z; (iii) −x+1, −y, −z+1; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C7H7F3N+·C8H3Cl2O4− |
Mr | 396.14 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 15.0048 (7), 14.5270 (9), 7.3292 (3) |
β (°) | 99.887 (4) |
V (Å3) | 1573.85 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.47 |
Crystal size (mm) | 0.58 × 0.45 × 0.25 |
Data collection | |
Diffractometer | Stoe IPDS 2 |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.776, 0.895 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28359, 3740, 2826 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.099, 1.06 |
No. of reflections | 3740 |
No. of parameters | 262 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.27 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3i | 0.88 (2) | 1.92 (2) | 2.788 (2) | 169 (2) |
N1—H1B···O3ii | 0.95 (3) | 2.72 (2) | 3.360 (2) | 125.8 (17) |
N1—H1B···O4ii | 0.95 (3) | 1.86 (3) | 2.789 (2) | 168 (2) |
N1—H1C···O2iii | 0.88 (2) | 1.89 (2) | 2.7717 (18) | 173.2 (19) |
N1—H1C···O1iii | 0.88 (2) | 2.54 (2) | 3.0518 (18) | 117.8 (15) |
O1—H1···O4 | 0.82 | 1.57 | 2.3908 (17) | 173.9 |
C3—H3···F1 | 0.94 (2) | 2.75 (2) | 3.637 (2) | 157.2 (15) |
C15—H15···F2iii | 0.95 (2) | 2.76 (2) | 3.582 (2) | 144.7 (15) |
C13—H13···O3i | 0.97 (2) | 2.95 (2) | 3.571 (2) | 122.7 (14) |
C13—H13···O3ii | 0.97 (2) | 2.60 (2) | 3.107 (2) | 112.5 (14) |
C13—H13···Cl1iv | 0.97 (2) | 2.85 (2) | 3.5693 (17) | 131.4 (14) |
Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x−1, y, z; (iii) −x+1, −y, −z+1; (iv) −x+1, −y+1, −z+1. |
Secondary interactions are proposed to be important in the biological activities of molecules involved in biochemical processes in the living cell. Molecular interactions find their origin in the dispersion, polarization, electrostatic, charge transfer and exchange forces (Rigby et al., 1986; Buckingham, 1993). There is considerable current interest in the preparation of compounds constructed from two molecular networks as they provide a source of novel materials with highly anisotropic electrical, optical and magnetic properties (Mas-Torrent et al., 2003; Setifi et al., 2002; Bryce & Petty, 1995; Peng et al., 1998; Rombaut et al., 2001; Bredas et al., 1994).
We have been interested in hydrogen-bonding systems formed by organic amines and carboxylic acids (Odabaşoğlu & Büyükgüngör, 2007a,b,c; 2006a,b; Odabaşoğlu et al., 2003; Yeşilel et al., 2006). The present work is part of a structural study of compounds of organic ammonium systems with hydrogen and halogen-bond donors and we report here the molecular and supramolecular structure of (I) (Fig. 1).
The C2–C7 ring and O1—C1—O2 and O3—C8—O4 planes are approximately coplanar with the dihedral angles between C2–C7 ring and O—C—O planes of 0.96 (2)° and 5.38 (1)°, respectively. The C1—C2 and C8—C7 bonds are approximately equal. This suggests some delocalization between the C2–C7 ring and the –COO- and –COOH groups that form an intramolecular hydrogen bond. Furthermore, these bonds, together with the C8—O3 and C8—O4 lengths indicate delocalization of the negative charge over the O3, C8 and O4 atoms. In the 4,5-dichlorohydrogenphthalate anion, the O1 and O4 distance is 2.3908 (17) Å and this distance is approximately 0.65 Å less than the sum of the van der Waals radii (3.04 Å) due to the presence of a strong intramolecular hydrogen bond in the anion (Table 1). The dihedral angle between the planes of the aromatic rings in the cation and anion is 34.86 (1)°.
Intramolecular O—H···O and C—H···F hydrogen bonds generate edge-fused [S(7)R44(24)S(7)R22(10)S(7)R44(24)S(7)] motifs (Etter, 1990) (Fig. 2). The ions are linked to each other by C—H···O hydrogen bonds chain along the z-axis (Fig. 3). This chain and other hydrogen bonds form [R32(6)R12(4)S(7)R12(4)R44(18)R55(24) R44(18)R12(4)R12(4)S(7)R12(4)R32(6)] motifs (Fig. 4).