The title salts, 4-chloroanilinium hydrogen phthalate (PCAHP), C
6H
7ClN
+·C
8H
5O
4-, 2-hydroxyanilinium hydrogen phthalate (2HAHP), C
6H
8NO
+·C
8H
5O
4-, and 3-hydroxyanilinium hydrogen phthalate (3HAHP), C
6H
8NO
+·C
8H
5O
4-, all crystallize in the space group
P2
1/
c. The asymmetric unit of 2HAHP contains two independent ion pairs. The hydrogen phthalate ions of 2HAHP and 3HAHP show a short intramolecular O-H

O hydrogen bond, with O

O distances ranging from 2.3832 (15) to 2.3860 (14) Å. N-H

O and O-H

O hydrogen bonds, together with short C-H

O contacts in PCAHP and 3HAHP, generate extended hydrogen-bond networks. PCAHP forms a two-dimensional supramolecular sheet extending in the (100) plane, whereas 2HAHP has a supramolecular chain running parallel to the [100] direction and 3HAHP has a two-dimensional network extending parallel to the (001) plane.
Supporting information
CCDC references: 746092; 746093; 746094
All three salts were prepared by taking equimolar (1:1) amounts of phtahalic
acid with 4-chloroaniline, 2-hydroxyaniline and 3-hydroxyaniline separately in
methanol as solvent. The solution was stirred well before being left to stand
for crystallization. Good diffraction quality crystals were obtained after a
few days of slow evaporation.
For all the three structures, H atoms bound to O and N atoms were located from
difference electron density maps. While the H atoms associated with O and N in
2HAHP and 3HAHP were refined freely, those for the N atom of PCAHP were
constrained to ride on their parent atoms with N—H distances of 0.89 Å and
Uiso(H) = 1.5Ueq(N). H atoms bound to C atoms of all the
compounds were constrained as riding [C—H = 0.93 Å and Uiso(H) =
1.2Ueq(C)]. The positions of three H atoms on N1 were identified from
a difference electron-density peak and were fixed geometrically during
refinement.
For all compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004); data reduction: XPREP in SAINT-Plus (Bruker, 2004); 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 Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).
(I) 4-chloroanilinium hydrogen phthalate
top
Crystal data top
C6H7ClN+·C8H5O4− | F(000) = 608 |
Mr = 293.70 | Dx = 1.393 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 4716 reflections |
a = 14.3610 (16) Å | θ = 3.1–24.9° |
b = 8.0094 (7) Å | µ = 0.28 mm−1 |
c = 13.0715 (14) Å | T = 292 K |
β = 111.301 (2)° | Prism, colourless |
V = 1400.8 (2) Å3 | 0.30 × 0.25 × 0.15 mm |
Z = 4 | |
Data collection top
Bruker KAPPA APEXII CCD diffractometer | 2471 independent reflections |
Radiation source: sealed tube | 1959 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω and ϕ scan | θmax = 25.1°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −17→17 |
Tmin = 0.831, Tmax = 0.959 | k = −9→8 |
12823 measured reflections | l = −15→15 |
Refinement top
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ^2^(Fo^2^) + (0.0698P)^2^ + 0.4349P] where P = (Fo^2^ + 2Fc^2^)/3 |
2471 reflections | (Δ/σ)max < 0.001 |
185 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
C6H7ClN+·C8H5O4− | V = 1400.8 (2) Å3 |
Mr = 293.70 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.3610 (16) Å | µ = 0.28 mm−1 |
b = 8.0094 (7) Å | T = 292 K |
c = 13.0715 (14) Å | 0.30 × 0.25 × 0.15 mm |
β = 111.301 (2)° | |
Data collection top
Bruker KAPPA APEXII CCD diffractometer | 2471 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 1959 reflections with I > 2σ(I) |
Tmin = 0.831, Tmax = 0.959 | Rint = 0.032 |
12823 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.20 e Å−3 |
2471 reflections | Δρmin = −0.33 e Å−3 |
185 parameters | |
Special details top
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 F^2^ against ALL reflections. The weighted
R-factor wR and goodness of fit S are based on
F^2^, conventional R-factors R are based on F,
with F set to zero for negative F^2^. The threshold expression
of F^2^ > σ(F^2^) is used only for calculating
R-factors(gt) etc. and is not relevant to the choice of
reflections for refinement. R-factors based on F^2^ are
statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.94211 (6) | 0.31525 (10) | 0.45813 (8) | 0.0852 (3) | |
N1 | 0.59536 (13) | −0.0980 (2) | 0.44284 (13) | 0.0351 (4) | |
H1A | 0.5393 | −0.0459 | 0.4024 | 0.053* | |
H1B | 0.5949 | −0.1161 | 0.5098 | 0.053* | |
H1C | 0.5994 | −0.1951 | 0.4116 | 0.053* | |
O1 | 0.37216 (11) | 0.12687 (18) | 0.17662 (11) | 0.0365 (4) | |
O2 | 0.42223 (11) | 0.09190 (19) | 0.35724 (11) | 0.0385 (4) | |
O3 | 0.47159 (12) | 0.44588 (19) | 0.30486 (12) | 0.0389 (4) | |
O4 | 0.43521 (15) | 0.6495 (2) | 0.39916 (17) | 0.0688 (6) | |
C1 | 0.29034 (15) | 0.2796 (3) | 0.27624 (16) | 0.0332 (5) | |
C2 | 0.31224 (16) | 0.4419 (3) | 0.31761 (17) | 0.0380 (5) | |
C3 | 0.2356 (2) | 0.5387 (3) | 0.3282 (2) | 0.0542 (7) | |
H3 | 0.2494 | 0.6467 | 0.3556 | 0.065* | |
C4 | 0.1404 (2) | 0.4776 (4) | 0.2990 (2) | 0.0662 (8) | |
H4 | 0.0905 | 0.5432 | 0.3081 | 0.079* | |
C5 | 0.11859 (19) | 0.3197 (4) | 0.2564 (2) | 0.0611 (7) | |
H5 | 0.0537 | 0.2787 | 0.2351 | 0.073* | |
C6 | 0.19335 (18) | 0.2221 (3) | 0.2452 (2) | 0.0481 (6) | |
H6 | 0.1781 | 0.1152 | 0.2162 | 0.058* | |
C7 | 0.36889 (15) | 0.1596 (2) | 0.26955 (16) | 0.0303 (5) | |
C8 | 0.41198 (17) | 0.5221 (3) | 0.34632 (18) | 0.0390 (5) | |
C9 | 0.68109 (15) | 0.0053 (3) | 0.45044 (16) | 0.0332 (5) | |
C10 | 0.77439 (17) | −0.0634 (3) | 0.4863 (2) | 0.0464 (6) | |
H10 | 0.7833 | −0.1747 | 0.5078 | 0.056* | |
C11 | 0.85540 (19) | 0.0323 (3) | 0.4905 (2) | 0.0554 (7) | |
H11 | 0.9193 | −0.0134 | 0.5154 | 0.067* | |
C12 | 0.84049 (18) | 0.1956 (3) | 0.4576 (2) | 0.0497 (6) | |
C13 | 0.74749 (18) | 0.2663 (3) | 0.4222 (2) | 0.0501 (6) | |
H13 | 0.7387 | 0.3775 | 0.4003 | 0.060* | |
C14 | 0.66681 (17) | 0.1699 (3) | 0.41951 (19) | 0.0427 (6) | |
H14 | 0.6032 | 0.2163 | 0.3968 | 0.051* | |
H3A | 0.532 (2) | 0.506 (3) | 0.320 (2) | 0.053 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0536 (5) | 0.0687 (5) | 0.1326 (8) | −0.0168 (4) | 0.0331 (5) | 0.0115 (5) |
N1 | 0.0409 (10) | 0.0376 (10) | 0.0288 (9) | −0.0005 (8) | 0.0153 (8) | −0.0008 (7) |
O1 | 0.0450 (9) | 0.0383 (8) | 0.0296 (8) | 0.0030 (6) | 0.0174 (7) | −0.0008 (6) |
O2 | 0.0428 (9) | 0.0453 (9) | 0.0288 (8) | 0.0059 (7) | 0.0148 (7) | 0.0066 (7) |
O3 | 0.0432 (9) | 0.0365 (8) | 0.0420 (9) | −0.0069 (7) | 0.0215 (7) | −0.0062 (7) |
O4 | 0.0750 (14) | 0.0550 (12) | 0.0873 (14) | −0.0179 (10) | 0.0425 (11) | −0.0378 (11) |
C1 | 0.0360 (11) | 0.0401 (12) | 0.0261 (11) | 0.0013 (9) | 0.0143 (9) | 0.0030 (9) |
C2 | 0.0431 (13) | 0.0424 (13) | 0.0316 (12) | 0.0030 (10) | 0.0172 (10) | −0.0016 (9) |
C3 | 0.0586 (16) | 0.0528 (15) | 0.0579 (16) | 0.0106 (12) | 0.0291 (13) | −0.0079 (12) |
C4 | 0.0504 (17) | 0.079 (2) | 0.078 (2) | 0.0203 (15) | 0.0344 (15) | −0.0038 (16) |
C5 | 0.0364 (14) | 0.080 (2) | 0.0689 (19) | 0.0008 (13) | 0.0222 (13) | −0.0004 (15) |
C6 | 0.0421 (13) | 0.0551 (15) | 0.0505 (14) | −0.0046 (11) | 0.0211 (11) | −0.0041 (11) |
C7 | 0.0341 (11) | 0.0289 (10) | 0.0299 (11) | −0.0060 (8) | 0.0141 (9) | −0.0014 (8) |
C8 | 0.0490 (13) | 0.0360 (12) | 0.0353 (12) | 0.0002 (10) | 0.0190 (10) | −0.0042 (10) |
C9 | 0.0370 (12) | 0.0383 (12) | 0.0261 (11) | −0.0019 (9) | 0.0137 (9) | −0.0034 (9) |
C10 | 0.0450 (14) | 0.0412 (13) | 0.0524 (15) | 0.0067 (11) | 0.0169 (11) | 0.0085 (11) |
C11 | 0.0379 (13) | 0.0545 (16) | 0.0718 (18) | 0.0046 (11) | 0.0174 (12) | 0.0097 (13) |
C12 | 0.0439 (14) | 0.0476 (14) | 0.0576 (16) | −0.0049 (11) | 0.0182 (12) | −0.0003 (11) |
C13 | 0.0523 (15) | 0.0358 (12) | 0.0611 (16) | −0.0016 (11) | 0.0193 (12) | 0.0037 (11) |
C14 | 0.0408 (13) | 0.0376 (12) | 0.0478 (14) | 0.0036 (10) | 0.0137 (11) | −0.0014 (10) |
Geometric parameters (Å, º) top
Cl1—C12 | 1.744 (3) | C3—H3 | 0.9300 |
N1—C9 | 1.457 (3) | C4—C5 | 1.371 (4) |
N1—H1A | 0.8900 | C4—H4 | 0.9300 |
N1—H1B | 0.8900 | C5—C6 | 1.378 (3) |
N1—H1C | 0.8900 | C5—H5 | 0.9300 |
O1—C7 | 1.260 (2) | C6—H6 | 0.9300 |
O2—C7 | 1.248 (2) | C9—C10 | 1.364 (3) |
O3—C8 | 1.318 (2) | C9—C14 | 1.372 (3) |
O3—H3A | 0.94 (3) | C10—C11 | 1.377 (3) |
O4—C8 | 1.209 (3) | C10—H10 | 0.9300 |
C1—C6 | 1.381 (3) | C11—C12 | 1.369 (4) |
C1—C2 | 1.399 (3) | C11—H11 | 0.9300 |
C1—C7 | 1.508 (3) | C12—C13 | 1.367 (3) |
C2—C3 | 1.393 (3) | C13—C14 | 1.382 (3) |
C2—C8 | 1.488 (3) | C13—H13 | 0.9300 |
C3—C4 | 1.370 (4) | C14—H14 | 0.9300 |
| | | |
C9—N1—H1A | 109.5 | O2—C7—O1 | 124.73 (19) |
C9—N1—H1B | 109.5 | O2—C7—C1 | 116.50 (17) |
H1A—N1—H1B | 109.5 | O1—C7—C1 | 118.62 (18) |
C9—N1—H1C | 109.5 | O4—C8—O3 | 122.7 (2) |
H1A—N1—H1C | 109.5 | O4—C8—C2 | 123.3 (2) |
H1B—N1—H1C | 109.5 | O3—C8—C2 | 113.93 (18) |
C8—O3—H3A | 111.2 (15) | C10—C9—C14 | 120.8 (2) |
C6—C1—C2 | 119.0 (2) | C10—C9—N1 | 119.65 (19) |
C6—C1—C7 | 117.82 (19) | C14—C9—N1 | 119.58 (19) |
C2—C1—C7 | 123.13 (18) | C9—C10—C11 | 120.0 (2) |
C3—C2—C1 | 118.7 (2) | C9—C10—H10 | 120.0 |
C3—C2—C8 | 117.2 (2) | C11—C10—H10 | 120.0 |
C1—C2—C8 | 124.00 (18) | C12—C11—C10 | 119.0 (2) |
C4—C3—C2 | 121.2 (3) | C12—C11—H11 | 120.5 |
C4—C3—H3 | 119.4 | C10—C11—H11 | 120.5 |
C2—C3—H3 | 119.4 | C13—C12—C11 | 121.6 (2) |
C3—C4—C5 | 120.0 (2) | C13—C12—Cl1 | 119.1 (2) |
C3—C4—H4 | 120.0 | C11—C12—Cl1 | 119.25 (19) |
C5—C4—H4 | 120.0 | C12—C13—C14 | 118.9 (2) |
C4—C5—C6 | 119.6 (2) | C12—C13—H13 | 120.5 |
C4—C5—H5 | 120.2 | C14—C13—H13 | 120.5 |
C6—C5—H5 | 120.2 | C9—C14—C13 | 119.7 (2) |
C5—C6—C1 | 121.5 (2) | C9—C14—H14 | 120.2 |
C5—C6—H6 | 119.3 | C13—C14—H14 | 120.2 |
C1—C6—H6 | 119.3 | | |
| | | |
C6—C1—C2—C3 | 1.3 (3) | C3—C2—C8—O4 | 16.4 (3) |
C7—C1—C2—C3 | −175.1 (2) | C1—C2—C8—O4 | −166.7 (2) |
C6—C1—C2—C8 | −175.5 (2) | C3—C2—C8—O3 | −160.8 (2) |
C7—C1—C2—C8 | 8.0 (3) | C1—C2—C8—O3 | 16.1 (3) |
C1—C2—C3—C4 | 0.0 (4) | C14—C9—C10—C11 | −0.7 (4) |
C8—C2—C3—C4 | 177.1 (2) | N1—C9—C10—C11 | 178.0 (2) |
C2—C3—C4—C5 | −1.3 (4) | C9—C10—C11—C12 | −0.5 (4) |
C3—C4—C5—C6 | 1.3 (4) | C10—C11—C12—C13 | 0.9 (4) |
C4—C5—C6—C1 | 0.1 (4) | C10—C11—C12—Cl1 | −177.7 (2) |
C2—C1—C6—C5 | −1.4 (3) | C11—C12—C13—C14 | −0.2 (4) |
C7—C1—C6—C5 | 175.2 (2) | Cl1—C12—C13—C14 | 178.51 (19) |
C6—C1—C7—O2 | −99.7 (2) | C10—C9—C14—C13 | 1.5 (3) |
C2—C1—C7—O2 | 76.8 (2) | N1—C9—C14—C13 | −177.2 (2) |
C6—C1—C7—O1 | 75.9 (2) | C12—C13—C14—C9 | −1.1 (4) |
C2—C1—C7—O1 | −107.6 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.89 | 1.85 | 2.716 (2) | 163 |
N1—H1C···O1ii | 0.89 | 1.97 | 2.836 (2) | 165 |
O3—H3A···O1iii | 0.94 (3) | 1.68 (3) | 2.608 (2) | 169 (2) |
N1—H1A···O2 | 0.89 | 1.92 | 2.779 (2) | 163 |
C13—H13···O1iii | 0.93 | 2.52 | 3.369 (3) | 151 |
C14—H14···O3 | 0.93 | 2.60 | 3.455 (3) | 154 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2. |
(II) 2-hydroxyanilinium hydrogen phthalate
top
Crystal data top
C6H8NO+·C8H5O4− | F(000) = 1152 |
Mr = 275.25 | Dx = 1.440 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 7544 reflections |
a = 12.7082 (4) Å | θ = 4.0–24.9° |
b = 14.4422 (5) Å | µ = 0.11 mm−1 |
c = 14.3394 (4) Å | T = 292 K |
β = 105.287 (2)° | Block, colourless |
V = 2538.65 (14) Å3 | 0.30 × 0.25 × 0.25 mm |
Z = 8 | |
Data collection top
Bruker KAPPA APEXII CCD diffractometer | 6404 independent reflections |
Radiation source: fine-focus sealed tube | 4195 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω and ϕ scan | θmax = 28.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −17→17 |
Tmin = 0.879, Tmax = 0.973 | k = −19→19 |
30515 measured reflections | l = −19→19 |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ^2^(Fo^2^) + (0.0667P)^2^ + 0.2899P] where P = (Fo^2^ + 2Fc^2^)/3 |
6404 reflections | (Δ/σ)max < 0.001 |
401 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C6H8NO+·C8H5O4− | V = 2538.65 (14) Å3 |
Mr = 275.25 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.7082 (4) Å | µ = 0.11 mm−1 |
b = 14.4422 (5) Å | T = 292 K |
c = 14.3394 (4) Å | 0.30 × 0.25 × 0.25 mm |
β = 105.287 (2)° | |
Data collection top
Bruker KAPPA APEXII CCD diffractometer | 6404 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 4195 reflections with I > 2σ(I) |
Tmin = 0.879, Tmax = 0.973 | Rint = 0.036 |
30515 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.23 e Å−3 |
6404 reflections | Δρmin = −0.17 e Å−3 |
401 parameters | |
Special details top
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 F^2^ against ALL reflections. The weighted
R-factor wR and goodness of fit S are based on
F^2^, conventional R-factors R are based on F,
with F set to zero for negative F^2^. The threshold expression
of F^2^ > σ(F^2^) is used only for calculating
R-factors(gt) etc. and is not relevant to the choice of
reflections for refinement. R-factors based on F^2^ are
statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1A | 0.71412 (11) | 0.30844 (10) | 0.13039 (11) | 0.0425 (3) | |
O1A | 0.55986 (10) | 0.31783 (10) | 0.64676 (12) | 0.0746 (4) | |
O2A | 0.46812 (10) | 0.19073 (9) | 0.63892 (11) | 0.0652 (4) | |
O3A | 0.28360 (11) | 0.14254 (9) | 0.61577 (11) | 0.0658 (4) | |
O4A | 0.12097 (10) | 0.19884 (10) | 0.59366 (11) | 0.0727 (4) | |
O5A | 0.91612 (10) | 0.33025 (10) | 0.10254 (8) | 0.0560 (3) | |
C1A | 0.37223 (12) | 0.33777 (11) | 0.63096 (10) | 0.0397 (3) | |
C2A | 0.26316 (12) | 0.30849 (11) | 0.61719 (10) | 0.0381 (3) | |
C3A | 0.18379 (14) | 0.37663 (13) | 0.61011 (12) | 0.0511 (4) | |
H3A | 0.1115 | 0.3584 | 0.6002 | 0.061* | |
C4A | 0.20772 (17) | 0.46917 (14) | 0.61711 (14) | 0.0633 (5) | |
H4A | 0.1526 | 0.5126 | 0.6127 | 0.076* | |
C5A | 0.31324 (18) | 0.49697 (13) | 0.63060 (16) | 0.0671 (5) | |
H5A | 0.3306 | 0.5597 | 0.6353 | 0.080* | |
C6A | 0.39387 (15) | 0.43192 (12) | 0.63718 (14) | 0.0558 (4) | |
H6A | 0.4654 | 0.4518 | 0.6461 | 0.067* | |
C7A | 0.47241 (12) | 0.27882 (12) | 0.63955 (12) | 0.0457 (4) | |
C8A | 0.21900 (13) | 0.21069 (12) | 0.60859 (11) | 0.0441 (4) | |
C9A | 0.81067 (12) | 0.30418 (10) | 0.21176 (11) | 0.0386 (3) | |
C10A | 0.91212 (12) | 0.31728 (11) | 0.19535 (11) | 0.0420 (3) | |
C11A | 1.00313 (14) | 0.31545 (13) | 0.27322 (13) | 0.0567 (4) | |
H11A | 1.0719 | 0.3252 | 0.2637 | 0.068* | |
C12A | 0.99275 (17) | 0.29937 (14) | 0.36448 (14) | 0.0631 (5) | |
H12A | 1.0545 | 0.2989 | 0.4166 | 0.076* | |
C13A | 0.89161 (18) | 0.28387 (13) | 0.37997 (13) | 0.0604 (5) | |
H13A | 0.8853 | 0.2718 | 0.4420 | 0.073* | |
C14A | 0.79992 (15) | 0.28640 (11) | 0.30285 (12) | 0.0500 (4) | |
H14A | 0.7313 | 0.2761 | 0.3125 | 0.060* | |
N1B | 0.82035 (11) | 0.02643 (11) | 0.41204 (10) | 0.0408 (3) | |
O1B | 0.66308 (8) | 0.15536 (8) | 0.42566 (8) | 0.0474 (3) | |
O2B | 0.56510 (9) | 0.03143 (8) | 0.37839 (10) | 0.0557 (3) | |
O3B | 0.38605 (9) | −0.02036 (8) | 0.37490 (9) | 0.0561 (3) | |
O4B | 0.23223 (9) | 0.03118 (9) | 0.39299 (11) | 0.0635 (4) | |
O5B | 1.02897 (10) | 0.05037 (10) | 0.40323 (9) | 0.0564 (3) | |
C1B | 0.47180 (12) | 0.17544 (10) | 0.39279 (10) | 0.0378 (3) | |
C2B | 0.36441 (11) | 0.14499 (10) | 0.38553 (10) | 0.0370 (3) | |
C3B | 0.28395 (13) | 0.21218 (12) | 0.37897 (12) | 0.0478 (4) | |
H3B | 0.2130 | 0.1932 | 0.3749 | 0.057* | |
C4B | 0.30548 (15) | 0.30488 (13) | 0.37829 (14) | 0.0569 (5) | |
H4B | 0.2497 | 0.3477 | 0.3734 | 0.068* | |
C5B | 0.40938 (16) | 0.33436 (13) | 0.38478 (15) | 0.0616 (5) | |
H5B | 0.4247 | 0.3973 | 0.3839 | 0.074* | |
C6B | 0.49096 (14) | 0.26988 (12) | 0.39261 (13) | 0.0513 (4) | |
H6B | 0.5617 | 0.2905 | 0.3980 | 0.062* | |
C7B | 0.57286 (12) | 0.11722 (11) | 0.40038 (10) | 0.0397 (3) | |
C8B | 0.32420 (12) | 0.04654 (11) | 0.38484 (11) | 0.0431 (4) | |
C9B | 0.84427 (11) | 0.04049 (10) | 0.31948 (11) | 0.0363 (3) | |
C10B | 0.95152 (12) | 0.05126 (10) | 0.31733 (11) | 0.0416 (3) | |
C11B | 0.97452 (15) | 0.06378 (13) | 0.22965 (13) | 0.0572 (5) | |
H11B | 1.0463 | 0.0713 | 0.2270 | 0.069* | |
C12B | 0.89127 (17) | 0.06512 (14) | 0.14593 (14) | 0.0624 (5) | |
H12B | 0.9074 | 0.0727 | 0.0868 | 0.075* | |
C13B | 0.78464 (16) | 0.05540 (13) | 0.14863 (13) | 0.0580 (5) | |
H13B | 0.7287 | 0.0572 | 0.0918 | 0.070* | |
C14B | 0.76114 (13) | 0.04302 (12) | 0.23608 (12) | 0.0484 (4) | |
H14B | 0.6892 | 0.0364 | 0.2387 | 0.058* | |
H1AA | 0.7323 (16) | 0.3047 (13) | 0.0751 (14) | 0.060 (6)* | |
H1AB | 0.6598 (19) | 0.2595 (16) | 0.1355 (15) | 0.084 (7)* | |
H1AC | 0.6809 (16) | 0.3701 (14) | 0.1305 (13) | 0.063 (5)* | |
H5AA | 0.9838 (19) | 0.3238 (15) | 0.1024 (14) | 0.074 (6)* | |
H2AA | 0.389 (2) | 0.1650 (15) | 0.6273 (15) | 0.088 (7)* | |
H1BA | 0.7726 (16) | 0.0730 (13) | 0.4219 (13) | 0.061 (5)* | |
H1BB | 0.8858 (19) | 0.0274 (15) | 0.4618 (17) | 0.084 (7)* | |
H1BC | 0.7880 (16) | −0.0312 (14) | 0.4130 (13) | 0.063 (6)* | |
H5BA | 1.0948 (19) | 0.0501 (16) | 0.3942 (15) | 0.081 (7)* | |
H2BA | 0.4807 (19) | 0.0068 (15) | 0.3704 (15) | 0.088 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1A | 0.0282 (7) | 0.0445 (8) | 0.0557 (9) | 0.0045 (6) | 0.0127 (6) | 0.0047 (6) |
O1A | 0.0298 (6) | 0.0642 (9) | 0.1291 (12) | −0.0070 (6) | 0.0198 (7) | −0.0203 (8) |
O2A | 0.0358 (7) | 0.0487 (8) | 0.1130 (11) | 0.0043 (6) | 0.0230 (7) | −0.0006 (7) |
O3A | 0.0470 (7) | 0.0440 (7) | 0.1110 (11) | −0.0060 (6) | 0.0290 (7) | −0.0002 (7) |
O4A | 0.0343 (7) | 0.0832 (10) | 0.1029 (11) | −0.0146 (7) | 0.0218 (7) | −0.0111 (8) |
O5A | 0.0286 (6) | 0.0867 (10) | 0.0537 (7) | 0.0065 (6) | 0.0126 (5) | 0.0035 (6) |
C1A | 0.0322 (8) | 0.0469 (9) | 0.0406 (8) | 0.0007 (6) | 0.0111 (6) | −0.0029 (6) |
C2A | 0.0309 (7) | 0.0501 (9) | 0.0353 (7) | 0.0011 (6) | 0.0121 (6) | −0.0038 (6) |
C3A | 0.0377 (9) | 0.0625 (11) | 0.0548 (10) | 0.0101 (8) | 0.0151 (7) | −0.0042 (8) |
C4A | 0.0599 (12) | 0.0568 (12) | 0.0772 (13) | 0.0210 (10) | 0.0250 (10) | 0.0015 (9) |
C5A | 0.0725 (14) | 0.0440 (10) | 0.0902 (15) | 0.0036 (9) | 0.0311 (11) | −0.0005 (9) |
C6A | 0.0472 (10) | 0.0493 (10) | 0.0740 (12) | −0.0060 (8) | 0.0216 (9) | −0.0052 (8) |
C7A | 0.0284 (8) | 0.0506 (10) | 0.0575 (10) | −0.0017 (7) | 0.0099 (7) | −0.0072 (7) |
C8A | 0.0350 (8) | 0.0565 (10) | 0.0436 (8) | −0.0060 (7) | 0.0155 (7) | −0.0052 (7) |
C9A | 0.0329 (8) | 0.0333 (7) | 0.0493 (9) | 0.0062 (6) | 0.0103 (6) | 0.0011 (6) |
C10A | 0.0322 (8) | 0.0442 (9) | 0.0483 (9) | 0.0047 (6) | 0.0083 (6) | −0.0005 (6) |
C11A | 0.0370 (9) | 0.0666 (12) | 0.0603 (11) | 0.0047 (8) | 0.0021 (8) | −0.0035 (8) |
C12A | 0.0611 (13) | 0.0629 (12) | 0.0534 (11) | 0.0123 (10) | −0.0058 (9) | −0.0044 (9) |
C13A | 0.0822 (15) | 0.0525 (11) | 0.0451 (10) | 0.0120 (10) | 0.0140 (9) | 0.0054 (8) |
C14A | 0.0560 (11) | 0.0392 (9) | 0.0594 (11) | 0.0048 (7) | 0.0232 (8) | 0.0045 (7) |
N1B | 0.0256 (7) | 0.0450 (8) | 0.0532 (8) | −0.0014 (6) | 0.0130 (6) | 0.0007 (6) |
O1B | 0.0257 (5) | 0.0567 (7) | 0.0605 (7) | −0.0041 (5) | 0.0125 (5) | −0.0029 (5) |
O2B | 0.0304 (6) | 0.0478 (7) | 0.0917 (9) | −0.0004 (5) | 0.0209 (6) | −0.0095 (6) |
O3B | 0.0358 (6) | 0.0443 (7) | 0.0923 (9) | −0.0039 (5) | 0.0241 (6) | −0.0060 (6) |
O4B | 0.0293 (6) | 0.0638 (8) | 0.1008 (10) | −0.0053 (5) | 0.0235 (6) | 0.0028 (7) |
O5B | 0.0260 (6) | 0.0848 (9) | 0.0584 (7) | −0.0014 (6) | 0.0112 (5) | 0.0127 (6) |
C1B | 0.0305 (7) | 0.0457 (9) | 0.0385 (8) | 0.0008 (6) | 0.0117 (6) | 0.0029 (6) |
C2B | 0.0272 (7) | 0.0464 (9) | 0.0375 (8) | 0.0020 (6) | 0.0087 (6) | 0.0012 (6) |
C3B | 0.0298 (8) | 0.0548 (10) | 0.0591 (10) | 0.0059 (7) | 0.0126 (7) | 0.0028 (8) |
C4B | 0.0437 (10) | 0.0536 (11) | 0.0728 (12) | 0.0151 (8) | 0.0142 (8) | 0.0057 (8) |
C5B | 0.0558 (12) | 0.0431 (10) | 0.0866 (14) | 0.0029 (8) | 0.0200 (10) | 0.0094 (9) |
C6B | 0.0366 (9) | 0.0478 (10) | 0.0715 (11) | −0.0027 (7) | 0.0176 (8) | 0.0060 (8) |
C7B | 0.0280 (8) | 0.0491 (9) | 0.0439 (8) | 0.0008 (7) | 0.0131 (6) | 0.0032 (6) |
C8B | 0.0262 (7) | 0.0524 (10) | 0.0503 (9) | −0.0015 (7) | 0.0096 (6) | 0.0012 (7) |
C9B | 0.0298 (7) | 0.0317 (7) | 0.0486 (8) | 0.0012 (6) | 0.0128 (6) | −0.0012 (6) |
C10B | 0.0311 (8) | 0.0411 (8) | 0.0537 (9) | 0.0008 (6) | 0.0132 (7) | 0.0029 (7) |
C11B | 0.0439 (10) | 0.0698 (12) | 0.0636 (12) | −0.0011 (8) | 0.0244 (9) | 0.0062 (9) |
C12B | 0.0702 (13) | 0.0697 (13) | 0.0525 (11) | −0.0029 (10) | 0.0253 (10) | 0.0024 (8) |
C13B | 0.0535 (11) | 0.0638 (12) | 0.0500 (10) | −0.0020 (9) | 0.0021 (8) | −0.0017 (8) |
C14B | 0.0337 (8) | 0.0514 (10) | 0.0581 (10) | −0.0023 (7) | 0.0086 (7) | −0.0034 (7) |
Geometric parameters (Å, º) top
N1A—C9A | 1.455 (2) | N1B—C9B | 1.4519 (19) |
N1A—H1AA | 0.88 (2) | N1B—H1BA | 0.94 (2) |
N1A—H1AB | 1.00 (2) | N1B—H1BB | 0.94 (2) |
N1A—H1AC | 0.99 (2) | N1B—H1BC | 0.93 (2) |
O1A—C7A | 1.2259 (19) | O1B—C7B | 1.2370 (17) |
O2A—C7A | 1.273 (2) | O2B—C7B | 1.276 (2) |
O2A—H2AA | 1.05 (2) | O2B—H2BA | 1.11 (2) |
O3A—C8A | 1.268 (2) | O3B—C8B | 1.2770 (19) |
O3A—H2AA | 1.34 (3) | O3B—H2BA | 1.28 (2) |
O4A—C8A | 1.2193 (19) | O4B—C8B | 1.2250 (18) |
O5A—C10A | 1.3582 (19) | O5B—C10B | 1.3591 (19) |
O5A—H5AA | 0.87 (2) | O5B—H5BA | 0.88 (2) |
C1A—C6A | 1.385 (2) | C1B—C6B | 1.386 (2) |
C1A—C2A | 1.412 (2) | C1B—C2B | 1.411 (2) |
C1A—C7A | 1.509 (2) | C1B—C7B | 1.515 (2) |
C2A—C3A | 1.394 (2) | C2B—C3B | 1.395 (2) |
C2A—C8A | 1.513 (2) | C2B—C8B | 1.510 (2) |
C3A—C4A | 1.368 (3) | C3B—C4B | 1.367 (2) |
C3A—H3A | 0.9300 | C3B—H3B | 0.9300 |
C4A—C5A | 1.364 (3) | C4B—C5B | 1.367 (3) |
C4A—H4A | 0.9300 | C4B—H4B | 0.9300 |
C5A—C6A | 1.375 (3) | C5B—C6B | 1.376 (2) |
C5A—H5A | 0.9300 | C5B—H5B | 0.9300 |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C9A—C14A | 1.373 (2) | C9B—C14B | 1.372 (2) |
C9A—C10A | 1.383 (2) | C9B—C10B | 1.380 (2) |
C10A—C11A | 1.380 (2) | C10B—C11B | 1.376 (2) |
C11A—C12A | 1.369 (3) | C11B—C12B | 1.375 (3) |
C11A—H11A | 0.9300 | C11B—H11B | 0.9300 |
C12A—C13A | 1.379 (3) | C12B—C13B | 1.373 (3) |
C12A—H12A | 0.9300 | C12B—H12B | 0.9300 |
C13A—C14A | 1.379 (3) | C13B—C14B | 1.375 (2) |
C13A—H13A | 0.9300 | C13B—H13B | 0.9300 |
C14A—H14A | 0.9300 | C14B—H14B | 0.9300 |
| | | |
C9A—N1A—H1AA | 110.6 (13) | C9B—N1B—H1BA | 109.6 (11) |
C9A—N1A—H1AB | 111.2 (12) | C9B—N1B—H1BB | 109.5 (13) |
H1AA—N1A—H1AB | 111.7 (17) | H1BA—N1B—H1BB | 110.5 (17) |
C9A—N1A—H1AC | 108.0 (11) | C9B—N1B—H1BC | 109.8 (11) |
H1AA—N1A—H1AC | 105.6 (16) | H1BA—N1B—H1BC | 109.4 (16) |
H1AB—N1A—H1AC | 109.4 (16) | H1BB—N1B—H1BC | 107.9 (17) |
C7A—O2A—H2AA | 113.2 (12) | C7B—O2B—H2BA | 110.3 (11) |
C8A—O3A—H2AA | 115.1 (10) | C8B—O3B—H2BA | 112.8 (10) |
C10A—O5A—H5AA | 106.3 (13) | C10B—O5B—H5BA | 110.9 (14) |
C6A—C1A—C2A | 118.27 (15) | C6B—C1B—C2B | 118.27 (14) |
C6A—C1A—C7A | 113.55 (14) | C6B—C1B—C7B | 113.60 (13) |
C2A—C1A—C7A | 128.18 (14) | C2B—C1B—C7B | 128.13 (14) |
C3A—C2A—C1A | 117.62 (15) | C3B—C2B—C1B | 117.75 (14) |
C3A—C2A—C8A | 114.05 (14) | C3B—C2B—C8B | 114.45 (13) |
C1A—C2A—C8A | 128.33 (14) | C1B—C2B—C8B | 127.80 (13) |
C4A—C3A—C2A | 122.80 (17) | C4B—C3B—C2B | 122.50 (16) |
C4A—C3A—H3A | 118.6 | C4B—C3B—H3B | 118.7 |
C2A—C3A—H3A | 118.6 | C2B—C3B—H3B | 118.7 |
C5A—C4A—C3A | 119.28 (17) | C5B—C4B—C3B | 119.73 (16) |
C5A—C4A—H4A | 120.4 | C5B—C4B—H4B | 120.1 |
C3A—C4A—H4A | 120.4 | C3B—C4B—H4B | 120.1 |
C4A—C5A—C6A | 119.71 (18) | C4B—C5B—C6B | 119.23 (17) |
C4A—C5A—H5A | 120.1 | C4B—C5B—H5B | 120.4 |
C6A—C5A—H5A | 120.1 | C6B—C5B—H5B | 120.4 |
C5A—C6A—C1A | 122.31 (17) | C5B—C6B—C1B | 122.50 (16) |
C5A—C6A—H6A | 118.8 | C5B—C6B—H6B | 118.8 |
C1A—C6A—H6A | 118.8 | C1B—C6B—H6B | 118.8 |
O1A—C7A—O2A | 119.74 (15) | O1B—C7B—O2B | 120.68 (14) |
O1A—C7A—C1A | 118.29 (15) | O1B—C7B—C1B | 118.46 (14) |
O2A—C7A—C1A | 121.97 (14) | O2B—C7B—C1B | 120.82 (13) |
O4A—C8A—O3A | 120.98 (16) | O4B—C8B—O3B | 120.30 (15) |
O4A—C8A—C2A | 119.03 (15) | O4B—C8B—C2B | 119.97 (14) |
O3A—C8A—C2A | 119.98 (14) | O3B—C8B—C2B | 119.74 (13) |
C14A—C9A—C10A | 121.22 (15) | C14B—C9B—C10B | 121.04 (14) |
C14A—C9A—N1A | 119.78 (14) | C14B—C9B—N1B | 120.13 (13) |
C10A—C9A—N1A | 118.99 (13) | C10B—C9B—N1B | 118.83 (13) |
O5A—C10A—C11A | 123.76 (15) | O5B—C10B—C11B | 123.51 (14) |
O5A—C10A—C9A | 117.57 (13) | O5B—C10B—C9B | 117.52 (14) |
C11A—C10A—C9A | 118.66 (15) | C11B—C10B—C9B | 118.96 (15) |
C12A—C11A—C10A | 120.35 (17) | C12B—C11B—C10B | 119.99 (16) |
C12A—C11A—H11A | 119.8 | C12B—C11B—H11B | 120.0 |
C10A—C11A—H11A | 119.8 | C10B—C11B—H11B | 120.0 |
C11A—C12A—C13A | 120.68 (17) | C13B—C12B—C11B | 120.78 (17) |
C11A—C12A—H12A | 119.7 | C13B—C12B—H12B | 119.6 |
C13A—C12A—H12A | 119.7 | C11B—C12B—H12B | 119.6 |
C12A—C13A—C14A | 119.52 (17) | C12B—C13B—C14B | 119.49 (16) |
C12A—C13A—H13A | 120.2 | C12B—C13B—H13B | 120.3 |
C14A—C13A—H13A | 120.2 | C14B—C13B—H13B | 120.3 |
C9A—C14A—C13A | 119.53 (17) | C9B—C14B—C13B | 119.74 (15) |
C9A—C14A—H14A | 120.2 | C9B—C14B—H14B | 120.1 |
C13A—C14A—H14A | 120.2 | C13B—C14B—H14B | 120.1 |
| | | |
C6A—C1A—C2A—C3A | 0.4 (2) | C6B—C1B—C2B—C3B | −0.3 (2) |
C7A—C1A—C2A—C3A | −179.15 (14) | C7B—C1B—C2B—C3B | −179.79 (14) |
C6A—C1A—C2A—C8A | −179.74 (15) | C6B—C1B—C2B—C8B | −179.61 (15) |
C7A—C1A—C2A—C8A | 0.7 (2) | C7B—C1B—C2B—C8B | 0.9 (2) |
C1A—C2A—C3A—C4A | −0.8 (2) | C1B—C2B—C3B—C4B | 0.7 (2) |
C8A—C2A—C3A—C4A | 179.30 (15) | C8B—C2B—C3B—C4B | −179.81 (15) |
C2A—C3A—C4A—C5A | 0.7 (3) | C2B—C3B—C4B—C5B | −0.4 (3) |
C3A—C4A—C5A—C6A | −0.2 (3) | C3B—C4B—C5B—C6B | −0.5 (3) |
C4A—C5A—C6A—C1A | −0.3 (3) | C4B—C5B—C6B—C1B | 1.0 (3) |
C2A—C1A—C6A—C5A | 0.1 (3) | C2B—C1B—C6B—C5B | −0.6 (3) |
C7A—C1A—C6A—C5A | 179.73 (17) | C7B—C1B—C6B—C5B | 179.01 (16) |
C6A—C1A—C7A—O1A | −3.0 (2) | C6B—C1B—C7B—O1B | 14.9 (2) |
C2A—C1A—C7A—O1A | 176.56 (16) | C2B—C1B—C7B—O1B | −165.54 (14) |
C6A—C1A—C7A—O2A | 177.41 (16) | C6B—C1B—C7B—O2B | −162.98 (15) |
C2A—C1A—C7A—O2A | −3.0 (3) | C2B—C1B—C7B—O2B | 16.6 (2) |
C3A—C2A—C8A—O4A | 2.2 (2) | C3B—C2B—C8B—O4B | −10.6 (2) |
C1A—C2A—C8A—O4A | −177.66 (15) | C1B—C2B—C8B—O4B | 168.81 (15) |
C3A—C2A—C8A—O3A | −178.63 (14) | C3B—C2B—C8B—O3B | 168.83 (14) |
C1A—C2A—C8A—O3A | 1.5 (2) | C1B—C2B—C8B—O3B | −11.8 (2) |
C14A—C9A—C10A—O5A | 177.00 (14) | C14B—C9B—C10B—O5B | 178.30 (14) |
N1A—C9A—C10A—O5A | −2.3 (2) | N1B—C9B—C10B—O5B | −1.6 (2) |
C14A—C9A—C10A—C11A | −2.3 (2) | C14B—C9B—C10B—C11B | −0.6 (2) |
N1A—C9A—C10A—C11A | 178.40 (15) | N1B—C9B—C10B—C11B | 179.44 (15) |
O5A—C10A—C11A—C12A | −178.12 (16) | O5B—C10B—C11B—C12B | −179.07 (16) |
C9A—C10A—C11A—C12A | 1.1 (3) | C9B—C10B—C11B—C12B | −0.2 (3) |
C10A—C11A—C12A—C13A | 0.6 (3) | C10B—C11B—C12B—C13B | 1.0 (3) |
C11A—C12A—C13A—C14A | −1.3 (3) | C11B—C12B—C13B—C14B | −0.8 (3) |
C10A—C9A—C14A—C13A | 1.7 (2) | C10B—C9B—C14B—C13B | 0.7 (2) |
N1A—C9A—C14A—C13A | −178.99 (15) | N1B—C9B—C14B—C13B | −179.32 (15) |
C12A—C13A—C14A—C9A | 0.1 (3) | C12B—C13B—C14B—C9B | 0.0 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1AA···O1Bi | 0.88 (2) | 2.169 (19) | 2.8824 (19) | 137.4 (17) |
N1A—H1AB···O1Ai | 1.00 (2) | 1.73 (2) | 2.7326 (19) | 175 (2) |
N1A—H1AC···O3Bii | 0.99 (2) | 1.79 (2) | 2.7727 (18) | 176.6 (17) |
O5A—H5AA···O4Aiii | 0.87 (2) | 1.81 (2) | 2.6728 (17) | 174 (2) |
N1B—H1BB···O5Biv | 0.94 (2) | 2.25 (2) | 3.0395 (19) | 140.5 (18) |
N1B—H1BC···O3Av | 0.93 (2) | 1.84 (2) | 2.7534 (19) | 166.7 (17) |
O5B—H5BA···O4Bvi | 0.88 (2) | 1.77 (2) | 2.6402 (16) | 169 (2) |
N1B—H1BA···O1B | 0.94 (2) | 1.84 (2) | 2.7760 (17) | 170.9 (17) |
O2A—H2AA···O3A | 1.05 (2) | 1.34 (3) | 2.3838 (17) | 173 (2) |
O2B—H2BA···O3B | 1.11 (2) | 1.28 (2) | 2.3832 (15) | 171 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x+1, −y+1/2, z−1/2; (iv) −x+2, −y, −z+1; (v) −x+1, −y, −z+1; (vi) x+1, y, z. |
(III) 3-hydroxyanilinium hydrogen phthalate
top
Crystal data top
C6H8NO+·C8H5O4− | F(000) = 576 |
Mr = 275.25 | Dx = 1.493 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 5610 reflections |
a = 5.8924 (3) Å | θ = 2.6–30.6° |
b = 8.1467 (4) Å | µ = 0.12 mm−1 |
c = 25.6509 (15) Å | T = 292 K |
β = 95.984 (2)° | Block, colourless |
V = 1224.63 (11) Å3 | 0.25 × 0.20 × 0.20 mm |
Z = 4 | |
Data collection top
Bruker KAPPA APEXII CCD diffractometer | 3812 independent reflections |
Radiation source: fine-focus sealed tube | 3009 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω and ϕ scan | θmax = 30.8°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −8→8 |
Tmin = 0.890, Tmax = 0.977 | k = −11→11 |
16385 measured reflections | l = −36→36 |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ^2^(Fo^2^) + (0.0545P)^2^ + 0.2907P] where P = (Fo^2^ + 2Fc^2^)/3 |
3812 reflections | (Δ/σ)max = 0.001 |
201 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C6H8NO+·C8H5O4− | V = 1224.63 (11) Å3 |
Mr = 275.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.8924 (3) Å | µ = 0.12 mm−1 |
b = 8.1467 (4) Å | T = 292 K |
c = 25.6509 (15) Å | 0.25 × 0.20 × 0.20 mm |
β = 95.984 (2)° | |
Data collection top
Bruker KAPPA APEXII CCD diffractometer | 3812 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 3009 reflections with I > 2σ(I) |
Tmin = 0.890, Tmax = 0.977 | Rint = 0.029 |
16385 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.34 e Å−3 |
3812 reflections | Δρmin = −0.19 e Å−3 |
201 parameters | |
Special details top
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 F^2^ against ALL reflections. The weighted
R-factor wR and goodness of fit S are based on
F^2^, conventional R-factors R are based on F,
with F set to zero for negative F^2^. The threshold expression
of F^2^ > σ(F^2^) is used only for calculating
R-factors(gt) etc. and is not relevant to the choice of
reflections for refinement. R-factors based on F^2^ are
statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 1.38047 (18) | 0.78081 (13) | 0.53029 (4) | 0.0290 (2) | |
O1 | 0.47417 (16) | 0.69570 (12) | 0.37286 (4) | 0.0417 (2) | |
O2 | 0.70580 (17) | 0.79180 (14) | 0.43792 (4) | 0.0436 (3) | |
O3 | 1.07524 (17) | 0.91467 (14) | 0.44915 (4) | 0.0431 (2) | |
O4 | 1.31217 (16) | 1.04838 (12) | 0.40439 (4) | 0.0388 (2) | |
O5 | 0.69212 (14) | 0.49173 (11) | 0.55470 (4) | 0.0325 (2) | |
C1 | 0.75819 (19) | 0.87817 (14) | 0.34914 (4) | 0.0266 (2) | |
C2 | 0.96985 (19) | 0.96069 (13) | 0.35657 (4) | 0.0253 (2) | |
C3 | 1.0443 (2) | 1.04456 (16) | 0.31415 (5) | 0.0328 (3) | |
H3 | 1.1856 | 1.0965 | 0.3185 | 0.039* | |
C4 | 0.9169 (3) | 1.05345 (19) | 0.26614 (5) | 0.0415 (3) | |
H4 | 0.9702 | 1.1125 | 0.2389 | 0.050* | |
C5 | 0.7103 (3) | 0.9742 (2) | 0.25890 (5) | 0.0459 (3) | |
H5 | 0.6223 | 0.9795 | 0.2267 | 0.055* | |
C6 | 0.6341 (2) | 0.88675 (18) | 0.29970 (5) | 0.0375 (3) | |
H6 | 0.4955 | 0.8316 | 0.2941 | 0.045* | |
C7 | 0.6382 (2) | 0.78111 (15) | 0.38858 (5) | 0.0313 (2) | |
C8 | 1.13118 (19) | 0.97532 (14) | 0.40644 (5) | 0.0274 (2) | |
C9 | 1.23460 (18) | 0.70102 (13) | 0.56582 (4) | 0.0246 (2) | |
C10 | 1.02698 (18) | 0.64022 (13) | 0.54460 (4) | 0.0253 (2) | |
H10 | 0.9772 | 0.6565 | 0.5094 | 0.030* | |
C11 | 0.89364 (18) | 0.55432 (13) | 0.57681 (4) | 0.0250 (2) | |
C12 | 0.9680 (2) | 0.53422 (15) | 0.62960 (5) | 0.0303 (2) | |
H12 | 0.8792 | 0.4765 | 0.6513 | 0.036* | |
C13 | 1.1742 (2) | 0.60029 (17) | 0.64966 (5) | 0.0337 (3) | |
H13 | 1.2219 | 0.5883 | 0.6852 | 0.040* | |
C14 | 1.3118 (2) | 0.68395 (15) | 0.61811 (5) | 0.0306 (2) | |
H14 | 1.4516 | 0.7272 | 0.6317 | 0.037* | |
H1A | 1.486 (3) | 0.850 (2) | 0.5491 (7) | 0.047 (5)* | |
H1B | 1.292 (3) | 0.836 (2) | 0.5049 (7) | 0.048 (5)* | |
H1C | 1.468 (3) | 0.700 (2) | 0.5148 (7) | 0.048 (5)* | |
H2A | 0.872 (4) | 0.854 (3) | 0.4422 (9) | 0.083 (7)* | |
H5A | 0.628 (3) | 0.430 (2) | 0.5797 (8) | 0.060 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0252 (5) | 0.0347 (5) | 0.0269 (5) | −0.0087 (4) | 0.0021 (4) | 0.0014 (4) |
O1 | 0.0355 (5) | 0.0412 (5) | 0.0487 (6) | −0.0146 (4) | 0.0060 (4) | 0.0033 (4) |
O2 | 0.0316 (5) | 0.0654 (7) | 0.0336 (5) | −0.0098 (4) | 0.0024 (4) | 0.0166 (4) |
O3 | 0.0355 (5) | 0.0640 (6) | 0.0280 (5) | −0.0121 (4) | −0.0049 (4) | 0.0111 (4) |
O4 | 0.0303 (5) | 0.0467 (5) | 0.0379 (5) | −0.0133 (4) | −0.0034 (4) | −0.0029 (4) |
O5 | 0.0250 (4) | 0.0428 (5) | 0.0295 (4) | −0.0112 (3) | 0.0012 (3) | 0.0027 (4) |
C1 | 0.0232 (5) | 0.0298 (5) | 0.0269 (5) | −0.0019 (4) | 0.0032 (4) | 0.0005 (4) |
C2 | 0.0224 (5) | 0.0282 (5) | 0.0250 (5) | −0.0007 (4) | 0.0018 (4) | −0.0013 (4) |
C3 | 0.0295 (6) | 0.0402 (6) | 0.0293 (6) | −0.0087 (5) | 0.0063 (5) | −0.0008 (5) |
C4 | 0.0447 (8) | 0.0557 (8) | 0.0248 (6) | −0.0099 (6) | 0.0070 (5) | 0.0045 (5) |
C5 | 0.0420 (8) | 0.0688 (10) | 0.0252 (6) | −0.0091 (7) | −0.0039 (5) | 0.0037 (6) |
C6 | 0.0284 (6) | 0.0515 (8) | 0.0316 (6) | −0.0097 (5) | −0.0023 (5) | 0.0001 (5) |
C7 | 0.0248 (5) | 0.0323 (6) | 0.0372 (6) | −0.0013 (4) | 0.0052 (4) | 0.0062 (5) |
C8 | 0.0246 (5) | 0.0293 (5) | 0.0276 (5) | −0.0015 (4) | −0.0004 (4) | −0.0020 (4) |
C9 | 0.0229 (5) | 0.0257 (5) | 0.0254 (5) | −0.0027 (4) | 0.0038 (4) | 0.0009 (4) |
C10 | 0.0245 (5) | 0.0280 (5) | 0.0231 (5) | −0.0033 (4) | 0.0008 (4) | 0.0014 (4) |
C11 | 0.0215 (5) | 0.0274 (5) | 0.0260 (5) | −0.0022 (4) | 0.0021 (4) | −0.0006 (4) |
C12 | 0.0288 (6) | 0.0377 (6) | 0.0250 (5) | −0.0040 (5) | 0.0051 (4) | 0.0038 (4) |
C13 | 0.0321 (6) | 0.0459 (7) | 0.0225 (5) | −0.0043 (5) | −0.0005 (4) | 0.0028 (5) |
C14 | 0.0257 (5) | 0.0375 (6) | 0.0276 (6) | −0.0060 (4) | −0.0018 (4) | 0.0004 (4) |
Geometric parameters (Å, º) top
N1—C9 | 1.4681 (14) | C3—C4 | 1.3757 (19) |
N1—H1A | 0.937 (19) | C3—H3 | 0.9300 |
N1—H1B | 0.910 (19) | C4—C5 | 1.373 (2) |
N1—H1C | 0.947 (18) | C4—H4 | 0.9300 |
O1—C7 | 1.2248 (15) | C5—C6 | 1.3794 (19) |
O2—C7 | 1.2895 (16) | C5—H5 | 0.9300 |
O2—H2A | 1.10 (2) | C6—H6 | 0.9300 |
O3—C8 | 1.2759 (14) | C9—C14 | 1.3775 (16) |
O3—H2A | 1.29 (2) | C9—C10 | 1.3782 (15) |
O4—C8 | 1.2272 (14) | C10—C11 | 1.3875 (15) |
O5—C11 | 1.3606 (14) | C10—H10 | 0.9300 |
O5—H5A | 0.93 (2) | C11—C12 | 1.3889 (16) |
C1—C6 | 1.3980 (17) | C12—C13 | 1.3787 (17) |
C1—C2 | 1.4121 (15) | C12—H12 | 0.9300 |
C1—C7 | 1.5158 (16) | C13—C14 | 1.3831 (17) |
C2—C3 | 1.3940 (16) | C13—H13 | 0.9300 |
C2—C8 | 1.5169 (16) | C14—H14 | 0.9300 |
| | | |
C9—N1—H1A | 110.3 (10) | C1—C6—H6 | 118.9 |
C9—N1—H1B | 109.4 (11) | O1—C7—O2 | 120.93 (11) |
H1A—N1—H1B | 111.8 (15) | O1—C7—C1 | 118.92 (12) |
C9—N1—H1C | 109.4 (10) | O2—C7—C1 | 120.14 (11) |
H1A—N1—H1C | 106.0 (14) | O4—C8—O3 | 121.87 (11) |
H1B—N1—H1C | 109.8 (14) | O4—C8—C2 | 118.22 (10) |
C7—O2—H2A | 108.1 (11) | O3—C8—C2 | 119.89 (10) |
C8—O3—H2A | 110.4 (10) | C14—C9—C10 | 122.52 (10) |
C11—O5—H5A | 108.5 (12) | C14—C9—N1 | 119.60 (10) |
C6—C1—C2 | 118.00 (10) | C10—C9—N1 | 117.83 (10) |
C6—C1—C7 | 113.29 (10) | C9—C10—C11 | 118.72 (10) |
C2—C1—C7 | 128.69 (10) | C9—C10—H10 | 120.6 |
C3—C2—C1 | 118.27 (10) | C11—C10—H10 | 120.6 |
C3—C2—C8 | 113.53 (10) | O5—C11—C10 | 117.68 (10) |
C1—C2—C8 | 128.18 (10) | O5—C11—C12 | 122.35 (10) |
C4—C3—C2 | 122.53 (11) | C10—C11—C12 | 119.96 (10) |
C4—C3—H3 | 118.7 | C13—C12—C11 | 119.60 (10) |
C2—C3—H3 | 118.7 | C13—C12—H12 | 120.2 |
C5—C4—C3 | 119.31 (12) | C11—C12—H12 | 120.2 |
C5—C4—H4 | 120.3 | C12—C13—C14 | 121.42 (11) |
C3—C4—H4 | 120.3 | C12—C13—H13 | 119.3 |
C4—C5—C6 | 119.63 (13) | C14—C13—H13 | 119.3 |
C4—C5—H5 | 120.2 | C9—C14—C13 | 117.74 (11) |
C6—C5—H5 | 120.2 | C9—C14—H14 | 121.1 |
C5—C6—C1 | 122.23 (12) | C13—C14—H14 | 121.1 |
C5—C6—H6 | 118.9 | | |
| | | |
C6—C1—C2—C3 | −0.64 (17) | C3—C2—C8—O4 | −4.14 (16) |
C7—C1—C2—C3 | −179.07 (11) | C1—C2—C8—O4 | 177.59 (11) |
C6—C1—C2—C8 | 177.55 (11) | C3—C2—C8—O3 | 174.77 (11) |
C7—C1—C2—C8 | −0.88 (19) | C1—C2—C8—O3 | −3.50 (18) |
C1—C2—C3—C4 | 1.85 (19) | C14—C9—C10—C11 | −1.96 (17) |
C8—C2—C3—C4 | −176.61 (12) | N1—C9—C10—C11 | 175.55 (10) |
C2—C3—C4—C5 | −1.4 (2) | C9—C10—C11—O5 | −178.31 (10) |
C3—C4—C5—C6 | −0.2 (2) | C9—C10—C11—C12 | 1.43 (16) |
C4—C5—C6—C1 | 1.4 (2) | O5—C11—C12—C13 | 179.84 (11) |
C2—C1—C6—C5 | −0.9 (2) | C10—C11—C12—C13 | 0.12 (18) |
C7—C1—C6—C5 | 177.74 (13) | C11—C12—C13—C14 | −1.2 (2) |
C6—C1—C7—O1 | 13.52 (17) | C10—C9—C14—C13 | 0.87 (18) |
C2—C1—C7—O1 | −167.99 (12) | N1—C9—C14—C13 | −176.60 (11) |
C6—C1—C7—O2 | −164.98 (12) | C12—C13—C14—C9 | 0.76 (19) |
C2—C1—C7—O2 | 13.51 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.937 (19) | 1.795 (19) | 2.7187 (13) | 168.1 (16) |
N1—H1C···O5ii | 0.947 (18) | 2.323 (17) | 3.0118 (15) | 129.2 (13) |
O5—H5A···O1iii | 0.93 (2) | 1.74 (2) | 2.6691 (13) | 175.7 (18) |
N1—H1B···O3 | 0.910 (19) | 1.924 (19) | 2.8241 (15) | 169.5 (16) |
O2—H2A···O3 | 1.10 (2) | 1.29 (2) | 2.3860 (14) | 174 (2) |
C12—H12···O1iii | 0.93 | 2.53 | 3.2041 (15) | 129 |
C10—H10···O2 | 0.93 | 2.55 | 3.3932 (15) | 150 |
Symmetry codes: (i) −x+3, −y+2, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C6H7ClN+·C8H5O4− | C6H8NO+·C8H5O4− | C6H8NO+·C8H5O4− |
Mr | 293.70 | 275.25 | 275.25 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 292 | 292 | 292 |
a, b, c (Å) | 14.3610 (16), 8.0094 (7), 13.0715 (14) | 12.7082 (4), 14.4422 (5), 14.3394 (4) | 5.8924 (3), 8.1467 (4), 25.6509 (15) |
β (°) | 111.301 (2) | 105.287 (2) | 95.984 (2) |
V (Å3) | 1400.8 (2) | 2538.65 (14) | 1224.63 (11) |
Z | 4 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.28 | 0.11 | 0.12 |
Crystal size (mm) | 0.30 × 0.25 × 0.15 | 0.30 × 0.25 × 0.25 | 0.25 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Bruker KAPPA APEXII CCD diffractometer | Bruker KAPPA APEXII CCD diffractometer | Bruker KAPPA APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) | Multi-scan (SADABS; Bruker, 1999) | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.831, 0.959 | 0.879, 0.973 | 0.890, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12823, 2471, 1959 | 30515, 6404, 4195 | 16385, 3812, 3009 |
Rint | 0.032 | 0.036 | 0.029 |
(sin θ/λ)max (Å−1) | 0.596 | 0.672 | 0.720 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.133, 1.10 | 0.045, 0.132, 1.01 | 0.043, 0.117, 1.05 |
No. of reflections | 2471 | 6404 | 3812 |
No. of parameters | 185 | 401 | 201 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.33 | 0.23, −0.17 | 0.34, −0.19 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.89 | 1.85 | 2.716 (2) | 163 |
N1—H1C···O1ii | 0.89 | 1.97 | 2.836 (2) | 165 |
O3—H3A···O1iii | 0.94 (3) | 1.68 (3) | 2.608 (2) | 169 (2) |
N1—H1A···O2 | 0.89 | 1.92 | 2.779 (2) | 163 |
C13—H13···O1iii | 0.93 | 2.52 | 3.369 (3) | 151 |
C14—H14···O3 | 0.93 | 2.60 | 3.455 (3) | 154 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1AA···O1Bi | 0.88 (2) | 2.169 (19) | 2.8824 (19) | 137.4 (17) |
N1A—H1AB···O1Ai | 1.00 (2) | 1.73 (2) | 2.7326 (19) | 175 (2) |
N1A—H1AC···O3Bii | 0.99 (2) | 1.79 (2) | 2.7727 (18) | 176.6 (17) |
O5A—H5AA···O4Aiii | 0.87 (2) | 1.81 (2) | 2.6728 (17) | 174 (2) |
N1B—H1BB···O5Biv | 0.94 (2) | 2.25 (2) | 3.0395 (19) | 140.5 (18) |
N1B—H1BC···O3Av | 0.93 (2) | 1.84 (2) | 2.7534 (19) | 166.7 (17) |
O5B—H5BA···O4Bvi | 0.88 (2) | 1.77 (2) | 2.6402 (16) | 169 (2) |
N1B—H1BA···O1B | 0.94 (2) | 1.84 (2) | 2.7760 (17) | 170.9 (17) |
O2A—H2AA···O3A | 1.05 (2) | 1.34 (3) | 2.3838 (17) | 173 (2) |
O2B—H2BA···O3B | 1.11 (2) | 1.28 (2) | 2.3832 (15) | 171 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x+1, −y+1/2, z−1/2; (iv) −x+2, −y, −z+1; (v) −x+1, −y, −z+1; (vi) x+1, y, z. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.937 (19) | 1.795 (19) | 2.7187 (13) | 168.1 (16) |
N1—H1C···O5ii | 0.947 (18) | 2.323 (17) | 3.0118 (15) | 129.2 (13) |
O5—H5A···O1iii | 0.93 (2) | 1.74 (2) | 2.6691 (13) | 175.7 (18) |
N1—H1B···O3 | 0.910 (19) | 1.924 (19) | 2.8241 (15) | 169.5 (16) |
O2—H2A···O3 | 1.10 (2) | 1.29 (2) | 2.3860 (14) | 174 (2) |
C12—H12···O1iii | 0.93 | 2.53 | 3.2041 (15) | 129 |
C10—H10···O2 | 0.93 | 2.55 | 3.3932 (15) | 150 |
Symmetry codes: (i) −x+3, −y+2, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1. |
Phthalic acid forms hydrogen phthalate salts with various organic and other compounds. Reported hydrogen phthalates include calcium phthalate monohydrate (Schuckmann et al., 1978), lithium hydrogen phthalate monohydrate (Küppers et al., 1985), tetramethyl ammonium hydrogen phthalate (Jessen, 1990), 2,4,6-triamino-1,3,5-triazinium hydrogen phthalate (Janczak & Perpétuo, 2001) and N,N'–diphenyl gunadinium dihydrogen phthalate (Pereira Silva et al., 2006). Analysis of the structures archived in the Cambridge Structural Database (Allen, 2002) shows that hydrogen phthalate ions of phthalate salts occur in two different forms: (i) nonplanar, where both the carboxyl (COOH) and the carboxylate (COO-) groups are twisted out of the plane of the benzene ring (Jessen, 1990; Janczak & Perpétuo, 2001; Jin et al., 2003), and (ii) planar, in which both the COOH and the COO- groups are coplanar with the benzene plane (Küppers, 1978). The planarity is achieved through an extraordinarily short intramolecular hydrogen bond linking the carboxyl and carboxylate groups (O···O ≈ 2.4 Å; Küppers et al., 1985; Steiner & Saenger, 1994). This intramolecular hydrogen bond with an S(7) graph set motif is a common occurrence in 1,2-substituted dicarboxylic acids (Leiserowitz, 1976). Hydrogen phthalates also form supramolecular assemblies, such as extended chains, ribbons and three-dimensional networks (Dale et al., 2004; Ballabh et al., 2005). In order to understand the nature of the intramolecular hydrogen bond and the N—H···O and O—H···O hydrogen-bond-assisted supramolecular motifs and networks, the crystal structures of three hydrogen phthalate salts were determined (Scheme 1).
The asymmetric unit of PCAHP (Fig. 1) contains a 4-chloroanilinium cation and a hydrogen phthalate anion. The hydrogen phthalate anion is almost planar except for the two carboxyl groups. The plane defined by the atoms of the COO- group with respect to the least-squares plane of the benzene ring is almost perpendicular, with an angle of 76.7 (1)°, while the plane defined by the COOH group is inclined at an angle of 16.8 (2)°. Similar out-of-plane and near-in-plane twisting is also found in the structures of ammonium hydrogen phthalate (Smith, 1975) and tetramethylammonium hydrogen phthalate (Jessen, 1990). Within the benzene ring the endocyclic angles at C1 and C2 are significantly smaller than 120° [119.0 (2) and 118.7 (2)°, respectively], compensating for the substitutional effects of the COO- and COOH groups. The C—C bond length joining the COO- group [C1—C7 = 1.508 (3) Å] is slightly longer than that of the COOH group [C2—C8 = 1.488 (3) Å] as a result of the dissociation of the H atom from the carboxyl group substituted at C1 to the neighboring 4-chloroaniline, making an acid–base salt (Janczak & Perpétuo, 2001). The 4-chloroanilinium cation shows characteristic values of bond lengths and angles, which are consistent with those of other reported structures (Glidewell et al., 2005). The C—N distance of the 4-chloroanilinium cation [C9—N1= 1.457 (3) Å] is longer than the C—N distance (C—N = 1.386 Å) of neutral p–chloroaniline. This lengthening is observed when the amine N atom of the p–chloroaniline accepts an H atom from the carboxyl group of phthalic acid (Markworth et al., 1987; Glidewell et al., 2005).
Both 2HAHP and 3HAHP crystallize in P21/c (Figs. 2 and 3). The asymmetric unit of 2HAHP comprises of two sets of hydrogen phthalate anions and 2-hydroxyanilinium cations, whereas 3HAHP contains only one hydrogen phthalate anion and one 3-hydroxyanilinium cation. The hydrogen phthalate anions of 2HAHP and 3HAHP are almost planar with distinctly asymmetric intramolecular hydrogen bonds (Jin et al., 2000). The non-centered H atoms H2AA, H2BA and H2A are found at distances of 1.05 (2), 1.11 (2) and 1.10 (2) Å from O2A, O2B and O2, and 1.34 (3), 1.28 (2) and 1.29 (2) Å from O3A, O3B and O3 of 2HAHP and 3HAHP in the short intramolecular hydrogen bonds O2A—H2AA···O3A, O2B—H2BA···O3B and O2—H2A···O3, respectively (Tables 2 and 3), with similar values as reported in related structures (Jessen & Küppers, 1991; Barrett et al., 1995). Formation of this intramolecular hydrogen bond is responsible for the lengthening of the C1—C2 bond [C1A—C2A = 1.412 (2) Å and C1B—C2B = 1.411 (2) Å for 2HAHP, and C1—C2 = 1.412 (2) Å for 3HAHP], where both the carboxy groups are substituted (Langkilde et al., 2004). The considerable strain produced by the presence of the intramolecular hydrogen bond within the molecule causes some displacement of the inner O atoms O2A, O3A, O2B and O3B (2HAHP) and O2 and O3 (3HAHP) (Adiwidjaja & Küppers, 1978). The dihedral angles between the least-squares plane of the benzene ring and the carboxyl–carboxylate groups are 3.2 (2)° (O1A/C7A/O2A), 2.0 (1)° (O3A/C8A/O4A), 11.8 (1)° (O1B/C7B/O2B), 13.5 (1)° (O3B/C8B/O4B) and 14.3 (1)° (O1/C7/O2), 5.5 (1)° (O3/C8/O4), respectively, for 2HAHP and 3HAHP. The cations of both the phthalate salts show normal aromatic C—C bond length value except for the bond distances C10—C11 [1.388 (2) Å] and C11—C12 [1.389 (2) Å] of the 3-hydroxyanilinium cation, which is slightly greater than the other C—C bond distances. This lengthening is due to the OH group substituted at C11, which is involved in a strong intermolecular interaction with the nearby cations and anions. The C—N bond lengths [C9A—N1A = 1.455 (2) Å and C9B—N1B = 1.452 (2) Å] of the 2-hydroxyanilinium cation and [C9—N1 = 1.468 (2) Å] and of the 3-hydroxyanilinium cation are longer than the C—N bond distance of neutral 2-hydroxyaniline and 3-hydroxyaniline (Allen et al., 1997) as a result of the proton transfer from the acid to the amine group of the base.
The hydrogen-bonded supramolecular motifs and network of PCAHP, 2HAHP and 3HAHP are determined primarily by the combination of N—H···O and O—H···O hydrogen bonds. In PCAHP, the hydrogen phthalate anions alone form chains through O3—H3A···O1iii [symmetry code: (iii) -x + 1, y + 1/2, -z + 1/2] hydrogen bonds running parallel to the [010] direction, forming a C(7) motif (Bernstein et al., 1995) generated by a 21 screw axis along (1/2, y, 1/2). In addition, along with the C(7) chain, N1—H1C···O1ii [symmetry code: (ii) -x + 1, y - 1/2, -z + 1/2] and N1—H1A···O2 hydrogen bonds form an infinite chain of edge fused R33 (13) rings parallel to the [010] {same direction as above?} direction. The third hydrogen bond, N1—H1B···O2i [symmety code: (i) -x + 1, -y, -z + 1] links these parallel chains with a hydrogen-bond motif of R24(8), which leads to a two-dimensional supramolecular sheet spreading infinitely in the (100) plane, as shown in Fig. 4. These supramolecular sheets are further strengthened by C13—H13···O1iii and C14—H14···O3 interactions. Overall, the N—H···O and O—H···O hydrogen bonds along with the C—H···O interactions link adjacent anions and cations to one another to form a network measuring one-unit-cell thickness and extending parallel to the [001] and [010] directions, with the sheets arranged in the form of a sandwich. The adjacent layers of the molecular network are linked through Cl···Cl interactions.
In 2HAHP, the A and B hydrogen phthalate anions are coplanar, facing opposite to each other, while their corresponding 2-hydroxyanilinium cations are linked to the anions through N1A—H1AB···O1Ai, N1A—H1AC···O3Bii, N1B—H1BA···O1B and N1B—H1BC···O3Av [symmetry codes: (i) x, -y + 1/2, z - 1/2; (ii) -x + 1, y + 1/2, -z + 1/2; (v) -x + 1, -y, -z + 1] hydrogen bonds with the phenyl planes of the A and B cations lying almost perpendicular to the planar A and B hydrogen phthalate ions. These N—H···O bonds result in a supramolecular R44(16) motif, which forms the asymmetric unit of A and B anion–cation pairs. Such units are joined together through two O—H···O hydrogen bonds, O5A—H5AA···O4Aiii and O5B—H5BA···O4Bvi [symmetry codes: (iii) x + 1, -y + 1/2, z - 1/2; (vi) x + 1, y, z], to generate a supramolecular R44(18) motif, which creates a chain of alternately fused R44(16) and R44(18) motifs extending parallel to the [100] direction, as shown in Fig. 5. The inversion-related antiparallel supramolecular chains are interlinked by N1A—H1AA···O1Bi and N1B—HIBB···O5Biv [symmetry code: (iv) -x + 2, -y, -z + 1] hydrogen bonds forming an infinite supramolecular chain extending along the [100] direction, illustrated in Fig. 6. In this supramolecular network the inversion-related B cations are connected to each other through N1B—H1BB···O5Biv hydrogen bonds to form an R22(10) dimer lying on the inversion center of the P21/c space group symmetry. The infinitely extending networks parallel to the [100] direction formed through all possible N—H···O and O—H···O hydrogen bonds along with C—H···O interactions are interconnected through C14A—H14A···O1B and C13A—H13A···O5A interactions. The centroid–centroid separation distance between the A and B 2-hydroxyanilinium cations is approximately 3.67 Å.
The hydrogen phthalate anions and 3-hydroxyanilinium cations of 3HAHP are linked through N1—H1A···O4viii [symmetry code: (viii) -x+3, -y+2, -z+1] and N1—H1B···O3 hydrogen bonds to form a supramolecular motif of type R44(12) (Fig. 7). An O5—H5A···O1x [symmetry code: (x) -x+1, -y+1, -z+1] hydrogen bond links these ionic pairs, resulting in an extended infinite supramolecular chain. All molecules link into a two-dimensional network parallel with the (001) plane. Apart from these N—H···O and O—H···O hydrogen bonds, two C—H···O hydrogen bonds, viz. C12—H12···O1x and C10—H10···O2 further strengthen the chain. The C10—H10···O2 and O5—H5A···O1x hydrogen bonds form a supramolecular R44(16) motif in addition to other supramolecular R12(6) and R22(8) motifs through N1—H1A···O4i and C12—H12···O1iii, and C10—H10···O2 and N1—H1B···O3 hydrogen bonds, respectively. The formation of R44(12), R44(16), R12(6) and R22(8) motifs constituting the supramolecular chain is shown in Fig. 7. Parallel arrays of these chains are linked through N1—H1C···O5ix hydrogen bonding [symmetry code: (ix) x+1, y, z], thus building up an extended two-dimensional network parallel to the (001) plane.