organic compounds
Table 1
Selected bond lengths (A).
p-phenylazoanilinium phenylphosphonate (Mahmoudkhani &
Langer, 2002) or tris(methylammonium) hydrogen phosphate
˚
´
dihydrogen phosphate (Fabry et al., 2006).
P1—O1
P1—O2
P1—O3
P1—O4
P2—O5
P2—O6
1.5588 (16)
P2—O7
P2—O8
P3—O9
P3—O10
P3—O11
P3—O12
1.5007 (16)
1.5211 (15)
1.5632 (15)
1.5607 (16)
1.5034 (16)
1.5169 (15)
Considering the strength of the N—Hꢀ ꢀ ꢀO hydrogen bonds
in (I), it can be assumed that their dynamics have an impact on
proton mobility along the strong O—Hꢀ ꢀ ꢀO hydrogen bonds
and vice versa. The strength of both O—Hꢀ ꢀ ꢀO and N—Hꢀ ꢀ ꢀO
hydrogen bonds is also documented by the absence of stan-
dard ꢀ(OH) and ꢀ(NH) bands in the IR spectrum of (I) and
their replacement with a diffuse asymmetric band rising slowly
1.5631 (16)
1.4972 (16)
1.5133 (16)
1.5574 (15)
1.5623 (16)
Table 2
Hydrogen-bond geometry (A, ).
ꢃ
˚
from ꢂ2000 cmꢁ1 and ending sharply at ꢂ3600 cmꢁ1
.
Despite favorable centroid–centroid distances between the
phenyl rings, their mutual orientations effectively prevent the
formation of ꢁ–ꢁ interactions.
The letters in the rightmost column are the bond labels used in Fig. 4.
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
Label
O1—H1ꢀ ꢀ ꢀO11iii
O2—H2ꢀ ꢀ ꢀO8iv
O5—H5ꢀ ꢀ ꢀO4ii
O6—H6ꢀ ꢀ ꢀO3i
O9—H9ꢀ ꢀ ꢀO12v
O10—H10ꢀ ꢀ ꢀO7
N11—H11Aꢀ ꢀ ꢀO8i
N11—H11Cꢀ ꢀ ꢀO3
N11—H11Cꢀ ꢀ ꢀO4
N11—H11Bꢀ ꢀ ꢀO7
0.84
0.84
0.84
0.84
0.84
0.84
1.76
1.81
1.77
1.75
1.81
1.78
2.563 (2)
2.627 (2)
2.592 (2)
2.545 (2)
2.636 (2)
2.541 (2)
158
165
164
157
166
150
Experimental
Aniline (99.8%, Acros) was purified via the preparation of anilinium
chloride as follows. Raw aniline was mixed with 2 M HCl with cooling
and the solution filtered through active carbon. The filtrate was
concentrated in vacuo and crystallization of anilinium chloride was
carried out in a refrigerator. The crystals were filtered off and washed
with a small amount of cold water. The wet product was dissolved in
water subsequently alkalized by the addition of NaHCO3, and the
mixture was extracted with chloroform four times. The organic phases
were collected, washed once with water and dried using anhydrous
Na2SO4. After filtration, the solution was evaporated in vacuo,
providing purified aniline. This was mixed with ꢂ0.03 M H3PO4
(Lachema, pure 85%), the concentration of which was determined by
titration on methyl orange, in a 1:1.5 molar ratio. The resulting
mixture was stirred with heating at 313 K and further diluted in order
to dissolve the small amount of salts formed immediately upon
mixing. Finally, the solution was filtered and the filtrate was left to
crystallize very slowly in air at room temperature.
0.91
0.91
0.91
0.91
1.93
2.39
2.40
1.83
2.839 (3)
2.917 (2)
3.296 (3)
2.743 (3)
174
117
169
179
a
b
c
d
N21—H21Aꢀ ꢀ ꢀO8
N21—H21Bꢀ ꢀ ꢀO12
N21—H21Cꢀ ꢀ ꢀO3
N21—H21Aꢀ ꢀ ꢀO7
0.91
0.91
0.91
0.91
2.01
1.88
1.91
2.59
2.924 (2)
2.791 (2)
2.819 (2)
3.075 (2)
177
177
176
114
e
f
g
h
N31—H31Bꢀ ꢀ ꢀO11
N31—H31Aꢀ ꢀ ꢀO11iii
N31—H31Bꢀ ꢀ ꢀO12
N31—H31Cꢀ ꢀ ꢀO4iii
0.91
0.91
0.91
0.91
2.49
1.85
2.15
1.94
2.965 (2)
2.757 (2)
3.051 (2)
2.849 (3)
113
174
174
172
i
j
k
l
Symmetry codes: (i) ꢁx + 1, ꢁy + 1, ꢁz; (ii) x + 1, y, z; (iii) ꢁx, ꢁy + 1, ꢁz + 1; (iv) x ꢁ 1,
y, z; (v) ꢁx + 1, ꢁy + 1, ꢁz + 1.
fixed, while the torsion angles were allowed to refine with starting
positions based on the circular Fourier synthesis averaged using the
local threefold axis, with Uiso(H) = 1.2Ueq(N) and a constrained
˚
N—H distance of 0.98 A. The positions of the H atoms of the dihy-
drogen phosphate anions were constrained to an ideal geometry,
Crystal data
C6H8N+ꢀH2PO4
Mr = 191.12
Triclinic, P1
ꢄ = 83.016 (2)ꢃ
V = 1243.71 (8) A
Z = 6
Mo Kꢂ radiation
ꢅ = 0.31 mmꢁ1
T = 150 K
0.18 ꢅ 0.18 ꢅ 0.05 mm
ꢁ
3
˚
˚
a = 8.8040 (3) A
˚
keeping the O—H bond length fixed at 0.84 A, while the O—H
˚
b = 10.4220 (4) A
˚
c = 14.0890 (6) A
vectors were allowed to rotate about the P—O bonds, and with
Uiso(H) = 1.2Ueq(O).
ꢂ = 86.418 (2)ꢃ
ꢃ = 75.8890 (19)ꢃ
Data collection: COLLECT (Nonius, 1998) and DENZO (Otwi-
nowski & Minor, 1997); cell refinement: COLLECT and DENZO;
data reduction: COLLECT and DENZO; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
DIAMOND (Brandenburg, 2000); software used to prepare material
for publication: PLATON (Spek, 2009).
Data collection
Nonius KappaCCD area-detector
diffractometer
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
Tmin = 0.919, Tmax = 0.987
23949 measured reflections
6720 independent reflections
3848 reflections with I > 2ꢆ(I)
Rint = 0.067
Refinement
Financial support from Charles University, Prague, through
project No. GAUK 13350, is acknowledged. This work was
also partially supported by the Slovak Grant Agency VEGA
under contract No. 2/0150/09.
R[F2 > 2ꢆ(F2)] = 0.051
wR(F2) = 0.144
S = 1.00
334 parameters
H-atom parameteꢁrs3 constrained
˚
Áꢇmax = 0.35 e A
ꢁ3
˚
6720 reflections
Áꢇmin = ꢁ0.57 e A
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: LG3072). Services for accessing these data are
described at the back of the journal.
Aromatic H atoms were constrained to an ideal geometry and
˚
refined using a riding model, with C—H = 0.95 A and Uiso(H) =
1.2Ueq(C). For the NH3 groups, C—N—H angles (109.5ꢃ) were kept
C6H8N+ꢀH2PO4
o59
ꢁ
ꢄ
Acta Cryst. (2012). C68, o57–o60
Kaman et al.