Syn and anti conformations in 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl] benzoic acid and two related salts

Article abstract of DOI:10.1107/S2053229614007827

The crystal structures of 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoic acid, C₁₃H₉N₃O₅, (I), ammonium 2-hydroxy-5-[(E)-phenyldiazenyl]benzoate, NH4 ⁺ C₁₃H ₉N₂O₃ ^-, (II), and sodium 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoate trihydrate, Na⁺ C₁₃H₈N₃O₅ ^- 3H2O, (III), have been determined using single-crystal X-ray diffraction. In (I) and (III), the phenyldiazenyl and carboxylic acid/carboxylate groups are in an anti orientation with respect to each other, which is in accord with the results of density functional theory (DFT) calculations, whereas in (II), the anion adopts a syn conformation. In (I), molecules form slanted stacks along the [100] direction. In (II), anions form bilayers parallel to (010), the inner part of the bilayers being formed by the benzene rings, with the -OH and -COO ^- substituents on the bilayer surface. The NH₄⁺ cations in (II) are located between the bilayers and are engaged in numerous N-H?O hydrogen bonds. In (III), anions form layers parallel to (001). Both Na⁺ cations have a distorted octahedral environment, with four octahedra edge-shared by bridging water O atoms, forming [Na₄(H ₂O)₁₂]⁴⁺ units.

Full text of DOI:10.1107/S2053229614007827

research papers
Acta Crystallographica Section C
methoxyphenyldiazenyl)salicylic acid (Basu Baul et al., 2000)
and 5-(phenyldiazenyl)salicylic acid (Saikia et al., 2012), and
one structure of a molecular complex, that of 5-(phenyl-
diazenyl)salicylic acid with dimethylpyrazole (Xu et al., 2011),
have been reported so far, and no structures of such salts with
alkaline metals or ammonium cations have been described.
Structural Chemistry
ISSN 2053-2296
syn and anti conformations in
2
-hydroxy-5-[(E)-(4-nitrophenyl)-
diazenyl]benzoic acid and two
related salts
Alexandr V. Yatsenko and Ksenia A. Paseshnichenko*
Department of Chemistry, Moscow State University, 119991 Moscow, Russian
Federation
Correspondence e-mail: ksenia@struct.chem.msu.ru
Received 4 March 2014
Accepted 8 April 2014
The crystal structures of 2-hydroxy-5-[(E)-(4-nitrophenyl)-
diazenyl]benzoic acid, C H N O , (I), ammonium 2-hydroxy-
1
3
9
3
5
+
4
À
5
-[(E)-phenyldiazenyl]benzoate, NH ÁC H N O , (II), and
13
9
2
3
sodium 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoate
+
À
trihydrate, Na ÁC H N O Á3H O, (III), have been deter-
1
3
8
3
5
2
mined using single-crystal X-ray diffraction. In (I) and (III),
the phenyldiazenyl and carboxylic acid/carboxylate groups are
in an anti orientation with respect to each other, which is in
accord with the results of density functional theory (DFT)
calculations, whereas in (II), the anion adopts a syn
conformation. In (I), molecules form slanted stacks along
the [100] direction. In (II), anions form bilayers parallel to
In the course of our studies on the structures of azo dyes
Aslanov et al., 2009), we have determined the X-ray crystal
(
structures of three compounds, viz. 2-hydroxy-5-[(E)-(4-
nitrophenyl)diazenyl]benzoic acid (C. I. Mordant Orange 1),
(I), the ammonium salt of (I), denoted (II), and the sodium
salt trihydrate of (I), denoted (III) (see Scheme above).
(010), the inner part of the bilayers being formed by the
benzene rings, with the –OH and –COO substituents on the
À
+
bilayer surface. The NH4 cations in (II) are located between
the bilayers and are engaged in numerous N—HÁ Á ÁO
hydrogen bonds. In (III), anions form layers parallel to
(
ment, with four octahedra edge-shared by bridging water O
+
001). Both Na cations have a distorted octahedral environ-
2. Experimental
2.1. Synthesis and crystallization
4
+
atoms, forming [Na (H O) ] units.
4
2
12
Diazo-coupling of 4-nitroaniline and 2-hydroxybenzoic acid
Keywords: crystal structure; syn/anti conformations; 2-hydroxy-
-[(E)-(4-nitrophenyl)diazenyl]benzoic acid; ammonium
salicylate salt; sodium salicylate salt; dyes; DFT calculations.
in alkaline solution afforded compound (I) in 48% yield.
Recrystallization from a toluene–acetone (3:1 v/v) mixture
gave red–orange crystals (prisms). Dropwise addition of a 10%
ammonia solution to a solution of 5-(phenyldiazenyl)salicylic
acid in ethanol until a pH of 7–8 was attained afforded
compound (II) in 77% yield. Recrystallization from a water–
ethanol (3:1 v/v) mixture gave dark-yellow crystals (plates).
Dropwise addition of an NaOH solution to a solution of 5-[(4-
nitrophenyl)diazenyl]salicylic acid in ethanol until a pH of 7–8
was attained afforded compound (III) in 72% yield. Recrys-
tallization from water gave dark-yellow crystals (prisms).
5
1
. Introduction
Arylazo derivatives of salicylic (2-hydroxybenzoic) acid and
their salts have been used as dyes for many years. A search of
the Cambridge Structural Database (CSD, Version 5.35; Allen,
2002) for the 5-phenylazosalicylic acid residue yielded 56 hits,
including coordination and organometallic compounds and
containing 109 such fragments. In particular, organotin(IV)
complexes were studied in great detail due to their biological
properties (Basu Baul et al., 2007, and references therein). At
the same time, only two structures of free acids, namely 5-(4-
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. In all three title compounds,
Acta Cryst. (2014). C70, 493–497
doi:10.1107/S2053229614007827
# 2014 International Union of Crystallography 493

research papers
Table 1
Experimental details.
(
I)
(II)
NH
(III)
Crystal data
Chemical formula
+
4
3À
+
ÀÁ3H
C
287.23
Monoclinic, P2
293
4.9319 (5), 11.6649 (14), 21.619 (2)
90, 94.991 (8), 90
1239.0 (2)
4
13
H
9
N
3
O
5
ÁC13
H
9
N
2
O
Na ÁC13
H
8
3
N O
5
2
O
M
r
259.26
Monoclinic, P2
293
6.0471 (1), 34.371 (1), 6.2824 (2)
90, 103.278 (2), 90
1270.85 (6)
4
363.26
Triclinic, P1
Crystal system, space group
Temperature (K)
1
/c
1
/n
293
7.2123 (5), 13.0205 (8), 17.0317 (11)
77.185 (6), 80.933 (5), 83.401 (5)
1534.76 (17)
˚
a, b, c (A)
ꢀ
ꢀ
, ꢁ, ꢂ ( )
˚
3
V (A )
Z
Radiation type
ꢃ (mm )
Crystal size (mm)
4
Cu Kꢀ
1.04
0.12 Â 0.04 Â 0.03
Cu Kꢀ
0.82
0.08 Â 0.05 Â 0.05
Mo Kꢀ
0.16
0.50 Â 0.45 Â 0.40
À1
Data collection
Diffractometer
Absorption correction
Stoe STADI VARI diffractometer
Multi-scan (Blessing, 1995)
0.925, 0.979
Stoe STADI VARI diffractometer
Multi-scan (Blessing, 1995)
0.945, 0.960
Stoe STADI VARI diffractometer
Multi-scan (Blessing, 1995)
0.926, 0.952
Tmin, Tmax
No. of measured, independent and
observed [I > 2ꢄ(I)] reflections
14169, 2334, 1804
15094, 2352, 1561
6773, 5936, 3776
R
int
0.074
0.609
0.052
0.605
0.026
0.617
˚
À1
)
(sin ꢅ/ꢆ)max (A
Refinement
2
2
2
R[F > 2ꢄ(F )], wR(F ), S
No. of reflections
0.041, 0.119, 1.00
2334
0.048, 0.141, 1.04
2352
0.041, 0.120, 0.92
5936
No. of parameters
No. of restraints
H-atom treatment
199
4
189
12
493
22
H atoms treated by a mixture of
independent and constrained
refinement
0.22, À0.18
H atoms treated by a mixture of
independent and constrained
refinement
0.14, À0.16
H atoms treated by a mixture of
independent and constrained
refinement
0.21, À0.27
˚
À3
)
ꢀ
ꢇ
max, ꢀꢇmin (e A
Computer programs: X-AREA (Stoe & Cie, 2012), X-RED32 (Stoe & Cie, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF
Westrip, 2010).
(
O- and N-bound H atoms were located in difference electron-
+
density maps and were refined with restraints. The NH4
cation in (II) was refined with distance restraints N—H =
anions and six water molecules. One of these water O atoms
has a large anisotropic displacement parameter value and is
˚
˚
0
.890 (5) A and HÁ Á ÁH = 1.453 (5) A, and with U (H) =
iso
1.5U (N), so as to provide the tetrahedral structure of the
ammonium cation. The H O molecules in (III) were refined
eq
2
˚
with distance restraints O—H = 0.820 (3) A and HÁ Á ÁH =
˚
.300 (5) A, and with U (H) = 1.5U (O), so as to provide a
1
H—O—H angle of 105 . The carboxylic acid group in (I) was
iso
eq
ꢀ
˚
refined with distance restraints O3—H13 = 0.820 (1) A and
˚
C13Á Á ÁH13 = 1.761 (1) A so as to reproduce the C—O—H
ꢀ
angle of 109 observed in salicylic acid (neutron structure
determination; Bacon & Jude, 1973). The phenol groups in (I)
and (II) were refined with distance restraints O1—H1 =
˚
˚
0
.820 (1) A and C2Á Á ÁH1 = 1.769 (1) A so as to reproduce the
ꢀ
C—O—H angle of 107 observed in salicylic acid (neutron
structure determination; Bacon & Jude, 1973). In (III), the
˚
corresponding restraints were O1—H1 = 0.820 (1) A and
˚
ꢀ
C2Á Á ÁH1 = 1.789 (1) A, and the C—O—H angle was 109 . All
C-bound H atoms were placed in idealized positions, with
˚
distance restraints of C—H = 0.93 A (SHELXL AFIX 43
instruction; Sheldrick, 2008) and with U (H) = 1.2U (C).
iso eq
3
. Results and discussion
For neutral salicylic acid (I) (Fig. 1) and its ammonium salt (II)
Fig. 1), there is one formula unit in the asymmetric part of the
unit cell, whereas the structure of sodium salt trihydrate (III)
(
Figure 1
Views of (a) (I) and (b) (II), showing the atom-numbering schemes.
Displacement ellipsoids are drawn at the 50% probability level.
(Fig. 2) contains two symmetry-independent cations, two
+
4
+
ꢁ
4
94 Yatsenko and Paseshnichenko
13 9 3
C H N O
5
and the NH
and Na salts
Acta Cryst. (2014). C70, 493–497

research papers
Table 2
Selected interatomic distances (A) in (I)–(III) compared with closely related structures.
˚
a
b
c
d,e
d
Distance
(I)
(II)
(III)
(III)A
ACEFIZ
FUGYIP
EXIZUH1
EXIZUH2
O1—C2
C1—C2
C1—C13
C5—N1
N1—N2
N2—C7
O2—C13
O3—C13
O1Á Á ÁO2
1.3400 (17)
1.403 (2)
1.350 (3)
1.419 (3)
1.500 (3)
1.421 (3)
1.249 (3)
1.428 (3)
1.265 (3)
1.246 (3)
2.524 (3)
1.352 (3)
1.399 (2)
1.503 (3)
1.420 (3)
1.266 (3)
1.419 (3)
1.286 (3)
1.257 (3)
2.534 (3)
1.347 (3)
1.421 (3)
1.496 (3)
1.405 (3)
1.245 (3)
1.420 (3)
1.281 (3)
1.234 (3)
2.532 (2)
1.354 (3)
1.401 (3)
1.454 (3)
1.451 (3)
1.246 (3)
1.431 (3)
1.240 (2)
1.313 (2)
2.630 (2)
1.355 (2)
1.403 (3)
1.462 (3)
1.432 (2)
1.260 (2)
1.424 (2)
1.241 (2)
1.311 (2)
2.631 (2)
1.350 (4)
1.396 (5)
1.479 (4)
1.413 (4)
1.242 (3)
1.431 (4)
1.229 (4)
1.300 (4)
2.574 (3)
1.362 (4)
1.397 (4)
1.482 (5)
1.421 (4)
1.245 (3)
1.437 (4)
1.228 (4)
1.290 (4)
2.605 (3)
1.4653 (19)
1.4213 (19)
1.2519 (19)
1.4256 (19)
1.2290 (17)
1.3081 (19)
2.619 (2)
Notes: (a) the second anion in (III) is labelled with the letter ‘A’; (b) 5-(phenyldiazenyl)salicylic acid (Saikia et al., 2012); (c) 5-(4-methoxyphenyldiazenyl)salicylic acid (Basu Baul et al.,
2000); (d) the molecular complex of 5-(phenyldiazenyl)salicylic acid with dimethylpyrazole (Xu et al.; 2011); (e) the structure contains two symmetry-independent molecules.
probably partially disordered. Acid molecule (I) and the
related anions in (II) and (III) are basically planar; the r.m.s.
with this, in the anions in (II) and (III), the O1Á Á ÁO2 distances
˚
are on average 0.1 A shorter than those in neutral molecule (I)
˚
deviations from the mean planes are 0.215 and 0.141 A,
˚
respectively, for (I) and (II), and 0.117 and 0.084 A for the two
independent anions of (III). The largest dihedral angle
between the mean planes of the two benzene rings is observed
and ACEFIZ, that is, the internal hydrogen bonds in the
anions are stronger than those in the neutral molecules.
Analogous tendencies in bond lengths are also observed in the
structures of salts of salicylic acid (Klepeis et al., 2009, and
references therein). The nitro groups in (I) and (III) do not
cause any noticeable changes in the bond lengths and
hydrogen-bonding parameters compared with those in
ACEFIZ and (II).
In (I) and (III), the phenyldiazenyl and carboxylic acid/
carboxylate groups are positioned anti to each other with
respect to the C5—N1 bond, whereas in (II), the anion adopts
a syn conformation. The predominance of anti conformers is
ꢀ
ꢀ
in (I) [21.00 (7) ]; this angle is 4.9 (1) in (II), and 7.5 (1) and
ꢀ
4.7 (1) in (III). Such an essentially flat geometry is typical for
most of the similar azo compounds, because the barrier to
rotation about the N—C bond in these compounds is ca
À1
40 kJ mol (Yazici et al., 2011). All three studied structures
contain intramolecular O—HÁ Á ÁO hydrogen bonds between
the hydroxy and carboxylic acid (or carboxylate) groups,
which further contribute to stabilization of the planarity of the
molecules and anions (Tables 2 and 3).
Comparison of neutral molecule (I) and 5-(phenyldiazen-
yl)salicylic acid (CSD refcode ACEFIZ; Saikia et al., 2012)
with the anions in (II) and (III) demonstrates that in the
anions the C—C bonds between the benzene ring and the
Table 3
Hydrogen-bonding geometry (A, ) in (I)–(III).
˚
ꢀ
D—HÁ Á ÁA
D—H
HÁ Á ÁA
DÁ Á ÁA
D—HÁ Á ÁA
˚
carboxylate group are longer by 0.04 A on average and the
C—O bond lengths in the latter group are more equal
(I)
O1—H1Á Á ÁO2
0.820 (14)
0.820 (14)
0.820 (13)
0.93
1.895 (14)
2.420 (14)
1.847 (14)
2.38
2.6189 (16)
3.0461 (18)
2.6651 (16)
3.202 (2)
146.8 (14)
134.0 (13)
176.4 (14)
147
a
O1—H1Á Á ÁO4
(Table 2). It should be noted that in the neutral molecules, the
shorter C O bonds are oriented towards the –OH group,
whereas in the anions, the C—O bonds adjacent to the –OH
˚
groups become longer (by 0.02–0.05 A) than the C—O bonds
not participating in intramolecular hydrogen bonding. Along
b
O3—H13Á Á ÁO2
c
C4—H4Á Á ÁO5
(II)
O1—H1Á Á ÁO2
N3—H21Á Á ÁO3
N3—H22Á Á ÁO2
N3—H23Á Á ÁO1
N3—H24Á Á ÁO3
0.82 (2)
0.89 (2)
0.89 (2)
0.89 (2)
0.89 (2)
1.78 (2)
1.99 (2)
1.91 (2)
2.38 (2)
1.91 (2)
2.524 (3)
2.788 (3)
2.779 (3)
3.052 (3)
2.799 (3)
151 (2)
150 (2)
164 (2)
132 (2)
172 (2)
d
e
f
(III)
O1—H1Á Á ÁO2
0.820 (11)
0.820 (10)
0.82 (2)
0.82 (2)
0.82 (2)
0.82 (2)
0.82 (2)
0.82 (2)
0.82 (3)
0.82 (3)
0.82 (3)
0.82 (2)
0.82 (4)
0.82 (3)
0.93
1.796 (17)
1.804 (18)
1.93 (2)
2.04 (2)
2.32 (2)
2.14 (3)
2.00 (2)
2.02 (2)
2.04 (2)
2.18 (2)
2.09 (3)
2.21 (2)
2.19 (5)
2.48 (5)
2.55
2.534 (3)
2.532 (3)
2.750 (2)
2.862 (2)
3.135 (3)
2.823 (3)
2.819 (3)
2.813 (3)
2.838 (3)
2.931 (3)
2.828 (3)
2.917 (3)
2.892 (4)
2.972 (4)
3.358 (3)
3.125 (3)
148.9 (16)
147.3 (17)
174 (3)
173 (2)
175 (2)
141 (2)
172 (2)
161 (3)
163 (3)
152 (3)
150 (3)
145 (3)
144 (4)
119 (4)
146
O1A—H1AÁ Á ÁO2A
g
O20—H21Á Á ÁO3A
h
O20—H22Á Á ÁO2
i
O30—H31Á Á ÁO5
j
O30—H32Á Á ÁO3A
j
O40—H41Á Á ÁO2A
k
O40—H42Á Á ÁO3
l
O50—H51Á Á ÁO60
O50—H52Á Á ÁO5A
h
O60—H61Á Á ÁO3
g
O60—H62Á Á ÁO2A
l
O70—H71Á Á ÁO50
m
O70—H72Á Á ÁO1A
g
C12—H12Á Á ÁO5A
i
C12A—H12AÁ Á ÁO5
0.93
2.34
141
Figure 2
1
2
1
2
1
2
1
2
Symmetry codes: (a) x + 2, Ày + , z À ; (b) Àx + 3, Ày + 1, Àz; (c) Àx, y À , Àz + ; (d)
A view of the two symmetry-independent molecules of (III), showing the
atom-numbering scheme. Displacement ellipsoids are drawn at the 50%
probability level.
x À 1, y, z + 1; (e) x À 1, y, z; (f) Àx + 1, Ày, Àz + 2; (g) Àx, Ày + 1, Àz + 1; (h) Àx, Ày + 1,
Àz; (i) Àx + 1, Ày, Àz + 1; (j) Àx + 1, Ày + 1, Àz + 1; (k) Àx + 1, Ày + 1, Àz; (l) Àx, Ày + 2,
Àz; (m) x, y + 1, z À 1.
+
4
+
ꢁ
Acta Cryst. (2014). C70, 493–497
Yatsenko and Paseshnichenko
13 9 3
C H N O
5
and the NH
and Na salts 495

research papers
Table 4
Results of DFT calculations for an isolated molecule of 2-hydroxy-5-
(phenyldiazenyl)benzoic acid, for the same molecule placed in a
polarizable continuum with parameters simulating acetone, for two
molecules bound as a dimer by a pair of hydrogen bonds between the
carboxylate groups and for the anion of 2-hydroxy-5-(phenyldiazen-
yl)benzoic acid placed in a polarizable continuum with parameters
simulating acetone.
E (anti)
Hartree)
E (syn)
(Hartree)
E (syn) À
(
E (anti)
À1
(kJ mol
)
Isolated molecule
Molecule in a polarizable
continuum
À836.78754
À836.79481
À836.78666
À836.79419
2.3
1.6
Hydrogen-bonded dimer
Anion in a polarizable
continuum
À1673.60221
À836.32959
À1673.60034
À836.32899
4.9
1.6
evident from an analysis of the CSD data: 83 out of 109
-(phenyldiazenyl)salicylic residues have an anti conformation
and only 26 adopt a syn conformation. In order to rationalize
the predominance of the anti conformation, we performed
DFT calculations of syn and anti conformers for the following
model systems: (i) the isolated molecule of 2-hydroxy-5-
5
Figure 4
The stacking arrangement of anions in (III). Hydrogen bonds are shown
as dashed lines.
continuum model) method (Tomasi et al., 2005, and references
therein). In all the above-mentioned cases, the energy of the
(
phenyldiazenyl)benzoic acid; (ii) the same molecule placed in
a polarizable continuum with parameters simulating acetone;
iii) two molecules bound as a dimer by a pair of hydrogen
À1
anti conformer appeared to be 1.6–2.4 kJ mol lower than
(
that of the syn conformer (see Table 4). This difference is
sufficient for rationalization of the predominance of the anti
conformation.
In (I), similar to ACEFIZ, molecules are paired into
centrosymmetric dimers by two O—HÁ Á ÁO hydrogen bonds
between the carboxylic acid groups (Table 3). Dimers, related
by translation along [100], form slanted stacks; the shortest
bonds between the carboxylate groups; (iv) the anion of this
acid placed into a polarizable continuum with parameters
simulating acetone. Calculations were carried out using
GAUSSIAN98 (Frisch et al., 1998) with a B3LYP exchange-
correlation functional (Becke, 1993; Lee et al., 1988) and a
6–311G** basis set (Krishnan et al., 1980). The effect of
continuum was accounted for by the PCM (polarizable
˚
intermolecular CÁ Á ÁC contact in a stack is 3.393 (2) A
[
C5Á Á ÁC13(x À 1, y, z)]. In contrast to ACEFIZ, where short
contacts between stacks are absent, in (I) neighbouring stacks
are connected by weak C—HÁ Á ÁO and O—HÁ Á ÁO hydrogen
bonds (Table 3). These interactions may explain the large
torsion angle between the aromatic rings in (I). In the struc-
tures of salts (II) and (III), anions also form stacks; in (II),
neighbouring anions in a stack are steeply inclined and related
by an [001] translation, with the shortest CÁ Á ÁC contact being
˚
3
.536 (3) A [C3Á Á ÁC7(x, y, z + 1)] (Fig. 3); in (III), which
contains two symmetry-independent anions, A and B, stacks
are formed via an . . . AABB . . . motif, with two adjacent
anions of each type being related by an inversion centre. The
stack axes are directed along [110]. The shortest CÁ Á ÁC
distances in the stacks are 3.415 (3) [C4Á Á ÁC9(Àx, Ày, Àz + 1)]
˚
and 3.271 (3) A (C2Á Á ÁC11A) between the crystallographically
identical anions and between the symmetry-independent
anions, respectively (Fig. 4). Thus, there is no evidence for
extensive ꢈ–ꢈ interactions in the three structures.
In (II), stacks of anions form bilayers parallel to (010); the
inner part of a bilayer is formed by benzene rings, whereas the
À
OH and –COO groups form the outer layer surface. NH
4
+
–
cations are located between the bilayers and are engaged in
numerous N—HÁ Á ÁO hydrogen bonds (Table 3). In (III),
Figure 3
The crystal packing of (II), viewed along [100], showing the bilayered
structure. Hydrogen bonds are shown as dashed lines.
stacks also form layers parallel to (001). The –NO , –OH and
2
À
+
–COO groups are located on the layer surface, and Na
+
4
+
ꢁ
4
96 Yatsenko and Paseshnichenko
13 9 3
C H N O
5
and the NH
and Na salts
Acta Cryst. (2014). C70, 493–497

research papers
et al., 2007) and n = 16 (Elacqua et al., 2012). Water molecules
are involved in hydrogen bonds with each other and with the
carboxylate O atoms of the anions (Table 3).
The X-ray part of this work was supported by M. V.
Lomonosov Moscow State University ‘Program of Develop-
ment’.
Supporting information for this paper is available from the IUCr
electronic archives (Reference: YF3059).
References
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
Aslanov, L. A., Paseshnichenko, K. A. & Yatsenko, A. V. (2009). Acta Cryst.
E65, o497.
Bacon, G. E. & Jude, R. J. (1973). Z. Kristallogr. 138, 19–40.
Basu Baul, T. S., Dhar, S. & Tiekink, E. R. T. (2000). Acta Cryst. C56, 1280–
1
281.
Figure 5
A view of the [Na
Basu Baul, T. S., Rynjah, W., Rivarola, E., Pettinari, C., Hol cˆ apek, M., Jir a´ sko,
R., Englert, U. & Linden, A. (2007). J. Organomet. Chem. 692, 3625–
3635.
4
+
4
(H
2
O)12
]
Table 3. Displacement ellipsoids are drawn at the 50% probability level.
units in (III). Symmetry codes are as in
Becke, A. D. (1993). J. Chem. Phys. 98, 5648–5652.
Blessing, R. H. (1995). Acta Cryst. A51, 33–38.
Dinoi, C., Taban, G., S o¨ zen, P., Demirhan, P., Daran, J.-C. & Poli, R. (2007).
J. Organomet. Chem. 692, 3743–3749.
Elacqua, E., Kaushik, P., Groeneman, R. H., Sumrak, J. C., Bukar, D.-K. &
MacGillivray, L. R. (2012). Angew. Chem. Int. Ed. 51, 1037–1041.
Frisch, M. J., et al. (1998). GAUSSIAN98. Gaussian Inc., Pittsburgh, PA,
USA.
Klepeis, J.-H. P., Evans, W. J., Zaitseva, N., Schwegler, E. & Teat, S. J. (2009).
Acta Cryst. E65, o2062.
Krishnan, R., Binkley, J. S., Seeger, R. & Pople, J. A. (1980). Chem. Phys. 72,
cations and solvent water molecules are located between the
layers.
+
In (III), both Na cations have a distorted octahedral
+
environment. One Na cation is coordinated by four water
molecules and two O atoms of two crystallographically inde-
pendent anions, one of which provides an O atom from the
À
–COO group and the other an O atom from the NO group.
The second Na cation is coordinated by five water molecules
2
650–654.
+
Lee, C., Yang, W. & Parr, R. G. (1988). Phys. Rev. B, 37, 785–789.
Saikia, J., Saha, B. & Das, G. (2012). RSC Adv. 2, 10015–10018.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
and an O atom of the NO group belonging to the first anion.
2
˚
The Na—O distances are in the range 2.321 (3)–2.680 (2) A
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
and angle deviations from ideal octahedral values attain a
ꢀ
Stoe & Cie (2012). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.
Tomasi, J., Mennucci, B. & Cammi, R. (2005). Chem. Rev. 105, 2999–3094.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
Xu, Y., Jin, S., Zhu, J., Liu, Y.-J. & Shi, C.-C. (2011). Acta Cryst. E67, o2528.
´
Yazici, S., Albayrak, C., G u¨ mr u¨ kc u¨ o gˆ lu, I., Senel, I. & B u¨ y u¨ kg u¨ ng o¨ r, O.
(2011). J. Mol. Struct. 985, 292–298.
value of 23 . Four octahedra are edge-shared by the bridging
4
+
O atoms of water molecules, forming [Na (H O) ] units
4
2
12
4+
(Fig. 5). Similar although not quite identical [Na (H O) ]
clusters are described in the literature, e.g. with n = 14 (Dinoi
4
2
n
+
4
+
ꢁ
Acta Cryst. (2014). C70, 493–497
Yatsenko and Paseshnichenko
13 9 3
C H N O
5
and the NH
and Na salts 497

supplementary materials
supplementary materials
Acta Cryst. (2014). C70, 493-497 [doi:10.1107/S2053229614007827]
syn and anti conformations in 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoic
acid and two related salts
Alexandr V. Yatsenko and Ksenia A. Paseshnichenko
Computing details
For all compounds, data collection: X-AREA (Stoe & Cie, 2012); cell refinement: X-AREA (Stoe & Cie, 2012); data
reduction: X-RED32 (Stoe & Cie, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s)
used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to
prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
(I) 2-Hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoic acid
Crystal data
C
M
13
H
9
N
3
O
5
F(000) = 592.0
= 1.540 Mg m
−3
r
= 287.23
D
x
Monoclinic, P2
1
/c
Melting point: 530 K
Hall symbol: -P 2ybc
a = 4.9319 (5) Å
b = 11.6649 (14) Å
c = 21.619 (2) Å
β = 94.991 (8)°
Cu Kα radiation, λ = 1.54186 Å
Cell parameters from 2234 reflections
θ = 3.8–56.3°
µ = 1.04 mm
T = 293 K
−1
3
V = 1239.0 (2) Å
Needle, red–orange
Z = 4
0.12 × 0.04 × 0.03 mm
Data collection
Stoe STADI VARI
diffractometer
Radiation source: microfocus sealed tube
None monochromator
Detector resolution: 5.81 pixels mm
rotation method scans
14169 measured reflections
2334 independent reflections
1804 reflections with I > 2σ(I)
R
int = 0.074
-1
θmax = 70.0°, θmin = 4.1°
h = −5→6
Absorption correction: multi-scan
k = −14→13
l = −22→26
(Blessing, 1995)
T
min = 0.925, Tmax = 0.979
Refinement
2
Refinement on F
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Least-squares matrix: full
R[F > 2σ(F )] = 0.041
2
2
2
wR(F ) = 0.119
S = 1.00
Hydrogen site location: inferred from
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
2
1
4
334 reflections
99 parameters
restraints
Acta Cryst. (2014). C70, 493-497
sup-1

supplementary materials
2
2
2
−3
w = 1/[σ (F
where P = (F
Δ/σ)max < 0.001
o
) + (0.0832P) ]
Δρmin = −0.18 e Å
Extinction correction: SHELXL97 (Sheldrick,
2
2
o
+ 2F )/3
c
*
2
3
-1/4
(
2008), Fc =kFc[1+0.001xFc λ /sin(2θ)]
Extinction coefficient: 0.0143 (13)
−3
Δρmax = 0.22 e Å
Special details
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.
2
2
Refinement. Refinement of F against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F ,
2
2
2
conventional R-factors R are based on F, with F set to zero for negative F . The threshold expression of F > σ(F ) 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. The C-
bound H atoms were placed in idealized positions, with constrained distances of 0.93 Å and with Uiso(H) = 1.2Ueq(C).
Phenol and carboxylic H atoms were restrained so that to reproduce the C—O—H angle values observed in salicylic acid
(
neutron structure determination, Bacon et al., 1973): 107° for phenol and 109° for COOH group.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
O1
H1
O2
O3
H13
O4
O5
N1
N2
N3
C1
1.1662 (2)
1.259 (4)
1.3733 (2)
1.2554 (2)
1.370 (3)
−0.3794 (3)
−0.3102 (3)
0.5734 (3)
0.4515 (3)
−0.2672 (3)
1.0527 (3)
1.0260 (3)
0.8421 (3)
0.8203
0.16995 (10)
0.2232 (6)
0.37681 (10)
0.50125 (10)
0.5406 (7)
0.26095 (12)
0.44066 (11)
0.30930 (12)
0.22991 (13)
0.34058 (12)
0.31879 (13)
0.20830 (13)
0.13098 (14)
0.0583
−0.01162 (5)
−0.0226 (7)
−0.00850 (5)
0.06235 (6)
0.0471 (7)
0.40909 (6)
0.39742 (6)
0.18177 (6)
0.20677 (6)
0.38566 (6)
0.05999 (6)
0.03457 (6)
0.05774 (7)
0.0404
0.0516 (3)
0.086 (8)*
0.0529 (3)
0.0559 (3)
0.074 (6)*
0.0658 (4)
0.0676 (4)
0.0470 (3)
0.0508 (4)
0.0488 (3)
0.0395 (3)
0.0413 (4)
0.0482 (4)
0.058*
C2
C3
H3
C4
0.6948 (3)
0.5739
0.16214 (14)
0.1101
0.10573 (7)
0.1209
0.0469 (4)
0.056*
H4
C5
0.7233 (3)
0.8975 (3)
0.9122
0.27134 (13)
0.34931 (13)
0.4228
0.13239 (7)
0.10875 (7)
0.1253
0.0423 (4)
0.0417 (4)
0.050*
C6
H6
C7
0.2843 (3)
0.2244 (3)
0.3036
0.26631 (14)
0.37942 (15)
0.4386
0.25364 (7)
0.26665 (7)
0.2457
0.0458 (4)
0.0510 (4)
0.061*
C8
H8
C9
0.0471 (3)
0.0063
0.40402 (15)
0.4796
0.31068 (7)
0.3200
0.0506 (4)
0.061*
H9
C10
C11
H11
C12
H12
C13
−0.0687 (3)
−0.0092 (3)
−0.0872
0.31457 (14)
0.20176 (15)
0.1431
0.34076 (6)
0.32949 (8)
0.3510
0.0435 (4)
0.0522 (4)
0.063*
0.1689 (4)
0.2119
0.17777 (15)
0.1021
0.28548 (8)
0.2771
0.0534 (4)
0.064*
1.2401 (3)
0.40097 (13)
0.03518 (7)
0.0422 (4)
Acta Cryst. (2014). C70, 493-497
sup-2

supplementary materials
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
O1
O2
O3
O4
O5
N1
N2
N3
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
0.0522 (7)
0.0544 (7)
0.0622 (7)
0.0675 (8)
0.0713 (9)
0.0430 (7)
0.0491 (8)
0.0450 (7)
0.0354 (7)
0.0364 (7)
0.0496 (9)
0.0441 (8)
0.0383 (8)
0.0409 (8)
0.0429 (8)
0.0534 (9)
0.0564 (10)
0.0412 (8)
0.0561 (10)
0.0603 (10)
0.0391 (8)
0.0533 (7)
0.0533 (7)
0.0464 (6)
0.0678 (8)
0.0625 (8)
0.0571 (8)
0.0597 (8)
0.0584 (8)
0.0450 (8)
0.0495 (8)
0.0461 (8)
0.0493 (8)
0.0508 (8)
0.0444 (8)
0.0561 (9)
0.0538 (9)
0.0479 (9)
0.0537 (9)
0.0508 (9)
0.0487 (9)
0.0459 (8)
0.0528 (6)
0.0554 (6)
0.0640 (7)
0.0679 (8)
0.0725 (8)
0.0426 (7)
0.0463 (7)
0.0446 (7)
0.0391 (7)
0.0390 (7)
0.0506 (9)
0.0492 (8)
0.0390 (7)
0.0415 (7)
0.0399 (7)
0.0479 (8)
0.0490 (8)
0.0369 (7)
0.0534 (9)
0.0546 (9)
0.0433 (8)
−0.0086 (5)
−0.0111 (5)
−0.0148 (5)
−0.0032 (6)
0.0196 (6)
0.0242 (5)
0.0299 (5)
0.0344 (6)
0.0393 (6)
0.0272 (6)
0.0141 (5)
0.0197 (6)
0.0132 (5)
0.0092 (6)
0.0095 (6)
0.0146 (7)
0.0145 (7)
0.0107 (6)
0.0129 (6)
0.0118 (6)
0.0165 (7)
0.0135 (7)
0.0112 (6)
0.0255 (7)
0.0252 (8)
0.0134 (6)
−0.0106 (5)
−0.0075 (5)
−0.0092 (5)
0.0040 (6)
0.0011 (6)
0.0007 (6)
0.0011 (6)
0.0027 (6)
0.0013 (6)
−0.0021 (6)
−0.0049 (7)
0.0029 (7)
0.0003 (6)
−0.0026 (6)
0.0009 (6)
0.0061 (7)
0.0017 (7)
0.0025 (6)
0.0051 (7)
−0.0009 (7)
−0.0004 (6)
−0.0059 (6)
−0.0077 (6)
0.0076 (6)
−0.0024 (6)
−0.0009 (6)
−0.0083 (7)
−0.0098 (7)
−0.0031 (6)
−0.0043 (6)
−0.0042 (7)
−0.0092 (7)
−0.0008 (7)
0.0014 (7)
−0.0038 (7)
−0.0025 (7)
−0.0035 (6)
Geometric parameters (Å, º)
O1—C2
O1—H1
O2—C13
O3—C13
O3—H13
O4—N3
O5—N3
N1—N2
N1—C5
N2—C7
N3—C10
C1—C6
C1—C2
C1—C13
C2—C3
C3—C4
1.3400 (17)
C3—H3
0.9300
0.820 (14)
1.2290 (17)
1.3081 (19)
0.820 (13)
1.2142 (18)
1.2173 (19)
1.2519 (19)
1.4213 (19)
1.4256 (19)
1.4691 (19)
1.4014 (19)
1.403 (2)
C4—C5
1.400 (2)
0.9300
C4—H4
C5—C6
1.379 (2)
0.9300
C6—H6
C7—C8
1.386 (2)
1.390 (2)
1.378 (2)
0.9300
C7—C12
C8—C9
C8—H8
C9—C10
C9—H9
C10—C11
C11—C12
C11—H11
C12—H12
1.379 (2)
0.9300
1.375 (2)
1.378 (2)
0.9300
1.4653 (19)
1.402 (2)
0.9300
1.367 (2)
C2—O1—H1
C13—O3—H13
N2—N1—C5
N1—N2—C7
O4—N3—O5
O4—N3—C10
107.5 (10)
109.6 (8)
C5—C6—H6
C1—C6—H6
C8—C7—C12
C8—C7—N2
C12—C7—N2
C9—C8—C7
119.7
119.7
113.24 (13)
114.56 (14)
123.55 (13)
118.15 (13)
120.18 (14)
125.06 (14)
114.70 (15)
119.86 (15)
Acta Cryst. (2014). C70, 493-497
sup-3

supplementary materials
O5—N3—C10
C6—C1—C2
C6—C1—C13
C2—C1—C13
O1—C2—C3
O1—C2—C1
C3—C2—C1
C4—C3—C2
C4—C3—H3
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
C6—C5—C4
C6—C5—N1
C4—C5—N1
C5—C6—C1
118.30 (14)
119.29 (13)
120.81 (13)
119.89 (12)
116.31 (13)
124.17 (13)
119.51 (13)
120.22 (14)
119.9
C9—C8—H8
120.1
C7—C8—H8
120.1
C8—C9—C10
C8—C9—H9
118.81 (16)
120.6
C10—C9—H9
C11—C10—C9
C11—C10—N3
C9—C10—N3
C10—C11—C12
C10—C11—H11
C12—C11—H11
C11—C12—C7
C11—C12—H12
C7—C12—H12
O2—C13—O3
O2—C13—C1
O3—C13—C1
120.6
122.48 (14)
118.66 (14)
118.85 (15)
118.38 (15)
120.8
119.9
120.88 (14)
119.6
120.8
120.26 (16)
119.9
119.6
119.40 (13)
117.03 (13)
123.52 (13)
120.64 (14)
119.9
122.43 (13)
121.83 (14)
115.74 (12)
C5—N1—N2—C7
C6—C1—C2—O1
C13—C1—C2—O1
C6—C1—C2—C3
C13—C1—C2—C3
O1—C2—C3—C4
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C6
C3—C4—C5—N1
N2—N1—C5—C6
N2—N1—C5—C4
C4—C5—C6—C1
N1—C5—C6—C1
C2—C1—C6—C5
C13—C1—C6—C5
N1—N2—C7—C8
N1—N2—C7—C12
−175.91 (12)
−179.33 (14)
1.1 (2)
C12—C7—C8—C9
N2—C7—C8—C9
C7—C8—C9—C10
C8—C9—C10—C11
C8—C9—C10—N3
O4—N3—C10—C11
O5—N3—C10—C11
O4—N3—C10—C9
O5—N3—C10—C9
C9—C10—C11—C12
N3—C10—C11—C12
C10—C11—C12—C7
C8—C7—C12—C11
N2—C7—C12—C11
C6—C1—C13—O2
C2—C1—C13—O2
C6—C1—C13—O3
C2—C1—C13—O3
−0.8 (3)
176.20 (15)
−0.4 (3)
0.9 (2)
1.5 (3)
−178.70 (14)
178.64 (14)
−1.6 (2)
−177.25 (14)
−3.1 (2)
176.89 (16)
175.76 (15)
−4.3 (2)
0.3 (2)
1.7 (2)
179.13 (15)
−170.02 (13)
12.4 (2)
−1.4 (3)
177.42 (15)
0.1 (3)
−2.3 (2)
1.0 (3)
−179.96 (13)
1.0 (2)
−176.32 (16)
−178.27 (14)
1.3 (2)
−179.36 (13)
8.5 (2)
1.5 (2)
−174.29 (14)
−178.89 (14)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O1—H1···O2
0.82 (1)
0.82 (1)
0.82 (1)
0.93
1.90 (1)
2.42 (1)
1.85 (1)
2.38
2.6189 (16)
3.0461 (18)
2.6651 (16)
3.202 (2)
147 (1)
134 (1)
176 (1)
147
i
O1—H1···O4
ii
O3—H13···O2
iii
C4—H4···O5
Symmetry codes: (i) x+2, −y+1/2, z−1/2; (ii) −x+3, −y+1, −z; (iii) −x, y−1/2, −z+1/2.
Acta Cryst. (2014). C70, 493-497
sup-4

supplementary materials
(
II) Ammonium 2-hydroxy-5-[(E)-phenyldiazenyl]benzoate
Crystal data
+
−
NH
4
·C13
H
9
N O
2 3
F(000) = 544
= 1.355 Mg m
−3
M
r
= 259.26
D
x
Monoclinic, P2
1
/n
Cu Kα radiation, λ = 1.54186 Å
Cell parameters from 3698 reflections
θ = 5.1–72.1°
µ = 0.82 mm
T = 293 K
Hall symbol: -P 2yn
a = 6.0471 (1) Å
b = 34.371 (1) Å
c = 6.2824 (2) Å
β = 103.278 (2)°
−1
Irregular block, dark yellow
0.08 × 0.05 × 0.05 mm
3
V = 1270.85 (6) Å
Z = 4
Data collection
Stoe STADI VARI
diffractometer
Radiation source: microfocus sealed tube
None monochromator
Detector resolution: 5.81 pixels mm
rotation method scans
15094 measured reflections
2352 independent reflections
1561 reflections with I > 2σ(I)
R
int = 0.052
-1
θmax = 69.0°, θmin = 5.2°
h = −7→6
k = −41→41
l = −7→7
Absorption correction: multi-scan
(Blessing, 1995)
T
min = 0.945, Tmax = 0.960
Refinement
2
Refinement on F
Hydrogen site location: inferred from
neighbouring sites
Least-squares matrix: full
R[F > 2σ(F )] = 0.048
2
2
H atoms treated by a mixture of independent
and constrained refinement
2
wR(F ) = 0.141
2
2
2
S = 1.04
w = 1/[σ (F
o
) + (0.063P) + 0.38P]
2
2
2
1
1
352 reflections
89 parameters
2 restraints
where P = (F
o
+ 2F )/3
c
(Δ/σ)max < 0.001
Δρmax = 0.14 e Å
−
3
−
3
Primary atom site location: structure-invariant
Δρmin = −0.16 e Å
Extinction correction: SHELXL97 (Sheldrick,
direct methods
*
2
3
-1/4
Secondary atom site location: difference Fourier
map
2008), Fc =kFc[1+0.001xFc λ /sin(2θ)]
Extinction coefficient: 0.0052 (7)
Special details
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles;
correlations between s.u.'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 s.u.'s involving l.s. planes.
2
2
Refinement. Refinement of F against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F ,
conventional R-factors R are based on F, with F set to zero for negative F . The threshold expression of F > σ(F ) 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
2
2
2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The C-
bound H atoms were placed in idealized positions, with constrained distances of 0.93 Å and with Uiso(H) = 1.2Ueq(C).
Phenol H atoms were restrained so that to reproduce the C—O—H angle value of 107° observed in salicylic acid
(
neutron structure determination, Bacon et al., 1973). All N—H distances and tetrahedral environment of the N atom
were also restrained.
Acta Cryst. (2014). C70, 493-497
sup-5

supplementary materials
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
O1
0.2531 (3)
0.370 (3)
0.6199 (3)
0.7530 (3)
0.2848 (4)
0.4682 (4)
0.4416 (4)
0.2647 (4)
0.0987 (4)
−0.0193
0.05503 (5)
0.0422 (7)
0.02302 (5)
0.03045 (5)
0.14683 (5)
0.14854 (6)
0.06971 (6)
0.07579 (6)
0.10345 (7)
0.1071
0.8971 (3)
0.930 (3)
0.8656 (3)
0.5682 (3)
0.1780 (4)
0.1187 (4)
0.6068 (4)
0.7175 (4)
0.6398 (4)
0.7101
0.0534 (5)
0.087 (12)*
0.0539 (5)
0.0534 (5)
0.0512 (5)
0.0508 (5)
0.0403 (5)
0.0432 (5)
0.0499 (6)
0.060*
H1
O2
O3
N1
N2
C1
C2
C3
H3
C4
0.1077 (4)
−0.0066
0.12544 (7)
0.1434
0.4601 (4)
0.4072
0.0509 (6)
0.061*
H4
C5
0.2866 (4)
0.4488 (4)
0.5656
0.12113 (6)
0.09291 (6)
0.0894
0.3555 (4)
0.4288 (4)
0.3567
0.0456 (6)
0.0425 (5)
0.051*
C6
H6
C7
0.4620 (4)
0.2868 (5)
0.1650
0.17474 (7)
0.20058 (7)
0.2022
−0.0590 (4)
−0.1365 (5)
−0.0696
0.0495 (6)
0.0634 (8)
0.076*
C8
H8
C9
0.2935 (6)
0.1763
0.22386 (8)
0.2414
−0.3135 (6)
−0.3648
0.0771 (10)
0.093*
H9
C10
H10
C11
H11
C12
H12
C13
N3
0.4716 (6)
0.4726
0.22141 (8)
0.2367
−0.4152 (5)
−0.5373
0.0723 (9)
0.087*
0.6476 (6)
0.7696
0.19641 (9)
0.1950
−0.3356 (5)
−0.4025
0.0703 (8)
0.084*
0.6445 (5)
0.7655
0.17321 (8)
0.1566
−0.1560 (5)
−0.1009
0.0619 (7)
0.074*
0.6177 (4)
−0.0209 (3)
−0.087 (3)
−0.127 (3)
0.066 (3)
0.065 (3)
0.03893 (6)
0.03147 (5)
0.0405 (6)
0.0243 (6)
0.0499 (4)
0.0110 (4)
0.6836 (4)
1.2283 (3)
1.331 (2)
1.111 (2)
1.191 (3)
1.281 (3)
0.0421 (5)
0.0487 (5)
0.073*
H21
H22
H23
H24
0.073*
0.073*
0.073*
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
O1
O2
O3
N1
N2
C1
C2
C3
C4
C5
C6
0.0507 (11)
0.0459 (10)
0.0461 (9)
0.0624 (11)
0.0673 (11)
0.0588 (10)
0.0437 (10)
0.0476 (11)
0.0407 (11)
0.0410 (12)
0.0515 (13)
0.0425 (12)
0.0398 (11)
0.0443 (12)
0.0521 (11)
0.0499 (10)
0.0618 (11)
0.0638 (14)
0.0605 (14)
0.0444 (13)
0.0481 (14)
0.0590 (16)
0.0680 (17)
0.0521 (15)
0.0468 (13)
0.0042 (8)
0.0061 (8)
0.0132 (7)
0.0045 (8)
0.0030 (8)
−0.0014 (8)
−0.0040 (9)
0.0055 (10)
0.0072 (10)
0.0018 (9)
−0.0002 (9)
0.0223 (9)
0.0140 (9)
0.0258 (9)
0.0186 (11)
0.0174 (11)
0.0129 (11)
0.0184 (12)
0.0231 (12)
0.0206 (13)
0.0136 (12)
0.0141 (11)
0.0090 (8)
0.0170 (8)
0.0138 (8)
0.0489 (11)
0.0469 (11)
0.0376 (12)
0.0442 (12)
0.0446 (13)
0.0459 (13)
0.0460 (13)
0.0384 (12)
0.0046 (9)
0.0067 (9)
−0.0016 (9)
−0.0008 (10)
−0.0027 (11)
0.0005 (11)
0.0034 (10)
−0.0011 (10)
Acta Cryst. (2014). C70, 493-497
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supplementary materials
C7
0.0488 (14)
0.0599 (16)
0.076 (2)
0.0438 (12)
0.0523 (15)
0.0567 (17)
0.0585 (17)
0.0738 (19)
0.0593 (16)
0.0444 (12)
0.0484 (11)
0.0585 (16)
0.083 (2)
−0.0022 (10)
0.0089 (12)
0.0123 (14)
−0.0127 (15)
−0.0055 (15)
0.0044 (12)
−0.0028 (9)
0.0040 (8)
0.0178 (13)
0.0273 (16)
0.031 (2)
0.0029 (11)
0.0201 (14)
0.0335 (16)
0.0154 (14)
0.0052 (16)
0.0078 (13)
0.0027 (10)
0.0039 (9)
C8
C9
0.103 (3)
C10
C11
C12
C13
N3
0.084 (2)
0.078 (2)
0.0248 (19)
0.0348 (18)
0.0273 (16)
0.0092 (11)
0.0182 (10)
0.0701 (19)
0.0557 (16)
0.0355 (11)
0.0473 (11)
0.076 (2)
0.077 (2)
0.0463 (13)
0.0536 (13)
Geometric parameters (Å, º)
O1—C2
O1—H1
O2—C13
O3—C13
N1—N2
N1—C5
N2—C7
C1—C6
C1—C2
C1—C13
C2—C3
C3—C4
C3—H3
C4—C5
C4—H4
C5—C6
1.350 (3)
C6—H6
0.9300
0.82 (2)
C7—C12
C7—C8
1.379 (3)
1.383 (4)
1.378 (4)
0.9300
1.265 (3)
1.246 (3)
1.249 (3)
1.421 (3)
1.428 (3)
1.382 (3)
1.419 (3)
1.500 (3)
1.387 (3)
1.370 (3)
0.9300
C8—C9
C8—H8
C9—C10
C9—H9
1.375 (4)
0.9300
C10—C11
C10—H10
C11—C12
C11—H11
C12—H12
N3—H21
N3—H22
N3—H23
N3—H24
1.370 (4)
0.9300
1.385 (4)
0.9300
0.9300
0.89 (2)
0.89 (2)
0.89 (2)
0.89 (2)
1.397 (3)
0.9300
1.381 (3)
C2—O1—H1
N2—N1—C5
N1—N2—C7
C6—C1—C2
C6—C1—C13
C2—C1—C13
O1—C2—C3
O1—C2—C1
C3—C2—C1
C4—C3—C2
C4—C3—H3
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
C6—C5—C4
C6—C5—N1
C4—C5—N1
C5—C6—C1
C5—C6—H6
C1—C6—H6
C12—C7—C8
106.6 (14)
114.6 (2)
113.4 (2)
118.6 (2)
C9—C8—C7
119.7 (3)
120.2
C9—C8—H8
C7—C8—H8
120.2
C10—C9—C8
C10—C9—H9
C8—C9—H9
120.7 (3)
119.7
121.01 (19)
120.4 (2)
119.0 (2)
121.4 (2)
119.6 (2)
120.4 (2)
119.8
119.7
C11—C10—C9
C11—C10—H10
C9—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
C7—C12—C11
C7—C12—H12
C11—C12—H12
O3—C13—O2
O3—C13—C1
O2—C13—C1
H21—N3—H22
H21—N3—H23
H22—N3—H23
H21—N3—H24
119.6 (3)
120.2
120.2
120.2 (3)
119.9
119.8
119.9
120.7 (2)
119.6
120.0 (3)
120.0
119.6
120.0
119.0 (2)
125.1 (2)
115.9 (2)
121.5 (2)
119.2
123.6 (2)
119.4 (2)
117.1 (2)
110 (2)
110 (2)
109 (2)
109 (2)
119.2
119.7 (2)
Acta Cryst. (2014). C70, 493-497
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supplementary materials
C12—C7—N2
C8—C7—N2
116.2 (2)
124.1 (2)
H22—N3—H24
H23—N3—H24
110 (2)
109 (2)
C5—N1—N2—C7
C6—C1—C2—O1
C13—C1—C2—O1
C6—C1—C2—C3
C13—C1—C2—C3
O1—C2—C3—C4
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C6
C3—C4—C5—N1
N2—N1—C5—C6
N2—N1—C5—C4
C4—C5—C6—C1
N1—C5—C6—C1
C2—C1—C6—C5
−179.7 (2)
−177.6 (2)
1.9 (3)
C13—C1—C6—C5
N1—N2—C7—C12
N1—N2—C7—C8
C12—C7—C8—C9
N2—C7—C8—C9
C7—C8—C9—C10
C8—C9—C10—C11
C9—C10—C11—C12
C8—C7—C12—C11
N2—C7—C12—C11
C10—C11—C12—C7
C6—C1—C13—O3
C2—C1—C13—O3
C6—C1—C13—O2
C2—C1—C13—O2
179.5 (2)
−169.5 (2)
10.1 (4)
1.6 (4)
2.8 (3)
−177.8 (2)
178.9 (2)
−1.4 (4)
−1.6 (4)
3.3 (4)
−178.0 (3)
0.6 (5)
−2.0 (5)
1.1 (5)
−2.5 (4)
177.2 (3)
1.1 (5)
−176.8 (2)
−15.3 (3)
164.9 (2)
−1.9 (4)
178.2 (2)
−1.1 (3)
−10.1 (3)
170.4 (2)
169.6 (2)
−9.9 (3)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O1—H1···O2
0.82 (2)
0.89 (2)
0.89 (2)
0.89 (2)
0.89 (2)
1.78 (2)
1.99 (2)
1.91 (2)
2.38 (2)
1.91 (2)
2.524 (3)
2.788 (3)
2.779 (3)
3.052 (3)
2.799 (3)
151 (2)
150 (2)
164 (2)
132 (2)
172 (2)
i
N3—H21···O3
ii
N3—H22···O2
N3—H23···O1
iii
N3—H24···O3
Symmetry codes: (i) x−1, y, z+1; (ii) x−1, y, z; (iii) −x+1, −y, −z+2.
(III) Sodium 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoate trihydrate
Crystal data
+
−
Na ·C13
H
8
N O
3 5
2
·3H O
Z = 4
M
r
= 363.26
F(000) = 752
D = 1.572 Mg m
x
−3
Triclinic, P1
Hall symbol: -P 1
a = 7.2123 (5) Å
b = 13.0205 (8) Å
c = 17.0317 (11) Å
α = 77.185 (6)°
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 5966 reflections
θ = 2.4–30.4°
µ = 0.16 mm
T = 293 K
−1
β = 80.933 (5)°
γ = 83.401 (5)°
V = 1534.76 (17) Å
Irregular block, dark yellow
0.50 × 0.45 × 0.40 mm
3
Data collection
Stoe STADI VARI
diffractometer
Absorption correction: multi-scan
(Blessing, 1995)
Radiation source: fine-focus sealed tube
Graphite monochromator
Detector resolution: 5.81 pixels mm
rotation method scans
Tmin = 0.926, Tmax = 0.952
6773 measured reflections
5936 independent reflections
3776 reflections with I > 2σ(I)
-1
R
int = 0.026
Acta Cryst. (2014). C70, 493-497
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supplementary materials
θ
max = 26.0°, θmin = 2.7°
k = −15→16
l = −19→20
h = −4→8
Refinement
2
Refinement on F
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
Least-squares matrix: full
R[F > 2σ(F )] = 0.041
2
2
2
wR(F ) = 0.120
S = 0.92
H atoms treated by a mixture of independent
and constrained refinement
5
4
2
936 reflections
93 parameters
2 restraints
2
2
2
w = 1/[σ (F
o
) + (0.0662P) ]
2
2
where P = (F
o
+ 2F )/3
c
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max < 0.001
Δρmax = 0.21 e Å
Δρmin = −0.27 e Å
−
3
−
3
Special details
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles;
correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate
(
isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.
2
2
Refinement. Refinement of F against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F ,
conventional R-factors R are based on F, with F set to zero for negative F . The threshold expression of F > σ(F ) 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
2
2
2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The C-
bound H atoms were placed in idealized positions, with constrained distances of 0.93 Å and with Uiso(H) = 1.2Ueq(C).
Phenol H atoms were restrained so that to reproduce the C—O—H angle value of 107° observed in salicylic acid
(
neutron structure determination, Bacon et al., 1973). For all water molecules, the O—H distances and H—O—H angles
of 106° were restrained.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
Na1
Na2
O20
H21
H22
O30
H31
H32
O40
H41
H42
O50
H51
H52
O60
H61
H62
O70
H71
0.29209 (14)
0.12688 (15)
−0.0003 (2)
−0.085 (2)
−0.055 (3)
0.5998 (3)
0.597 (4)
0.54778 (7)
0.81138 (8)
0.63987 (14)
0.651 (2)
0.04310 (5)
−0.01809 (6)
0.01501 (10)
0.0511 (11)
−0.0212 (11)
0.09144 (10)
0.1286 (12)
0.0997 (17)
−0.00868 (10)
0.0187 (13)
−0.0508 (9)
0.08695 (13)
0.072 (2)
0.0411 (2)
0.0489 (3)
0.0413 (4)
0.062*
0.630 (2)
0.062*
0.48619 (14)
0.4339 (14)
0.5201 (19)
0.71079 (14)
0.742 (2)
0.0447 (4)
0.067*
0.681 (3)
0.067*
0.4292 (3)
0.478 (3)
0.0424 (4)
0.064*
0.503 (3)
0.713 (2)
0.064*
0.0461 (4)
0.106 (5)
0.90808 (16)
0.9606 (18)
0.876 (2)
0.0630 (6)
0.095*
0.086 (5)
0.1289 (13)
−0.05485 (12)
−0.0806 (15)
−0.0083 (7)
−0.0899 (2)
−0.100 (3)
0.095*
−0.1860 (3)
−0.257 (4)
−0.210 (5)
0.2955 (5)
0.236 (7)
0.88960 (16)
0.870 (3)
0.0536 (5)
0.080*
0.856 (2)
0.080*
0.9520 (2)
1.010 (2)
0.1026 (10)
0.154*
Acta Cryst. (2014). C70, 493-497
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supplementary materials
H72
O1
0.360 (7)
−0.0793 (3)
−0.018 (3)
0.1590 (3)
0.3135 (3)
0.1739 (3)
0.3900 (3)
0.1704 (3)
0.1011 (3)
0.2706 (3)
0.1194 (3)
−0.0165 (3)
−0.0952 (4)
−0.1871
0.946 (4)
−0.1331 (16)
0.22701 (10)
0.1823 (4)
0.154*
0.46163 (13)
0.4605 (14)
0.39434 (13)
0.23308 (14)
−0.22444 (16)
−0.29157 (14)
0.12249 (15)
0.12523 (16)
−0.21953 (15)
0.30052 (17)
0.37726 (17)
0.36977 (18)
0.4210
0.0473 (4)
0.057*
H1
O2
0.11992 (9)
0.15024 (10)
0.84208 (10)
0.76258 (11)
0.45539 (11)
0.52805 (11)
0.77658 (11)
0.25700 (12)
0.28110 (14)
0.36155 (14)
0.3761
0.0436 (4)
0.0458 (4)
0.0604 (6)
0.0505 (5)
0.0371 (4)
0.0404 (5)
0.0365 (4)
0.0311 (5)
0.0362 (5)
0.0380 (5)
0.046*
O3
O4
O5
N1
N2
N3
C1
C2
C3
H3
C4
−0.0366 (4)
−0.0902
0.28584 (18)
0.2800
0.42029 (14)
0.4743
0.0386 (5)
0.046*
H4
C5
0.1029 (3)
0.1779 (3)
0.2685
0.21024 (17)
0.21715 (17)
0.1653
0.39831 (13)
0.31709 (13)
0.3027
0.0337 (5)
0.0326 (5)
0.039*
C6
H6
C7
0.1589 (3)
0.2876 (4)
0.3462
0.03711 (17)
−0.04755 (19)
−0.0474
0.58710 (13)
0.57064 (14)
0.5179
0.0342 (5)
0.0391 (5)
0.047*
C8
H8
C9
0.3263 (3)
0.4103
−0.13020 (18)
−0.1870
0.63268 (13)
0.6224
0.0364 (5)
0.044*
H9
C10
C11
H11
C12
H12
C13
O1A
H1A
O2A
O3A
O4A
O5A
N1A
N2A
N3A
C1A
C2A
C3A
H3A
C4A
H4A
C5A
C6A
H6A
C7A
0.2389 (3)
0.1150 (4)
0.0575
−0.12844 (18)
−0.0458 (2)
−0.0465
0.71104 (13)
0.72882 (14)
0.7818
0.0367 (5)
0.0453 (6)
0.054*
0.0773 (4)
−0.0029
0.0385 (2)
0.66638 (15)
0.6775
0.0510 (7)
0.061*
0.0963
0.2054 (3)
0.6032 (3)
0.560 (4)
0.4361 (3)
0.2881 (3)
0.2033 (3)
0.0646 (3)
0.3363 (3)
0.3935 (3)
0.1545 (3)
0.4205 (3)
0.5323 (4)
0.5708 (4)
0.6399
0.30891 (18)
0.07174 (15)
0.0856 (15)
0.18204 (14)
0.33815 (14)
0.66000 (15)
0.75726 (14)
0.38085 (16)
0.36973 (16)
0.67607 (16)
0.23760 (17)
0.14575 (18)
0.1304 (2)
0.16969 (13)
0.80581 (11)
0.85009 (16)
0.90509 (10)
0.86157 (10)
0.15994 (10)
0.24188 (11)
0.55961 (11)
0.48885 (11)
0.22755 (12)
0.76376 (13)
0.74698 (14)
0.66745 (16)
0.6567
0.0356 (5)
0.0539 (5)
0.065*
0.0493 (5)
0.0470 (4)
0.0525 (5)
0.0526 (5)
0.0384 (5)
0.0423 (5)
0.0399 (5)
0.0322 (5)
0.0380 (5)
0.0482 (6)
0.058*
0.0691
0.5078 (4)
0.5349
0.2049 (2)
0.60525 (15)
0.5524
0.0461 (6)
0.055*
0.1939
0.4012 (3)
0.3575 (3)
0.2846
0.29899 (17)
0.31237 (18)
0.3727
0.62036 (13)
0.70010 (14)
0.7109
0.0342 (5)
0.0367 (5)
0.044*
0.3266 (3)
0.45134 (18)
0.42707 (13)
0.0362 (5)
Acta Cryst. (2014). C70, 493-497
sup-10

supplementary materials
C8A
0.2047 (4)
0.1622
0.53881 (19)
0.5473
0.44037 (13)
0.4932
0.0408 (6)
0.049*
H8A
C9A
0.1465 (4)
0.0645
0.61303 (19)
0.6714
0.37529 (14)
0.3835
0.0395 (5)
0.047*
H9A
C10A
C11A
H11A
C12A
H12A
C13A
0.2138 (3)
0.3370 (3)
0.3811
0.59775 (17)
0.51270 (18)
0.5049
0.29782 (12)
0.28285 (13)
0.2300
0.0322 (5)
0.0370 (5)
0.044*
0.3923 (4)
0.4752
0.43972 (19)
0.3818
0.34866 (14)
0.3401
0.0395 (5)
0.047*
0.3759 (4)
0.2550 (2)
0.84887 (14)
0.0389 (5)
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
Na1
Na2
O20
O30
O40
O50
O60
O70
O1
0.0435 (6)
0.0394 (5)
0.0389 (5)
0.0368 (5)
−0.0051 (4)
−0.0043 (4)
−0.0057 (8)
−0.0039 (8)
−0.0103 (8)
−0.0096 (11)
−0.0114 (10)
−0.0298 (15)
0.0063 (8)
−0.0020 (4)
−0.0044 (5)
−0.0055 (7)
−0.0060 (8)
−0.0040 (7)
−0.0190 (11)
−0.0044 (9)
−0.006 (2)
−0.0016 (4)
−0.0123 (5)
−0.0112 (8)
−0.0076 (7)
−0.0103 (8)
−0.0041 (9)
−0.0149 (9)
−0.0059 (16)
0.0046 (8)
0.0520 (6)
0.0562 (6)
0.0345 (9)
0.0351 (9)
0.0319 (9)
0.0484 (12)
0.0440 (10)
0.129 (3)
0.0436 (10)
0.0524 (11)
0.0480 (11)
0.0938 (17)
0.0611 (13)
0.113 (3)
0.0475 (10)
0.0462 (10)
0.0491 (10)
0.0480 (12)
0.0582 (12)
0.0613 (16)
0.0376 (9)
0.0568 (12)
0.0574 (11)
0.0586 (12)
0.0763 (14)
0.0551 (12)
0.0443 (12)
0.0534 (13)
0.0437 (12)
0.0388 (13)
0.0424 (14)
0.0485 (14)
0.0464 (14)
0.0408 (13)
0.0338 (12)
0.0435 (14)
0.0458 (14)
0.0402 (13)
0.0415 (14)
0.0633 (18)
0.0685 (19)
0.0405 (13)
0.0668 (13)
0.0659 (13)
0.0658 (12)
0.0711 (13)
0.0676 (13)
0.0431 (12)
0.0502 (13)
0.0408 (10)
0.0317 (8)
0.0308 (8)
0.0291 (9)
0.0476 (10)
0.0290 (10)
0.0261 (10)
0.0278 (10)
0.0258 (10)
0.0361 (12)
0.0349 (12)
0.0304 (11)
0.0265 (11)
0.0348 (12)
0.0291 (11)
0.0277 (11)
0.0312 (11)
0.0273 (11)
0.0237 (11)
0.0318 (12)
0.0308 (11)
0.0422 (10)
0.0308 (9)
0.0319 (9)
0.0258 (9)
0.0413 (10)
0.0300 (10)
0.0293 (10)
−0.0115 (8)
−0.0054 (8)
0.0024 (8)
O2
0.0397 (9)
−0.0162 (8)
−0.0037 (9)
0.0013 (11)
0.0069 (9)
0.0024 (7)
O3
0.0470 (10)
0.0646 (12)
0.0411 (10)
0.0340 (10)
0.0403 (11)
0.0383 (11)
0.0301 (11)
0.0290 (11)
0.0289 (11)
0.0375 (12)
0.0325 (11)
0.0282 (11)
0.0301 (11)
0.0408 (13)
0.0353 (12)
0.0398 (13)
0.0424 (13)
0.0462 (15)
0.0365 (12)
0.0477 (11)
0.0486 (10)
0.0454 (10)
0.0586 (11)
0.0427 (10)
0.0428 (11)
0.0460 (12)
−0.0124 (7)
0.0025 (8)
O4
0.0036 (9)
O5
−0.0087 (9)
−0.0054 (8)
−0.0065 (9)
−0.0046 (8)
−0.0052 (9)
−0.0103 (10)
−0.0053 (10)
−0.0019 (10)
−0.0064 (9)
−0.0042 (9)
−0.0089 (10)
0.0039 (10)
−0.0002 (10)
−0.0028 (10)
−0.0012 (11)
−0.0023 (12)
−0.0085 (10)
−0.0099 (9)
−0.0116 (8)
−0.0066 (8)
−0.0067 (8)
−0.0057 (9)
−0.0059 (8)
−0.0035 (9)
0.0028 (8)
N1
−0.0009 (9)
0.0012 (9)
0.0008 (8)
N2
−0.0058 (8)
−0.0044 (8)
−0.0045 (8)
0.0000 (9)
N3
−0.0095 (9)
−0.0107 (9)
−0.0047 (10)
0.0060 (10)
0.0016 (11)
−0.0012 (10)
−0.0004 (9)
−0.0028 (10)
−0.0023 (11)
−0.0010 (10)
−0.0045 (10)
0.0081 (12)
0.0155 (13)
−0.0100 (10)
0.0057 (9)
C1
C2
C3
−0.0078 (9)
−0.0083 (10)
−0.0027 (9)
−0.0060 (9)
−0.0041 (9)
−0.0078 (10)
−0.0061 (9)
−0.0046 (9)
−0.0027 (10)
−0.0075 (11)
−0.0028 (10)
−0.0023 (8)
−0.0009 (8)
−0.0181 (7)
−0.0084 (8)
−0.0044 (8)
−0.0078 (8)
−0.0068 (9)
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
O1A
O2A
O3A
O4A
O5A
N1A
N2A
−0.0013 (9)
0.0063 (9)
0.0027 (10)
0.0097 (9)
−0.0050 (9)
−0.0023 (10)
Acta Cryst. (2014). C70, 493-497
sup-11

supplementary materials
N3A
C1A
C2A
C3A
C4A
C5A
C6A
C7A
C8A
C9A
C10A
C11A
C12A
C13A
0.0435 (12)
0.0330 (12)
0.0457 (14)
0.0531 (16)
0.0563 (17)
0.0396 (13)
0.0389 (13)
0.0408 (13)
0.0554 (16)
0.0441 (14)
0.0371 (13)
0.0415 (13)
0.0472 (15)
0.0424 (14)
0.0418 (11)
0.0345 (12)
0.0320 (12)
0.0401 (14)
0.0477 (14)
0.0348 (12)
0.0331 (12)
0.0354 (12)
0.0429 (13)
0.0389 (13)
0.0345 (11)
0.0424 (13)
0.0414 (13)
0.0471 (14)
0.0331 (11)
0.0292 (11)
0.0326 (12)
0.0476 (15)
0.0334 (13)
0.0295 (11)
0.0377 (12)
0.0315 (11)
0.0241 (11)
0.0351 (12)
0.0240 (10)
0.0280 (11)
0.0316 (12)
0.0273 (11)
−0.0092 (9)
−0.0069 (9)
−0.0037 (10)
0.0024 (12)
0.0055 (12)
−0.0038 (10)
−0.0026 (10)
−0.0058 (10)
0.0016 (11)
−0.0019 (11)
−0.0071 (9)
−0.0034 (10)
−0.0040 (11)
−0.0149 (11)
−0.0029 (9)
−0.0046 (9)
−0.0079 (10)
0.0014 (12)
−0.0080 (11)
−0.0078 (9)
−0.0011 (10)
−0.0024 (10)
−0.0054 (10)
−0.0047 (10)
−0.0063 (9)
−0.0020 (10)
−0.0001 (10)
−0.0052 (10)
−0.0038 (9)
−0.0044 (9)
0.0029 (9)
−0.0102 (11)
−0.0100 (11)
−0.0071 (9)
−0.0099 (10)
−0.0054 (9)
−0.0101 (10)
−0.0081 (10)
−0.0006 (9)
−0.0111 (10)
−0.0148 (10)
−0.0016 (10)
Geometric parameters (Å, º)
Na1—O2
Na1—O20
Na1—O40
2.3474 (18)
C3—H3
0.9300
2.366 (2)
2.3743 (19)
2.4211 (19)
2.474 (2)
2.679 (2)
3.3560 (19)
3.4857 (14)
2.319 (3)
2.372 (2)
2.420 (2)
2.428 (2)
2.481 (3)
2.491 (2)
2.67 (3)
C4—C5
1.392 (3)
0.9300
C4—H4
i
Na1—O30
C5—C6
1.391 (3)
0.9300
Na1—O30
C6—H6
Na1—O4A
C7—C12
1.388 (3)
1.406 (3)
1.368 (3)
0.9300
i
Na1—Na1
C7—C8
Na1—Na2
Na2—O70
Na2—O50
Na2—O40
Na2—O20
Na2—O60
C8—C9
C8—H8
C9—C10
1.387 (3)
0.9300
C9—H9
C10—C11
C11—C12
C11—H11
C12—H12
O1A—C2A
O1A—H1A
O2A—C13A
O3A—C13A
O4A—N3A
O5A—N3A
N1A—N2A
N1A—C5A
N2A—C7A
N3A—C10A
C1A—C6A
C1A—C2A
C1A—C13A
C2A—C3A
C3A—C4A
C3A—H3A
C4A—C5A
C4A—H4A
1.374 (3)
1.384 (3)
0.9300
ii
Na2—O4
Na2—H21
Na2—H62
O20—H21
O20—H22
0.9300
2.42 (3)
1.347 (3)
0.8200 (10)
1.281 (3)
1.234 (3)
1.207 (2)
1.226 (3)
1.245 (3)
1.405 (3)
1.420 (3)
1.475 (3)
1.384 (3)
1.421 (3)
1.496 (3)
1.393 (4)
1.365 (4)
0.9300
0.821 (3)
0.820 (3)
2.4212 (19)
0.820 (3)
0.820 (3)
0.820 (3)
0.820 (3)
0.821 (3)
0.821 (3)
0.821 (3)
0.820 (3)
0.821 (3)
0.821 (3)
1.352 (3)
0.8201 (10)
1.286 (3)
1.257 (3)
i
O30—Na1
O30—H31
O30—H32
O40—H41
O40—H42
O50—H51
O50—H52
O60—H61
O60—H62
O70—H71
O70—H72
O1—C2
O1—H1
O2—C13
O3—C13
1.421 (3)
0.9300
Acta Cryst. (2014). C70, 493-497
sup-12

supplementary materials
O4—N3
O4—Na2
O5—N3
N1—N2
N1—C5
N2—C7
N3—C10
C1—C6
C1—C2
C1—C13
C2—C3
C3—C4
1.212 (3)
2.491 (2)
1.236 (3)
1.266 (3)
1.420 (3)
1.419 (3)
1.462 (3)
1.394 (3)
1.399 (3)
1.503 (3)
1.385 (3)
1.384 (3)
C5A—C6A
C6A—H6A
C7A—C12A
C7A—C8A
C8A—C9A
C8A—H8A
C9A—C10A
C9A—H9A
C10A—C11A
C11A—C12A
C11A—H11A
C12A—H12A
1.390 (3)
0.9300
iii
1.380 (3)
1.394 (3)
1.384 (3)
0.9300
1.382 (3)
0.9300
1.381 (3)
1.379 (3)
0.9300
0.9300
O2—Na1—O20
O2—Na1—O40
O20—Na1—O40
94.62 (7)
168.45 (7)
87.33 (7)
106.34 (7)
97.26 (7)
84.66 (7)
91.35 (7)
165.76 (7)
84.32 (7)
93.44 (6)
95.53 (7)
76.60 (6)
73.82 (6)
157.77 (7)
89.97 (7)
102.72 (6)
143.67 (6)
81.95 (6)
47.38 (5)
46.07 (5)
131.87 (7)
135.26 (6)
44.06 (5)
43.88 (5)
97.02 (5)
125.25 (6)
63.55 (5)
120.90 (4)
86.84 (11)
86.28 (11)
111.51 (8)
159.68 (11)
113.44 (8)
84.92 (7)
96.60 (11)
82.84 (8)
C13—O2—Na1
139.59 (16)
149.03 (19)
112.87 (19)
114.96 (19)
121.8 (2)
119.2 (2)
118.96 (18)
117.82 (19)
120.6 (2)
121.53 (19)
116.7 (2)
121.8 (2)
121.5 (2)
119.8 (2)
120.1
iii
N3—O4—Na2
N2—N1—C5
N1—N2—C7
O4—N3—O5
O4—N3—C10
O5—N3—C10
C6—C1—C2
C6—C1—C13
C2—C1—C13
O1—C2—C3
O1—C2—C1
C3—C2—C1
C4—C3—C2
C4—C3—H3
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
C6—C5—C4
C6—C5—N1
C4—C5—N1
C5—C6—C1
C5—C6—H6
C1—C6—H6
C12—C7—C8
C12—C7—N2
C8—C7—N2
C9—C8—C7
C9—C8—H8
C7—C8—H8
C8—C9—C10
C8—C9—H9
C10—C9—H9
C11—C10—C9
C11—C10—N3
i
O2—Na1—O30
i
i
O20—Na1—O30
O40—Na1—O30
O2—Na1—O30
O20—Na1—O30
O40—Na1—O30
i
O30 —Na1—O30
O2—Na1—O4A
O20—Na1—O4A
O40—Na1—O4A
i
O30 —Na1—O4A
O30—Na1—O4A
i
O2—Na1—Na1
120.1
i
O20—Na1—Na1
119.8 (2)
120.1
i
O40—Na1—Na1
i
i
O30 —Na1—Na1
120.1
i
O30—Na1—Na1
119.9 (2)
117.2 (2)
122.8 (2)
121.0 (2)
119.5
i
O4A—Na1—Na1
O2—Na1—Na2
O20—Na1—Na2
O40—Na1—Na2
i
O30 —Na1—Na2
119.5
O30—Na1—Na2
O4A—Na1—Na2
120.0 (2)
114.8 (2)
125.2 (2)
119.6 (2)
120.2
i
Na1 —Na1—Na2
O70—Na2—O50
O70—Na2—O40
O50—Na2—O40
O70—Na2—O20
O50—Na2—O20
O40—Na2—O20
O70—Na2—O60
O50—Na2—O60
120.2
119.3 (2)
120.3
120.3
122.2 (2)
118.3 (2)
Acta Cryst. (2014). C70, 493-497
sup-13

supplementary materials
O40—Na2—O60
O20—Na2—O60
165.54 (8)
87.70 (7)
78.88 (11)
158.56 (8)
83.66 (7)
81.96 (7)
83.01 (7)
128.35 (10)
115.65 (6)
42.85 (5)
42.65 (5)
130.21 (6)
85.78 (6)
174.1 (5)
96.7 (3)
96.7 (5)
17.7 (3)
79.3 (5)
96.4 (3)
54.0 (5)
112.2 (5)
73.5 (7)
161.3 (6)
76.8 (6)
19.22 (10)
97.0 (5)
118.5 (6)
64.7 (7)
93.28 (7)
122.3 (19)
98 (2)
C9—C10—N3
119.5 (2)
118.7 (2)
120.7
C10—C11—C12
C10—C11—H11
C12—C11—H11
C11—C12—C7
C11—C12—H12
C7—C12—H12
O3—C13—O2
ii
O70—Na2—O4
ii
O50—Na2—O4
120.7
ii
O40—Na2—O4
120.2 (2)
119.9
ii
O20—Na2—O4
ii
O60—Na2—O4
119.9
O70—Na2—Na1
O50—Na2—Na1
O40—Na2—Na1
O20—Na2—Na1
O60—Na2—Na1
124.9 (2)
118.8 (2)
116.3 (2)
108.9 (14)
157.52 (16)
114.6 (2)
115.0 (2)
123.8 (2)
O3—C13—C1
O2—C13—C1
C2A—O1A—H1A
N3A—O4A—Na1
N2A—N1A—C5A
N1A—N2A—C7A
O4A—N3A—O5A
ii
O4 —Na2—Na1
O70—Na2—H21
O50—Na2—H21
O40—Na2—H21
O20—Na2—H21
O60—Na2—H21
O4A—N3A—C10A
O5A—N3A—C10A
C6A—C1A—C2A
C6A—C1A—C13A
C2A—C1A—C13A
O1A—C2A—C3A
O1A—C2A—C1A
C3A—C2A—C1A
C4A—C3A—C2A
C4A—C3A—H3A
C2A—C3A—H3A
C3A—C4A—C5A
C3A—C4A—H4A
C5A—C4A—H4A
C6A—C5A—N1A
C6A—C5A—C4A
N1A—C5A—C4A
C1A—C6A—C5A
C1A—C6A—H6A
C5A—C6A—H6A
C12A—C7A—C8A
C12A—C7A—N2A
C8A—C7A—N2A
C9A—C8A—C7A
C9A—C8A—H8A
C7A—C8A—H8A
C10A—C9A—C8A
C10A—C9A—H9A
C8A—C9A—H9A
C9A—C10A—C11A
C9A—C10A—N3A
C11A—C10A—N3A
C12A—C11A—C10A
C12A—C11A—H11A
119.3 (2)
116.80 (19)
119.2 (2)
120.2 (2)
120.5 (2)
118.2 (2)
122.1 (2)
119.7 (2)
120.4 (2)
119.8
ii
O4 —Na2—H21
Na1—Na2—H21
O70—Na2—H62
O50—Na2—H62
O40—Na2—H62
O20—Na2—H62
O60—Na2—H62
ii
O4 —Na2—H62
119.8
Na1—Na2—H62
H21—Na2—H62
Na1—O20—Na2
Na1—O20—H21
Na2—O20—H21
Na1—O20—H22
Na2—O20—H22
H21—O20—H22
120.8 (2)
119.6
119.6
117.0 (2)
118.7 (2)
124.3 (2)
121.2 (2)
119.4
122.5 (19)
112 (2)
105 (2)
i
Na1 —O30—Na1
86.56 (6)
116 (2)
119.4
i
Na1 —O30—H31
119.8 (2)
114.9 (2)
125.2 (2)
120.3 (2)
119.9
Na1—O30—H31
114 (2)
i
Na1 —O30—H32
104 (2)
Na1—O30—H32
H31—O30—H32
Na1—O40—Na2
Na1—O40—H41
Na2—O40—H41
Na1—O40—H42
Na2—O40—H42
H41—O40—H42
Na2—O50—H51
Na2—O50—H52
H51—O50—H52
130 (2)
105 (3)
93.27 (7)
124 (2)
119.9
118.0 (2)
121.0
102 (2)
115 (2)
121.0
117 (2)
122.9 (2)
119.0 (2)
118.11 (19)
118.0 (2)
121.0
105 (3)
106 (3)
111 (3)
105 (3)
Acta Cryst. (2014). C70, 493-497
sup-14

supplementary materials
Na2—O60—H61
Na2—O60—H62
H61—O60—H62
Na2—O70—H71
Na2—O70—H72
H71—O70—H72
C2—O1—H1
130 (3)
76 (2)
C10A—C11A—H11A
121.0
C11A—C12A—C7A
C11A—C12A—H12A
C7A—C12A—H12A
O3A—C13A—O2A
O3A—C13A—C1A
O2A—C13A—C1A
121.0 (2)
119.5
105 (3)
117 (4)
118 (4)
105 (5)
108.3 (13)
119.5
123.4 (2)
119.5 (2)
117.1 (2)
O2—Na1—Na2—O70
O20—Na1—Na2—O70
O40—Na1—Na2—O70
176.45 (14)
−154.96 (15)
12.97 (14)
−61.76 (14)
37.51 (15)
106.88 (14)
−17.94 (15)
68.87 (11)
97.46 (10)
−94.61 (10)
−169.34 (9)
−70.07 (10)
−0.69 (9)
C6—C1—C2—C3
C13—C1—C2—C3
O1—C2—C3—C4
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C6
C3—C4—C5—N1
N2—N1—C5—C6
N2—N1—C5—C4
C4—C5—C6—C1
N1—C5—C6—C1
C2—C1—C6—C5
C13—C1—C6—C5
N1—N2—C7—C12
N1—N2—C7—C8
C12—C7—C8—C9
N2—C7—C8—C9
C7—C8—C9—C10
C8—C9—C10—C11
C8—C9—C10—N3
O4—N3—C10—C11
O5—N3—C10—C11
O4—N3—C10—C9
O5—N3—C10—C9
C9—C10—C11—C12
N3—C10—C11—C12
C10—C11—C12—C7
C8—C7—C12—C11
N2—C7—C12—C11
Na1—O2—C13—O3
Na1—O2—C13—C1
C6—C1—C13—O3
C2—C1—C13—O3
C6—C1—C13—O2
C2—C1—C13—O2
O2—Na1—O4A—N3A
O20—Na1—O4A—N3A
O40—Na1—O4A—N3A
−1.8 (3)
−179.7 (2)
−179.6 (2)
1.3 (4)
i
O30 —Na1—Na2—O70
O30—Na1—Na2—O70
O4A—Na1—Na2—O70
0.8 (4)
−2.3 (4)
179.6 (2)
176.9 (2)
−5.0 (3)
1.7 (4)
i
Na1 —Na1—Na2—O70
O2—Na1—Na2—O50
O20—Na1—Na2—O50
O40—Na1—Na2—O50
i
O30 —Na1—Na2—O50
179.9 (2)
0.3 (3)
O30—Na1—Na2—O50
O4A—Na1—Na2—O50
178.2 (2)
−177.8 (2)
2.1 (4)
i
Na1 —Na1—Na2—O50
−125.52 (9)
163.48 (10)
−167.93 (9)
−74.73 (8)
24.54 (8)
O2—Na1—Na2—O40
O20—Na1—Na2—O40
2.5 (4)
i
O30 —Na1—Na2—O40
−177.4 (2)
−0.6 (4)
−0.4 (4)
176.2 (2)
7.3 (3)
O30—Na1—Na2—O40
O4A—Na1—Na2—O40
93.92 (8)
i
Na1 —Na1—Na2—O40
−30.91 (7)
−28.60 (10)
167.93 (9)
93.20 (8)
O2—Na1—Na2—O20
O40—Na1—Na2—O20
−175.7 (2)
−169.4 (2)
7.6 (3)
i
O30 —Na1—Na2—O20
O30—Na1—Na2—O20
O4A—Na1—Na2—O20
−167.53 (9)
−98.16 (8)
137.02 (8)
−34.14 (12)
−5.54 (9)
−0.4 (4)
−177.0 (3)
2.2 (4)
i
Na1 —Na1—Na2—O20
O2—Na1—Na2—O60
O20—Na1—Na2—O60
O40—Na1—Na2—O60
−3.3 (4)
176.6 (3)
−71.7 (3)
109.3 (2)
8.7 (3)
162.38 (10)
87.65 (9)
i
O30 —Na1—Na2—O60
O30—Na1—Na2—O60
O4A—Na1—Na2—O60
−173.08 (9)
−103.70 (9)
131.48 (8)
−111.30 (10)
−82.71 (8)
85.22 (8)
i
Na1 —Na1—Na2—O60
−173.5 (2)
−172.3 (2)
5.6 (3)
ii
O2—Na1—Na2—O4
ii
O20—Na1—Na2—O4
ii
O40—Na1—Na2—O4
15.2 (5)
108.6 (5)
−160.3 (5)
−175.2 (4)
−76.2 (5)
−97.4 (5)
i
ii
O30 —Na1—Na2—O4
10.49 (8)
ii
O30—Na1—Na2—O4
109.76 (8)
179.14 (8)
54.31 (8)
ii
i
O4A—Na1—Na2—O4
O30 —Na1—O4A—N3A
i
ii
Na1 —Na1—Na2—O4
O30—Na1—O4A—N3A
i
O2—Na1—O20—Na2
160.25 (7)
Na1 —Na1—O4A—N3A
Acta Cryst. (2014). C70, 493-497
sup-15

supplementary materials
O40—Na1—O20—Na2
−8.34 (6)
−92.61 (7)
45.8 (3)
Na2—Na1—O4A—N3A
153.7 (5)
179.2 (2)
−148.3 (3)
35.5 (6)
177.8 (2)
−0.5 (4)
−2.4 (4)
179.4 (2)
−177.7 (3)
2.5 (4)
i
O30 —Na1—O20—Na2
C5A—N1A—N2A—C7A
Na1—O4A—N3A—O5A
Na1—O4A—N3A—C10A
C6A—C1A—C2A—O1A
C13A—C1A—C2A—O1A
C6A—C1A—C2A—C3A
C13A—C1A—C2A—C3A
O1A—C2A—C3A—C4A
C1A—C2A—C3A—C4A
C2A—C3A—C4A—C5A
N2A—N1A—C5A—C6A
N2A—N1A—C5A—C4A
C3A—C4A—C5A—C6A
C3A—C4A—C5A—N1A
C2A—C1A—C6A—C5A
C13A—C1A—C6A—C5A
N1A—C5A—C6A—C1A
C4A—C5A—C6A—C1A
N1A—N2A—C7A—C12A
N1A—N2A—C7A—C8A
C12A—C7A—C8A—C9A
N2A—C7A—C8A—C9A
C7A—C8A—C9A—C10A
C8A—C9A—C10A—C11A
C8A—C9A—C10A—N3A
O4A—N3A—C10A—C9A
O5A—N3A—C10A—C9A
O4A—N3A—C10A—C11A
O5A—N3A—C10A—C11A
C9A—C10A—C11A—C12A
N3A—C10A—C11A—C12A
C10A—C11A—C12A—C7A
C8A—C7A—C12A—C11A
N2A—C7A—C12A—C11A
C6A—C1A—C13A—O3A
C2A—C1A—C13A—O3A
C6A—C1A—C13A—O2A
C2A—C1A—C13A—O2A
O30—Na1—O20—Na2
O4A—Na1—O20—Na2
65.65 (6)
−80.88 (12)
72.9 (3)
i
Na1 —Na1—O20—Na2
O70—Na2—O20—Na1
O50—Na2—O20—Na1
O40—Na2—O20—Na1
O60—Na2—O20—Na1
−103.05 (9)
8.21 (6)
175.77 (7)
92.50 (7)
106.46 (7)
−138.7 (3)
−84.28 (6)
0.0
ii
O4 —Na2—O20—Na1
i
O2—Na1—O30—Na1
−0.3 (4)
173.7 (2)
−6.1 (3)
−1.9 (4)
177.9 (3)
0.2 (4)
i
O20—Na1—O30—Na1
i
O40—Na1—O30—Na1
i
i
O30 —Na1—O30—Na1
i
O4A—Na1—O30—Na1
−158.02 (7)
−101.09 (7)
−91.7 (4)
8.37 (6)
i
Na2—Na1—O30—Na1
O2—Na1—O40—Na2
O20—Na1—O40—Na2
178.4 (2)
−177.9 (2)
1.9 (4)
i
O30 —Na1—O40—Na2
105.92 (7)
−160.07 (7)
−68.45 (7)
153.57 (6)
−169.84 (11)
105.03 (8)
−8.18 (6)
−67.7 (3)
−90.63 (7)
−165.9 (2)
−66.6 (5)
95.1 (2)
O30—Na1—O40—Na2
O4A—Na1—O40—Na2
179.1 (2)
−0.6 (4)
1.2 (4)
i
Na1 —Na1—O40—Na2
O70—Na2—O40—Na1
O50—Na2—O40—Na1
O20—Na2—O40—Na1
O60—Na2—O40—Na1
−179.1 (2)
−0.4 (4)
−0.6 (4)
−179.7 (2)
−175.5 (2)
8.1 (3)
ii
O4 —Na2—O40—Na1
O20—Na1—O2—C13
O40—Na1—O2—C13
5.3 (3)
i
O30 —Na1—O2—C13
−171.1 (2)
0.8 (4)
O30—Na1—O2—C13
O4A—Na1—O2—C13
1.2 (2)
−88.9 (2)
46.2 (2)
179.9 (2)
0.0 (4)
i
Na1 —Na1—O2—C13
Na2—Na1—O2—C13
C5—N1—N2—C7
−146.4 (2)
177.7 (2)
90.3 (4)
−1.0 (4)
179.3 (2)
−2.5 (4)
175.7 (2)
179.0 (2)
−2.8 (3)
iii
Na2 —O4—N3—O5
iii
Na2 —O4—N3—C10
−92.8 (3)
179.0 (2)
1.1 (3)
C6—C1—C2—O1
C13—C1—C2—O1
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z−1; (iii) x, y−1, z+1.
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O1—H1···O2
0.82 (1)
0.82 (1)
0.82 (2)
0.82 (2)
0.82 (2)
1.80 (2)
1.80 (2)
1.93 (2)
2.04 (2)
2.32 (2)
2.534 (3)
2.532 (3)
2.750 (2)
2.862 (2)
3.135 (3)
149 (2)
147 (2)
174 (3)
173 (2)
175 (2)
O1A—H1A···O2A
O20—H21···O3A
O20—H22···O2
iv
v
vi
O30—H31···O5
Acta Cryst. (2014). C70, 493-497
sup-16

supplementary materials
vii
vii
O30—H32···O3A
O40—H41···O2A
O40—H42···O3
0.82 (2)
0.82 (2)
0.82 (2)
0.82 (3)
0.82 (3)
0.82 (3)
0.82 (2)
0.82 (4)
0.82 (3)
0.93
2.14 (3)
2.00 (2)
2.02 (2)
2.04 (2)
2.18 (2)
2.09 (3)
2.21 (3)
2.19 (5)
2.48 (5)
2.55
2.823 (3)
2.819 (3)
2.813 (3)
2.838 (3)
2.931 (3)
2.828 (3)
2.917 (3)
2.892 (4)
2.972 (4)
3.358 (3)
3.125 (3)
141 (2)
172 (2)
161 (3)
163 (3)
152 (3)
150 (3)
145 (3)
144 (4)
119 (4)
146
i
viii
O50—H51···O60
O50—H52···O5A
v
O60—H61···O3
iv
O60—H62···O2A
O70—H71···O50
viii
ii
O70—H72···O1A
iv
C12—H12···O5A
C12A—H12A···O5
vi
0.93
2.34
141
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z−1; (iv) −x, −y+1, −z+1; (v) −x, −y+1, −z; (vi) −x+1, −y, −z+1; (vii) −x+1, −y+1, −z+1; (viii) −x, −y+2,
z.
−
Selected interatomic distances (Å) in (I)–(III) compared with closely related structures
d
e
Distance
O1—C2
C1—C2
C1—C13
C5—N1
N1—N2
N2—C7
(I)
1.3400 (17) 1.350 (3)
1.403 (2) 1.419 (3)
(II)
(III)
(III)A
ACEFIZ
1.354 (3)
1.401 (3)
1.454 (3)
1.451 (3)
1.246 (3)
1.431 (3)
1.240 (2)
1.313 (2)
2.630 (2)
FUGYIP
1.355 (2)
1.403 (3)
1.462 (3)
1.432 (2)
1.260 (2)
1.424 (2)
1.241 (2)
1.311 (2)
2.631 (2)
EXIZUH1 EXIZUH2
1.352 (3)
1.399 (2)
1.503 (3)
1.420 (3)
1.266 (3)
1.419 (3)
1.286 (3)
1.257 (3)
2.534 (3)
1.347 (3)
1.421 (3)
1.496 (3)
1.405 (3)
1.245 (3)
1.420 (3)
1.281 (3)
1.234 (3)
2.532 (2)
1.350 (4)
1.396 (5)
1.479 (4)
1.413 (4)
1.242 (3)
1.431 (4)
1.229 (4)
1.300 (4)
2.574 (3)
1.362 (4)
1.397 (4)
1.482 (5)
1.421 (4)
1.245 (3)
1.437 (4)
1.228 (4)
1.290 (4)
2.605 (3)
1.4653 (19) 1.500 (3)
1.4213 (19) 1.421 (3)
1.2519 (19) 1.249 (3)
1.4256 (19) 1.428 (3)
O2—C13 1.2290 (17) 1.265 (3)
O3—C13 1.3081 (19) 1.246 (3)
O1···O2
2.619 (2)
2.524 (3)
Notes: (a) 5-(phenyldiazenyl)salicylic acid (Saikia et al., 2012); (b) 5-(4-methoxyphenyldiazenyl)salicylic acid (Basu Baul et al., 2000); (c) the molecular
complex of 5-(phenyldiazenyl)salicylic acid with dimethylpyrazole (Xu et al.; 2011); (d) the second anion in (III) is labelled with the letter `A′; (e) the
structure contains two symmetry-independent molecules.
Hydrogen-bonding geometry (Å, °) in (I)–(III)
D—H···A
I)
D—H
H···A
D···A
D—H···A
(
O1—H1···O2
O1—H1···O4
0.820 (14)
0.820 (14)
0.820 (13)
0.93
1.895 (14)
2.420 (14)
1.847 (14)
2.38
2.6189 (16)
3.0461 (18)
2.6651 (16)
3.202 (2)
146.8 (14)
134.0 (13)
176.4 (14)
147
a
b
O3—H13···O2
c
C4—H4···O5
(
II)
O1—H1···O2
N3—H21···O3
N3—H22···O2
N3—H23···O1
N3—H24···O3
0.82 (2)
0.89 (2)
0.89 (2)
0.89 (2)
0.89 (2)
1.78 (2)
1.99 (2)
1.91 (2)
2.38 (2)
1.91 (2)
2.524 (3)
2.788 (3)
2.779 (3)
3.052 (3)
2.799 (3)
151 (2)
150 (2)
164 (2)
132 (2)
172 (2)
d
e
f
(
III)
O1—H1···O2
0.820 (11)
0.820 (10)
0.82 (2)
1.796 (17)
1.804 (18)
1.93 (2)
2.534 (3)
2.532 (3)
2.750 (2)
148.9 (16)
147.3 (17)
174 (3)
O1A—H1A···O2A
g
O20—H21···O3A
Acta Cryst. (2014). C70, 493-497
sup-17

supplementary materials
h
i
O20—H22···O2
O30—H31···O5
0.82 (2)
0.82 (2)
0.82 (2)
0.82 (2)
0.82 (2)
0.82 (3)
0.82 (3)
0.82 (3)
0.82 (2)
0.82 (4)
0.82 (3)
0.93
2.04 (2)
2.32 (2)
2.14 (3)
2.00 (2)
2.02 (2)
2.04 (2)
2.18 (2)
2.09 (3)
2.21 (2)
2.19 (5)
2.48 (5)
2.55
2.862 (2)
173 (2)
175 (2)
141 (2)
172 (2)
161 (3)
163 (3)
152 (3)
150 (3)
145 (3)
144 (4)
119 (4)
146
3.135 (3)
2.823 (3)
2.819 (3)
2.813 (3)
2.838 (3)
2.931 (3)
2.828 (3)
2.917 (3)
2.892 (4)
2.972 (4)
3.358 (3)
3.125 (3)
j
O30—H32···O3A
j
O40—H41···O2A
k
O40—H42···O3
l
O50—H51···O60
O50—H52···O5A
h
O60—H61···O3
g
O60—H62···O2A
l
O70—H71···O50
m
O70—H72···O1A
g
C12—H12···O5A
i
C12A—H12A···O5
0.93
2.34
141
Symmetry codes: (a) x+2, -y+1/2, z-1/2; (b) -x+3, -y+1, -z; (c) -x, y-1/2, -z+1/2; (d) x-1, y, z+1; (e) x-1, y, z; (f) -x+1, -y, -z+2; (g) -x, -y+1, -z+1; (h) -x, -
y+1, -z; (i) -x+1, -y, -z+1; (j) -x+1, -y+1, -z+1; (k) -x+1, -y+1, -z; (l) -x, -y+2, -z; (m) x, y+1, z-1.
Results of DFT calculations for an isolated molecule of 2-hydroxy-5-(phenyldiazenyl)benzoic acid, for the same molecule
placed in a polarizable continuum with parameters simulating acetone, for two molecules bound as a dimer by a pair of
hydrogen bonds between the carboxylate groups and for the anion of 2-hydroxy-5-(phenyldiazenyl)benzoic acid placed in
a polarizable continuum with parameters simulating acetone
-1
E (anti) (Hartree)
E (syn) (Hartree)
E (syn) – E (anti) (kJ mol )
Isolated molecule
-836.78754
-836.78666
2.3
Molecule in a polarizable
continuum
-
836.79481
-1673.60221
836.32959
-836.79419
-1673.60034
-836.32899
1.6
4.9
1.6
Hydrogen-bonded dimer
Anion in a polarizable
continuum
-
Acta Cryst. (2014). C70, 493-497
sup-18

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