Supra-molecular association in proton-transfer adducts containing benzamidinium cations. II. Concomitant polymorphs of the mol-ecular salt of 2,6-dimeth-oxy-benzoic acid with benzamidine

Article abstract of DOI:10.1107/S010827011204067X

Two concomitant polymorphs of the mol-ecular salt formed by 2,6-dimeth-oxy-benzoic acid, C9H10O4 (Dmb), with benzamidine, C7H8N2 (benzene-carboximidamide, Benzam) from water solution have been identified. Benzamidinidium 2,6-dimeth-oxy-benzoate, C7H9N2 ⁺·C9H9O4 ^- (BenzamH⁺·Dmb^-), was obtained through protonation at the imino N atom of Benzam as a result of proton transfer from the acidic hydroxy group of Dmb. In the monoclinic polymorph, (I) (space group P21/n), the asymmetric unit consists of two Dmb^- anions and two monoprotonated BenzamH⁺ cations. In the ortho-rhom-bic polymorph, (II) (space group P212121), one Dmb^- anion and one BenzamH ⁺ cation constitute the asymmetric unit. In both polymorphic salts, the amidinium fragments and carboxyl-ate groups are completely delocalized. This delocalization favours the aggregation of the mol-ecular components of these acid-base complexes into nonplanar dimers with an R ² 2(8) graph-set motif via N⁺ - H...O^- charge-assisted hydrogen bonding. Both the monoclinic and ortho-rhom-bic forms exhibit one-dimensional isostructurality, as the crystal structures feature identical hydrogen-bonding motifs consisting of dimers and catemers.

Full text of DOI:10.1107/S010827011204067X

organic compounds
via N+—Hꢀ ꢀ ꢀOꢁ (ꢂ)-CAHB (charge-assisted hydrogen bonds
with both plus and minus charges on the donor and acceptor
atoms, respectively; Gilli & Gilli, 2009), provided that ÁpKa is
sufficiently large [ÁpKa = pKa(conjugate acid of the base) ꢁ
pKa(acid), where the pKa values are for aqueous solutions at
298 K]. It is generally accepted that for large ÁpKa values (i.e.
greater than 3), salts of the type B+ꢀ ꢀ ꢀAꢁ are formed, while
with smaller ÁpKa values, Bꢀ ꢀ ꢀH—A compounds (cocrystals)
can be expected, but this parameter seems inappropriate for
accurately predicting salt or cocrystal formation in the solid
state when ÁpKa is between 0 and 3 (Portalone & Colapietro,
2009; Portalone, 2011a; Delori et al., 2012). This dimeric motif
is commonly observed in biological systems between arginine
and aspartic and glutamic acids (Saenger, 1984).
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
Supramolecular association in proton-
transfer adducts containing benz-
amidinium cations. II. Concomitant
polymorphs of the molecular salt of
2,6-dimethoxybenzoic acid with
benzamidine1
Simona Irrera, Giancarlo Ortaggi and Gustavo Portalone*
Chemistry Department, University of Rome I ‘La Sapienza’, P. le A. Moro 5, I-00185
Rome, Italy
Correspondence e-mail: g.portalone@caspur.it
Received 18 August 2012
Accepted 26 September 2012
Online 18 October 2012
Two concomitant polymorphs of the molecular salt formed by
2,6-dimethoxybenzoic acid, C9H10O4 (Dmb), with benzami-
dine, C7H8N2 (benzenecarboximidamide, Benzam) from water
solution have been identified. Benzamidinidium 2,6-dimeth-
In this study, we report the molecular and supramolecular
structures of two concomitant polymorphs, i.e. two different
polymorphs simultaneously crystallized from the same solvent
(Bernstein et al., 1999), of the acid–base complex formed by
benzamidine (Benzam) with 2,6-dimethoxybenzoic acid
(Dmb). Interestingly, Dmb has two polymorphic modifica-
tions, viz. the orthorhombic form (Portalone, 2009) and the
tetragonal form (Portalone, 2011b). In the former polymorph,
the carboxyl group is twisted away from the plane of the
aromatic ring by 56.1 (1)ꢃ and the OH group adopts an anti-
planar conformation, while in the latter the twist angle is
65.7 (2)ꢃ and the OH group is synplanar. The molecular
components of the orthorhombic polymorph do not form the
conventional R22(8) dimeric units [see Etter et al. (1990),
Bernstein et al. (1995) and Motherwell et al. (1999) for graph-
set nomenclature of hydrogen bonds] as they do in the
tetragonal polymorph, but are associated in the crystal struc-
ture as catemers through single O—Hꢀ ꢀ ꢀO(carbonyl)
hydrogen bonds between adjacent molecules. As the obser-
vation of polymorphism in multicomponent systems such as
cocrystals and molecular salts is scant, although of topical
interest given the growing relevance of pharmaceutical
cocrystals (Tiekink & Vittal, 2006), we have been attracted by
the planned synthesis of polymorphic molecular salts resulting
from the combination of two conformationally flexible mol-
ecules, such as Dmb and benzamidine. For BenzamH+ꢀDmbꢁ,
since ÁpKa = 7.5, the salt is expected. Indeed, in this proton-
transfer compound protonation occurs at the imino N atom
attached to Benzam as a result of proton transfer from the
acidic hydroxy group of Dmb.
+
ꢁ
oxybenzoate, C7H9N2 ꢀC9H9O4 (BenzamH+ꢀDmbꢁ), was
obtained through protonation at the imino N atom of Benzam
as a result of proton transfer from the acidic hydroxy group of
Dmb. In the monoclinic polymorph, (I) (space group P21/n),
the asymmetric unit consists of two Dmbꢁ anions and two
monoprotonated BenzamH+ cations. In the orthorhombic
polymorph, (II) (space group P212121), one Dmbꢁ anion and
one BenzamH+ cation constitute the asymmetric unit. In both
polymorphic salts, the amidinium fragments and carboxylate
groups are completely delocalized. This delocalization favours
the aggregation of the molecular components of these acid–
base complexes into nonplanar dimers with an R22(8) graph-set
motif via N+—Hꢀ ꢀ ꢀOꢁ charge-assisted hydrogen bonding.
Both the monoclinic and orthorhombic forms exhibit one-
dimensional isostructurality, as the crystal structures feature
identical hydrogen-bonding motifs consisting of dimers and
catemers.
Comment
The present study is a continuation of work carried out in our
laboratory on the design and synthesis of hydrogen-bonding
systems formed by benzamidine with benzoic acid derivatives.
The protonated analogue of benzamidine is a multiple
hydrogen-bond donor, and its amidinium group exhibits ideal
requirements to couple with carboxylate groups in crystal
structures. These acid–base complexes are usually arranged in
a dimeric motif similar to that found in carboxylic acid dimers
Polymorph (I) crystallizes in the monoclinic space group
P21/n, with two crystallographically independent dimers of
monoprotonated benzamidinium cations (BenzamH+) and
1 Part I: Portalone (2010).
Acta Cryst. (2012). C68, o447–o451
doi:10.1107/S010827011204067X
# 2012 International Union of Crystallography o447

organic compounds
Figure 1
The asymmetric unit of polymorph (I), showing the atom-labelling scheme and hydrogen bonding (dashed lines). The asymmetric unit was selected so
that the four ions are linked by N+—Hꢀ ꢀ ꢀOꢁ (ꢂ)-CAHB hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level.
benzoate anions (Dmbꢁ) in the asymmetric unit (Fig. 1).
Polymorph (II) crystallizes in the orthorhombic space group
P212121, with one BenzamH+ cation and one Dmbꢁ anion in
the asymmetric unit (Fig. 2).
force the carboxylate groups to be almost orthogonal to the
plane of the aromatic fragment [the twist angles between the
aromatic ring and the carboxylate group are 88.7 (1) and
72.3 (1)ꢃ for polymorph (I), and 78.9 (1)ꢃ for polymorph (II)].
In these anions, the bond lengths and angles of the benzene
ring are in accord with the corresponding values obtained for
both the orthorhombic and tetragonal forms of 2,6-dimeth-
oxybenzoic acid (Portalone, 2009, 2011b) and for 4-methoxy-
benzamidinium 2,6-dimethoxybenzoate (Portalone, 2012).
The C—O distances of the carboxylate group range from
The molecular structures of polymorphs (I) and (II) are
very similar. In both polymorphic forms, the BenzamH+
cations are not planar. The dihedral angles between the mean
plane of the benzene ring and the amidinium group [20.2 (1)
and 14.4 (1)ꢃ for polymorph (I), and 23.6 (1)ꢃ for polymorph
(II)] are close to the values observed in benzamidine
[22.7 (1)ꢃ; Barker et al., 1996], benzamidinium (2-acetamido-
benzoyl)formate [16 (3)ꢃ; Joshi et al., 1994] and benzamidin-
ium acetylsalicylate [15.2 (2)ꢃ; Kolev et al., 2009]. For both
polymorphs this disposition is a consequence of an over-
crowding effect, i.e. steric hindrance between the NH2 group
and the benzene ring, as indicated by the N—C(ortho)
˚
1.246 (2) to 1.255 (2) A, indicating delocalization of the
negative charge.
The molecular components of both polymorphs are joined
by two N+—Hꢀ ꢀ ꢀOꢁ (ꢂ)-CAHB hydrogen bonds to form
ionic dimers with graph-set motif R22(8). Remarkably, at
variance with the well known carboxylic acid dimer R22(8)
motif, in both polymorphs the carboxylate–amidinium pairs
are not planar, as the dihedral angles for the planes defined by
˚
contacts in the range 2.859 (2)–2.893 (2) A, and prevents
conjugation between the N—C—N system and the benzene
ring. Indeed, the C—C(amidine) distances are in the range
˚
1.479 (3)–1.481 (3) A and compare well with the expected
2
2
˚
Csp —Csp single-bond length of 1.482 (1) A (Allen et al.,
1987). Interestingly, only the nonplanar conformation has
been observed in small-molecule crystal structures, whereas in
structures containing benzamidinium in the Protein Data
Bank (PDB; Berman et al., 2000), the most frequently
encountered one is the planar conformation (Li et al., 2009).
˚
The C—N bond lengths are in the range 1.305 (2)–1.317 (2) A,
evidencing the delocalization of the ꢀ electrons and double-
bond character compared with the corresponding bond
˚
lengths found in benzamidine [1.294 (3) and 1.344 (3) A;
Figure 2
The asymmetric unit of polymorph (II), showing the atom-labelling
scheme and hydrogen bonding (dashed lines). The asymmetric unit was
selected so that the two ions are linked by N+—Hꢀ ꢀ ꢀOꢁ (ꢂ)-CAHB
hydrogen bonds. Displacement ellipsoids are drawn at the 50%
probability level.
Barker et al., 1996] and benzdiamidine [1.283 (2) and
˚
The benzene rings in the Dmbꢁ anions of polymorphs (I)
and (II) are essentially planar, and the methoxy substituents
´
1.349 (2) A; Jokic et al., 2001].
+
ꢁ
ꢄ
o448 Irrera et al. Two polymorphs of C7H9N2 ꢀC9H9O4
Acta Cryst. (2012). C68, o447–o451

organic compounds
into linear chains through hydrogen bonding to adjacent
antiparallel dimers. Such a disposition of dimers and catemers
has frequently been observed in the solid-state structures of
´
amides (Melendez & Hamilton, 1998).
From a supramolecular retrosynthesis perspective, only
those synthons that occur repeatedly in crystal structures,
namely robust synthons of a particular set of functional
groups, are useful in crystal design (Nangia & Desiraju, 1998).
Moreover, hydrogen bonds are often formed in a hierarchical
fashion (Etter, 1990; Allen et al., 1999; Bis et al., 2007; Shattock
et al., 2008) and there is a need to ascertain the prevalence of a
particular heterosynthon over another in a competitive
environment. From the results reported herein, the crystal
structures of polymorphs (I) and (II) are both consistent with
the R22(8) supramolecular heterosynthon persistence exhibited
by the benzamidinium adducts that have been archived in the
Cambridge Structural Database (CSD, Version 5.33,
November 2011; Allen, 2002). Consequently, the existence of
polymorphism in these molecular salts should be related to the
conformational flexibility of the carboxylate and amidinium
groups. Polymorphs (I) and (II) therefore represent examples
of conformational polymorphism. To the best of our knowl-
edge, the only exception to the complementarity of amidinium
and carboxylate groups has been reported for benzamidinium
isoorotate (Portalone, 2010).
Figure 3
The supramolecular structure of polymorph (I), viewed approximately
down a. For the sake of clarity, H atoms not involved in hydrogen bonding
have been omitted. Hydrogen bonding is indicated by dashed lines.
+
ꢁ
the CN2 and CO2 atoms are in the range 26.8–29.5ꢃ.
Nonetheless, the interface is very stable, as indicated by the
N+—Hꢀ ꢀ ꢀOꢁ parameters: N+ꢀ ꢀ ꢀOꢁ diꢁstances in the range
+
˚
2.785 (2)–2.868 (2) A) and N —Hꢀ ꢀ ꢀO angles in the range
148 (2)–177 (2)ꢃ. This deviation from planarity of carboxyl-
ate–amidinium pairs has previously been observed in the
crystal structure of 3-amidinium benzoate (Papoutsakis et al.,
1999).
Due to the protonated base, supramolecular aggregations in
(I) and (II) are dominated by an extensive series of N+—
Hꢀ ꢀ ꢀOꢁ (ꢂ)-CAHB hydrogen bonds (Tables 1 and 2). In the
supramolecular structures of polymorphs (I) and (II) (Figs. 3
and 4), eight and four hydrogen bonds, respectively, link the
molecular components into a one-dimensional structure. As
mentioned previously, each subunit, built from the ion pairs of
the asymmetric unit, forms R22(8) dimers via the interaction of
the N—H and C O groups. These subunits are then joined
Experimental
Equimolar amounts of benzamidine (Fluka, 95%) and 2,6-dimeth-
oxybenzoic acid (Sigma Aldrich, 99%), dissolved in ethanol (20 ml),
were refluxed for 8 h at 323 K. The mixture was cooled to room
temperature and the solvent evaporated under vacuum. The product
was then recrystallized from water to give, after one week, colourless
crystals suitable for X-ray analysis. Careful examination of the batch
under a microscope showed crystals in the form of tablets of (I) and
small prisms of (II). The majority of the crystals were (II), with a
small quantity of (I). Unfortunately, any attempts to produce more
crystals of polymorph (I) by repeating the crystallization conditions
were unsuccessful. Crystallization of the molecular salt carried out
under a wide range of different sets of conditions (different solvents,
different molar ratios etc.) led systematically to the orthorhombic
polymorph, (II).
Polymorph (I)
Crystal data
+
ꢁ
3
˚
V = 3212.39 (8) A
Z = 8
Mo Kꢂ radiation
ꢃ = 0.09 mmꢁ1
T = 298 K
C7H9N2 ꢀC9H9O4
Mr = 302.32
Monoclinic, P21=n
a = 14.7103 (2) A
˚
˚
b = 11.7174 (1) A
˚
c = 19.7281 (3) A
0.20 ꢅ 0.15 ꢅ 0.14 mm
ꢁ = 109.145 (2)ꢃ
Data collection
Oxford Xcalibur S CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis RED; Oxford
Diffraction, 2006)
248320 measured reflections
5682 independent reflections
4978 reflections with I > 2ꢄ(I)
Rint = 0.041
Figure 4
The supramolecular structure of polymorph (II), viewed approximately
down c. For the sake of clarity, H atoms not involved in hydrogen bonding
have been omitted. Hydrogen bonding is indicated by dashed lines.
Tmin = 0.982, Tmax = 0.987
+
ꢁ
ꢄ
Acta Cryst. (2012). C68, o447–o451
Irrera et al.
Two polymorphs of C7H9N2 ꢀC9H9O4
o449

organic compounds
Table 1
Hydrogen-bond geometry (A, ) for polymorph (I).
Table 2
Hydrogen-bond geometry (A, ) for polymorph (II).
ꢃ
ꢃ
˚
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1Aꢀ ꢀ ꢀO1
0.92 (2)
0.90 (3)
0.95 (2)
0.93 (2)
0.92 (2)
0.91 (3)
0.92 (2)
0.92 (3)
1.89 (3)
2.03 (3)
1.85 (2)
1.93 (2)
1.87 (3)
1.95 (3)
1.95 (2)
1.94 (3)
2.799 (2)
2.827 (2)
2.796 (2)
2.763 (2)
2.785 (2)
2.773 (2)
2.868 (2)
2.789 (2)
171 (2)
148 (2)
176.3 (19)
148.7 (19)
175 (2)
150 (2)
173.0 (19)
153 (2)
N1—H1Aꢀ ꢀ ꢀO1
N1—H1Bꢀ ꢀ ꢀO2i
N2—H2Bꢀ ꢀ ꢀO1ii
N2—H2Aꢀ ꢀ ꢀO2
1.00 (3)
0.84 (3)
0.96 (3)
0.86 (3)
1.82 (3)
2.00 (3)
1.90 (3)
1.97 (3)
2.802 (2)
2.792 (2)
2.794 (2)
2.821 (2)
166 (2)
157 (3)
154 (3)
177 (3)
N1—H1Bꢀ ꢀ ꢀO1A
N2—H2Aꢀ ꢀ ꢀO2
N2—H2Bꢀ ꢀ ꢀO2i
N1A—H1A1ꢀ ꢀ ꢀO1A
N1A—H1A2ꢀ ꢀ ꢀO1
N2A—H2A1ꢀ ꢀ ꢀO2A
N2A—H2A2ꢀ ꢀ ꢀO2Aii
1
2
1
2
1
2
1
2
Symmetry codes: (i) x ꢁ ; ꢁy þ ; ꢁz; (ii) x þ ; ꢁy þ ; ꢁz.
Symmetry codes: (i) ꢁx; ꢁy; ꢁz; (ii) ꢁx; ꢁy; ꢁz þ 1.
refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
ORTEP-3 (Farrugia, 1997); software used to prepare material for
publication: WinGX (Farrugia, 1999).
Refinement
R[F2 > 2ꢄ(F2)] = 0.058
wR(F2) = 0.129
S = 1.18
5682 reflections
437 parameters
H atoms treated by a mixture of
independent and constrained
refinement
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: UK3051). Services for accessing these data are
described at the back of the journal.
ꢁ3
˚
Áꢅmax = 0.18 e A
ꢁ3
˚
Áꢅmin = ꢁ0.17 e A
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˚
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C7H9N2 ꢀC9H9O4
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˚
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˚
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˚
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Acta Cryst. (2012). C68, o447–o451
Irrera et al.
Two polymorphs of C7H9N2 ꢀC9H9O4
o451

supplementary materials
supplementary materials
Acta Cryst. (2012). C68, o447–o451 [doi:10.1107/S010827011204067X]
Supramolecular association in proton-transfer adducts containing
benzamidinium cations. II. Concomitant polymorphs of the molecular salt of
2,6-dimethoxybenzoic acid with benzamidine
Simona Irrera, Giancarlo Ortaggi and Gustavo Portalone
(I) Benzamidinidium 2,6-dimethoxybenzoate
Crystal data
C7H9N2+·C9H9O4−
Mr = 302.32
F(000) = 1280
Dx = 1.250 Mg m−3
Mo Kα radiation, λ = 0.71069 Å
Cell parameters from 71996 reflections
θ = 2.7–32.5°
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 14.7103 (2) Å
b = 11.7174 (1) Å
c = 19.7281 (3) Å
β = 109.145 (2)°
V = 3212.39 (8) Å3
Z = 8
µ = 0.09 mm−1
T = 298 K
Tablet, colourless
0.20 × 0.15 × 0.14 mm
Data collection
Oxford Xcalibur S CCD area-detector
diffractometer
Radiation source: Enhance (Mo) X-ray source
Graphite monochromator
Detector resolution: 16.0696 pixels mm-1
ω and φ scans
248320 measured reflections
5682 independent reflections
4978 reflections with I > 2σ(I)
Rint = 0.041
θmax = 25.1°, θmin = 2.7°
h = −17→17
k = −13→13
l = −23→23
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)
T
min = 0.982, Tmax = 0.987
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.058
wR(F2) = 0.129
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.18
5682 reflections
437 parameters
0 restraints
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0502P)2 + 1.0275P]
where P = (Fo2 + 2Fc2)/3
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max < 0.001
Δρmax = 0.18 e Å−3
Δρmin = −0.17 e Å−3
Acta Cryst. (2012). C68, o447–o451
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supplementary materials
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.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
N1
0.03204 (13)
−0.0078 (16)
0.0478 (17)
0.05603 (13)
0.0065 (15)
0.0836 (16)
0.15214 (13)
0.19618 (18)
0.1780
−0.09912 (16)
−0.037 (2)
−0.127 (2)
−0.08038 (15)
−0.0247 (19)
−0.1015 (19)
−0.22020 (16)
−0.2465 (2)
−0.2063
0.19097 (9)
0.1779 (12)
0.2356 (14)
0.08423 (8)
0.0728 (11)
0.0499 (12)
0.16763 (9)
0.23911 (12)
0.2757
0.0442 (4)
0.058 (6)*
0.064 (7)*
0.0434 (4)
0.051 (6)*
0.057 (6)*
0.0375 (4)
0.0658 (7)
0.079*
H1A
H1B
N2
H2A
H2B
C1
C2
H2
C3
0.2663 (2)
−0.3302 (3)
−0.3487
0.25849 (14)
0.3087
0.0894 (10)
0.107*
H3
0.2971
C4
0.29260 (19)
0.3416
−0.3871 (2)
−0.4460
0.20706 (14)
0.2210
0.0726 (8)
0.087*
H4
C5
0.24997 (19)
0.2692
−0.3609 (2)
−0.4007
0.13663 (14)
0.1004
0.0661 (7)
0.079*
H5
C6
0.17957 (16)
0.1492
−0.27801 (19)
−0.2602
0.11630 (11)
0.0659
0.0539 (6)
0.065*
H6
C7
0.07768 (12)
−0.07302 (11)
−0.08607 (10)
−0.28794 (11)
0.01547 (13)
−0.13889 (14)
−0.23748 (15)
−0.27836 (19)
−0.3474
−0.13012 (15)
0.10458 (12)
0.08850 (11)
0.17659 (14)
0.33083 (15)
0.26004 (16)
0.27510 (18)
0.3830 (2)
0.3930
0.14702 (9)
0.16122 (7)
0.04679 (6)
0.06376 (10)
0.10538 (12)
0.08429 (9)
0.06566 (11)
0.05061 (13)
0.0377
0.0337 (4)
0.0517 (4)
0.0468 (3)
0.0719 (5)
0.0840 (6)
0.0397 (4)
0.0491 (5)
0.0647 (7)
0.078*
O1
O2
O3
O4
C8
C9
C10
H10
C11
H11
C12
H12
C13
C14
C15
H15A
H15B
H15C
C16
−0.2192 (2)
−0.2473
0.4750 (2)
0.5504
0.05443 (14)
0.0436
0.0752 (8)
0.090*
−0.1210 (2)
−0.0804
0.4630 (2)
0.5293
0.07318 (14)
0.0761
0.0722 (7)
0.087*
−0.08068 (17)
−0.09559 (13)
−0.39002 (19)
−0.4099 (5)
−0.4160 (6)
−0.4156 (6)
0.0817 (3)
0.35450 (19)
0.14224 (16)
0.1817 (3)
0.237 (2)
0.08794 (12)
0.09883 (9)
0.0417 (2)
0.0725 (11)
0.0464 (14)
−0.0092 (11)
0.1170 (2)
0.0552 (6)
0.0352 (4)
0.1092 (13)
0.164*
0.1048 (17)
0.207 (2)
0.164*
0.164*
0.4227 (3)
0.1181 (14)
Acta Cryst. (2012). C68, o447–o451
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supplementary materials
H16A
H16B
H16C
N1A
0.0782 (15)
0.0656 (13)
0.1476 (15)
−0.03060 (14)
0.0110 (17)
−0.0469 (17)
−0.04005 (13)
−0.0029 (15)
−0.0631 (16)
−0.12632 (13)
−0.16792 (17)
−0.1555
0.4693 (18)
0.4706 (18)
0.3922 (7)
0.09627 (16)
0.036 (2)
0.1579 (13)
0.0734 (11)
0.1279 (16)
0.30888 (9)
0.3226 (12)
0.2637 (14)
0.42044 (9)
0.4282 (11)
0.4560 (13)
0.34031 (9)
0.27002 (11)
0.2315
0.177*
0.177*
0.177*
0.0496 (5)
0.061 (7)*
0.063 (7)*
0.0440 (4)
0.051 (6)*
0.064 (7)*
0.0377 (4)
0.0550 (6)
0.066*
H1A1
H1A2
N2A
0.125 (2)
0.09148 (15)
0.0266 (19)
0.115 (2)
H2A1
H2A2
C1A
0.24195 (15)
0.27778 (18)
0.2362
C2A
H2A3
C3A
−0.2270 (2)
−0.2562
0.3725 (2)
0.3968
0.25458 (13)
0.2052
0.0727 (8)
0.087*
H3A
C4A
−0.24465 (19)
−0.2862
0.4325 (2)
0.4990
0.30864 (14)
0.2975
0.0695 (7)
0.083*
H4A
C5A
−0.20335 (18)
−0.2153
0.3982 (2)
0.4412
0.37838 (13)
0.4166
0.0620 (6)
0.074*
H5A
C6A
−0.14501 (15)
−0.1169
0.30321 (18)
0.2790
0.39470 (11)
0.4442
0.0495 (5)
0.059*
H6A
C7A
−0.06351 (13)
0.08851 (11)
0.06223 (10)
0.25262 (11)
−0.04000 (12)
0.10499 (14)
0.19058 (15)
0.20891 (19)
0.2683
0.13984 (15)
−0.09474 (11)
−0.12115 (11)
−0.25549 (13)
−0.29495 (15)
−0.28187 (16)
−0.33014 (17)
−0.4456 (2)
−0.4790
0.35715 (9)
0.34245 (7)
0.44559 (7)
0.47826 (9)
0.29483 (9)
0.38908 (10)
0.43287 (11)
0.42869 (14)
0.4597
0.0344 (4)
0.0477 (4)
0.0459 (3)
0.0638 (4)
0.0738 (5)
0.0390 (4)
0.0461 (5)
0.0643 (6)
0.077*
O1A
O2A
O3A
O4A
C8A
C9A
C10A
H10A
C11A
H11A
C12A
H12A
C13A
C14A
C15A
H15D
H15E
H15F
C16A
H16D
H16E
H16F
0.1415 (2)
−0.5118 (2)
−0.5929
0.37979 (16)
0.3774
0.0798 (8)
0.096*
0.1535
0.0574 (2)
−0.4663 (2)
−0.5141
0.33399 (15)
0.2993
0.0762 (8)
0.091*
0.0111
0.04010 (16)
0.08406 (12)
0.34956 (18)
0.3773 (7)
−0.35059 (18)
−0.15605 (15)
−0.2927 (2)
−0.3192 (17)
−0.3577 (16)
−0.2275 (12)
−0.3497 (3)
−0.2944 (11)
−0.4139 (17)
−0.3794 (18)
0.33850 (12)
0.39317 (9)
0.51199 (17)
0.4742 (6)
0.5457 (10)
0.5398 (10)
0.23207 (17)
0.2015 (8)
0.2448 (3)
0.2055 (8)
0.0540 (5)
0.0340 (4)
0.0819 (8)
0.123*
0.3505 (2)
0.123*
0.3892 (8)
0.123*
−0.0970 (2)
−0.1438 (14)
−0.1323 (14)
−0.0553 (8)
0.0950 (10)
0.143*
0.143*
0.143*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N1
N2
C1
0.0567 (11)
0.0488 (10)
0.0415 (10)
0.0485 (10)
0.0528 (10)
0.0392 (10)
0.0307 (9)
0.0309 (8)
0.0343 (10)
0.0184 (9)
0.0144 (8)
0.0026 (8)
0.0186 (8)
0.0164 (8)
0.0157 (8)
0.0060 (8)
0.0074 (8)
0.0010 (8)
Acta Cryst. (2012). C68, o447–o451
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supplementary materials
C2
0.0752 (16)
0.099 (2)
0.0860 (17)
0.120 (2)
0.0402 (12)
0.0519 (14)
0.0750 (17)
0.0630 (15)
0.0387 (11)
0.0277 (9)
0.0298 (7)
0.0301 (7)
0.1058 (14)
0.1257 (16)
0.0258 (9)
0.0414 (11)
0.0587 (14)
0.0655 (16)
0.0734 (17)
0.0495 (12)
0.0285 (9)
0.174 (4)
0.0412 (14)
0.0678 (19)
0.0401 (14)
0.0240 (13)
0.0166 (11)
−0.0015 (8)
0.0258 (7)
0.0174 (7)
0.0119 (8)
−0.0100 (9)
0.0085 (9)
0.0154 (10)
0.0304 (13)
0.0296 (15)
0.0017 (13)
0.0051 (11)
0.0060 (8)
0.0153 (16)
−0.033 (2)
0.0242 (10)
0.0151 (9)
0.0009 (8)
0.0196 (11)
0.0349 (14)
0.0307 (13)
0.0179 (12)
0.0124 (10)
0.0002 (8)
0.0150 (7)
0.0154 (7)
0.0168 (7)
0.0100 (9)
0.0065 (9)
0.0127 (10)
0.0239 (12)
0.0138 (14)
−0.0016 (13)
0.0063 (10)
0.0066 (8)
0.0125 (13)
−0.0080 (17)
0.0243 (11)
0.0286 (15)
0.0369 (14)
0.0376 (13)
0.0211 (10)
0.0101 (7)
0.0218 (7)
0.0172 (6)
0.0250 (9)
0.0227 (11)
0.0144 (8)
0.0159 (10)
0.0149 (12)
0.0194 (15)
0.0243 (15)
0.0154 (11)
0.0126 (8)
0.0370 (19)
0.026 (2)
0.0112 (12)
0.0290 (15)
0.0194 (14)
−0.0042 (12)
0.0006 (10)
−0.0026 (7)
0.0097 (6)
0.0016 (6)
C3
C4
0.0754 (17)
0.0802 (17)
0.0672 (14)
0.0364 (9)
0.0754 (10)
0.0641 (9)
0.0472 (9)
0.0628 (11)
0.0550 (12)
0.0556 (13)
0.0701 (16)
0.106 (2)
0.0763 (17)
0.0654 (15)
0.0586 (13)
0.0368 (9)
0.0533 (8)
0.0474 (8)
0.0626 (10)
0.0574 (10)
0.0392 (10)
0.0502 (12)
0.0607 (15)
0.0473 (14)
0.0397 (13)
0.0472 (12)
0.0400 (10)
0.104 (2)
C5
C6
C7
O1
O2
O3
0.0152 (10)
−0.0006 (10)
0.0022 (8)
0.0049 (9)
0.0070 (12)
0.0064 (12)
0.0010 (12)
0.0010 (10)
0.0030 (8)
0.022 (2)
O4
C8
C9
C10
C11
C12
C13
C14
C15
C16
N1A
N2A
C1A
C2A
C3A
C4A
C5A
C6A
C7A
O1A
O2A
O3A
O4A
C8A
C9A
C10A
C11A
C12A
C13A
C14A
C15A
C16A
0.101 (2)
0.0663 (15)
0.0382 (10)
0.0492 (16)
0.092 (2)
0.090 (2)
0.161 (4)
−0.008 (2)
0.0069 (8)
0.0038 (7)
−0.0009 (8)
0.0047 (9)
0.0172 (12)
0.0128 (12)
−0.0037 (11)
−0.0009 (9)
−0.0022 (7)
0.0098 (6)
0.0035 (6)
−0.0038 (8)
−0.0177 (9)
0.0019 (8)
0.0050 (9)
0.0699 (12)
0.0607 (11)
0.0441 (10)
0.0788 (15)
0.101 (2)
0.0519 (10)
0.0437 (10)
0.0356 (10)
0.0495 (12)
0.0633 (15)
0.0506 (13)
0.0519 (13)
0.0488 (12)
0.0357 (9)
0.0423 (7)
0.0450 (8)
0.0563 (9)
0.0666 (10)
0.0384 (10)
0.0431 (11)
0.0490 (13)
0.0378 (13)
0.0474 (14)
0.0479 (12)
0.0381 (10)
0.0728 (17)
0.088 (2)
0.0312 (9)
0.0306 (9)
0.0348 (10)
0.0382 (11)
0.0506 (13)
0.0767 (17)
0.0614 (14)
0.0408 (11)
0.0282 (9)
0.0379 (7)
0.0323 (7)
0.0671 (10)
0.0649 (10)
0.0334 (9)
0.0428 (11)
0.0703 (15)
0.097 (2)
0.0223 (8)
0.0191 (8)
0.0150 (8)
0.0210 (11)
0.0212 (13)
0.0321 (14)
0.0342 (13)
0.0207 (10)
0.0115 (8)
0.0299 (7)
0.0246 (6)
−0.0003 (8)
−0.0074 (8)
0.0202 (9)
0.0186 (10)
0.0232 (13)
0.0305 (18)
0.0141 (15)
0.0165 (11)
0.0114 (7)
0.0030 (14)
−0.0094 (16)
0.0853 (18)
0.0806 (17)
0.0618 (13)
0.0397 (10)
0.0716 (10)
0.0665 (9)
0.0533 (9)
0.0683 (11)
0.0499 (11)
0.0544 (12)
0.0732 (16)
0.103 (2)
0.0100 (12)
−0.0053 (13)
−0.0186 (13)
−0.0063 (10)
0.0010 (8)
0.0060 (16)
−0.0218 (17)
0.0861 (19)
0.0612 (14)
0.0377 (10)
0.0538 (15)
0.086 (2)
0.0850 (18)
0.0516 (12)
0.0268 (9)
0.103 (2)
0.084 (2)
Geometric parameters (Å, º)
N1—C7
1.310 (2)
N1A—C7A
1.305 (2)
N1—H1A
N1—H1B
N2—C7
0.92 (2)
0.90 (3)
1.310 (2)
0.95 (2)
0.93 (2)
N1A—H1A1
N1A—H1A2
N2A—C7A
N2A—H2A1
N2A—H2A2
0.92 (2)
0.91 (3)
1.310 (2)
0.92 (2)
0.92 (3)
N2—H2A
N2—H2B
Acta Cryst. (2012). C68, o447–o451
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supplementary materials
C1—C2
1.380 (3)
1.384 (3)
1.479 (3)
1.383 (3)
0.9700
C1A—C2A
C1A—C6A
1.385 (3)
1.391 (3)
1.481 (3)
1.381 (3)
0.9700
C1—C6
C1—C7
C1A—C7A
C2—C3
C2A—C3A
C2—H2
C2A—H2A3
C3A—C4A
C3—C4
1.372 (4)
0.9700
1.371 (3)
0.9700
C3—H3
C3A—H3A
C4A—C5A
C4—C5
1.359 (3)
0.9700
1.370 (3)
0.9700
C4—H4
C4A—H4A
C5A—C6A
C5—C6
1.380 (3)
0.9700
1.378 (3)
0.9700
C5—H5
C5A—H5A
C6A—H6A
O1A—C14A
O2A—C14A
O3A—C9A
O3A—C15A
O4A—C13A
O4A—C16A
C8A—C13A
C8A—C9A
C6—H6
0.9700
0.9700
O1—C14
O2—C14
O3—C9
1.246 (2)
1.251 (2)
1.366 (3)
1.421 (3)
1.370 (3)
1.419 (3)
1.386 (3)
1.387 (3)
1.508 (3)
1.389 (3)
1.372 (4)
0.9700
1.251 (2)
1.248 (2)
1.365 (3)
1.430 (3)
1.375 (3)
1.402 (3)
1.389 (3)
1.392 (3)
1.514 (3)
1.387 (3)
1.374 (4)
0.9700
O3—C15
O4—C13
O4—C16
C8—C9
C8—C13
C8—C14
C9—C10
C10—C11
C10—H10
C11—C12
C11—H11
C12—C13
C12—H12
C15—H15A
C15—H15B
C15—H15C
C16—H16A
C16—H16B
C16—H16C
C8A—C14A
C9A—C10A
C10A—C11A
C10A—H10A
C11A—C12A
C11A—H11A
C12A—C13A
C12A—H12A
C15A—H15D
C15A—H15E
C15A—H15F
C16A—H16D
C16A—H16E
C16A—H16F
1.375 (4)
0.9700
1.378 (4)
0.9700
1.393 (3)
0.9700
1.387 (3)
0.9700
0.9946
1.0080
0.9946
1.0080
0.9946
1.0080
0.9886
0.9925
0.9886
0.9925
0.9886
0.9925
C7—N1—H1A
C7—N1—H1B
H1A—N1—H1B
C7—N2—H2A
C7—N2—H2B
H2A—N2—H2B
C2—C1—C6
C2—C1—C7
C6—C1—C7
C1—C2—C3
C1—C2—H2
C3—C2—H2
C4—C3—C2
C4—C3—H3
117.0 (14)
121.7 (15)
120 (2)
C7A—N1A—H1A1
C7A—N1A—H1A2
H1A1—N1A—H1A2
C7A—N2A—H2A1
C7A—N2A—H2A2
H2A1—N2A—H2A2
C2A—C1A—C6A
C2A—C1A—C7A
C6A—C1A—C7A
C3A—C2A—C1A
C3A—C2A—H2A3
C1A—C2A—H2A3
C4A—C3A—C2A
C4A—C3A—H3A
117.3 (14)
121.7 (15)
121 (2)
117.5 (12)
122.8 (14)
119.6 (19)
119.12 (18)
119.83 (16)
121.04 (17)
119.9 (2)
120.1
118.2 (13)
123.3 (15)
118 (2)
118.80 (18)
120.53 (16)
120.68 (16)
120.3 (2)
119.9
120.1
119.9
120.4 (2)
119.8
120.4 (2)
119.8
Acta Cryst. (2012). C68, o447–o451
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supplementary materials
C2—C3—H3
119.8
C2A—C3A—H3A
C5A—C4A—C3A
C5A—C4A—H4A
C3A—C4A—H4A
C4A—C5A—C6A
C4A—C5A—H5A
C6A—C5A—H5A
C5A—C6A—C1A
C5A—C6A—H6A
C1A—C6A—H6A
N1A—C7A—N2A
N1A—C7A—C1A
N2A—C7A—C1A
119.8
C5—C4—C3
119.9 (2)
120.0
119.7 (2)
120.1
C5—C4—H4
C3—C4—H4
120.0
120.1
C4—C5—C6
120.5 (2)
119.8
120.6 (2)
119.7
C4—C5—H5
C6—C5—H5
119.8
119.7
C5—C6—C1
120.2 (2)
119.9
120.14 (19)
119.9
C5—C6—H6
C1—C6—H6
119.9
119.9
N1—C7—N2
118.95 (18)
120.66 (16)
120.39 (16)
118.9 (2)
119.0 (2)
119.14 (18)
120.48 (18)
120.37 (18)
114.31 (17)
124.7 (2)
121.0 (2)
118.7 (2)
120.6
118.76 (18)
120.36 (16)
120.88 (16)
N1—C7—C1
N2—C7—C1
C9—O3—C15
C13—O4—C16
C9—C8—C13
C9—C8—C14
C13—C8—C14
O3—C9—C8
C9A—O3A—C15A
C13A—O4A—C16A
C13A—C8A—C9A
C13A—C8A—C14A
C9A—C8A—C14A
O3A—C9A—C10A
O3A—C9A—C8A
117.38 (18)
118.5 (2)
118.60 (18)
119.93 (17)
121.40 (17)
124.2 (2)
114.88 (17)
120.9 (2)
118.9 (2)
120.6
O3—C9—C10
C8—C9—C10
C11—C10—C9
C11—C10—H10
C9—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
C11—C12—C13
C11—C12—H12
C13—C12—H12
O4—C13—C8
O4—C13—C12
C8—C13—C12
O1—C14—O2
O1—C14—C8
O2—C14—C8
O3—C15—H15A
O3—C15—H15B
H15A—C15—H15B
O3—C15—H15C
H15A—C15—H15C
H15B—C15—H15C
O4—C16—H16A
O4—C16—H16B
H16A—C16—H16B
O4—C16—H16C
H16A—C16—H16C
H16B—C16—H16C
C10A—C9A—C8A
C11A—C10A—C9A
C11A—C10A—H10A
C9A—C10A—H10A
C10A—C11A—C12A
C10A—C11A—H11A
C12A—C11A—H11A
C11A—C12A—C13A
C11A—C12A—H12A
C13A—C12A—H12A
O4A—C13A—C12A
O4A—C13A—C8A
C12A—C13A—C8A
O2A—C14A—O1A
O2A—C14A—C8A
O1A—C14A—C8A
O3A—C15A—H15D
O3A—C15A—H15E
H15D—C15A—H15E
O3A—C15A—H15F
H15D—C15A—H15F
H15E—C15A—H15F
O4A—C16A—H16D
O4A—C16A—H16E
H16D—C16A—H16E
O4A—C16A—H16F
H16D—C16A—H16F
H16E—C16A—H16F
120.6
120.6
121.7 (2)
119.1
121.8 (2)
119.1
119.1
119.1
119.1 (2)
120.4
118.7 (2)
120.7
120.4
120.7
114.87 (19)
124.8 (2)
120.3 (2)
124.56 (17)
118.12 (15)
117.31 (15)
109.5
124.1 (2)
114.90 (18)
121.0 (2)
124.75 (16)
118.39 (15)
116.85 (15)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
Acta Cryst. (2012). C68, o447–o451
sup-6

supplementary materials
C6—C1—C2—C3
C7—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C6
C4—C5—C6—C1
C2—C1—C6—C5
C7—C1—C6—C5
C2—C1—C7—N1
C6—C1—C7—N1
C2—C1—C7—N2
C6—C1—C7—N2
C15—O3—C9—C8
C15—O3—C9—C10
C13—C8—C9—O3
C14—C8—C9—O3
C13—C8—C9—C10
C14—C8—C9—C10
O3—C9—C10—C11
C8—C9—C10—C11
C9—C10—C11—C12
C10—C11—C12—C13
C16—O4—C13—C8
C16—O4—C13—C12
C9—C8—C13—O4
C14—C8—C13—O4
C9—C8—C13—C12
C14—C8—C13—C12
C11—C12—C13—O4
C11—C12—C13—C8
C9—C8—C14—O1
C13—C8—C14—O1
C9—C8—C14—O2
C13—C8—C14—O2
−0.4 (4)
−179.6 (2)
0.2 (5)
C6A—C1A—C2A—C3A
−0.1 (3)
179.5 (2)
0.4 (4)
C7A—C1A—C2A—C3A
C1A—C2A—C3A—C4A
C2A—C3A—C4A—C5A
C3A—C4A—C5A—C6A
C4A—C5A—C6A—C1A
C2A—C1A—C6A—C5A
C7A—C1A—C6A—C5A
C2A—C1A—C7A—N1A
C6A—C1A—C7A—N1A
C2A—C1A—C7A—N2A
C6A—C1A—C7A—N2A
C15A—O3A—C9A—C10A
C15A—O3A—C9A—C8A
C13A—C8A—C9A—O3A
C14A—C8A—C9A—O3A
C13A—C8A—C9A—C10A
C14A—C8A—C9A—C10A
O3A—C9A—C10A—C11A
C8A—C9A—C10A—C11A
C9A—C10A—C11A—C12A
C10A—C11A—C12A—C13A
C16A—O4A—C13A—C12A
C16A—O4A—C13A—C8A
C11A—C12A—C13A—O4A
C11A—C12A—C13A—C8A
C9A—C8A—C13A—O4A
C14A—C8A—C13A—O4A
C9A—C8A—C13A—C12A
C14A—C8A—C13A—C12A
C13A—C8A—C14A—O2A
C9A—C8A—C14A—O2A
C13A—C8A—C14A—O1A
C9A—C8A—C14A—O1A
0.3 (5)
0.0 (4)
−0.6 (5)
0.4 (4)
−0.7 (4)
0.9 (4)
0.1 (3)
−0.5 (3)
179.8 (2)
14.1 (3)
179.3 (2)
−20.8 (3)
160.0 (2)
159.5 (2)
−19.7 (3)
−176.9 (2)
3.1 (4)
−166.25 (19)
−165.8 (2)
13.9 (3)
14.0 (3)
−165.6 (2)
176.49 (18)
−0.5 (3)
−3.1 (3)
179.93 (19)
−178.8 (2)
0.8 (3)
−179.92 (18)
1.4 (3)
0.1 (3)
−178.58 (18)
−179.9 (2)
0.1 (3)
−0.5 (4)
0.7 (4)
1.3 (4)
−1.0 (5)
−15.1 (4)
164.8 (2)
178.6 (3)
−1.4 (4)
−176.55 (18)
0.5 (3)
−174.1 (3)
7.0 (4)
−178.76 (19)
−0.1 (3)
0.1 (3)
178.79 (19)
178.3 (2)
−0.5 (4)
−88.9 (2)
92.5 (2)
90.2 (2)
3.4 (3)
−179.6 (2)
108.7 (2)
−74.3 (2)
−70.1 (2)
106.8 (2)
−88.4 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1A···O1
N1—H1B···O1A
N2—H2A···O2
N2—H2B···O2i
N1A—H1A1···O1A
N1A—H1A2···O1
N2A—H2A1···O2A
N2A—H2A2···O2Aii
0.92 (2)
0.90 (3)
0.95 (2)
0.93 (2)
0.92 (2)
0.91 (3)
0.92 (2)
0.92 (3)
1.89 (3)
2.03 (3)
1.85 (2)
1.93 (2)
1.87 (3)
1.95 (3)
1.95 (2)
1.94 (3)
2.799 (2)
2.827 (2)
2.796 (2)
2.763 (2)
2.785 (2)
2.773 (2)
2.868 (2)
2.789 (2)
171 (2)
148 (2)
176.3 (19)
148.7 (19)
175 (2)
150 (2)
173.0 (19)
153 (2)
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y, −z+1.
Acta Cryst. (2012). C68, o447–o451
sup-7

supplementary materials
(II) Benzamidinidium 2,6-dimethoxybenzoate
Crystal data
C7H9N2+·C9H9O4−
Mr = 302.32
F(000) = 640
Dx = 1.283 Mg m−3
Orthorhombic, P212121
Hall symbol: P 2ac 2ab
a = 9.8921 (1) Å
b = 10.4471 (1) Å
c = 15.1403 (2) Å
V = 1564.65 (3) Å3
Z = 4
Mo Kα radiation, λ = 0.71069 Å
Cell parameters from 116123 reflections
θ = 2.8–32.6°
µ = 0.09 mm−1
T = 298 K
Small prism, colourless
0.20 × 0.15 × 0.12 mm
Data collection
Oxford Xcalibur S CCD area-detector
diffractometer
Radiation source: Enhance (Mo) X-ray source
Graphite monochromator
Detector resolution: 16.0696 pixels mm-1
ω and φ scans
327892 measured reflections
3175 independent reflections
2872 reflections with I > 2σ(I)
Rint = 0.040
θmax = 32.6°, θmin = 2.8°
h = −15→14
k = −15→15
l = −22→22
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
T
min = 0.935, Tmax = 0.986
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.058
wR(F2) = 0.156
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.19
3175 reflections
219 parameters
0 restraints
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0886P)2 + 0.1272P]
where P = (Fo2 + 2Fc2)/3
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max < 0.001
Δρmax = 0.30 e Å−3
Δρmin = −0.18 e Å−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.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
N1
0.24030 (16)
0.248 (2)
0.15399 (19)
0.225 (2)
−0.03437 (12)
0.0091 (16)
0.0400 (4)
0.034 (6)*
0.043 (7)*
0.0420 (4)
H1A
H1B
N2
0.165 (3)
0.130 (3)
−0.0539 (19)
−0.03504 (13)
0.46956 (16)
0.1472 (2)
Acta Cryst. (2012). C68, o447–o451
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supplementary materials
H2A
H2B
C1
0.468 (3)
0.557 (3)
0.34893 (17)
0.2336 (2)
0.1576
0.209 (3)
0.002 (2)
0.051 (8)*
0.051 (8)*
0.0301 (3)
0.0479 (5)
0.058*
0.112 (3)
−0.048 (2)
−0.13753 (11)
−0.14905 (17)
−0.1091
0.00992 (15)
−0.0641 (2)
−0.0543
C2
H2
C3
0.2269 (3)
0.1463
−0.1521 (3)
−0.2038
−0.21747 (19)
−0.2253
0.0569 (6)
0.068*
H3
C4
0.3339 (3)
0.3286
−0.1663 (3)
−0.2270
−0.27409 (18)
−0.3224
0.0577 (6)
0.069*
H4
C5
0.4486 (3)
0.5244
−0.0945 (3)
−0.1057
−0.26236 (19)
−0.3023
0.0663 (8)
0.080*
H5
C6
0.4578 (2)
0.5394
−0.0058 (2)
0.0444
−0.19409 (16)
−0.1862
0.0501 (6)
0.060*
H6
C7
0.35372 (17)
0.24645 (12)
0.46808 (13)
0.4554 (2)
0.2968 (2)
0.36935 (16)
0.4143 (2)
0.4192 (3)
0.4480
0.10679 (16)
0.37862 (14)
0.35660 (15)
0.6099 (2)
0.4922 (2)
0.55819 (17)
0.6527 (2)
0.7809 (2)
0.8471
−0.06615 (12)
0.06668 (10)
0.08260 (12)
−0.02050 (12)
0.25686 (10)
0.11803 (12)
0.06053 (15)
0.0872 (2)
0.0299 (3)
0.0377 (3)
0.0438 (4)
0.0595 (5)
0.0552 (5)
0.0318 (3)
0.0420 (4)
0.0575 (6)
0.069*
O1
O2
O3
O4
C8
C9
C10
H10
C11
H11
C12
H12
C13
C14
C15
H15A
H15B
H15C
C16
H16A
H16B
H16C
0.0464
0.3826 (3)
0.3857
0.8113 (2)
0.9000
0.1723 (3)
0.0680 (8)
0.082*
0.1910
0.3416 (3)
0.3179
0.7191 (3)
0.7424
0.23192 (19)
0.2920
0.0595 (7)
0.071*
0.3349 (2)
0.36127 (16)
0.5270 (4)
0.466 (2)
0.559 (3)
0.607 (3)
0.2997 (3)
0.227 (2)
0.388 (3)
0.285 (3)
0.5912 (2)
0.42050 (16)
0.6947 (4)
0.767 (3)
0.20401 (15)
0.08702 (10)
−0.0758 (3)
−0.094 (2)
−0.1298 (18)
−0.0430 (12)
0.35037 (17)
0.3672 (5)
0.3676 (5)
0.0410 (4)
0.0286 (3)
0.0815 (10)
0.122*
0.6477 (16)
0.730 (3)
0.122*
0.122*
0.5119 (4)
0.572 (3)
0.0696 (8)
0.104*
0.548 (2)
0.104*
0.430 (2)
0.3808 (8)
0.104*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N1
N2
C1
C2
C3
C4
C5
C6
C7
O1
0.0227 (6)
0.0240 (7)
0.0274 (7)
0.0304 (8)
0.0455 (11)
0.0728 (16)
0.0710 (16)
0.0439 (10)
0.0247 (6)
0.0240 (5)
0.0471 (9)
0.0473 (9)
0.0274 (6)
0.0466 (11)
0.0490 (12)
0.0485 (12)
0.0700 (17)
0.0511 (12)
0.0285 (7)
0.0409 (7)
0.0502 (9)
0.0013 (6)
−0.0006 (6)
−0.0022 (6)
0.0000 (6)
−0.0191 (8)
−0.0209 (9)
−0.0047 (6)
−0.0205 (11)
−0.0253 (13)
−0.0192 (10)
−0.0268 (13)
−0.0166 (10)
−0.0042 (6)
−0.0131 (6)
0.0546 (10)
0.0354 (7)
0.0668 (13)
0.0762 (16)
0.0518 (12)
0.0579 (14)
0.0552 (12)
0.0366 (7)
0.0481 (7)
0.0006 (6)
−0.0009 (6)
−0.0078 (8)
−0.0064 (10)
−0.0024 (12)
−0.0136 (15)
−0.0135 (10)
−0.0007 (6)
−0.0046 (5)
0.0030 (9)
−0.0115 (11)
−0.0034 (12)
0.0275 (13)
0.0188 (10)
0.0010 (6)
−0.0001 (5)
Acta Cryst. (2012). C68, o447–o451
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supplementary materials
O2
0.0260 (6)
0.0740 (12)
0.0642 (11)
0.0225 (6)
0.0365 (9)
0.0570 (14)
0.0660 (17)
0.0561 (14)
0.0323 (8)
0.0242 (6)
0.096 (2)
0.0437 (7)
0.0593 (10)
0.0634 (10)
0.0339 (7)
0.0407 (9)
0.0361 (10)
0.0393 (11)
0.0564 (13)
0.0453 (10)
0.0333 (7)
0.077 (2)
0.0617 (9)
0.0451 (8)
0.0380 (7)
0.0392 (8)
0.0486 (10)
0.0795 (17)
0.099 (2)
0.0014 (5)
−0.0011 (6)
0.0083 (8)
0.0119 (7)
−0.0191 (7)
0.0012 (7)
O3
−0.0179 (10)
−0.0107 (9)
−0.0014 (6)
−0.0029 (8)
−0.0045 (10)
0.0001 (12)
0.0015 (11)
−0.0015 (7)
−0.0026 (6)
−0.017 (2)
O4
−0.0117 (7)
−0.0094 (7)
−0.0022 (8)
−0.0004 (11)
−0.0243 (13)
−0.0340 (12)
−0.0175 (8)
−0.0067 (6)
0.0166 (17)
−0.0101 (13)
C8
−0.0016 (6)
−0.0056 (8)
−0.0055 (13)
0.0005 (16)
0.0068 (12)
0.0034 (7)
0.0034 (6)
0.0219 (19)
0.0022 (11)
C9
C10
C11
C12
C13
C14
C15
C16
0.0662 (14)
0.0454 (9)
0.0283 (6)
0.0720 (19)
0.0388 (11)
0.0728 (18)
0.097 (2)
0.0119 (18)
Geometric parameters (Å, º)
N1—C7
N1—H1A
N1—H1B
N2—C7
N2—H2A
N2—H2B
C1—C6
C1—C2
C1—C7
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C4—H4
C5—C6
C5—H5
C6—H6
O1—C14
O2—C14
1.317 (2)
O3—C9
1.368 (3)
1.00 (3)
0.84 (3)
1.309 (2)
0.86 (3)
0.96 (3)
1.386 (3)
1.389 (3)
1.481 (2)
1.387 (3)
0.9700
O3—C15
1.410 (4)
1.361 (3)
1.431 (3)
1.389 (3)
1.389 (3)
1.515 (2)
1.400 (3)
1.376 (5)
0.9700
O4—C13
O4—C16
C8—C13
C8—C9
C8—C14
C9—C10
C10—C11
C10—H10
C11—C12
C11—H11
C12—C13
C12—H12
C15—H15A
C15—H15B
C15—H15C
C16—H16A
C16—H16B
C16—H16C
1.380 (5)
0.9700
1.370 (4)
0.9700
1.403 (3)
0.9700
1.371 (4)
0.9700
1.0051
1.391 (3)
0.9700
1.0051
1.0051
0.9700
0.9863
1.255 (2)
1.252 (2)
0.9863
0.9863
C7—N1—H1A
C7—N1—H1B
H1A—N1—H1B
C7—N2—H2A
C7—N2—H2B
H2A—N2—H2B
C6—C1—C2
C6—C1—C7
C2—C1—C7
C3—C2—C1
C3—C2—H2
C1—C2—H2
C4—C3—C2
C4—C3—H3
117.3 (14)
121 (2)
C9—C8—C14
O3—C9—C8
119.81 (16)
115.16 (19)
124.1 (2)
120.7 (2)
118.8 (3)
120.6
121 (2)
O3—C9—C10
C8—C9—C10
C11—C10—C9
C11—C10—H10
C9—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
C11—C12—C13
C11—C12—H12
C13—C12—H12
O4—C13—C8
117 (2)
126.0 (19)
116 (3)
119.64 (17)
120.47 (16)
119.88 (16)
120.1 (2)
119.9
120.6
121.9 (2)
119.0
119.0
118.8 (2)
120.6
119.9
120.1 (2)
119.9
120.6
115.48 (18)
Acta Cryst. (2012). C68, o447–o451
sup-10

supplementary materials
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
C4—C5—C6
C4—C5—H5
C6—C5—H5
C1—C6—C5
C1—C6—H6
C5—C6—H6
N2—C7—N1
N2—C7—C1
N1—C7—C1
C9—O3—C15
C13—O4—C16
C13—C8—C9
C13—C8—C14
119.9
O4—C13—C12
C8—C13—C12
O2—C14—O1
O2—C14—C8
O1—C14—C8
O3—C15—H15A
O3—C15—H15B
124.0 (2)
120.5 (2)
124.38 (15)
118.58 (15)
117.03 (15)
109.5
119.9 (2)
120.0
120.0
121.0 (2)
119.5
119.5
109.5
119.2 (2)
120.4
H15A—C15—H15B
O3—C15—H15C
H15A—C15—H15C
H15B—C15—H15C
O4—C16—H16A
O4—C16—H16B
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
120.4
119.58 (15)
120.72 (15)
119.69 (15)
118.4 (2)
117.9 (2)
119.29 (18)
120.88 (17)
H16A—C16—H16B
O4—C16—H16C
H16A—C16—H16C
H16B—C16—H16C
C6—C1—C2—C3
C7—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C6
C2—C1—C6—C5
C7—C1—C6—C5
C4—C5—C6—C1
C6—C1—C7—N2
C2—C1—C7—N2
C6—C1—C7—N1
C2—C1—C7—N1
C15—O3—C9—C8
C15—O3—C9—C10
C13—C8—C9—O3
C14—C8—C9—O3
C13—C8—C9—C10
−0.8 (4)
178.0 (2)
−0.1 (4)
0.9 (5)
C14—C8—C9—C10
O3—C9—C10—C11
C8—C9—C10—C11
C9—C10—C11—C12
C10—C11—C12—C13
C16—O4—C13—C8
C16—O4—C13—C12
C9—C8—C13—O4
C14—C8—C13—O4
C9—C8—C13—C12
C14—C8—C13—C12
C11—C12—C13—O4
C11—C12—C13—C8
C13—C8—C14—O2
C9—C8—C14—O2
C13—C8—C14—O1
C9—C8—C14—O1
178.4 (2)
−176.1 (3)
1.9 (4)
0.1 (5)
−0.7 (5)
0.9 (4)
−1.2 (5)
161.5 (2)
−17.9 (4)
−177.59 (18)
1.1 (3)
−177.8 (2)
−0.2 (5)
−23.6 (3)
157.6 (2)
155.5 (2)
−23.3 (3)
−167.5 (3)
10.7 (4)
1.8 (3)
−179.5 (2)
179.6 (3)
0.2 (4)
−101.0 (2)
77.7 (2)
175.32 (18)
−3.4 (3)
−2.9 (3)
79.5 (2)
−101.8 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1A···O1
N1—H1B···O2i
N2—H2B···O1ii
N2—H2A···O2
1.00 (3)
0.84 (3)
0.96 (3)
0.86 (3)
1.82 (3)
2.00 (3)
1.90 (3)
1.97 (3)
2.802 (2)
2.792 (2)
2.794 (2)
2.821 (2)
166 (2)
157 (3)
154 (3)
177 (3)
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) x+1/2, −y+1/2, −z.
Acta Cryst. (2012). C68, o447–o451
sup-11