Hydrogen-bonded structures of the 1:1 and 1:2 compounds of chloranilic acid with pyrrolidin-2-one and piperidin-2-one

Article abstract of DOI:10.1107/S0108270111048165

In the four compounds of chloranilic acid (2,5-dichloro-3,6-dihy-droxy- cyclo-hexa-2,5-diene-1,4-dione) with pyrrolidin-2-one and piperidin-2-one, namely, chloranilic acid-pyrrolidin-2-one (1/1), C₆H ₂Cl₂O₄·C₄H₇NO, (I), chloranilic acid-pyrrolidin-2-one (1/2), C₆H₂Cl ₂O1·2C₄H7NO, (II), chloranilic acid-piperidin-2-one (1/1), C₆H₂Cl₂O₄·C ₅H₉NO, (III), and chloranilic acid-piperidin-2-one (1/2), C₆H₂Cl₂O₄·2C ₅H₉NO, (IV), the shortest inter-actions between the two components are O - H...O hydrogen bonds, which act as the primary inter-molecular inter-action in the crystal structures. In (II), (III) and (IV), the chloranilic acid mol-ecules lie about inversion centres. For (III), this necessitates the presence of two independent acid molecules. In (I), there are two formula units in the asymmetric unit. The O...O distances are 2.4728 (11) and 2.4978 (11) A in (I), 2.5845 (11) A in (II), 2.6223 (11) and 2.5909 (10) A in (III), and 2.4484 (10) A in (IV). In the hydrogen bond of (IV), the H atom is disordered over two positions with site occupancies of 0.44 (3) and 0.56 (3). This indicates that proton transfer between the acid and base has partly taken place to form ion pairs. In (I) and (II), N - H...O hydrogen bonds, the secondary inter-molecular inter-actions, connect the pyrrolidin-2-one mol-ecules into a dimer, while in (III) and (IV) these hydrogen bonds link the acid and base to afford three- and two-dimensional hydrogen-bonded networks, respectively.

Full text of DOI:10.1107/S0108270111048165

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
bond systems (Ikeda et al., 2005; Suzuki et al., 2007; Gotoh et
al., 2008; Gotoh, Asaji & Ishida, 2010; Seliger et al., 2009, 2011;
Asaji, Hoshino et al., 2010; Asaji, Seliger et al., 2010).
Furthermore, salts and cocrystals of chloranilic acid with
pyridine derivatives have recently attracted much interest with
respect to organic ferroelectrics (Horiuchi, Ishii et al., 2005;
Horiuchi, Kumai & Tokura, 2005; Asaji et al., 2007; Gotoh et
al., 2007; Horiuchi & Tokura, 2008; Horiuchi et al., 2010).
ISSN 0108-2701
Hydrogen-bonded structures of the
1:1 and 1:2 compounds of chloranilic
acid with pyrrolidin-2-one and
piperidin-2-one
Kazuma Gotoh and Hiroyuki Ishida*
Department of Chemistry, Faculty of Science, Okayama University, Okayama
700-8530, Japan
Correspondence e-mail: ishidah@cc.okayama-u.ac.jp
Received 14 October 2011
Accepted 13 November 2011
Online 19 November 2011
In the four compounds of chloranilic acid (2,5-dichloro-3,6-
dihydroxycyclohexa-2,5-diene-1,4-dione) with pyrrolidin-2-
one and piperidin-2-one, namely, chloranilic acid–pyrrolidin-
2-one (1/1), C6H2Cl2O4ꢀC4H7NO, (I), chloranilic acid–pyrro-
lidin-2-one (1/2), C6H2Cl2O4ꢀ2C4H7NO, (II), chloranilic acid–
piperidin-2-one (1/1), C6H2Cl2O4ꢀC5H9NO, (III), and chlor-
anilic acid–piperidin-2-one (1/2), C6H2Cl2O4ꢀ2C5H9NO, (IV),
the shortest interactions between the two components are
O—Hꢀ ꢀ ꢀO hydrogen bonds, which act as the primary inter-
molecular interaction in the crystal structures. In (II), (III) and
(IV), the chloranilic acid molecules lie about inversion centres.
For (III), this necessitates the presence of two independent
acid molecules. In (I), there are two formula units in the
asymmetric unit. The Oꢀ ꢀ ꢀO distances are 2.4728 (11) and
˚
˚
2.4978 (11) A in (I), 2.5845 (11) A in (II), 2.6223 (11) and
˚
˚
2.5909 (10) A in (III), and 2.4484 (10) A in (IV). In the
hydrogen bond of (IV), the H atom is disordered over two
positions with site occupancies of 0.44 (3) and 0.56 (3). This
indicates that proton transfer between the acid and base has
partly taken place to form ion pairs. In (I) and (II), N—Hꢀ ꢀ ꢀO
hydrogen bonds, the secondary intermolecular interactions,
connect the pyrrolidin-2-one molecules into a dimer, while in
(III) and (IV) these hydrogen bonds link the acid and base to
afford three- and two-dimensional hydrogen-bonded
networks, respectively.
In the present study, we have prepared four compounds of
chloranilic acid with pyrrolidin-2-one and piperidin-2-one,
Comment
Chloranilic acid (2,5-dichloro-3,6-dihydroxycyclohexa-2,5-di-
ene-1,4-dione), a strong dibasic acid with hydrogen-bond
donor and acceptor groups, appears particularly attractive as a
template for generating tightly bound self-assemblies with
various organic bases (Ishida & Kashino, 1999a,b, 2002;
Zaman et al., 1999, 2004; Gotoh, Maruyama & Ishida, 2010),
and also as a model compound for investigating hydrogen-
transfer mechanisms in O—Hꢀ ꢀ ꢀN and N—Hꢀ ꢀ ꢀO hydrogen-
Figure 1
The asymmetric unit of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level. O—
Hꢀ ꢀ ꢀO and N—Hꢀ ꢀ ꢀO hydrogen bonds are indicated by dashed lines.
o500 # 2011 International Union of Crystallography
doi:10.1107/S0108270111048165
Acta Cryst. (2011). C67, o500–o504

organic compounds
Figure 2
The molecular structure of (II), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level. O—
Hꢀ ꢀ ꢀO hydrogen bonds are indicated by dashed lines. [Symmetry code:
(iii) ꢃx + 1, ꢃy + 1, ꢃz + 2.]
Figure 5
A partial packing diagram for (I), showing the hydrogen-bonded tape
structure formed by the 2+2 aggregates. Dashed lines show N—Hꢀ ꢀ ꢀO
and O—Hꢀ ꢀ ꢀO hydrogen bonds. H atoms not involved in hydrogen
bonding have been omitted. [Symmetry codes: (i) x, y ꢃ 1, z; (ii) x, y + 1,
z.]
ture with two long and two short C—C bonds, as described by
Andersen (1967). The pyrrolidin-2-one molecules in (I) and
(II) adopt an approximate envelope conformation, while the
piperidin-2-one molecules in (III) and (IV) have half-chair
conformations.
The asymmetric unit of (I) contains two crystallographically
independent pyrrolidin-2-one molecules and two chloranilic
acid molecules (Fig. 1). The acid and base are held together by
short O—Hꢀ ꢀ ꢀO hydrogen bonds (O2—H2Aꢀ ꢀ ꢀO9 and O6—
H6ꢀ ꢀ ꢀO10; Table 1), and the two bases are further connected
to each other by a pair of N—Hꢀ ꢀ ꢀO hydrogen bonds (N1—
H1ꢀ ꢀ ꢀO10 and N2—H2Bꢀ ꢀ ꢀO9; Table 1), thus forming a quasi-
centrosymmetric 2+2 aggregate. These 2+2 aggregates are
linked through a pair of O—Hꢀ ꢀ ꢀO hydrogen bonds between
adjacent chloranilic acid molecules (O4—H4ꢀ ꢀ ꢀO5i and O8—
H8ꢀ ꢀ ꢀO1ii; details and symmetry codes in Table 1), forming an
approximately flat tape structure along the b axis (Fig. 5). In
this tape, the dihedral angle between the acid C1–C6 and C7–
C12 rings is 2.67 (5)ꢁ, and those between the least-squares
plane of atoms N1/C13–C16/O9/N2/C17–C20/O10 of the
hydrogen-bonded pyrrolidin-2-one dimer and the acid C1–C6
and C7–C12 rings are 9.23 (4) and 6.92 (4)ꢁ, respectively. The
tapes, related to each other by an inversion centre, are stacked
alternately along the a axis, forming a layer parallel to the ab
plane.
Figure 3
The molecular structure of (III), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level. O—
Hꢀ ꢀ ꢀO hydrogen bonds are indicated by dashed lines. [Symmetry codes:
(iii) ꢃx, ꢃy, ꢃz; (iv) ꢃx + 1, ꢃy, ꢃz + 1.]
Figure 4
The molecular structure of (IV), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level.
Oꢀ ꢀ ꢀHꢀ ꢀ ꢀO hydrogen bonds are indicated by dashed lines. [Symmetry
code: (iv) ꢃx + 1, ꢃy + 1, ꢃz + 1.]
In compound (II), the acid molecule is located on an
inversion centre, so that the asymmetric unit contains one
pyrrolidin-2-one molecule and one half-molecule of chlor-
anilic acid (Fig. 2). The acid and the base are connected by a
short O—Hꢀ ꢀ ꢀO hydrogen bond (O2—H2ꢀ ꢀ ꢀO3; Table 2) and
the two components are further connected by an N—
Hꢀ ꢀ ꢀ(O,O) bifurcated hydrogen bond [N1—H1ꢀ ꢀ ꢀ(O1i,O3ii);
details and symmetry codes in Table 2], such that the
hydrogen-bonded pyrrolidin-2-one dimer and the chloranilic
acid molecules are arranged alternately into an essentially
planar molecular tape along the [111] direction (Fig. 6). In this
tape, the dihedral angle between the acid ring and the least-
squares plane of atoms N1/C4–C7/O3 of pyrrolidin-2-one is
8.81 (12)ꢁ. The tapes are stacked along the a axis and form a
layer parallel to the (011) plane.
namely, chloranilic acid–pyrrolidin-2-one (1/1), (I), chloranilic
acid–pyrrolidin-2-one (1/2), (II), chloranilic acid–piperidin-2-
one (1/1), (III), and chloranilic acid–piperidin-2-one (1/2),
(IV), and determined their crystal structures at 180 K in order
to extend our study of D—Hꢀ ꢀ ꢀA hydrogen bonding (D = N, O
or C; A = N, O or Cl) in chloranilic acid–organic base systems
(Gotoh et al., 2009; Gotoh & Ishida, 2009).
The molecular structures of (I), (II), (III) and (IV) are
shown in Figs. 1, 2, 3 and 4, respectively. The chloranilic acid
molecules in all four compounds show a characteristic struc-
ꢂ
Acta Cryst. (2011). C67, o500–o504
Gotoh and Ishida
C6H2Cl2O4ꢀxC4H7NO and C6H2Cl2O4ꢀxC5H9NO (x = 1 and 2) o501

organic compounds
Figure 6
A partial packing diagram for (II), showing the hydrogen-bonded tape
structure. Dashed lines show N—Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀO hydrogen bonds.
H atoms not involved in hydrogen bonding have been omitted.
[Symmetry codes: (i) x ꢃ 1, y ꢃ 1, z ꢃ 1; (ii) ꢃx, ꢃy, ꢃz + 1; (iii)
ꢃx + 1, ꢃy + 1, ꢃz + 2.]
Figure 8
A partial packing diagram for (III), showing the three-dimensional
hydrogen-bonded network. Dashed lines show N—Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀO
hydrogen bonds. H atoms not involved in hydrogen bonding have been
omitted. [Symmetry codes: (ii) x + 1, ꢃy + 12, z + 21; (iii) ꢃx, ꢃy, ꢃz; (iv)
ꢃx + 1, ꢃy, ꢃz + 1; (v) ꢃx, y ꢃ , ꢃz + 12.]
1
2
Figure 7
A partial packing diagram for (III), showing the hydrogen-bonded chain
structure. Dashed lines show O—Hꢀ ꢀ ꢀO hydrogen bonds. H atoms not
involved in hydrogen bonding have been omitted. [Symmetry codes: (iii)
ꢃx, ꢃy, ꢃz; (iv) ꢃx + 1, ꢃy, ꢃz + 1.]
In the asymmetric unit of (III), there is one piperidin-2-one
molecule and two crystallographically independent half-mol-
ecules of chloranilic acid, with each of the acid molecules lying
about an inversion centre (Fig. 3). No formation of dimers of
piperidin-2-one molecules is observed, while the piperidin-2-
one O atom participates in two O—Hꢀ ꢀ ꢀO hydrogen bonds as
an acceptor for two chloranilic acid O—H groups (O2—
H2ꢀ ꢀ ꢀO5 and O4—H4ꢀ ꢀ ꢀO5; Table 3), forming a zigzag chain
along the [101] direction in which the two components are
arranged alternately (Fig. 7). An N—Hꢀ ꢀ ꢀO hydrogen bond
(N1—H1ꢀ ꢀ ꢀO3i; symmetry code in Table 3) formed between
the piperidin-2-one and chloranilic acid molecules connects
the chains into a three-dimensional network (Fig. 8).
Figure 9
A packing diagram for (IV), viewed along the b axis, showing the
hydrogen-bonded layer structure. Dashed lines show N—Hꢀ ꢀ ꢀO and O—
Hꢀ ꢀ ꢀO hydrogen bonds. H atoms not involved in hydrogen bonding have
been omitted. [Symmetry codes: (i) x ꢃ , ꢃy + 12, z ꢃ ; (ii) ꢃx + 21, y ꢃ ,
1
2
1
2
1
2
ꢃz + 12; (iv) ꢃx + 1, ꢃy + 1, ꢃz + 1; (v) ꢃx + 21, y + 12, ꢃz + 21; (vi) x + 21, ꢃy + 12,
1
z + .]
2
acid and base has partly taken place to form ion pairs. This
disordered feature is confirmed in a difference Fourier map
(see Supplementary materials). The acid and base are further
connected by an N—Hꢀ ꢀ ꢀ(O,O) bifurcated hydrogen bond
[N1—H1ꢀ ꢀ ꢀ(O1i,O2ii); details and symmetry codes in Table 4],
forming a layer parallel to the (101) plane (Fig. 9).
We have shown that in all compounds the primary inter-
molecular interactions are O—Hꢀ ꢀ ꢀO hydrogen bonds formed
between the acid and the base. The secondary interactions are
N—Hꢀ ꢀ ꢀO hydrogen bonds, which connect the pyrrolidin-2-
one molecules into a dimer in (I) and (II), and link the acid
and base into three- and two-dimensional hydrogen-bonded
networks in (III) and (IV), respectively. Furthermore, in (IV)
The asymmetric unit of (IV) contains one piperidin-2-one
molecule and one half-molecule of chloranilic acid, which is
located on an inversion centre (Fig. 4). A short O—Hꢀ ꢀ ꢀO
˚
hydrogen bond with an Oꢀ ꢀ ꢀO distance of 2.4484 (10) A
connects the two components. The H atom in the hydrogen
bond is disordered over two positions with refined occu-
pancies of 0.44 (3) and 0.56 (3) at the O2 and O3 sites,
respectively, which indicates that proton transfer between the
ꢂ
o502 Gotoh and Ishida C6H2Cl2O4ꢀxC4H7NO and C6H2Cl2O4ꢀxC5H9NO (x = 1 and 2)
Acta Cryst. (2011). C67, o500–o504

organic compounds
Table 2
Hydrogen-bond geometry (A, ) for (II).
it is noteworthy that (a) the orientation of the O—H group of
the acid is different from that in (I), (II) and (III), in that the
O—H group in (IV) points to the Cl atom due to the N—
Hꢀ ꢀ ꢀ(O,O) hydrogen bond; and (b) the O atom of the base acts
as a single acceptor only for the O—H group. These may cause
the disorder of the H atom in the Oꢀ ꢀ ꢀHꢀ ꢀ ꢀO hydrogen bond.
ꢁ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1ꢀ ꢀ ꢀO1i
N1—H1ꢀ ꢀ ꢀO3ii
O2—H2ꢀ ꢀ ꢀO3
0.73 (2)
0.73 (2)
0.84 (2)
2.537 (19)
2.22 (2)
1.76 (2)
3.0036 (12)
2.9185 (13)
2.5845 (11)
123.8 (17)
162.0 (19)
164 (2)
Symmetry codes: (i) x ꢃ 1; y ꢃ 1; z ꢃ 1; (ii) ꢃx; ꢃy; ꢃz þ 1.
Experimental
Single crystals of the 1:1 compounds (I) and (III) were obtained by
slow evaporation from acetonitrile solutions [120 and 200 ml for (I)
and (III), respectively] of chloranilic acid with pyrrolidin-2-one or
piperidin-2-one in a 1:1 molar ratio [0.475 g of chloranilic acid and
0.194 g of pyrrolidin-2-one for (I), and 1.03 g of chloranilic acid and
0.49 g of piperidin-2-one for (III)] at room temperature. Single
crystals of the 1:2 compounds (II) and (IV) were obtained by slow
evaporation from acetonitrile solutions [200 and 125 ml for (II) and
(IV), respectively] of chloranilic acid with pyrrolidin-2-one or
piperidin-2-one in a 1:2.2 molar ratio [0.452 g of chloranilic acid and
0.405 g of pyrrolidin-2-one for (II), and 0.367 g of chloranilic acid and
0.383 g of piperidin-2-one for (IV)] at room temperature. About 10%
excess pyrrolidin-2-one or piperidin-2-one was used to avoid con-
tamination by the 1:1 compound.
Compound (II)
Crystal data
C6H2Cl2O4ꢀ2C4H7NO
ꢅ = 108.734 (2)ꢁ
3
˚
V = 396.42 (4) A
Z = 1
Mr = 379.20
Triclinic, P1
a = 4.9665 (3) A
˚
Mo Kꢁ radiation
ꢂ = 0.44 mmꢃ1
T = 180 K
0.38 ꢄ 0.32 ꢄ 0.25 mm
˚
b = 7.4767 (4) A
˚
c = 11.8445 (6) A
ꢁ = 106.7904 (19)ꢁ
ꢀ = 90.299 (2)ꢁ
Data collection
Rigaku R-AXIS RAPID II
diffractometer
Absorption correction: numerical
(NUMABS; Higashi, 1999)
Tmin = 0.853, Tmax = 0.895
9315 measured reflections
2296 independent reflections
2156 reflections with I > 2ꢃ(I)
Rint = 0.024
Compound (I)
Crystal data
Refinement
3
R[F2 > 2ꢃ(F2)] = 0.030
wR(F2) = 0.081
S = 1.11
2296 reflections
117 parameters
H atoms treated by a mixture of
independent and constrained
refinement
˚
C4H7NOꢀC6H2Cl2O4
V = 2276.2 (2) A
Z = 8
Mr = 294.09
Monoclinic, P21=c
Mo Kꢁ radiation
ꢂ = 0.58 mmꢃ1
T = 180 K
0.35 ꢄ 0.20 ꢄ 0.15 mm
ꢃ3
˚
a = 7.7256 (4) A
˚
Áꢄmax = 0.31 e A
ꢃ3
˚
b = 19.3792 (11) A
˚
Áꢄmin = ꢃ0.39 e A
˚
c = 15.2486 (8) A
ꢀ = 94.404 (2)ꢁ
Compound (III)
Data collection
Crystal data
Rigaku R-AXIS RAPID II
diffractometer
Absorption correction: numerical
(NUMABS; Higashi, 1999)
Tmin = 0.858, Tmax = 0.916
47031 measured reflections
6636 independent reflections
5477 reflections with I > 2ꢃ(I)
Rint = 0.022
3
˚
V = 1244.42 (7) A
Z = 4
C6H2Cl2O4ꢀC5H9NO
Mr = 308.12
Monoclinic, P21=c
Mo Kꢁ radiation
ꢂ = 0.54 mmꢃ1
T = 180 K
0.43 ꢄ 0.36 ꢄ 0.26 mm
˚
a = 9.41079 (17) A
˚
b = 8.0690 (4) A
˚
c = 18.1026 (3) A
ꢀ = 115.1397 (7)ꢁ
Refinement
R[F2 > 2ꢃ(F2)] = 0.038
wR(F2) = 0.108
S = 1.06
6636 reflections
349 parameters
H atoms treated by a mixture of
independent and constrained
refinement
Data collection
ꢃ3
˚
Áꢄmax = 1.05 e A
Rigaku R-AXIS RAPID II
diffractometer
Absorption correction: numerical
(NUMABS; Higashi, 1999)
Tmin = 0.793, Tmax = 0.870
22572 measured reflections
3626 independent reflections
3461 reflections with I > 2ꢃ(I)
Rint = 0.018
ꢃ3
˚
Áꢄmin = ꢃ0.30 e A
Table 1
Hydrogen-bond geometry (A, ) for (I).
ꢁ
˚
Table 3
Hydrogen-bond geometry (A, ) for (III).
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
ꢁ
˚
N1—H1ꢀ ꢀ ꢀO10
O2—H2Aꢀ ꢀ ꢀO9
N2—H2Bꢀ ꢀ ꢀO9
O4—H4ꢀ ꢀ ꢀO5i
O6—H6ꢀ ꢀ ꢀO10
O8—H8ꢀ ꢀ ꢀO1ii
0.870 (15)
1.05 (2)
0.839 (15)
0.849 (17)
0.99 (2)
2.056 (15)
1.44 (2)
2.108 (15)
2.002 (17)
1.54 (2)
2.9065 (13)
2.4728 (11)
2.9249 (13)
2.7774 (11)
2.4978 (11)
2.7850 (11)
165.5 (14)
167 (2)
164.6 (15)
151.6 (15)
163 (2)
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1ꢀ ꢀ ꢀO3i
O2—H2ꢀ ꢀ ꢀO5
O4—H4ꢀ ꢀ ꢀO5
0.869 (18)
0.909 (19)
0.843 (19)
2.213 (19)
1.743 (18)
1.767 (18)
2.8871 (12)
2.6223 (11)
2.5909 (10)
134.2 (14)
162.1 (18)
165.1 (19)
0.850 (17)
2.025 (17)
148.5 (15)
1
2
1
2
Symmetry code: (i) x ꢃ 1; ꢃy þ ; z ꢃ .
Symmetry codes: (i) x; y ꢃ 1; z; (ii) x; y þ 1; z.
ꢂ
Acta Cryst. (2011). C67, o500–o504
Gotoh and Ishida
C6H2Cl2O4ꢀxC4H7NO and C6H2Cl2O4ꢀxC5H9NO (x = 1 and 2) o503

organic compounds
Table 4
Hydrogen-bond geometry (A, ) for (IV).
For all four compounds, data collection: PROCESS-AUTO
(Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO; data
reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to
solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to
refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics:
ORTEP-3 (Farrugia, 1997) for (I), (II) and (III); ORTEP-3 and
WinGX (Farrugia, 1999) for (IV). For all compounds, software used
to prepare material for publication: CrystalStructure and PLATON
(Spek, 2009).
ꢁ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1ꢀ ꢀ ꢀO1i
N1—H1ꢀ ꢀ ꢀO2ii
O3—H3ꢀ ꢀ ꢀO2
O2—H2ꢀ ꢀ ꢀO3
0.845 (18)
0.845 (18)
0.84 (2)
2.398 (17)
2.214 (17)
1.61 (2)
2.9561 (12)
3.0358 (12)
2.4484 (10)
2.4484 (10)
124.1 (14)
164.3 (15)
173 (3)
0.82 (3)
1.66 (3)
161 (4)
1
1
1
2
1
2
1
2
1
2
Symmetry codes: (i) x ꢃ ; ꢃy þ ; z ꢃ ; (ii) ꢃx þ ; y ꢃ ; ꢃz þ .
2
2
This work was supported by a Grant-in-Aid for Scientific
Research (C) (No. 22550013) from the Japan Society for the
Promotion of Science.
Refinement
R[F2 > 2ꢃ(F2)] = 0.029
wR(F2) = 0.083
S = 1.06
3626 reflections
184 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢃ3
˚
Áꢄmax = 0.48 e A
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FG3233). Services for accessing these data are
described at the back of the journal.
ꢃ3
˚
Áꢄmin = ꢃ0.30 e A
Compound (IV)
References
Andersen, E. K. (1967). Acta Cryst. 22, 191–196.
Asaji, T., Hoshino, M., Ishida, H., Konnai, A., Shinoda, Y., Seliger, J. & Zagar,
V. (2010). Hyperfine Interact. 198, 85–91.
Crystal data
ˇ
3
˚
V = 1732.12 (12) A
Z = 4
Mo Kꢁ radiation
ꢂ = 0.41 mmꢃ1
T = 180 K
C6H0.88Cl2O4ꢀ2C5H9.56NO
Mr = 407.25
Monoclinic, C2=c
ˇ
Asaji, T., Seliger, J., Zagar, V. & Ishida, H. (2010). Magn. Reson. Chem. 48,
531–536.
Asaji, T., Seliger, J., Zager, V., Sekiguchi, M., Watanabe, J., Gotoh, K., Ishida,
˚
a = 17.8438 (5) A
ˇ
˚
b = 5.4253 (3) A
H., Vrtnik, S. & Dolinsek, J. (2007). J. Phys. Condens. Matter, 19, 226203–
226213.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
˚
c = 19.5958 (5) A
ꢀ = 114.0658 (7)ꢁ
0.45 ꢄ 0.40 ꢄ 0.15 mm
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Data collection
Gotoh, K., Asaji, T. & Ishida, H. (2007). Acta Cryst. C63, o17–o20.
Gotoh, K., Asaji, T. & Ishida, H. (2008). Acta Cryst. C64, o550–o553.
Gotoh, K., Asaji, T. & Ishida, H. (2010). Acta Cryst. C66, o114–o118.
Gotoh, K. & Ishida, H. (2009). Acta Cryst. E65, o2467.
Gotoh, K., Maruyama, S. & Ishida, H. (2010). Acta Cryst. E66, o3255.
Gotoh, K., Nagoshi, H. & Ishida, H. (2009). Acta Cryst. E65, o614.
Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan.
Horiuchi, S., Ishii, F., Kumai, R., Okimoto, Y., Tachibana, H., Nagaosa, N. &
Tokura, Y. (2005). Nat. Mater. 4, 163–166.
Rigaku R-AXIS RAPID II
diffractometer
Absorption correction: numerical
(NUMABS; Higashi, 1999)
Tmin = 0.835, Tmax = 0.940
17611 measured reflections
2524 independent reflections
2382 reflections with I > 2ꢃ(I)
Rint = 0.024
Refinement
R[F2 > 2ꢃ(F2)] = 0.031
wR(F2) = 0.083
S = 1.07
2524 reflections
129 parameters
2 restraints
H atoms treated by a mixture of
independent and constrained
refinement
Horiuchi, S., Kumai, R. & Tokura, Y. (2005). J. Am. Chem. Soc. 127, 5010–
5011.
Horiuchi, S., Tokunaga, Y., Giovanetti, G., Picozzi, S., Itoh, H., Shimano, R.,
Kumai, R. & Tokura, Y. (2010). Nature (London), 463, 789–792.
Horiuchi, S. & Tokura, Y. (2008). Nat. Mater. 7, 357–366.
Ikeda, R., Takahashi, S., Nihei, T., Ishihara, H. & Ishida, H. (2005). Bull. Chem.
Soc. Jpn, 78, 1241–1245.
ꢃ3
˚
Áꢄmax = 0.51 e A
ꢃ3
˚
Áꢄmin = ꢃ0.24 e A
Ishida, H. & Kashino, S. (1999a). Acta Cryst. C55, 1149–1152.
Ishida, H. & Kashino, S. (1999b). Acta Cryst. C55, 1714–1717.
Ishida, H. & Kashino, S. (2002). Z. Naturforsch. Teil A, 57, 829–836.
Rigaku/MSC (2004). PROCESS-AUTO and CrystalStructure. Rigaku/MSC
Inc., The Woodlands, Texas, USA.
Seliger, J., Zagar, V., Asaji, T., Gotoh, K. & Ishida, H. (2011). Phys. Chem.
Chem. Phys. 13, 9165–9172.
ˇ
Seliger, J., Zagar, V., Gotoh, K., Ishida, H., Konnai, A., Amino, D. & Asaji, T.
(2009). Phys. Chem. Chem. Phys. 11, 2281–2286.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Suzuki, H., Mori, H., Yamashita, J., Matsuda, M., Tajima, H. & Mochida, T.
(2007). Chem. Lett. pp. 402–403.
Zaman, Md. B., Tomura, M. & Yamashita, Y. (1999). Chem. Commun. pp. 999–
1000.
Zaman, Md. B., Udachin, K. A. & Ripmeester, J. A. (2004). Cryst. Growth Des.
4, 585–589.
H atoms attached to O and N atoms were found in difference
Fourier maps and refined isotropically (refined O—H and N—H
distances are given in Tables 1–4). For compound (IV), the O-bound
H atom, which is involved in the Oꢀ ꢀ ꢀHꢀ ꢀ ꢀO hydrogen bond, was
found to be disordered over two positions in a difference Fourier
map. Since the site-occupancy factors and isotropic displacement
parameters were strongly correlated, the positional parameters and
occupancy factors were refined, with O—H bond-length restraints of
ˇ
˚
0.84 (2) A and with Uiso(H) = 1.5Ueq(O). Other H atoms were treated
˚
as riding, with C—H = 0.99 A and Uiso(H) = 1.2Ueq(C). For
compound (Iꢃ),3the two highest residual electron-density peaks of 1.05
˚
˚
and 0.90 e A are located 0.60 and 0.63 A, respectively, from atoms
C18 and C16.
ꢂ
o504 Gotoh and Ishida C6H2Cl2O4ꢀxC4H7NO and C6H2Cl2O4ꢀxC5H9NO (x = 1 and 2)
Acta Cryst. (2011). C67, o500–o504