X-(Diiodo-arsan-yl)benzoic acid (X = 3 and 4)

Article abstract of DOI:10.1107/S0108270112040000

The title compounds, 4-(diiodo-arsanyl)benzoic acid, (I), and 3-(diiodo-arsanyl)benzoic acid, (II), both [As(C7H5O2)I2], which possess a -COOH coordinating group, form mol-ecular crystal structures composed of hydrogen-bonded dimers, the packing differenc

Full text of DOI:10.1107/S0108270112040000

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
dienyl), the As atom has additional contacts with a double
bond of the cyclopentadienyl (Cp) ring of the same molecule
Communications
(Megges et al., 1996; Avtomonov et al., 1996). As a conse-
ISSN 0108-2701
quence, the As atom, hidden by the bulky substituent, has no
additional contacts with the other molecules.
X-(Diiodoarsanyl)benzoic acid (X = 3
and 4)
Igor Yu. Ilyin,* Nikolay A. Pushkarevsky, Natalia V.
Kuratieva, Dmitry Yu. Naumov and Sergey N. Konchenko
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of
Sciences, Akademician Lavrentiev prospekt 3, Novosibirsk, 630090, Russian
Federation
Correspondence e-mail: ilyin@niic.nsc.ru
The structures of 4-(diiodoarsanyl)benzoic acid, (I) (Fig. 1),
and 3-(diiodoarsanyl)benzoic acid, (II) (Fig. 2), have asym-
metric units with one and three crystallographically indepen-
dent molecules, respectively. The molecules of both
compounds are dimerized by hydrogen bonding between the
Received 6 September 2012
Accepted 20 September 2012
Online 19 October 2012
The title compounds, 4-(diiodoarsanyl)benzoic acid, (I), and
3-(diiodoarsanyl)benzoic acid, (II), both [As(C H O )I ],
7 5 2 2
which possess a –COOH coordinating group, form molecular
crystal structures composed of hydrogen-bonded dimers, the
packing differences of which are caused by the relative
0
position of the diiodoarsanyl groups. The para isomer, with Z
= 1, crystallizes in a layered structure with shortened contacts
of the As atoms to only the arene rings of adjacent molecules.
0
In contrast, the meta isomer, with Z = 3, forms separate
rectangular blocks of three ribbons, each composed of dimeric
molecular units positioned almost directly above each other
and with the As atoms possessing only two Asꢀ ꢀ ꢀI contacts to
the I atoms of neighbouring molecules.
Figure 1
The asymmetric unit of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level.
Comment
III
Organoarsenic (As ) halogenides are easily accessible com-
pounds of the type R AsHal
n
(n = 1, 2) and are widely used
3ꢁn
for the preparation of various organoarsenic derivatives
Gross et al., 1997), including arsa-heterocycles (Matuska et
al., 2010; Avtomonov et al., 1997), diarsenes (Twamley et al.,
999), and organometallic complexes such as arsinidenes
Huttner & Evertz, 1986; Jutzi & Kroos, 1990) and cluster
(
1
(
compounds (Song et al., 2001; Deck & Vahrenkamp, 1991;
Deck et al., 1987). Iodine derivatives, with the I atoms as good
leaving groups, have been shown to be particularly good
reagents for introducing the RAs group into cluster complexes
as a result of nucleophilic substitution reactions (Konchenko
et al., 1999; Pushkarevsky et al., 2006; Winter et al., 1983; Ilyin
et al., 2012). There are only three known structures of RAsI2
compounds, and in all three cases the As atom has additional
contacts with the donor atoms of neighbouring groups or
molecules. Thus, in the case of CH AsI , the As atom contacts
3
2
the two I atoms of a neighbouring molecule, which determines
the stacked arrangement of the molecules (Camerman &
Trotter, 1963). In the other two structures, which have bulky
substituents (R = pentamethyl or tetraisopropylcyclopenta-
Figure 2
The asymmetric unit of (II), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level.
Acta Cryst. (2012). C68, m323–m325
doi:10.1107/S0108270112040000
# 2012 International Union of Crystallography m323

metal-organic compounds
Figure 3
The layered packing in the structure of (I).
Figure 5
Bundles of three ribbons in (II), forming parquet-like layered packing
parallel to (101).
carboxylic acid groups. The acidic H atom in (II) is disordered
over two positions, refined with 0.5 constrained occupancy in
each of the independent molecules, which agrees with the
almost equal C—O bond lengths. The dimer packings in (I)
and (II) are different. The planar molecules in (I) are located
parallel to each other to form infinite stacks (Fig. 3). Inter-
estingly, the environment of the As atoms is completed by the
˚
contacts with a mean Asꢀ ꢀ ꢀI distance of 3.56 [9] A (cf. 3.605
˚
and 3.658 A for CH AsI ; Camerman & Trotter, 1963),
noticeably shorter than the sum of the van der Waals radii of
3
2
˚
the elements (3.98 A; Bondi, 1964; Fig. 4). Being sufficiently
˚
arene ring of a neighbouring molecule [3.469 (5) A for
large, the I atoms make it impossible for the arene cycles to
remain parallel as in (I), so the rings are skewed with respect
to the line of hydrogen bonding (Fig. 4). Such bending makes
it possible for only three molecules to pack on top of each
other, so infinite packing analogous to (I) is not possible.
Consequently, the three dimeric units are translated to form
bundles of three ribbons of different bending (Fig. 5). The
bundles themselves form a parquet-like layered packing
parallel to (101).
Asꢀ ꢀ ꢀring centroid], which resembles the known interactions
in the molecules of Cp*-substituted diiodoarsenides (Cp* is
pentamethylcyclopentadienyl; Avtomonov et al., 1996). The
aromatic rings are shifted apart, so there is no ꢀ–ꢀ stacking
between them in (I). In contrast, the ꢀ systems of the aryl
fragments in (II) are most probably bound by ꢀ–ꢀ interactions
[the distances between the centroids of the aryl rings of the
three independent molecules (Fig. 1) are 3.967 (7) and
˚
.902 (7) A, with the nearest rings almost fully overlapped].
3
The different position of the diiodoarsanyl group relative to
neighbouring molecules causes the two packing modes.
Consequently, the orientation of this group with respect to the
Also in contrast with (I), each As atom is positioned close to
the two I atoms of a neighbouring molecule, thus forming two
arene ring is different: the I1—As1—C5—C4 torsion angle is
ꢂ
0.0 (5) in (I), and the equivalent angles are 38.7 (3), 38.0 (3)
and 36.3 (3) in (II), while the I1—As1—I2 angle for both
ꢂ
ꢂ
compounds has nearly the same value (101 [1] ). The average
As—C bond lengths do not seem to depend on the position of
˚
the carboxylic acid group, viz. 1.977 (5) A for (I) and
˚
.976 (5) A for (II).
1
As a consequence of (II) having more interactions evident
between the molecules in the crystal packing, namely ꢀ–ꢀ and
Asꢀ ꢀ ꢀI versus only Asꢀ ꢀ ꢀC interactions in the packing of (I),
6
the packing of isomer (II) is slightly denser than that of (I)
(
ꢁ
3
Dcalc = 2.843 and 2.789 Mg m , respectively).
Experimental
Figure 4
6 4 2
For the syntheses of arsonic acids [p- or m-HOOCC H AsO(OH) ],
A stack of three pairs of the dimers of (II), as part of the molecular
ribbons, viewed along the a axis (the I atoms of neighbouring ribbons are
marked with asterisks; the bending of the ribbons is schematically
depicted by thick dashed lines).
the corresponding aminobenzoic acids (4.00 g, 29.2 mmol) were
diazotized in dilute HCl (44 mmol). The diazo solution was added
2
dropwise to a solution containing NaAsO (5.68 g, 43.8 mmol) in the
ꢃ
m324 Ilyin et al. Two isomers of [As(C
7 5
H O
2
)I
2
]
Acta Cryst. (2012). C68, m323–m325

metal-organic compounds
presence of excess KOH (53.8 mmol; Bart reaction). The mixture was
heated for 30 min with activated charcoal and filtered. The solution
was acidified with HCl and cooled. A crystalline powder of p- or m-
For both compounds, H atoms were located in difference Fourier
˚
maps and subsequently positioned geometrically, with C—H = 0.93 A
˚
and O—H = 0.82 A. They were refined as riding, with Uiso(H) =
1.2Ueq(C,O).
HOOCC
derivatives, p- or m-HOOCC
treated with excess NaI (0.61 g, 4.1 mmol) and Na
.63 mmol) in aqueous solution (10 ml) and the solution was acidified
to pH 1. Yellow precipitates of p- or m-HOOCC AsI were filtered
6
H
4
AsO(OH)
2
precipitated at pH 3. To obtain the iodide
AsO(OH) (0.20 g, 0.82 mmol) was
SO (0.12 g,
6
H
4
2
For both compounds, data collection: APEX2 (Bruker, 2004); cell
refinement: SAINT (Bruker, 2004); data reduction: SAINT;
program(s) used to solve structure: SHELXTL (Sheldrick, 2008);
program(s) used to refine structure: SHELXTL; molecular graphics:
DIAMOND (Bergerhoff et al., 1996); software used to prepare
material for publication: SHELXTL.
2
3
0
6
H
4
2
off, dried and recrystallized from chloroform–diethyl ether (1:1 v/v)
mixtures.
The authors are grateful to the Russian Foundation for
Basic Research (grant Nos. 10-03-00385, 12-03-31759 and 12-
03-31530) and the Federal target program ‘Kadry’ (contract
No. 8631, registration No. 1012-1.3.1-12-000-1012-009) for
financial support.
Compound (I)
Crystal data
ꢂ
ꢃ = 96.376 (2)
V = 535.59 (5) A
Z = 2
[
M
As(C
= 449.83
Triclinic, P1
7
H
5
O
2
)I
2
]
˚
3
r
˚
a = 4.8992 (2) A
Mo Kꢁ radiation
˚
b = 8.4434 (5) A
ꢁ1
ꢄ = 8.90 mm
T = 296 K
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3449). Services for accessing these data are
described at the back of the journal.
˚
c = 13.6616 (9) A
ꢂ
ꢁ
= 107.148 (2)
ꢂ
0.35 ꢄ 0.20 ꢄ 0.18 mm
ꢂ = 91.569 (2)
Data collection
References
Bruker Nonius X8 APEXII CCD
area-detector diffractometer
Absorption correction: multi-scan
3909 measured reflections
2144 independent reflections
1859 reflections with I > 2ꢅ(I)
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Harms, K., Churakov, A. V. & Howard, J. A. K. (1997). J. Organomet. Chem.
544, 79–89.
(
T
SADABS; Bruker, 2004)
min = 0.147, Tmax = 0.297
R
int = 0.027
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2
2
R[F > 2ꢅ(F )] = 0.038
wR(F ) = 0.109
110 parameters
H-atom parameters constrained
2
˚
ꢁ3
Áꢆmax = 1.87 e A
S = 1.07
2144 reflections
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Crystal data
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˚
V = 3152.9 (3) A
3
[
M
As(C
7
H
5
O
2
)I
2
]
r
= 449.83
Z = 12
Mo Kꢁ radiation
Monoclinic, P2 =n
˚
a = 7.6751 (5) A
b = 18.6142 (12) A
˚
c = 22.0692 (12) A
ꢂ = 90.206 (2)
1
ꢁ1
ꢄ = 9.07 mm
T = 296 K
670.
˚
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0.18 ꢄ 0.15 ꢄ 0.06 mm
ꢂ
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3069.
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Bruker Nonius X8 APEX CCD
area-detector diffractometer
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23397 measured reflections
5996 independent reflections
5277 reflections with I > 2ꢅ(I)
(
T
SADABS; Bruker, 2004)
min = 0.292, Tmax = 0.612
Rint = 0.033
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2
(2001). J. Organomet. Chem. 627, 255–262.
2
R[F > 2ꢅ(F )] = 0.021
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325 parameters
H-atom parameters constrained
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2
˚
ꢁ3
Áꢆmax = 0.88 e A
S = 1.04
5996 reflections
Áꢆmin = ꢁ0.78 e A˚
ꢁ3
ꢃ
Acta Cryst. (2012). C68, m323–m325
Ilyin et al.
7 5
Two isomers of [As(C H O
2
)I
2
]
m325