Interplay of carbonyl-carbonyl, CH?O and CH?π interactions in hierarchical supramolecular assembly of tartaric anhydrides - Tartaric acid and its O-acyl derivatives: Part 11

Article abstract of DOI:10.1016/j.molstruc.2012.02.053

The detailed analysis of molecular and crystal structure of the O-acyltartaric anhydrides is presented. The role of both intra- and intermolecular weak interactions is discussed. The Hirshfeld surfaces analysis in form of d_norm representation a

Full text of DOI:10.1016/j.molstruc.2012.02.053

Journal of Molecular Structure 1017 (2012) 98–105
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Interplay of carbonyl–carbonyl, CAHꢀ ꢀ ꢀO and CAHꢀ ꢀ ꢀ
p interactions in hierarchical
supramolecular assembly of tartaric anhydrides – Tartaric acid and its
O-acyl derivatives: Part 11
⇑
Izabela D. Madura , Janusz Zachara, Halina Hajmowicz, Ludwik Synoradzki
Warsaw University of Technology, Faculty of Chemistry, Noakowskiego 3, 00-664 Warsaw, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
The detailed analysis of molecular and crystal structure of the O-acyltartaric anhydrides is presented. The
role of both intra- and intermolecular weak interactions is discussed. The Hirshfeld surfaces analysis in
form of dnorm representation and decomposed finger print plots was used to find out the types of weak
Received 21 December 2011
Received in revised form 21 February 2012
Accepted 21 February 2012
Available online 14 March 2012
but directional carbonyl–carbonyl, CAHꢀ ꢀ ꢀO and CAHꢀ ꢀ ꢀ
p interactions. The major interactions at the sub-
sequent levels of the crystal architecture were identified. The interplay between carbonyl–carbonyl inter-
actions and CAHꢀ ꢀ ꢀO hydrogen bonds both at the molecular level as well as in basic supramolecular
motives was analyzed. In all cases the primary supramolecular motif was found to be the ribbon showing
Keywords:
Carbonyl–carbonyl interactions
Hydrogen bond
the p2
1
rod group symmetry. The key role of the ribbon motif is reflected in the hexagonal packing of
rods.
Hirshfeld surface
Ó 2012 Elsevier B.V. All rights reserved.
Rod symmetry groups
Acyltartaric anhydride
Hexagonal packing of rods
1
. Introduction
The nature and properties of weak intermolecular interactions are
co-workers as well as Diederich’s group, the attractive dispersion and
electrostatic interactions are the major energetic contributors for car-
bonyl–carbonyl interactions [3–5,7]. These calculations are in agree-
ment with the observed antiparallel or orthogonal alignment of
interacting C@O groups in the case of both inter- as well as intramolec-
ular interactions in crystals. There are also other explanations which
connect the origin of the close C@OꢀꢀꢀC@O contacts with a simple Cou-
lombic attraction between the negatively polarized O atom and posi-
tively polarized C atom of the second carbonyl group [5]. Further,
Palusiak et al. [12] using Atoms in Molecules analysis [16], proved that
there are the bond critical points and the corresponding bond paths
present for these interactions in the case of maleimido organometallic
the subject of ongoing studies [1,2]. Special attention is paid to so called
non-hydrogen mediated intermolecular interactions [2], also including
close contacts between pairs of carbonyl groups C@OꢀꢀꢀC@O [3–14].
Although carbonyl–carbonyl interactions are very weak there are
numerous literature reports claiming that these interactions take part
in stabilizing molecular geometry [6,9–12] as well as in self-association
in the case of small molecules [3,4,6–8,13]. They are also important in
biomolecules [5,6,9–11] and can be found both in crystalline state as
well as in solution [7]. The existence of these carbonyl–carbonyl inter-
actions has been approached by various methods, nevertheless as a
starting point the crystal structure is chosen [3,4,6–8,11]. Allen et al.
derivatives. Other approach, based on Natural Bond Orbital analysis
ꢁ
[17], points out to a stabilizing n ?
p
interaction type [9–11]. In such
[
3], on the basis of systematic crystal database (CSD [15]) analysis for or-
an interaction a lone pair (n) of the oxygen atom overlaps with the anti-
ꢁ
ganic ketones, followed by intermolecular perturbation theory calcula-
tions (IMPT), showed the importance of interactions between carbonyl
groups in stabilizing the packing modes and their contribution to supra-
molecular recognition processes. The energy estimation revealed that
their energy is comparable to medium strength hydrogen bonds. Fur-
ther, it also has been shown that C@OꢀꢀꢀC@O interactions are com-
monly observed in crystal structures of transition metals carbonyls
and may have a role in designing novel carbonyl-containing inorganic
and metal–organic hybrid materials [4,12]. According to Allen and his
bonding orbital (
p
) of the carbonyl group in proximity. The authors
connect this interaction with the Bürgi–Dunitz trajectory which was de-
duced initially from a survey of small-molecule crystal structures [18].
Nowadays, the high quality data from X-ray or neutron diffrac-
tion methods can be obtained, hence their results can be used to
interpret even very weak interactions. The Hirshfeld surface analy-
sis, based on spherically averaged electron density approximation
and using precise crystallographic data, has been proven to be very
useful in investigation of intermolecular contacts in crystals
[
19–22]. We have recently shown, basing on high quality data and
⇑
Corresponding author. Tel.: +48 22 6225186; fax: +48 22 6282741.
E-mail address: izabela@ch.pw.edu.pl (I.D. Madura).
Hirshfeld surface analysis, that carbonyl–carbonyl interactions
interplay with OAHꢀ ꢀ ꢀO and CAHꢀ ꢀ ꢀO hydrogen bonds in forming
0
022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.02.053

I.D. Madura et al. / Journal of Molecular Structure 1017 (2012) 98–105
99
Table 1
using spherical harmonics, implemented in mutli-scan scaling algo-
rithm. The structures were solved using direct methods, and refined
with the full-matrix least-squares technique using the SHELXS97
and SHELXL97 programs respectively [28], both implemented in
OLEX-2 suite [29]. All non-hydrogen atoms were refined with aniso-
tropic temperature factors. The hydrogen atoms were placed in cal-
culated positions with fixed isotropic thermal parameters and
included in the structure factor calculations in the final stage of
the refinement. The ꢄ0.11(17) value of the Flack x parameter [30]
at the end of the refinement indicates that the assigned R,R absolute
configuration is correct and in agreement with the tartaric acid sub-
strate. Relevant crystallographic data are given in Table 1. Molecular
and packing diagrams were generated using ORTEP-3 for Windows
Crystal data, data collection and refinement parameters
for 1.
Empirical formula
Crystal size (mm)
18 12 7
C H O
0.60 ꢅ 0.12 ꢅ 0.08
M
r
340.28
Crystal system
Space group
Temperature (K)
a (Å)
b (Å)
c (Å)
Volume (Å )
Z
F(000)
Orthorhombic
P2 2 2
1 1 1
100(2)
5.79954(12)
11.7955(2)
22.3383(4)
1528.13(5)
4
704
1.479
0.983
7642
2715 [Rint = 3.02%]
ꢄ6 6 h 6 6
ꢄ14 6 k 6 12
ꢄ26 6 l 6 26
2715/0/227
1.084
3
ꢄ3
q
l
calc. (Mg m
(mm
)
[
31] while the geometric calculations were done by PLATON pack-
ꢄ1
)
age [32]. Values involving hydrogen atoms in the calculated posi-
tions are given without estimated standard deviations.
CCDC-856934 record contain the Supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Reflections collected
Reflections with I > 2
Index range
r
(I)
Data/restraints/parameters
Goodness-of-fit on F
Final R indices (I > 2
2
a
r
(I))b
R
1
= 0.0316
wR = 0.0776
= 0.0351
wR = 0.0807
2
R indices (all data)b
R
1
2
2.3. Hirshfeld surface analysis
Flack parameter x
ꢄ0.11(17)
ꢄ3
D
q
max/min (eÅ
)
0.201/ꢄ0.179
The molecular Hirshfeld surface in the crystal structure is
a
Goodness of fit I ¼ f½wðF ꢄ F Þ2ꢂ=ðn ꢄ pÞg1=2,
2
o
2
c
defined as a set of points in 3-D space where the contribution to
the electron density from the molecule of interest is equal to the
contribution from all the other molecules. The basis for construct-
ing molecular Hirshfeld surfaces is the electron distribution calcu-
lated as the sum of spherical atom electron densities [19]. As a
result, an isosurface is obtained on which two distances can be
where n is the number of reflections and p is the total
number of parameters refined.
b
R
1
=
R
||F
o
| ꢄ |F
c c
||/R|F |,
2
2
c
2
½wðF Þ ꢂg1=2.
2
o
2
wR
2
¼ f
R
½wðFo ꢄ F Þ ꢂ=
R
the primary supramolecular motif in monobenzoyltartaric anhy-
dride [23]. It is consistent with Allen’s conclusions derived on the
basis of systematic data base study and the theoretical energy calcu-
lations [3], showing that the estimated energy of 8–20 kJ/mol is at
similar level for both C@Oꢀ ꢀ ꢀC@O and CAHꢀ ꢀ ꢀO types of contacts.
Following the current research focused on non-hydrogen med-
iated interactions and continuing our study on tartaric acid deriv-
atives, this contribution reports the detailed analysis of crystals of
tartaric anhydrides, which are important intermediates in asym-
metric synthesis [24,25] and are used as resolving agents [26].
defined: d
external to the surface, and d
e
, the distance from the point to the nearest nucleus
the distance to the nearest nucleus
i
internal to the surface. Such surface allows the qualitative and
quantitative investigation and visualization of intermolecular close
contacts in molecular crystals [20]. Moreover, the identification of
the regions of particular importance to intermolecular interactions
is provided by mapping normalized contact distance (dnorm) based
e i
on both d and d , and the vdW radii of the atom [21]. The value of
dnorm is negative/positive when intermolecular contacts are short-
er/longer than vdW separations. Graphical plots of the molecular
Hirshfeld surfaces mapped with dnorm use the red–white–blue
color scheme with red highlighting the shorter intermolecular con-
tacts, white showing the contacts around the vdW separation, and
blue being used to indicate the longer contact distances. Because of
2
. Experimental
2.1. Synthesis
e i
the symmetry between d and d in the expression for dnorm, where
two Hirshfeld surfaces touch, both will display a red spot identical
in color intensity as well as size and shape.
(
R,R)-tartaric acid (31.5 g; 0.21 mol), benzoyl chloride (88.5 g;
0
.63 mol), H SO (0.50 g, 5 mmol) and toluene (30 mL) was heated
2
4
up to boiling temperature and refluxed until the end of evolution of
HCl. After addition of toluene (95 mL) the mixture was cooled
down to 45 °C, washed with toluene (95 mL), filtered and dried giv-
ing white crystalline product (65 g, 0.19 mol) with 91% yield. After
In addition, the Hirshfeld surface can be presented in form of 2-
D fingerprint plots in which the distance d
distance d [21]. In particular, a fingerprint plot displays the frac-
tion of points on the Hirshfeld surface with specific d , d values.
i
is plotted against the
e
i
e
0
recrystallization from dry toluene pure crystalline O,O -dibenzoyl-
Such plots are unique for a given crystal structure, and encode
information about the intermolecular interactions in the immedi-
ate environment of each molecule in the asymmetric unit. More-
over, the close contacts between particular atom types can be
highlighted in so-called decomposed fingerprint plots [22], there-
fore allows the facile assignment to a certain type of interaction
and quantitatively summarize the nature and type of intermolecu-
lar contacts. The graphical representation of 2-D plots is created by
(
R,R)-tartaric anhydride (1) was obtained, mp. 198–201 °C;
20
D
ꢃ
1
½
a
8
ꢂ
¼ þ195 (c 1, DCM) [24]. H NMR (400 MHz, DMSO) d/ppm:
.03 (m, 4H), 7.74 (m, 2H), 7.58 (m, 4H), 6.70 (s, 2H). Crystals suit-
able for single-crystal X-ray diffraction measurement were recrys-
tallized from saturated toluene.
2
.2. X-ray data collection and refinement
e i
binning (d , d ) pairs in intervals (eq. of 0.01 Å) and coloring each
Single crystal data for 1 were collected on Gemini A Ultra Diffrac-
bin (essentially a pixel) of the resulting 2-D histogram as a function
of the fraction of surface points in that bin, ranging from blue (few
points) through green to red (many points). To provide context, the
outline of the full fingerprint is shown in gray.
tometer (Agilent Technologies) using CuK
a
radiation (k = 1.5418 Å).
[27] program was used for data collection, cell
refinement, data reduction and the empirical absorption corrections
Pro
The CrysAlis

1
00
I.D. Madura et al. / Journal of Molecular Structure 1017 (2012) 98–105
Table 2
O
O
O
O
O
O
O
O
O
Selected geometrical parameters for compound 1. For comparison the corresponding
H
H
H
H
H
H
data for QACXUP [23] and KAMRAS [34] are given.
O
OH
O
O
O
O
1
QACXUP
KAMRAS
O O
Me
O
O
Me
Bond lengths (Å)
O(1)AC(1)
O(2)AC(1)
O(2)AC(4)
O(3)AC(3)
O(3)AC(12)
O(4)AC(4)
O(5)AC(2)
O(5)AC(5)
O
1.187(2)
1.385(2)
1.389(2)
1.426(2)
1.363(2)
1.181(2)
1.425(2)
1.361(2)
1.209(2)
1.204(2)
1.528(3)
1.190(2)
1.3802(19)
1.392(2)
1.403(2)
–
1.184(2)
1.4256(18)
1.354(2)
1.211(2)
–
1.176(2)
1.380(2)
1.389(2)
1.415(2)
1.359(3)
1.174(2)
1.413(2)
1.355(3)
1.191(4)
1.180(3)
1.506(3)
QACXUP
(1)
KAMRAS
Scheme 1.
The Hirshfeld surfaces mapped with dnorm and in form of
decomposed 2-D fingerprint plots presented in this paper in Figs.
and 4 were generated using CrystalExplorer 2.1 program [33].
O(6)AC(5)
O(7)AC(12)
C(2)AC(3)
3
1.520(2)
Bond angles (°)
C(1)AO(2)AC(4)
O(5)AC(2)AC(3)
O(3)AC(3)AC(2)
O(5)AC(5)AO(6)
O(3)AC(12)AO(7)
Torsion angles (°)
C(1)AC(2)AC(3)AC(4)
O(1)AC(1)AC(2)AO(5)
O(3)AC(3)AC(4)AO(4)
O(2)AC(1)AC(2)AO(5)
O(2)AC(4)AC(3)AO(3)
C(1)AC(2)AO(5)AC(5)
C(4)AC(3)AO(3)AC(12)
C(2)AO(5)AC(5)AO(6)
C(3)AO(3)AC(12)AO(7)
O(5)AC(2)AC(3)AO(3)
111.50(14)
117.10(14)
115.14(15)
121.76(16)
122.34(17)
110.14(12)
111.96(13)
115.87(14)
122.49(15)
–
110.22(15)
111.84(17)
115.06(17)
121.9(2)
3
. Results and discussion
The search of the CSD database [15] revealed only two examples
122.2(2)
of tartaric anhydride structurally determined so far, namely (R,R)-
O-benzoyl [23] and (R,R)-O,O -diacetyl [34] tartaric acid anhydrides
0
ꢄ16.62(18)
ꢄ40.6(3)
ꢄ46.9(3)
141.68(14)
135.91(14)
ꢄ54.79(19)
165.52(14)
0.8(2)
ꢄ25.32(15)
ꢄ38.2(2)
ꢄ33.9(3)
141.59(13)
146.35(13)
86.25(17)
–
–0.2(2)
–
94.80(16)
ꢄ24.69(19)
ꢄ40.1(3)
ꢄ35.9(3)
138.94(16)
145.98(16)
97.6(2)
142.36(18)
1.8(3)
2.1(3)
(
the CSD refcode names are QACXUP and KAMRAS, respectively).
0
Herein presented (R,R)-O,O -dibenzoyl derivative (1) posses similar
fragments to both above mentioned molecules Scheme 1), but
simultaneously allow us to show the impact of (i) the presence
of the second benzoyl substituent (equivalent to the absence of hy-
droxyl group) and (ii) the change from methyl groups to aromatic
rings, on both the molecular as well as crystal structure of these
anhydrides.
5.5(2)
103.92(18)
97.79(19)
3
.1. Molecular structures
experimental conditions (X-ray source and temperature). The con-
formation of anhydride five-membered C(1)C(2)C(3)C(4)O(1) ring
1 1 1
The anhydride 1 crystallizes in the chiral space group P2 2 2
2
in all cases can be approximated with C symmetry (the ring puck-
(Table 1). The molecular structure of the R,R enantiomer, with
ering phase parameter close to 90° [35]) and with the twist on
u
the atom numbering scheme is presented in Fig. 1. The selected
geometrical parameters are summarized in Table 2. All the corre-
sponding bond lengths and bond angles in 1 and QACXUP are iden-
tical within the error margin. A slight elongation (ꢆ0.01 Å) of all
C@O bonds as well as of the C(2)AC(3) bond is observed while
comparing 1 and KAMRAS. This may be attributed to different
C(2)AC(3) bond. This twist is the smallest in 1 (the puckering
amplitude Q = 0.170(2)) while both QACXUP and KAMRAS mole-
cules show similar Q values around 0.25. Comparing to the flat con-
formation of succinic acid anhydride [36], the deviation from
planarity in the discussed anhydrides may come from the engaging
O(2)
O(4)
O(1)
C(1)
C(4)
C(3)
O(6)
C(2)
H(2)
C(5)
O(5)
O(3)
H(3)
C(11)
C(6)
C(10)
C(12)
C(13)
O(7)
C(14)
C(15)
C(7)
C(9)
C(8)
C(18) C(16)
C(17)
Fig. 1. An ORTEP [31] drawing of a molecule 1 with atom numbering scheme. Thermal ellipsoids are drawn with 50% probability.

I.D. Madura et al. / Journal of Molecular Structure 1017 (2012) 98–105
101
(
a)
(b)
O(6)
C(2)
C(2) C(3)
C(3)
O(3)
O(5)
O(3)
O(5)
O(6)
O(7)
O(7)
Fig. 2. Projection along C(2)AC(3) bond showing different orientation of two acyl groups in anhydrides: (a) 1 and (b) KAMRAS. Intramolecular contacts are shown with dotted
lines.
Table 3
Geometrical parameters for intra- and intermolecular contacts (distances in Å, angles in degrees) in 1 and KAMRAS [34]. Atoms numbering for KAMRAS was changed to be
consistent with that used in this contribution.
Dꢀ ꢀ ꢀA or Cꢀ ꢀ ꢀO
DAHꢀ ꢀ ꢀA or C@Oꢀ ꢀ ꢀC
Hꢀ ꢀ ꢀA or Oꢀ ꢀ ꢀC@O
Intramolecular interactions
1
C3AH3ꢀ ꢀ ꢀO6
2.903(2)
2.639(2)
106
87.1(1)
2.46
99.2(1)
C5@O6ꢀ ꢀ ꢀC1@O1
KAMRAS
C3–H3ꢀ ꢀ ꢀO7
C2AH2ꢀ ꢀ ꢀO6
2.631(3)
2.634(3)
102
101
2.24
2.27
Intermolecular interaction leading to 1-D ribbon motif
i
1
C1@O1ꢀ ꢀ ꢀC4@O4
2.931(2)
3.070(2)
3.174(2)
3.420(2)
3.463(2)
3.546(2)
123.2(1)
131.4(1)
123
142
157
89.1(1)
91.7(1)
2.52
2.58
2.57
ii
C5@O6ꢀ ꢀ ꢀC12@O7
iii
C2AH2ꢀ ꢀ ꢀO2
iv
C2AH2ꢀ ꢀ ꢀO6
ii
C11AH11ꢀ ꢀ ꢀO7
ii
C3AH3ꢀ ꢀ ꢀcg2
140
2.72
iv
KAMRAS
C7@O7ꢀ ꢀ ꢀC4@O4
2.793(2)
2.951(2)
3.280(3)
3.109(3)
3.529(3)
141.6(2)
124.0(2)
119
112
162
95.8(2)
91.7(2)
2.70
2.60
2.60
v
C1@O1...C4@O4
vi
C3AH3ꢀ ꢀ ꢀO1
ii
C2AH2ꢀ ꢀ ꢀO7
iv
C6AH6aꢀ ꢀ ꢀO6
Intermolecular interaction between ribbons leading to 3-D structure
vii
1
C15AH15ꢀ ꢀ ꢀO7
3.228(2)
3.403(2)
3.399(2)
3.4572(19)
3.5123(19)
3.6588(19)
128
151
142
143
129
131
2.56
2.54
2.60
2.65
2.84
2.97
viii
C17AH17ꢀ ꢀ ꢀO4
ix
C9AH9ꢀ ꢀ ꢀO1
vii
C16AH16ꢀ ꢀ ꢀcg1
x
C7AH7ꢀ ꢀ ꢀcg1
xi
C10AH10ꢀ ꢀ ꢀcg2
xii
KAMRAS
C8AH8aꢀ ꢀ ꢀO4
3.412(4)
151
2.54
Cg1 and cg2 denote the aromatic rings’ gravity centers.
Symmetry codes: (i) 1/2 + x, 3/2 ꢄ y, 1 ꢄ z; (ii) 1 + x, y, z; (iii) ꢄ1/2 + x, 3/2 ꢄ y, 1 ꢄ z;(iv) ꢄ1 + x, y, z; (v) 1/2 + x, ꢄ1/2 ꢄ y, 1 ꢄ z; (vi) ꢄ1/2 + x, ꢄ1/2 ꢄ y, 1 ꢄ z; (vii) 1 ꢄ x, ꢄ1/
+ y, 3/2 ꢄ z; (viii) 1 ꢄ x, 1/2 + y, 3/2 ꢄ z; (ix) 1/2 + x, 5/2 ꢄ y,1 ꢄ z; (x) ꢄ1/2 + x, 5/2 ꢄ y,1 ꢄ z; (xi) 2 ꢄ x, 1/2 + y, 3/2 ꢄ z; (xii) ꢄx, 1/2 + y, 1/2 ꢄ z.
2
the acyl substituents in significant intra- or intermolecular interac-
tions. This also may be reflected in the subtle difference observed
for the torsion angle O(5)AC(2)AC(3)AO(3) which is the biggest
in 1 (103.9(2)°), drops by 6° in KAMRAS and reaches the smallest
value of 94.8(2)° in QACXUP.
Nonetheless, the most striking difference in molecular structure
is observed when comparing the orientation of the acyl groups in 1
and KAMRAS. (Fig. 2a). The position of one benzoyl group in 1 can
be described as trans with the C(12)AO(3)AC(3)AC(4) torsion an-
gle equal to 165.5(1)° while the second one with the torsion angle
C(5)AO(5)AC(2)AC(1)A54.8(2)° as gauche. In the latter the car-
bonyl C@O bond is placed almost parallel to anhydride ring with
the angle between the anhydride ring’s normal and the line
through the carbonyl bond equals to 70.49(9)°. In KAMRAS one
acyl substituent adopts conformation close to trans with the appro-
priate torsion angle reaching the value of 142.4(2)° whereas the
second one is located almost perpendicularly to the anhydride ring
with the torsion angle equal to 97.6(2)°. The diversified conforma-
tion of acyl carbonyl groups towards anhydride five-membered
ring is thus reflected in intramolecular interactions present in
these compounds (Fig. 2b, Table 3). In KAMRAS the orientation of
carbonyl groups allows the formation of two intramolecular
CAHꢀ ꢀ ꢀO hydrogen bonds between CAH donors located at chiral
centers and acyl carbonyls attached to the same chiral atom. Such

1
02
I.D. Madura et al. / Journal of Molecular Structure 1017 (2012) 98–105
relevance of this interaction is also indicated by very slight pyrami-
dalization of C(1) atom which perches out of the plane defined by
neighboring atoms by 0.015(2) Å. The analogous to observed in
KAMRAS CAHꢀ ꢀ ꢀO hydrogen bonds are not formed. On the other
hand the same gauche benzoyl oxygen atom, O(6), may be regarded
as an acceptor to intramolecular hydrogen bond with CAH donor
located at second chiral center resulting in formation of a six-
memebered H-bonded ring with S(6) graph set [39]. These inramo-
lecular interaction may also influence the nonplanarity of this ester
substituent for which the value of the dihedral angle between the
l.s. plane of the phenyl ring and the plane defined by O(6)C(5)O(5)
atoms equals to 14.9(3)°. It is worth noting that second ester group
is less twisted (the corresponding dihedral angle reaches 10.6(3)°)
and the benzoyl oxygen atom, O(7), does not take part in formation
of any significant intramolecular interactions rather it is engaged
in intermolecular contacts. Similar observation have been drawn
for QACXUP where the close to perpendicular orientation of the
benzoyl carbonyl group should favor the intramolecular CAHꢀ ꢀ ꢀO
bond formation, but due to engaging the carbonyl oxygen in ques-
tion into strong intermolecular OAHꢀ ꢀ ꢀO interactions, the intramo-
lecular H-bond it is not observed. Moreover, in the case of QACXUP
molecule the ester group and the phenyl ring of the benzoyl frag-
ment are almost coplanar with the dihedral angle of only 4.0(3)°.
Fig. 3. Hirshfeld surfaces mapped with dnorm for (a) dibenzoyltartaric acid anhy-
dride 1 and (b) diacetyltartaric acid anhydride KAMRAS. View of the both sides of
the molecules.
hydrogen bonding is also present in tartaric acid acyl derivatives
and it is regarded to be enhanced by an electrostatic component
resulting from interactions between CAH and C@O antiparallel di-
poles [37,38]. In case of 1 the close to orthogonal orientation of car-
bonyl group from the gauche located benzoyl and the one carbonyl
of the anhydride ring is observed. The O(6)ꢀ ꢀ ꢀC(1)@O(1) angle of
3.2. Primary supramolecular structure
The presence of hydroxy group in QACXUP causes its crystal
structure to be directed by relatively strong intermolecular
OAHꢀ ꢀ ꢀO hydrogen bonds [23]. They are formed between the hy-
droxy group and the carbonyl oxygen of the benzoyl substituent
linking into a chain adjacent molecules related by translation.
9
2
9.2(1)° together with the short C@Oꢀ ꢀ ꢀC@O contact of
ꢁ
.639(2) Å points out an interaction of n?
p type that arises from
an overlap of lone electron pair of the acyl carbonyl’s oxygen with
ꢁ
the
p
antibonding orbital of the ring carbonyl group [9–11]. The
(
a)
d
e
d
e
d
e
2
2
2
1
1
1
1
1
0
0
.4
.2
.0
.8
.6
.4
.2
.0
.8
.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
C...O/O...C 6.0%
d
O...H/H...O 33.4%
di
C...H/H...C 27.9%
di
i
(
Å) 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
(Å) 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
(Å)
0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
(
b)
d
e
d
e
d
e
2
.4
.2
.0
.8
.6
.4
.2
.0
.8
.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
2
2
1
1
1
1
1
0
0
C...O/O...C 6.7%
d
O...H/H...O 52.2%
di
C...H/H...C 2.3%
di
i
(
Å) 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
(Å)
0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
(Å) 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
Fig. 4. Decomposed fingerprint plots for (a) 1 and (b) KAMRAS showing intermolecular contacts between Cꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀC, Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO and Cꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀC. The percentage show the
contacts contribution to the total Hirshfeld surface area.

I.D. Madura et al. / Journal of Molecular Structure 1017 (2012) 98–105
103
The lack of strong hydrogen bond donors in 1 and KAMRAS causes
the weak interactions to take part in building their supramolecular
structure.
can be described as the perpendicular motif. Further, the some-
0
what longer C@Oꢀ ꢀ ꢀC@O contacts (d O(1)ꢀ ꢀ ꢀC(1) @2.951(2) Å) occur
between anhydride ring carbonyls of the neighboring molecules
To elucidate the nature and importance of weak intermolecular
contacts the Hirshfeld surface analysis was performed for 1 and
KAMRAS. Fig. 3 presents their Hirshfeld surfaces mapped with
1
related by 2 screw axis (Fig. 5b). The analogous to the later inter-
actions are present in the crystals of 1 (Table 3, Fig. 5a). There are
also carbonyl–carbonyl interactions between molecules related by
translation, but in 1 they are formed between both benzoyl carbon-
yls and they are weaker than those formed along the screw axis (d
d
norm showing the regions of important intermolecular contacts
as red spots.
0
The most visible difference between these two surfaces is a
number of red spots. In case of 1 there is a great number of red
regions present all over the surface involving anhydride carbonyls
as well as whole benzoyl substituents. Most of these regions are of
the same size (intensity) indicating intermolecular interactions of
the similar importance. In case of KAMRAS there are two big deple-
tion near acyl and one of the anhydride ring’s carbonyls pointing
out the primary interaction.
In order to find out directional interactions the characteristic
features in the fingerprint plots obtained from the Hirshfeld sur-
face were further analyzed [20]. Following the observations made
on the basis of dnorm surfaces, in Fig. 4 we present the decomposed
fingerprint plots [22] highlighting expected intermolecular con-
tacts. The first column shows Cꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀC contacts. For both 1
and KAMRAS there are two sharp red spikes with the minimum va-
O(1)ꢀ ꢀ ꢀC(1) = 3.071(2) Å). It is important to note that in both cases
1
the symmetry of ribbons is in accordance to p2 rod group [40].
Moreover, the similar ribbon motif of the same symmetry is ob-
served in QAXCUP where OAHꢀ ꢀ ꢀO H-bonded transnational chains
combine with carbonyl–carbonyl interactions and CAHꢀ ꢀ ꢀO hydro-
gen bonds [23].
The later bonds are also observed in 1 and KAMRAS underling
the interplay with carbonyl–carbonyl interactions. The CAHꢀ ꢀ ꢀO
hydrogen bonds appear on the Oꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀO finger print as red
e i
spikes with the shortest contact (i.e. min d + d ) around 2.5 Å
(Fig. 4). The geometry analysis preformed with the aid of PLATON
package [32] for both 1 and KAMRAS revealed that the primary rib-
bons are enhanced by several weak CAHꢀ ꢀ ꢀO hydrogen bonds. In
both cases there are CAHꢀ ꢀ ꢀO interactions joining the molecules re-
lated by screw axis where CAH donor belongs to one of the chiral
ꢁ
lue of d
e
+ d
i
below 3.0 Å. These spikes point out the directional
centers. In KAMRAS the chiral C(3) AH(3) group interacts with
interactions between carbonyl groups. In KAMRAS they are formed
between one acyl carbonyl and one carbonyl of the anhydride ring
joining molecules related by translation in [100] direction
anhydride ring’s oxygen O(1) atom, that is the carbonyl oxygen
which also take part in carbonyl–carbonyl interaction. In 1 the
ꢁ
donor is the chiral C(2) AH(2) group and the acceptor is the etheral
(
Fig. 5b). The distance between acyl carbonyl oxygen atom and
O(2) oxygen atom. These H-bond motives (Table 3) are both
described with C(4) graph [39]. Further, in both cases there are also
CAHꢀ ꢀ ꢀO interactions between molecules related by translation
along the ribbon. In acetyl derivative these H-bonds are formed
0
rings’s carbon atom is only 2.793(2) Å while the C(1)@O(1)ꢀ ꢀ ꢀC(1)
00
and O(1)@C(1)ꢀ ꢀ ꢀO(1) angles are equal to 141.6(2) and 95.8(2)°,
respectively. According to Allen et al. [3] the observed geometry
Fig. 5. Primary supramolecular ribbon motif in (a) 1 and (b) KAMRAS formed by carbonylꢀ ꢀ ꢀcarbonyl (dashed lines) and CAHꢀ ꢀ ꢀO intermolecular interactions (dotted lines).
The symmetry of these motives is in accordance to p2 rod group symmetry.
1

1
04
I.D. Madura et al. / Journal of Molecular Structure 1017 (2012) 98–105
1
Fig. 6. Crystal packing of (a) 1 and (b) KAMRAS showing secondary intermolecular interactions. Views along [100] direction. The 2 screw axis symbols indicate the position
and direction of the primary ribbons.
ꢁ
by the second chiral donor while in 1 C (2)AH(2) acts as bifurcated
donor. In both cases the acyl carbonyl oxygen atom which takes
part in carbonyl–carbonyl interaction is an acceptor (Fig. 5 and
Table 3). Further, there are also H-bonds between acyl substitu-
ents. In acetyl derivative the CAHꢀ ꢀ ꢀO bonds are formed by methyl
group and second acetyl oxygen, while in 1 it is an aromatic CAH
donor. It should be noted (Table 3) that all these H-bonds in 1
are significantly stronger than in KAMRAS whereas carbonyl–car-
bonyl interactions are more potent in the latter.
2.65 Å (Table 3). In case of KAMRAS there are methyl groups that
surround the main ribbons, hence much weaker CAH donors. The
Hirshfeld surface analysis of KAMRAS revealed two such contacts
involving both methyl groups (Fig. 5b). One was detected in the
primary motif while the second one is formed between four neigh-
boring ribbons leading to 3-D structure. It should be underlined
that this is the shortest CAHꢀ ꢀ ꢀO contact observed in crystals of
KAMRAS.
The difference in acidity of CAH donors in 1 and KAMRAS as
well as the number of the weak intermolecular interactions, are re-
flected in packing index [43], which is 71.1% in 1 while only 67.3%
in case of acetyl derivative. Important to note is the fact that in
both cases each ribbon is surrounded by six neighbors (Fig. 6).
Hence both structures can be considered as close to hexagonal
packing of rods [44] underlying the importance of the primary
ribbon motif in the crystal architecture.
Inspection of decomposed fingerprint plots for Cꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀC
e
contacts only (Fig. 4) shows the characteristic ‘‘wings’’ (min (d +
d
i
) ꢇ 2.8 Å) that correspond to weak CAHꢀ ꢀ ꢀ
of 1. There are no such features in fingerprint of KAMRAS due to
the absence of acceptors with CAC bonds in the molecule. These
p interactions in case
p
CAHꢀ ꢀ ꢀ
p
interactions also occur within the primary ribbon in 1 and
ꢁ
they are formed between C (3)AH(3) group and the phenyl ring of
the adjacent molecule related by translation. The geometry of this
interaction analyzed according to the method proposed by Umez-
awa et al. [41] points out that the shortest contact is directed to-
wards the ring’s gravity center (cg2) with the Hꢀ ꢀ ꢀcg2 distance
equal to 2.72 Å. As we have previously shown [42] it is clearly re-
flected on the Hirshfeld surface showing the regions of aromatic
rings engaged in these type of interactions (Fig. 3).
4
. Conclusions
The detailed analysis of crystal structure of the O-acyltartaric
anhydrides let us show the role of weak interactions both at the
molecular as well as supramolecular level. In case of diacyl deriv-
atives, the lack of strong hydrogen bond donors causes the weak
interactions to play a key role in molecular organization. The use
of decomposed finger print plots of Hirshfeld surfaces allowed us
to find out the types of directional carbonyl–carbonyl, CAHꢀ ꢀ ꢀO
3.3. Secondary supramolecular structure
The views along the direction of the ribbons (i.e. down the a
and CAHꢀ ꢀ ꢀ
p interactions. We identified the major interactions at
the subsequent levels of the crystal architecture starting from the
crystallographic axis, Fig. 6) show that both phenyl rings as well
as methyl groups in 1 and KAMRAS, respectively, are perching out-
side. One can expect that phenyl rings in 1 can act as CAH donors
for weak intermolecular interactions. Indeed, three CAH
phenylꢀ ꢀ ꢀO bonds are formed building up the 3-D structure of 1
molecule and ending with the 3D crystal. In both cases the primary
supramolecular motif is the ribbon showing the p2 rod group
1
symmetry directed by carbonyl–carbonyl and CAHꢀ ꢀ ꢀO interaction.
We have shown the interplay between these interactions both at
the molecular level as well as in a basic supramolecular ribbon mo-
tif. Comparing the supramolecular assemblies of diacyltartaric
anhydrides we noticed that the strengthening of the carbonyl–car-
bonyl interactions causes the weakening of the CAHꢀ ꢀ ꢀO hydrogen
(
Fig. 6, Table 3) Additionally, the different orientation of both phe-
nyl moieties in molecules of 1 enables the formation of C-Hꢀ ꢀ ꢀ
p
interactions between the rings in neighboring ribbons. Three such
interactions were detected with the shortest Hꢀ ꢀ ꢀcg distance being

I.D. Madura et al. / Journal of Molecular Structure 1017 (2012) 98–105
[15] F.H. Allen, Acta Crystallogr. B 58 (2002) 380.
105
bonds (acetyl derivative) and vice versa (benzoyl derivative). We
[
16] R.F.W. Bader, Atoms in Molecules, Clarendon Press, Oxford,
Theory, 1994.
A
Quantum
have also pointed out that ribbons act as basic 1-D building blocks
hexagonally packed in the crystal.
[
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Acknowledgment
(
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This work was supported by the Warsaw University of Technology.
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Appendix A. Supplementary material
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