Similarities and differences in the structures of 5-bromo-6-hydroxy-7,8- dimethylchroman-2-one and 6-hydroxy-7,8-dimethyl-5-nitrochroman-2-one

Article abstract of DOI:10.1107/S0108270113005325

The title compounds, C₁₁H₁₁BrO₃, (I), and C₁₁H₁₁NO₅, (II), respectively, are derivatives of 6-hydroxy-5,7,8-trimethylchroman-2-one substituted at the 5-position by a Br atom in (I) and by a

Full text of DOI:10.1107/S0108270113005325

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
The synthesis of dimethylpropylquinones proceeds through a
coumarin intermediate and we have previously reported the
crystallographic details and intermolecular interactions of
several of these (Goswami et al., 2011, 2012; Cameron et al.,
2011).
ISSN 0108-2701
Similarities and differences in the
structures of 5-bromo-6-hydroxy-
7,8-dimethylchroman-2-one and
6-hydroxy-7,8-dimethyl-5-nitro-
chroman-2-one
Shailesh K. Goswami, Lyall R. Hanton, C. John McAdam,
Stephen C. Moratti and Jim Simpson*
In the course of this work, attempts to attach electron-
withdrawing substituents to the dimethylpropylquinone frag-
ment generated crystalline coumarins with bromo, (I), nitro,
(II), and trifluoromethyl, (III), substituent groups at the
5-position. The structures of (I) and (II) are reported here.
However, the data obtained from crystals of the trifluoro-
methyl derivative, 6-hydroxy-7,8-dimethyl-5-(trifluoromethyl)-
chroman-2-one, (III), were not of sufficient quality to provide
a definitive refinement of the structure and gave poor resi-
duals, although the data did provide us with a connectivity
map that showed all non-H atoms in the structure in reason-
able locations, allowing confirmation of the proposed mol-
ecular identity. The data for (III) have been deposited with the
Cambridge Structural Database [CSD (Allen, 2002); Goswami,
Hanton et al., 2013], but synthetic details are included here.
Compound (I) was isolated as an intermediate during the
preparation of quinone monomers in a three-step process
Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
Correspondence e-mail: jsimpson@alkali.otago.ac.nz
Received 8 February 2013
Accepted 24 February 2013
Online 6 March 2013
The title compounds, C11H11BrO3, (I), and C11H11NO5, (II),
respectively, are derivatives of 6-hydroxy-5,7,8-trimethyl-
chroman-2-one substituted at the 5-position by a Br atom in
(I) and by a nitro group in (II). The pyranone rings in both
molecules adopt half-chair conformations, and intramolecular
O—Hꢀ ꢀ ꢀBr [in (I)] and O—Hꢀ ꢀ ꢀOnitro [in (II)] hydrogen
bonds affect the dispositions of the hydroxy groups. Classical
intermolecular O—Hꢀ ꢀ ꢀO hydrogen bonds are found in both
molecules but play quite dissimilar roles in the crystal
structures. In (I), O—Hꢀ ꢀ ꢀO hydrogen bonds form zigzag
C(9) chains of molecules along the a axis. Because of the
tetragonal symmetry, similar chains also form along b. In (II),
however, similar contacts involving an O atom of the nitro
group form inversion dimers and generate R22(12) rings. These
also result in a close intermolecular Oꢀ ꢀ ꢀO contact of
˚
2.686 (4) A. For (I), four additional C—Hꢀ ꢀ ꢀO hydrogen
bonds combine with ꢀ–ꢀ stacking interactions between the
benzene rings to build an extensive three-dimensional
network with molecules stacked along the c axis. The packing
in (II) is much simpler and centres on the inversion dimers
formed through O—Hꢀ ꢀ ꢀO contacts. These dimers are stacked
through additional C—Hꢀ ꢀ ꢀO hydrogen bonds, and further
weak C—Hꢀ ꢀ ꢀO interactions generate a three-dimensional
network of dimer stacks.
Comment
We are currently interested in polymer gel actuators and, in
particular, the utilization of an electric potential as the
actuation stimulus (Goswami, McAdam et al., 2013). The
search for suitable components for such gels leads readily to
quinone-based systems, due to the accessibility and versatility
of their synthetic chemistry, and their reversible redox beha-
viour which is tunable by variation of the quinone substituents.
Figure 1
Reaction scheme showing the preparation of (I) and (II). Details: (i) Br2/
HOAc; (ii) HNO3/H2SO4; (iii) dimethyl malonate/magnesium methoxide;
(iv) dilute HCl reflux; (v) 4-methylbenzenesulfonic acid/toluene reflux.
Acta Cryst. (2013). C69, 407–411
doi:10.1107/S0108270113005325
# 2013 International Union of Crystallography 407

organic compounds
Both structures reported here contain the archetypal
6-hydroxy-5,7,8-trimethylchroman-2-one unit (Goswami et al.,
2011), substituted at the 5-position by a Br atom in (I) and a
nitro group in (II) (Fig. 3). Both molecules display intra-
molecular hydrogen bonds involving the O6 hydroxy substi-
tuents and atom Br5 in (I) or atom O51 of the nitro group in
(II). These contacts generate S5 and S6 ring motifs, respec-
tively (Bernstein et al., 1995). The fused pyranone rings in both
molecules adopt half-chair conformations, with the C3
methylene groups lying out of the mean planes through the
remaining atoms (O1/C2/C4/C9/C10; r.m.s. deviations = 0.0759
˚
˚
and 0.0896 A) by 0.485 (7) and 0.628 (3) A in (I) and (II),
respectively. The planes of the C5–C10 aromatic rings form
dihedral angles of 5.8 (2) and 9.15 (14)ꢁ, respectively, with
these planes. The methyl and bromo substituents lie very close
to the aromatic ring plane in (I) [maximum deviation =
Figure 2
The molecular structure of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level. The
intramolecular hydrogen bond is shown as a dashed line.
˚
0.127 (6) A for atom Br5], while the nitro substituent in (II) is
inclined to the aromatic ring plane at an angle of 24.8 (3)ꢁ.
Although classical intermolecular O—Hꢀ ꢀ ꢀO hydrogen
bonds are found in both molecules, they play quite dissimilar
roles in the crystal structures. In (I) (Table 1), O6—H6Oꢀ ꢀ ꢀO2i
from trimethyl-p-benzoquinone (Fieser & Ardao, 1956), as
described in the Experimental section. A reasonable yield of
5-nitro-6-hydroxy-7,8-dimethylchroman-2-one, (II), was ob-
tained from nitrotrimethylquinone (Smith & Cutler, 1949) in a
similar series of steps (Fig. 1).
Compound (I) (Fig. 2) is isomorphous with 5-chloro-6-hy-
droxy-7,8-dimethylchroman-2-one, (IV) (Cameron et al.,
2011). The unit-cell volumes of the two structures [V =
1
1
1
[symmetry code: (i) ꢂx þ ; y þ ; ꢂz þ ] hydrogen bonds
2
2
2
form zigzag C(9) chains of molecules (Bernstein et al., 1995)
along the a axis, with similar chains generated along b under
tetragonal symmetry. In contrast, for (II), an intramolecular
O6—H6Oꢀ ꢀ ꢀO51 contact occurs generating an S(6) ring, while
intermolecular O6—H6Oꢀ ꢀ ꢀO51v contacts also involve this O
atom of the nitro group and form inversion dimers with R22(12)
rings (Table 2). This also imposes a close intermolecular
3
3
˚
˚
2016.1 (4) A in (I) and 1976.24 (19) A in (IV)] reveal a small
but not unexpected increase for the bromo derivative. The
molecular structures of (I) and (IV) are similar, with the major
v
˚
O51ꢀ ꢀ ꢀO51 contact of 2.686 (4) A [symmetry code: (v) ꢂx ꢂ 1,
ꢂy + 1, ꢂz + 1].
˚
In the crystal structure of (I), the C3—H3Aꢀ ꢀ ꢀO2ii
difference being the C5—Br5 distance which, at 1.891 (4) A, is
predictably extended from the equivalent vector observed for
[symmetry code: (ii) ꢂx; ꢂy; z] hydrogen bond links the
˚
(IV) [1.735 (3) A; Cameron et al., 2011]. Other bond distances
(Allen et al., 1987) and angles in (I) are normal and similar to
those found in (IV) (Cameron et al., 2011) and four other
related structures (Budzianowski & Katrusiak, 2002; Goswami
et al., 2011, 2012; Patel et al., 2007) found in the CSD.
Figure 4
The corrugated sheets of (I), viewed along c, with hydrogen bonds drawn
as dashed lines. For clarity, H atoms on atoms not involved in hydrogen-
bond formation have been omitted from this and all subsequent packing
Figure 3
The molecular structure of (II), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level. The
intramolecular hydrogen bond is shown as a dashed line.
1
1
1
1
1
diagrams. [Symmetry codes: (i) ꢂx þ ; y þ ; ꢂz þ ; (viii) x þ ; ꢂy þ ,
2
2
2
2
2
1
ꢂz þ .]
2
ꢃ
408 Goswami et al.
C11H11BrO3 and C11H11NO5
Acta Cryst. (2013). C69, 407–411

organic compounds
Figure 5
ꢀ–ꢀ contacts (thin dashed lines) and C—Hꢀ ꢀ ꢀO hydrogen bonds (thick
dashed lines), stacking molecules of (I) in a head-to-tail fashion along c.
[Symmetry codes: (iv) ꢂy þ ; ꢂx þ ; z ꢂ ; (ix) ꢂy þ ; ꢂx þ ; z þ .]
Figure 7
1
1
1
1
1
1
Stacks of inversion dimers of (II) approximately parallel to (113). Dashed
lines indicate hydrogen bonds. [Symmetry codes: (v) ꢂx ꢂ 1; ꢂy þ 1,
ꢂz þ 1; (x) x þ 1; y; z.]
2
2
2
2
2
2
molecules into inversion dimers and generates R22(8) ring
motifs. A classical O6—H6Oꢀ ꢀ ꢀO2i hydrogen bonds and its
symmetry-related counterparts link each dimer to four others,
forming a corrugated sheet in the (001) plane (Fig. 4). The
zigzag C(9) chains mentioned above are also seen clearly in
this view. Bifurcated C4—H4Bꢀ ꢀ ꢀO1iii and C4—H4Bꢀ ꢀ ꢀO2iii
[symmetry code: (iii) ꢂy; x; ꢂz þ 1] hydrogen bonds extend
the packing to three dimensions. Molecules are also stacked in
a head-to-tail fashion along c through ꢀ–ꢀ stacking inter-
actions between adjacent C5–C10 benzene rings [Cgꢀ ꢀ ꢀCgiv =
˚
3.885 (3) A, where Cg denotes the ring centroid; symmetry
iv
1
code: (iv) ꢂy + 12, ꢂx + 21, z ꢂ ], supported by C3—H3Bꢀ ꢀ ꢀO6
2
contacts (Fig. 5). The overall packing thus comprises an
intricate three-dimensional network of molecules stacked
along c (Fig. 6).
Figure 8
The overall packing of (II), viewed along the a axis.
In contrast, the crystal structure of (II) is dominated by the
inversion dimers formed through intermolecular O6—
H6Oꢀ ꢀ ꢀO51v contacts. Additional C3—H3Bꢀ ꢀ ꢀO2vi [symmetry
code: (vi) x ꢂ 1; y; z] contacts stack adjacent dimers approxi-
mately parallel to (113) (Fig. 7). Additional weak C81—
H81Aꢀ ꢀ ꢀO52vii [symmetry code: (vii) x þ 1; y ꢂ 1; z] contacts
link these dimer stacks to generate a much simpler three-
dimensional network (Fig. 8).
Experimental
Compound (I) was synthesized from trimethyl-p-benzoquinone
(Fieser & Ardao, 1956) in three steps. The first two steps, bromination
of the quinone and coumarin ring formation, follow a literature
Figure 6
The overall packing of (I), viewed along the c axis. Dashed lines indicate
hydrogen bonds.
ꢃ
Acta Cryst. (2013). C69, 407–411
Goswami et al.
C11H11BrO3 and C11H11NO5 409

organic compounds
preparation utilizing bromine/acetic acid and then dimethyl malon-
ate/magnesium methoxide (Smith & Wiley, 1946). Characterization
was by NMR (previously unreported). The third step is hydrolysis of
the methyl ester followed by decarboxylation, a methodology used in
the preparation of the chloro analogue (Cameron et al., 2011), which
in turn was based on the work of Stoffman & Clive (2009). The
product was obtained in 72% yield and X-ray quality crystals of (I)
were obtained from CDCl3 layered with EtOH (m.p. 444–445 K). FT–
IR (ATR, ꢁ, cmꢂ1): 1735 (O—C O); 1H NMR (400 MHz, CDCl3): ꢂ
2.20 (s, 3H), 2.24 (s, 3H), 2.74 (t, J = 8 Hz, 2H), 3.04 (t, J = 8 Hz, 2H),
5.48 (s, 1H); 13C NMR (100 MHz, CDCl3): ꢂ 11.8, 12.8, 24.7, 28.8,
107.3, 119.3, 123.6, 125.7, 144.0, 146.8, 168.4.
Table 1
Hydrogen-bond geometry (A, ) for (I).
ꢁ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O6—H6Oꢀ ꢀ ꢀBr5
O6—H6Oꢀ ꢀ ꢀO2i
C3—H3Aꢀ ꢀ ꢀO2ii
C4—H4Bꢀ ꢀ ꢀO1iii
C4—H4Bꢀ ꢀ ꢀO2iii
C3—H3Bꢀ ꢀ ꢀO6iv
0.79 (2)
0.79 (2)
0.99
0.99
0.99
2.57 (4)
2.12 (4)
2.57
2.62
2.68
3.089 (3)
2.778 (4)
3.469 (6)
3.575 (6)
3.349 (6)
3.343 (6)
124 (4)
140 (5)
152
162
125
0.99
2.41
156
1
2
1
2
1
2
Symmetry codes: (i) ꢂx þ ; y þ ; ꢂz þ ; (ii) ꢂx; ꢂy; z; (iii) ꢂy; x; ꢂz þ 1; (iv)
1
2
1
2
1
2
ꢂy þ ; ꢂx þ ; z ꢂ .
Nitrotrimethylquinone (Smith & Cutler, 1949) was similarly used
to prepare the nitro derivative, (II). The product was obtained in 66%
Table 2
Hydrogen-bond geometry (A, ) for (II).
ꢁ
˚
1
yield and X-ray quality crystals were obtained from Et2O. H NMR
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
(400 MHz, CDCl3): ꢂ 2.23 (s, 3H, CH3), 2.27 (s, 3H, CH3), 2.65 (t, J =
8 Hz, 2H, CH2), 3.27 (t, J = 8 Hz, 2H, CH2). HR–MS (ESI), calculated
for C11H10NO5: [M ꢂ H]ꢂ m/z 236.0553; found: m/z 236.0564. Details
of the preparative routes to (I) and (II) are shown in Fig. 1.
O6—H6Oꢀ ꢀ ꢀO51
O6—H6Oꢀ ꢀ ꢀO51v
C3—H3Bꢀ ꢀ ꢀO2vi
C81—H81Aꢀ ꢀ ꢀO52vii
0.86 (3)
0.86 (3)
0.99
1.80 (3)
2.45 (3)
2.59
2.588 (3)
3.078 (3)
3.245 (3)
3.362 (3)
151 (3)
130 (3)
124
0.98
2.63
131
Compound (III), the trifluoromethyl analogue of (I) and (II), was
prepared from 6-hydroxy-7,8-dimethylchroman-2-one (Goswami et
al., 2012) via photoredox catalysis utilizing the methodology of Nagib
& MacMillan (2011). The product was obtained in 35% yield and
Symmetry codes: (v) ꢂx ꢂ 1; ꢂy þ 1; ꢂz þ 1; (vi) x ꢂ 1; y; z; (vii) x þ 1; y ꢂ 1; z.
1
Data collection
poor quality crystals were obtained from Et2O. H NMR (400 MHz,
CDCl3): ꢂ 2.15 (s, 3H, CH3), 2.20 (s, 3H, CH3), 2.70 (t, J = 8 Hz, 2H,
CH2), 2.87 (t, J = 8 Hz, 2H, CH2).
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2011)
Tmin = 0.649, Tmax = 0.746
7686 measured reflections
2317 independent reflections
1367 reflections with I > 2ꢅ(I)
Rint = 0.300
Compound (I)
Crystal data
Refinement
C11H11BrO3
Mr = 271.11
Tetragonal, P421c
Z = 8
R[F2 > 2ꢅ(F2)] = 0.076
wR(F2) = 0.204
S = 0.96
2317 reflections
160 parameters
H atoms treated by a mixture of
independent and constrained
refinement
Mo Kꢃ radiation
ꢄ = 4.06 mmꢂ1
T = 91 K
0.25 ꢄ 0.13 ꢄ 0.13 mm
˚
a = 16.2247 (19) A
ꢂ3
˚
Áꢆmax = 0.55 e A
˚
c = 7.6586 (8) A
˚
V = 2016.1 (4) A
ꢂ3
˚
Áꢆmin = ꢂ0.49 e A
3
Data collection
In both molecules, the O-bound H atoms, labelled H6O, were
clearly located in difference Fourier maps and their coordinates were
refined, with Uiso(H) = 1.5Ueq(O) and with the O—H bond length
˚
restrained to 0.80 (2) A. Methyl and methylene H atoms were refined
˚
using a riding model, with C—H = 0.98 A and Uiso(H) = 1.5Ueq(C) for
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2011)
Tmin = 0.579, Tmax = 0.745
9841 measured reflections
1715 independent reflections
1615 reflections with I > 2ꢅ(I)
Rint = 0.043
˚
methyl, and with C—H = 0.99 A and Uiso(H) = 1.2Ueq(C) for
methylene H atoms.
Refinement
R[F2 > 2ꢅ(F2)] = 0.032
wR(F2) = 0.078
S = 1.10
1715 reflections
141 parameters
7 restraints
H atoms treated by a mixture of
independent and constrained
refinement
For (I), the absolute structure was determined unequivocally, with
the Flack parameter (Flack, 1983) refining to 0.022 (16). For (II), the
data were clearly not of the best quality, despite several attempts with
different crystals. The best of these gave data for which Rint = 0.2995.
Despite this, a solution was readily obtained and clearly revealed full
details of the molecular structure and crystal packing, and the
refinement converged with acceptable residuals and s.u. values for the
geometric data. Despite the high Rint value there were no unusual
characteristics in the multi-scan absorption correction applied with
SADABS (Bruker, 2011).
ꢂ3
˚
Áꢆmax = 0.47 e A
ꢂ3
˚
Áꢆmin = ꢂ0.32 e A
Absolute structure: Flack (1983),
with 717 Friedel pairs
Flack parameter: 0.023 (15)
Compound (II)
For both compounds, data collection: APEX2 (Bruker, 2011); cell
refinement: APEX2 and SAINT (Bruker, 2011); data reduction:
SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick,
2008) and TITAN2000 (Hunter & Simpson, 1999); program(s) used
to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN2000;
molecular graphics: Mercury (Macrae et al., 2008); software used to
prepare material for publication: SHELXL97, enCIFer (Allen et al.,
2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Crystal data
C11H11NO5
Mr = 237.21
Triclinic, P1
a = 5.0922 (12) A
˚
b = 7.3347 (15) A
ꢈ = 90.862 (12)ꢁ
V = 507.75 (19) A
Z = 2
Mo Kꢃ radiation
ꢄ = 0.12 mmꢂ1
T = 93 K
3
˚
˚
˚
c = 13.942 (3) A
ꢃ = 97.657 (12)ꢁ
ꢇ = 100.072 (11)ꢁ
0.43 ꢄ 0.17 ꢄ 0.05 mm
ꢃ
410 Goswami et al.
C11H11BrO3 and C11H11NO5
Acta Cryst. (2013). C69, 407–411

organic compounds
Fieser, L. F. & Ardao, M. I. (1956). J. Am. Chem. Soc. 78, 774–781.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Goswami, S. K., Hanton, L. R., McAdam, C. J., Moratti, S. C. & Simpson, J.
(2011). Acta Cryst. E67, o1566–o1567.
The authors thank the New Economy Research Fund (grant
No. UOO-X0808) for support of this work, and the University
of Otago for the purchase of the diffractometer.
Goswami, S. K., Hanton, L. R., McAdam, C. J., Moratti, S. C. & Simpson, J.
(2012). Acta Cryst. E68, o2332–o2333.
Goswami, S. K., Hanton, L. R., McAdam, C. J., Moratti, S. C. & Simpson, J.
(2013). Private communication (CCDC 923651). CCDC, Cambridge,
England.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FA3310). Services for accessing these data are
described at the back of the journal.
Goswami, S. K., McAdam, C. J., Lee, A. M. M., Hanton, L. R. & Moratti, S. C. J.
(2013). Mater. Chem. A. doi:10.1039/C3TA01202F.
Hunter, K. A. & Simpson, J. (1999). TITAN2000. University of Otago, New
Zealand.
References
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ꢃ
Acta Cryst. (2013). C69, 407–411
Goswami et al.
C11H11BrO3 and C11H11NO5 411

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 407-411 [doi:10.1107/S0108270113005325]
Similarities and differences in the structures of 5-bromo-6-hydroxy-7,8-di-
methylchroman-2-one and 6-hydroxy-7,8-dimethyl-5-nitrochroman-2-one
Shailesh K. Goswami, Lyall R. Hanton, C. John McAdam, Stephen C. Moratti and Jim Simpson
(I) 5-Bromo-6-hydroxy-7,8-dimethylchroman-2-one
Crystal data
C11H11BrO3
Dx = 1.786 Mg m−3
Mr = 271.11
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 3775 reflections
θ = 2.5–24.6°
Tetragonal, P421c
Hall symbol: P -4 2n
a = 16.2247 (19) Å
c = 7.6586 (8) Å
V = 2016.1 (4) Å3
Z = 8
µ = 4.06 mm−1
T = 91 K
Rectangular block, colourless
0.25 × 0.13 × 0.13 mm
F(000) = 1088
Data collection
Bruker APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω scans
9841 measured reflections
1715 independent reflections
1615 reflections with I > 2σ(I)
Rint = 0.043
θ
max = 24.8°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2011)
h = −19→15
k = −14→19
l = −9→6
T
min = 0.579, Tmax = 0.745
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.032
wR(F2) = 0.078
S = 1.10
1715 reflections
Hydrogen site location: inferred from
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0336P)2 + 1.9393P]
where P = (Fo2 + 2Fc2)/3
141 parameters
7 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
(Δ/σ)max = 0.001
Δρmax = 0.47 e Å−3
Δρmin = −0.32 e Å−3
Absolute structure: Flack (1983), with 717
Friedel pairs
Flack parameter: 0.023 (15)
Acta Cryst. (2013). C69, 407-411
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supplementary materials
Special details
Experimental. ADDITIONAL EXPERIMENTAL & CHARACTERISATION DETAILS
Bromotrimethylquinone: 70% yield. 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 2.04 (s, 3H, CH3), 2.08 (s, 3H, CH3), 2.21 (s,
3H, CH3); 13C NMR (100 MHz, CDCl3, δ, p.p.m.): 12.6, 13.2, 17.1, 135.4, 140.7, 140.9, 145.6, 179.4, 184.4.
Methyl 5-bromo-6-hydroxy-7,8-dimethyl-2-oxochroman-3-carboxylate: 76% yield. 1H NMR (400 MHz, CDCl3, δ,
p.p.m.): 2.20 (s, 3H, CH3), 2.24 (s, 3H, CH3), 3.23 (dd, J = 4 and 16 Hz, 1H, CH), 3.45 (dd, J = 8 and 16 Hz, 1H, CH),
3.76 (m, 1H, CH), 3.37 (s, 3H, OCH3),5.51 (bs, 1H, OH); 13C NMR (100 MHz, CDCl3, δ, p.p.m.): 12.1, 13.0, 20.1, 45.8,
53.1, 107.4, 117.8, 124.3, 125.8, 143.3, 147.2, 164.3, 167.7. HR MS (ESI): calculated for C13H13BrO5: [M]+ m/z
327.9940, found: m/z 327.9682.
5-Bromo-6-hydroxy-7,8-dimethylchroman-2-one, (I), 72% yield. 13C NMR (100 MHz, CDCl3, δ, p.p.m.): 11.8, 12.8,
24.7, 28.8, 107.3, 119.3, 123.6, 125.7, 144.0, 146.8, 168.4.
Nitrotrimethylquinone: 60% yield. 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 2.06 (s, 3H, CH3), 2.09 (m, 6H, CH3); 13C
NMR (100 MHz, CDCl3, δ, p.p.m.): 11.3, 12.2, 12.8, 134.3, 139.7, 142.2, 150.2, 177.2, 185.5.
Methyl 7,8-dimethyl-5-nitro-2,6-dioxo-3,4,6,8a-tetrahydro-2H-chromene- 3-carboxylate: 50% yield. 1H NMR (400 MHz,
CDCl3, δ, p.p.m.): 2.28 (s, 3H, CH3), 2.32 (s, 3H, CH3), 3.52 (dd, J = 4 and 16 Hz, 1H, CH), 3.67–3.75 (m, 2H, CH2),
3.77 (s, 3H, OCH3); 13C NMR (100 MHz, CDCl3, δ, p.p.m.): 12.2, 13.4, 25.5, 45.0, 53.3, 114.9, 117.8, 127.8, 135.8,
143.2, 150.5, 163.5, 167.3. HR MS (ESI): calculated for C13H13NO7: [M]+ m/z 295.0686, found: m/z 295.0687.
5-Nitro-6-hydroxy-7,8-dimethylchroman-2-one (II) 66% yield. 13C NMR (100 MHz, CDCl3, δ, p.p.m.): 12.1, 12.6, 23.7,
29.1, 116.8, 127.1, 131.1, 135.7, 143.8, 149.9, 167.5.
6-Hydroxy-7,8-dimethyl-5-(trifluoromethyl)chroman-2-one,(III). 13C NMR (100 MHz, CDCl3, δ, p.p.m.): 12.1, 13.3,
22.2, 28.1, 118.0, 126.2, 132.2, 140.5, 145.2, 148.7, 168.1; 19F NMR (376 MHz, CDCl3, δ, p.p.m.): -79.1.
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
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
O1
0.20618 (19)
0.0990 (2)
0.1321 (3)
0.1009 (3)
0.0400
0.02966 (18)
−0.04812 (19)
0.0176 (3)
0.0836 (3)
0.0810
0.4131 (4)
0.3584 (4)
0.3337 (6)
0.2165 (7)
0.2146
0.0138 (7)
0.0196 (8)
0.0139 (10)
0.0168 (10)
0.020*
O2
C2
C3
H3A
H3B
C4
0.1206
0.0724
0.0965
0.020*
0.1266 (2)
0.1175
0.1706 (3)
0.2082
0.2666 (6)
0.1666
0.0147 (10)
0.018*
H4A
H4B
C5
0.0924
0.1900
0.3654
0.018*
0.2662 (3)
0.22113 (3)
0.3503 (3)
0.4009 (2)
0.377 (3)
0.3844 (3)
0.4768 (2)
0.4810
0.2413 (2)
0.34214 (3)
0.2402 (3)
0.30533 (19)
0.342 (2)
0.1678 (3)
0.1693 (3)
0.1523
0.3011 (6)
0.22181 (7)
0.3475 (6)
0.3291 (4)
0.284 (6)
0.4196 (6)
0.4774 (5)
0.5998
0.0120 (9)
0.02019 (16)
0.0129 (10)
0.0175 (8)
0.026*
Br5
C6
O6
H6O
C7
0.0125 (10)
0.0054 (9)
0.008*
C71
H71A
H71B
H71C
0.4986
0.2253
0.4644
0.008*
0.5086
0.1314
0.4042
0.008*
Acta Cryst. (2013). C69, 407-411
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supplementary materials
C8
0.3351 (3)
0.3700 (3)
0.3989
0.0981 (3)
0.0164 (3)
−0.0128
0.4391 (6)
0.5104 (6)
0.4168
0.0118 (10)
0.0098 (10)
0.015*
C81
H81A
H81B
H81C
C9
0.3247
−0.0178
0.5540
0.015*
0.4085
0.0280
0.6059
0.015*
0.2528 (3)
0.2159 (3)
0.1024 (3)
0.1724 (3)
0.3874 (6)
0.3178 (5)
0.0134 (10)
0.0111 (10)
C10
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O1
O2
C2
0.0118 (17)
0.0179 (18)
0.014 (3)
0.014 (2)
0.007 (2)
0.013 (2)
0.0211 (3)
0.013 (2)
0.0148 (18)
0.015 (2)
0.0053 (12)
0.009 (2)
0.008 (2)
0.020 (3)
0.013 (2)
0.0080 (16)
0.0118 (18)
0.016 (3)
0.017 (2)
0.018 (2)
0.009 (2)
0.0144 (3)
0.015 (2)
0.0153 (18)
0.013 (2)
0.0054 (12)
0.016 (2)
0.011 (2)
0.008 (2)
0.013 (2)
0.0218 (17)
−0.0011 (14)
−0.0020 (14)
0.001 (2)
−0.0016 (15)
0.0033 (16)
0.0053 (19)
0.001 (2)
0.0034 (13)
−0.0020 (15)
−0.0043 (19)
0.000 (2)
0.0291 (19)
0.011 (2)
0.020 (2)
0.019 (2)
0.013 (2)
0.0250 (3)
0.011 (2)
0.0223 (19)
0.010 (2)
0.0054 (12)
0.011 (2)
0.010 (2)
0.012 (2)
0.008 (2)
C3
−0.0031 (19)
0.0015 (17)
0.0015 (18)
0.00195 (19)
0.0016 (19)
−0.0047 (14)
0.003 (2)
C4
0.001 (2)
0.002 (2)
C5
−0.002 (2)
0.0010 (2)
0.003 (2)
0.002 (2)
Br5
C6
0.0031 (2)
−0.0018 (18)
0.0031 (15)
0.000 (2)
O6
C7
−0.0046 (15)
0.001 (2)
C71
C8
−0.0004 (9)
0.003 (2)
0.0018 (9)
0.001 (2)
0.0002 (9)
−0.002 (2)
−0.0003 (19)
−0.0022 (19)
−0.0038 (18)
C81
C9
−0.0035 (19)
−0.0031 (19)
0.0033 (19)
0.0010 (19)
0.005 (2)
C10
−0.0010 (19)
Geometric parameters (Å, º)
O1—C2
O1—C9
O2—C2
C2—C3
C3—C4
C3—H3A
C3—H3B
C4—C10
C4—H4A
C4—H4B
C5—C10
C5—C6
C5—Br5
C6—O6
1.361 (6)
C6—C7
1.411 (6)
1.416 (5)
1.209 (5)
1.486 (6)
1.520 (6)
0.9900
O6—H6O
C7—C8
0.794 (19)
1.392 (6)
1.563 (6)
0.9800
C7—C71
C71—H71A
C71—H71B
C71—H71C
C8—C9
0.9800
0.9900
0.9800
1.500 (6)
0.9900
1.395 (6)
1.541 (6)
0.9800
C8—C81
0.9900
C81—H81A
C81—H81B
C81—H81C
C9—C10
1.390 (6)
1.409 (6)
1.892 (4)
1.347 (5)
0.9800
0.9800
1.390 (6)
C2—O1—C9
O2—C2—O1
O2—C2—C3
O1—C2—C3
C2—C3—C4
C2—C3—H3A
121.9 (3)
116.7 (4)
125.4 (4)
117.8 (4)
115.0 (4)
108.5
C8—C7—C71
122.3 (4)
118.3 (4)
109.5
C6—C7—C71
C7—C71—H71A
C7—C71—H71B
H71A—C71—H71B
C7—C71—H71C
109.5
109.5
109.5
Acta Cryst. (2013). C69, 407-411
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supplementary materials
C4—C3—H3A
C2—C3—H3B
C4—C3—H3B
H3A—C3—H3B
C10—C4—C3
C10—C4—H4A
C3—C4—H4A
C10—C4—H4B
C3—C4—H4B
H4A—C4—H4B
C10—C5—C6
C10—C5—Br5
C6—C5—Br5
O6—C6—C5
108.5
H71A—C71—H71C
109.5
108.5
H71B—C71—H71C
C7—C8—C9
109.5
108.5
118.6 (4)
121.7 (4)
119.6 (4)
109.5
107.5
C7—C8—C81
110.4 (3)
109.6
C9—C8—C81
C8—C81—H81A
C8—C81—H81B
H81A—C81—H81B
C8—C81—H81C
H81A—C81—H81C
H81B—C81—H81C
C10—C9—C8
109.6
109.5
109.6
109.5
109.6
109.5
108.1
109.5
122.3 (4)
119.8 (3)
117.8 (3)
123.6 (4)
117.1 (4)
119.3 (4)
110 (4)
119.5 (4)
109.5
124.2 (4)
120.3 (4)
115.5 (4)
116.0 (4)
124.0 (4)
120.0 (4)
C10—C9—O1
C8—C9—O1
O6—C6—C7
C5—C10—C9
C5—C6—C7
C5—C10—C4
C6—O6—H6O
C8—C7—C6
C9—C10—C4
C9—O1—C2—O2
C9—O1—C2—C3
O2—C2—C3—C4
O1—C2—C3—C4
C2—C3—C4—C10
C10—C5—C6—O6
Br5—C5—C6—O6
C10—C5—C6—C7
Br5—C5—C6—C7
O6—C6—C7—C8
C5—C6—C7—C8
O6—C6—C7—C71
C5—C6—C7—C71
C6—C7—C8—C9
C71—C7—C8—C9
C6—C7—C8—C81
C71—C7—C8—C81
176.9 (4)
0.3 (6)
C7—C8—C9—C10
C81—C8—C9—C10
C7—C8—C9—O1
C81—C8—C9—O1
C2—O1—C9—C10
C2—O1—C9—C8
C6—C5—C10—C9
Br5—C5—C10—C9
C6—C5—C10—C4
Br5—C5—C10—C4
C8—C9—C10—C5
O1—C9—C10—C5
C8—C9—C10—C4
O1—C9—C10—C4
C3—C4—C10—C5
C3—C4—C10—C9
−0.4 (7)
−178.5 (4)
−179.2 (4)
2.7 (6)
152.6 (4)
−31.2 (6)
43.1 (5)
178.5 (4)
−3.9 (6)
−2.4 (6)
175.2 (3)
−179.0 (4)
1.8 (7)
16.8 (6)
−164.3 (4)
1.5 (6)
−176.0 (3)
−178.7 (4)
3.7 (6)
−0.1 (6)
1.8 (6)
178.6 (4)
−179.9 (4)
−1.1 (6)
−177.4 (4)
−0.4 (7)
178.7 (4)
177.6 (4)
−3.2 (7)
152.4 (4)
−27.9 (6)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O6—H6O···Br5
O6—H6O···O2i
C3—H3A···O2ii
C4—H4B···O1iii
C4—H4B···O2iii
C3—H3B···O6iv
0.79 (2)
0.79 (2)
0.99
2.57 (4)
2.12 (4)
2.57
3.089 (3)
2.778 (4)
3.469 (6)
3.575 (6)
3.349 (6)
3.343 (6)
124 (4)
140 (5)
152
0.99
2.62
162
0.99
2.68
125
0.99
2.41
156
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x, −y, z; (iii) −y, x, −z+1; (iv) −y+1/2, −x+1/2, z−1/2.
Acta Cryst. (2013). C69, 407-411
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supplementary materials
(II) 6-Hydroxy-7,8-dimethyl-5-nitrochroman-2-one
Crystal data
C11H11NO5
Z = 2
Mr = 237.21
Triclinic, P1
F(000) = 248
Dx = 1.552 Mg m−3
Hall symbol: -P 1
a = 5.0922 (12) Å
b = 7.3347 (15) Å
c = 13.942 (3) Å
α = 97.657 (12)°
β = 100.072 (11)°
γ = 90.862 (12)°
V = 507.75 (19) Å3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 1620 reflections
θ = 3.0–27.4°
µ = 0.12 mm−1
T = 93 K
Plate, yellow
0.43 × 0.17 × 0.05 mm
Data collection
Bruker APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω scans
7686 measured reflections
2317 independent reflections
1367 reflections with I > 2σ(I)
Rint = 0.300
θ
max = 27.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2011)
h = −6→6
k = −9→8
l = −17→18
T
min = 0.649, Tmax = 0.746
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.076
wR(F2) = 0.204
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 0.96
2317 reflections
160 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0872P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.55 e Å−3
Δρmin = −0.49 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
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
O1
O2
C2
0.5980 (3)
0.7046 (3)
0.5337 (5)
0.5812 (2)
0.7507 (3)
0.7046 (4)
0.88673 (12)
1.03108 (14)
0.96087 (19)
0.0211 (5)
0.0278 (5)
0.0211 (6)
Acta Cryst. (2013). C69, 407-411
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supplementary materials
C3
0.2542 (5)
0.2431
0.7678 (4)
0.8830
0.9441 (2)
0.9890
0.0241 (6)
0.029*
H3A
H3B
C4
0.1338
0.6736
0.9602
0.029*
0.1604 (5)
−0.0314
0.8018 (4)
0.8295
0.83830 (19)
0.8281
0.0218 (6)
0.026*
H4A
H4B
C5
0.2619
0.9085
0.8245
0.026*
0.0373 (5)
−0.1732 (4)
−0.3682 (3)
−0.1494 (4)
0.0720 (5)
−0.0884 (3)
−0.223 (6)
0.2890 (5)
0.3268 (5)
0.3359
0.5664 (3)
0.6805 (3)
0.6060 (3)
0.8473 (3)
0.3954 (3)
0.3227 (3)
0.393 (4)
0.2897 (3)
0.1090 (4)
0.0113
0.68000 (19)
0.63995 (16)
0.58054 (14)
0.66469 (14)
0.62688 (18)
0.54185 (13)
0.541 (2)
0.66103 (19)
0.6017 (2)
0.6436
0.0192 (6)
0.0209 (5)
0.0251 (5)
0.0307 (5)
0.0180 (6)
0.0222 (5)
0.033*
N5
O51
O52
C6
O6
H6O
C7
0.0178 (6)
0.0240 (6)
0.036*
C71
H71A
H71B
H71C
C8
0.4930
0.1157
0.5757
0.036*
0.1762
0.0820
0.5469
0.036*
0.4606 (5)
0.6915 (5)
0.7798
0.3538 (3)
0.2437 (4)
0.1912
0.74836 (18)
0.7883 (2)
0.7344
0.0178 (6)
0.0219 (6)
0.033*
C81
H81A
H81B
H81C
C9
0.6259
0.1441
0.8193
0.033*
0.8193
0.3240
0.8371
0.033*
0.4106 (5)
0.2038 (5)
0.5231 (3)
0.6325 (3)
0.80064 (19)
0.77009 (19)
0.0176 (6)
0.0190 (6)
C10
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O1
O2
C2
0.0141 (9)
0.0191 (9)
0.0203 (12)
0.0206 (13)
0.0187 (12)
0.0146 (12)
0.0203 (11)
0.0149 (9)
0.0343 (11)
0.0171 (12)
0.0167 (9)
0.0174 (12)
0.0237 (13)
0.0141 (11)
0.0179 (12)
0.0157 (11)
0.0161 (12)
0.0273 (10)
0.0378 (12)
0.0248 (14)
0.0299 (15)
0.0240 (14)
0.0216 (14)
0.0237 (12)
0.0313 (11)
0.0246 (11)
0.0215 (14)
0.0254 (11)
0.0187 (13)
0.0234 (15)
0.0221 (14)
0.0240 (14)
0.0211 (14)
0.0203 (14)
0.0217 (11)
0.0010 (7)
0.0036 (7)
0.0033 (8)
0.0085 (11)
0.0097 (11)
0.0043 (11)
0.0073 (10)
0.0085 (9)
0.0004 (7)
0.0012 (9)
0.0050 (10)
0.0018 (8)
0.0086 (10)
0.0035 (11)
0.0076 (10)
0.0065 (11)
0.0057 (10)
0.0091 (10)
0.0019 (8)
0.0016 (9)
0.0053 (12)
0.0044 (12)
0.0051 (12)
0.0063 (12)
0.0048 (10)
0.0037 (9)
0.0036 (9)
0.0041 (11)
0.0027 (8)
0.0052 (11)
0.0038 (12)
0.0067 (11)
0.0042 (12)
0.0047 (11)
0.0051 (11)
0.0254 (11)
0.0205 (15)
0.0240 (15)
0.0236 (15)
0.0236 (15)
0.0211 (12)
0.0278 (11)
0.0316 (12)
0.0163 (13)
0.0236 (11)
0.0200 (14)
0.0248 (15)
0.0199 (14)
0.0251 (15)
0.0175 (13)
0.0231 (15)
−0.0019 (8)
−0.0032 (10)
0.0025 (11)
0.0025 (10)
0.0020 (10)
0.0041 (9)
C3
C4
C5
N5
O51
O52
C6
0.0003 (7)
0.0079 (8)
−0.0025 (10)
0.0026 (7)
O6
C7
0.0010 (10)
0.0031 (11)
0.0007 (9)
C71
C8
C81
C9
0.0044 (10)
−0.0009 (10)
−0.0019 (10)
C10
Acta Cryst. (2013). C69, 407-411
sup-6

supplementary materials
Geometric parameters (Å, º)
O1—C2
O1—C9
O2—C2
C2—C3
1.369 (3)
1.409 (3)
1.198 (3)
1.492 (4)
1.524 (4)
0.9900
O51—O51i
C6—O6
2.686 (4)
1.355 (3)
1.410 (3)
0.86 (3)
1.389 (3)
1.500 (4)
0.9800
C6—C7
O6—H6O
C7—C8
C3—C4
C3—H3A
C3—H3B
C4—C10
C4—H4A
C4—H4B
C5—C6
C7—C71
0.9900
C71—H71A
C71—H71B
C71—H71C
C8—C9
1.504 (4)
0.9900
0.9800
0.9800
0.9900
1.404 (4)
1.505 (3)
0.9800
1.399 (4)
1.409 (4)
1.450 (3)
1.225 (3)
1.243 (3)
C8—C81
C5—C10
C5—N5
N5—O52
N5—O51
C81—H81A
C81—H81B
C81—H81C
C9—C10
0.9800
0.9800
1.376 (3)
C2—O1—C9
O2—C2—O1
O2—C2—C3
O1—C2—C3
C2—C3—C4
121.11 (19)
117.5 (2)
127.2 (2)
115.3 (2)
112.2 (2)
109.2
C6—O6—H6O
C8—C7—C6
101 (2)
119.7 (2)
121.7 (2)
118.6 (2)
109.5
C8—C7—C71
C6—C7—C71
C7—C71—H71A
C7—C71—H71B
C2—C3—H3A
C4—C3—H3A
C2—C3—H3B
C4—C3—H3B
H3A—C3—H3B
C10—C4—C3
C10—C4—H4A
C3—C4—H4A
C10—C4—H4B
C3—C4—H4B
H4A—C4—H4B
C6—C5—C10
C6—C5—N5
C10—C5—N5
O52—N5—O51
O52—N5—C5
O51—N5—C5
N5—O51—O51i
O6—C6—C5
O6—C6—C7
109.5
109.2
H71A—C71—H71B
C7—C71—H71C
H71A—C71—H71C
H71B—C71—H71C
C7—C8—C9
109.5
109.2
109.5
109.2
109.5
107.9
109.5
108.9 (2)
109.9
118.5 (2)
121.4 (2)
120.1 (2)
109.5
C7—C8—C81
109.9
C9—C8—C81
109.9
C8—C81—H81A
C8—C81—H81B
H81A—C81—H81B
C8—C81—H81C
H81A—C81—H81C
H81B—C81—H81C
C10—C9—C8
109.9
109.5
108.3
109.5
122.0 (2)
118.9 (2)
119.1 (2)
122.5 (2)
118.6 (2)
118.9 (2)
157.66 (18)
124.3 (2)
116.3 (2)
119.4 (2)
109.5
109.5
109.5
124.2 (2)
120.7 (2)
115.0 (2)
116.1 (2)
118.1 (2)
125.6 (2)
C10—C9—O1
C8—C9—O1
C9—C10—C5
C9—C10—C4
C5—C10—C4
C5—C6—C7
Symmetry code: (i) −x−1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
151 (3)
O6—H6O···O51
0.86 (3)
1.80 (3)
2.588 (3)
Acta Cryst. (2013). C69, 407-411
sup-7

supplementary materials
O6—H6O···O51i
C3—H3B···O2ii
C81—H81A···O52iii
0.86 (3)
0.99
2.45 (3)
2.59
3.078 (3)
3.245 (3)
3.362 (3)
130 (3)
124
0.98
2.63
131
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) x−1, y, z; (iii) x+1, y−1, z.
Acta Cryst. (2013). C69, 407-411
sup-8

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