(Z)-Ethyl 2-hydroxyimino-2-(4-nitro-
benzyl)ethanoate

Ignez Caracelli,a* Antonio C. Trindade,b Paulo J. S.

Moran,c Luciana Hinoue,c Julio Zukerman-Schpectord and

Edward R. T. Tiekinke

aBioMat-Physics Department, UNESP – Univ Estadual Paulista, 17033-360 Bauru,

SP, Brazil, bInstituto de Quı́mica e Biotecnologia, Universidade Federal de Alagoas,

57072-970 Maceió, AL, Brazil, cInstituto de Quı́mica, Universidade Estadual de

Campinas, CP 6154, 13083-970 Campinas, SP, Brazil, dDepartment of Chemistry,

Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, and
eDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia

Correspondence e-mail: ignez@fc.unesp.br

Received 29 November 2009; accepted 5 December 2009

Key indicators: single-crystal X-ray study; T = 290 K; mean �(C–C) = 0.002 Å;

disorder in main residue; R factor = 0.048; wR factor = 0.128; data-to-parameter

ratio = 14.6.

The title molecule, C11H10N2O6, has a Z conformation about

the C N bond of the oxime unit. There are significant twists

from planarity throughout the molecule, the most significant

being between the hydroxyimino and ester groups which are

effectively orthogonal with an N—C—C—Ocarbonyl torsion

angle of 91.4 (2)�. The crystal packing features oxime–benzoyl

O—H� � �O contacts that lead to chains along [010] and C—

H� � �O interactions also occur.

Related literature

For background to the synthesis of chiral hydroxyaminoacids

and hydroxyaminoalcohols, see: Corrêa & Moran (1999);

Kreutz et al. (1997, 2000). For related structures, see: Ramos

Silva et al. (2004); Forsyth et al. (2006). For the synthesis, see:

Adkins & Reeve (1938).

Experimental

Crystal data

C11H10N2O6

Mr = 266.21
Monoclinic, C2=c
a = 23.2347 (7) Å

b = 12.0698 (6) Å
c = 8.9698 (4) Å
� = 106.100 (2)�

V = 2416.82 (18) Å3

Z = 8
Mo K� radiation
� = 0.12 mm�1

T = 290 K
0.18 � 0.15 � 0.12 mm

Data collection

Nonius KappaCCD diffractometer
8147 measured reflections
2752 independent reflections

2004 reflections with I > 2�(I)
Rint = 0.033

Refinement

R[F 2 > 2�(F 2)] = 0.048
wR(F 2) = 0.128
S = 1.05
2752 reflections

189 parameters
H-atom parameters constrained
��max = 0.20 e �3

��min = �0.19 e �3

Table 1
Hydrogen-bond geometry (Å, �).

D—H� � �A D—H H� � �A D� � �A D—H� � �A

O4—H4o� � �O3i 0.82 1.91 2.7165 (16) 166
C5—H5� � �O5i 0.93 2.58 3.371 (2) 144
C2—H2� � �O1ii 0.93 2.55 3.393 (3) 151
C11—H11a� � �O1iii 0.96 2.52 3.426 (5) 158

Symmetry codes: (i) �xþ 1
2; y þ 1

2;�zþ 1
2; (ii) �xþ 1;�y;�zþ 2; (iii)

x � 1
2; y� 1

2; z� 1.

Data collection: COLLECT (Nonius, 1999); cell refinement:

SCALEPACK (Otwinowski & Minor, 1997); data reduction:

DENZO (Otwinowski & Minor, 1997) and SCALEPACK;

program(s) used to solve structure: SIR97 (Altomare et al., 1999);

program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);

molecular graphics: DIAMOND (Brandenburg, 2006); software used

to prepare material for publication: WinGX (Farrugia, 1999), PARST

(Nardelli, 1995) and publCIF (Westrip, 2009).

We thank FAPESP, CNPq and CAPES for financial support.

Publication costs were met by FAPESP (Proc. 2008/02531–5).

Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: HG2614).

References

Adkins, H. & Reeve, E. W. (1938). J. Am. Chem. Soc. 60, 1328–1331.
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C.,

Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J.
Appl. Cryst. 32, 115–119.

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Corrêa, I. R. & Moran, P. J. S. (1999). Tetrahedron, 55, 14221–14232.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Forsyth, C. M., Langford, S. J. & Lee, K. A. (2006). Acta Cryst. E62, o5654–

o5655.
Kreutz, O. C., Moran, P. J. S. & Rodrigues, J. A. R. (1997). Tetrahedron

Asymmetry, 8, 2649–2653.
Kreutz, O. C., Segura, R. C. M., Rodrigues, J. A. R. & Moran, P. J. S. (2000).

Tetrahedron Asymmetry, 11, 2107–2115.
Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,

Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.
Sweet, pp. 307–326. New York: Academic Press.

Ramos Silva, M., Matos Beja, A., Paixão, J. A., Lopes, S. H., Cabral, A. M. T.
D. P. V., d’A. Rocha Gonsalves, A. M. & Sobral, A. J. F. N. (2004). Z.
Kristallogr. New Cryst. Struct. 219, 145–146.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2009). publCIF. In preparation.

organic compounds

Acta Cryst. (2010). E66, o137 doi:10.1107/S1600536809052386 Caracelli et al. o137

Acta Crystallographica Section E

Structure Reports
Online

ISSN 1600-5368

http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB1
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB2
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB2
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB2
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB3
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB4
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB5
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB6
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB6
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB7
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB7
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB8
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB8
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB9
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB10
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB11
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB11
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB11
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB12
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB12
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB12
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB13
http://scripts.iucr.org/cgi-bin/cr.cgi?rm=pdfbb&cnor=hg2614&bbid=BB14
http://crossmark.crossref.org/dialog/?doi=10.1107/S1600536809052386&domain=pdf&date_stamp=2009-12-16


supplementary materials



supplementary materials

sup-1

Acta Cryst. (2010). E66, o137    [ doi:10.1107/S1600536809052386 ]

(Z)-Ethyl 2-hydroxyimino-2-(4-nitrobenzyl)ethanoate

I. Caracelli, A. C. Trindade, P. J. S. Moran, L. Hinoue, J. Zukerman-Schpector and E. R. T. Tiekink

Comment

The title compound (I) was prepared as an intermediary during the synthesis of chiral hydroxyaminoacids and hy-
droxyaminoalcohols, as α-ketomethoxyimino compounds are reduced by sodium borohydride (Corrêa & Moran, 1999) and
enantioselectively bio-reduced by whole cells of yeast (Kreutz et al., 1997; Kreutz et al., 2000).

The structure of (I) is non-planar as seen by the values of the C3–C4–C7–O3 and C4–C7–C8–N2 torsion angles within
the central moiety of 8.8 (2) and 15.8 (2) °, respectively. The peripheral residues are twisted with respect to the inner atoms.
Thus, the nitro ring is twisted out of the plane of the benzene ring to which it is connected: the C2–C1–N1–O1 torsion angle
is -13.7 (3) °. Even more dramatic is the twist about the C8—C9 bond with the C7–C8–C9–O6 torsion angle being 94.77
(17)°, indicating the terminal ester group is orthogonal to the hydroxyimino residue. With respect to the C8═N2 bond, the
conformation is Z. There are two other structures in the literature containing the basic C(═O)C(═NOH)C(═O)OC frame-
work. In benzyl 2-(hydroxyimino)acetoacetate a Z conformation is found for the oxime group (Forsyth et al., 2006) whereas
in each of the two independent molecules comprising the asymmetric unit in ethyl 2-(hydroxyimino)-3-oxo-3-phenylpropi-
onate, an E conformation is found (Ramos Silva et al., 2004).

The crystal packing of (I) is dominated by O—H···O hydrogen bonding involving the oxime-O4—H and benzoyl-O3
atoms which leads to the formation of supramolecular chains along [0 1 0] with a flat topology, Fig. 2 and Table 1. The pres-
ence of C–H···O contacts provide stability to the chain. These C5–H···O5 contacts close 13-membered {···OC3O···HC4NOH}

synthons, Fig. 3 and Table 1. The chains are linked into 2-D arrays in the [3 0 1] plane by further C–H···O contacts involving
the nitro groups and centrosymmetric 10-membered {···ONC2H}2 synthons, Fig. 3 and Table 1. The resultant layer is es-

sentially flat with the ethoxy groups lying above and below the layer. The methyl-H atoms of one of the disordered ethoxy
groups form C–H···O contacts with the nitro-O1 atoms providing stability to the stacked layers, Fig. 4 and Table 1.

Experimental

The title compound, (I), was prepared following a modified literature method (Adkins and Reeve, 1938). A solution of
sodium nitrite (5 mmol) and water (2 ml) was added drop-wise to a solution of ethyl 3-oxo-3-(4-nitrophenyl)propanoate
(2 mmol) in glacial acetic acid (3 ml) at 273 K. The resulting solution was stirred for 1 h at 273 K. The temperature was
then raised to 303 K and the reaction left for a further hour. The reaction mixture was quenched with water (2.5 ml) and
treated with ether (4 x 5 ml). The organic layer was dried with Mg(SO4) and the solvent evaporated to afford a mixture of

Z:E (40:60) isomers in 87% yield that were separated by dissolving in ethyl acetate and precipitating with hexane.

Refinement

The O– and C-bound H atoms were geometrically placed (O–H = 0.82 Å and C–H = 0.9–0.97 Å) and refined as riding with
Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O and methyl-C).

http://dx.doi.org/10.1107/S1600536809052386
http://scripts.iucr.org/cgi-bin/citedin?search_on=name&author_name=Caracelli,%20I.
http://scripts.iucr.org/cgi-bin/citedin?search_on=name&author_name=Trindade,%20A.C.
http://scripts.iucr.org/cgi-bin/citedin?search_on=name&author_name=Moran,%20P.J.S.
http://scripts.iucr.org/cgi-bin/citedin?search_on=name&author_name=Hinoue,%20L.
http://scripts.iucr.org/cgi-bin/citedin?search_on=name&author_name=Zukerman-Schpector,%20J.
http://scripts.iucr.org/cgi-bin/citedin?search_on=name&author_name=Tiekink,%20E.R.T.


supplementary materials

sup-2

Disorder was modelled for the ethyl group with two positions resolved for each of the C10 and C11 atoms. Fractional
refinement (anisotropic) showed that the site occupancy factors were equal within experimental error and thus these were
fixed at 0.5 in the final cycles of refinement.

Figures

Fig. 1. Molecular structure of (I) showing atom labelling scheme and displacement ellipsoids
at the 50% probability level (arbitrary spheres for the H atoms). Only one component of the
disordered ethyl group is shown for reasons of clarity.

Fig. 2. Supramolecular chain aligned along [0 1 0] in (I) mediated by oxime-O—H···O-ben-
zoyl hydrogen bonding (orange dashed lines). Colour code: O, red; N, blue; C, grey; and H,
green.

Fig. 3. 2-D array in (I) whereby the chains shown in Fig. 2 are reinforced by and are connec-
ted by C–H···O contacts (blue dashed lines). Colour code as for Fig. 2.

Fig. 4. A view of the crystal packing in (I) showing the stacking of layers. Colour code as for
Fig. 2.

(Z)-Ethyl 2-hydroxyimino-2-(4-nitrobenzyl)ethanoate

Crystal data

C11H10N2O6 F(000) = 1104

Mr = 266.21 Dx = 1.463 Mg m−3

Monoclinic, C2/c Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc Cell parameters from 4194 reflections



supplementary materials

sup-3

a = 23.2347 (7) Å θ = 27.5–1.0°
b = 12.0698 (6) Å µ = 0.12 mm−1

c = 8.9698 (4) Å T = 290 K
β = 106.100 (2)° Irregular, colourless

V = 2416.82 (18) Å3 0.18 × 0.15 × 0.12 mm
Z = 8

Data collection

Nonius KappaCCD
diffractometer 2004 reflections with I > 2σ(I)

Radiation source: fine-focus sealed tube Rint = 0.033

graphite θmax = 27.5°, θmin = 1.9°
CCD rotation images, thick slices scans h = −30→28
8147 measured reflections k = −15→14
2752 independent reflections l = −8→11

Refinement

Refinement on F2 Primary atom site location: structure-invariant direct
methods

Least-squares matrix: full Secondary atom site location: difference Fourier map

R[F2 > 2σ(F2)] = 0.048
Hydrogen site location: inferred from neighbouring
sites

wR(F2) = 0.128 H-atom parameters constrained

S = 1.05
w = 1/[σ2(Fo

2) + (0.0493P)2 + 1.3639P]
where P = (Fo

2 + 2Fc
2)/3

2752 reflections (Δ/σ)max < 0.001

189 parameters Δρmax = 0.20 e Å−3

0 restraints Δρmin = −0.19 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The
cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between
s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is
used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional

R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(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 Occ. (<1)
O1 0.50114 (9) 0.16899 (16) 1.0271 (2) 0.1080 (7)
O2 0.47793 (8) 0.32527 (15) 0.9163 (2) 0.0950 (6)



supplementary materials

sup-4

O3 0.29936 (6) −0.09600 (9) 0.44259 (15) 0.0585 (4)
O4 0.21512 (6) 0.18581 (10) 0.13275 (15) 0.0581 (4)
H4O 0.2168 0.2525 0.1169 0.087*
O5 0.21223 (6) −0.07843 (11) 0.10633 (16) 0.0652 (4)
O6 0.15870 (6) −0.01284 (12) 0.25941 (16) 0.0662 (4)
N1 0.47188 (8) 0.22595 (16) 0.9220 (2) 0.0685 (5)
N2 0.26049 (6) 0.15679 (11) 0.26243 (16) 0.0477 (3)
C1 0.42724 (8) 0.17138 (15) 0.7937 (2) 0.0517 (4)
C2 0.42939 (8) 0.05779 (16) 0.7813 (2) 0.0586 (5)
H2 0.4580 0.0165 0.8527 0.070*
C3 0.38815 (8) 0.00701 (15) 0.6605 (2) 0.0539 (4)
H3 0.3893 −0.0695 0.6489 0.065*
C4 0.34459 (7) 0.06915 (13) 0.55497 (18) 0.0426 (4)
C5 0.34325 (8) 0.18320 (13) 0.5725 (2) 0.0489 (4)
H5 0.3140 0.2249 0.5036 0.059*
C6 0.38527 (8) 0.23516 (15) 0.6919 (2) 0.0537 (4)
H6 0.3851 0.3118 0.7030 0.064*
C7 0.30018 (7) 0.00492 (13) 0.43324 (19) 0.0434 (4)
C8 0.25518 (7) 0.05606 (13) 0.29990 (18) 0.0423 (4)
C9 0.20639 (7) −0.02027 (13) 0.2087 (2) 0.0460 (4)
C10 0.1039 (4) −0.0815 (6) 0.1899 (9) 0.066 (2) 0.50
H10A 0.0680 −0.0394 0.1868 0.079* 0.50
H10B 0.1026 −0.1031 0.0849 0.079* 0.50
C11 0.1074 (2) −0.1772 (4) 0.2855 (6) 0.0772 (13) 0.50
H11A 0.0750 −0.2264 0.2390 0.116* 0.50
H11B 0.1048 −0.1552 0.3863 0.116* 0.50
H11C 0.1448 −0.2143 0.2954 0.116* 0.50
C10A 0.1143 (2) −0.0975 (4) 0.1926 (6) 0.093 (5) 0.50
H10C 0.1335 −0.1679 0.1858 0.112* 0.50
H10D 0.0907 −0.0761 0.0895 0.112* 0.50
C11A 0.0755 (3) −0.1055 (8) 0.3013 (8) 0.127 (3) 0.50
H11D 0.0423 −0.1540 0.2578 0.190* 0.50
H11E 0.0607 −0.0333 0.3162 0.190* 0.50
H11F 0.0986 −0.1344 0.3993 0.190* 0.50

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

O1 0.1132 (14) 0.0968 (14) 0.0788 (11) 0.0063 (10) −0.0320 (10) −0.0089 (10)
O2 0.1013 (13) 0.0768 (12) 0.0881 (12) −0.0268 (9) −0.0050 (9) −0.0171 (9)
O3 0.0739 (8) 0.0300 (6) 0.0639 (8) −0.0020 (5) 0.0064 (6) 0.0004 (5)
O4 0.0661 (8) 0.0380 (6) 0.0606 (8) 0.0033 (6) 0.0019 (6) 0.0087 (6)
O5 0.0750 (9) 0.0528 (8) 0.0690 (9) −0.0128 (6) 0.0219 (7) −0.0214 (7)
O6 0.0567 (8) 0.0706 (9) 0.0725 (9) −0.0230 (6) 0.0200 (7) −0.0229 (7)
N1 0.0640 (10) 0.0740 (12) 0.0597 (10) −0.0055 (9) 0.0045 (8) −0.0137 (9)
N2 0.0525 (8) 0.0343 (7) 0.0530 (8) −0.0005 (6) 0.0090 (6) 0.0020 (6)
C1 0.0474 (9) 0.0570 (11) 0.0489 (9) −0.0046 (8) 0.0102 (7) −0.0072 (8)
C2 0.0537 (10) 0.0581 (11) 0.0564 (11) 0.0083 (8) 0.0026 (8) 0.0019 (9)



supplementary materials

sup-5

C3 0.0572 (10) 0.0403 (9) 0.0599 (11) 0.0054 (8) 0.0090 (8) 0.0003 (8)
C4 0.0437 (8) 0.0358 (8) 0.0483 (9) −0.0003 (6) 0.0127 (7) −0.0003 (6)
C5 0.0513 (9) 0.0356 (8) 0.0553 (10) 0.0010 (7) 0.0071 (7) −0.0010 (7)
C6 0.0604 (10) 0.0399 (9) 0.0581 (10) −0.0047 (8) 0.0120 (8) −0.0070 (8)
C7 0.0482 (9) 0.0328 (8) 0.0496 (9) −0.0010 (7) 0.0144 (7) −0.0007 (6)
C8 0.0463 (8) 0.0328 (8) 0.0474 (9) −0.0017 (6) 0.0126 (7) −0.0028 (6)
C9 0.0515 (9) 0.0344 (8) 0.0492 (9) −0.0023 (7) 0.0089 (7) 0.0022 (7)
C10 0.043 (2) 0.057 (3) 0.087 (5) −0.016 (2) 0.001 (3) −0.004 (3)
C11 0.068 (3) 0.074 (3) 0.081 (3) −0.027 (2) 0.005 (2) 0.007 (3)
C10A 0.061 (5) 0.139 (10) 0.085 (6) −0.044 (5) 0.031 (4) −0.056 (6)
C11A 0.105 (5) 0.187 (8) 0.105 (4) −0.088 (5) 0.057 (4) −0.057 (5)

Geometric parameters (Å, °)

O1—N1 1.212 (2) C4—C7 1.494 (2)
O2—N1 1.210 (2) C5—C6 1.384 (2)
O3—C7 1.2215 (19) C5—H5 0.9300
O4—N2 1.3809 (18) C6—H6 0.9300
O4—H4O 0.8200 C7—C8 1.487 (2)
O5—C9 1.193 (2) C8—C9 1.513 (2)
O6—C9 1.312 (2) C10—C11 1.427 (10)
O6—C10A 1.458 (5) C10—H10A 0.9700
O6—C10 1.502 (6) C10—H10B 0.9700
N1—C1 1.474 (2) C11—H11A 0.9600
N2—C8 1.276 (2) C11—H11B 0.9600
C1—C6 1.372 (3) C11—H11C 0.9600
C1—C2 1.378 (3) C10A—C11A 1.503 (8)
C2—C3 1.376 (3) C10A—H10C 0.9700
C2—H2 0.9300 C10A—H10D 0.9700
C3—C4 1.397 (2) C11A—H11D 0.9600
C3—H3 0.9300 C11A—H11E 0.9600
C4—C5 1.387 (2) C11A—H11F 0.9600

N2—O4—H4O 109.5 N2—C8—C9 123.39 (14)
C9—O6—C10A 112.3 (3) C7—C8—C9 115.87 (13)
C9—O6—C10 121.3 (4) O5—C9—O6 126.44 (16)
O2—N1—O1 123.25 (18) O5—C9—C8 123.10 (16)
O2—N1—C1 118.35 (18) O6—C9—C8 110.45 (14)
O1—N1—C1 118.39 (19) C11—C10—O6 107.2 (6)
C8—N2—O4 110.88 (13) C11—C10—H10A 110.3
C6—C1—C2 122.63 (16) O6—C10—H10A 110.3
C6—C1—N1 119.02 (17) C11—C10—H10B 110.3
C2—C1—N1 118.35 (17) O6—C10—H10B 110.3
C3—C2—C1 118.33 (17) H10A—C10—H10B 108.5
C3—C2—H2 120.8 C10—C11—H11A 109.5
C1—C2—H2 120.8 C10—C11—H11B 109.5
C2—C3—C4 120.66 (17) H11A—C11—H11B 109.5
C2—C3—H3 119.7 C10—C11—H11C 109.5
C4—C3—H3 119.7 H11A—C11—H11C 109.5
C5—C4—C3 119.42 (16) H11B—C11—H11C 109.5



supplementary materials

sup-6

C5—C4—C7 124.40 (15) O6—C10A—C11A 105.2 (4)
C3—C4—C7 116.12 (15) O6—C10A—H10C 110.7
C6—C5—C4 120.29 (16) C11A—C10A—H10C 110.7
C6—C5—H5 119.9 O6—C10A—H10D 110.7
C4—C5—H5 119.9 C11A—C10A—H10D 110.7
C1—C6—C5 118.66 (16) H10C—C10A—H10D 108.8
C1—C6—H6 120.7 C10A—C11A—H11D 109.5
C5—C6—H6 120.7 C10A—C11A—H11E 109.5
O3—C7—C8 116.64 (14) H11D—C11A—H11E 109.5
O3—C7—C4 119.20 (15) C10A—C11A—H11F 109.5
C8—C7—C4 124.15 (14) H11D—C11A—H11F 109.5
N2—C8—C7 120.63 (14) H11E—C11A—H11F 109.5

O2—N1—C1—C6 −14.5 (3) O4—N2—C8—C7 177.96 (13)
O1—N1—C1—C6 166.2 (2) O4—N2—C8—C9 1.9 (2)
O2—N1—C1—C2 165.6 (2) O3—C7—C8—N2 −165.30 (16)
O1—N1—C1—C2 −13.7 (3) C4—C7—C8—N2 15.8 (2)
C6—C1—C2—C3 0.9 (3) O3—C7—C8—C9 11.0 (2)
N1—C1—C2—C3 −179.25 (16) C4—C7—C8—C9 −167.90 (14)
C1—C2—C3—C4 −1.1 (3) C10A—O6—C9—O5 8.9 (3)
C2—C3—C4—C5 0.2 (3) C10—O6—C9—O5 0.4 (4)
C2—C3—C4—C7 −176.95 (16) C10A—O6—C9—C8 −170.7 (2)
C3—C4—C5—C6 1.0 (3) C10—O6—C9—C8 −179.1 (3)
C7—C4—C5—C6 177.94 (15) N2—C8—C9—O5 91.4 (2)
C2—C1—C6—C5 0.3 (3) C7—C8—C9—O5 −84.8 (2)
N1—C1—C6—C5 −179.55 (16) N2—C8—C9—O6 −89.0 (2)
C4—C5—C6—C1 −1.3 (3) C7—C8—C9—O6 94.77 (17)
C5—C4—C7—O3 −168.26 (17) C9—O6—C10—C11 96.0 (7)
C3—C4—C7—O3 8.8 (2) C10A—O6—C10—C11 53.9 (18)
C5—C4—C7—C8 10.7 (2) C9—O6—C10A—C11A 159.5 (4)
C3—C4—C7—C8 −172.33 (15) C10—O6—C10A—C11A −59 (2)

Hydrogen-bond geometry (Å, °)

D—H···A D—H H···A D···A D—H···A

O4—H4o···O3i 0.82 1.91 2.7165 (16) 166

C5—H5···O5i 0.93 2.58 3.371 (2) 144

C2—H2···O1ii 0.93 2.55 3.393 (3) 151

C11—H11a···O1iii 0.96 2.52 3.426 (5) 158
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y, −z+2; (iii) x−1/2, y−1/2, z−1.



supplementary materials

sup-7

Fig. 1



supplementary materials

sup-8

Fig. 2



supplementary materials

sup-9

Fig. 3



supplementary materials

sup-10

Fig. 4