Diethyl 2,6,11-trioxo-2,3-dihydro-1H-anthra[1,2-d]imidazole-1,3-diacetate

Afrakssou, Z.; Haoudi, A.; Capet, F.; Rolando, C.; El Ammari, L.

doi:10.1107/S1600536811028091

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2081

doi:10.1107/S1600536811028091

Open

access

Diethyl 2,6,11-trioxo-2,3-dihydro-1H-anthra[1,2-d]imidazole-1,3-diacetate

Zahra Afrakssou,^a ^* Amal Haoudi,^a Frédéric Capet,^b Christian Rolando ^c and Lahcen El Ammari ^d

^aLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Immouzzer, BP 2202 Fès, Morocco, ^bUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, France, ^cUSR 3290 Miniaturisation pour l'Analyse, la Synthèse et la Protéomique, 59655 Villeneuve d'Ascq Cedex, Université Lille 1, France, and ^dLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: afrassou@yahoo.fr

(Received 11 July 2011; accepted 13 July 2011; online 23 July 2011)

The title compound, C₂₃H₂₀N₂O₇, consists of three fused six-membered rings (A, B and C) and one five-membered ring (D), linked to two ethyl acetate groups. The four fused rings are slightly folded around the O=C⋯C=O direction of the anthraquinone system, with a dihedral angle of 3.07 (8)° between the fused five- and six-membered rings (C and D) and the terminal ring (A). The planes through the atoms forming each acetate group are nearly perpendicular to the mean plane of the anthra[1,2-d]imidazole system, as indicated by the dihedral angles between them of 79.94 (9) and 85.90 (9)°. The crystal packing displays non-classical C—H⋯O hydrogen bonds.

Related literature

For the biological activity of anthraquinone derivatives, see: Afrakssou et al. (2011 ); Guimarães et al. (2009 ); Zoń et al. (2003 ). For their applications as colourants, see: Mori et al. (1990 ); Kowalczyk et al. (2010 ); Ossowski et al. (2005 ).

Experimental

Crystal data

C₂₃H₂₀N₂O₇
M_r = 436.41
Monoclinic, P 2₁ /c
a = 17.462 (1) Å
b = 13.0646 (9) Å
c = 9.1411 (6) Å
β = 103.915 (3)°
V = 2024.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.49 × 0.11 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.602, T_max = 0.746
32055 measured reflections
5006 independent reflections
3339 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.153
S = 1.01
5006 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O1ⁱ	0.95	2.49	3.353 (2)	151
C12—H12⋯O6ⁱⁱ	0.95	2.56	3.380 (2)	145
C16—H16A⋯O6ⁱⁱ	0.99	2.47	3.369 (3)	151
C16—H16B⋯O4ⁱⁱ	0.99	2.22	3.120 (2)	151
Symmetry codes: (i) -x, -y+1, -z; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811028091/bt5578sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028091/bt5578Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028091/bt5578Isup3.cml

checkCIF report

Comment top

Anthraquinones, the largest group of naturally occurring quinones, present in bacteria, fungi and many higher plant families contain π-electrons, reducible p-quinone system and are redoxactive (Zoń et al., 2003). That is the reason why they found many practical applications (Kowalczyk et al., 2010; Ossowski et al., 2005). Both natural and synthetic derivatives have been used as colourants in food, cosmetics, textiles and hair dyes (Mori et al., 1990).

The present work is a continuation of the preparation of new derivatives of anthra [1,2-d]imidazole-2,6,11–trione for biological application (Afrakssou et al., 2011; Guimarães et al., 2009). The reactivity of ethyl acetate bromide towards 1H-anthra [2, 1 - d] imidazole-2, 6, 11(3H)-trione under phase-transfer catalysis conditions using tetra n-butyl ammonium bromide (TBAB) as catalyst and potassium carbonate as base, leads to the formation of the title compound with good yields about 90% (Scheme 1).

The molecule of the title compound consists of three fused six-membered rings (A,B,C) and one five-membered ring (D) linked to two ethyl acetate groups as shown in Fig.1. The fused five and six-membered rings (C,D) are essentially planar with the largest deviation from the mean plane being -0.0185 (16) Å and built a dihedral angle of 3.07 (8) ° with (A) ring. The planes through the atoms forming each acetate group are nearly perpendicular to the mean plane of the anthra[1,2-d]imidazole system, as indicated by the dihedral angles between them of 79.94 (9) and 85.90 (9) °. The crystal packing displays intermolecular C—H···O no classic hydrogen bonding (Table 1).

Related literature top

For the biological activity of anthraquinone derivative, see: Afrakssou et al. (2011); Guimarães et al. (2009); Zoń et al. (2003). For their applications as colourants, see: Mori et al. (1990); Kowalczyk et al. (2010); Ossowski et al. (2005).

Experimental top

To a solution of 1H-anthra [2,1-d]imidazole-2,6,11(3H)-trione (0.4 g, 1.51 mmol), potassium carbonate (1.56 g, 4.54 mmol) and tetra n-butyl ammonium bromide (0.62 g, 1.51 mmol) in DMF (20 ml) was added ethyl acetate bromide (0.41 ml, 3.78 mmol). Stirring was continued at room temperature for 24 h. The mixture was filtered and the solvent removed. The residue was extracted with water. The organic compound was chromatographed on a column of silica gel with ethyl acetate-hexane (1/1) as eluent. The crystals of the title compound were obtained by dissolving 50 mg of product in 5 ml of ethanol at about 363 K, followed by a slow evaporation of the solvent. The melting point of the isolated orange crystals is about 443 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Molecular plot of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

Diethyl 2,6,11-trioxo-2,3-dihydro-1H-anthra[1,2-d]imidazole-1,3-diacetate top

Crystal data top

C₂₃H₂₀N₂O₇	F(000) = 912
M_r = 436.41	D_x = 1.432 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 443 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 17.462 (1) Å	Cell parameters from 5953 reflections
b = 13.0646 (9) Å	θ = 2.8–28.2°
c = 9.1411 (6) Å	µ = 0.11 mm⁻¹
β = 103.915 (3)°	T = 100 K
V = 2024.2 (2) Å³	Needle, orange
Z = 4	0.49 × 0.11 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	5006 independent reflections
Radiation source: fine-focus sealed tube	3339 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −23→17
T_min = 0.602, T_max = 0.746	k = −17→17
32055 measured reflections	l = −12→12

Refinement top

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0807P)² + 0.7872P] where P = (F_o² + 2F_c²)/3
5006 reflections	(Δ/σ)_max < 0.001
291 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₂₃H₂₀N₂O₇	V = 2024.2 (2) Å³
M_r = 436.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.462 (1) Å	µ = 0.11 mm⁻¹
b = 13.0646 (9) Å	T = 100 K
c = 9.1411 (6) Å	0.49 × 0.11 × 0.09 mm
β = 103.915 (3)°

Data collection top

Bruker APEXII CCD diffractometer	5006 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	3339 reflections with I > 2σ(I)
T_min = 0.602, T_max = 0.746	R_int = 0.057
32055 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.01	Δρ_max = 0.57 e Å⁻³
5006 reflections	Δρ_min = −0.32 e Å⁻³
291 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.03454 (11)	0.81216 (15)	0.1634 (2)	0.0212 (4)
C2	−0.01666 (12)	0.88216 (16)	0.0739 (2)	0.0251 (4)
H2	−0.0120	0.9531	0.0970	0.030*
C3	−0.07428 (12)	0.84794 (18)	−0.0487 (2)	0.0291 (5)
H3	−0.1089	0.8956	−0.1099	0.035*
C4	−0.08148 (12)	0.74399 (17)	−0.0823 (2)	0.0300 (5)
H4	−0.1204	0.7211	−0.1674	0.036*
C5	−0.03235 (11)	0.67372 (16)	0.0073 (2)	0.0251 (4)
H5	−0.0378	0.6027	−0.0153	0.030*
C6	0.02552 (11)	0.70791 (15)	0.1315 (2)	0.0213 (4)
C7	0.07787 (11)	0.63253 (15)	0.2280 (2)	0.0211 (4)
C8	0.13726 (11)	0.67067 (15)	0.3619 (2)	0.0195 (4)
C9	0.14819 (11)	0.77711 (14)	0.3921 (2)	0.0180 (4)
C10	0.09975 (11)	0.85232 (15)	0.2866 (2)	0.0207 (4)
C11	0.18249 (11)	0.59666 (14)	0.4533 (2)	0.0208 (4)
H11	0.1729	0.5263	0.4296	0.025*
C12	0.24099 (11)	0.62368 (15)	0.5779 (2)	0.0213 (4)
H12	0.2722	0.5733	0.6399	0.026*
C13	0.25240 (11)	0.72640 (15)	0.6087 (2)	0.0196 (4)
C14	0.20748 (11)	0.80493 (14)	0.5205 (2)	0.0184 (4)
C15	0.29890 (11)	0.87703 (15)	0.7166 (2)	0.0219 (4)
C16	0.36449 (12)	0.71882 (15)	0.8400 (2)	0.0229 (4)
H16A	0.3382	0.6635	0.8836	0.028*
H16B	0.3880	0.7670	0.9221	0.028*
C17	0.42943 (11)	0.67314 (16)	0.7757 (2)	0.0229 (4)
C18	0.51981 (13)	0.53472 (18)	0.8019 (3)	0.0358 (5)
H18A	0.5572	0.4993	0.8851	0.043*
H18B	0.5506	0.5789	0.7491	0.043*
C19	0.47416 (16)	0.4572 (2)	0.6938 (4)	0.0512 (7)
H19A	0.4439	0.4135	0.7465	0.077*
H19B	0.5109	0.4149	0.6539	0.077*
H19C	0.4380	0.4926	0.6105	0.077*
C20	0.21415 (12)	1.00388 (15)	0.5665 (2)	0.0238 (4)
H20A	0.2225	1.0390	0.6651	0.029*
H20B	0.1573	1.0081	0.5163	0.029*
C21	0.26099 (12)	1.05796 (16)	0.4711 (2)	0.0250 (4)
C22	0.29699 (17)	1.22304 (19)	0.4012 (3)	0.0454 (6)
H22A	0.2759	1.2132	0.2915	0.054*
H22B	0.3536	1.2046	0.4272	0.054*
C23	0.2867 (2)	1.3309 (2)	0.4429 (3)	0.0564 (8)
H23A	0.2304	1.3476	0.4199	0.085*
H23B	0.3135	1.3761	0.3855	0.085*
H23C	0.3096	1.3403	0.5510	0.085*
N1	0.30651 (9)	0.77227 (12)	0.72586 (17)	0.0199 (3)
N2	0.23663 (9)	0.89680 (12)	0.59127 (18)	0.0203 (3)
O1	0.07231 (9)	0.54083 (10)	0.19817 (16)	0.0272 (3)
O2	0.11351 (9)	0.94387 (11)	0.29568 (17)	0.0309 (4)
O3	0.33699 (8)	0.94101 (11)	0.80032 (15)	0.0260 (3)
O4	0.44572 (9)	0.70173 (12)	0.66182 (16)	0.0325 (4)
O5	0.46530 (9)	0.59785 (12)	0.86323 (17)	0.0336 (4)
O6	0.29952 (9)	1.01755 (12)	0.39486 (17)	0.0320 (4)
O7	0.25385 (10)	1.15896 (12)	0.48532 (19)	0.0374 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0234 (9)	0.0248 (10)	0.0172 (9)	−0.0005 (8)	0.0085 (7)	−0.0014 (7)
C2	0.0291 (10)	0.0255 (10)	0.0215 (10)	0.0010 (8)	0.0077 (8)	0.0019 (8)
C3	0.0274 (10)	0.0357 (12)	0.0234 (10)	0.0036 (9)	0.0044 (8)	0.0035 (9)
C4	0.0267 (10)	0.0387 (13)	0.0230 (10)	−0.0040 (9)	0.0030 (8)	−0.0016 (9)
C5	0.0251 (10)	0.0264 (11)	0.0252 (10)	−0.0045 (8)	0.0087 (8)	−0.0055 (8)
C6	0.0210 (9)	0.0261 (10)	0.0194 (9)	−0.0022 (8)	0.0097 (7)	−0.0007 (7)
C7	0.0241 (9)	0.0228 (10)	0.0193 (9)	−0.0035 (8)	0.0111 (8)	−0.0016 (7)
C8	0.0228 (9)	0.0199 (10)	0.0184 (9)	−0.0014 (7)	0.0099 (7)	−0.0012 (7)
C9	0.0203 (9)	0.0190 (9)	0.0167 (9)	0.0016 (7)	0.0084 (7)	0.0005 (7)
C10	0.0239 (9)	0.0214 (10)	0.0181 (9)	0.0005 (8)	0.0080 (7)	0.0001 (7)
C11	0.0278 (10)	0.0149 (9)	0.0216 (9)	−0.0014 (8)	0.0097 (8)	−0.0012 (7)
C12	0.0260 (10)	0.0210 (10)	0.0187 (9)	0.0026 (8)	0.0088 (8)	0.0033 (7)
C13	0.0207 (9)	0.0228 (10)	0.0170 (9)	0.0007 (7)	0.0078 (7)	0.0008 (7)
C14	0.0212 (9)	0.0168 (9)	0.0198 (9)	−0.0007 (7)	0.0099 (7)	−0.0004 (7)
C15	0.0229 (9)	0.0243 (10)	0.0207 (9)	0.0008 (8)	0.0096 (8)	0.0001 (8)
C16	0.0269 (10)	0.0257 (10)	0.0161 (9)	0.0015 (8)	0.0050 (8)	0.0018 (8)
C17	0.0216 (9)	0.0281 (11)	0.0178 (9)	0.0002 (8)	0.0023 (7)	0.0024 (8)
C18	0.0273 (11)	0.0401 (14)	0.0414 (13)	0.0138 (10)	0.0107 (10)	0.0111 (10)
C19	0.0367 (14)	0.0409 (16)	0.078 (2)	0.0058 (11)	0.0164 (14)	−0.0043 (14)
C20	0.0282 (10)	0.0188 (10)	0.0249 (10)	0.0003 (8)	0.0077 (8)	−0.0028 (8)
C21	0.0260 (10)	0.0241 (10)	0.0249 (10)	−0.0004 (8)	0.0063 (8)	−0.0003 (8)
C22	0.0604 (16)	0.0309 (13)	0.0533 (16)	−0.0024 (12)	0.0305 (13)	0.0111 (11)
C23	0.082 (2)	0.0395 (16)	0.0500 (17)	−0.0095 (15)	0.0199 (15)	0.0078 (13)
N1	0.0225 (8)	0.0196 (8)	0.0174 (8)	0.0010 (6)	0.0047 (6)	−0.0013 (6)
N2	0.0234 (8)	0.0179 (8)	0.0202 (8)	−0.0005 (6)	0.0062 (6)	−0.0014 (6)
O1	0.0325 (8)	0.0224 (8)	0.0270 (7)	−0.0027 (6)	0.0078 (6)	−0.0044 (6)
O2	0.0374 (8)	0.0211 (8)	0.0301 (8)	−0.0007 (6)	0.0000 (6)	0.0032 (6)
O3	0.0281 (7)	0.0247 (8)	0.0253 (7)	−0.0037 (6)	0.0067 (6)	−0.0054 (6)
O4	0.0330 (8)	0.0458 (10)	0.0213 (7)	0.0098 (7)	0.0116 (6)	0.0105 (6)
O5	0.0315 (8)	0.0438 (10)	0.0276 (8)	0.0139 (7)	0.0114 (6)	0.0144 (7)
O6	0.0389 (9)	0.0311 (8)	0.0304 (8)	−0.0011 (7)	0.0167 (7)	−0.0025 (6)
O7	0.0519 (10)	0.0224 (8)	0.0454 (10)	−0.0007 (7)	0.0261 (8)	0.0036 (7)

Geometric parameters (Å, º) top

C1—C6	1.394 (3)	C15—N2	1.401 (2)
C1—C2	1.397 (3)	C16—N1	1.447 (2)
C1—C10	1.492 (3)	C16—C17	1.519 (3)
C2—C3	1.388 (3)	C16—H16A	0.9900
C2—H2	0.9500	C16—H16B	0.9900
C3—C4	1.391 (3)	C17—O4	1.203 (2)
C3—H3	0.9500	C17—O5	1.326 (2)
C4—C5	1.383 (3)	C18—O5	1.469 (3)
C4—H4	0.9500	C18—C19	1.503 (4)
C5—C6	1.399 (3)	C18—H18A	0.9900
C5—H5	0.9500	C18—H18B	0.9900
C6—C7	1.482 (3)	C19—H19A	0.9800
C7—O1	1.227 (2)	C19—H19B	0.9800
C7—C8	1.487 (3)	C19—H19C	0.9800
C8—C11	1.393 (3)	C20—N2	1.456 (2)
C8—C9	1.422 (3)	C20—C21	1.508 (3)
C9—C14	1.413 (3)	C20—H20A	0.9900
C9—C10	1.489 (3)	C20—H20B	0.9900
C10—O2	1.219 (2)	C21—O6	1.201 (2)
C11—C12	1.380 (3)	C21—O7	1.335 (3)
C11—H11	0.9500	C22—O7	1.462 (3)
C12—C13	1.376 (3)	C22—C23	1.482 (4)
C12—H12	0.9500	C22—H22A	0.9900
C13—N1	1.383 (2)	C22—H22B	0.9900
C13—C14	1.419 (3)	C23—H23A	0.9800
C14—N2	1.400 (2)	C23—H23B	0.9800
C15—O3	1.217 (2)	C23—H23C	0.9800
C15—N1	1.376 (2)

C6—C1—C2	119.54 (18)	N1—C16—H16B	109.3
C6—C1—C10	121.94 (17)	C17—C16—H16B	109.3
C2—C1—C10	118.47 (18)	H16A—C16—H16B	108.0
C3—C2—C1	119.95 (19)	O4—C17—O5	125.21 (19)
C3—C2—H2	120.0	O4—C17—C16	124.53 (18)
C1—C2—H2	120.0	O5—C17—C16	110.26 (16)
C2—C3—C4	120.1 (2)	O5—C18—C19	109.85 (19)
C2—C3—H3	119.9	O5—C18—H18A	109.7
C4—C3—H3	119.9	C19—C18—H18A	109.7
C5—C4—C3	120.47 (19)	O5—C18—H18B	109.7
C5—C4—H4	119.8	C19—C18—H18B	109.7
C3—C4—H4	119.8	H18A—C18—H18B	108.2
C4—C5—C6	119.52 (19)	C18—C19—H19A	109.5
C4—C5—H5	120.2	C18—C19—H19B	109.5
C6—C5—H5	120.2	H19A—C19—H19B	109.5
C1—C6—C5	120.32 (18)	C18—C19—H19C	109.5
C1—C6—C7	120.17 (17)	H19A—C19—H19C	109.5
C5—C6—C7	119.51 (18)	H19B—C19—H19C	109.5
O1—C7—C6	120.79 (17)	N2—C20—C21	112.12 (16)
O1—C7—C8	120.81 (18)	N2—C20—H20A	109.2
C6—C7—C8	118.40 (17)	C21—C20—H20A	109.2
C11—C8—C9	122.16 (17)	N2—C20—H20B	109.2
C11—C8—C7	116.35 (17)	C21—C20—H20B	109.2
C9—C8—C7	121.47 (17)	H20A—C20—H20B	107.9
C14—C9—C8	116.75 (16)	O6—C21—O7	124.74 (19)
C14—C9—C10	123.82 (17)	O6—C21—C20	125.98 (19)
C8—C9—C10	119.39 (16)	O7—C21—C20	109.28 (16)
O2—C10—C9	122.11 (17)	O7—C22—C23	107.4 (2)
O2—C10—C1	119.91 (17)	O7—C22—H22A	110.2
C9—C10—C1	117.94 (16)	C23—C22—H22A	110.2
C12—C11—C8	121.18 (18)	O7—C22—H22B	110.2
C12—C11—H11	119.4	C23—C22—H22B	110.2
C8—C11—H11	119.4	H22A—C22—H22B	108.5
C13—C12—C11	117.42 (17)	C22—C23—H23A	109.5
C13—C12—H12	121.3	C22—C23—H23B	109.5
C11—C12—H12	121.3	H23A—C23—H23B	109.5
C12—C13—N1	128.30 (17)	C22—C23—H23C	109.5
C12—C13—C14	123.76 (17)	H23A—C23—H23C	109.5
N1—C13—C14	107.94 (16)	H23B—C23—H23C	109.5
N2—C14—C9	135.76 (17)	C15—N1—C13	110.22 (15)
N2—C14—C13	105.53 (16)	C15—N1—C16	124.39 (16)
C9—C14—C13	118.71 (17)	C13—N1—C16	125.37 (16)
O3—C15—N1	127.91 (18)	C14—N2—C15	110.13 (15)
O3—C15—N2	125.93 (18)	C14—N2—C20	134.24 (16)
N1—C15—N2	106.15 (16)	C15—N2—C20	115.56 (16)
N1—C16—C17	111.62 (15)	C17—O5—C18	116.20 (16)
N1—C16—H16A	109.3	C21—O7—C22	116.27 (17)
C17—C16—H16A	109.3

C6—C1—C2—C3	−2.2 (3)	C10—C9—C14—N2	3.2 (3)
C10—C1—C2—C3	175.18 (18)	C8—C9—C14—C13	0.8 (2)
C1—C2—C3—C4	0.4 (3)	C10—C9—C14—C13	−177.01 (17)
C2—C3—C4—C5	1.1 (3)	C12—C13—C14—N2	178.95 (17)
C3—C4—C5—C6	−0.7 (3)	N1—C13—C14—N2	−0.7 (2)
C2—C1—C6—C5	2.5 (3)	C12—C13—C14—C9	−0.9 (3)
C10—C1—C6—C5	−174.73 (17)	N1—C13—C14—C9	179.43 (16)
C2—C1—C6—C7	−178.23 (17)	N1—C16—C17—O4	21.5 (3)
C10—C1—C6—C7	4.5 (3)	N1—C16—C17—O5	−158.68 (16)
C4—C5—C6—C1	−1.1 (3)	N2—C20—C21—O6	15.8 (3)
C4—C5—C6—C7	179.67 (18)	N2—C20—C21—O7	−163.51 (17)
C1—C6—C7—O1	−177.49 (17)	O3—C15—N1—C13	−179.68 (19)
C5—C6—C7—O1	1.8 (3)	N2—C15—N1—C13	1.4 (2)
C1—C6—C7—C8	2.6 (3)	O3—C15—N1—C16	−1.2 (3)
C5—C6—C7—C8	−178.19 (17)	N2—C15—N1—C16	179.85 (16)
O1—C7—C8—C11	−3.0 (3)	C12—C13—N1—C15	179.94 (18)
C6—C7—C8—C11	176.95 (16)	C14—C13—N1—C15	−0.4 (2)
O1—C7—C8—C9	175.54 (17)	C12—C13—N1—C16	1.5 (3)
C6—C7—C8—C9	−4.5 (3)	C14—C13—N1—C16	−178.88 (16)
C11—C8—C9—C14	−0.1 (3)	C17—C16—N1—C15	−107.4 (2)
C7—C8—C9—C14	−178.58 (16)	C17—C16—N1—C13	70.9 (2)
C11—C8—C9—C10	177.81 (17)	C9—C14—N2—C15	−178.6 (2)
C7—C8—C9—C10	−0.6 (3)	C13—C14—N2—C15	1.6 (2)
C14—C9—C10—O2	7.6 (3)	C9—C14—N2—C20	4.7 (4)
C8—C9—C10—O2	−170.20 (18)	C13—C14—N2—C20	−175.14 (19)
C14—C9—C10—C1	−174.76 (16)	O3—C15—N2—C14	179.19 (18)
C8—C9—C10—C1	7.5 (3)	N1—C15—N2—C14	−1.8 (2)
C6—C1—C10—O2	168.12 (18)	O3—C15—N2—C20	−3.4 (3)
C2—C1—C10—O2	−9.2 (3)	N1—C15—N2—C20	175.55 (15)
C6—C1—C10—C9	−9.6 (3)	C21—C20—N2—C14	−95.1 (2)
C2—C1—C10—C9	173.13 (17)	C21—C20—N2—C15	88.3 (2)
C9—C8—C11—C12	−0.6 (3)	O4—C17—O5—C18	−10.5 (3)
C7—C8—C11—C12	177.95 (17)	C16—C17—O5—C18	169.61 (17)
C8—C11—C12—C13	0.5 (3)	C19—C18—O5—C17	−80.1 (2)
C11—C12—C13—N1	179.80 (18)	O6—C21—O7—C22	−0.2 (3)
C11—C12—C13—C14	0.2 (3)	C20—C21—O7—C22	179.08 (19)
C8—C9—C14—N2	−178.98 (19)	C23—C22—O7—C21	−175.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.95	2.49	3.353 (2)	151
C12—H12···O6ⁱⁱ	0.95	2.56	3.380 (2)	145
C16—H16A···O6ⁱⁱ	0.99	2.47	3.369 (3)	151
C16—H16B···O4ⁱⁱ	0.99	2.22	3.120 (2)	151

Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₀N₂O₇
M_r	436.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	17.462 (1), 13.0646 (9), 9.1411 (6)
β (°)	103.915 (3)
V (Å³)	2024.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.49 × 0.11 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.602, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	32055, 5006, 3339
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.153, 1.01
No. of reflections	5006
No. of parameters	291
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.32

Computer programs: APEX2 (Bruker, 2009), SAINT-Plus (Bruker, 2009), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), ORTEP-3 for Windows (Farrugia, 1997) and ORTEPIII (Burnett & Johnson, 1996), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.95	2.49	3.353 (2)	151.3
C12—H12···O6ⁱⁱ	0.95	2.56	3.380 (2)	145.1
C16—H16A···O6ⁱⁱ	0.99	2.47	3.369 (3)	151.0
C16—H16B···O4ⁱⁱ	0.99	2.22	3.120 (2)	150.8

Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+3/2, z+1/2.

References

Afrakssou, Z., Rodi, Y. K., Saffon, N., Essassi, E. M. & Ng, S. W. (2011). Acta Cryst. E67, o1730. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2009). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Guimarães, T. T., Da Silva Júnior, E. N., Carvalho, C. E. M., De Simone, C. A. & Pinto, A. V. (2009). Acta Cryst. E65, o1063. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kowalczyk, A., Nowicka, A. M., Jurczakowski, R., Niedziałkowski, P., Ossowski, T. & Stojek, Z. (2010). Electroanalysis, 22, 49–59. CrossRef CAS Google Scholar
Mori, H., Yoshimi, N., Iwata, H., Mori, Y., Hara, A., Tanaka, T. & Kawai, K. (1990). Carcinogenesis, 11, 799–802. CrossRef CAS PubMed Web of Science Google Scholar
Ossowski, T., Zarzeczan' ska, D., Zalewski, L., Niedziałkowski, P., Majewski, R. & Szyman' ska, A. (2005). Tetrahedron Lett. 46, 1735–1738. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zoń, A., Pałys, M., Stojek, Z., Sulowska, H. & Ossowski, T. (2003). Electroanalysis, 15, 579–585. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2081

doi:10.1107/S1600536811028091

Open

access