organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoIUCrDATA
ISSN: 2414-3146

2-Methyl-3′-(4-methyl­phen­yl)-4′-(2-nitro­phen­yl)-4′H-spiro­[chroman-3,5′-isoxazol]-4-one

CROSSMARK_Color_square_no_text.svg

aLaboratoire de Chimie Organique, Faculté des Sciences Dhar EL Mahraz, Université Sidi Mohamed Ben Abdellah, BP 1796, 30000, Fès, Morocco, and bLaboratoire de Chimie Appliquée des Matériaux, Centres des Sciences des Matériaux, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: asmae.mahfoud@yahoo.fr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 21 June 2018; accepted 4 July 2018; online 10 July 2018)

The title compound, C25H20N2O5, crystallizes with two mol­ecules (A and B) in the asymmetric unit with similar conformations. The five-membered rings are both in envelope conformations with the spiro C atom as the flap. The six-membered heterocycles display half-chair conformations. The mean plane through the isoxazole ring is nearly perpendicular to those through the spiro-chroman system and the 4-nitro­phenyl moieties, as indicated by the dihedral angles of 81.42 (9) and 87.58 (8)°, respectively, between them in mol­ecule A. Equivalent data for mol­ecule B are 75.58 (9) and 84.15 (8)°, respectively. The p-tolyl plane makes a dihedral angles of 24.10 (9) and 28.78 (8)° with the isoxazole ring in mol­ecules A and B, respectively. In the crystal, mol­ecules are linked by C—H⋯O and C—H⋯N hydrogen bonds and C—H⋯π inter­action, forming a three-dimensional network.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

Spiro­isoxazolines have various biological properties such as herbicidal (De Amici et al., 1990[De Amici, M., De Micheli, C. & Misani, V. (1990). Tetrahedron, 46, 1975-1986.])and plant-growth regulatory activities (Howe & Shelton, 1990[Howe, R. K. & Shelton, B. R. (1990). J. Org. Chem. 55, 4603-4607.]) and have applications as anti­tumor agents (Smietana et al., 1999[Smietana, M., Gouverneur, V. & Mioskowski, C. (1999). Tetrahedron Lett. 40, 1291-1294.]) and anti-HIV agents (Liu et al., 1997[Liu, S., Fu, X., Schmitz, F. J. & Kelly-Borges, M. (1997). J. Nat. Prod. 60, 614-615.]). In this work we have studied the regio- and stereoselective synthesis of spiro­isoxazoline 2-methyl-4′-(nitro­phen­yl)-3′-(p-tol­yl)-4′H-spiro­[chroman-3,5′-isoxazol]-4-one obtained by the 1,3-dipolar cyclo­addition (Mahfoud et al., 2015[Mahfoud, A., Al Houari, G., El Yazidi, M., Saadi, M. & El Ammari, L. (2015). Acta Cryst. E71, o873-o874.], Boughaleb et al., 2011[Boughaleb, A., Zouihri, H., Gmouh, S., Kerbal, A. & El yazidi, M. (2011). Acta Cryst. E67, o1850.]) of (E)-2-methyl-3-(4-nitro­benzyl­idene)chroman-4-one and 4-tolyl­benzo­nitrile oxide. This concerted reaction affords a single regio-isomer which is the trans-spiro­isoxazoline (Bakhouch et al., 2014[Bakhouch, M., Al Houari, G., El Yazidi, M., Saadi, M. & El Ammari, L. (2014). Acta Cryst. E70, o587.]). The structure of the product was confirmed by the present X-ray study.

The asymmetric unit of the title compound is formed by two mol­ecules (A and B) with almost the same conformation, as shown in Fig. 1[link]. The most important difference between them lies in the orientation of the phenyl rings, as can be seen in the overlay plot (Fig. 2[link]). The isoxazole ring belonging to each mol­ecule is linked to a spiro-chroman system with additional 3′-p-tolyl and 4-nitro­phenyl ring substituents. The five-membered rings (N1/O3/C9/C10/C18) and (N3/O8/C34/C35/C43) display envelope conformations on C9 and C43, as indicated by the total puckering amplitudes Q2 = 0.3093 (15) and 0.3143 (15) Å and spherical polar angles φ2 = 138.2 (3) and 138.4 (3)°, respectively. Moreover, the six-membered heterocycles adopt half-chair conformations with the following puckering parameters: Q = 0.4758 (17) Å, θ = 129.2 (2)°, φ2 = 97.0 (2)° for mol­ecule A and Q = 0.4409 (17) Å, θ = 50.5 (2)°, φ2 = 270.8 (3)°, for B. The dihedral angles between the mean plane through the isoxazole rings and the p-tolyl planes are 24.10 (9) and 28.78 (8)°, in mol­ecules A and B, respectively. The mean plane through the isoxazole ring is nearly perpendicular to those through the spiro-chroman system and the 4-nitro­phenyl moieties, as indicated by the dihedral angles of 81.42 (9) and 87.58 (8)°, respectively, between them in mol­ecule A [75.58 (9) and 84.15 (8)°, respectively in B].

[Figure 1]
Figure 1
Plot of the mol­ecules of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are represented as small circles.
[Figure 2]
Figure 2
Overlay plot of mol­ecule B (red) on mol­ecule A (black).

In the crystal, the mol­ecules are linked by C10—H10⋯O1, C35—H35⋯O6 and C16—H16⋯N3 hydrogen bonds, in addition to C23—H23⋯π(Cg1) and C30—H30⋯π(Cg2) inter­actions, forming a three-dimensional network as shown in Fig. 3[link] and Table 1[link].

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C44–C49 and C11–C16 rings, respectively.

D—H⋯A D—H H⋯A DA D—H⋯A
C10—H10⋯O1i 0.98 2.40 3.3466 (17) 162
C35—H35⋯O6ii 0.98 2.25 3.2072 (17) 164
C16—H16⋯N3i 0.93 2.56 3.3091 (19) 138
C23—H23⋯Cg1 0.93 2.95 3.581 (2) 127
C30—H30⋯Cg2iii 0.93 3.00 3.758 (2) 140
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+2, -z; (iii) x, y, z-1.
[Figure 3]
Figure 3
Crystal packing for the title compound showing mol­ecules linked by hydrogen bonds (dashed blue lines) and C—H⋯π inter­action (green lines).

Synthesis and crystallization

In a 100 ml flask, 2 mmol of (E)-2-methyl-3-(4-nitro­benzyl­idene) chroman-4-one and 2.4 mmol of p-tolyl­nitrioxide were dissolved in 20 ml of chloro­form. The mixture was cooled to 273 K under magnetic stirring in an ice bath. Then, 15 ml of bleach (NaOCl) at 18° was added in small doses without exceeding 278 K. The mixture was left under magnetic stirring for 16 h at room temperature, then washed with water until the pH was neutral and dried on sodium sulfate. The solvent was removed under reduced pressure to leave an oily residue. The precipitated compound was then recrystallized from ethanol solution as colourless blocks.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C25H20N2O5
Mr 428.43
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 296
a, b, c (Å) 11.5219 (6), 14.2321 (7), 14.7033 (7)
α, β, γ (°) 72.201 (2), 73.469 (2), 73.647 (2)
V3) 2150.18 (19)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.09
Crystal size (mm) 0.36 × 0.28 × 0.25
 
Data collection
Diffractometer Bruker X8 APEX
Absorption correction Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.])
Tmin, Tmax 0.639, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections 86936, 10255, 7363
Rint 0.043
(sin θ/λ)max−1) 0.658
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.122, 1.02
No. of reflections 10255
No. of parameters 581
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.23, −0.26
Computer programs: APEX2 and SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Structural data


Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).

2-Methyl-3'-(4-methylphenyl)-4'-(2-nitrophenyl)-4'H-spiro[chroman-3,5'-isoxazol]-4-one top
Crystal data top
C25H20N2O5Z = 4
Mr = 428.43F(000) = 896
Triclinic, P1Dx = 1.323 Mg m3
a = 11.5219 (6) ÅMo Kα radiation, λ = 0.71073 Å
b = 14.2321 (7) ÅCell parameters from 10255 reflections
c = 14.7033 (7) Åθ = 2.1–27.9°
α = 72.201 (2)°µ = 0.09 mm1
β = 73.469 (2)°T = 296 K
γ = 73.647 (2)°Block, colourless
V = 2150.18 (19) Å30.36 × 0.28 × 0.25 mm
Data collection top
Bruker X8 APEX
diffractometer
10255 independent reflections
Radiation source: fine-focus sealed tube7363 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
φ and ω scansθmax = 27.9°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
h = 1515
Tmin = 0.639, Tmax = 0.747k = 1818
86936 measured reflectionsl = 1919
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.122 w = 1/[σ2(Fo2) + (0.0486P)2 + 0.6603P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.010
10255 reflectionsΔρmax = 0.23 e Å3
581 parametersΔρmin = 0.26 e Å3
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.71087 (13)0.49608 (11)0.37433 (10)0.0365 (3)
C20.79239 (13)0.45907 (11)0.29001 (10)0.0388 (3)
C30.75481 (16)0.48309 (12)0.20169 (11)0.0495 (4)
H30.6765910.5227130.1960500.059*
C40.83235 (19)0.44868 (15)0.12350 (13)0.0623 (5)
H40.8062490.4639730.0653310.075*
C50.9494 (2)0.39122 (16)0.13101 (14)0.0678 (5)
H51.0022420.3692060.0772030.081*
C60.98877 (17)0.36613 (15)0.21703 (13)0.0600 (5)
H61.0674770.3269190.2215500.072*
C70.91024 (14)0.39975 (12)0.29698 (11)0.0428 (3)
C80.86434 (14)0.37965 (12)0.47069 (11)0.0421 (3)
H80.9149020.3730530.5178650.051*
C90.77534 (12)0.48180 (11)0.45741 (10)0.0357 (3)
C100.68255 (12)0.51028 (10)0.54800 (10)0.0343 (3)
H100.6025630.4946340.5545340.041*
C110.72823 (12)0.46262 (10)0.64259 (10)0.0346 (3)
C120.82793 (14)0.48833 (12)0.65780 (11)0.0443 (4)
H120.8626190.5401550.6121520.053*
C130.87597 (15)0.43763 (14)0.74007 (12)0.0493 (4)
H130.9424950.4550010.7502030.059*
C140.82365 (15)0.36116 (13)0.80655 (11)0.0460 (4)
C150.72337 (15)0.33473 (12)0.79497 (11)0.0466 (4)
H150.6890020.2830010.8411080.056*
C160.67506 (14)0.38710 (11)0.71294 (11)0.0405 (3)
H160.6060590.3715050.7048440.049*
C170.79860 (17)0.29277 (12)0.50363 (13)0.0533 (4)
H17A0.7525550.2984410.4564000.080*
H17B0.7429740.2947190.5659100.080*
H17C0.8585760.2300320.5094830.080*
C180.67423 (14)0.62358 (11)0.51415 (10)0.0392 (3)
C190.56998 (15)0.69988 (11)0.54889 (11)0.0418 (3)
C200.48044 (16)0.67386 (13)0.63232 (12)0.0504 (4)
H200.4880540.6071060.6686330.060*
C210.37977 (18)0.74655 (15)0.66194 (14)0.0599 (5)
H210.3207230.7278940.7182080.072*
C220.3655 (2)0.84620 (14)0.60948 (15)0.0637 (5)
C230.4534 (2)0.87148 (14)0.52541 (16)0.0673 (5)
H230.4441830.9380280.4884950.081*
C240.55390 (19)0.80070 (13)0.49508 (13)0.0566 (4)
H240.6119320.8198380.4382590.068*
C250.2545 (3)0.9249 (2)0.6427 (2)0.1065 (10)
H25A0.2130140.9599600.5898520.160*
H25B0.2819230.9721990.6620350.160*
H25C0.1984590.8923280.6972070.160*
C260.52270 (13)0.81733 (11)0.02227 (10)0.0380 (3)
C270.53883 (15)0.73810 (11)0.02741 (11)0.0425 (3)
C280.44133 (18)0.72885 (14)0.06096 (12)0.0541 (4)
H280.3660420.7750900.0542260.065*
C290.4568 (2)0.65138 (17)0.10395 (15)0.0704 (6)
H290.3913150.6442280.1246950.084*
C300.5697 (2)0.58434 (17)0.11614 (16)0.0773 (6)
H300.5797130.5326030.1457510.093*
C310.6673 (2)0.59255 (14)0.08550 (14)0.0642 (5)
H310.7432920.5477400.0954990.077*
C320.65154 (16)0.66868 (12)0.03921 (11)0.0466 (4)
C330.74921 (14)0.76072 (12)0.01846 (11)0.0425 (3)
H330.8110560.7385370.0584440.051*
C340.62391 (13)0.80089 (10)0.07759 (10)0.0353 (3)
C350.61372 (13)0.89159 (10)0.11657 (10)0.0346 (3)
H350.5863050.9550240.0705350.041*
C360.72907 (13)0.89408 (10)0.14622 (10)0.0350 (3)
C370.76963 (14)0.82115 (11)0.22526 (11)0.0406 (3)
H370.7279480.7690010.2582680.049*
C380.87077 (14)0.82544 (12)0.25505 (11)0.0437 (3)
H380.8976240.7770300.3079610.052*
C390.93090 (14)0.90306 (12)0.20459 (11)0.0440 (3)
C400.89462 (15)0.97603 (12)0.12563 (12)0.0458 (4)
H400.9376581.0273060.0924450.055*
C410.79271 (14)0.97113 (11)0.09698 (11)0.0406 (3)
H410.7663661.0199840.0441010.049*
C420.78724 (17)0.83952 (14)0.07436 (13)0.0570 (4)
H42A0.8679090.8128010.1093430.085*
H42B0.7894210.8989540.0574770.085*
H42C0.7283970.8565440.1148370.085*
C430.51140 (13)0.87094 (10)0.20643 (10)0.0356 (3)
C440.43061 (13)0.94700 (11)0.25823 (11)0.0389 (3)
C450.46515 (16)1.03638 (12)0.24885 (13)0.0490 (4)
H450.5411651.0480680.2094290.059*
C460.38805 (18)1.10767 (13)0.29729 (14)0.0572 (4)
H460.4135161.1663400.2906980.069*
C470.27383 (17)1.09373 (14)0.35538 (14)0.0581 (5)
C480.23854 (17)1.00576 (16)0.36250 (15)0.0634 (5)
H480.1612580.9953750.4001640.076*
C490.31503 (15)0.93341 (14)0.31522 (13)0.0521 (4)
H490.2890060.8750700.3215680.063*
C500.1902 (2)1.17146 (19)0.40908 (19)0.0893 (7)
H50A0.2045111.1544310.4739570.134*
H50B0.1052621.1725620.4128700.134*
H50C0.2075631.2368310.3745900.134*
N10.76748 (13)0.64877 (10)0.44746 (10)0.0468 (3)
N20.87729 (15)0.30507 (15)0.89270 (11)0.0638 (4)
N30.50112 (11)0.77822 (9)0.23520 (9)0.0402 (3)
N41.03716 (16)0.90838 (14)0.23749 (13)0.0704 (5)
O10.60250 (9)0.53733 (9)0.37823 (8)0.0499 (3)
O20.95481 (9)0.37380 (9)0.37996 (8)0.0501 (3)
O30.84776 (9)0.56013 (8)0.42149 (8)0.0463 (3)
O40.85062 (15)0.22382 (14)0.93883 (11)0.0900 (5)
O50.94819 (19)0.34191 (16)0.91234 (13)0.1043 (6)
O60.43257 (10)0.88679 (8)0.02632 (9)0.0499 (3)
O70.74976 (11)0.66992 (8)0.00674 (9)0.0509 (3)
O80.58807 (10)0.72448 (7)0.16663 (7)0.0404 (2)
O91.06326 (16)0.84887 (14)0.31079 (13)0.1002 (6)
O101.0951 (2)0.97103 (19)0.18936 (18)0.1604 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0335 (7)0.0356 (7)0.0364 (7)0.0062 (6)0.0071 (6)0.0045 (6)
C20.0390 (7)0.0379 (7)0.0358 (7)0.0058 (6)0.0073 (6)0.0066 (6)
C30.0542 (9)0.0471 (9)0.0401 (8)0.0006 (7)0.0155 (7)0.0061 (7)
C40.0780 (13)0.0640 (11)0.0383 (9)0.0036 (10)0.0189 (9)0.0144 (8)
C50.0712 (13)0.0766 (13)0.0453 (10)0.0061 (10)0.0070 (9)0.0259 (9)
C60.0494 (10)0.0700 (12)0.0533 (10)0.0074 (8)0.0082 (8)0.0260 (9)
C70.0395 (8)0.0469 (9)0.0400 (8)0.0043 (6)0.0086 (6)0.0126 (7)
C80.0369 (7)0.0488 (9)0.0384 (8)0.0009 (6)0.0120 (6)0.0131 (7)
C90.0317 (7)0.0386 (7)0.0356 (7)0.0092 (6)0.0056 (6)0.0075 (6)
C100.0313 (6)0.0357 (7)0.0354 (7)0.0100 (5)0.0048 (5)0.0075 (6)
C110.0330 (7)0.0369 (7)0.0335 (7)0.0092 (6)0.0035 (5)0.0101 (6)
C120.0438 (8)0.0511 (9)0.0417 (8)0.0224 (7)0.0058 (7)0.0085 (7)
C130.0432 (8)0.0671 (11)0.0462 (9)0.0174 (8)0.0111 (7)0.0195 (8)
C140.0445 (8)0.0567 (10)0.0336 (8)0.0023 (7)0.0088 (6)0.0141 (7)
C150.0490 (9)0.0481 (9)0.0367 (8)0.0149 (7)0.0041 (7)0.0027 (7)
C160.0376 (7)0.0451 (8)0.0394 (8)0.0161 (6)0.0054 (6)0.0071 (6)
C170.0674 (11)0.0400 (9)0.0477 (9)0.0034 (8)0.0174 (8)0.0067 (7)
C180.0452 (8)0.0370 (7)0.0352 (7)0.0119 (6)0.0078 (6)0.0066 (6)
C190.0506 (9)0.0374 (8)0.0393 (8)0.0070 (7)0.0137 (7)0.0104 (6)
C200.0561 (10)0.0443 (9)0.0448 (9)0.0032 (7)0.0102 (7)0.0103 (7)
C210.0608 (11)0.0646 (12)0.0488 (10)0.0025 (9)0.0099 (8)0.0227 (9)
C220.0754 (13)0.0543 (11)0.0639 (12)0.0133 (9)0.0297 (10)0.0292 (9)
C230.0902 (15)0.0396 (9)0.0699 (13)0.0016 (9)0.0311 (12)0.0119 (9)
C240.0722 (12)0.0413 (9)0.0519 (10)0.0091 (8)0.0155 (9)0.0062 (8)
C250.112 (2)0.0837 (17)0.106 (2)0.0373 (15)0.0270 (17)0.0469 (16)
C260.0407 (8)0.0341 (7)0.0365 (7)0.0111 (6)0.0106 (6)0.0003 (6)
C270.0535 (9)0.0424 (8)0.0336 (7)0.0158 (7)0.0121 (7)0.0045 (6)
C280.0623 (11)0.0620 (11)0.0444 (9)0.0198 (9)0.0188 (8)0.0094 (8)
C290.0932 (16)0.0805 (14)0.0586 (11)0.0307 (12)0.0320 (11)0.0214 (10)
C300.1142 (19)0.0693 (13)0.0666 (13)0.0174 (13)0.0323 (13)0.0326 (11)
C310.0874 (14)0.0557 (11)0.0537 (11)0.0046 (10)0.0203 (10)0.0245 (9)
C320.0604 (10)0.0428 (8)0.0359 (8)0.0109 (7)0.0120 (7)0.0075 (7)
C330.0407 (8)0.0419 (8)0.0450 (8)0.0058 (6)0.0115 (7)0.0114 (7)
C340.0386 (7)0.0301 (7)0.0350 (7)0.0084 (6)0.0101 (6)0.0019 (6)
C350.0360 (7)0.0295 (7)0.0372 (7)0.0088 (5)0.0114 (6)0.0020 (6)
C360.0345 (7)0.0338 (7)0.0365 (7)0.0086 (6)0.0078 (6)0.0070 (6)
C370.0426 (8)0.0365 (7)0.0415 (8)0.0141 (6)0.0127 (6)0.0007 (6)
C380.0440 (8)0.0444 (8)0.0400 (8)0.0104 (7)0.0142 (7)0.0007 (7)
C390.0383 (8)0.0520 (9)0.0453 (8)0.0153 (7)0.0130 (7)0.0082 (7)
C400.0462 (8)0.0464 (9)0.0460 (9)0.0226 (7)0.0094 (7)0.0021 (7)
C410.0434 (8)0.0373 (8)0.0388 (8)0.0122 (6)0.0118 (6)0.0001 (6)
C420.0566 (10)0.0591 (11)0.0499 (10)0.0184 (8)0.0016 (8)0.0124 (8)
C430.0342 (7)0.0353 (7)0.0397 (7)0.0105 (6)0.0124 (6)0.0054 (6)
C440.0370 (7)0.0392 (8)0.0425 (8)0.0069 (6)0.0137 (6)0.0095 (6)
C450.0486 (9)0.0418 (8)0.0582 (10)0.0117 (7)0.0094 (8)0.0148 (7)
C460.0646 (11)0.0438 (9)0.0684 (12)0.0050 (8)0.0210 (9)0.0208 (8)
C470.0550 (10)0.0566 (11)0.0634 (11)0.0103 (8)0.0245 (9)0.0250 (9)
C480.0395 (9)0.0773 (13)0.0705 (12)0.0049 (9)0.0051 (8)0.0274 (10)
C490.0412 (8)0.0539 (10)0.0641 (11)0.0128 (7)0.0089 (8)0.0185 (8)
C500.0798 (15)0.0837 (16)0.1007 (18)0.0227 (12)0.0250 (13)0.0491 (14)
N10.0513 (8)0.0419 (7)0.0457 (7)0.0175 (6)0.0037 (6)0.0079 (6)
N20.0560 (9)0.0849 (12)0.0437 (8)0.0007 (8)0.0156 (7)0.0160 (8)
N30.0422 (7)0.0383 (7)0.0400 (7)0.0119 (5)0.0073 (5)0.0079 (5)
N40.0658 (10)0.0810 (12)0.0736 (11)0.0375 (9)0.0357 (9)0.0068 (9)
O10.0344 (5)0.0627 (7)0.0452 (6)0.0009 (5)0.0107 (5)0.0114 (5)
O20.0335 (5)0.0671 (7)0.0467 (6)0.0048 (5)0.0110 (5)0.0217 (6)
O30.0390 (6)0.0497 (6)0.0490 (6)0.0186 (5)0.0026 (5)0.0132 (5)
O40.0839 (11)0.0959 (12)0.0638 (9)0.0095 (9)0.0254 (8)0.0176 (9)
O50.1184 (14)0.1341 (16)0.0819 (11)0.0263 (12)0.0629 (11)0.0194 (11)
O60.0460 (6)0.0428 (6)0.0627 (7)0.0033 (5)0.0236 (5)0.0102 (5)
O70.0531 (7)0.0428 (6)0.0575 (7)0.0001 (5)0.0162 (5)0.0187 (5)
O80.0507 (6)0.0296 (5)0.0380 (5)0.0095 (4)0.0095 (5)0.0035 (4)
O90.0981 (12)0.1161 (13)0.0996 (12)0.0536 (11)0.0689 (10)0.0269 (10)
O100.161 (2)0.188 (2)0.1607 (19)0.1428 (19)0.1137 (17)0.0853 (17)
Geometric parameters (Å, º) top
C1—O11.2141 (17)C27—C321.395 (2)
C1—C21.468 (2)C27—C281.400 (2)
C1—C91.538 (2)C28—C291.378 (3)
C2—C71.396 (2)C28—H280.9300
C2—C31.399 (2)C29—C301.382 (3)
C3—C41.369 (2)C29—H290.9300
C3—H30.9300C30—C311.369 (3)
C4—C51.381 (3)C30—H300.9300
C4—H40.9300C31—C321.393 (2)
C5—C61.376 (3)C31—H310.9300
C5—H50.9300C32—O71.354 (2)
C6—C71.387 (2)C33—O71.4471 (18)
C6—H60.9300C33—C341.514 (2)
C7—O21.3649 (18)C33—C421.521 (2)
C8—O21.4495 (18)C33—H330.9754
C8—C171.513 (2)C34—O81.4636 (16)
C8—C91.518 (2)C34—C351.5288 (19)
C8—H80.9943C35—C431.514 (2)
C9—O31.4598 (17)C35—C361.5243 (19)
C9—C101.5353 (19)C35—H350.9800
C10—C181.5187 (19)C36—C411.3891 (19)
C10—C111.5199 (19)C36—C371.395 (2)
C10—H100.9800C37—C381.379 (2)
C11—C161.3895 (19)C37—H370.9300
C11—C121.392 (2)C38—C391.374 (2)
C12—C131.383 (2)C38—H380.9300
C12—H120.9300C39—C401.377 (2)
C13—C141.374 (2)C39—N41.466 (2)
C13—H130.9300C40—C411.381 (2)
C14—C151.379 (2)C40—H400.9300
C14—N21.474 (2)C41—H410.9300
C15—C161.385 (2)C42—H42A0.9600
C15—H150.9300C42—H42B0.9600
C16—H160.9300C42—H42C0.9600
C17—H17A0.9600C43—N31.2855 (18)
C17—H17B0.9600C43—C441.467 (2)
C17—H17C0.9600C44—C491.387 (2)
C18—N11.2833 (19)C44—C451.394 (2)
C18—C191.462 (2)C45—C461.378 (2)
C19—C201.387 (2)C45—H450.9300
C19—C241.400 (2)C46—C471.380 (3)
C20—C211.385 (2)C46—H460.9300
C20—H200.9300C47—C481.388 (3)
C21—C221.380 (3)C47—C501.509 (3)
C21—H210.9300C48—C491.378 (3)
C22—C231.380 (3)C48—H480.9300
C22—C251.516 (3)C49—H490.9300
C23—C241.371 (3)C50—H50A0.9600
C23—H230.9300C50—H50B0.9600
C24—H240.9300C50—H50C0.9600
C25—H25A0.9600N1—O31.4245 (17)
C25—H25B0.9600N2—O51.222 (2)
C25—H25C0.9600N2—O41.222 (2)
C26—O61.2174 (17)N3—O81.4389 (16)
C26—C271.466 (2)N4—O101.193 (2)
C26—C341.532 (2)N4—O91.205 (2)
O1—C1—C2123.70 (13)C29—C28—C27120.12 (19)
O1—C1—C9121.97 (13)C29—C28—H28119.9
C2—C1—C9114.30 (12)C27—C28—H28119.9
C7—C2—C3118.94 (14)C28—C29—C30119.80 (19)
C7—C2—C1119.87 (13)C28—C29—H29120.1
C3—C2—C1121.19 (13)C30—C29—H29120.1
C4—C3—C2120.46 (16)C31—C30—C29121.33 (18)
C4—C3—H3119.8C31—C30—H30119.3
C2—C3—H3119.8C29—C30—H30119.3
C3—C4—C5119.97 (17)C30—C31—C32119.34 (19)
C3—C4—H4120.0C30—C31—H31120.3
C5—C4—H4120.0C32—C31—H31120.3
C6—C5—C4120.87 (17)O7—C32—C31116.44 (16)
C6—C5—H5119.6O7—C32—C27123.28 (14)
C4—C5—H5119.6C31—C32—C27120.28 (17)
C5—C6—C7119.52 (16)O7—C33—C34111.37 (12)
C5—C6—H6120.2O7—C33—C42109.51 (13)
C7—C6—H6120.2C34—C33—C42111.25 (13)
O2—C7—C6117.00 (14)O7—C33—H33103.8
O2—C7—C2122.76 (13)C34—C33—H33109.9
C6—C7—C2120.23 (15)C42—C33—H33110.9
O2—C8—C17110.12 (13)O8—C34—C33110.83 (11)
O2—C8—C9109.52 (12)O8—C34—C35103.02 (11)
C17—C8—C9112.49 (13)C33—C34—C35116.73 (12)
O2—C8—H8103.9O8—C34—C26102.43 (10)
C17—C8—H8110.1C33—C34—C26110.00 (12)
C9—C8—H8110.3C35—C34—C26112.65 (11)
O3—C9—C8108.26 (11)C43—C35—C36110.13 (11)
O3—C9—C10103.38 (11)C43—C35—C3498.22 (11)
C8—C9—C10118.42 (12)C36—C35—C34115.46 (11)
O3—C9—C1104.48 (11)C43—C35—H35110.8
C8—C9—C1109.41 (12)C36—C35—H35110.8
C10—C9—C1111.76 (11)C34—C35—H35110.8
C18—C10—C11113.03 (11)C41—C36—C37119.08 (13)
C18—C10—C997.56 (11)C41—C36—C35120.38 (12)
C11—C10—C9114.07 (11)C37—C36—C35120.50 (12)
C18—C10—H10110.5C38—C37—C36120.79 (13)
C11—C10—H10110.5C38—C37—H37119.6
C9—C10—H10110.5C36—C37—H37119.6
C16—C11—C12118.93 (13)C39—C38—C37118.32 (14)
C16—C11—C10119.63 (12)C39—C38—H38120.8
C12—C11—C10121.31 (12)C37—C38—H38120.8
C13—C12—C11120.70 (14)C38—C39—C40122.75 (14)
C13—C12—H12119.7C38—C39—N4118.18 (14)
C11—C12—H12119.7C40—C39—N4119.06 (14)
C14—C13—C12118.80 (14)C39—C40—C41118.30 (14)
C14—C13—H13120.6C39—C40—H40120.9
C12—C13—H13120.6C41—C40—H40120.9
C13—C14—C15122.21 (14)C40—C41—C36120.76 (14)
C13—C14—N2118.79 (15)C40—C41—H41119.6
C15—C14—N2119.01 (16)C36—C41—H41119.6
C14—C15—C16118.38 (14)C33—C42—H42A109.5
C14—C15—H15120.8C33—C42—H42B109.5
C16—C15—H15120.8H42A—C42—H42B109.5
C15—C16—C11120.93 (14)C33—C42—H42C109.5
C15—C16—H16119.5H42A—C42—H42C109.5
C11—C16—H16119.5H42B—C42—H42C109.5
C8—C17—H17A109.5N3—C43—C44121.72 (13)
C8—C17—H17B109.5N3—C43—C35113.51 (13)
H17A—C17—H17B109.5C44—C43—C35124.77 (12)
C8—C17—H17C109.5C49—C44—C45118.06 (15)
H17A—C17—H17C109.5C49—C44—C43120.57 (14)
H17B—C17—H17C109.5C45—C44—C43121.32 (14)
N1—C18—C19121.23 (13)C46—C45—C44120.82 (16)
N1—C18—C10113.52 (13)C46—C45—H45119.6
C19—C18—C10125.20 (13)C44—C45—H45119.6
C20—C19—C24118.06 (15)C45—C46—C47121.32 (17)
C20—C19—C18121.30 (14)C45—C46—H46119.3
C24—C19—C18120.53 (15)C47—C46—H46119.3
C21—C20—C19120.48 (16)C46—C47—C48117.63 (16)
C21—C20—H20119.8C46—C47—C50121.2 (2)
C19—C20—H20119.8C48—C47—C50121.2 (2)
C22—C21—C20121.21 (18)C49—C48—C47121.71 (17)
C22—C21—H21119.4C49—C48—H48119.1
C20—C21—H21119.4C47—C48—H48119.1
C23—C22—C21118.18 (17)C48—C49—C44120.43 (17)
C23—C22—C25121.2 (2)C48—C49—H49119.8
C21—C22—C25120.6 (2)C44—C49—H49119.8
C24—C23—C22121.48 (18)C47—C50—H50A109.5
C24—C23—H23119.3C47—C50—H50B109.5
C22—C23—H23119.3H50A—C50—H50B109.5
C23—C24—C19120.58 (18)C47—C50—H50C109.5
C23—C24—H24119.7H50A—C50—H50C109.5
C19—C24—H24119.7H50B—C50—H50C109.5
C22—C25—H25A109.5C18—N1—O3108.80 (12)
C22—C25—H25B109.5O5—N2—O4123.94 (18)
H25A—C25—H25B109.5O5—N2—C14117.70 (18)
C22—C25—H25C109.5O4—N2—C14118.34 (17)
H25A—C25—H25C109.5C43—N3—O8108.27 (11)
H25B—C25—H25C109.5O10—N4—O9122.85 (17)
O6—C26—C27123.78 (14)O10—N4—C39118.15 (16)
O6—C26—C34121.71 (13)O9—N4—C39118.99 (15)
C27—C26—C34114.29 (12)C7—O2—C8116.92 (11)
C32—C27—C28119.08 (15)N1—O3—C9106.63 (10)
C32—C27—C26119.90 (14)C32—O7—C33117.78 (12)
C28—C27—C26120.99 (15)N3—O8—C34106.52 (9)
Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the C44–C49 and C11–C16 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C10—H10···O1i0.982.403.3466 (17)162
C35—H35···O6ii0.982.253.2072 (17)164
C16—H16···N3i0.932.563.3091 (19)138
C23—H23···Cg10.932.953.581 (2)127
C30—H30···Cg2iii0.933.003.758 (2)140
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+2, z; (iii) x, y, z1.
 

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

References

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