3-Benzyl-3-hy­droxy-2-phenyl-3H-indole 1-oxide

Rizzoli, C.; Astolfi, P.; Marku, E.; Greci, L.

doi:10.1107/S1600536810026176

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages o1986-o1987

https://doi.org/10.1107/S1600536810026176

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3-Benzyl-3-hydroxy-2-phenyl-3H-indole 1-oxide

Corrado Rizzoli,^a ^* Paola Astolfi,^b Elda Marku ^c and Lucedio Greci ^b

^aDipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universitá degli Studi di Parma, Viale G. P. Usberti 17/A, I-43100 Parma, Italy, ^bDipartimento ISAC, Universitá Politecnica delle Marche, Via Brecce Bianche, I-60131 Ancona, Italy, and ^cFakulteti i Shkencave të Natyrës, Departamenti i Kimise, Universiteti i Tiranes, Bulevardi "Zogu I", Tirana, Albania
^*Correspondence e-mail: corrado.rizzoli@unipr.it

(Received 18 June 2010; accepted 2 July 2010; online 10 July 2010)

The asymmetric unit of the title compound, C₂₁H₁₇NO₂, contains two crystallographically independent molecules of similar geometry. The indole ring systems form dihedral angles of 8.30 (5) and 9.58 (5)° with the attached phenyl rings, and 56.96 (5) and 57.68 (5)° with the aromatic rings of the respective benzyl groups. The molecular conformations are stabilized by intramolecular C—H⋯O hydrogen bonds. In the crystal structure, centrosymmetrically related pairs of molecules are linked into dimers through pairs of intermolecular O—H⋯O hydrogen bonds, generating 12-membered rings with R₂²(12) motifs. The dimers are further linked into a three-dimensional network by C—H⋯O interactions.

Related literature

For the use of nitrones in the spin-trapping technique and in organic synthesis, see: Janzen (1971 ); Zubarev (1979 ); Balasubramanian (1985 ); Pisaneschi et al. (2002 ); Jones et al. (2000 ); Bernotas et al. (1999 ); Ali & Wazeer (1988 ); Merino (2005 ); Chiacchio et al. (2006 ); Revuelta et al. (2008 ); Astolfi et al. (2003 ); Greci et al. (2001 ); Tommasi et al. (1999 ); Bruni et al. (1998 ). For a related structure, see: Yamada et al. (2003 ). For graph-set notation, see: Bernstein et al. (1995 ). For the preparation of 2-phenylisatogen, see: Bond & Hooper (1974 ).

Experimental

Crystal data

C₂₁H₁₇NO₂
M_r = 315.36
Triclinic, $[P \overline 1]$
a = 11.635 (2) Å
b = 11.971 (2) Å
c = 12.063 (3) Å
α = 84.773 (5)°
β = 88.882 (6)°
γ = 88.635 (6)°
V = 1672.5 (6) Å³
Z = 4
Cu Kα radiation
μ = 0.64 mm⁻¹
T = 294 K
0.26 × 0.24 × 0.18 mm

Data collection

Siemens AED diffractometer
6045 measured reflections
6045 independent reflections
5126 reflections with I > 2σ(I)
3 standard reflections every 100 reflections intensity decay: 0.02%

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.162
S = 1.05
6045 reflections
442 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1	0.93	2.19	2.817 (3)	124
C14—H14⋯O2	0.93	2.34	2.996 (2)	127
C31—H31⋯O4	0.93	2.47	3.107 (2)	126
C35—H35⋯O3	0.93	2.37	2.989 (3)	124
C11—H11⋯O4	0.93	2.48	3.404 (3)	175
O2—H2O⋯O1ⁱ	0.90 (2)	1.88 (2)	2.769 (2)	174 (2)
O4—H4O⋯O3ⁱⁱ	0.98 (2)	1.82 (2)	2.793 (2)	178 (2)
C24—H24⋯O1ⁱⁱ	0.93	2.48	3.310 (3)	148
C3—H3⋯O3ⁱⁱⁱ	0.93	2.46	3.327 (3)	154
C34—H34⋯O2^iv	0.93	2.49	3.415 (3)	176
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y+1, -z+1; (iii) -x+1, -y+1, -z+1; (iv) x, y+1, z.

Data collection: AED (Belletti et al., 1993 ); cell refinement: AED; data reduction: AED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and SCHAKAL97 (Keller, 1997 ); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810026176/ez2222sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810026176/ez2222Isup2.hkl

checkCIF report

Comment top

Many types of cyclic and acyclic nitrones, such as N-tert-butyl-α-phenylnitrone and 5,5-dimethyl-pyrroline-N-oxide, have been used frequently in the spin trapping technique since its inception (Janzen, 1971; Zubarev, 1979). Nitrones are also used in the syntheses of isoxazolidines through 1,3-dipolar cycloaddition with a series of dipolarophiles (Balasubramanian, 1985). Although the most used nitrones in cyclization reactions are acyclic, several papers have appeared in the last two decades describing cycloaddition reactions with cyclic nitrones (Pisaneschi et al., 2002; Jones et al., 2000; Bernotas et al., 1999; Ali & Wazeer, 1988). Significant advances have been described in the use of nitrones derived from sugars and aminoacids for the synthesis of interesting biological compounds including aminoacids, amino alcohols and nucleoside analogs (Merino, 2005). On this basis, enantioselective syntheses of homo-carboxylic-2'-oxo-3'-azo-nucleosides were achieved by cycloaddition reactions of N-glycosyl nitrones with allylic nucleobases (Chiacchio et al., 2006). Moreover, a series of 3-spirocyclopropane dihydro- and tetrahydropyrid-4-ones were synthesized by nitrone cycloaddition to 1,1'-bicyclopropylidene (Revuelta et al., 2008). The title compound was synthesized in order to continue our studies on 1,3-dipolar cycloaddition with different dipolarophiles, with particular focus on the catalytic activity of metal cations such as cobalt(II), calcium(II), zinc(II) and nickel(II) (Astolfi et al., 2003; Greci et al., 2001; Tommasi et al., 1999; Bruni et al., 1998).

The asymmetric unit of the title compound (Fig. 1) contains two crystallographically independent molecules with similar geometry. The indole ring systems including the N1 and N2 atoms form dihedral angles of 8.30 (5) and 9.58 (5)°, respectively, with the attached phenyl rings, and 56.96 (5) and 57.68 (5)°, respectively, with the aromatic ring of the benzyl groups. The N–O (mean value 1.304 (2) Å) and C–O (mean value 1.420 (2) Å) bond lengths are comparable with those found in 3-hydroxy-2,3-dimethyl-3H-indole N-oxide [1.3093 (17) and 1.418 (2) Å respectively; Yamada et al., 2003]. The molecular conformations are stabilized by intramolecular C—H···O hydrogen bonds (Table 1). In the crystal packing, centrosymmetrically related molecules are linked into dimers (Fig. 2) through intermolecular O—H···O hydrogen bonds resulting in twelve-membered rings with R₂²(12) motifs (Bernstein et al., 1995). Within the dimers, the centroid-to-centroid separations between the opposite C1–C6/C9ⁱ–C14ⁱ and C22–C27/C30ⁱⁱ–C35ⁱⁱ aromatic rings are 3.893 (2) and 3.920 (2) Å, respectively (symmetry codes: (i) 1 - x. -y, 1 - z; (ii) -x, 1 - y, 1 - z). The dimers are further connected by C—H···O hydrogen bonds into a three-dimensional network (Fig. 3).

Related literature top

For the use of nitrones in the spin trapping technique and organic synthesis, see: Janzen (1971); Zubarev (1979); Balasubramanian (1985); Pisaneschi et al. (2002); Jones et al. (2000); Bernotas et al. (1999); Ali & Wazeer (1988); Merino (2005); Chiacchio et al. (2006); Revuelta et al. (2008); Astolfi et al. (2003); Greci et al. (2001); Tommasi et al. (1999); Bruni et al. (1998). For a related structure, see: Yamada et al. (2003). For graph-set notation, see: Bernstein et al. (1995). For the preparation of 2-phenylisatogen, see: Bond & Hooper (1974).

Experimental top

A solution of benzylmagnesium bromide (20 mmoles in 30 ml of dried THF, obtained from 0.46 g of magnesium and 2.54 g of benzyl chloride in a current of argon) was added to a solution of 2-phenylisatogen (10 mmoles, 2.23 g in 50 ml of dried THF; Bond & Hooper, 1974), at room temperature and under magnetic stirring. After the addition, the reaction mixture was kept at room temperature for 2 h, then it was poured into 10% aqueous NH₄Cl (100 ml) solution. The mixture was extracted with chloroform (2 × 50 ml) and the separated organic layer was dried on Na₂SO₄ and evaporated to dryness. The residue was treated with diethyl ether to give a white solid corresponding to the expected nitrone, which was separated by filtration under vacuum and washed with diethyl ether (obtained 2.04 g, yield 65%, m.p. 200–201 °C. FT—IR, ν, cm^-1, 3143 (OH). 1601 (O<-N=C<), 1519. ¹H NMR, δ, CDCl₃: 3.36 (2H, pseudo-q, –CH₂Ph, distereotopic H atoms), 6.41 (2H, d, arom.), 6.81–7.07 (5H,m, arom.). 7.13–7.55 (3H, m, arom.), 7.3–7.4 (2H. m, arom.), 8.6 (2H, pseudo-q, arom). Mass. calcd. for C₂₁H₁₇NO₂, 315.39; found: m/z (%): 315 (M+, 5.7), 224 (34.4), 208 (58.6), 179 (100). The melting point was measured on a Mitamura Riken Kogyo mp D electrochemical apparartus and was not corrected. FT—IR spectrum was recorded in KBr with a Perkin-Elmer MGX1 spectrophotometer equipped with Spectra Tech. ¹H NMR spectrum was recorded on a Gemini Varian 200 MHz. Mass spectrum was recorded on a Carlo Erba QMD 1000 mass spectrometer in positive electron impact (EI) mode. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature.

Structure description top

Computing details top

Data collection: AED (Belletti et al., 1993); cell refinement: AED (Belletti et al., 1993); data reduction: AED (Belletti et al., 1993); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and SCHAKAL97 (Keller, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PARST95 (Nardelli, 1995).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. View of the centrosymmetric dimers of the title formed through intermolecular O—H···O hydrogen bonds (dashed lines). Symmetry codes: (i) 1 - x, -y, 1 - z; (ii) -x, 1 - y, 1 - z.
	Fig. 3. Crystal packing of the title compound viewed approximately along the c axis. Intra- and intermolecular hydrogen bonds are shown as dashed lines.

3-Benzyl-3-hydroxy-2-phenyl-3H-indole 1-oxide top

Crystal data top

C₂₁H₁₇NO₂	Z = 4
M_r = 315.36	F(000) = 664
Triclinic, P1	D_x = 1.252 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 11.635 (2) Å	Cell parameters from 48 reflections
b = 11.971 (2) Å	θ = 16.4–48.4°
c = 12.063 (3) Å	µ = 0.64 mm⁻¹
α = 84.773 (5)°	T = 294 K
β = 88.882 (6)°	Block, pale yellow
γ = 88.635 (6)°	0.26 × 0.24 × 0.18 mm
V = 1672.5 (6) Å³

Data collection top

Siemens AED diffractometer	R_int = 0.000
Radiation source: fine-focus sealed tube	θ_max = 68.0°, θ_min = 3.7°
Graphite monochromator	h = −9→13
θ/2θ scans	k = −14→10
6045 measured reflections	l = −14→14
6045 independent reflections	3 standard reflections every 100 reflections
5126 reflections with I > 2σ(I)	intensity decay: 0.02%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.162	w = 1/[σ²(F_o²) + (0.0996P)² + 0.2753P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
6045 reflections	Δρ_max = 0.22 e Å⁻³
442 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0034 (5)

Crystal data top

C₂₁H₁₇NO₂	γ = 88.635 (6)°
M_r = 315.36	V = 1672.5 (6) Å³
Triclinic, P1	Z = 4
a = 11.635 (2) Å	Cu Kα radiation
b = 11.971 (2) Å	µ = 0.64 mm⁻¹
c = 12.063 (3) Å	T = 294 K
α = 84.773 (5)°	0.26 × 0.24 × 0.18 mm
β = 88.882 (6)°

Data collection top

Siemens AED diffractometer	R_int = 0.000
6045 measured reflections	3 standard reflections every 100 reflections
6045 independent reflections	intensity decay: 0.02%
5126 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.22 e Å⁻³
6045 reflections	Δρ_min = −0.24 e Å⁻³
442 parameters

Special details top

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
O1	0.46993 (13)	0.19070 (10)	0.43394 (10)	0.0705 (4)
O2	0.54286 (11)	−0.16774 (9)	0.33565 (11)	0.0571 (3)
H2O	0.534 (2)	−0.172 (2)	0.410 (2)	0.088 (7)*
O3	0.03259 (14)	0.68855 (10)	0.44282 (11)	0.0754 (4)
O4	−0.00423 (11)	0.33865 (9)	0.32592 (12)	0.0628 (3)
H4O	−0.013 (2)	0.328 (2)	0.407 (2)	0.097 (8)*
N1	0.52177 (13)	0.10469 (10)	0.39161 (11)	0.0549 (4)
N2	−0.00636 (14)	0.60551 (10)	0.39494 (11)	0.0565 (4)
C1	0.64142 (16)	0.08049 (13)	0.40690 (13)	0.0555 (4)
C2	0.7148 (2)	0.14275 (16)	0.45982 (15)	0.0696 (5)
H2	0.6920	0.2085	0.4904	0.084*
C3	0.8267 (2)	0.10075 (19)	0.46471 (17)	0.0784 (6)
H3	0.8815	0.1401	0.4995	0.094*
C4	0.86049 (19)	0.0018 (2)	0.41950 (17)	0.0772 (6)
H4	0.9363	−0.0239	0.4261	0.093*
C5	0.78426 (17)	−0.05788 (16)	0.36581 (16)	0.0654 (5)
H5	0.8061	−0.1236	0.3348	0.079*
C6	0.67341 (15)	−0.01605 (13)	0.35970 (13)	0.0541 (4)
C7	0.57370 (14)	−0.05489 (12)	0.30169 (13)	0.0511 (4)
C8	0.47831 (15)	0.02996 (12)	0.33305 (12)	0.0499 (4)
C9	0.36031 (15)	0.03120 (13)	0.30073 (13)	0.0537 (4)
C10	0.28318 (18)	0.12083 (16)	0.31429 (16)	0.0669 (5)
H10	0.3074	0.1834	0.3471	0.080*
C11	0.1726 (2)	0.1165 (2)	0.2795 (2)	0.0818 (6)
H11	0.1214	0.1759	0.2885	0.098*
C12	0.1379 (2)	0.0260 (2)	0.23201 (19)	0.0826 (6)
H12	0.0623	0.0235	0.2087	0.099*
C13	0.21224 (19)	−0.06358 (19)	0.21721 (19)	0.0772 (6)
H13	0.1866	−0.1253	0.1839	0.093*
C14	0.32193 (17)	−0.06139 (15)	0.25114 (16)	0.0652 (5)
H14	0.3719	−0.1217	0.2414	0.078*
C15	0.60383 (16)	−0.04876 (14)	0.17393 (14)	0.0588 (4)
H151	0.6698	−0.0979	0.1630	0.071*
H152	0.5396	−0.0773	0.1357	0.071*
C16	0.63050 (16)	0.06764 (15)	0.12009 (13)	0.0592 (4)
C17	0.5463 (2)	0.13279 (18)	0.06942 (16)	0.0734 (5)
H17	0.4716	0.1067	0.0693	0.088*
C18	0.5709 (3)	0.2378 (2)	0.0179 (2)	0.0979 (8)
H18	0.5122	0.2798	−0.0183	0.117*
C19	0.6775 (3)	0.2818 (2)	0.0181 (2)	0.1036 (9)
H19	0.6915	0.3532	−0.0160	0.124*
C20	0.7618 (3)	0.2195 (2)	0.0687 (2)	0.1025 (9)
H20	0.8356	0.2475	0.0706	0.123*
C21	0.7385 (2)	0.1121 (2)	0.11877 (17)	0.0803 (6)
H21	0.7982	0.0693	0.1523	0.096*
C22	−0.12773 (16)	0.58215 (13)	0.40787 (13)	0.0560 (4)
C23	−0.2149 (2)	0.63966 (15)	0.46520 (15)	0.0696 (5)
H23	−0.1988	0.7036	0.5000	0.084*
C24	−0.3243 (2)	0.59772 (18)	0.46771 (17)	0.0768 (6)
H24	−0.3838	0.6331	0.5045	0.092*
C25	−0.34455 (18)	0.5030 (2)	0.41531 (17)	0.0753 (6)
H25	−0.4183	0.4744	0.4180	0.090*
C26	−0.25587 (17)	0.44760 (17)	0.35706 (16)	0.0674 (5)
H26	−0.2717	0.3839	0.3219	0.081*
C27	−0.14607 (15)	0.48919 (14)	0.35319 (13)	0.0555 (4)
C28	−0.03287 (15)	0.45255 (13)	0.29552 (14)	0.0534 (4)
C29	0.05241 (15)	0.53448 (12)	0.33312 (13)	0.0520 (4)
C30	0.17631 (16)	0.53540 (13)	0.30252 (13)	0.0552 (4)
C31	0.22917 (17)	0.44455 (16)	0.25119 (16)	0.0667 (5)
H31	0.1845	0.3840	0.2378	0.080*
C32	0.34565 (19)	0.4425 (2)	0.22003 (19)	0.0775 (6)
H32	0.3769	0.3814	0.1865	0.093*
C33	0.41384 (19)	0.5308 (2)	0.23898 (19)	0.0807 (6)
H33	0.4914	0.5306	0.2188	0.097*
C34	0.3640 (2)	0.62003 (19)	0.28893 (19)	0.0802 (6)
H34	0.4097	0.6801	0.3017	0.096*
C35	0.24684 (18)	0.62393 (15)	0.32136 (16)	0.0667 (5)
H35	0.2169	0.6853	0.3552	0.080*
C36	−0.03763 (17)	0.46461 (16)	0.16720 (15)	0.0658 (5)
H361	0.0389	0.4511	0.1372	0.079*
H362	−0.0872	0.4075	0.1436	0.079*
C37	−0.08058 (18)	0.5768 (2)	0.11951 (14)	0.0698 (5)
C38	−0.1895 (2)	0.5879 (3)	0.0830 (2)	0.1048 (9)
H38	−0.2381	0.5270	0.0890	0.126*
C39	−0.2281 (3)	0.6934 (4)	0.0360 (3)	0.1300 (13)
H39	−0.3022	0.7011	0.0083	0.156*
C40	−0.1597 (4)	0.7850 (3)	0.0297 (2)	0.1215 (12)
H40	−0.1878	0.8545	0.0001	0.146*
C41	−0.0534 (3)	0.7740 (3)	0.0660 (2)	0.1153 (10)
H41	−0.0058	0.8356	0.0616	0.138*
C42	−0.0136 (2)	0.6711 (2)	0.11025 (19)	0.0886 (7)
H42	0.0616	0.6644	0.1351	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1094 (11)	0.0420 (6)	0.0622 (7)	0.0093 (6)	−0.0094 (7)	−0.0169 (5)
O2	0.0737 (8)	0.0372 (5)	0.0614 (7)	−0.0032 (5)	−0.0124 (6)	−0.0074 (5)
O3	0.1173 (11)	0.0449 (6)	0.0674 (8)	−0.0154 (7)	−0.0035 (7)	−0.0198 (6)
O4	0.0762 (8)	0.0421 (6)	0.0721 (8)	−0.0051 (5)	0.0043 (6)	−0.0153 (5)
N1	0.0815 (10)	0.0375 (6)	0.0462 (7)	−0.0018 (6)	−0.0049 (6)	−0.0057 (5)
N2	0.0861 (10)	0.0369 (6)	0.0472 (7)	−0.0038 (6)	−0.0050 (7)	−0.0061 (5)
C1	0.0762 (11)	0.0465 (8)	0.0440 (8)	−0.0124 (8)	−0.0081 (7)	−0.0009 (6)
C2	0.0989 (15)	0.0541 (10)	0.0573 (10)	−0.0246 (10)	−0.0130 (10)	−0.0049 (8)
C3	0.0884 (15)	0.0805 (14)	0.0672 (12)	−0.0354 (12)	−0.0210 (10)	0.0015 (10)
C4	0.0696 (12)	0.0928 (15)	0.0682 (12)	−0.0163 (11)	−0.0189 (9)	0.0065 (11)
C5	0.0699 (11)	0.0632 (10)	0.0631 (10)	−0.0044 (9)	−0.0128 (9)	−0.0018 (8)
C6	0.0659 (10)	0.0487 (8)	0.0481 (8)	−0.0080 (7)	−0.0076 (7)	−0.0033 (6)
C7	0.0633 (10)	0.0385 (7)	0.0526 (9)	−0.0030 (7)	−0.0087 (7)	−0.0076 (6)
C8	0.0681 (10)	0.0379 (7)	0.0439 (8)	−0.0024 (7)	−0.0035 (7)	−0.0044 (6)
C9	0.0639 (10)	0.0481 (8)	0.0477 (8)	0.0011 (7)	−0.0040 (7)	0.0022 (6)
C10	0.0798 (13)	0.0537 (10)	0.0663 (11)	0.0101 (9)	−0.0030 (9)	−0.0034 (8)
C11	0.0777 (14)	0.0766 (14)	0.0881 (15)	0.0244 (11)	−0.0061 (11)	0.0034 (11)
C12	0.0699 (13)	0.0929 (16)	0.0826 (14)	0.0056 (11)	−0.0164 (11)	0.0074 (12)
C13	0.0748 (13)	0.0748 (13)	0.0827 (14)	−0.0044 (10)	−0.0230 (11)	−0.0054 (10)
C14	0.0683 (11)	0.0548 (10)	0.0729 (11)	0.0040 (8)	−0.0137 (9)	−0.0072 (8)
C15	0.0707 (11)	0.0566 (9)	0.0514 (9)	−0.0022 (8)	−0.0059 (8)	−0.0162 (7)
C16	0.0731 (11)	0.0647 (10)	0.0410 (8)	−0.0062 (8)	−0.0036 (7)	−0.0099 (7)
C17	0.0818 (13)	0.0790 (13)	0.0582 (10)	−0.0040 (10)	−0.0081 (9)	0.0018 (9)
C18	0.120 (2)	0.0863 (16)	0.0831 (16)	0.0026 (15)	−0.0070 (14)	0.0172 (13)
C19	0.150 (3)	0.0783 (15)	0.0802 (16)	−0.0247 (17)	−0.0084 (16)	0.0105 (12)
C20	0.117 (2)	0.112 (2)	0.0792 (15)	−0.0545 (17)	−0.0068 (14)	0.0015 (14)
C21	0.0802 (14)	0.0930 (15)	0.0670 (12)	−0.0187 (12)	−0.0094 (10)	0.0032 (11)
C22	0.0791 (11)	0.0433 (8)	0.0445 (8)	0.0054 (7)	−0.0003 (7)	0.0000 (6)
C23	0.1010 (16)	0.0503 (9)	0.0556 (10)	0.0192 (10)	0.0048 (10)	−0.0009 (7)
C24	0.0853 (14)	0.0756 (13)	0.0647 (11)	0.0298 (11)	0.0087 (10)	0.0088 (10)
C25	0.0662 (12)	0.0928 (15)	0.0640 (11)	0.0098 (10)	−0.0006 (9)	0.0066 (10)
C26	0.0694 (11)	0.0719 (12)	0.0611 (10)	−0.0019 (9)	−0.0027 (9)	−0.0058 (9)
C27	0.0680 (10)	0.0522 (9)	0.0464 (8)	0.0010 (7)	−0.0018 (7)	−0.0057 (7)
C28	0.0637 (10)	0.0451 (8)	0.0529 (9)	−0.0041 (7)	−0.0012 (7)	−0.0121 (7)
C29	0.0722 (10)	0.0395 (7)	0.0446 (8)	−0.0036 (7)	−0.0050 (7)	−0.0048 (6)
C30	0.0697 (11)	0.0474 (8)	0.0483 (8)	−0.0096 (7)	−0.0100 (7)	0.0013 (7)
C31	0.0690 (11)	0.0613 (10)	0.0711 (11)	−0.0095 (9)	−0.0002 (9)	−0.0101 (9)
C32	0.0707 (12)	0.0822 (14)	0.0799 (13)	−0.0007 (10)	−0.0004 (10)	−0.0089 (11)
C33	0.0653 (12)	0.0951 (16)	0.0788 (13)	−0.0150 (11)	−0.0116 (10)	0.0137 (12)
C34	0.0828 (14)	0.0735 (13)	0.0830 (14)	−0.0281 (11)	−0.0235 (11)	0.0119 (11)
C35	0.0826 (13)	0.0528 (9)	0.0647 (11)	−0.0149 (9)	−0.0196 (9)	0.0027 (8)
C36	0.0715 (11)	0.0758 (12)	0.0534 (10)	−0.0076 (9)	−0.0023 (8)	−0.0229 (9)
C37	0.0718 (12)	0.0986 (15)	0.0402 (8)	0.0051 (10)	−0.0028 (8)	−0.0143 (9)
C38	0.0843 (16)	0.148 (3)	0.0839 (16)	0.0134 (16)	−0.0179 (13)	−0.0224 (16)
C39	0.101 (2)	0.193 (4)	0.095 (2)	0.056 (3)	−0.0255 (17)	−0.017 (2)
C40	0.139 (3)	0.143 (3)	0.0747 (16)	0.051 (2)	0.0073 (18)	0.0141 (18)
C41	0.138 (3)	0.109 (2)	0.0904 (18)	0.0069 (19)	−0.0045 (17)	0.0307 (16)
C42	0.0984 (17)	0.0911 (16)	0.0722 (13)	−0.0070 (13)	−0.0114 (12)	0.0182 (11)

Geometric parameters (Å, º) top

O1—N1	1.3186 (18)	C19—C20	1.341 (4)
O2—C7	1.4276 (18)	C19—H19	0.9300
O2—H2O	0.90 (3)	C20—C21	1.400 (3)
O3—N2	1.2898 (17)	C20—H20	0.9300
O4—C28	1.413 (2)	C21—H21	0.9300
O4—H4O	0.98 (3)	C22—C27	1.367 (2)
N1—C8	1.306 (2)	C22—C23	1.417 (3)
N1—C1	1.427 (2)	C23—C24	1.378 (3)
N2—C29	1.347 (2)	C23—H23	0.9300
N2—C22	1.449 (2)	C24—C25	1.375 (3)
C1—C2	1.353 (2)	C24—H24	0.9300
C1—C6	1.375 (2)	C25—C26	1.422 (3)
C2—C3	1.385 (3)	C25—H25	0.9300
C2—H2	0.9300	C26—C27	1.381 (3)
C3—C4	1.394 (3)	C26—H26	0.9300
C3—H3	0.9300	C27—C28	1.550 (2)
C4—C5	1.361 (3)	C28—C29	1.516 (2)
C4—H4	0.9300	C28—C36	1.543 (2)
C5—C6	1.373 (3)	C29—C30	1.481 (3)
C5—H5	0.9300	C30—C35	1.393 (2)
C6—C7	1.473 (2)	C30—C31	1.421 (3)
C7—C8	1.551 (2)	C31—C32	1.400 (3)
C7—C15	1.569 (2)	C31—H31	0.9300
C8—C9	1.434 (2)	C32—C33	1.375 (3)
C9—C14	1.393 (2)	C32—H32	0.9300
C9—C10	1.401 (2)	C33—C34	1.383 (3)
C10—C11	1.365 (3)	C33—H33	0.9300
C10—H10	0.9300	C34—C35	1.412 (3)
C11—C12	1.344 (3)	C34—H34	0.9300
C11—H11	0.9300	C35—H35	0.9300
C12—C13	1.384 (3)	C36—C37	1.491 (3)
C12—H12	0.9300	C36—H361	0.9700
C13—C14	1.349 (3)	C36—H362	0.9700
C13—H13	0.9300	C37—C38	1.350 (3)
C14—H14	0.9300	C37—C42	1.382 (3)
C15—C16	1.519 (2)	C38—C39	1.403 (5)
C15—H151	0.9700	C38—H38	0.9300
C15—H152	0.9700	C39—C40	1.366 (5)
C16—C17	1.357 (3)	C39—H39	0.9300
C16—C21	1.375 (3)	C40—C41	1.319 (5)
C17—C18	1.384 (3)	C40—H40	0.9300
C17—H17	0.9300	C41—C42	1.371 (4)
C18—C19	1.359 (4)	C41—H41	0.9300
C18—H18	0.9300	C42—H42	0.9300

C7—O2—H2O	106.0 (15)	C21—C20—H20	120.1
C28—O4—H4O	106.1 (14)	C16—C21—C20	122.4 (2)
C8—N1—O1	128.88 (16)	C16—C21—H21	118.8
C8—N1—C1	109.39 (14)	C20—C21—H21	118.8
O1—N1—C1	121.73 (14)	C27—C22—C23	124.02 (19)
O3—N2—C29	128.03 (17)	C27—C22—N2	106.63 (15)
O3—N2—C22	118.08 (14)	C23—C22—N2	129.34 (16)
C29—N2—C22	113.89 (13)	C24—C23—C22	117.77 (19)
C2—C1—C6	123.80 (19)	C24—C23—H23	121.1
C2—C1—N1	125.66 (18)	C22—C23—H23	121.1
C6—C1—N1	110.54 (14)	C25—C24—C23	119.37 (19)
C1—C2—C3	114.6 (2)	C25—C24—H24	120.3
C1—C2—H2	122.7	C23—C24—H24	120.3
C3—C2—H2	122.7	C24—C25—C26	121.8 (2)
C2—C3—C4	122.57 (18)	C24—C25—H25	119.1
C2—C3—H3	118.7	C26—C25—H25	119.1
C4—C3—H3	118.7	C27—C26—C25	119.44 (19)
C5—C4—C3	121.1 (2)	C27—C26—H26	120.3
C5—C4—H4	119.5	C25—C26—H26	120.3
C3—C4—H4	119.5	C22—C27—C26	117.58 (17)
C4—C5—C6	116.65 (19)	C22—C27—C28	109.74 (15)
C4—C5—H5	121.7	C26—C27—C28	132.67 (16)
C6—C5—H5	121.7	O4—C28—C29	114.21 (14)
C5—C6—C1	121.32 (16)	O4—C28—C36	105.78 (13)
C5—C6—C7	130.23 (16)	C29—C28—C36	109.38 (14)
C1—C6—C7	108.35 (15)	O4—C28—C27	111.76 (14)
O2—C7—C6	114.25 (13)	C29—C28—C27	102.27 (13)
O2—C7—C8	111.51 (13)	C36—C28—C27	113.64 (15)
C6—C7—C8	101.63 (12)	N2—C29—C30	127.86 (15)
O2—C7—C15	107.19 (12)	N2—C29—C28	107.32 (15)
C6—C7—C15	108.21 (14)	C30—C29—C28	124.79 (14)
C8—C7—C15	114.13 (13)	C35—C30—C31	116.51 (18)
N1—C8—C9	123.70 (15)	C35—C30—C29	122.62 (17)
N1—C8—C7	109.85 (14)	C31—C30—C29	120.87 (15)
C9—C8—C7	126.41 (13)	C32—C31—C30	122.72 (18)
C14—C9—C10	118.79 (17)	C32—C31—H31	118.6
C14—C9—C8	117.56 (15)	C30—C31—H31	118.6
C10—C9—C8	123.64 (16)	C33—C32—C31	119.9 (2)
C11—C10—C9	120.11 (19)	C33—C32—H32	120.0
C11—C10—H10	119.9	C31—C32—H32	120.0
C9—C10—H10	119.9	C32—C33—C34	118.2 (2)
C12—C11—C10	119.8 (2)	C32—C33—H33	120.9
C12—C11—H11	120.1	C34—C33—H33	120.9
C10—C11—H11	120.1	C33—C34—C35	122.91 (19)
C11—C12—C13	121.3 (2)	C33—C34—H34	118.5
C11—C12—H12	119.3	C35—C34—H34	118.5
C13—C12—H12	119.3	C30—C35—C34	119.7 (2)
C14—C13—C12	120.0 (2)	C30—C35—H35	120.1
C14—C13—H13	120.0	C34—C35—H35	120.1
C12—C13—H13	120.0	C37—C36—C28	113.77 (14)
C13—C14—C9	119.97 (19)	C37—C36—H361	108.8
C13—C14—H14	120.0	C28—C36—H361	108.8
C9—C14—H14	120.0	C37—C36—H362	108.8
C16—C15—C7	115.08 (13)	C28—C36—H362	108.8
C16—C15—H151	108.5	H361—C36—H362	107.7
C7—C15—H151	108.5	C38—C37—C42	117.8 (3)
C16—C15—H152	108.5	C38—C37—C36	119.2 (2)
C7—C15—H152	108.5	C42—C37—C36	122.99 (19)
H151—C15—H152	107.5	C37—C38—C39	118.7 (3)
C17—C16—C21	116.76 (19)	C37—C38—H38	120.7
C17—C16—C15	120.24 (18)	C39—C38—H38	120.7
C21—C16—C15	123.00 (18)	C40—C39—C38	121.7 (3)
C16—C17—C18	120.4 (2)	C40—C39—H39	119.1
C16—C17—H17	119.8	C38—C39—H39	119.1
C18—C17—H17	119.8	C41—C40—C39	119.5 (3)
C19—C18—C17	122.5 (3)	C41—C40—H40	120.2
C19—C18—H18	118.7	C39—C40—H40	120.2
C17—C18—H18	118.7	C40—C41—C42	119.5 (3)
C20—C19—C18	118.1 (2)	C40—C41—H41	120.3
C20—C19—H19	120.9	C42—C41—H41	120.3
C18—C19—H19	120.9	C41—C42—C37	122.8 (3)
C19—C20—C21	119.8 (3)	C41—C42—H42	118.6
C19—C20—H20	120.1	C37—C42—H42	118.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1	0.93	2.19	2.817 (3)	124
C14—H14···O2	0.93	2.34	2.996 (2)	127
C31—H31···O4	0.93	2.47	3.107 (2)	126
C35—H35···O3	0.93	2.37	2.989 (3)	124
C11—H11···O4	0.93	2.48	3.404 (3)	175
O2—H2O···O1ⁱ	0.90 (2)	1.88 (2)	2.769 (2)	174 (2)
O4—H4O···O3ⁱⁱ	0.98 (2)	1.82 (2)	2.793 (2)	178 (2)
C24—H24···O1ⁱⁱ	0.93	2.48	3.310 (3)	148
C3—H3···O3ⁱⁱⁱ	0.93	2.46	3.327 (3)	154
C34—H34···O2^iv	0.93	2.49	3.415 (3)	176

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₇NO₂
M_r	315.36
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	11.635 (2), 11.971 (2), 12.063 (3)
α, β, γ (°)	84.773 (5), 88.882 (6), 88.635 (6)
V (Å³)	1672.5 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.26 × 0.24 × 0.18

Data collection
Diffractometer	Siemens AED
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6045, 6045, 5126
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.162, 1.05
No. of reflections	6045
No. of parameters	442
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.24

Computer programs: AED (Belletti et al., 1993), SIR97 (Altomare et al., 1999), ORTEP-3 for Windows (Farrugia, 1997) and SCHAKAL97 (Keller, 1997), SHELXL97 (Sheldrick, 2008) and PARST95 (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1	0.93	2.19	2.817 (3)	124
C14—H14···O2	0.93	2.34	2.996 (2)	127
C31—H31···O4	0.93	2.47	3.107 (2)	126
C35—H35···O3	0.93	2.37	2.989 (3)	124
C11—H11···O4	0.93	2.48	3.404 (3)	175
O2—H2O···O1ⁱ	0.90 (2)	1.88 (2)	2.769 (2)	174 (2)
O4—H4O···O3ⁱⁱ	0.98 (2)	1.82 (2)	2.793 (2)	178 (2)
C24—H24···O1ⁱⁱ	0.93	2.48	3.310 (3)	148
C3—H3···O3ⁱⁱⁱ	0.93	2.46	3.327 (3)	154
C34—H34···O2^iv	0.93	2.49	3.415 (3)	176

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z.

Acknowledgements

Financial support from the Universitá Politecnica delle Marche and the Universitá degli Studi di Parma is gratefully acknowledged.

References

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