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In the title compound, C43H36Cl2N4O3·0.5C6H6, there exists a tri­spiro ring system, which consists of a planar 2-ox­indole ring, an envelope pyrrolidine ring, an envelope isoxazoline ring and a boat-shaped piperidone ring. The crystal structure is stabilized by N—H...N intermolecular interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803015423/su6032sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803015423/su6032Isup2.hkl
Contains datablock I

CCDC reference: 222855

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.047
  • wR factor = 0.128
  • Data-to-parameter ratio = 13.6

checkCIF/PLATON results

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Alert level B PLAT331_ALERT_2_B Small Av. Phenyl C-C Dist. C44 - C46_a = 1.35 Ang.
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ..... 0.99 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .. ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) . 3.16 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) . 3.06 Ratio PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang.. 5
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Spiro-compounds represent an important class of naturally occurring substances characterized by highly pronounced biological properties (Kobayashi et al., 1991; James et al., 1991). 1,3-Dipolar cycloaddition reactions are important for the construction of spiro-compounds (Caramella & Grunanger, 1984). The title compound, (I), was synthesized by a double dipolar cycloaddition. Azomethine ylide, derived from isatin and sarcosine by a decarboxylative route, was first reacted with 1-benzyl-3,5-dibenzylidenepiperidin-4-one. The resulting cycloaddition product was then reacted with 2,6-dichlorobenzonitrile oxide to give (I). The molecular structure of (I) (Fig. 1), revealed the presence of a trispiro ring system, centered about atoms C8, C11 and C14. It consists of a 2-oxindole ring, a pyrrolidine ring, an isoxazoline ring and a piperidone ring.

The bond lengths and angles in (I) are normal within experimental error. Those involving the spiro centers, atoms C8, C11 and C14, are given in Table 1. The pyrrolidine ring (N2/C9/C10/C11/C8) has an envelope conformation with atom C9 displaced by −0.600 (2) Å from the mean plane through atoms N2/C8/C11/C10 [planar to within 0.053 (3) Å]. The dihedral angle between plane N2/C9/C10 and mean plane N2/C8/C11/C10 is 40.9 (4)°. The C19–C24 phenyl ring is inclined to mean plane N2/C8/C11/C10 by 90.4 (3)°.

The 2-oxindole ring (C8/C7/C6/C5/C4/C3/C2/N1/C1) is planar to within 0.018 (3)%A. The dihedral angle between the 2-oxindole ring mean plane and mean plane N2/C8/C11/C10 is 93.1 (3)°.

The isoxazoline ring O3/N4/C17/C16/C14 has an envelope conformation with atom C14 displaced by 0.240 (2) Å from the best plane through atoms O3/N4/C17/C16 [planar to within 0.006 (2) Å]. Phenyl rings C38–C43 and C32–C37 are inclined by 57.9 (4) and 84.9 (2)°, respectively, to mean plane O3/N4/C17/C16.

The piperidone ring has a boat conformation with atoms C12 and C14 displaced by 0.713 (3) and 0.341 (3) Å, respectively, from the best plane through atoms N3/C13/C15/C11.

In the crystal structure, the molecules are linked by an intermolecular N—H···N hydrogen bond, involving atoms N1 and N4 (Table 2 and Fig. 2), so forming a hydrogen-bonded polymer extending in the c direction. A benzene molecule of crystallization, disordered about a center of symmetry, is located between centrosymmetrcally related molecules of (I).

Experimental top

A mixture of 1-benzyl-3,5-dibenzylidenepiperidin-4-one (2 mmol), isatin (2 mmol) and sarcosine (2 mmol) was refluxed in methanol (80 ml) until the disappearance of the starting material, shown by thin-layer chromatography. After the reaction was complete the solvent was removed in vacuo and the residue separated by column chromatography (silica gel, petroleum ether/ethyl acetate = 5:1) to give the intermediate compound. This was then reacted with 2,6-dichlorobenzonitrile oxide in refluxing dry benzene for 24 h. The mixture was then cooled and filtered. Recrystalization from benzene–THF gave the title compound, (I). Further synthetic and other details are given in the CIF. Colourless crystals, suitable for X-ray analysis, were obtained by slow evaporation of a solution of (I) in chloroform–benzene.

Refinement top

The H atoms were introduced at calculated positions as riding atoms, with bond lengths of 0.93 (CH-aromatic), 0.98 (CH), 0.98 (CH3), and 0.86 Å (N—H). The displacement parameters were 1.2 (CH, NH) or 1.5 (CH3) times thoses of the parent atoms.

Computing details top

Data collection: SMART (Bruker,1997); cell refinement: SMART; data reduction: SAINT (Bruker,1997); program(s) used to solve structure: SHELXS97 (Sheldrick,1997); program(s) used to refine structure: SHELXL97 (Sheldrick,1997); molecular graphics: SHELXTL (Bruker,1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The crystal structure of (I), viewed along the a axis. The dashed lines indicate the N—H···H intermolecular hydrogen bonds. The benzene molecule of crystallization and the C—H H atoms have been omitted for clarity.
3-(2,6-dichlorophenyl)-spiro[5.3']1'-benzyl-4-piperidone- spiro[5'.3'']1-N-methyl-4-phenyl-pyrrolidine-spiro[2''.3''']oxindole- 4-phenyl-isoxazoline top
Crystal data top
C43H36Cl2N4O3·0.5C6H6F(000) = 1604
Mr = 766.71Dx = 1.314 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1017 reflections
a = 19.005 (7) Åθ = 2.4–22.6°
b = 12.611 (4) ŵ = 0.22 mm1
c = 17.986 (6) ÅT = 293 K
β = 115.937 (5)°Plate, colourless
V = 3877 (2) Å30.38 × 0.22 × 0.20 mm
Z = 4
Data collection top
Bruker CCD area-detector
diffractometer
6770 independent reflections
Radiation source: fine-focus sealed tube3692 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
ϕ and ω scansθmax = 25.0°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2220
Tmin = 0.945, Tmax = 0.958k = 814
15867 measured reflectionsl = 1621
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.047 w = 1/[σ2(Fo2) + (0.084P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.128(Δ/σ)max = 0.001
S = 1.02Δρmax = 0.19 e Å3
6770 reflectionsΔρmin = 0.27 e Å3
497 parameters
Crystal data top
C43H36Cl2N4O3·0.5C6H6V = 3877 (2) Å3
Mr = 766.71Z = 4
Monoclinic, P21/cMo Kα radiation
a = 19.005 (7) ŵ = 0.22 mm1
b = 12.611 (4) ÅT = 293 K
c = 17.986 (6) Å0.38 × 0.22 × 0.20 mm
β = 115.937 (5)°
Data collection top
Bruker CCD area-detector
diffractometer
6770 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3692 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.958Rint = 0.055
15867 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.128H-atom parameters constrained
S = 1.02Δρmax = 0.19 e Å3
6770 reflectionsΔρmin = 0.27 e Å3
497 parameters
Special details top

Experimental. A mixture of 1-benzyl-3,5-dibenzylidene-piperidin-4-one(2 mmol), isatin (2 mmol) and sarcosine (2 mmol) was refluxed in methanol (80 ml) until the disappearance of the starting material as evidenced by the TLC. After the reaction was completed the solvent was removed in vacuo and the residue was separated by column chromatography (silica gel, petroleum ether/ethyl acetate=5:1) to give the intermediate compound, then reacted the intermediate compound with 2,6-dichlorobenzonitrile oxide in reflux dry benzene at reflux for 24 h, cooled and filtered, recrystalized from benzene-THF to give title compound (I). M.p 498–500 K; IR (KBr): 3493(N—H), 1694,1682 (C=O), cm−1; 1H-NMR(CDCl3, p.p.m.): 1.54–1.59 (1H, d), 2.13(3H, s), 2.28–2.33(1H, d.), 2.69–2.73(1H, d.), 3.09–3.17(1H, d.), 3.21–3.28 (1H, d), 3.38–3.49 (2H, m), 4.04 (1H, t), 4.46 (1H,t) 5.87(1H, s), 6.62–7.53 (22H, m), 7.70(1H,br). 20 mg of (I) was dissolved in 15 ml chloroform-benzene mixed solvent; the solution was kept at room temperature for 15 d by natural evaporation to give colorless single crystals of (I), suitable for X-Ray analysis.

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. The H atoms were introduced at calculated positions as riding atoms, with bond lengths of 0.93(CH-aromatic), 0.98(CH), 0.98(CH3), and 0.86(N—H) Å. The displacement parameters were made equal to 1.2(CH, NH) or 1.5(CH3) times thoses of the parent atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.47238 (5)0.54992 (8)0.72067 (6)0.0729 (3)
Cl20.18291 (5)0.39801 (6)0.65293 (6)0.0547 (3)
N10.27442 (15)0.8979 (2)0.32184 (15)0.0434 (7)
H10.24930.90660.26920.052*
N20.37791 (15)1.00461 (19)0.51041 (16)0.0429 (7)
N30.17091 (12)0.80949 (16)0.41109 (13)0.0296 (6)
N40.24324 (13)0.61690 (17)0.64265 (13)0.0318 (6)
O10.21792 (13)1.03250 (16)0.36281 (13)0.0500 (6)
O20.36875 (11)0.77894 (14)0.63040 (12)0.0392 (5)
O30.21158 (11)0.69358 (14)0.57922 (11)0.0334 (5)
C10.26226 (18)0.9576 (2)0.37851 (19)0.0372 (8)
C20.33232 (18)0.8214 (2)0.3591 (2)0.0387 (8)
C30.3609 (2)0.7505 (3)0.3213 (2)0.0567 (10)
H30.34000.74630.26400.068*
C40.4214 (2)0.6858 (3)0.3708 (3)0.0621 (10)
H40.44090.63610.34640.075*
C50.4538 (2)0.6930 (3)0.4558 (2)0.0543 (9)
H50.49510.64880.48800.065*
C60.42488 (18)0.7664 (2)0.4937 (2)0.0425 (8)
H60.44730.77270.55100.051*
C70.36259 (16)0.8292 (2)0.44467 (18)0.0321 (7)
C80.32184 (17)0.9197 (2)0.46607 (17)0.0319 (7)
C90.3413 (2)1.0701 (2)0.5499 (2)0.0490 (9)
H9A0.29981.11310.50960.059*
H9B0.37931.11600.59130.059*
C100.30916 (17)0.9891 (2)0.58902 (17)0.0348 (7)
H100.35380.96200.63810.042*
C110.28085 (15)0.8961 (2)0.52446 (16)0.0292 (7)
C120.19205 (16)0.8872 (2)0.47711 (16)0.0298 (7)
H12A0.17030.86620.51470.036*
H12B0.17020.95570.45390.036*
C130.19978 (17)0.7023 (2)0.43903 (17)0.0350 (7)
H13A0.22530.67620.40620.042*
H13B0.15520.65660.42810.042*
C140.25643 (15)0.6924 (2)0.52942 (16)0.0275 (7)
C150.30967 (16)0.7892 (2)0.56673 (17)0.0274 (7)
C160.30354 (16)0.5878 (2)0.55477 (16)0.0284 (7)
H160.35880.60310.57060.034*
C170.29353 (16)0.5604 (2)0.63111 (16)0.0280 (7)
C180.4076 (2)1.0640 (3)0.4602 (2)0.0645 (11)
H18A0.36531.10170.41750.097*
H18B0.43041.01580.43560.097*
H18C0.44661.11360.49460.097*
C190.25062 (18)1.0296 (2)0.61794 (19)0.0399 (8)
C200.1904 (2)1.0987 (2)0.5725 (2)0.0548 (9)
H200.18581.12370.52190.066*
C210.1372 (2)1.1310 (3)0.6009 (3)0.0746 (13)
H210.09721.17740.56950.090*
C220.1432 (3)1.0952 (4)0.6748 (4)0.0864 (15)
H220.10681.11670.69340.104*
C230.2017 (3)1.0283 (3)0.7215 (3)0.0782 (13)
H230.20581.00450.77220.094*
C240.2556 (2)0.9955 (3)0.6934 (2)0.0562 (10)
H240.29580.94990.72580.067*
C250.08685 (17)0.8133 (2)0.35701 (18)0.0453 (8)
H25A0.07230.88630.34030.054*
H25B0.05910.79110.38850.054*
C260.06000 (18)0.7457 (2)0.28053 (19)0.0405 (8)
C270.1040 (2)0.7338 (3)0.2377 (2)0.0552 (9)
H270.15280.76620.25710.066*
C280.0769 (3)0.6744 (3)0.1660 (2)0.0698 (11)
H280.10730.66740.13750.084*
C290.0057 (3)0.6259 (3)0.1370 (2)0.0755 (13)
H290.01230.58530.08900.091*
C300.0389 (2)0.6370 (3)0.1781 (3)0.0734 (12)
H300.08770.60460.15790.088*
C310.01225 (19)0.6966 (3)0.2500 (2)0.0567 (10)
H310.04320.70350.27800.068*
C320.27833 (17)0.4946 (2)0.49544 (17)0.0316 (7)
C330.3304 (2)0.4494 (3)0.47003 (19)0.0497 (9)
H330.37920.48030.48500.060*
C340.3103 (3)0.3584 (3)0.4225 (2)0.0685 (11)
H340.34620.32820.40650.082*
C350.2391 (3)0.3124 (3)0.3986 (2)0.0631 (11)
H350.22630.25120.36650.076*
C360.1862 (2)0.3569 (3)0.4223 (2)0.0560 (10)
H360.13700.32660.40550.067*
C370.20608 (19)0.4469 (2)0.47113 (18)0.0428 (8)
H370.17030.47570.48790.051*
C380.32903 (16)0.4665 (2)0.68391 (17)0.0308 (7)
C390.40999 (17)0.4503 (2)0.72235 (18)0.0422 (8)
C400.4434 (2)0.3588 (3)0.7644 (2)0.0574 (10)
H400.49750.35070.78940.069*
C410.3961 (2)0.2796 (3)0.7691 (2)0.0600 (10)
H410.41820.21650.79590.072*
C420.3161 (2)0.2929 (2)0.73429 (19)0.0492 (9)
H420.28440.23930.73850.059*
C430.28323 (17)0.3853 (2)0.69342 (18)0.0377 (8)
C440.0106 (3)0.5626 (6)0.5659 (4)0.0985 (15)
H440.01790.60550.61070.118*
C450.0215 (3)0.6018 (4)0.5019 (5)0.0971 (17)
H450.03640.67220.50290.117*
C460.0110 (3)0.5397 (6)0.4360 (4)0.0976 (16)
H460.01870.56770.39220.117*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0335 (5)0.0824 (7)0.0804 (7)0.0091 (5)0.0043 (5)0.0301 (6)
Cl20.0391 (5)0.0493 (5)0.0719 (6)0.0058 (4)0.0208 (4)0.0117 (5)
N10.0479 (17)0.0498 (16)0.0318 (15)0.0014 (14)0.0169 (13)0.0078 (14)
N20.0421 (16)0.0338 (14)0.0541 (18)0.0133 (12)0.0222 (14)0.0064 (13)
N30.0273 (14)0.0254 (13)0.0274 (14)0.0016 (10)0.0039 (11)0.0000 (11)
N40.0342 (15)0.0293 (13)0.0304 (14)0.0001 (11)0.0127 (12)0.0032 (12)
O10.0533 (15)0.0415 (13)0.0545 (15)0.0125 (12)0.0228 (12)0.0164 (11)
O20.0366 (13)0.0329 (11)0.0334 (13)0.0048 (9)0.0019 (10)0.0026 (9)
O30.0338 (12)0.0325 (11)0.0368 (12)0.0063 (9)0.0181 (10)0.0074 (10)
C10.039 (2)0.0331 (18)0.041 (2)0.0036 (15)0.0195 (16)0.0077 (16)
C20.045 (2)0.0368 (18)0.041 (2)0.0055 (15)0.0247 (17)0.0007 (16)
C30.074 (3)0.055 (2)0.053 (2)0.001 (2)0.039 (2)0.005 (2)
C40.076 (3)0.053 (2)0.077 (3)0.004 (2)0.053 (2)0.009 (2)
C50.045 (2)0.048 (2)0.077 (3)0.0125 (17)0.033 (2)0.009 (2)
C60.037 (2)0.0432 (19)0.049 (2)0.0020 (15)0.0201 (17)0.0018 (17)
C70.0309 (17)0.0298 (16)0.0372 (19)0.0049 (13)0.0165 (15)0.0018 (14)
C80.0327 (17)0.0286 (16)0.0335 (18)0.0027 (13)0.0137 (14)0.0011 (14)
C90.050 (2)0.0332 (18)0.058 (2)0.0105 (15)0.0176 (18)0.0086 (16)
C100.0369 (18)0.0270 (16)0.0312 (18)0.0003 (13)0.0063 (15)0.0032 (14)
C110.0285 (17)0.0276 (15)0.0267 (16)0.0004 (13)0.0078 (13)0.0023 (13)
C120.0317 (17)0.0265 (15)0.0300 (17)0.0034 (12)0.0123 (14)0.0009 (14)
C130.0360 (18)0.0286 (16)0.0328 (18)0.0020 (13)0.0082 (14)0.0016 (14)
C140.0285 (16)0.0272 (15)0.0282 (17)0.0001 (12)0.0138 (14)0.0000 (13)
C150.0243 (16)0.0330 (16)0.0245 (17)0.0013 (13)0.0101 (14)0.0032 (13)
C160.0253 (16)0.0273 (15)0.0321 (17)0.0005 (12)0.0121 (13)0.0004 (14)
C170.0251 (16)0.0284 (16)0.0272 (17)0.0040 (13)0.0084 (13)0.0047 (13)
C180.059 (3)0.053 (2)0.093 (3)0.0204 (19)0.044 (2)0.000 (2)
C190.047 (2)0.0294 (17)0.035 (2)0.0028 (15)0.0105 (16)0.0100 (15)
C200.057 (2)0.042 (2)0.056 (2)0.0074 (18)0.0152 (19)0.0119 (18)
C210.054 (3)0.059 (3)0.094 (4)0.009 (2)0.017 (3)0.033 (3)
C220.080 (4)0.077 (3)0.122 (5)0.013 (3)0.062 (3)0.045 (3)
C230.110 (4)0.068 (3)0.083 (3)0.020 (3)0.066 (3)0.020 (3)
C240.076 (3)0.042 (2)0.052 (3)0.0006 (18)0.029 (2)0.0071 (18)
C250.0334 (19)0.0423 (19)0.044 (2)0.0065 (15)0.0024 (16)0.0003 (16)
C260.036 (2)0.0308 (17)0.0355 (19)0.0004 (14)0.0021 (16)0.0012 (15)
C270.050 (2)0.060 (2)0.043 (2)0.0094 (18)0.0075 (19)0.0028 (19)
C280.075 (3)0.076 (3)0.044 (2)0.007 (2)0.013 (2)0.003 (2)
C290.069 (3)0.059 (3)0.058 (3)0.005 (2)0.009 (2)0.019 (2)
C300.044 (2)0.052 (2)0.084 (3)0.0096 (19)0.008 (2)0.015 (2)
C310.037 (2)0.046 (2)0.065 (2)0.0023 (17)0.0026 (18)0.0054 (19)
C320.0392 (19)0.0236 (15)0.0297 (18)0.0067 (13)0.0130 (15)0.0052 (13)
C330.049 (2)0.046 (2)0.053 (2)0.0037 (17)0.0219 (18)0.0083 (18)
C340.082 (3)0.056 (2)0.069 (3)0.017 (2)0.033 (2)0.019 (2)
C350.085 (3)0.036 (2)0.054 (2)0.000 (2)0.016 (2)0.0161 (18)
C360.067 (3)0.039 (2)0.052 (2)0.0141 (18)0.017 (2)0.0063 (18)
C370.050 (2)0.0351 (18)0.043 (2)0.0075 (16)0.0203 (17)0.0074 (16)
C380.0337 (18)0.0305 (16)0.0265 (17)0.0003 (13)0.0117 (14)0.0031 (13)
C390.0315 (19)0.051 (2)0.039 (2)0.0040 (15)0.0108 (15)0.0102 (17)
C400.042 (2)0.069 (3)0.055 (2)0.0199 (19)0.0157 (18)0.025 (2)
C410.068 (3)0.047 (2)0.061 (3)0.022 (2)0.025 (2)0.0211 (19)
C420.059 (2)0.0357 (19)0.049 (2)0.0006 (17)0.0207 (18)0.0082 (16)
C430.0371 (19)0.0359 (18)0.0381 (19)0.0056 (14)0.0147 (15)0.0040 (15)
C440.063 (3)0.112 (5)0.117 (5)0.012 (3)0.036 (3)0.022 (4)
C450.058 (3)0.071 (3)0.158 (5)0.011 (2)0.043 (4)0.013 (4)
C460.064 (3)0.126 (5)0.103 (5)0.001 (3)0.038 (3)0.031 (4)
Geometric parameters (Å, º) top
Cl1—C391.737 (3)C19—C241.386 (4)
Cl2—C431.725 (3)C20—C211.380 (5)
N1—C11.365 (4)C20—H200.9300
N1—C21.395 (4)C21—C221.361 (5)
N1—H10.8600C21—H210.9300
N2—C91.449 (4)C22—C231.355 (6)
N2—C181.463 (4)C22—H220.9300
N2—C81.475 (3)C23—C241.389 (5)
N3—C121.454 (3)C23—H230.9300
N3—C131.463 (3)C24—H240.9300
N3—C251.463 (3)C25—C261.505 (4)
N4—C171.280 (3)C25—H25A0.9700
N4—O31.414 (3)C25—H25B0.9700
O1—C11.214 (3)C26—C271.371 (5)
O2—C151.210 (3)C26—C311.383 (4)
O3—C141.482 (3)C27—C281.381 (5)
C1—C81.559 (4)C27—H270.9300
C2—C31.371 (4)C28—C291.364 (5)
C2—C71.391 (4)C28—H280.9300
C3—C41.372 (5)C29—C301.353 (5)
C3—H30.9300C29—H290.9300
C4—C51.379 (5)C30—C311.386 (5)
C4—H40.9300C30—H300.9300
C5—C61.397 (4)C31—H310.9300
C5—H50.9300C32—C331.382 (4)
C6—C71.376 (4)C32—C371.384 (4)
C6—H60.9300C33—C341.381 (5)
C7—C81.520 (4)C33—H330.9300
C8—C111.585 (4)C34—C351.359 (5)
C9—C101.513 (4)C34—H340.9300
C9—H9A0.9700C35—C361.371 (5)
C9—H9B0.9700C35—H350.9300
C10—C191.508 (4)C36—C371.382 (4)
C10—C111.571 (4)C36—H360.9300
C10—H100.9800C37—H370.9300
C11—C121.526 (4)C38—C391.399 (4)
C11—C151.527 (4)C38—C431.403 (4)
C12—H12A0.9700C39—C401.373 (4)
C12—H12B0.9700C40—C411.370 (5)
C13—C141.512 (4)C40—H400.9300
C13—H13A0.9700C41—C421.379 (5)
C13—H13B0.9700C41—H410.9300
C14—C151.540 (4)C42—C431.373 (4)
C14—C161.547 (3)C42—H420.9300
C16—C171.507 (4)C44—C46i1.349 (7)
C16—C321.517 (4)C44—C451.349 (6)
C16—H160.9800C44—H440.9300
C17—C381.483 (4)C45—C461.362 (7)
C18—H18A0.9600C45—H450.9300
C18—H18B0.9600C46—C44i1.349 (7)
C18—H18C0.9600C46—H460.9300
C19—C201.385 (4)
C1—N1—C2112.2 (3)H18A—C18—H18C109.5
C1—N1—H1123.9H18B—C18—H18C109.5
C2—N1—H1123.9C20—C19—C24117.2 (3)
C9—N2—C18114.0 (2)C20—C19—C10123.6 (3)
C9—N2—C8106.9 (2)C24—C19—C10119.2 (3)
C18—N2—C8114.9 (2)C21—C20—C19121.2 (4)
C12—N3—C13114.5 (2)C21—C20—H20119.4
C12—N3—C25110.6 (2)C19—C20—H20119.4
C13—N3—C25113.3 (2)C22—C21—C20120.2 (4)
C17—N4—O3109.5 (2)C22—C21—H21119.9
N4—O3—C14109.06 (18)C20—C21—H21119.9
O1—C1—N1125.6 (3)C23—C22—C21120.5 (4)
O1—C1—C8126.7 (3)C23—C22—H22119.8
N1—C1—C8107.4 (3)C21—C22—H22119.8
C3—C2—C7122.2 (3)C22—C23—C24119.7 (4)
C3—C2—N1127.8 (3)C22—C23—H23120.1
C7—C2—N1109.9 (3)C24—C23—H23120.1
C2—C3—C4117.9 (3)C19—C24—C23121.2 (4)
C2—C3—H3121.1C19—C24—H24119.4
C4—C3—H3121.1C23—C24—H24119.4
C3—C4—C5121.4 (3)N3—C25—C26115.1 (2)
C3—C4—H4119.3N3—C25—H25A108.5
C5—C4—H4119.3C26—C25—H25A108.5
C4—C5—C6120.3 (3)N3—C25—H25B108.5
C4—C5—H5119.9C26—C25—H25B108.5
C6—C5—H5119.9H25A—C25—H25B107.5
C7—C6—C5118.7 (3)C27—C26—C31118.1 (3)
C7—C6—H6120.7C27—C26—C25122.0 (3)
C5—C6—H6120.7C31—C26—C25119.8 (3)
C6—C7—C2119.5 (3)C26—C27—C28121.0 (4)
C6—C7—C8131.3 (3)C26—C27—H27119.5
C2—C7—C8108.8 (3)C28—C27—H27119.5
N2—C8—C7110.8 (2)C29—C28—C27120.2 (4)
N2—C8—C1110.9 (2)C29—C28—H28119.9
C7—C8—C1101.5 (2)C27—C28—H28119.9
N2—C8—C11103.1 (2)C30—C29—C28119.9 (4)
C7—C8—C11118.7 (2)C30—C29—H29120.1
C1—C8—C11112.1 (2)C28—C29—H29120.1
N2—C9—C10102.8 (2)C29—C30—C31120.4 (4)
N2—C9—H9A111.2C29—C30—H30119.8
C10—C9—H9A111.2C31—C30—H30119.8
N2—C9—H9B111.2C26—C31—C30120.5 (4)
C10—C9—H9B111.2C26—C31—H31119.7
H9A—C9—H9B109.1C30—C31—H31119.7
C19—C10—C9116.2 (2)C33—C32—C37118.1 (3)
C19—C10—C11116.2 (2)C33—C32—C16120.1 (3)
C9—C10—C11103.7 (2)C37—C32—C16121.6 (3)
C19—C10—H10106.7C34—C33—C32120.3 (3)
C9—C10—H10106.7C34—C33—H33119.9
C11—C10—H10106.7C32—C33—H33119.9
C12—C11—C15106.3 (2)C35—C34—C33121.2 (4)
C12—C11—C10113.9 (2)C35—C34—H34119.4
C15—C11—C10111.0 (2)C33—C34—H34119.4
C12—C11—C8112.8 (2)C34—C35—C36119.4 (3)
C15—C11—C8108.8 (2)C34—C35—H35120.3
C10—C11—C8104.0 (2)C36—C35—H35120.3
N3—C12—C11110.4 (2)C35—C36—C37120.0 (3)
N3—C12—H12A109.6C35—C36—H36120.0
C11—C12—H12A109.6C37—C36—H36120.0
N3—C12—H12B109.6C36—C37—C32121.0 (3)
C11—C12—H12B109.6C36—C37—H37119.5
H12A—C12—H12B108.1C32—C37—H37119.5
N3—C13—C14115.4 (2)C39—C38—C43116.1 (3)
N3—C13—H13A108.4C39—C38—C17121.8 (3)
C14—C13—H13A108.4C43—C38—C17121.9 (3)
N3—C13—H13B108.4C40—C39—C38122.6 (3)
C14—C13—H13B108.4C40—C39—Cl1117.6 (3)
H13A—C13—H13B107.5C38—C39—Cl1119.8 (2)
O3—C14—C13108.8 (2)C41—C40—C39119.2 (3)
O3—C14—C1599.82 (19)C41—C40—H40120.4
C13—C14—C15115.2 (2)C39—C40—H40120.4
O3—C14—C16104.0 (2)C40—C41—C42120.5 (3)
C13—C14—C16115.8 (2)C40—C41—H41119.8
C15—C14—C16111.3 (2)C42—C41—H41119.8
O2—C15—C11123.2 (2)C43—C42—C41119.9 (3)
O2—C15—C14119.2 (2)C43—C42—H42120.1
C11—C15—C14117.3 (2)C41—C42—H42120.1
C17—C16—C32109.7 (2)C42—C43—C38121.6 (3)
C17—C16—C14100.2 (2)C42—C43—Cl2117.7 (2)
C32—C16—C14119.3 (2)C38—C43—Cl2120.7 (2)
C17—C16—H16109.0C46i—C44—C45119.2 (5)
C32—C16—H16109.0C46i—C44—H44120.4
C14—C16—H16109.0C45—C44—H44120.4
N4—C17—C38120.2 (2)C44—C45—C46120.9 (5)
N4—C17—C16114.9 (2)C44—C45—H45119.6
C38—C17—C16124.3 (2)C46—C45—H45119.6
N2—C18—H18A109.5C44i—C46—C45119.9 (5)
N2—C18—H18B109.5C44i—C46—H46120.1
H18A—C18—H18B109.5C45—C46—H46120.1
N2—C18—H18C109.5
C17—N4—O3—C148.7 (3)C13—C14—C15—O2161.3 (3)
C2—N1—C1—O1176.4 (3)C16—C14—C15—O226.9 (3)
C2—N1—C1—C82.4 (3)O3—C14—C15—C1192.5 (2)
C1—N1—C2—C3177.9 (3)C13—C14—C15—C1123.8 (3)
C1—N1—C2—C71.1 (3)C16—C14—C15—C11158.2 (2)
C7—C2—C3—C40.0 (5)O3—C14—C16—C1714.0 (2)
N1—C2—C3—C4176.4 (3)C13—C14—C16—C17133.3 (2)
C2—C3—C4—C51.4 (5)C15—C14—C16—C1792.6 (2)
C3—C4—C5—C60.6 (5)O3—C14—C16—C32105.5 (3)
C4—C5—C6—C71.5 (5)C13—C14—C16—C3213.8 (4)
C5—C6—C7—C22.8 (4)C15—C14—C16—C32147.9 (2)
C5—C6—C7—C8175.4 (3)O3—N4—C17—C38173.3 (2)
C3—C2—C7—C62.1 (4)O3—N4—C17—C161.5 (3)
N1—C2—C7—C6174.9 (3)C32—C16—C17—N4116.1 (3)
C3—C2—C7—C8176.3 (3)C14—C16—C17—N410.2 (3)
N1—C2—C7—C80.7 (3)C32—C16—C17—C3855.4 (3)
C9—N2—C8—C7162.9 (2)C14—C16—C17—C38178.4 (2)
C18—N2—C8—C769.4 (3)C9—C10—C19—C2043.1 (4)
C9—N2—C8—C185.1 (3)C11—C10—C19—C2079.4 (4)
C18—N2—C8—C142.5 (3)C9—C10—C19—C24137.8 (3)
C9—N2—C8—C1135.0 (3)C11—C10—C19—C2499.7 (3)
C18—N2—C8—C11162.6 (2)C24—C19—C20—C210.8 (5)
C6—C7—C8—N257.4 (4)C10—C19—C20—C21178.3 (3)
C2—C7—C8—N2115.9 (3)C19—C20—C21—C220.0 (6)
C6—C7—C8—C1175.2 (3)C20—C21—C22—C230.6 (6)
C2—C7—C8—C12.0 (3)C21—C22—C23—C240.5 (6)
C6—C7—C8—C1161.5 (4)C20—C19—C24—C230.9 (5)
C2—C7—C8—C11125.3 (3)C10—C19—C24—C23178.2 (3)
O1—C1—C8—N258.8 (4)C22—C23—C24—C190.3 (6)
N1—C1—C8—N2115.1 (3)C12—N3—C25—C26172.7 (2)
O1—C1—C8—C7176.5 (3)C13—N3—C25—C2657.2 (3)
N1—C1—C8—C72.6 (3)N3—C25—C26—C2737.2 (4)
O1—C1—C8—C1155.8 (4)N3—C25—C26—C31145.1 (3)
N1—C1—C8—C11130.3 (2)C31—C26—C27—C280.0 (5)
C18—N2—C9—C10174.3 (3)C25—C26—C27—C28177.7 (3)
C8—N2—C9—C1046.2 (3)C26—C27—C28—C290.4 (5)
N2—C9—C10—C19165.7 (2)C27—C28—C29—C300.7 (6)
N2—C9—C10—C1136.9 (3)C28—C29—C30—C310.6 (6)
C19—C10—C11—C1221.3 (3)C27—C26—C31—C300.0 (5)
C9—C10—C11—C12107.5 (3)C25—C26—C31—C30177.8 (3)
C19—C10—C11—C1598.7 (3)C29—C30—C31—C260.3 (5)
C9—C10—C11—C15132.5 (2)C17—C16—C32—C33122.0 (3)
C19—C10—C11—C8144.5 (2)C14—C16—C32—C33123.4 (3)
C9—C10—C11—C815.7 (3)C17—C16—C32—C3752.2 (3)
N2—C8—C11—C12134.5 (2)C14—C16—C32—C3762.4 (4)
C7—C8—C11—C12102.8 (3)C37—C32—C33—C340.7 (5)
C1—C8—C11—C1215.1 (3)C16—C32—C33—C34173.8 (3)
N2—C8—C11—C15107.8 (2)C32—C33—C34—C351.0 (5)
C7—C8—C11—C1515.0 (3)C33—C34—C35—C360.1 (6)
C1—C8—C11—C15132.9 (2)C34—C35—C36—C371.0 (5)
N2—C8—C11—C1010.5 (3)C35—C36—C37—C321.3 (5)
C7—C8—C11—C10133.3 (2)C33—C32—C37—C360.5 (4)
C1—C8—C11—C10108.8 (2)C16—C32—C37—C36174.8 (3)
C13—N3—C12—C1160.1 (3)N4—C17—C38—C39130.2 (3)
C25—N3—C12—C11170.5 (2)C16—C17—C38—C3958.8 (4)
C15—C11—C12—N365.3 (3)N4—C17—C38—C4354.4 (4)
C10—C11—C12—N3172.1 (2)C16—C17—C38—C43116.5 (3)
C8—C11—C12—N353.8 (3)C43—C38—C39—C402.5 (5)
C12—N3—C13—C148.7 (3)C17—C38—C39—C40173.1 (3)
C25—N3—C13—C14136.8 (3)C43—C38—C39—Cl1175.4 (2)
N4—O3—C14—C13138.5 (2)C17—C38—C39—Cl18.9 (4)
N4—O3—C14—C15100.4 (2)C38—C39—C40—C410.2 (5)
N4—O3—C14—C1614.6 (2)Cl1—C39—C40—C41178.2 (3)
N3—C13—C14—O378.7 (3)C39—C40—C41—C422.1 (5)
N3—C13—C14—C1532.4 (3)C40—C41—C42—C431.1 (5)
N3—C13—C14—C16164.7 (2)C41—C42—C43—C381.8 (5)
C12—C11—C15—O2151.9 (3)C41—C42—C43—Cl2178.8 (3)
C10—C11—C15—O227.5 (4)C39—C38—C43—C423.4 (4)
C8—C11—C15—O286.3 (3)C17—C38—C43—C42172.2 (3)
C12—C11—C15—C1422.8 (3)C39—C38—C43—Cl2177.1 (2)
C10—C11—C15—C14147.2 (2)C17—C38—C43—Cl27.2 (4)
C8—C11—C15—C1499.0 (3)C46i—C44—C45—C460.0 (8)
O3—C14—C15—O282.4 (3)C44—C45—C46—C44i0.0 (8)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N4ii0.862.253.017 (3)149
C6—H6···O20.932.483.083 (4)123
C10—H10···O20.982.342.850 (3)112
C12—H12A···O30.972.432.979 (3)115
C12—H12B···O10.972.402.951 (4)116
C16—H16···Cl10.982.703.325 (3)122
C16—H16···O20.982.442.779 (3)100
C30—H30···O1iii0.932.513.415 (5)166
C40—H40···O2iv0.932.483.381 (5)163
Symmetry codes: (ii) x, y+3/2, z1/2; (iii) x, y1/2, z+1/2; (iv) x+1, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC43H36Cl2N4O3·0.5C6H6
Mr766.71
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)19.005 (7), 12.611 (4), 17.986 (6)
β (°) 115.937 (5)
V3)3877 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.38 × 0.22 × 0.20
Data collection
DiffractometerBruker CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.945, 0.958
No. of measured, independent and
observed [I > 2σ(I)] reflections
15867, 6770, 3692
Rint0.055
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.128, 1.02
No. of reflections6770
No. of parameters497
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.27

Computer programs: SMART (Bruker,1997), SMART, SAINT (Bruker,1997), SHELXS97 (Sheldrick,1997), SHELXL97 (Sheldrick,1997), SHELXTL (Bruker,1997), SHELXTL.

Selected geometric parameters (Å, º) top
N2—C81.475 (3)C11—C121.526 (4)
O3—C141.482 (3)C11—C151.527 (4)
C1—C81.559 (4)C13—C141.512 (4)
C7—C81.520 (4)C14—C151.540 (4)
C8—C111.585 (4)C14—C161.547 (3)
C10—C111.571 (4)
N2—C8—C7110.8 (2)C12—C11—C8112.8 (2)
N2—C8—C1110.9 (2)C15—C11—C8108.8 (2)
C7—C8—C1101.5 (2)C10—C11—C8104.0 (2)
N2—C8—C11103.1 (2)O3—C14—C13108.8 (2)
C7—C8—C11118.7 (2)O3—C14—C1599.82 (19)
C1—C8—C11112.1 (2)C13—C14—C15115.2 (2)
C12—C11—C15106.3 (2)O3—C14—C16104.0 (2)
C12—C11—C10113.9 (2)C13—C14—C16115.8 (2)
C15—C11—C10111.0 (2)C15—C14—C16111.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N4i0.862.253.017 (3)149
Symmetry code: (i) x, y+3/2, z1/2.
 

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