1,1′′-Bis(prop-2-en-1-yl)-1,1′′,2,2′′-tetra­hydro­dispiro­[indole-3,7′-[6,9]diaza­tricyclo­[7.3.0.02,6]dodecane-8′,3′′-indole]-2,2′′-dione

Al Mamari, K.; Ennajih, H.; Bouhfid, R.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536812019216

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1637

doi:10.1107/S1600536812019216

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1,1′′-Bis(prop-2-en-1-yl)-1,1′′,2,2′′-tetrahydrodispiro[indole-3,7′-[6,9]diazatricyclo[7.3.0.0^2,6]dodecane-8′,3′′-indole]-2,2′′-dione

Khalil Al Mamari,^a Hamid Ennajih,^a Rachid Bouhfid,^b El Mokhtar Essassi ^a and Seik Weng Ng ^c,^d ^*

^aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V–Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, ^bInstitute of Nanomaterials and Nanotechnology MAScIR, Avenue de l'Armée Royale, Rabat, Morocco, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^dChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 28 April 2012; accepted 29 April 2012; online 5 May 2012)

The molecule of the title compound, C₃₀H₃₂N₄O₂, lies on a twofold rotation axis that passes through the mid-points of the C—C bonds of the piperazine ring, which adopts a chair conformation. The pyrrolidine ring that is fused to the piperazine ring adopts an envelope conformation (in which the N atom represents the flap). The indoline fused-ring system is nearly planar (r.m.s. deviation = 0.044 Å); the two symmetry-related indoline fused-rings systems are aligned at 71.44 (3)°.

Related literature

For background to the class of dispiro compounds, see: Al Mamari et al. (2012 ). For a related structure, see: Sugaleshini et al. (2006 ).

Experimental

Crystal data

C₃₀H₃₂N₄O₂
M_r = 480.60
Monoclinic, C 2/c
a = 14.9484 (2) Å
b = 9.9173 (1) Å
c = 17.5713 (3) Å
β = 111.119 (1)°
V = 2429.94 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.18 × 0.16 × 0.14 mm

Data collection

Bruker APEX DUO diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.985, T_max = 0.988
13297 measured reflections
2797 independent reflections
2441 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.119
S = 1.00
2797 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812019216/xu5527sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019216/xu5527Isup2.hkl

checkCIF report

Comment top

We reported the the 1,3-dipolar cycloaddition of 1-allyl-5-haloisatin derivatives as dipolarophiles with the azomethine ylides generated in situ from N-allylisatin and L-proline to yield dispiro-oxindoles (Al Mamari et al., 2012). Although one of the reactants is optically active, the product crystallizes in a centrosymmetric space group, as does the unsubstituted compound, C₃₀H₃₂N₄O₂₀(Scheme I), which represents the homolog of this class of compounds. The molecule lies on a two-fold rotation axis that passes through the two mid-points of the C–C bonds of the piperazine ring, which adopts a chair conformation. The pyrrolidine ring that is fused to the piperazine ring adopts an envelope conformation (in which the N atom represents the flap) (Fig. 1). The indoline fused-ring system is planar (r.m.s. deviation 0.044 Å); the two fused-rings are aligned at 71.44 (3) °.

The reaction of acenaphthracenequinone and L-proline gave acenapthene-2-spiro-5'-perhydrodipyrrolo[1,2-a;2',1'-c]pyrazine-6'-spiro-2''-acenapthene-1,1''-dione, which also crystallizes in a centrosymmetric space group (Sugaleshini et al., 2006).

Related literature top

For background to the class of dispiro compounds, see: Al Mamari et al. (2012). For a related structure, see: Sugaleshini et al. (2006).

Experimental top

A mixture of 1-allyl-indoline-2,3-dione (1 g, 0.005 mol) and proline (0.5 g, 0.004 mole) in ethanol (20 ml) was heated for 2 hours. On completion of the reaction as indicated by TLC, water (50 ml) was added. The precipitate was collected and recrystallized from ethanol to yield colorless crystals.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₃₀H₃₂N₄O₂ at the 50% probability level. Symmetry-related atoms are not labeled.

1,1''-Bis(prop-2-en-1-yl)-1,1'',2,2''-tetrahydrodispiro[indole-3,7'- [6,9]diazatricyclo[7.3.0.0^2,6]dodecane-8',3''-indole]-2,2''-dione top

Crystal data top

C₃₀H₃₂N₄O₂	F(000) = 1024
M_r = 480.60	D_x = 1.314 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8483 reflections
a = 14.9484 (2) Å	θ = 2.5–32.7°
b = 9.9173 (1) Å	µ = 0.08 mm⁻¹
c = 17.5713 (3) Å	T = 293 K
β = 111.119 (1)°	Prism, colorless
V = 2429.94 (6) Å³	0.18 × 0.16 × 0.14 mm
Z = 4

Data collection top

Bruker APEX DUO diffractometer	2797 independent reflections
Radiation source: fine-focus sealed tube	2441 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→19
T_min = 0.985, T_max = 0.988	k = −12→12
13297 measured reflections	l = −22→20

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0678P)² + 1.2982P] where P = (F_o² + 2F_c²)/3
2797 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₃₀H₃₂N₄O₂	V = 2429.94 (6) Å³
M_r = 480.60	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.9484 (2) Å	µ = 0.08 mm⁻¹
b = 9.9173 (1) Å	T = 293 K
c = 17.5713 (3) Å	0.18 × 0.16 × 0.14 mm
β = 111.119 (1)°

Data collection top

Bruker APEX DUO diffractometer	2797 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2441 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.988	R_int = 0.024
13297 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.00	Δρ_max = 0.27 e Å⁻³
2797 reflections	Δρ_min = −0.18 e Å⁻³
163 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.43126 (6)	0.47958 (9)	0.37259 (6)	0.0390 (2)
N1	0.52761 (7)	0.66607 (10)	0.39788 (6)	0.0315 (2)
N2	0.59105 (6)	0.39146 (9)	0.30977 (6)	0.0285 (2)
C1	0.49026 (7)	0.54901 (11)	0.35787 (6)	0.0283 (2)
C2	0.53923 (7)	0.51947 (10)	0.29458 (6)	0.0255 (2)
C3	0.61013 (7)	0.63591 (11)	0.31150 (7)	0.0272 (2)
C4	0.68373 (8)	0.66113 (12)	0.28314 (8)	0.0348 (3)
H4	0.6923	0.6064	0.2433	0.042*
C5	0.74493 (8)	0.76994 (13)	0.31530 (9)	0.0406 (3)
H5	0.7937	0.7891	0.2958	0.049*
C6	0.73379 (9)	0.84936 (13)	0.37577 (9)	0.0409 (3)
H6	0.7752	0.9215	0.3964	0.049*
C7	0.66169 (9)	0.82346 (12)	0.40655 (8)	0.0373 (3)
H7	0.6546	0.8762	0.4478	0.045*
C8	0.60104 (8)	0.71628 (11)	0.37335 (7)	0.0289 (2)
C9	0.50268 (10)	0.72080 (14)	0.46422 (8)	0.0419 (3)
H9A	0.5611	0.7350	0.5110	0.050*
H9B	0.4644	0.6548	0.4797	0.050*
C10	0.44850 (11)	0.85017 (16)	0.44444 (10)	0.0520 (4)
H10	0.4341	0.8903	0.4865	0.062*
C11	0.41912 (12)	0.91320 (17)	0.37480 (12)	0.0618 (4)
H11A	0.4316	0.8775	0.3307	0.074*
H11B	0.3857	0.9939	0.3691	0.074*
C12	0.66448 (9)	0.37194 (13)	0.39119 (7)	0.0376 (3)
H12A	0.6392	0.3916	0.4337	0.045*
H12B	0.7200	0.4284	0.3989	0.045*
C13	0.68964 (10)	0.22205 (14)	0.39088 (9)	0.0486 (4)
H13A	0.7495	0.2111	0.3819	0.058*
H13B	0.6959	0.1804	0.4425	0.058*
C14	0.60698 (9)	0.15842 (13)	0.32126 (9)	0.0424 (3)
H14A	0.6275	0.1318	0.2770	0.051*
H14B	0.5822	0.0799	0.3401	0.051*
C15	0.53166 (8)	0.26936 (11)	0.29411 (7)	0.0315 (3)
H15	0.4925	0.2690	0.3284	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0364 (4)	0.0421 (5)	0.0445 (5)	−0.0111 (4)	0.0218 (4)	0.0000 (4)
N1	0.0325 (5)	0.0313 (5)	0.0345 (5)	−0.0039 (4)	0.0167 (4)	−0.0031 (4)
N2	0.0229 (4)	0.0263 (5)	0.0318 (5)	0.0005 (3)	0.0046 (4)	0.0013 (4)
C1	0.0253 (5)	0.0298 (5)	0.0297 (5)	−0.0008 (4)	0.0099 (4)	0.0028 (4)
C2	0.0213 (5)	0.0263 (5)	0.0293 (5)	−0.0012 (4)	0.0095 (4)	0.0006 (4)
C3	0.0222 (5)	0.0264 (5)	0.0315 (5)	−0.0012 (4)	0.0078 (4)	0.0021 (4)
C4	0.0276 (5)	0.0384 (6)	0.0411 (6)	−0.0026 (5)	0.0156 (5)	−0.0004 (5)
C5	0.0270 (6)	0.0423 (7)	0.0547 (7)	−0.0064 (5)	0.0173 (5)	0.0041 (6)
C6	0.0289 (6)	0.0313 (6)	0.0579 (8)	−0.0081 (5)	0.0101 (5)	−0.0005 (5)
C7	0.0345 (6)	0.0309 (6)	0.0443 (7)	−0.0042 (5)	0.0116 (5)	−0.0060 (5)
C8	0.0253 (5)	0.0271 (5)	0.0337 (5)	−0.0005 (4)	0.0099 (4)	0.0027 (4)
C9	0.0484 (7)	0.0470 (7)	0.0361 (6)	−0.0057 (6)	0.0223 (6)	−0.0062 (5)
C10	0.0529 (8)	0.0475 (8)	0.0669 (9)	−0.0053 (6)	0.0353 (7)	−0.0185 (7)
C11	0.0509 (9)	0.0482 (9)	0.0854 (12)	0.0068 (7)	0.0234 (9)	−0.0022 (8)
C12	0.0302 (6)	0.0380 (6)	0.0362 (6)	0.0025 (5)	0.0017 (5)	0.0024 (5)
C13	0.0389 (7)	0.0392 (7)	0.0537 (8)	0.0078 (5)	−0.0004 (6)	0.0065 (6)
C14	0.0386 (7)	0.0292 (6)	0.0515 (7)	0.0049 (5)	0.0066 (6)	0.0061 (5)
C15	0.0281 (5)	0.0261 (5)	0.0375 (6)	−0.0008 (4)	0.0085 (5)	0.0022 (4)

Geometric parameters (Å, º) top

O1—C1	1.2178 (13)	C7—H7	0.9300
N1—C1	1.3677 (15)	C9—C10	1.490 (2)
N1—C8	1.4070 (14)	C9—H9A	0.9700
N1—C9	1.4511 (15)	C9—H9B	0.9700
N2—C2	1.4608 (13)	C10—C11	1.301 (3)
N2—C15	1.4677 (14)	C10—H10	0.9300
N2—C12	1.4688 (14)	C11—H11A	0.9300
C1—C2	1.5637 (14)	C11—H11B	0.9300
C2—C3	1.5226 (14)	C12—C13	1.5339 (18)
C2—C2ⁱ	1.583 (2)	C12—H12A	0.9700
C3—C4	1.3843 (15)	C12—H12B	0.9700
C3—C8	1.3933 (16)	C13—C14	1.5273 (19)
C4—C5	1.3958 (17)	C13—H13A	0.9700
C4—H4	0.9300	C13—H13B	0.9700
C5—C6	1.380 (2)	C14—C15	1.5226 (16)
C5—H5	0.9300	C14—H14A	0.9700
C6—C7	1.3929 (18)	C14—H14B	0.9700
C6—H6	0.9300	C15—C15ⁱ	1.497 (2)
C7—C8	1.3824 (16)	C15—H15	0.9800

C1—N1—C8	111.22 (9)	C10—C9—H9A	108.7
C1—N1—C9	123.71 (10)	N1—C9—H9B	108.7
C8—N1—C9	124.63 (10)	C10—C9—H9B	108.7
C2—N2—C15	115.95 (8)	H9A—C9—H9B	107.6
C2—N2—C12	116.96 (9)	C11—C10—C9	127.15 (14)
C15—N2—C12	105.26 (9)	C11—C10—H10	116.4
O1—C1—N1	124.30 (10)	C9—C10—H10	116.4
O1—C1—C2	127.27 (10)	C10—C11—H11A	120.0
N1—C1—C2	108.39 (9)	C10—C11—H11B	120.0
N2—C2—C3	109.72 (8)	H11A—C11—H11B	120.0
N2—C2—C1	112.72 (8)	N2—C12—C13	102.86 (10)
C3—C2—C1	100.98 (8)	N2—C12—H12A	111.2
N2—C2—C2ⁱ	109.62 (6)	C13—C12—H12A	111.2
C3—C2—C2ⁱ	114.12 (7)	N2—C12—H12B	111.2
C1—C2—C2ⁱ	109.52 (9)	C13—C12—H12B	111.2
C4—C3—C8	119.41 (10)	H12A—C12—H12B	109.1
C4—C3—C2	130.87 (10)	C14—C13—C12	105.93 (10)
C8—C3—C2	109.23 (9)	C14—C13—H13A	110.5
C3—C4—C5	118.94 (11)	C12—C13—H13A	110.5
C3—C4—H4	120.5	C14—C13—H13B	110.5
C5—C4—H4	120.5	C12—C13—H13B	110.5
C6—C5—C4	120.64 (11)	H13A—C13—H13B	108.7
C6—C5—H5	119.7	C15—C14—C13	104.24 (10)
C4—C5—H5	119.7	C15—C14—H14A	110.9
C5—C6—C7	121.24 (11)	C13—C14—H14A	110.9
C5—C6—H6	119.4	C15—C14—H14B	110.9
C7—C6—H6	119.4	C13—C14—H14B	110.9
C8—C7—C6	117.35 (12)	H14A—C14—H14B	108.9
C8—C7—H7	121.3	N2—C15—C15ⁱ	107.95 (8)
C6—C7—H7	121.3	N2—C15—C14	102.03 (9)
C7—C8—C3	122.38 (11)	C15ⁱ—C15—C14	116.41 (10)
C7—C8—N1	127.46 (11)	N2—C15—H15	110.0
C3—C8—N1	110.04 (9)	C15ⁱ—C15—H15	110.0
N1—C9—C10	114.21 (11)	C14—C15—H15	110.0
N1—C9—H9A	108.7

C8—N1—C1—O1	173.93 (11)	C4—C5—C6—C7	0.1 (2)
C9—N1—C1—O1	1.24 (18)	C5—C6—C7—C8	−0.85 (19)
C8—N1—C1—C2	−3.80 (12)	C6—C7—C8—C3	−0.04 (18)
C9—N1—C1—C2	−176.49 (10)	C6—C7—C8—N1	175.65 (11)
C15—N2—C2—C3	−178.61 (9)	C4—C3—C8—C7	1.66 (17)
C12—N2—C2—C3	56.22 (12)	C2—C3—C8—C7	174.50 (10)
C15—N2—C2—C1	69.71 (11)	C4—C3—C8—N1	−174.70 (10)
C12—N2—C2—C1	−55.46 (12)	C2—C3—C8—N1	−1.86 (12)
C15—N2—C2—C2ⁱ	−52.56 (13)	C1—N1—C8—C7	−172.47 (11)
C12—N2—C2—C2ⁱ	−177.72 (10)	C9—N1—C8—C7	0.14 (19)
O1—C1—C2—N2	−58.18 (14)	C1—N1—C8—C3	3.66 (13)
N1—C1—C2—N2	119.46 (10)	C9—N1—C8—C3	176.27 (11)
O1—C1—C2—C3	−175.17 (11)	C1—N1—C9—C10	−113.01 (14)
N1—C1—C2—C3	2.47 (11)	C8—N1—C9—C10	75.28 (15)
O1—C1—C2—C2ⁱ	64.14 (12)	N1—C9—C10—C11	3.0 (2)
N1—C1—C2—C2ⁱ	−118.22 (7)	C2—N2—C12—C13	169.82 (10)
N2—C2—C3—C4	52.23 (15)	C15—N2—C12—C13	39.45 (12)
C1—C2—C3—C4	171.40 (11)	N2—C12—C13—C14	−17.94 (15)
C2ⁱ—C2—C3—C4	−71.23 (15)	C12—C13—C14—C15	−8.73 (15)
N2—C2—C3—C8	−119.51 (10)	C2—N2—C15—C15ⁱ	60.60 (14)
C1—C2—C3—C8	−0.34 (11)	C12—N2—C15—C15ⁱ	−168.44 (11)
C2ⁱ—C2—C3—C8	117.03 (11)	C2—N2—C15—C14	−176.24 (10)
C8—C3—C4—C5	−2.36 (17)	C12—N2—C15—C14	−45.28 (12)
C2—C3—C4—C5	−173.40 (11)	C13—C14—C15—N2	32.17 (13)
C3—C4—C5—C6	1.51 (19)	C13—C14—C15—C15ⁱ	149.40 (12)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₃₀H₃₂N₄O₂
M_r	480.60
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.9484 (2), 9.9173 (1), 17.5713 (3)
β (°)	111.119 (1)
V (Å³)	2429.94 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.18 × 0.16 × 0.14

Data collection
Diffractometer	Bruker APEX DUO diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.985, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	13297, 2797, 2441
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.119, 1.00
No. of reflections	2797
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.18

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank Université Mohammed V-Agdal, and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

References

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