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

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)°.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.040
• wR factor = 0.119
• Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          5
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT793_ALERT_4_G The Model has Chirality at C2      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at C15     (Verify) ....          R

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

The aromatic and methylene H-atoms were placed in calculated positions (C–H 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C).

Computing details

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

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

Crystal data

C30H32N4O2	F(000) = 1024
Mr = 480.60	Dx = 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) Å^3	0.18 × 0.16 × 0.14 mm
Z = 4

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0678P)^2 + 1.2982P] where P = (Fo^2 + 2Fc^2)/3
2797 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—C2^i	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—C15^i	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—C2^i	109.62 (6)	C13—C12—H12A	111.2
C3—C2—C2^i	114.12 (7)	N2—C12—H12B	111.2
C1—C2—C2^i	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—C15^i	107.95 (8)
C6—C7—H7	121.3	N2—C15—C14	102.03 (9)
C7—C8—C3	122.38 (11)	C15^i—C15—C14	116.41 (10)
C7—C8—N1	127.46 (11)	N2—C15—H15	110.0
C3—C8—N1	110.04 (9)	C15^i—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—C2^i	−52.56 (13)	C1—N1—C8—C7	−172.47 (11)
C12—N2—C2—C2^i	−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—C2^i	64.14 (12)	N1—C9—C10—C11	3.0 (2)
N1—C1—C2—C2^i	−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)
C2^i—C2—C3—C4	−71.23 (15)	C12—C13—C14—C15	−8.73 (15)
N2—C2—C3—C8	−119.51 (10)	C2—N2—C15—C15^i	60.60 (14)
C1—C2—C3—C8	−0.34 (11)	C12—N2—C15—C15^i	−168.44 (11)
C2^i—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—C15^i	149.40 (12)

Symmetry code: (i) −x+1, y, −z+1/2.