6'-Amino-3'-methyl-2-oxo-1'-phenyl-1',3a',4',7a'-tetra-hydrospiro-[1H-indole-3(2H),4'-pyrano[2,3-d]pyrazole]-5'-carbonitrile.

In the crystal structure of the title compound, C(21)H(15)N(5)O(2), the planar indolone unit and the pyran ring are almost perpendicular to each other [dihedral angle = 89.41 (2)°], and the pyrazole and phenyl rings are oriented at an angle of 25.74 (1)°. The mol-ecular packing is stabilized by inter- and intra-molecular C-H⋯O, N-H⋯O and C-H⋯π hydrogen bonds.

Related literature

For related literature, see: Houlihan et al. (1992 ▶); Jeyabharathi et al. (2001 ▶); Kang et al. (2002 ▶); Khafagy et al. (2002 ▶); McSweeney et al. (2004 ▶), Selvanayagam et al. (2005 ▶); Usui et al. (1998 ▶).

Experimental

Crystal data

C21H15N5O2

M = 369.38

Monoclinic,

a = 10.0370 (3) Å

b = 21.9705 (6) Å

c = 8.2325 (2) Å

β = 98.761 (1)°

V = 1794.23 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 293 (2) K

0.24 × 0.21 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer

Absorption correction: multi-scan (SAINT; Bruker, 1999 ▶) T min = 0.978, T max = 0.982

21620 measured reflections

4485 independent reflections

3277 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.118

S = 1.02

4485 reflections

254 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97 and PARST97 (Nardelli, 1995 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807064926/lw2047sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064926/lw2047Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H15N5O2	F000 = 768
Mr = 369.38	Dx = 1.367 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 4485 reflections
a = 10.0370 (3) Å	θ = 2.7–28.4º
b = 21.9705 (6) Å	µ = 0.09 mm−1
c = 8.2325 (2) Å	T = 293 (2) K
β = 98.761 (1)º	Cubic, colourless
V = 1794.23 (8) Å3	0.24 × 0.21 × 0.20 mm
Z = 4

Bruker Kappa APEXII diffractometer	4485 independent reflections
Radiation source: fine-focus sealed tube	3277 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.028
T = 293(2) K	θmax = 28.4º
ω and φ scans	θmin = 2.7º
Absorption correction: multi-scan(SAINT; Bruker, 1999)	h = −13→13
Tmin = 0.978, Tmax = 0.982	k = −29→29
21620 measured reflections	l = −10→10

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.041	Calculated w = 1/[σ2(Fo2) + (0.0549P)2 + 0.3722P] where P = (Fo2 + 2Fc2)/3 ?
wR(F2) = 0.118	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.24 e Å−3
4485 reflections	Δρmin = −0.17 e Å−3
254 parameters	Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (11)
Secondary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq
N1	0.94447 (12)	0.45685 (6)	0.30510 (15)	0.0484 (3)
H1	1.0221	0.4718	0.3436	0.058*
N2	0.63637 (18)	0.56417 (7)	0.0884 (2)	0.0705 (4)
N3	0.37828 (13)	0.49908 (6)	0.28737 (17)	0.0560 (4)
H3A	0.3820	0.5318	0.2309	0.067*
H3B	0.3071	0.4910	0.3298	0.067*
N4	0.53791 (11)	0.31470 (5)	0.49407 (14)	0.0416 (3)
N5	0.65120 (12)	0.27975 (6)	0.49024 (16)	0.0467 (3)
O1	0.83478 (10)	0.47928 (5)	0.52173 (12)	0.0524 (3)
O2	0.45453 (9)	0.41161 (4)	0.40050 (12)	0.0434 (2)
C1	0.71934 (12)	0.42403 (6)	0.27907 (15)	0.0354 (3)
C2	0.83874 (13)	0.45672 (6)	0.38640 (16)	0.0400 (3)
C3	0.91361 (14)	0.42960 (6)	0.14910 (17)	0.0423 (3)
C4	0.99616 (17)	0.42282 (8)	0.0305 (2)	0.0555 (4)
H4	1.0852	0.4360	0.0477	0.067*
C5	0.9396 (2)	0.39532 (8)	−0.1154 (2)	0.0611 (5)
H5	0.9915	0.3907	−0.1991	0.073*
C6	0.80860 (19)	0.37474 (7)	−0.13958 (19)	0.0567 (4)
H6	0.7738	0.3561	−0.2384	0.068*
C7	0.72765 (16)	0.38144 (6)	−0.01793 (17)	0.0459 (3)
H7	0.6393	0.3673	−0.0339	0.055*
C8	0.78159 (14)	0.40946 (6)	0.12661 (16)	0.0375 (3)
C9	0.60089 (13)	0.46759 (6)	0.24995 (16)	0.0374 (3)
C10	0.48299 (14)	0.46081 (6)	0.30913 (16)	0.0392 (3)
C11	0.55303 (12)	0.36842 (6)	0.41973 (16)	0.0366 (3)
C12	0.73234 (14)	0.31320 (6)	0.41359 (17)	0.0418 (3)
C13	0.67407 (12)	0.37005 (6)	0.36648 (15)	0.0359 (3)
C14	0.61894 (15)	0.52139 (7)	0.16089 (18)	0.0445 (3)
C15	0.42476 (13)	0.28945 (7)	0.55574 (16)	0.0414 (3)
C16	0.33155 (19)	0.32592 (8)	0.6121 (2)	0.0658 (5)
H16	0.3417	0.3680	0.6131	0.079*
C17	0.2218 (2)	0.29945 (10)	0.6676 (3)	0.0811 (6)
H17	0.1579	0.3241	0.7058	0.097*
C18	0.20561 (18)	0.23795 (9)	0.6674 (2)	0.0682 (5)
H18	0.1310	0.2207	0.7042	0.082*
C19	0.29922 (18)	0.20212 (9)	0.6129 (2)	0.0669 (5)
H19	0.2893	0.1600	0.6138	0.080*
C20	0.40913 (17)	0.22731 (7)	0.5562 (2)	0.0580 (4)
H20	0.4726	0.2023	0.5183	0.070*
C21	0.86622 (16)	0.28962 (8)	0.3862 (2)	0.0615 (5)
H21A	0.8791	0.2494	0.4314	0.092*
H21B	0.9359	0.3160	0.4391	0.092*
H21C	0.8699	0.2883	0.2704	0.092*

	U11	U22	U33	U12	U13	U23
N1	0.0335 (6)	0.0648 (8)	0.0489 (7)	−0.0131 (6)	0.0126 (5)	−0.0126 (6)
N2	0.0949 (12)	0.0515 (8)	0.0673 (9)	−0.0072 (8)	0.0194 (8)	0.0063 (7)
N3	0.0533 (8)	0.0583 (8)	0.0608 (8)	0.0199 (6)	0.0225 (6)	0.0096 (6)
N4	0.0356 (6)	0.0435 (6)	0.0475 (6)	−0.0009 (5)	0.0122 (5)	0.0011 (5)
N5	0.0378 (6)	0.0464 (7)	0.0569 (7)	0.0024 (5)	0.0108 (5)	0.0051 (6)
O1	0.0406 (5)	0.0763 (7)	0.0418 (5)	−0.0155 (5)	0.0111 (4)	−0.0182 (5)
O2	0.0358 (5)	0.0462 (5)	0.0508 (6)	0.0044 (4)	0.0146 (4)	0.0022 (4)
C1	0.0312 (6)	0.0404 (7)	0.0349 (6)	−0.0042 (5)	0.0063 (5)	−0.0047 (5)
C2	0.0334 (7)	0.0466 (7)	0.0407 (7)	−0.0057 (6)	0.0082 (5)	−0.0040 (6)
C3	0.0418 (7)	0.0423 (7)	0.0455 (7)	0.0001 (6)	0.0150 (6)	−0.0029 (6)
C4	0.0509 (9)	0.0594 (9)	0.0623 (10)	0.0043 (7)	0.0280 (8)	−0.0017 (8)
C5	0.0773 (12)	0.0601 (10)	0.0535 (9)	0.0170 (9)	0.0338 (9)	−0.0017 (8)
C6	0.0802 (12)	0.0495 (9)	0.0418 (8)	0.0128 (8)	0.0140 (8)	−0.0073 (6)
C7	0.0544 (9)	0.0417 (7)	0.0412 (7)	0.0015 (6)	0.0064 (6)	−0.0050 (6)
C8	0.0409 (7)	0.0358 (6)	0.0374 (7)	0.0009 (5)	0.0109 (5)	−0.0007 (5)
C9	0.0381 (7)	0.0375 (7)	0.0367 (6)	−0.0006 (5)	0.0057 (5)	−0.0046 (5)
C10	0.0398 (7)	0.0416 (7)	0.0363 (7)	0.0029 (6)	0.0060 (5)	−0.0044 (5)
C11	0.0320 (6)	0.0400 (7)	0.0382 (7)	−0.0002 (5)	0.0066 (5)	−0.0029 (5)
C12	0.0342 (7)	0.0445 (7)	0.0469 (8)	0.0000 (6)	0.0063 (6)	0.0001 (6)
C13	0.0299 (6)	0.0413 (7)	0.0364 (6)	−0.0033 (5)	0.0047 (5)	−0.0028 (5)
C14	0.0482 (8)	0.0430 (8)	0.0429 (7)	−0.0006 (6)	0.0086 (6)	−0.0049 (6)
C15	0.0366 (7)	0.0502 (8)	0.0388 (7)	−0.0049 (6)	0.0099 (5)	−0.0001 (6)
C16	0.0685 (11)	0.0557 (10)	0.0830 (13)	−0.0057 (8)	0.0431 (10)	−0.0117 (9)
C17	0.0702 (12)	0.0807 (14)	0.1060 (16)	0.0021 (10)	0.0569 (12)	−0.0063 (12)
C18	0.0531 (10)	0.0820 (13)	0.0748 (12)	−0.0128 (9)	0.0268 (9)	0.0111 (10)
C19	0.0603 (11)	0.0599 (10)	0.0837 (13)	−0.0114 (9)	0.0218 (9)	0.0131 (9)
C20	0.0517 (9)	0.0494 (9)	0.0772 (11)	0.0013 (7)	0.0237 (8)	0.0091 (8)
C21	0.0414 (8)	0.0590 (10)	0.0872 (13)	0.0085 (7)	0.0196 (8)	0.0120 (9)

N1—C2	1.3381 (17)	C6—C7	1.390 (2)
N1—C3	1.4081 (18)	C6—H6	0.9300
N1—H1	0.8600	C7—C8	1.3754 (19)
N2—C14	1.141 (2)	C7—H7	0.9300
N3—C10	1.3366 (18)	C9—C10	1.3548 (18)
N3—H3A	0.8600	C9—C14	1.417 (2)
N3—H3B	0.8600	C11—C13	1.3534 (17)
N4—C11	1.3488 (17)	C12—C13	1.4084 (19)
N4—N5	1.3764 (16)	C12—C21	1.489 (2)
N4—C15	1.4251 (16)	C15—C16	1.366 (2)
N5—C12	1.3258 (17)	C15—C20	1.374 (2)
O1—C2	1.2255 (16)	C16—C17	1.384 (2)
O2—C11	1.3620 (15)	C16—H16	0.9300
O2—C10	1.3716 (16)	C17—C18	1.361 (3)
C1—C13	1.4935 (18)	C17—H17	0.9300
C1—C9	1.5166 (18)	C18—C19	1.353 (3)
C1—C8	1.5189 (17)	C18—H18	0.9300
C1—C2	1.5525 (18)	C19—C20	1.378 (2)
C3—C4	1.3813 (19)	C19—H19	0.9300
C3—C8	1.3824 (19)	C20—H20	0.9300
C4—C5	1.387 (2)	C21—H21A	0.9600
C4—H4	0.9300	C21—H21B	0.9600
C5—C6	1.376 (3)	C21—H21C	0.9600
C5—H5	0.9300
C2—N1—C3	111.98 (11)	C10—C9—C1	125.48 (12)
C2—N1—H1	124.0	C14—C9—C1	116.69 (11)
C3—N1—H1	124.0	N3—C10—C9	126.49 (13)
C10—N3—H3A	120.0	N3—C10—O2	110.13 (12)
C10—N3—H3B	120.0	C9—C10—O2	123.38 (12)
H3A—N3—H3B	120.0	N4—C11—C13	109.79 (11)
C11—N4—N5	109.11 (10)	N4—C11—O2	122.18 (11)
C11—N4—C15	130.78 (11)	C13—C11—O2	127.99 (12)
N5—N4—C15	119.80 (11)	N5—C12—C13	111.30 (12)
C12—N5—N4	105.73 (11)	N5—C12—C21	120.88 (13)
C11—O2—C10	113.87 (10)	C13—C12—C21	127.82 (13)
C13—C1—C9	106.77 (10)	C11—C13—C12	104.06 (11)
C13—C1—C8	115.12 (11)	C11—C13—C1	122.07 (12)
C9—C1—C8	114.43 (11)	C12—C13—C1	133.86 (11)
C13—C1—C2	111.00 (11)	N2—C14—C9	178.35 (17)
C9—C1—C2	108.46 (10)	C16—C15—C20	119.84 (14)
C8—C1—C2	100.88 (10)	C16—C15—N4	121.12 (14)
O1—C2—N1	126.29 (13)	C20—C15—N4	119.03 (13)
O1—C2—C1	125.13 (11)	C15—C16—C17	119.13 (17)
N1—C2—C1	108.58 (11)	C15—C16—H16	120.4
C4—C3—C8	122.46 (14)	C17—C16—H16	120.4
C4—C3—N1	128.18 (14)	C18—C17—C16	121.16 (17)
C8—C3—N1	109.36 (11)	C18—C17—H17	119.4
C3—C4—C5	116.65 (16)	C16—C17—H17	119.4
C3—C4—H4	121.7	C19—C18—C17	119.31 (16)
C5—C4—H4	121.7	C19—C18—H18	120.3
C6—C5—C4	121.65 (14)	C17—C18—H18	120.3
C6—C5—H5	119.2	C18—C19—C20	120.70 (17)
C4—C5—H5	119.2	C18—C19—H19	119.6
C5—C6—C7	120.77 (15)	C20—C19—H19	119.6
C5—C6—H6	119.6	C15—C20—C19	119.85 (16)
C7—C6—H6	119.6	C15—C20—H20	120.1
C8—C7—C6	118.32 (15)	C19—C20—H20	120.1
C8—C7—H7	120.8	C12—C21—H21A	109.5
C6—C7—H7	120.8	C12—C21—H21B	109.5
C7—C8—C3	120.14 (12)	H21A—C21—H21B	109.5
C7—C8—C1	130.69 (12)	C12—C21—H21C	109.5
C3—C8—C1	109.17 (11)	H21A—C21—H21C	109.5
C10—C9—C14	117.73 (12)	H21B—C21—H21C	109.5
C11—N4—N5—C12	0.01 (15)	C11—O2—C10—N3	176.12 (11)
C15—N4—N5—C12	174.29 (12)	C11—O2—C10—C9	−3.13 (18)
C3—N1—C2—O1	−177.13 (15)	N5—N4—C11—C13	−0.03 (15)
C3—N1—C2—C1	1.82 (17)	C15—N4—C11—C13	−173.48 (13)
C13—C1—C2—O1	−60.38 (18)	N5—N4—C11—O2	177.86 (11)
C9—C1—C2—O1	56.62 (18)	C15—N4—C11—O2	4.4 (2)
C8—C1—C2—O1	177.16 (14)	C10—O2—C11—N4	−174.36 (12)
C13—C1—C2—N1	120.66 (12)	C10—O2—C11—C13	3.11 (19)
C9—C1—C2—N1	−122.35 (12)	N4—N5—C12—C13	0.02 (16)
C8—C1—C2—N1	−1.81 (15)	N4—N5—C12—C21	−179.85 (14)
C2—N1—C3—C4	178.50 (15)	N4—C11—C13—C12	0.04 (15)
C2—N1—C3—C8	−1.03 (18)	O2—C11—C13—C12	−177.69 (13)
C8—C3—C4—C5	0.9 (2)	N4—C11—C13—C1	180.00 (11)
N1—C3—C4—C5	−178.53 (15)	O2—C11—C13—C1	2.3 (2)
C3—C4—C5—C6	−1.3 (3)	N5—C12—C13—C11	−0.03 (16)
C4—C5—C6—C7	0.6 (3)	C21—C12—C13—C11	179.83 (15)
C5—C6—C7—C8	0.4 (2)	N5—C12—C13—C1	−179.99 (13)
C6—C7—C8—C3	−0.7 (2)	C21—C12—C13—C1	−0.1 (3)
C6—C7—C8—C1	179.10 (14)	C9—C1—C13—C11	−6.46 (16)
C4—C3—C8—C7	0.0 (2)	C8—C1—C13—C11	−134.66 (13)
N1—C3—C8—C7	179.58 (13)	C2—C1—C13—C11	111.56 (14)
C4—C3—C8—C1	−179.81 (14)	C9—C1—C13—C12	173.49 (14)
N1—C3—C8—C1	−0.25 (16)	C8—C1—C13—C12	45.3 (2)
C13—C1—C8—C7	61.85 (19)	C2—C1—C13—C12	−68.48 (18)
C9—C1—C8—C7	−62.41 (18)	C10—C9—C14—N2	−176 (100)
C2—C1—C8—C7	−178.61 (14)	C1—C9—C14—N2	8(6)
C13—C1—C8—C3	−118.34 (13)	C11—N4—C15—C16	−29.0 (2)
C9—C1—C8—C3	117.40 (13)	N5—N4—C15—C16	158.13 (15)
C2—C1—C8—C3	1.21 (14)	C11—N4—C15—C20	150.19 (16)
C13—C1—C9—C10	6.56 (17)	N5—N4—C15—C20	−22.7 (2)
C8—C1—C9—C10	135.16 (13)	C20—C15—C16—C17	−0.5 (3)
C2—C1—C9—C10	−113.12 (14)	N4—C15—C16—C17	178.65 (17)
C13—C1—C9—C14	−177.13 (11)	C15—C16—C17—C18	0.2 (3)
C8—C1—C9—C14	−48.53 (16)	C16—C17—C18—C19	0.5 (4)
C2—C1—C9—C14	63.20 (14)	C17—C18—C19—C20	−0.8 (3)
C14—C9—C10—N3	2.5 (2)	C16—C15—C20—C19	0.2 (3)
C1—C9—C10—N3	178.78 (13)	N4—C15—C20—C19	−178.97 (15)
C14—C9—C10—O2	−178.36 (12)	C18—C19—C20—C15	0.5 (3)
C1—C9—C10—O2	−2.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O2	0.93	2.42	2.959 (2)	117
N1—H1···O1i	0.86	1.99	2.819 (2)	161
N3—H3B···O1ii	0.86	2.12	2.880 (1)	148
C6—H6···Cgiii	0.92	2.85	3.771 (3)	173

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the pyrazole ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯O2	0.93	2.42	2.959 (2)	117
N1—H1⋯O1i	0.86	1.99	2.819 (2)	161
N3—H3B⋯O1ii	0.86	2.12	2.880 (1)	148
C6—H6⋯Cgiii	0.92	2.85	3.771 (3)	173

Symmetry codes: (i) ; (ii) ; (iii) .