1′-(1,3-Diphenyl-1H-pyrazol-4-yl)-1′′-(prop-2-en-1-yl)-2′,3′,5′,6′,7′,7a'-hexa­hydro-1′H-di­spiro­[1-benzo­pyran-3,2′-pyrrolizine-3′,3′′-indoline]-2′′,4-dione 0.75-hydrate

Jagadeesan, G.; Kathirvelan, D.; Haribabu, J.; Reddy, B.S.R.; Sethusankar, K.

doi:10.1107/S160053681301773X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages o1194-o1195

doi:10.1107/S160053681301773X

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1′-(1,3-Diphenyl-1H-pyrazol-4-yl)-1′′-(prop-2-en-1-yl)-2′,3′,5′,6′,7′,7a'-hexahydro-1′H-dispiro[1-benzopyran-3,2′-pyrrolizine-3′,3′′-indoline]-2′′,4-dione 0.75-hydrate

G. Jagadeesan,^a D. Kathirvelan,^b J. Haribabu,^b B. S. R. Reddy ^b and K. Sethusankar ^c ^*

^aDepartment of Physics, Meenakshi College of Engineering, West K.K. Nagar, Chennai 600 078, India, ^bIndustrial Chemistry Lab, Central Leather Research Institute, Adyar, Chennai 600 020, India, and ^cDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India
^*Correspondence e-mail: ksethusankar@yahoo.co.in

(Received 17 May 2013; accepted 27 June 2013; online 3 July 2013)

In the central aza-bicyclooctane unit of the title compound, C₄₀H₃₄N₄O₃·0.75H₂O, the peripheral pyrrolidine ring adopts an envelope conformation with the N atom deviating by 0.209 (2) Å, whereas the other pyrrolidine ring adopts a twisted conformation with the bridging N and C atoms deviating by −0.218 (2) and 0.236 (3) Å, respectively, from the rest of the ring. The pyrazole ring forms dihedral angles of 42.36 (7) and 24.07 (8)° with its C- and N-attached phenyl groups, respectively. The solvent water molecule has a partial occupancy of 0.75. In the crystal, the water molecules link the fused-ring molecules into chains along the b axis via O—H⋯N and O—H⋯O hydrogen bonds. The crystal packing is further stabilized by C—H⋯π interactions involving a methylene group of the pyran ring and the C-attached benzene ring on the pyrazole ring.

Related literature

For the biological activity of pyrazole derivatives, see: Mahajan et al. (1991 ); Baraldi et al. (1998 ); Katayama & Oshiyama (1997 ); Chen & Li (1998 ). For a related structure, see: Jagadeesan et al. (2013 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₄₀H₃₄N₄O₃·0.75H₂O
M_r = 632.22
Monoclinic, P 2₁ /n
a = 11.451 (2) Å
b = 13.496 (2) Å
c = 20.815 (3) Å
β = 96.206 (9)°
V = 3198.0 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.975, T_max = 0.983
32619 measured reflections
6870 independent reflections
4468 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.153
S = 1.02
6870 reflections
439 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4W—H1W⋯N3ⁱ	0.91 (2)	2.02 (3)	2.892 (4)	161 (4)
O4W—H2W⋯O2ⁱⁱ	0.90 (1)	1.96 (1)	2.841 (3)	165 (3)
C40—H40A⋯Cg1ⁱⁱⁱ	0.97	2.78	3.540 (3)	136
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681301773X/ld2105sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681301773X/ld2105Isup2.hkl

checkCIF report

Comment top

Pyrazole derivatives in general are well known nitrogen containing heterocyclic compounds and have been the subject of enormous research due to their importance in various applications and their widespread potential biological and pharmacological activities such as antimicrobial (Mahajan et al., 1991), antiviral (Baraldi et al., 1998), antitumor (Katayama & Oshiyama, 1997) and antifungal activities (Chen & Li, 1998).

The molecular structure of the title compound C₄₀H₃₄N₄O₃.0.75H₂O, is shown in Fig. 1. The mean planes of the phenyl rings (C1–C6) and (C7–C12) form a dihedral angle of 62.08 (7)° between them. The mean plane of the pyrazole ring (C13/C14/C15/N1/N2) forms dihedral angles of 42.36 (7)° and 24.07 (8)° with the mean planes of the two phenyl rings (C1–C6) and (C7–C12), respectively. The mean plane of the pyrrolizine ring (C16–C21/C32/N3) forms dihedral angles of 78.04 (7)° and 74.97 (6)° with the mean planes of the chromene ring (C32–C40/O1) and the indole ring (C21–C28/N4), respectively. The solvent water molecule is partially occupied, with a refined occupancy of 0.75.

The sum of angles around the N2 atom (356 °) indicates sp² hybridization, whereas that around N3 atom (336.7 °) indicates sp³ hybridization. The pyrrolidine ring (C16/C17/C21/C32/N3) adopts an envelope conformation on N3, with puckering parameters (Cremer & Pople, 1975) of q₂ = 0.332 (2) Å and ϕ₂= 187.4 (4)°. Also, the atom N3 deviates from the mean planes of the remaining ring atoms by -0.208 (19) Å. The other pyrrolidine ring (C17–C20/N3) adopts a twisted conformation on N3 and C20, with puckering parameters of q₂ = 0.380 (2) Å and ϕ₂= 155.3 (4)°. Also, the atoms N3 and C20 deviate from the mean planes of the remaining ring atoms by -0.218 (2) Å and 0.236 (3) Å, respectively. The title compound exhibits structural similarities with an already reported related structure (Jagadeesan et al., 2013).

In the crystal packing, the molecules are linked to the water molecules via intermolecular O4W–H1W···N3ⁱ and O4W–H2W···O2ⁱⁱ interactions is view down the a axis. The crystal packing is further stabilized by C40–H40A···Cg1ⁱⁱⁱ hydrogen bond interaction, where Cg1 is the center of gravity of (C1–C6) ring (Table 1). The symmetry codes: (i) -x + 1/2, y + 1/2, -z + 1/2, (ii) x, y + 1, z, (iii) -x + 1, -y, -z. The packing view of the title compound is shown in Fig. 2 and Fig. 3.

Related literature top

For the biological activity of pyrazole derivatives, see: Mahajan et al. (1991); Baraldi et al. (1998); Katayama & Oshiyama (1997); Chen & Li (1998). For a related structure, see: Jagadeesan et al. (2013). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

A mixture of allyl isatin (1.05 mmol), sarcosine (1.1 mmol) and dipolarophile (1.0 mmol) in ethanol was refluxed for 85 minute and cooled to room temperature. Then the mixture was poured into a beaker containing crushed ice and the solid formed in the mixture was filtered, dried and recrystallized from ethanol to obtain the pure product in good yield 89%.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound, viewed down the a axis showing intermolecular O—H···N and O—H···O hydrogen bonds (dashed lines). The H–atoms not involved in hydrogen bonds have been excluded for clarity.
	Fig. 3. The crystal packing arrangement of the title compound viewed down the a axis showing intermolecular C—H···π hydrogen bonds (dashed lines). The isolated water molecule and H–atoms not involved in hydrogen bonds have been excluded for clarity.

1'-(1,3-Diphenyl-1H-pyrazol-4-yl)-1''-(prop-2-en-1-yl)-2',3',5',6',7',7a'-hexahydro-1'H-dispiro[1-benzopyran-3,2'-pyrrolizine-3',3''-indoline]-2'',4-dione 0.75-hydrate top

Crystal data top

C₄₀H₃₄N₄O₃·0.75H₂O	F(000) = 1334
M_r = 632.22	D_x = 1.313 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6870 reflections
a = 11.451 (2) Å	θ = 2.0–26.9°
b = 13.496 (2) Å	µ = 0.09 mm⁻¹
c = 20.815 (3) Å	T = 296 K
β = 96.206 (9)°	Block, colourless
V = 3198.0 (9) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	6870 independent reflections
Radiation source: fine-focus sealed tube	4468 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω scans	θ_max = 26.9°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
T_min = 0.975, T_max = 0.983	k = −17→16
32619 measured reflections	l = −26→26

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0677P)² + 1.1541P] where P = (F_o² + 2F_c²)/3
6870 reflections	(Δ/σ)_max < 0.001
439 parameters	Δρ_max = 0.53 e Å⁻³
3 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₄₀H₃₄N₄O₃·0.75H₂O	V = 3198.0 (9) Å³
M_r = 632.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.451 (2) Å	µ = 0.09 mm⁻¹
b = 13.496 (2) Å	T = 296 K
c = 20.815 (3) Å	0.30 × 0.25 × 0.20 mm
β = 96.206 (9)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	6870 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	4468 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.983	R_int = 0.041
32619 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	3 restraints
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.53 e Å⁻³
6870 reflections	Δρ_min = −0.25 e Å⁻³
439 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.3646 (2)	−0.09434 (16)	0.00940 (10)	0.0520 (5)
H1	0.4169	−0.0873	0.0465	0.062*
C2	0.3490 (2)	−0.18622 (17)	−0.01924 (12)	0.0618 (6)
H2	0.3895	−0.2409	−0.0010	0.074*
C3	0.2736 (2)	−0.19691 (18)	−0.07481 (12)	0.0590 (6)
H3	0.2620	−0.2590	−0.0938	0.071*
C4	0.21576 (19)	−0.11638 (18)	−0.10203 (11)	0.0551 (6)
H4	0.1664	−0.1234	−0.1403	0.066*
C5	0.23008 (18)	−0.02496 (16)	−0.07328 (10)	0.0476 (5)
H5	0.1900	0.0294	−0.0922	0.057*
C6	0.30383 (17)	−0.01291 (14)	−0.01625 (9)	0.0407 (5)
C7	0.3903 (2)	0.35239 (18)	−0.06490 (11)	0.0619 (6)
H7	0.4125	0.2978	−0.0880	0.074*
C8	0.4026 (3)	0.4471 (2)	−0.08857 (13)	0.0741 (8)
H8	0.4335	0.4562	−0.1277	0.089*
C9	0.3697 (3)	0.52715 (19)	−0.05491 (14)	0.0726 (8)
H9	0.3775	0.5906	−0.0713	0.087*
C10	0.3252 (2)	0.51435 (18)	0.00313 (14)	0.0676 (7)
H10	0.3040	0.5693	0.0262	0.081*
C11	0.3118 (2)	0.42039 (16)	0.02735 (12)	0.0565 (6)
H11	0.2807	0.4117	0.0664	0.068*
C12	0.34474 (19)	0.33968 (15)	−0.00683 (10)	0.0462 (5)
N2	0.33424 (15)	0.24231 (12)	0.01741 (8)	0.0442 (4)
C14	0.33160 (18)	0.21340 (15)	0.07935 (9)	0.0432 (5)
H14	0.3362	0.2548	0.1153	0.052*
C15	0.32098 (17)	0.11219 (14)	0.07987 (9)	0.0390 (4)
C16	0.30271 (16)	0.04839 (14)	0.13713 (9)	0.0378 (4)
H16	0.2682	−0.0142	0.1205	0.045*
C17	0.21513 (18)	0.09593 (17)	0.17936 (10)	0.0475 (5)
H17	0.2233	0.1682	0.1789	0.057*
C18	0.0875 (2)	0.0674 (2)	0.16208 (14)	0.0777 (8)
H18A	0.0379	0.1259	0.1588	0.093*
H18B	0.0774	0.0323	0.1212	0.093*
C19	0.0572 (2)	0.0020 (2)	0.21576 (17)	0.0856 (9)
H19A	0.0121	−0.0548	0.1988	0.103*
H19B	0.0116	0.0381	0.2447	0.103*
C20	0.1725 (2)	−0.03022 (19)	0.25043 (13)	0.0641 (7)
H20A	0.1651	−0.0465	0.2952	0.077*
H20B	0.2041	−0.0869	0.2295	0.077*
C21	0.37282 (17)	0.05038 (14)	0.25424 (9)	0.0373 (4)
C22	0.41957 (17)	−0.01102 (15)	0.31226 (9)	0.0401 (4)
C23	0.4085 (2)	−0.10970 (16)	0.32683 (10)	0.0485 (5)
H23	0.3644	−0.1518	0.2983	0.058*
C24	0.4642 (2)	−0.14571 (18)	0.38482 (11)	0.0604 (6)
H24	0.4570	−0.2122	0.3953	0.072*
C25	0.5296 (2)	−0.0836 (2)	0.42650 (11)	0.0663 (7)
H25	0.5675	−0.1092	0.4647	0.080*
C26	0.5407 (2)	0.0153 (2)	0.41352 (11)	0.0609 (6)
H26	0.5843	0.0572	0.4424	0.073*
C27	0.48488 (18)	0.05012 (16)	0.35618 (9)	0.0441 (5)
C28	0.42046 (18)	0.15474 (15)	0.27428 (10)	0.0432 (5)
C29	0.5406 (2)	0.23204 (18)	0.36684 (12)	0.0657 (7)
H29A	0.5566	0.2825	0.3358	0.079*
H29B	0.6149	0.2112	0.3896	0.079*
C30	0.4627 (4)	0.2760 (2)	0.41537 (14)	0.0914 (10)
H30	0.3821	0.2748	0.4034	0.110*
C31	0.4951 (4)	0.3122 (3)	0.46756 (18)	0.1216 (14)
H31A	0.5748	0.3153	0.4819	0.146*
H31B	0.4402	0.3369	0.4933	0.146*
C32	0.41258 (16)	0.02229 (13)	0.18492 (8)	0.0332 (4)
C33	0.44132 (18)	−0.08767 (14)	0.18398 (9)	0.0384 (4)
C34	0.56279 (18)	−0.11499 (15)	0.20664 (9)	0.0422 (5)
C35	0.5953 (2)	−0.21383 (18)	0.21540 (10)	0.0574 (6)
H35	0.5416	−0.2637	0.2027	0.069*
C36	0.7059 (3)	−0.2382 (2)	0.24262 (12)	0.0723 (8)
H36	0.7278	−0.3043	0.2478	0.087*
C37	0.7845 (3)	−0.1643 (3)	0.26227 (13)	0.0760 (8)
H37	0.8590	−0.1811	0.2813	0.091*
C38	0.7549 (2)	−0.0671 (2)	0.25432 (12)	0.0619 (6)
H38	0.8088	−0.0179	0.2681	0.074*
C39	0.64463 (18)	−0.04197 (16)	0.22576 (9)	0.0445 (5)
C40	0.52334 (16)	0.07518 (15)	0.16948 (9)	0.0394 (4)
H40A	0.5435	0.0533	0.1277	0.047*
H40B	0.5088	0.1460	0.1670	0.047*
O4W	0.3354 (3)	0.6451 (2)	0.14051 (16)	0.1037 (10)	0.75
N1	0.32593 (16)	0.16460 (12)	−0.02365 (8)	0.0460 (4)
C13	0.31812 (17)	0.08557 (14)	0.01392 (9)	0.0398 (4)
N3	0.24531 (15)	0.05827 (13)	0.24518 (8)	0.0457 (4)
N4	0.48377 (16)	0.14756 (13)	0.33290 (8)	0.0478 (4)
O1	0.61974 (11)	0.05582 (11)	0.21763 (7)	0.0460 (4)
O2	0.36699 (14)	−0.14969 (10)	0.16740 (7)	0.0555 (4)
O3	0.40355 (15)	0.23089 (10)	0.24343 (7)	0.0570 (4)
H2W	0.337 (3)	0.7119 (8)	0.1421 (15)	0.086*	0.75
H1W	0.328 (4)	0.618 (2)	0.1800 (9)	0.086*	0.75

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0632 (14)	0.0459 (13)	0.0450 (11)	0.0053 (11)	−0.0024 (10)	−0.0013 (10)
C2	0.0813 (18)	0.0418 (13)	0.0620 (14)	0.0087 (12)	0.0054 (13)	0.0002 (11)
C3	0.0612 (15)	0.0484 (14)	0.0686 (15)	−0.0075 (12)	0.0120 (12)	−0.0180 (12)
C4	0.0430 (13)	0.0641 (15)	0.0570 (13)	−0.0029 (11)	0.0001 (10)	−0.0183 (12)
C5	0.0421 (12)	0.0519 (13)	0.0478 (11)	0.0041 (10)	0.0008 (9)	−0.0050 (10)
C6	0.0422 (11)	0.0390 (11)	0.0410 (10)	−0.0008 (9)	0.0052 (8)	−0.0009 (8)
C7	0.0895 (19)	0.0483 (14)	0.0472 (12)	0.0022 (13)	0.0042 (12)	0.0065 (10)
C8	0.104 (2)	0.0608 (17)	0.0568 (14)	−0.0025 (15)	0.0055 (14)	0.0200 (13)
C9	0.087 (2)	0.0464 (15)	0.0810 (19)	−0.0020 (13)	−0.0072 (15)	0.0213 (14)
C10	0.0740 (18)	0.0412 (13)	0.0847 (19)	0.0039 (12)	−0.0038 (14)	0.0015 (13)
C11	0.0641 (15)	0.0432 (13)	0.0609 (14)	0.0014 (11)	0.0015 (11)	0.0020 (11)
C12	0.0523 (13)	0.0381 (11)	0.0453 (11)	−0.0017 (9)	−0.0074 (9)	0.0067 (9)
N2	0.0552 (11)	0.0351 (9)	0.0409 (9)	−0.0004 (8)	−0.0020 (8)	0.0023 (7)
C14	0.0498 (12)	0.0396 (11)	0.0384 (10)	0.0017 (9)	−0.0031 (9)	0.0009 (9)
C15	0.0370 (11)	0.0371 (11)	0.0413 (10)	0.0017 (8)	−0.0031 (8)	0.0019 (8)
C16	0.0361 (10)	0.0343 (10)	0.0417 (10)	−0.0035 (8)	−0.0025 (8)	0.0014 (8)
C17	0.0373 (11)	0.0508 (13)	0.0547 (12)	0.0059 (9)	0.0069 (9)	0.0107 (10)
C18	0.0375 (13)	0.109 (2)	0.0862 (19)	0.0051 (14)	0.0043 (13)	0.0211 (17)
C19	0.0485 (16)	0.091 (2)	0.116 (2)	−0.0173 (15)	0.0034 (15)	0.0197 (18)
C20	0.0529 (15)	0.0649 (16)	0.0758 (16)	−0.0104 (12)	0.0124 (12)	0.0119 (13)
C21	0.0393 (11)	0.0324 (10)	0.0406 (10)	−0.0005 (8)	0.0062 (8)	0.0013 (8)
C22	0.0434 (11)	0.0420 (11)	0.0358 (9)	0.0031 (9)	0.0088 (8)	0.0012 (8)
C23	0.0607 (14)	0.0423 (12)	0.0436 (11)	0.0033 (10)	0.0109 (10)	0.0054 (9)
C24	0.0782 (17)	0.0538 (14)	0.0506 (13)	0.0118 (12)	0.0142 (12)	0.0142 (11)
C25	0.0786 (18)	0.0758 (18)	0.0431 (12)	0.0169 (14)	0.0001 (12)	0.0134 (12)
C26	0.0662 (16)	0.0733 (17)	0.0416 (12)	0.0021 (13)	−0.0016 (11)	−0.0032 (11)
C27	0.0473 (12)	0.0467 (12)	0.0392 (10)	0.0014 (9)	0.0082 (9)	−0.0041 (9)
C28	0.0486 (12)	0.0375 (11)	0.0446 (11)	0.0000 (9)	0.0098 (9)	−0.0037 (9)
C29	0.0843 (19)	0.0569 (15)	0.0557 (14)	−0.0255 (13)	0.0060 (13)	−0.0129 (12)
C30	0.150 (3)	0.0558 (17)	0.0662 (17)	−0.0111 (18)	0.0020 (19)	−0.0303 (14)
C31	0.150 (4)	0.121 (3)	0.101 (3)	−0.014 (3)	0.042 (3)	−0.026 (2)
C32	0.0335 (10)	0.0302 (9)	0.0354 (9)	−0.0008 (7)	0.0021 (7)	0.0011 (7)
C33	0.0477 (12)	0.0341 (10)	0.0335 (9)	0.0002 (9)	0.0051 (8)	0.0001 (8)
C34	0.0488 (12)	0.0438 (11)	0.0347 (9)	0.0123 (9)	0.0079 (8)	0.0032 (8)
C35	0.0748 (16)	0.0505 (13)	0.0478 (12)	0.0216 (12)	0.0103 (11)	0.0027 (10)
C36	0.085 (2)	0.0721 (18)	0.0613 (15)	0.0433 (16)	0.0147 (14)	0.0145 (13)
C37	0.0571 (16)	0.106 (2)	0.0645 (16)	0.0366 (17)	0.0062 (13)	0.0196 (16)
C38	0.0425 (13)	0.0850 (19)	0.0575 (13)	0.0096 (12)	0.0022 (10)	0.0089 (13)
C39	0.0391 (11)	0.0561 (13)	0.0389 (10)	0.0074 (10)	0.0075 (8)	0.0036 (9)
C40	0.0358 (10)	0.0412 (11)	0.0407 (10)	−0.0019 (8)	0.0022 (8)	0.0032 (8)
O4W	0.156 (3)	0.0594 (16)	0.107 (2)	−0.0196 (18)	0.066 (2)	−0.0095 (15)
N1	0.0571 (11)	0.0391 (10)	0.0407 (9)	0.0014 (8)	−0.0007 (8)	0.0003 (8)
C13	0.0395 (11)	0.0384 (11)	0.0401 (10)	0.0033 (8)	−0.0015 (8)	0.0011 (8)
N3	0.0400 (9)	0.0472 (10)	0.0509 (10)	−0.0007 (8)	0.0100 (7)	0.0076 (8)
N4	0.0564 (11)	0.0432 (10)	0.0441 (9)	−0.0071 (8)	0.0068 (8)	−0.0091 (8)
O1	0.0355 (7)	0.0502 (9)	0.0510 (8)	−0.0042 (6)	−0.0018 (6)	0.0035 (7)
O2	0.0629 (10)	0.0363 (8)	0.0647 (10)	−0.0066 (7)	−0.0055 (8)	0.0004 (7)
O3	0.0769 (11)	0.0326 (8)	0.0617 (9)	−0.0020 (7)	0.0081 (8)	0.0016 (7)

Geometric parameters (Å, º) top

C1—C6	1.377 (3)	C21—C22	1.514 (3)
C1—C2	1.379 (3)	C21—C28	1.551 (3)
C1—H1	0.9300	C21—C32	1.605 (3)
C2—C3	1.374 (3)	C22—C23	1.375 (3)
C2—H2	0.9300	C22—C27	1.388 (3)
C3—C4	1.364 (3)	C23—C24	1.390 (3)
C3—H3	0.9300	C23—H23	0.9300
C4—C5	1.373 (3)	C24—C25	1.370 (4)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.390 (3)	C25—C26	1.370 (4)
C5—H5	0.9300	C25—H25	0.9300
C6—C13	1.472 (3)	C26—C27	1.374 (3)
C7—C12	1.378 (3)	C26—H26	0.9300
C7—C8	1.382 (3)	C27—N4	1.401 (3)
C7—H7	0.9300	C28—O3	1.216 (2)
C8—C9	1.363 (4)	C28—N4	1.354 (3)
C8—H8	0.9300	C29—N4	1.457 (3)
C9—C10	1.372 (4)	C29—C30	1.537 (4)
C9—H9	0.9300	C29—H29A	0.9700
C10—C11	1.379 (3)	C29—H29B	0.9700
C10—H10	0.9300	C30—C31	1.212 (4)
C11—C12	1.376 (3)	C30—H30	0.9300
C11—H11	0.9300	C31—H31A	0.9300
C12—N2	1.417 (3)	C31—H31B	0.9300
N2—N1	1.350 (2)	C32—C40	1.520 (3)
N2—C14	1.351 (2)	C32—C33	1.521 (3)
C14—C15	1.371 (3)	C33—O2	1.217 (2)
C14—H14	0.9300	C33—C34	1.467 (3)
C15—C13	1.416 (3)	C34—C39	1.388 (3)
C15—C16	1.503 (3)	C34—C35	1.392 (3)
C16—C17	1.543 (3)	C35—C36	1.371 (4)
C16—C32	1.558 (3)	C35—H35	0.9300
C16—H16	0.9800	C36—C37	1.374 (4)
C17—N3	1.467 (3)	C36—H36	0.9300
C17—C18	1.517 (3)	C37—C38	1.361 (4)
C17—H17	0.9800	C37—H37	0.9300
C18—C19	1.493 (4)	C38—C39	1.379 (3)
C18—H18A	0.9700	C38—H38	0.9300
C18—H18B	0.9700	C39—O1	1.357 (3)
C19—C20	1.499 (4)	C40—O1	1.433 (2)
C19—H19A	0.9700	C40—H40A	0.9700
C19—H19B	0.9700	C40—H40B	0.9700
C20—N3	1.468 (3)	O4W—H2W	0.902 (10)
C20—H20A	0.9700	O4W—H1W	0.912 (10)
C20—H20B	0.9700	N1—C13	1.331 (2)
C21—N3	1.456 (3)

C6—C1—C2	120.9 (2)	C28—C21—C32	109.30 (14)
C6—C1—H1	119.6	C23—C22—C27	119.11 (19)
C2—C1—H1	119.6	C23—C22—C21	132.30 (19)
C3—C2—C1	119.9 (2)	C27—C22—C21	108.60 (17)
C3—C2—H2	120.0	C22—C23—C24	119.0 (2)
C1—C2—H2	120.0	C22—C23—H23	120.5
C4—C3—C2	119.9 (2)	C24—C23—H23	120.5
C4—C3—H3	120.0	C25—C24—C23	120.3 (2)
C2—C3—H3	120.0	C25—C24—H24	119.9
C3—C4—C5	120.3 (2)	C23—C24—H24	119.9
C3—C4—H4	119.8	C24—C25—C26	121.8 (2)
C5—C4—H4	119.8	C24—C25—H25	119.1
C4—C5—C6	120.7 (2)	C26—C25—H25	119.1
C4—C5—H5	119.7	C25—C26—C27	117.4 (2)
C6—C5—H5	119.7	C25—C26—H26	121.3
C1—C6—C5	118.22 (19)	C27—C26—H26	121.3
C1—C6—C13	121.79 (18)	C26—C27—C22	122.4 (2)
C5—C6—C13	119.96 (18)	C26—C27—N4	127.4 (2)
C12—C7—C8	119.4 (2)	C22—C27—N4	110.24 (17)
C12—C7—H7	120.3	O3—C28—N4	125.15 (19)
C8—C7—H7	120.3	O3—C28—C21	126.43 (18)
C9—C8—C7	120.3 (3)	N4—C28—C21	108.42 (17)
C9—C8—H8	119.8	N4—C29—C30	111.1 (2)
C7—C8—H8	119.8	N4—C29—H29A	109.4
C8—C9—C10	120.2 (2)	C30—C29—H29A	109.4
C8—C9—H9	119.9	N4—C29—H29B	109.4
C10—C9—H9	119.9	C30—C29—H29B	109.4
C9—C10—C11	120.3 (3)	H29A—C29—H29B	108.0
C9—C10—H10	119.9	C31—C30—C29	127.0 (4)
C11—C10—H10	119.9	C31—C30—H30	116.5
C12—C11—C10	119.4 (2)	C29—C30—H30	116.5
C12—C11—H11	120.3	C30—C31—H31A	120.0
C10—C11—H11	120.3	C30—C31—H31B	120.0
C11—C12—C7	120.4 (2)	H31A—C31—H31B	120.0
C11—C12—N2	120.8 (2)	C40—C32—C33	105.60 (15)
C7—C12—N2	118.8 (2)	C40—C32—C16	113.19 (15)
N1—N2—C14	111.88 (16)	C33—C32—C16	111.93 (15)
N1—N2—C12	119.87 (16)	C40—C32—C21	113.81 (15)
C14—N2—C12	128.25 (17)	C33—C32—C21	108.96 (14)
N2—C14—C15	107.84 (17)	C16—C32—C21	103.45 (14)
N2—C14—H14	126.1	O2—C33—C34	121.89 (18)
C15—C14—H14	126.1	O2—C33—C32	121.95 (18)
C14—C15—C13	103.76 (17)	C34—C33—C32	116.12 (17)
C14—C15—C16	126.64 (18)	C39—C34—C35	118.7 (2)
C13—C15—C16	129.25 (17)	C39—C34—C33	120.07 (18)
C15—C16—C17	111.61 (16)	C35—C34—C33	120.9 (2)
C15—C16—C32	117.64 (15)	C36—C35—C34	120.4 (3)
C17—C16—C32	105.08 (15)	C36—C35—H35	119.8
C15—C16—H16	107.3	C34—C35—H35	119.8
C17—C16—H16	107.3	C35—C36—C37	119.7 (2)
C32—C16—H16	107.3	C35—C36—H36	120.2
N3—C17—C18	104.90 (18)	C37—C36—H36	120.2
N3—C17—C16	106.62 (16)	C38—C37—C36	121.1 (2)
C18—C17—C16	115.4 (2)	C38—C37—H37	119.4
N3—C17—H17	109.9	C36—C37—H37	119.4
C18—C17—H17	109.9	C37—C38—C39	119.6 (3)
C16—C17—H17	109.9	C37—C38—H38	120.2
C19—C18—C17	105.5 (2)	C39—C38—H38	120.2
C19—C18—H18A	110.6	O1—C39—C38	117.6 (2)
C17—C18—H18A	110.6	O1—C39—C34	121.90 (18)
C19—C18—H18B	110.6	C38—C39—C34	120.5 (2)
C17—C18—H18B	110.6	O1—C40—C32	111.35 (15)
H18A—C18—H18B	108.8	O1—C40—H40A	109.4
C18—C19—C20	105.6 (2)	C32—C40—H40A	109.4
C18—C19—H19A	110.6	O1—C40—H40B	109.4
C20—C19—H19A	110.6	C32—C40—H40B	109.4
C18—C19—H19B	110.6	H40A—C40—H40B	108.0
C20—C19—H19B	110.6	H2W—O4W—H1W	111.8 (16)
H19A—C19—H19B	108.8	C13—N1—N2	104.78 (16)
N3—C20—C19	101.9 (2)	N1—C13—C15	111.74 (17)
N3—C20—H20A	111.4	N1—C13—C6	118.97 (17)
C19—C20—H20A	111.4	C15—C13—C6	129.25 (17)
N3—C20—H20B	111.4	C21—N3—C17	106.14 (15)
C19—C20—H20B	111.4	C21—N3—C20	120.07 (17)
H20A—C20—H20B	109.3	C17—N3—C20	105.84 (18)
N3—C21—C22	113.99 (15)	C28—N4—C27	111.27 (16)
N3—C21—C28	106.68 (15)	C28—N4—C29	123.27 (19)
C22—C21—C28	101.45 (15)	C27—N4—C29	125.44 (18)
N3—C21—C32	106.20 (15)	C39—O1—C40	113.59 (15)
C22—C21—C32	118.54 (15)

C6—C1—C2—C3	1.2 (4)	C28—C21—C32—C40	25.4 (2)
C1—C2—C3—C4	1.0 (4)	N3—C21—C32—C33	−102.37 (17)
C2—C3—C4—C5	−1.7 (4)	C22—C21—C32—C33	27.4 (2)
C3—C4—C5—C6	0.2 (3)	C28—C21—C32—C33	142.89 (16)
C2—C1—C6—C5	−2.7 (3)	N3—C21—C32—C16	16.86 (18)
C2—C1—C6—C13	179.3 (2)	C22—C21—C32—C16	146.65 (16)
C4—C5—C6—C1	2.0 (3)	C28—C21—C32—C16	−97.88 (17)
C4—C5—C6—C13	−179.98 (19)	C40—C32—C33—O2	−148.26 (18)
C12—C7—C8—C9	−0.2 (4)	C16—C32—C33—O2	−24.7 (3)
C7—C8—C9—C10	0.7 (4)	C21—C32—C33—O2	89.1 (2)
C8—C9—C10—C11	−1.0 (4)	C40—C32—C33—C34	34.1 (2)
C9—C10—C11—C12	0.8 (4)	C16—C32—C33—C34	157.65 (15)
C10—C11—C12—C7	−0.3 (4)	C21—C32—C33—C34	−88.56 (19)
C10—C11—C12—N2	178.7 (2)	O2—C33—C34—C39	−179.32 (19)
C8—C7—C12—C11	0.0 (4)	C32—C33—C34—C39	−1.6 (3)
C8—C7—C12—N2	−179.0 (2)	O2—C33—C34—C35	−5.7 (3)
C11—C12—N2—N1	156.5 (2)	C32—C33—C34—C35	172.01 (18)
C7—C12—N2—N1	−24.5 (3)	C39—C34—C35—C36	0.2 (3)
C11—C12—N2—C14	−23.8 (3)	C33—C34—C35—C36	−173.5 (2)
C7—C12—N2—C14	155.2 (2)	C34—C35—C36—C37	1.0 (4)
N1—N2—C14—C15	−0.1 (2)	C35—C36—C37—C38	−1.0 (4)
C12—N2—C14—C15	−179.7 (2)	C36—C37—C38—C39	−0.4 (4)
N2—C14—C15—C13	0.2 (2)	C37—C38—C39—O1	−178.7 (2)
N2—C14—C15—C16	−173.55 (18)	C37—C38—C39—C34	1.7 (3)
C14—C15—C16—C17	40.7 (3)	C35—C34—C39—O1	178.81 (18)
C13—C15—C16—C17	−131.4 (2)	C33—C34—C39—O1	−7.4 (3)
C14—C15—C16—C32	−80.9 (3)	C35—C34—C39—C38	−1.6 (3)
C13—C15—C16—C32	107.0 (2)	C33—C34—C39—C38	172.20 (19)
C15—C16—C17—N3	−153.12 (16)	C33—C32—C40—O1	−62.21 (19)
C32—C16—C17—N3	−24.6 (2)	C16—C32—C40—O1	175.01 (15)
C15—C16—C17—C18	90.9 (2)	C21—C32—C40—O1	57.3 (2)
C32—C16—C17—C18	−140.57 (19)	C14—N2—N1—C13	−0.1 (2)
N3—C17—C18—C19	−8.0 (3)	C12—N2—N1—C13	179.63 (18)
C16—C17—C18—C19	109.0 (3)	N2—N1—C13—C15	0.2 (2)
C17—C18—C19—C20	−16.8 (3)	N2—N1—C13—C6	178.01 (17)
C18—C19—C20—N3	35.1 (3)	C14—C15—C13—N1	−0.2 (2)
N3—C21—C22—C23	64.7 (3)	C16—C15—C13—N1	173.26 (19)
C28—C21—C22—C23	178.9 (2)	C14—C15—C13—C6	−177.8 (2)
C32—C21—C22—C23	−61.5 (3)	C16—C15—C13—C6	−4.3 (3)
N3—C21—C22—C27	−115.54 (19)	C1—C6—C13—N1	137.5 (2)
C28—C21—C22—C27	−1.3 (2)	C5—C6—C13—N1	−40.5 (3)
C32—C21—C22—C27	118.32 (18)	C1—C6—C13—C15	−45.1 (3)
C27—C22—C23—C24	−0.7 (3)	C5—C6—C13—C15	136.9 (2)
C21—C22—C23—C24	179.1 (2)	C22—C21—N3—C17	−165.29 (17)
C22—C23—C24—C25	−0.4 (3)	C28—C21—N3—C17	83.59 (18)
C23—C24—C25—C26	1.3 (4)	C32—C21—N3—C17	−32.92 (19)
C24—C25—C26—C27	−1.0 (4)	C22—C21—N3—C20	−45.6 (3)
C25—C26—C27—C22	−0.2 (3)	C28—C21—N3—C20	−156.67 (19)
C25—C26—C27—N4	179.9 (2)	C32—C21—N3—C20	86.8 (2)
C23—C22—C27—C26	1.0 (3)	C18—C17—N3—C21	159.25 (19)
C21—C22—C27—C26	−178.8 (2)	C16—C17—N3—C21	36.4 (2)
C23—C22—C27—N4	−179.04 (18)	C18—C17—N3—C20	30.6 (2)
C21—C22—C27—N4	1.1 (2)	C16—C17—N3—C20	−92.22 (19)
N3—C21—C28—O3	−58.7 (3)	C19—C20—N3—C21	−160.7 (2)
C22—C21—C28—O3	−178.3 (2)	C19—C20—N3—C17	−40.8 (2)
C32—C21—C28—O3	55.8 (3)	O3—C28—N4—C27	178.9 (2)
N3—C21—C28—N4	120.64 (17)	C21—C28—N4—C27	−0.4 (2)
C22—C21—C28—N4	1.0 (2)	O3—C28—N4—C29	0.0 (3)
C32—C21—C28—N4	−124.93 (17)	C21—C28—N4—C29	−179.33 (19)
N4—C29—C30—C31	145.0 (4)	C26—C27—N4—C28	179.5 (2)
C15—C16—C32—C40	5.8 (2)	C22—C27—N4—C28	−0.4 (2)
C17—C16—C32—C40	−119.09 (17)	C26—C27—N4—C29	−1.7 (4)
C15—C16—C32—C33	−113.42 (18)	C22—C27—N4—C29	178.4 (2)
C17—C16—C32—C33	121.71 (17)	C30—C29—N4—C28	95.5 (3)
C15—C16—C32—C21	129.42 (17)	C30—C29—N4—C27	−83.2 (3)
C17—C16—C32—C21	4.56 (18)	C38—C39—O1—C40	159.71 (18)
N3—C21—C32—C40	140.09 (16)	C34—C39—O1—C40	−20.7 (3)
C22—C21—C32—C40	−90.1 (2)	C32—C40—O1—C39	57.4 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O4W—H1W···N3ⁱ	0.91 (2)	2.02 (3)	2.892 (4)	161 (4)
O4W—H2W···O2ⁱⁱ	0.90 (1)	1.96 (1)	2.841 (3)	165 (3)
C40—H40A···Cg1ⁱⁱⁱ	0.97	2.78	3.540 (3)	136

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₄₀H₃₄N₄O₃·0.75H₂O
M_r	632.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	11.451 (2), 13.496 (2), 20.815 (3)
β (°)	96.206 (9)
V (Å³)	3198.0 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.975, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	32619, 6870, 4468
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.636

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.153, 1.02
No. of reflections	6870
No. of parameters	439
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.25

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O4W—H1W···N3ⁱ	0.91 (2)	2.02 (3)	2.892 (4)	161 (4)
O4W—H2W···O2ⁱⁱ	0.902 (11)	1.961 (14)	2.841 (3)	165 (3)
C40—H40A···Cg1ⁱⁱⁱ	0.97	2.78	3.540 (3)	136

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) −x+1, −y, −z.

Acknowledgements

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection. KS thanks the University Grant Commission (UGC), India, for a Minor Research Project.

References

Baraldi, P. G., Manfredini, S., Romagnoli, R., Stevanato, L., Zaid, A. N. & Manservigi, R. (1998). Nucleosides Nucleotides, 17, 2165–2171. Web of Science CrossRef CAS Google Scholar
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Volume 69| Part 8| August 2013| Pages o1194-o1195

doi:10.1107/S160053681301773X

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1′-(1,3-Di­phenyl-1H-pyrazol-4-yl)-1′′-(prop-2-en-1-yl)-2′,3′,5′,6′,7′,7a'-hexa­hydro-1′H-di­spiro­[1-benzo­pyran-3,2′-pyrrolizine-3′,3′′-indoline]-2′′,4-dione 0.75-hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1′-(1,3-Diphenyl-1H-pyrazol-4-yl)-1′′-(prop-2-en-1-yl)-2′,3′,5′,6′,7′,7a'-hexahydro-1′H-dispiro[1-benzopyran-3,2′-pyrrolizine-3′,3′′-indoline]-2′′,4-dione 0.75-hydrate