2′-Amino-1′-(4-chloro­phen­yl)-1,7′,7′-trimethyl-2,5′-dioxo-5′,6′,7′,8′-tetra­hydrospiro­[indoline-3,4′(1′H)-quinoline]-3′-carbonitrile dimethyl­formamide solvate dihydrate

Wang, J.; Zhu, S.-L.

doi:10.1107/S1600536809010551

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o875

doi:10.1107/S1600536809010551

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2′-Amino-1′-(4-chlorophenyl)-1,7′,7′-trimethyl-2,5′-dioxo-5′,6′,7′,8′-tetrahydrospiro[indoline-3,4′(1′H)-quinoline]-3′-carbonitrile dimethylformamide solvate dihydrate

Jing Wang ^a and Song-Lei Zhu ^a ^*

^aDepartment of Chemistry, Xuzhou Medical College, Xuzhou 221002, People's Republic of China
^*Correspondence e-mail: songleizhu@126.com

(Received 13 February 2009; accepted 23 March 2009; online 28 March 2009)

In the molecule of the title compound, C₂₆H₂₃ClN₄O₂·C₃H₇NO·2H₂O, the indole and dihydropyridine rings are planar and make a dihedral angle of 89.86 (7)°. The dihydropyridine ring forms a dihedral angle of 79.95 (7)° with the attached benzene ring. In the crystal structure, intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the molecules. Intermolecular C—H⋯N and C—H⋯Cl interactions are also present.

Related literature

For the indole nucleus, see: da Silva et al. (2001 ). For the antibacterial and fungicidal activities of indole compounds, see: Joshi & Chand (1982 ). For spirooxindole ring systems in alkaloids, see: Abdel-Rahman et al. (2004 ). For the preparation of heterocyclic compounds involving indole derivatives, see: Zhu et al. (2007 ).

Experimental

Crystal data

C₂₆H₂₃ClN₄O₂·C₃H₇NO·2H₂O
M_r = 568.06
Triclinic, $[P \overline 1]$
a = 9.237 (1) Å
b = 12.9553 (17) Å
c = 14.4554 (11) Å
α = 66.162 (11)°
β = 71.619 (12)°
γ = 84.595 (15)°
V = 1500.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 293 K
0.60 × 0.57 × 0.30 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ) T_min = 0.760, T_max = 0.950
14714 measured reflections
5445 independent reflections
4310 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.155
S = 1.13
5445 reflections
379 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C28—H28B⋯N3ⁱ	0.96	2.60	3.528 (5)	163
C15—H15⋯Cl1ⁱⁱ	0.93	2.74	3.647 (3)	167
N4—H4D⋯O4ⁱⁱⁱ	0.86	2.23	2.934 (3)	139
N4—H4C⋯O3^iv	0.86	2.24	3.071 (3)	162
O5—H5B⋯O3	0.82 (4)	2.03 (4)	2.830 (4)	163 (4)
O5—H5A⋯O1	0.83 (3)	2.017 (16)	2.816 (3)	164 (4)
O4—H4B⋯O2^v	0.82 (3)	2.17 (3)	2.974 (3)	167 (4)
O4—H4A⋯O5^vi	0.82 (4)	1.99 (4)	2.800 (4)	170 (4)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y-1, z+1; (iii) -x+1, -y+2, -z; (iv) x, y+1, z; (v) x-1, y, z; (vi) -x+1, -y+1, -z.

Data collection: CrystalClear (Rigaku/MSC, 2001 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010551/bq2126sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010551/bq2126Isup2.hkl

checkCIF report

Comment top

The indole nucleus is the well known heterocyclic compound (da Silva et al., 2001). Compounds carrying the indole moiety exhibit antibacterial and fungicidal activities (Joshi & Chand, 1982). Spirooxindole ring systems are found in a number of alkaloids like horsifiline, spirotryprostatin and elacomine (Abdel-Rahman et al., 2004). As a part of our program devoted to the preparation of heterocyclic compounds involving indole derivatives (Zhu et al., 2007), we have synthesized a series of spirooxindoles via reactions of substituted isatins together with malononitrile and enaminones. We report herein the crystal structure of the title compound, (I).

In the molecule of (I), (Fig. 1), the indole ring A (C3/C12/N2/C13-C18) and the dihydropyridine ring B (N1/C1-C5), are planar. The dihedral angle between them is 89.86 (7)°, and the benzene ring C (C21-C26) is oriented at a dihedral angle of 79.95 (7)° with the attached ring B. Ring D (C1/C2/C6-C9) adopts twisted conformation, with C8 deviating the C1/C2/C6/C7 plan by 0.636 (3)Å.

In the crystal structure, intermolecular N-H···O and O-H···O, hydrogen bonds link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For the indole nucleus, see: da Silva et al. (2001). For the antibacterial and fungicidal activities of indole compounds, see: Joshi & Chand (1982). For spirooxindole ring systems in alkaloids, see: Abdel-Rahman et al. (2004). For the preparation of heterocyclic compounds involving indole derivatives, see: Zhu et al. (2007).[Scheme should show solvent molecules]

Experimental top

Compound (I) was prepared by one-pot reaction of 1-methylisatin (2 mmol), malononitrile (2 mmol) and 3-(4-chlorophenylamino) -5,5-dimethylcyclohex-2-enone (2 mmol) in ethanol. After stirring at 343 K for 5 h, the reaction mixture was cooled and washed with small amount of ethanol. The crude product was filtered and single crystals of the title compound were obtained from DMF and water mixture solution by slow evaporation at room temperature (yield; 80%, m.p. > 573 K). Spectroscopic analysis: IR (KBr, n, cm^-1): 3463, 3312, 2190, 1716, 1650, 1568, 1491, 1364, 1090, 1018, 915, 753. ¹H NMR (400 MHz, DMSO-d₆): 7.65 (d, J = 8.4 Hz, 2H, Ar-H), 7.51-7.54 (m, 2H, ArH), 7.23 (t, J = 8.0 Hz, 2H, ArH), 6.93-6.70 (m, 2H, ArH), 5.55 (s, 2H, NH₂), 3.13 (s, 3H, NCH₃), 2.05-2.17 (m, 2H, CH₂), 1.81-1.93 (m, 2H, CH₂), 0.89 (s, 3H, CH₃), 0.81 (s, 3H, CH₃).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The solvent DMF and the two water molecules are not shown for clarity.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

2'-Amino-1'-(4-chlorophenyl)-1,7',7'-trimethyl-2,5'-dioxo-5',6',7',8'- tetrahydrospiro[indoline-3,4'(1'H)-quinoline]-3'-carbonitrile dimethylformamide solvate dihydrate top

Crystal data top

C₂₆H₂₃ClN₄O₂·C₃H₇NO·2(H₂O)	Z = 2
M_r = 568.06	F(000) = 600
Triclinic, P1	D_x = 1.257 Mg m⁻³
Hall symbol: -P 1	Melting point > 573 K
a = 9.237 (1) Å	Mo Kα radiation, λ = 0.71070 Å
b = 12.9553 (17) Å	Cell parameters from 5610 reflections
c = 14.4554 (11) Å	θ = 3.0–25.3°
α = 66.162 (11)°	µ = 0.17 mm⁻¹
β = 71.619 (12)°	T = 293 K
γ = 84.595 (15)°	Block, colorless
V = 1500.5 (3) Å³	0.60 × 0.57 × 0.30 mm

Data collection top

Rigaku Mercury diffractometer	5445 independent reflections
Radiation source: fine-focus sealed tube	4310 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.4°, θ_min = 3.0°
ω scans	h = −10→11
Absorption correction: multi-scan (Jacobson, 1998)	k = −15→15
T_min = 0.760, T_max = 0.950	l = −16→17
14714 measured reflections

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0606P)² + 0.5335P] where P = (F_o² + 2F_c²)/3
5445 reflections	(Δ/σ)_max = 0.001
379 parameters	Δρ_max = 0.21 e Å⁻³
4 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₂₆H₂₃ClN₄O₂·C₃H₇NO·2(H₂O)	γ = 84.595 (15)°
M_r = 568.06	V = 1500.5 (3) Å³
Triclinic, P1	Z = 2
a = 9.237 (1) Å	Mo Kα radiation
b = 12.9553 (17) Å	µ = 0.17 mm⁻¹
c = 14.4554 (11) Å	T = 293 K
α = 66.162 (11)°	0.60 × 0.57 × 0.30 mm
β = 71.619 (12)°

Data collection top

Rigaku Mercury diffractometer	5445 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	4310 reflections with I > 2σ(I)
T_min = 0.760, T_max = 0.950	R_int = 0.028
14714 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	4 restraints
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.21 e Å⁻³
5445 reflections	Δρ_min = −0.31 e Å⁻³
379 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl1	0.98120 (12)	1.26623 (8)	−0.42483 (7)	0.1045 (4)
O1	0.7477 (2)	0.47841 (13)	0.12855 (14)	0.0562 (5)
O2	0.9204 (2)	0.60921 (17)	0.22240 (15)	0.0609 (5)
O3	0.5785 (4)	0.07513 (19)	0.2612 (2)	0.1004 (9)
O4	0.1363 (4)	0.7917 (2)	0.0471 (2)	0.0956 (8)
H4A	0.148 (5)	0.772 (4)	−0.002 (2)	0.115*
H4B	0.076 (4)	0.747 (3)	0.101 (2)	0.115*
O5	0.7925 (3)	0.2586 (2)	0.1329 (2)	0.0918 (8)
H5A	0.781 (5)	0.317 (2)	0.144 (3)	0.110*
H5B	0.721 (3)	0.214 (3)	0.176 (3)	0.110*
N1	0.7639 (2)	0.87742 (14)	−0.01571 (14)	0.0364 (4)
N2	0.6913 (3)	0.51570 (16)	0.33166 (15)	0.0490 (5)
N3	0.5786 (3)	0.79554 (19)	0.35627 (18)	0.0595 (6)
N4	0.7018 (2)	0.98819 (15)	0.08330 (15)	0.0436 (5)
H4C	0.6681	0.9967	0.1424	0.052*
H4D	0.7271	1.0464	0.0242	0.052*
N5	0.3930 (5)	0.0797 (3)	0.4056 (3)	0.1189 (14)
C1	0.7780 (2)	0.77324 (18)	−0.02435 (17)	0.0351 (5)
C2	0.7457 (2)	0.67493 (18)	0.06225 (17)	0.0357 (5)
C3	0.6836 (2)	0.66875 (18)	0.17425 (17)	0.0361 (5)
C4	0.6775 (2)	0.78666 (18)	0.17317 (17)	0.0348 (5)
C5	0.7150 (2)	0.88302 (17)	0.08337 (17)	0.0336 (5)
C6	0.7733 (3)	0.5680 (2)	0.04972 (19)	0.0422 (6)
C7	0.8399 (3)	0.5698 (2)	−0.0597 (2)	0.0521 (7)
H7A	0.8078	0.5007	−0.0600	0.063*
H7B	0.9504	0.5711	−0.0777	0.063*
C8	0.7935 (3)	0.6698 (2)	−0.1438 (2)	0.0499 (6)
C9	0.8308 (3)	0.7769 (2)	−0.13491 (18)	0.0457 (6)
H9A	0.9405	0.7912	−0.1630	0.055*
H9B	0.7845	0.8399	−0.1790	0.055*
C10	0.6231 (4)	0.6592 (3)	−0.1279 (3)	0.0723 (9)
H10A	0.6032	0.5937	−0.1380	0.108*
H10B	0.5932	0.7254	−0.1785	0.108*
H10C	0.5659	0.6519	−0.0573	0.108*
C11	0.8872 (4)	0.6759 (3)	−0.2544 (2)	0.0767 (10)
H11A	0.9938	0.6831	−0.2636	0.115*
H11B	0.8585	0.7402	−0.3074	0.115*
H11C	0.8678	0.6083	−0.2614	0.115*
C12	0.7833 (3)	0.5956 (2)	0.24294 (19)	0.0439 (6)
C13	0.5405 (3)	0.52001 (19)	0.32746 (19)	0.0457 (6)
C14	0.4138 (4)	0.4527 (2)	0.4012 (2)	0.0673 (9)
H14	0.4199	0.3940	0.4636	0.081*
C15	0.2771 (4)	0.4775 (3)	0.3771 (3)	0.0768 (10)
H15	0.1900	0.4339	0.4250	0.092*
C16	0.2652 (3)	0.5628 (3)	0.2865 (3)	0.0700 (9)
H16	0.1714	0.5767	0.2735	0.084*
C17	0.3932 (3)	0.6290 (2)	0.2137 (2)	0.0506 (6)
H17	0.3866	0.6874	0.1512	0.061*
C18	0.5295 (3)	0.60722 (18)	0.23519 (18)	0.0387 (5)
C19	0.7487 (4)	0.4264 (3)	0.4093 (2)	0.0743 (9)
H19A	0.7541	0.3587	0.3967	0.111*
H19B	0.6814	0.4131	0.4792	0.111*
H19C	0.8487	0.4482	0.4035	0.111*
C20	0.6241 (3)	0.79382 (19)	0.27326 (19)	0.0413 (6)
C21	0.8148 (2)	0.97855 (18)	−0.11100 (17)	0.0350 (5)
C22	0.7118 (3)	1.04436 (19)	−0.15805 (19)	0.0432 (6)
H22	0.6077	1.0277	−0.1254	0.052*
C23	0.7629 (3)	1.1353 (2)	−0.2540 (2)	0.0523 (7)
H23	0.6939	1.1808	−0.2863	0.063*
C24	0.9163 (3)	1.1575 (2)	−0.3009 (2)	0.0554 (7)
C25	1.0204 (3)	1.0947 (2)	−0.2537 (2)	0.0598 (7)
H25	1.1243	1.1127	−0.2860	0.072*
C26	0.9691 (3)	1.0041 (2)	−0.1572 (2)	0.0492 (6)
H26	1.0382	0.9607	−0.1237	0.059*
C27	0.4592 (6)	0.0402 (3)	0.3331 (3)	0.0904 (12)
H27	0.4101	−0.0214	0.3366	0.108*
C28	0.4561 (9)	0.1747 (5)	0.4057 (5)	0.187 (3)
H28A	0.5649	0.1780	0.3746	0.280*
H28B	0.4322	0.1686	0.4774	0.280*
H28C	0.4141	0.2420	0.3652	0.280*
C29	0.2537 (8)	0.0312 (7)	0.4884 (5)	0.205 (4)
H29A	0.2198	−0.0318	0.4806	0.307*
H29B	0.1771	0.0869	0.4839	0.307*
H29C	0.2710	0.0060	0.5562	0.307*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1137 (8)	0.0718 (6)	0.0595 (5)	−0.0027 (5)	0.0020 (5)	0.0216 (4)
O1	0.0800 (13)	0.0305 (9)	0.0487 (11)	0.0064 (8)	−0.0133 (9)	−0.0120 (8)
O2	0.0489 (11)	0.0686 (13)	0.0630 (12)	0.0095 (9)	−0.0250 (9)	−0.0194 (10)
O3	0.158 (3)	0.0573 (14)	0.0778 (18)	−0.0061 (15)	−0.0191 (18)	−0.0296 (13)
O4	0.133 (2)	0.0648 (15)	0.0736 (18)	−0.0345 (14)	−0.0062 (16)	−0.0228 (13)
O5	0.0887 (18)	0.0642 (16)	0.126 (2)	0.0034 (13)	−0.0146 (15)	−0.0546 (16)
N1	0.0479 (11)	0.0275 (10)	0.0295 (10)	−0.0011 (8)	−0.0091 (8)	−0.0086 (8)
N2	0.0682 (14)	0.0371 (11)	0.0335 (11)	0.0104 (10)	−0.0172 (10)	−0.0063 (9)
N3	0.0835 (17)	0.0514 (14)	0.0413 (13)	0.0010 (11)	−0.0124 (12)	−0.0209 (11)
N4	0.0590 (13)	0.0328 (10)	0.0358 (11)	−0.0035 (9)	−0.0092 (9)	−0.0131 (9)
N5	0.197 (4)	0.101 (3)	0.075 (2)	0.080 (3)	−0.058 (3)	−0.055 (2)
C1	0.0369 (12)	0.0329 (12)	0.0343 (12)	0.0008 (9)	−0.0100 (10)	−0.0128 (10)
C2	0.0401 (12)	0.0329 (12)	0.0333 (12)	0.0023 (9)	−0.0107 (10)	−0.0127 (10)
C3	0.0401 (12)	0.0314 (12)	0.0331 (12)	−0.0001 (9)	−0.0092 (10)	−0.0104 (10)
C4	0.0401 (12)	0.0315 (12)	0.0311 (12)	−0.0018 (9)	−0.0082 (9)	−0.0121 (10)
C5	0.0344 (12)	0.0301 (11)	0.0365 (12)	−0.0005 (9)	−0.0108 (9)	−0.0129 (10)
C6	0.0507 (14)	0.0343 (13)	0.0415 (14)	0.0059 (10)	−0.0147 (11)	−0.0153 (11)
C7	0.0681 (17)	0.0425 (14)	0.0511 (16)	0.0109 (12)	−0.0194 (13)	−0.0248 (12)
C8	0.0699 (18)	0.0439 (14)	0.0421 (14)	0.0063 (12)	−0.0200 (13)	−0.0217 (12)
C9	0.0588 (15)	0.0411 (14)	0.0347 (13)	0.0019 (11)	−0.0113 (11)	−0.0147 (11)
C10	0.081 (2)	0.070 (2)	0.080 (2)	0.0025 (16)	−0.0420 (18)	−0.0305 (17)
C11	0.125 (3)	0.0619 (19)	0.0506 (18)	0.0082 (18)	−0.0236 (18)	−0.0325 (16)
C12	0.0545 (16)	0.0385 (13)	0.0375 (13)	0.0091 (11)	−0.0159 (11)	−0.0141 (11)
C13	0.0562 (16)	0.0327 (13)	0.0417 (14)	−0.0007 (11)	−0.0042 (12)	−0.0159 (11)
C14	0.094 (2)	0.0401 (15)	0.0464 (17)	−0.0152 (15)	0.0039 (16)	−0.0107 (13)
C15	0.062 (2)	0.069 (2)	0.085 (2)	−0.0284 (17)	0.0098 (18)	−0.034 (2)
C16	0.0542 (18)	0.068 (2)	0.092 (3)	−0.0113 (15)	−0.0084 (16)	−0.043 (2)
C17	0.0484 (15)	0.0431 (14)	0.0641 (17)	0.0001 (11)	−0.0155 (13)	−0.0258 (13)
C18	0.0437 (13)	0.0307 (12)	0.0382 (13)	−0.0026 (10)	−0.0060 (10)	−0.0143 (10)
C19	0.109 (3)	0.0574 (18)	0.0457 (17)	0.0280 (17)	−0.0305 (17)	−0.0095 (14)
C20	0.0504 (14)	0.0316 (12)	0.0392 (14)	−0.0024 (10)	−0.0120 (11)	−0.0116 (10)
C21	0.0405 (13)	0.0309 (11)	0.0293 (11)	−0.0043 (9)	−0.0080 (10)	−0.0084 (9)
C22	0.0387 (13)	0.0386 (13)	0.0454 (14)	0.0048 (10)	−0.0097 (11)	−0.0130 (11)
C23	0.0582 (17)	0.0428 (14)	0.0461 (15)	0.0105 (12)	−0.0186 (13)	−0.0079 (12)
C24	0.0668 (18)	0.0381 (14)	0.0413 (15)	−0.0031 (12)	−0.0086 (13)	−0.0008 (11)
C25	0.0456 (15)	0.0581 (17)	0.0542 (17)	−0.0143 (13)	−0.0035 (13)	−0.0062 (14)
C26	0.0444 (14)	0.0496 (15)	0.0467 (15)	−0.0026 (11)	−0.0168 (12)	−0.0091 (12)
C27	0.144 (4)	0.067 (2)	0.070 (2)	0.030 (2)	−0.039 (2)	−0.038 (2)
C28	0.386 (11)	0.122 (4)	0.147 (5)	0.106 (6)	−0.168 (6)	−0.102 (4)
C29	0.208 (7)	0.245 (8)	0.109 (4)	0.123 (6)	−0.015 (5)	−0.068 (5)

Geometric parameters (Å, º) top

Cl1—C24	1.730 (3)	C9—H9B	0.9700
O1—C6	1.230 (3)	C10—H10A	0.9600
O2—C12	1.219 (3)	C10—H10B	0.9600
O3—C27	1.221 (5)	C10—H10C	0.9600
O4—H4A	0.82 (4)	C11—H11A	0.9600
O4—H4B	0.82 (3)	C11—H11B	0.9600
O5—H5A	0.83 (3)	C11—H11C	0.9600
O5—H5B	0.82 (4)	C13—C18	1.383 (3)
N1—C5	1.389 (3)	C13—C14	1.386 (4)
N1—C1	1.395 (3)	C14—C15	1.389 (5)
N1—C21	1.444 (3)	C14—H14	0.9300
N2—C12	1.357 (3)	C15—C16	1.358 (5)
N2—C13	1.408 (3)	C15—H15	0.9300
N2—C19	1.445 (3)	C16—C17	1.385 (4)
N3—C20	1.148 (3)	C16—H16	0.9300
N4—C5	1.356 (3)	C17—C18	1.368 (3)
N4—H4C	0.8600	C17—H17	0.9300
N4—H4D	0.8600	C19—H19A	0.9600
N5—C27	1.306 (4)	C19—H19B	0.9600
N5—C28	1.410 (7)	C19—H19C	0.9600
N5—C29	1.434 (7)	C21—C22	1.372 (3)
C1—C2	1.351 (3)	C21—C26	1.377 (3)
C1—C9	1.499 (3)	C22—C23	1.381 (3)
C2—C6	1.458 (3)	C22—H22	0.9300
C2—C3	1.508 (3)	C23—C24	1.365 (4)
C3—C18	1.514 (3)	C23—H23	0.9300
C3—C4	1.517 (3)	C24—C25	1.367 (4)
C3—C12	1.544 (3)	C25—C26	1.384 (4)
C4—C5	1.361 (3)	C25—H25	0.9300
C4—C20	1.412 (3)	C26—H26	0.9300
C6—C7	1.497 (3)	C27—H27	0.9300
C7—C8	1.514 (4)	C28—H28A	0.9600
C7—H7A	0.9700	C28—H28B	0.9600
C7—H7B	0.9700	C28—H28C	0.9600
C8—C9	1.524 (3)	C29—H29A	0.9600
C8—C10	1.528 (4)	C29—H29B	0.9600
C8—C11	1.533 (4)	C29—H29C	0.9600
C9—H9A	0.9700

H4A—O4—H4B	110 (4)	H11A—C11—H11C	109.5
H5A—O5—H5B	108 (4)	H11B—C11—H11C	109.5
C5—N1—C1	120.56 (17)	O2—C12—N2	125.9 (2)
C5—N1—C21	120.44 (17)	O2—C12—C3	125.8 (2)
C1—N1—C21	118.74 (18)	N2—C12—C3	108.3 (2)
C12—N2—C13	111.0 (2)	C18—C13—C14	121.1 (3)
C12—N2—C19	123.1 (2)	C18—C13—N2	110.0 (2)
C13—N2—C19	125.0 (2)	C14—C13—N2	128.9 (3)
C5—N4—H4C	120.0	C13—C14—C15	116.5 (3)
C5—N4—H4D	120.0	C13—C14—H14	121.7
H4C—N4—H4D	120.0	C15—C14—H14	121.7
C27—N5—C28	120.9 (5)	C16—C15—C14	122.9 (3)
C27—N5—C29	123.0 (5)	C16—C15—H15	118.6
C28—N5—C29	116.1 (5)	C14—C15—H15	118.6
C2—C1—N1	121.7 (2)	C15—C16—C17	119.8 (3)
C2—C1—C9	122.1 (2)	C15—C16—H16	120.1
N1—C1—C9	116.17 (19)	C17—C16—H16	120.1
C1—C2—C6	119.9 (2)	C18—C17—C16	118.9 (3)
C1—C2—C3	123.27 (19)	C18—C17—H17	120.6
C6—C2—C3	116.87 (19)	C16—C17—H17	120.6
C2—C3—C18	113.90 (18)	C17—C18—C13	120.9 (2)
C2—C3—C4	109.84 (17)	C17—C18—C3	130.3 (2)
C18—C3—C4	110.71 (17)	C13—C18—C3	108.7 (2)
C2—C3—C12	111.04 (18)	N2—C19—H19A	109.5
C18—C3—C12	101.58 (18)	N2—C19—H19B	109.5
C4—C3—C12	109.47 (18)	H19A—C19—H19B	109.5
C5—C4—C20	119.5 (2)	N2—C19—H19C	109.5
C5—C4—C3	124.29 (19)	H19A—C19—H19C	109.5
C20—C4—C3	116.16 (18)	H19B—C19—H19C	109.5
N4—C5—C4	123.7 (2)	N3—C20—C4	177.4 (2)
N4—C5—N1	116.05 (19)	C22—C21—C26	120.6 (2)
C4—C5—N1	120.16 (19)	C22—C21—N1	120.5 (2)
O1—C6—C2	120.0 (2)	C26—C21—N1	118.8 (2)
O1—C6—C7	121.1 (2)	C21—C22—C23	119.9 (2)
C2—C6—C7	118.9 (2)	C21—C22—H22	120.1
C6—C7—C8	113.4 (2)	C23—C22—H22	120.1
C6—C7—H7A	108.9	C24—C23—C22	119.0 (2)
C8—C7—H7A	108.9	C24—C23—H23	120.5
C6—C7—H7B	108.9	C22—C23—H23	120.5
C8—C7—H7B	108.9	C23—C24—C25	121.9 (2)
H7A—C7—H7B	107.7	C23—C24—Cl1	119.1 (2)
C7—C8—C9	108.1 (2)	C25—C24—Cl1	119.0 (2)
C7—C8—C10	110.0 (2)	C24—C25—C26	119.1 (2)
C9—C8—C10	110.9 (2)	C24—C25—H25	120.5
C7—C8—C11	109.8 (2)	C26—C25—H25	120.5
C9—C8—C11	107.8 (2)	C21—C26—C25	119.5 (2)
C10—C8—C11	110.2 (2)	C21—C26—H26	120.3
C1—C9—C8	114.7 (2)	C25—C26—H26	120.3
C1—C9—H9A	108.6	O3—C27—N5	127.2 (4)
C8—C9—H9A	108.6	O3—C27—H27	116.4
C1—C9—H9B	108.6	N5—C27—H27	116.4
C8—C9—H9B	108.6	N5—C28—H28A	109.5
H9A—C9—H9B	107.6	N5—C28—H28B	109.5
C8—C10—H10A	109.5	H28A—C28—H28B	109.5
C8—C10—H10B	109.5	N5—C28—H28C	109.5
H10A—C10—H10B	109.5	H28A—C28—H28C	109.5
C8—C10—H10C	109.5	H28B—C28—H28C	109.5
H10A—C10—H10C	109.5	N5—C29—H29A	109.5
H10B—C10—H10C	109.5	N5—C29—H29B	109.5
C8—C11—H11A	109.5	H29A—C29—H29B	109.5
C8—C11—H11B	109.5	N5—C29—H29C	109.5
H11A—C11—H11B	109.5	H29A—C29—H29C	109.5
C8—C11—H11C	109.5	H29B—C29—H29C	109.5

C5—N1—C1—C2	−0.3 (3)	C2—C3—C12—O2	54.8 (3)
C21—N1—C1—C2	173.8 (2)	C18—C3—C12—O2	176.3 (2)
C5—N1—C1—C9	179.7 (2)	C4—C3—C12—O2	−66.6 (3)
C21—N1—C1—C9	−6.2 (3)	C2—C3—C12—N2	−127.1 (2)
N1—C1—C2—C6	−175.3 (2)	C18—C3—C12—N2	−5.6 (2)
C9—C1—C2—C6	4.8 (3)	C4—C3—C12—N2	111.5 (2)
N1—C1—C2—C3	3.7 (3)	C12—N2—C13—C18	−1.9 (3)
C9—C1—C2—C3	−176.2 (2)	C19—N2—C13—C18	−171.3 (2)
C1—C2—C3—C18	119.9 (2)	C12—N2—C13—C14	179.3 (2)
C6—C2—C3—C18	−61.1 (3)	C19—N2—C13—C14	10.0 (4)
C1—C2—C3—C4	−4.9 (3)	C18—C13—C14—C15	0.2 (4)
C6—C2—C3—C4	174.08 (19)	N2—C13—C14—C15	178.8 (3)
C1—C2—C3—C12	−126.2 (2)	C13—C14—C15—C16	0.0 (5)
C6—C2—C3—C12	52.9 (3)	C14—C15—C16—C17	0.2 (5)
C2—C3—C4—C5	3.4 (3)	C15—C16—C17—C18	−0.4 (4)
C18—C3—C4—C5	−123.3 (2)	C16—C17—C18—C13	0.6 (4)
C12—C3—C4—C5	125.6 (2)	C16—C17—C18—C3	−176.1 (2)
C2—C3—C4—C20	−178.80 (19)	C14—C13—C18—C17	−0.5 (4)
C18—C3—C4—C20	54.6 (3)	N2—C13—C18—C17	−179.3 (2)
C12—C3—C4—C20	−56.6 (3)	C14—C13—C18—C3	176.9 (2)
C20—C4—C5—N4	−1.2 (3)	N2—C13—C18—C3	−2.0 (3)
C3—C4—C5—N4	176.5 (2)	C2—C3—C18—C17	−59.0 (3)
C20—C4—C5—N1	−178.3 (2)	C4—C3—C18—C17	65.4 (3)
C3—C4—C5—N1	−0.6 (3)	C12—C3—C18—C17	−178.5 (2)
C1—N1—C5—N4	−178.59 (19)	C2—C3—C18—C13	123.9 (2)
C21—N1—C5—N4	7.4 (3)	C4—C3—C18—C13	−111.7 (2)
C1—N1—C5—C4	−1.3 (3)	C12—C3—C18—C13	4.5 (2)
C21—N1—C5—C4	−175.3 (2)	C5—C4—C20—N3	163 (6)
C1—C2—C6—O1	178.2 (2)	C3—C4—C20—N3	−15 (6)
C3—C2—C6—O1	−0.9 (3)	C5—N1—C21—C22	−85.8 (3)
C1—C2—C6—C7	1.1 (3)	C1—N1—C21—C22	100.1 (3)
C3—C2—C6—C7	−178.0 (2)	C5—N1—C21—C26	98.0 (3)
O1—C6—C7—C8	151.3 (2)	C1—N1—C21—C26	−76.1 (3)
C2—C6—C7—C8	−31.7 (3)	C26—C21—C22—C23	1.8 (4)
C6—C7—C8—C9	53.2 (3)	N1—C21—C22—C23	−174.4 (2)
C6—C7—C8—C10	−68.0 (3)	C21—C22—C23—C24	0.5 (4)
C6—C7—C8—C11	170.5 (2)	C22—C23—C24—C25	−2.4 (4)
C2—C1—C9—C8	20.2 (3)	C22—C23—C24—Cl1	176.2 (2)
N1—C1—C9—C8	−159.8 (2)	C23—C24—C25—C26	1.9 (4)
C7—C8—C9—C1	−47.8 (3)	Cl1—C24—C25—C26	−176.6 (2)
C10—C8—C9—C1	72.9 (3)	C22—C21—C26—C25	−2.2 (4)
C11—C8—C9—C1	−166.4 (2)	N1—C21—C26—C25	174.0 (2)
C13—N2—C12—O2	−177.0 (2)	C24—C25—C26—C21	0.4 (4)
C19—N2—C12—O2	−7.5 (4)	C28—N5—C27—O3	1.6 (7)
C13—N2—C12—C3	4.9 (3)	C29—N5—C27—O3	−178.8 (5)
C19—N2—C12—C3	174.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C28—H28B···N3ⁱ	0.96	2.60	3.528 (5)	163
C15—H15···Cl1ⁱⁱ	0.93	2.74	3.647 (3)	167
N4—H4D···O4ⁱⁱⁱ	0.86	2.23	2.934 (3)	139
N4—H4C···O3^iv	0.86	2.24	3.071 (3)	162
O5—H5B···O3	0.82 (4)	2.03 (4)	2.830 (4)	163 (4)
O5—H5A···O1	0.83 (3)	2.02 (2)	2.816 (3)	164 (4)
O4—H4B···O2^v	0.82 (3)	2.17 (3)	2.974 (3)	167 (4)
O4—H4A···O5^vi	0.82 (4)	1.99 (4)	2.800 (4)	170 (4)

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

Experimental details

Crystal data
Chemical formula	C₂₆H₂₃ClN₄O₂·C₃H₇NO·2(H₂O)
M_r	568.06
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.237 (1), 12.9553 (17), 14.4554 (11)
α, β, γ (°)	66.162 (11), 71.619 (12), 84.595 (15)
V (Å³)	1500.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.60 × 0.57 × 0.30

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.760, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	14714, 5445, 4310
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.155, 1.13
No. of reflections	5445
No. of parameters	379
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.31

Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C28—H28B···N3ⁱ	0.96	2.60	3.528 (5)	163.1
C15—H15···Cl1ⁱⁱ	0.93	2.74	3.647 (3)	166.6
N4—H4D···O4ⁱⁱⁱ	0.86	2.23	2.934 (3)	138.6
N4—H4C···O3^iv	0.86	2.24	3.071 (3)	162.0
O5—H5B···O3	0.82 (4)	2.03 (4)	2.830 (4)	163 (4)
O5—H5A···O1	0.83 (3)	2.017 (16)	2.816 (3)	164 (4)
O4—H4B···O2^v	0.82 (3)	2.17 (3)	2.974 (3)	167 (4)
O4—H4A···O5^vi	0.82 (4)	1.99 (4)	2.800 (4)	170 (4)

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

Acknowledgements

The authors are deeply indebted to Professor S. J. Ji for his invaluable help. This work was partially supported by the Special Foundation of the President of Xuzhou Medical College and by a grant from the Chemistry and Biochemistry Experimental Center of Xuzhou Medical College.

References

Abdel-Rahman, A. H., Keshk, E. M., Hanna, M. A. & El-Bady, Sh. M. (2004). Bioorg. Med. Chem. 12, 2483–2488. Web of Science CrossRef PubMed CAS Google Scholar
Jacobson, R. (1998). Private communication to the Rigaku Corporation, Tokyo, Japan. Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Joshi, K. C. & Chand, P. (1982). Pharmazie, 37, 1–12. CAS PubMed Web of Science Google Scholar
Rigaku/MSC (2001). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Silva, J. F. M. da, Garden, S. J. & Pinto, A. C. (2001). J. Braz. Chem. Soc. 12, 273–324. CrossRef Google Scholar
Zhu, S. L., Ji, S. J. & Zhang, Y. (2007). Tetrahedron, 63, 9365–9372. Web of Science CSD CrossRef CAS Google Scholar

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

2′-Amino-1′-(4-chloro­phen­yl)-1,7′,7′-tri­methyl-2,5′-dioxo-5′,6′,7′,8′-tetra­hydro­spiro­[indoline-3,4′(1′H)-quinoline]-3′-carbo­nitrile di­methyl­formamide solvate dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2′-Amino-1′-(4-chlorophenyl)-1,7′,7′-trimethyl-2,5′-dioxo-5′,6′,7′,8′-tetrahydrospiro[indoline-3,4′(1′H)-quinoline]-3′-carbonitrile dimethylformamide solvate dihydrate