2-Amino-4′-bromo-2′,5-dioxo-4H,5H-pyrano[3,2-c]chromene-4-spiro-3′(2′H)-1′H-indole-3-carbonitrile N,N-dimethyl­formamide solvate

Zhu, S.-L.

doi:10.1107/S1600536808015626

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1162

doi:10.1107/S1600536808015626

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2-Amino-4′-bromo-2′,5-dioxo-4H,5H-pyrano[3,2-c]chromene-4-spiro-3′(2′H)-1′H-indole-3-carbonitrile N,N-dimethylformamide solvate

Song-Lei Zhu ^a ^*

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

(Received 22 May 2008; accepted 23 May 2008; online 30 May 2008)

In the molecule of the title compound, C₂₀H₁₀BrN₃O₄·C₃H₇NO, the spiro pyran ring adopts a twist conformation. The indole and coumarin ring systems are each nearly planar, and are oriented at a dihedral angle of 79.29 (3)°. In the crystal structure, intermolecular N—H⋯O, N—H⋯N, C—H⋯O and C—H⋯N hydrogen bonds link the molecules.

Related literature

For general background, see: da Silva et al. (2001 ); Joshi & Chand (1982 ); Abdel-Rahman et al. (2004 ); Zhu et al. (2007 ). For ring-puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₀H₁₀BrN₃O₄·C₃H₇NO
M_r = 509.32
Monoclinic, P 2₁ /c
a = 17.004 (3) Å
b = 9.0452 (15) Å
c = 14.415 (3) Å
β = 108.340 (3)°
V = 2104.5 (7) Å³
Z = 4
Mo Kα radiation
μ = 2.00 mm⁻¹
T = 153 (2) K
0.45 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ) T_min = 0.434, T_max = 0.670
19919 measured reflections
3847 independent reflections
3597 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.067
S = 1.09
3847 reflections
309 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89 (3)	2.02 (3)	2.891 (2)	165 (2)
N1—H1B⋯N2ⁱⁱ	0.84 (3)	2.27 (3)	3.090 (3)	166 (2)
N3—H3⋯O5ⁱⁱⁱ	0.88	1.93	2.785 (2)	163
C11—H11⋯O2^iv	0.95	2.54	3.462 (3)	165
C19—H19⋯O4ⁱ	0.95	2.50	3.173 (3)	128
C22—H22A⋯N2^v	0.98	2.48	3.443 (3)	166
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+2, -y, -z+1; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x, y-1, z; (v) x, 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/S1600536808015626/hk2467sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015626/hk2467Isup2.hkl

checkCIF report

Comment top

The indole nucleus is the well known heterocycle (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 programme 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 4-hydroxycoumarin in water. We report herein the crystal structure of the title compound, (I).

In the molecule of (I), (Fig. 1), rings B (N3/C3/C7/C8/C13), C (C8-C13), D (O3/C4/C5/C14/C15/C20) and E (C15-C20) are, of course, planar. The dihedral angles between them are B/C = 1.51 (3)° and D/E = 4.24 (3)°. So, rings B, C and D,E are nearly coplanar. The coplanar ring systems are oriented at a dihedral angle of 79.29 (3)°. Ring A (O1/C1-C5) adopts twisted conformation, having total puckering amplitude, Q_T, of 0.122 (3) Å (Cremer & Pople, 1975).

In the crystal structure, intermolecular N-H···O, N-H···N, C-H···O and C-H···N hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: da-Silva et al. (2001); Joshi & Chand (1982); Abdel-Rahman et al. (2004); Zhu et al. (2007). For ring-puckering parameters, see: Cremer & Pople (1975).

Experimental top

Compound (I) was prepared by the reaction of 4-bromoisatin (1 mmol), malononitrile (1 mmol) and 4-hydroxycoumarin (1 mmol) in water (5 ml). The reaction was catalyzed by TEBAC (triethylbenzylammonium chloride, 1 mmol). After stirring at 333 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 solution by slow evaporation at room temperature (yield; 80%, m.p. > 573 K). Spectroscopic analysis: IR (KBr, n, cm^-1): 3372, 3310, 3179, 2192, 1728, 1674, 1605, 1450, 1358, 1234, 1111, 1080, 972, 910, 872, 764, 578. ¹H NMR (400 MHz, DMSO-d₆): 10.99 (s, 1H, NH), 7.96 (d, 1H, J = 7.6 Hz, ArH), 7.84 (br s, 2H, NH2), 7.79 (t, 1H, J = 8.4 Hz, ArH), 7.53–7.59 (m, 2H, ArH), 7.21 (t, 1H, J = 8.0 Hz, ArH), 7.12 (d, 1H, J = 8.0 Hz, ArH), 6.91 (d, 1H, J = 7.6 Hz, ArH).

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 40% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

2-Amino-4'-bromo-2',5-dioxo-4H,5H-pyrano[3,2-c]chromene-4-spiro-3'(2'H)- 1'H-indole-3-carbonitrile N,N-dimethylformamide solvate top

Crystal data top

C₂₀H₁₀BrN₃O₄·C₃H₇NO	F(000) = 1032
M_r = 509.32	D_x = 1.607 Mg m⁻³
Monoclinic, P2₁/c	Melting point > 573 K
Hall symbol: -P 2 y b c	Mo Kα radiation, λ = 0.71070 Å
a = 17.004 (3) Å	Cell parameters from 7931 reflections
b = 9.0452 (15) Å	θ = 3.2–25.3°
c = 14.415 (3) Å	µ = 2.00 mm⁻¹
β = 108.340 (3)°	T = 153 K
V = 2104.5 (7) Å³	Block, colorless
Z = 4	0.45 × 0.30 × 0.20 mm

Data collection top

Rigaku Mercury diffractometer	3847 independent reflections
Radiation source: fine-focus sealed tube	3597 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.3°, θ_min = 3.2°
ω scans	h = −17→20
Absorption correction: multi-scan (Jacobson, 1998)	k = −10→9
T_min = 0.434, T_max = 0.670	l = −17→17
19919 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0219P)² + 2.2795P] where P = (F_o² + 2F_c²)/3
3847 reflections	(Δ/σ)_max = 0.002
309 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₂₀H₁₀BrN₃O₄·C₃H₇NO	V = 2104.5 (7) Å³
M_r = 509.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.004 (3) Å	µ = 2.00 mm⁻¹
b = 9.0452 (15) Å	T = 153 K
c = 14.415 (3) Å	0.45 × 0.30 × 0.20 mm
β = 108.340 (3)°

Data collection top

Rigaku Mercury diffractometer	3847 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	3597 reflections with I > 2σ(I)
T_min = 0.434, T_max = 0.670	R_int = 0.031
19919 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.56 e Å⁻³
3847 reflections	Δρ_min = −0.38 e Å⁻³
309 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 > 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
Br1	0.674546 (15)	−0.23487 (3)	0.370899 (16)	0.02528 (8)
O1	0.72297 (9)	0.17427 (16)	0.38347 (10)	0.0165 (3)
O2	0.80028 (9)	0.17370 (16)	0.69972 (11)	0.0195 (3)
O3	0.54289 (9)	0.16195 (17)	0.51984 (11)	0.0205 (3)
O4	0.61528 (9)	0.00093 (17)	0.62894 (11)	0.0218 (3)
O5	0.86929 (11)	0.5130 (2)	0.42641 (12)	0.0350 (4)
N1	0.84875 (12)	0.1416 (2)	0.37211 (14)	0.0165 (4)
H1A	0.8332 (15)	0.211 (3)	0.3263 (19)	0.022 (7)*
H1B	0.8976 (16)	0.110 (3)	0.3921 (17)	0.018 (6)*
N2	0.97044 (12)	−0.0393 (2)	0.58997 (14)	0.0245 (4)
N3	0.80382 (11)	−0.07714 (19)	0.72793 (13)	0.0170 (4)
H3	0.8267	−0.0767	0.7918	0.020*
N4	0.94175 (11)	0.5142 (2)	0.58794 (13)	0.0216 (4)
C1	0.79982 (12)	0.1140 (2)	0.42627 (15)	0.0135 (4)
C2	0.81869 (12)	0.0379 (2)	0.51188 (15)	0.0135 (4)
C3	0.75548 (12)	−0.0029 (2)	0.56233 (15)	0.0132 (4)
C4	0.67684 (12)	0.0815 (2)	0.51288 (15)	0.0135 (4)
C5	0.66610 (13)	0.1649 (2)	0.43275 (15)	0.0143 (4)
C6	0.90223 (13)	−0.0065 (2)	0.55498 (15)	0.0159 (4)
C7	0.78839 (12)	0.0454 (2)	0.67200 (15)	0.0154 (4)
C8	0.74743 (12)	−0.1686 (2)	0.57294 (15)	0.0140 (4)
C9	0.71969 (13)	−0.2801 (2)	0.50567 (15)	0.0166 (4)
C10	0.72305 (14)	−0.4273 (2)	0.53575 (17)	0.0206 (5)
H10	0.7035	−0.5039	0.4891	0.025*
C11	0.75512 (14)	−0.4604 (2)	0.63403 (18)	0.0229 (5)
H11	0.7577	−0.5607	0.6543	0.027*
C12	0.78381 (13)	−0.3505 (2)	0.70414 (17)	0.0199 (5)
H12	0.8059	−0.3739	0.7716	0.024*
C13	0.77895 (13)	−0.2058 (2)	0.67179 (15)	0.0153 (4)
C14	0.61196 (13)	0.0753 (2)	0.55878 (15)	0.0168 (5)
C15	0.53467 (13)	0.2528 (2)	0.44043 (16)	0.0178 (5)
C16	0.46555 (14)	0.3429 (3)	0.41187 (18)	0.0247 (5)
H16	0.4252	0.3389	0.4448	0.030*
C17	0.45632 (14)	0.4387 (3)	0.33474 (18)	0.0264 (5)
H17	0.4097	0.5026	0.3153	0.032*
C18	0.51418 (14)	0.4430 (3)	0.28502 (17)	0.0240 (5)
H18	0.5066	0.5087	0.2315	0.029*
C19	0.58252 (13)	0.3522 (2)	0.31330 (16)	0.0195 (5)
H19	0.6220	0.3550	0.2791	0.023*
C20	0.59384 (13)	0.2557 (2)	0.39248 (15)	0.0156 (4)
C21	0.90376 (15)	0.5775 (3)	0.50259 (18)	0.0290 (6)
H21	0.9034	0.6825	0.5007	0.035*
C22	0.98163 (16)	0.6027 (3)	0.67431 (19)	0.0330 (6)
H22A	0.9725	0.7079	0.6581	0.050*
H22B	1.0412	0.5821	0.6968	0.050*
H22C	0.9580	0.5777	0.7262	0.050*
C23	0.94561 (18)	0.3560 (3)	0.6002 (2)	0.0376 (7)
H23A	0.9097	0.3257	0.6382	0.056*
H23B	1.0028	0.3264	0.6347	0.056*
H23C	0.9270	0.3082	0.5359	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03215 (15)	0.02519 (14)	0.01580 (13)	−0.00378 (10)	0.00365 (10)	−0.00394 (9)
O1	0.0129 (7)	0.0220 (8)	0.0152 (8)	0.0032 (6)	0.0053 (6)	0.0050 (6)
O2	0.0243 (8)	0.0164 (8)	0.0170 (8)	−0.0025 (6)	0.0051 (7)	−0.0043 (6)
O3	0.0157 (8)	0.0256 (9)	0.0225 (8)	0.0047 (6)	0.0095 (7)	0.0063 (7)
O4	0.0234 (8)	0.0243 (9)	0.0204 (8)	0.0027 (7)	0.0110 (7)	0.0059 (7)
O5	0.0318 (10)	0.0512 (12)	0.0194 (9)	0.0038 (9)	0.0042 (8)	−0.0030 (8)
N1	0.0130 (10)	0.0197 (10)	0.0172 (10)	0.0038 (8)	0.0051 (8)	0.0054 (8)
N2	0.0193 (11)	0.0316 (12)	0.0235 (10)	0.0053 (9)	0.0079 (9)	0.0070 (9)
N3	0.0199 (10)	0.0187 (10)	0.0105 (9)	0.0003 (8)	0.0022 (7)	0.0023 (7)
N4	0.0205 (10)	0.0256 (11)	0.0180 (10)	−0.0003 (8)	0.0051 (8)	0.0019 (8)
C1	0.0119 (10)	0.0122 (10)	0.0160 (10)	−0.0005 (8)	0.0037 (8)	−0.0037 (8)
C2	0.0129 (10)	0.0137 (11)	0.0139 (10)	0.0000 (8)	0.0043 (8)	−0.0003 (8)
C3	0.0137 (10)	0.0142 (11)	0.0119 (10)	−0.0009 (8)	0.0045 (8)	−0.0006 (8)
C4	0.0131 (10)	0.0135 (10)	0.0133 (10)	−0.0008 (8)	0.0034 (8)	−0.0025 (8)
C5	0.0141 (10)	0.0153 (11)	0.0143 (10)	−0.0015 (8)	0.0055 (8)	−0.0040 (8)
C6	0.0216 (12)	0.0145 (11)	0.0140 (11)	−0.0012 (9)	0.0089 (9)	0.0020 (8)
C7	0.0122 (10)	0.0194 (12)	0.0151 (11)	0.0003 (8)	0.0051 (9)	0.0014 (9)
C8	0.0121 (10)	0.0137 (11)	0.0179 (11)	0.0012 (8)	0.0070 (9)	0.0016 (8)
C9	0.0137 (10)	0.0213 (11)	0.0158 (11)	0.0000 (9)	0.0063 (9)	−0.0006 (9)
C10	0.0195 (11)	0.0158 (11)	0.0290 (13)	−0.0023 (9)	0.0112 (10)	−0.0042 (9)
C11	0.0224 (12)	0.0145 (11)	0.0356 (14)	0.0031 (9)	0.0146 (11)	0.0060 (10)
C12	0.0191 (11)	0.0201 (12)	0.0222 (12)	0.0030 (9)	0.0090 (10)	0.0061 (9)
C13	0.0133 (10)	0.0172 (11)	0.0167 (11)	0.0013 (8)	0.0064 (9)	0.0009 (9)
C14	0.0161 (11)	0.0160 (11)	0.0172 (11)	0.0000 (9)	0.0036 (9)	−0.0026 (9)
C15	0.0163 (11)	0.0187 (11)	0.0175 (11)	−0.0012 (9)	0.0042 (9)	0.0002 (9)
C16	0.0181 (12)	0.0276 (13)	0.0312 (13)	0.0031 (10)	0.0117 (10)	0.0008 (10)
C17	0.0180 (12)	0.0272 (13)	0.0313 (13)	0.0085 (10)	0.0041 (10)	0.0050 (10)
C18	0.0186 (12)	0.0263 (13)	0.0237 (12)	0.0025 (10)	0.0016 (10)	0.0071 (10)
C19	0.0179 (11)	0.0212 (12)	0.0182 (11)	0.0009 (9)	0.0040 (9)	0.0015 (9)
C20	0.0131 (10)	0.0158 (11)	0.0159 (11)	−0.0019 (8)	0.0018 (9)	−0.0014 (8)
C21	0.0244 (13)	0.0374 (15)	0.0263 (14)	0.0049 (11)	0.0097 (11)	0.0008 (11)
C22	0.0299 (14)	0.0340 (15)	0.0299 (14)	0.0011 (11)	0.0017 (11)	−0.0052 (11)
C23	0.0446 (17)	0.0293 (15)	0.0357 (15)	−0.0074 (12)	0.0078 (13)	0.0020 (12)

Geometric parameters (Å, º) top

Br1—C9	1.895 (2)	C8—C9	1.376 (3)
O1—C1	1.370 (2)	C8—C13	1.396 (3)
O1—C5	1.371 (2)	C9—C10	1.395 (3)
O2—C7	1.223 (3)	C10—C11	1.381 (3)
O3—C14	1.376 (3)	C10—H10	0.9500
O3—C15	1.380 (3)	C11—C12	1.392 (3)
O4—C14	1.201 (3)	C11—H11	0.9500
O5—C21	1.219 (3)	C12—C13	1.383 (3)
N1—C1	1.331 (3)	C12—H12	0.9500
N1—H1A	0.89 (3)	C15—C16	1.382 (3)
N1—H1B	0.84 (3)	C15—C20	1.389 (3)
N2—C6	1.149 (3)	C16—C17	1.379 (3)
N3—C7	1.347 (3)	C16—H16	0.9500
N3—C13	1.404 (3)	C17—C18	1.388 (3)
N3—H3	0.8800	C17—H17	0.9500
N4—C21	1.326 (3)	C18—C19	1.376 (3)
N4—C23	1.441 (3)	C18—H18	0.9500
N4—C22	1.456 (3)	C19—C20	1.401 (3)
C1—C2	1.360 (3)	C19—H19	0.9500
C2—C6	1.418 (3)	C21—H21	0.9500
C2—C3	1.521 (3)	C22—H22A	0.9800
C3—C4	1.509 (3)	C22—H22B	0.9800
C3—C8	1.517 (3)	C22—H22C	0.9800
C3—C7	1.564 (3)	C23—H23A	0.9800
C4—C5	1.343 (3)	C23—H23B	0.9800
C4—C14	1.455 (3)	C23—H23C	0.9800
C5—C20	1.440 (3)

C1—O1—C5	118.06 (16)	C12—C11—H11	119.2
C14—O3—C15	121.88 (16)	C13—C12—C11	117.5 (2)
C1—N1—H1A	118.2 (16)	C13—C12—H12	121.3
C1—N1—H1B	118.0 (16)	C11—C12—H12	121.3
H1A—N1—H1B	122 (2)	C12—C13—C8	122.3 (2)
C7—N3—C13	111.74 (17)	C12—C13—N3	127.9 (2)
C7—N3—H3	124.1	C8—C13—N3	109.74 (18)
C13—N3—H3	124.1	O4—C14—O3	118.06 (19)
C21—N4—C23	122.2 (2)	O4—C14—C4	124.3 (2)
C21—N4—C22	121.1 (2)	O3—C14—C4	117.68 (18)
C23—N4—C22	116.8 (2)	O3—C15—C16	116.93 (19)
N1—C1—C2	127.9 (2)	O3—C15—C20	121.61 (19)
N1—C1—O1	110.17 (18)	C16—C15—C20	121.4 (2)
C2—C1—O1	121.94 (18)	C17—C16—C15	118.8 (2)
C1—C2—C6	117.31 (18)	C17—C16—H16	120.6
C1—C2—C3	123.80 (18)	C15—C16—H16	120.6
C6—C2—C3	118.89 (18)	C16—C17—C18	121.0 (2)
C4—C3—C8	116.89 (17)	C16—C17—H17	119.5
C4—C3—C2	107.82 (17)	C18—C17—H17	119.5
C8—C3—C2	112.82 (17)	C19—C18—C17	120.0 (2)
C4—C3—C7	108.55 (16)	C19—C18—H18	120.0
C8—C3—C7	100.89 (16)	C17—C18—H18	120.0
C2—C3—C7	109.49 (16)	C18—C19—C20	120.0 (2)
C5—C4—C14	119.68 (19)	C18—C19—H19	120.0
C5—C4—C3	123.41 (18)	C20—C19—H19	120.0
C14—C4—C3	116.85 (18)	C15—C20—C19	118.8 (2)
C4—C5—O1	123.57 (19)	C15—C20—C5	116.64 (19)
C4—C5—C20	122.36 (19)	C19—C20—C5	124.40 (19)
O1—C5—C20	114.06 (18)	O5—C21—N4	125.8 (3)
N2—C6—C2	178.5 (2)	O5—C21—H21	117.1
O2—C7—N3	127.16 (19)	N4—C21—H21	117.1
O2—C7—C3	124.40 (19)	N4—C22—H22A	109.5
N3—C7—C3	108.38 (17)	N4—C22—H22B	109.5
C9—C8—C13	118.63 (19)	H22A—C22—H22B	109.5
C9—C8—C3	132.46 (19)	N4—C22—H22C	109.5
C13—C8—C3	108.84 (18)	H22A—C22—H22C	109.5
C8—C9—C10	120.6 (2)	H22B—C22—H22C	109.5
C8—C9—Br1	120.17 (16)	N4—C23—H23A	109.5
C10—C9—Br1	119.23 (16)	N4—C23—H23B	109.5
C11—C10—C9	119.3 (2)	H23A—C23—H23B	109.5
C11—C10—H10	120.3	N4—C23—H23C	109.5
C9—C10—H10	120.3	H23A—C23—H23C	109.5
C10—C11—C12	121.7 (2)	H23B—C23—H23C	109.5
C10—C11—H11	119.2

C5—O1—C1—N1	−175.77 (17)	C13—C8—C9—Br1	178.87 (15)
C5—O1—C1—C2	4.4 (3)	C3—C8—C9—Br1	−4.6 (3)
N1—C1—C2—C6	6.6 (3)	C8—C9—C10—C11	−0.4 (3)
O1—C1—C2—C6	−173.60 (18)	Br1—C9—C10—C11	−179.33 (16)
N1—C1—C2—C3	−172.6 (2)	C9—C10—C11—C12	0.4 (3)
O1—C1—C2—C3	7.1 (3)	C10—C11—C12—C13	0.1 (3)
C1—C2—C3—C4	−11.5 (3)	C11—C12—C13—C8	−0.6 (3)
C6—C2—C3—C4	169.26 (18)	C11—C12—C13—N3	−179.9 (2)
C1—C2—C3—C8	119.1 (2)	C9—C8—C13—C12	0.5 (3)
C6—C2—C3—C8	−60.1 (2)	C3—C8—C13—C12	−176.78 (19)
C1—C2—C3—C7	−129.4 (2)	C9—C8—C13—N3	179.94 (18)
C6—C2—C3—C7	51.3 (2)	C3—C8—C13—N3	2.6 (2)
C8—C3—C4—C5	−122.6 (2)	C7—N3—C13—C12	−178.8 (2)
C2—C3—C4—C5	5.7 (3)	C7—N3—C13—C8	1.8 (2)
C7—C3—C4—C5	124.3 (2)	C15—O3—C14—O4	178.80 (19)
C8—C3—C4—C14	60.4 (2)	C15—O3—C14—C4	−0.4 (3)
C2—C3—C4—C14	−171.33 (17)	C5—C4—C14—O4	178.0 (2)
C7—C3—C4—C14	−52.8 (2)	C3—C4—C14—O4	−4.8 (3)
C14—C4—C5—O1	−178.31 (18)	C5—C4—C14—O3	−2.9 (3)
C3—C4—C5—O1	4.7 (3)	C3—C4—C14—O3	174.33 (17)
C14—C4—C5—C20	3.2 (3)	C14—O3—C15—C16	−175.4 (2)
C3—C4—C5—C20	−173.79 (19)	C14—O3—C15—C20	3.4 (3)
C1—O1—C5—C4	−10.4 (3)	O3—C15—C16—C17	178.0 (2)
C1—O1—C5—C20	168.17 (17)	C20—C15—C16—C17	−0.8 (3)
C13—N3—C7—O2	177.2 (2)	C15—C16—C17—C18	1.3 (4)
C13—N3—C7—C3	−5.3 (2)	C16—C17—C18—C19	−0.8 (4)
C4—C3—C7—O2	−52.7 (3)	C17—C18—C19—C20	−0.2 (3)
C8—C3—C7—O2	−176.1 (2)	O3—C15—C20—C19	−178.96 (19)
C2—C3—C7—O2	64.8 (3)	C16—C15—C20—C19	−0.2 (3)
C4—C3—C7—N3	129.72 (18)	O3—C15—C20—C5	−3.0 (3)
C8—C3—C7—N3	6.3 (2)	C16—C15—C20—C5	175.7 (2)
C2—C3—C7—N3	−112.82 (19)	C18—C19—C20—C15	0.7 (3)
C4—C3—C8—C9	60.5 (3)	C18—C19—C20—C5	−174.9 (2)
C2—C3—C8—C9	−65.3 (3)	C4—C5—C20—C15	−0.3 (3)
C7—C3—C8—C9	177.9 (2)	O1—C5—C20—C15	−178.91 (18)
C4—C3—C8—C13	−122.70 (19)	C4—C5—C20—C19	175.4 (2)
C2—C3—C8—C13	111.45 (19)	O1—C5—C20—C19	−3.2 (3)
C7—C3—C8—C13	−5.3 (2)	C23—N4—C21—O5	−0.7 (4)
C13—C8—C9—C10	0.0 (3)	C22—N4—C21—O5	179.4 (2)
C3—C8—C9—C10	176.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89 (3)	2.02 (3)	2.891 (2)	165 (2)
N1—H1B···N2ⁱⁱ	0.84 (3)	2.27 (3)	3.090 (3)	166 (2)
N3—H3···O5ⁱⁱⁱ	0.88	1.93	2.785 (2)	163
C11—H11···O2^iv	0.95	2.54	3.462 (3)	165
C19—H19···O4ⁱ	0.95	2.50	3.173 (3)	128
C22—H22A···N2^v	0.98	2.48	3.443 (3)	166

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

Experimental details

Crystal data
Chemical formula	C₂₀H₁₀BrN₃O₄·C₃H₇NO
M_r	509.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	17.004 (3), 9.0452 (15), 14.415 (3)
β (°)	108.340 (3)
V (Å³)	2104.5 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.00
Crystal size (mm)	0.45 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.434, 0.670
No. of measured, independent and observed [I > 2σ(I)] reflections	19919, 3847, 3597
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.067, 1.09
No. of reflections	3847
No. of parameters	309
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.38

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
N1—H1A···O2ⁱ	0.89 (3)	2.02 (3)	2.891 (2)	165 (2)
N1—H1B···N2ⁱⁱ	0.84 (3)	2.27 (3)	3.090 (3)	166 (2)
N3—H3···O5ⁱⁱⁱ	0.88	1.93	2.785 (2)	162.7
C11—H11···O2^iv	0.95	2.54	3.462 (3)	165.1
C19—H19···O4ⁱ	0.95	2.50	3.173 (3)	128.0
C22—H22A···N2^v	0.98	2.48	3.443 (3)	165.7

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

Acknowledgements

This work was partially supported by the Natural Science Foundation of Jiangsu Province (grant No. BK2006048), the National Natural Science Foundation of China (grant No. 20672079) and a research grant from the Innovation Project for Graduate Students of Jiangsu Province.

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
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science 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. Version 1.30. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Version 3.6.0. 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-4′-bromo-2′,5-dioxo-4H,5H-pyrano[3,2-c]chromene-4-spiro-3′(2′H)-1′H-indole-3-carbo­nitrile N,N-di­methyl­formamide solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-Amino-4′-bromo-2′,5-dioxo-4H,5H-pyrano[3,2-c]chromene-4-spiro-3′(2′H)-1′H-indole-3-carbonitrile N,N-dimethylformamide solvate