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-dimethyl-formamide solvate.

In the mol-ecule of the title compound, C(20)H(10)BrN(3)O(4)·C(3)H(7)NO, 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, inter-molecular N-H⋯O, N-H⋯N, C-H⋯O and C-H⋯N hydrogen bonds link the mol-ecules.

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 = 509.32

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.067

S = 1.09

3847 reflections

309 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.56 e Å−3

Δρmin = −0.38 e Å−3

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015626/hk2467sup1.cif

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

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

C20H10BrN3O4·C3H7NO	F000 = 1032
Mr = 509.32	Dx = 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 = 3.2–25.3º
c = 14.415 (3) Å	µ = 2.00 mm−1
β = 108.340 (3)º	T = 153 (2) K
V = 2104.5 (7) Å3	Block, colorless
Z = 4	0.45 × 0.30 × 0.20 mm

Rigaku Mercury diffractometer	3847 independent reflections
Radiation source: fine-focus sealed tube	3597 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.031
Detector resolution: 7.31 pixels mm-1	θmax = 25.3º
T = 153(2) K	θmin = 3.2º
ω scans	h = −17→20
Absorption correction: multi-scan(Jacobson, 1998)	k = −10→9
Tmin = 0.434, Tmax = 0.670	l = −17→17
19919 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.067	w = 1/[σ2(Fo2) + (0.0219P)2 + 2.2795P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.002
3847 reflections	Δρmax = 0.56 e Å−3
309 parameters	Δρmin = −0.38 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O2iv	0.95	2.54	3.462 (3)	165
C19—H19···O4i	0.95	2.50	3.173 (3)	128
C22—H22A···N2v	0.98	2.48	3.443 (3)	166

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⋯O2iv	0.95	2.54	3.462 (3)	165
C19—H19⋯O4i	0.95	2.50	3.173 (3)	128
C22—H22A⋯N2v	0.98	2.48	3.443 (3)	166

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