6-Bromo-3-hydr­oxy-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid dimethyl­formamide disolvate

Wen, H.-L.; Chen, D.-D.; Liu, C.-B.

doi:10.1107/S1600536808019454

6-Bromo-3-hydroxy-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid dimethylformamide disolvate

In the title compound, C₁₆H₉BrO₅·2C₃H₇NO, the chromene ring system is essentially planar. The two dimethylformamide solvent molecules are linked by intermolecular O-H

O hydrogen bonds to the 6-bromo-3-hydroxy-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid molecules.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808019454/dn2358sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808019454/dn2358Isup2.hkl Contains datablock I

CCDC reference: 700447

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.003 Å
R factor = 0.036
wR factor = 0.098
Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.26
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N2
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C3 H7 N O

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Flavonoids are widely present in nature, which have potential biological activity such as antiviral (Zwaagstra et al., 1996; Zwaagstra et al., 1998a), anticancer (Valenti et al., 1998), treating leukemia (Kagechika et al., 1989), antihypertensive, antimicrobial (Gills et al., 1980; Walenta et al., 1991) et al. Due to the varieties of its biological activity, the structure-activity relationships study of flavonoids carboxylic acids has been the hot spot all along. In a continuation of our recent studies of flavonoids carboxylic acids (Liu et al., 2007), we report here the title compound, C₁₆H₉BrO₅—C₆H₁₄N₂O₂, (I).

In compound (I), the chromene molecule is roughly planar, with a mean deviation of 0.0521 Å. The dihedral angle between the chromene ring and the phenyl ring is 7.5 (2)°. Two O—H···O hydrogen bonds (Table 1, Fig. 1) involving the H atoms of hydroxyl group and carboxylic acid group connect the dimethylformamide molecules and 6-bromo-3-hydroxy-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid.

Related literature top

For related literature, see: Gills et al. (1980); Liu et al. (2007); Jin & Xiao (2005); Kagechika et al. (1989); Valenti et al. (1998); Walenta et al. (1991); Zwaagstra et al. (1996, 1998a,b).

Experimental top

The title compound was synthesized by the ring closure of 5'-bromo-3'-carboxy-2'-hydroxychalcone under the existence of a certain oxidant, according to the route published by Zwaagstra et al. (Zwaagstra et al., 1998b). Single crystals of (I) suitable for X-ray diffraction analysis were obtained from a solution in N,N-dimethylformamide.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson,1996); ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. : The molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented as small spheres of arbitrary radii. The hydrogen bonds are shown as dashed lines.

6-Bromo-3-hydroxy-4-oxo-2-phenyl-4H-chromene-8-carboxylic acid dimethylformamide solvate top

Crystal data top

C₁₆H₉BrO₅·2C₃H₇NO	F(000) = 1040
M_r = 507.33	D_x = 1.491 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3645 reflections
a = 10.489 (2) Å	θ = 2.6–23.5°
b = 11.470 (2) Å	µ = 1.86 mm⁻¹
c = 18.803 (4) Å	T = 294 K
β = 92.127 (3)°	Block, yellow
V = 2260.6 (8) Å³	0.49 × 0.38 × 0.17 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	4203 independent reflections
Radiation source: fine-focus sealed tube	2889 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→11
T_min = 0.462, T_max = 0.742	k = −13→13
14295 measured reflections	l = −22→22

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0482P)² + 0.6824P] where P = (F_o² + 2F_c²)/3
4203 reflections	(Δ/σ)_max = 0.017
294 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₆H₉BrO₅·2C₃H₇NO	V = 2260.6 (8) Å³
M_r = 507.33	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.489 (2) Å	µ = 1.86 mm⁻¹
b = 11.470 (2) Å	T = 294 K
c = 18.803 (4) Å	0.49 × 0.38 × 0.17 mm
β = 92.127 (3)°

Data collection top

Bruker SMART CCD diffractometer	4203 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2889 reflections with I > 2σ(I)
T_min = 0.462, T_max = 0.742	R_int = 0.028
14295 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.00	Δρ_max = 0.32 e Å⁻³
4203 reflections	Δρ_min = −0.35 e Å⁻³
294 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 > 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
Br1	0.06013 (3)	0.88028 (2)	0.582768 (19)	0.07113 (15)
O1	−0.0368 (2)	0.44074 (18)	0.65009 (12)	0.0911 (8)
O2	0.06856 (17)	0.31912 (16)	0.58290 (9)	0.0577 (5)
H2A	0.0279	0.2704	0.6046	0.087*
O3	0.24560 (16)	0.40314 (13)	0.50359 (9)	0.0460 (4)
O4	0.41242 (18)	0.68075 (16)	0.41187 (10)	0.0652 (6)
O5	0.49923 (18)	0.46087 (15)	0.38343 (11)	0.0610 (5)
H5	0.5303	0.5237	0.3727	0.091*
C1	0.1082 (2)	0.5216 (2)	0.57023 (13)	0.0439 (6)
C2	0.0684 (2)	0.6327 (2)	0.58763 (14)	0.0517 (7)
H2	0.0041	0.6416	0.6199	0.062*
C3	0.1222 (2)	0.7312 (2)	0.55796 (14)	0.0495 (7)
C4	0.2183 (2)	0.7207 (2)	0.51073 (14)	0.0485 (6)
H4	0.2544	0.7869	0.4912	0.058*
C5	0.2615 (2)	0.6101 (2)	0.49221 (13)	0.0422 (6)
C6	0.2067 (2)	0.5112 (2)	0.52147 (12)	0.0411 (6)
C7	0.3634 (2)	0.5972 (2)	0.44191 (14)	0.0456 (6)
C8	0.4030 (2)	0.4787 (2)	0.42805 (13)	0.0443 (6)
C9	0.3421 (2)	0.3864 (2)	0.45729 (13)	0.0429 (6)
C10	0.0406 (3)	0.4222 (2)	0.60528 (14)	0.0518 (7)
C11	0.3633 (2)	0.2608 (2)	0.44578 (13)	0.0442 (6)
C12	0.4628 (3)	0.2186 (3)	0.40674 (19)	0.0821 (11)
H12	0.5188	0.2708	0.3865	0.099*
C13	0.4800 (4)	0.1012 (3)	0.3976 (2)	0.0944 (13)
H13	0.5482	0.0752	0.3716	0.113*
C14	0.3998 (3)	0.0217 (2)	0.42550 (17)	0.0686 (9)
H14	0.4114	−0.0578	0.4184	0.082*
C15	0.3021 (3)	0.0619 (2)	0.46419 (18)	0.0736 (9)
H15	0.2464	0.0089	0.4839	0.088*
C16	0.2840 (3)	0.1793 (2)	0.47476 (16)	0.0629 (8)
H16	0.2169	0.2041	0.5020	0.075*
N1	−0.2166 (3)	0.1136 (2)	0.71663 (13)	0.0631 (7)
O6	−0.0563 (2)	0.15290 (18)	0.64329 (11)	0.0722 (6)
C17	−0.1516 (3)	0.1828 (3)	0.67549 (16)	0.0626 (8)
H17	−0.1792	0.2595	0.6703	0.075*
C18	−0.3276 (4)	0.1567 (3)	0.7524 (2)	0.0983 (13)
H18A	−0.3072	0.1649	0.8024	0.147*
H18B	−0.3968	0.1026	0.7456	0.147*
H18C	−0.3521	0.2311	0.7329	0.147*
C19	−0.1781 (3)	−0.0070 (3)	0.72818 (18)	0.0840 (10)
H19A	−0.2251	−0.0565	0.6955	0.126*
H19B	−0.1953	−0.0294	0.7761	0.126*
H19C	−0.0885	−0.0147	0.7206	0.126*
N2	0.7254 (2)	0.78411 (18)	0.28823 (12)	0.0554 (6)
O7	0.6435 (2)	0.60874 (17)	0.31631 (12)	0.0773 (7)
C20	0.6539 (3)	0.7141 (3)	0.32545 (16)	0.0642 (8)
H20	0.6076	0.7473	0.3615	0.077*
C21	0.7365 (4)	0.9061 (3)	0.3036 (3)	0.1108 (15)
H21A	0.6909	0.9239	0.3456	0.166*
H21B	0.7012	0.9503	0.2642	0.166*
H21C	0.8248	0.9260	0.3113	0.166*
C22	0.8037 (3)	0.7385 (3)	0.23293 (16)	0.0746 (9)
H22A	0.8853	0.7160	0.2532	0.112*
H22B	0.8151	0.7974	0.1975	0.112*
H22C	0.7626	0.6718	0.2114	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0723 (2)	0.04462 (18)	0.0983 (3)	0.00670 (14)	0.02689 (18)	−0.00929 (15)
O1	0.1120 (19)	0.0564 (13)	0.1106 (18)	−0.0065 (12)	0.0794 (16)	−0.0021 (12)
O2	0.0641 (13)	0.0440 (11)	0.0672 (12)	−0.0095 (9)	0.0321 (10)	0.0013 (9)
O3	0.0491 (10)	0.0358 (9)	0.0546 (10)	−0.0028 (7)	0.0219 (8)	0.0004 (7)
O4	0.0696 (14)	0.0428 (11)	0.0860 (14)	−0.0029 (9)	0.0389 (11)	0.0106 (10)
O5	0.0621 (13)	0.0421 (10)	0.0814 (13)	−0.0017 (9)	0.0392 (10)	0.0058 (9)
C1	0.0440 (15)	0.0429 (14)	0.0454 (14)	−0.0045 (11)	0.0098 (12)	0.0000 (11)
C2	0.0483 (16)	0.0522 (16)	0.0557 (16)	−0.0010 (12)	0.0179 (13)	−0.0043 (12)
C3	0.0501 (16)	0.0402 (14)	0.0587 (17)	0.0007 (12)	0.0073 (13)	−0.0050 (12)
C4	0.0486 (16)	0.0375 (13)	0.0600 (17)	−0.0043 (11)	0.0085 (13)	0.0032 (12)
C5	0.0411 (14)	0.0389 (13)	0.0472 (14)	−0.0012 (11)	0.0078 (11)	0.0025 (11)
C6	0.0411 (14)	0.0372 (13)	0.0455 (14)	−0.0011 (11)	0.0080 (11)	−0.0015 (11)
C7	0.0425 (15)	0.0412 (14)	0.0540 (15)	−0.0033 (11)	0.0125 (12)	0.0060 (11)
C8	0.0413 (15)	0.0429 (14)	0.0494 (14)	−0.0025 (11)	0.0131 (12)	0.0040 (11)
C9	0.0401 (14)	0.0432 (13)	0.0460 (14)	−0.0022 (11)	0.0116 (11)	0.0022 (11)
C10	0.0528 (17)	0.0501 (15)	0.0537 (16)	−0.0041 (13)	0.0197 (14)	−0.0009 (12)
C11	0.0448 (15)	0.0383 (13)	0.0500 (15)	−0.0009 (11)	0.0102 (12)	−0.0001 (11)
C12	0.083 (2)	0.0446 (16)	0.123 (3)	−0.0012 (15)	0.061 (2)	0.0002 (17)
C13	0.099 (3)	0.0519 (19)	0.137 (3)	0.0085 (18)	0.070 (3)	−0.0067 (19)
C14	0.079 (2)	0.0396 (16)	0.089 (2)	0.0024 (15)	0.0210 (18)	−0.0071 (15)
C15	0.085 (2)	0.0397 (15)	0.099 (2)	−0.0087 (16)	0.0338 (19)	0.0043 (16)
C16	0.069 (2)	0.0440 (15)	0.078 (2)	−0.0023 (14)	0.0344 (16)	−0.0023 (14)
N1	0.0694 (17)	0.0582 (15)	0.0630 (15)	−0.0122 (12)	0.0213 (13)	0.0075 (11)
O6	0.0710 (15)	0.0588 (12)	0.0889 (15)	−0.0066 (10)	0.0320 (12)	0.0131 (11)
C17	0.064 (2)	0.0532 (17)	0.072 (2)	−0.0080 (15)	0.0209 (16)	0.0106 (15)
C18	0.096 (3)	0.088 (3)	0.114 (3)	−0.014 (2)	0.057 (2)	0.004 (2)
C19	0.104 (3)	0.064 (2)	0.084 (2)	−0.0043 (19)	0.016 (2)	0.0247 (18)
N2	0.0544 (14)	0.0404 (12)	0.0727 (15)	−0.0045 (10)	0.0200 (12)	0.0015 (11)
O7	0.0906 (17)	0.0485 (13)	0.0959 (16)	−0.0178 (10)	0.0453 (13)	−0.0037 (10)
C20	0.065 (2)	0.0550 (18)	0.075 (2)	−0.0054 (15)	0.0276 (16)	−0.0033 (15)
C21	0.114 (3)	0.0420 (18)	0.180 (4)	−0.0070 (19)	0.056 (3)	−0.007 (2)
C22	0.087 (2)	0.072 (2)	0.067 (2)	−0.0156 (17)	0.0320 (18)	−0.0041 (16)

Geometric parameters (Å, º) top

Br1—C3	1.894 (2)	C14—C15	1.359 (4)
O1—C10	1.210 (3)	C14—H14	0.9300
O2—C10	1.293 (3)	C15—C16	1.376 (4)
O2—H2A	0.8200	C15—H15	0.9300
O3—C6	1.351 (3)	C16—H16	0.9300
O3—C9	1.372 (3)	N1—C17	1.316 (3)
O4—C7	1.235 (3)	N1—C18	1.453 (4)
O5—C8	1.352 (3)	N1—C19	1.455 (4)
O5—H5	0.8200	O6—C17	1.236 (3)
C1—C2	1.384 (3)	C17—H17	0.9300
C1—C6	1.412 (3)	C18—H18A	0.9600
C1—C10	1.507 (3)	C18—H18B	0.9600
C2—C3	1.389 (4)	C18—H18C	0.9600
C2—H2	0.9300	C19—H19A	0.9600
C3—C4	1.373 (3)	C19—H19B	0.9600
C4—C5	1.396 (3)	C19—H19C	0.9600
C4—H4	0.9300	N2—C20	1.318 (3)
C5—C6	1.394 (3)	N2—C21	1.433 (4)
C5—C7	1.460 (3)	N2—C22	1.447 (3)
C7—C8	1.447 (3)	O7—C20	1.225 (3)
C8—C9	1.363 (3)	C20—H20	0.9300
C9—C11	1.475 (3)	C21—H21A	0.9600
C11—C16	1.377 (3)	C21—H21B	0.9600
C11—C12	1.386 (4)	C21—H21C	0.9600
C12—C13	1.371 (4)	C22—H22A	0.9600
C12—H12	0.9300	C22—H22B	0.9600
C13—C14	1.359 (4)	C22—H22C	0.9600
C13—H13	0.9300

C10—O2—H2A	109.5	C13—C14—H14	121.0
C6—O3—C9	121.48 (18)	C14—C15—C16	121.4 (3)
C8—O5—H5	109.5	C14—C15—H15	119.3
C2—C1—C6	117.8 (2)	C16—C15—H15	119.3
C2—C1—C10	116.2 (2)	C15—C16—C11	121.2 (3)
C6—C1—C10	126.0 (2)	C15—C16—H16	119.4
C1—C2—C3	121.6 (2)	C11—C16—H16	119.4
C1—C2—H2	119.2	C17—N1—C18	120.6 (3)
C3—C2—H2	119.2	C17—N1—C19	120.9 (3)
C4—C3—C2	120.5 (2)	C18—N1—C19	118.5 (3)
C4—C3—Br1	120.38 (19)	O6—C17—N1	124.5 (3)
C2—C3—Br1	119.14 (19)	O6—C17—H17	117.7
C3—C4—C5	119.6 (2)	N1—C17—H17	117.7
C3—C4—H4	120.2	N1—C18—H18A	109.5
C5—C4—H4	120.2	N1—C18—H18B	109.5
C6—C5—C4	119.9 (2)	H18A—C18—H18B	109.5
C6—C5—C7	119.7 (2)	N1—C18—H18C	109.5
C4—C5—C7	120.4 (2)	H18A—C18—H18C	109.5
O3—C6—C5	121.0 (2)	H18B—C18—H18C	109.5
O3—C6—C1	118.3 (2)	N1—C19—H19A	109.5
C5—C6—C1	120.6 (2)	N1—C19—H19B	109.5
O4—C7—C8	121.3 (2)	H19A—C19—H19B	109.5
O4—C7—C5	123.0 (2)	N1—C19—H19C	109.5
C8—C7—C5	115.7 (2)	H19A—C19—H19C	109.5
O5—C8—C9	120.3 (2)	H19B—C19—H19C	109.5
O5—C8—C7	118.7 (2)	C20—N2—C21	122.1 (3)
C9—C8—C7	120.9 (2)	C20—N2—C22	120.7 (2)
C8—C9—O3	121.0 (2)	C21—N2—C22	117.0 (2)
C8—C9—C11	128.6 (2)	O7—C20—N2	125.2 (3)
O3—C9—C11	110.38 (19)	O7—C20—H20	117.4
O1—C10—O2	123.6 (2)	N2—C20—H20	117.4
O1—C10—C1	120.7 (2)	N2—C21—H21A	109.5
O2—C10—C1	115.7 (2)	N2—C21—H21B	109.5
C16—C11—C12	116.8 (2)	H21A—C21—H21B	109.5
C16—C11—C9	120.6 (2)	N2—C21—H21C	109.5
C12—C11—C9	122.7 (2)	H21A—C21—H21C	109.5
C13—C12—C11	121.0 (3)	H21B—C21—H21C	109.5
C13—C12—H12	119.5	N2—C22—H22A	109.5
C11—C12—H12	119.5	N2—C22—H22B	109.5
C14—C13—C12	121.6 (3)	H22A—C22—H22B	109.5
C14—C13—H13	119.2	N2—C22—H22C	109.5
C12—C13—H13	119.2	H22A—C22—H22C	109.5
C15—C14—C13	118.0 (3)	H22B—C22—H22C	109.5
C15—C14—H14	121.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O6	0.82	1.78	2.598 (2)	173
O5—H5···O7	0.82	1.89	2.627 (2)	149
O5—H5···O4	0.82	2.32	2.741 (3)	113

Experimental details

Crystal data
Chemical formula	C₁₆H₉BrO₅·2C₃H₇NO
M_r	507.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	10.489 (2), 11.470 (2), 18.803 (4)
β (°)	92.127 (3)
V (Å³)	2260.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.86
Crystal size (mm)	0.49 × 0.38 × 0.17

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.462, 0.742
No. of measured, independent and observed [I > 2σ(I)] reflections	14295, 4203, 2889
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.00
No. of reflections	4203
No. of parameters	294
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.35

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson,1996); ORTEP-3 for Windows (Farrugia, 1997).