Ethyl 2-amino-4-(4-bromo­phen­yl)-6-meth­oxy-4H-benzo[h]chromene-3-carboxyl­ate

El-Agrody, A.M.; Fouda, A.M.; Al-Omar, M.A.; Amr, A.E.-G.E.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S160053681300490X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 3| March 2013| Pages o435-o436

doi:10.1107/S160053681300490X

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Ethyl 2-amino-4-(4-bromophenyl)-6-methoxy-4H-benzo[h]chromene-3-carboxylate

Ahmed M. El-Agrody,^a,^b Ahmed M. Fouda,^a Mohamed A. Al-Omar,^c,^d Abd El-Galil E. Amr,^d,^e ‡ Seik Weng Ng ^f,^g and Edward R. T. Tiekink ^f ^*

^aChemistry Department, Faculty of Science, King Khalid University, Abha 61413, PO Box 9004, Saudi Arabia, ^bChemistry Department, Faculty of Science, Al-Azhar University, Nasr City, Cairo, 11884, Egypt, ^cDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, ^dDrug Exploration & Development Chair (DEDC), College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, ^eApplied Organic Chemistry Department, National Research Center, Dokki 12622, Cairo, Egypt, ^fDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^gChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 19 February 2013; accepted 19 February 2013; online 23 February 2013)

In the title compound, C₂₃H₂₀BrNO₄, the pyran ring has a flattened boat conformation with the O and methine C atoms lying to one side of the plane [0.160 (5) and 0.256 (6) Å, respectively] defined by the remaining atoms. Nevertheless, the 4H-benzo[h]chromene ring system approximates a plane (r.m.s. deviation = 0.116 Å) with the bromobenzene ring almost perpendicular [dihedral angle = 83.27 (16)°] and the ester group coplanar [C—C—C—O = 3.4 (5)°]; the methoxy substituent is also coplanar [C—O—C—C = 174.5 (3)°]. In addition to an intramolecular N—H⋯O(ester carbonyl) hydrogen bond, the ester carbonyl O atom also forms an intermolecular N—H⋯O hydrogen bond with the second amine H atom, generating a zigzag supramolecular chain along the c axis in the crystal packing. The chains are linked into layers in the bc plane by N—H⋯Br hydrogen bonds, and these layers are consolidated into a three-dimensional architecture by C—H⋯π interactions.

Related literature

For background to the pharmaceutical activity of 4H-chromene and its derivatives, see: Abd-El-Aziz et al. (2004 , 2007 ); Kemnitzer et al. (2007 ); Alvey et al. (2009 ). For the isostructural 4-fluoro analogue, see: El-Agrody et al. (2012 ).

Experimental

Crystal data

C₂₃H₂₀BrNO₄
M_r = 454.31
Monoclinic, P 2₁ /c
a = 13.1543 (14) Å
b = 16.8110 (18) Å
c = 9.3672 (12) Å
β = 96.628 (10)°
V = 2057.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.03 mm⁻¹
T = 295 K
0.30 × 0.20 × 0.03 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.828, T_max = 1.000
12041 measured reflections
4740 independent reflections
2533 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.164
S = 1.02
4740 reflections
270 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2 and Cg3 are the centroids of the C1,C2,C7–C10, C17–C22 and C2–C7 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2⋯O2	0.88 (1)	2.09 (5)	2.744 (5)	131 (5)
N1—H1⋯O2ⁱ	0.88 (1)	2.22 (2)	3.075 (5)	163 (3)
N1—H2⋯Br1ⁱⁱ	0.88 (4)	2.76 (4)	3.547 (4)	149 (5)
C4—H4⋯Cg1ⁱ	0.93	2.90	3.673 (5)	142
C6—H6⋯Cg2ⁱⁱⁱ	0.93	2.98	3.743 (5)	140
C23—H23C⋯Cg3ⁱⁱⁱ	0.96	2.70	3.593 (5)	154
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681300490X/hg5295sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681300490X/hg5295Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681300490X/hg5295Isup3.cml

checkCIF report

Comment top

4H-Chromene and its derivatives are biologically interesting compounds known for their anti-microbial, anti-fungal and other pharmaceutical activities (Alvey et al., 2009; Kemnitzer et al., 2007). In continuation of on-going interest in the chemical and pharmacological properties of 4H-chromene and fused 4H-chromene derivatives (Abd-El-Aziz et al., 2004; Abd-El-Aziz et al., 2007), the crystal structure of the title compound, (I), is described herein.

The molecular structure of (I), Fig. 1, is isostructural to the recently reported 4-fluoro analogue (El-Agrody et al., 2012). The pyran ring has a flattened boat conformation with the O1 and C11 atoms lying 0.160 (5) and 0.256 (6) Å, respectively, out of the plane defined by the four remaining atoms (r.m.s. deviation = 0.0174 Å). Overall, the 4H-benzo[h]chromene ring system is approximately planar with the r.m.s. deviation of the 14 non-hydrogen atoms being 0.116 Å. The bromobenzene ring is almost perpendicular to this plane, forming a dihedral angle of 83.27 (16)°. By contrast, the ester group, with an anti conformation [C14—O3—C15—C16 torsion angle = -166.9 (4)°], is co-planar [C11—C12—C14—O3 = 3.4 (5)°] due, in part, to an intramolecular N—H···O2 hydrogen bond, Table 1. The methoxy [C23—O4—C7—C7 = 174.5 (3)°] substituent is also co-planar to the ring to which it is attached.

Zigzag (glide symmetry) supramolecular chains along the c axis feature in the crystal packing owing to N—H···O2 hydrogen bonding, Fig. 2 and Table 1. Chains are linked into layers in the bc plane by N—H···Br hydrogen bonds involving the H atom involved in the intramolecular interaction to the O2 atom, Table 1. A consequence of this interaction is that the Br1 and O2 atoms are brought into close proximity, i.e. Br1···O2ⁱ = 3.179 (3) Å [i: -x, 1/2 + y, 3/2 - z]. The three-dimensional architecture is consolidated by C—H···π interactions, Fig. 3 and Table 1.

Related literature top

For background to the pharmaceutical activity of 4H-chromene and its derivatives, see: Abd-El-Aziz et al. (2004, 2007); Kemnitzer et al. (2007); Alvey et al. (2009). For the isostructural 4-fluoro analogue, see: El-Agrody et al. (2012).

Experimental top

A solution of 4-methoxy-1-naphthol (0.01 mol) in EtOH (30 ml) was treated with ethyl α-cyano-p-bromocinnamate (0.01 mol) and piperidine (0.5 ml). The reaction mixture was heated until complete precipitation occurred after 2 h. The solid product was collected by filtration and recrystallized from ethanol to give (I); M.pt: 438–439 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.
	Fig. 2. A view of the zigzag supramolecular chain along the c axis in (I) sustained by N—H···N hydrogen bonds, shown as blue dashed lines.
	Fig. 3. view in projection down the c axis of the crystal packing in (I). The N—H···N, N—H···Br and C—H···π interactions are shown as blue, orange and purple dashed lines, respectively.

Ethyl 2-amino-4-(4-bromophenyl)-6-methoxy-4H-benzo[h]chromene-3-carboxylate top

Crystal data top

C₂₃H₂₀BrNO₄	F(000) = 928
M_r = 454.31	D_x = 1.467 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1932 reflections
a = 13.1543 (14) Å	θ = 2.8–27.5°
b = 16.8110 (18) Å	µ = 2.03 mm⁻¹
c = 9.3672 (12) Å	T = 295 K
β = 96.628 (10)°	Plate, light-orange
V = 2057.6 (4) Å³	0.30 × 0.20 × 0.03 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	4740 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2533 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.054
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 2.9°
ω scan	h = −16→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −21→21
T_min = 0.828, T_max = 1.000	l = −7→12
12041 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0575P)² + 0.7996P] where P = (F_o² + 2F_c²)/3
4740 reflections	(Δ/σ)_max = 0.001
270 parameters	Δρ_max = 0.91 e Å⁻³
2 restraints	Δρ_min = −0.90 e Å⁻³

Crystal data top

C₂₃H₂₀BrNO₄	V = 2057.6 (4) Å³
M_r = 454.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.1543 (14) Å	µ = 2.03 mm⁻¹
b = 16.8110 (18) Å	T = 295 K
c = 9.3672 (12) Å	0.30 × 0.20 × 0.03 mm
β = 96.628 (10)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	4740 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2533 reflections with I > 2σ(I)
T_min = 0.828, T_max = 1.000	R_int = 0.054
12041 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	2 restraints
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.91 e Å⁻³
4740 reflections	Δρ_min = −0.90 e Å⁻³
270 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
Br1	0.04105 (4)	0.70821 (4)	0.50571 (7)	0.0900 (3)
O1	0.30720 (18)	0.30429 (15)	0.7238 (3)	0.0464 (7)
O2	0.1283 (2)	0.34197 (17)	1.0635 (3)	0.0539 (7)
O3	0.1749 (2)	0.47024 (17)	1.0602 (3)	0.0558 (7)
O4	0.6285 (2)	0.50690 (18)	0.6512 (3)	0.0634 (8)
N1	0.1869 (3)	0.2527 (2)	0.8418 (4)	0.0538 (9)
H2	0.138 (3)	0.260 (4)	0.897 (5)	0.11 (2)*
H1	0.182 (3)	0.2203 (18)	0.768 (3)	0.044 (12)*
C1	0.3874 (3)	0.3580 (2)	0.7136 (4)	0.0397 (9)
C2	0.4654 (3)	0.3302 (2)	0.6337 (4)	0.0399 (9)
C3	0.4637 (3)	0.2537 (2)	0.5709 (4)	0.0447 (9)
H3	0.4095	0.2194	0.5807	0.054*
C4	0.5416 (3)	0.2300 (3)	0.4959 (4)	0.0533 (11)
H4	0.5404	0.1792	0.4562	0.064*
C5	0.6228 (3)	0.2812 (3)	0.4783 (5)	0.0613 (12)
H5	0.6752	0.2644	0.4267	0.074*
C6	0.6260 (3)	0.3553 (3)	0.5359 (5)	0.0579 (12)
H6	0.6802	0.3889	0.5223	0.069*
C7	0.5480 (3)	0.3824 (2)	0.6167 (4)	0.0436 (9)
C8	0.5483 (3)	0.4599 (2)	0.6797 (4)	0.0464 (10)
C9	0.4730 (3)	0.4824 (2)	0.7582 (4)	0.0463 (10)
H9	0.4756	0.5325	0.8007	0.056*
C10	0.3900 (3)	0.4308 (2)	0.7768 (4)	0.0409 (9)
C11	0.3054 (3)	0.4576 (2)	0.8616 (4)	0.0428 (9)
H11	0.3369	0.4829	0.9501	0.051*
C12	0.2446 (3)	0.3864 (2)	0.9034 (4)	0.0390 (9)
C13	0.2453 (3)	0.3168 (2)	0.8286 (4)	0.0394 (9)
C14	0.1773 (3)	0.3946 (2)	1.0137 (4)	0.0428 (9)
C15	0.1070 (4)	0.4882 (3)	1.1673 (5)	0.0741 (14)
H15A	0.1343	0.4669	1.2601	0.089*
H15B	0.0400	0.4652	1.1401	0.089*
C16	0.0999 (5)	0.5766 (3)	1.1742 (6)	0.097 (2)
H16A	0.0550	0.5913	1.2435	0.146*
H16B	0.0736	0.5968	1.0814	0.146*
H16C	0.1667	0.5984	1.2020	0.146*
C17	0.2379 (3)	0.5190 (2)	0.7770 (4)	0.0426 (9)
C18	0.1791 (3)	0.4979 (2)	0.6511 (5)	0.0516 (10)
H18	0.1789	0.4454	0.6199	0.062*
C19	0.1203 (3)	0.5538 (3)	0.5709 (5)	0.0582 (12)
H19	0.0813	0.5392	0.4858	0.070*
C20	0.1202 (3)	0.6312 (3)	0.6184 (5)	0.0568 (12)
C21	0.1771 (4)	0.6536 (3)	0.7419 (5)	0.0659 (13)
H21	0.1764	0.7061	0.7731	0.079*
C22	0.2362 (3)	0.5972 (3)	0.8208 (5)	0.0588 (12)
H22	0.2756	0.6124	0.9052	0.071*
C23	0.6286 (3)	0.5869 (3)	0.6996 (5)	0.0624 (12)
H23A	0.6879	0.6138	0.6725	0.094*
H23B	0.6302	0.5878	0.8023	0.094*
H23C	0.5680	0.6133	0.6566	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0945 (4)	0.0850 (5)	0.0981 (5)	0.0486 (3)	0.0437 (3)	0.0394 (3)
O1	0.0453 (14)	0.0431 (16)	0.0537 (18)	−0.0112 (12)	0.0179 (12)	−0.0067 (13)
O2	0.0601 (17)	0.0524 (19)	0.0521 (18)	−0.0043 (14)	0.0187 (13)	0.0031 (14)
O3	0.0770 (19)	0.0445 (17)	0.0495 (18)	0.0043 (14)	0.0229 (14)	−0.0045 (14)
O4	0.0519 (17)	0.058 (2)	0.083 (2)	−0.0210 (15)	0.0179 (14)	−0.0057 (17)
N1	0.058 (2)	0.046 (2)	0.062 (3)	−0.0103 (19)	0.0252 (19)	−0.0082 (19)
C1	0.0367 (19)	0.042 (2)	0.041 (2)	−0.0061 (17)	0.0063 (16)	0.0040 (18)
C2	0.0375 (19)	0.042 (2)	0.040 (2)	0.0000 (17)	0.0032 (15)	0.0032 (18)
C3	0.043 (2)	0.043 (2)	0.047 (2)	−0.0030 (19)	0.0062 (17)	−0.0026 (19)
C4	0.059 (3)	0.050 (3)	0.052 (3)	0.004 (2)	0.012 (2)	−0.006 (2)
C5	0.049 (3)	0.069 (3)	0.068 (3)	0.001 (2)	0.019 (2)	−0.008 (3)
C6	0.046 (2)	0.063 (3)	0.068 (3)	−0.007 (2)	0.018 (2)	−0.002 (2)
C7	0.036 (2)	0.047 (2)	0.048 (2)	−0.0049 (18)	0.0054 (16)	0.0043 (19)
C8	0.041 (2)	0.047 (2)	0.051 (3)	−0.0103 (18)	0.0025 (17)	0.001 (2)
C9	0.045 (2)	0.040 (2)	0.054 (3)	−0.0053 (18)	0.0043 (18)	−0.0024 (19)
C10	0.039 (2)	0.041 (2)	0.041 (2)	−0.0011 (17)	0.0025 (16)	0.0002 (18)
C11	0.049 (2)	0.041 (2)	0.039 (2)	−0.0021 (18)	0.0034 (16)	−0.0040 (18)
C12	0.043 (2)	0.036 (2)	0.039 (2)	0.0007 (17)	0.0069 (16)	0.0008 (17)
C13	0.0392 (19)	0.037 (2)	0.043 (2)	−0.0039 (17)	0.0095 (16)	0.0037 (18)
C14	0.044 (2)	0.044 (2)	0.040 (2)	0.0026 (19)	0.0023 (17)	0.0041 (19)
C15	0.102 (4)	0.071 (4)	0.055 (3)	0.018 (3)	0.029 (3)	−0.008 (3)
C16	0.151 (6)	0.073 (4)	0.073 (4)	0.044 (4)	0.037 (4)	−0.005 (3)
C17	0.046 (2)	0.035 (2)	0.048 (2)	−0.0047 (17)	0.0116 (17)	−0.0024 (18)
C18	0.060 (2)	0.038 (2)	0.056 (3)	0.001 (2)	0.007 (2)	0.001 (2)
C19	0.056 (3)	0.064 (3)	0.054 (3)	0.002 (2)	0.007 (2)	0.010 (2)
C20	0.056 (3)	0.050 (3)	0.070 (3)	0.018 (2)	0.031 (2)	0.016 (2)
C21	0.093 (3)	0.038 (3)	0.072 (3)	0.014 (2)	0.032 (3)	0.000 (2)
C22	0.077 (3)	0.042 (3)	0.058 (3)	0.000 (2)	0.012 (2)	−0.008 (2)
C23	0.061 (3)	0.050 (3)	0.074 (3)	−0.016 (2)	−0.001 (2)	0.008 (2)

Geometric parameters (Å, º) top

Br1—C20	1.903 (4)	C9—H9	0.9300
O1—C13	1.362 (4)	C10—C11	1.508 (5)
O1—C1	1.400 (4)	C11—C12	1.517 (5)
O2—C14	1.218 (4)	C11—C17	1.524 (5)
O3—C14	1.346 (5)	C11—H11	0.9800
O3—C15	1.450 (5)	C12—C13	1.364 (5)
O4—C8	1.369 (4)	C12—C14	1.442 (5)
O4—C23	1.419 (5)	C15—C16	1.489 (7)
N1—C13	1.338 (5)	C15—H15A	0.9700
N1—H2	0.876 (10)	C15—H15B	0.9700
N1—H1	0.878 (10)	C16—H16A	0.9600
C1—C10	1.359 (5)	C16—H16B	0.9600
C1—C2	1.417 (5)	C16—H16C	0.9600
C2—C3	1.413 (5)	C17—C22	1.378 (5)
C2—C7	1.420 (5)	C17—C18	1.380 (5)
C3—C4	1.366 (5)	C18—C19	1.382 (6)
C3—H3	0.9300	C18—H18	0.9300
C4—C5	1.397 (6)	C19—C20	1.375 (6)
C4—H4	0.9300	C19—H19	0.9300
C5—C6	1.355 (6)	C20—C21	1.356 (6)
C5—H5	0.9300	C21—C22	1.384 (6)
C6—C7	1.418 (6)	C21—H21	0.9300
C6—H6	0.9300	C22—H22	0.9300
C7—C8	1.430 (6)	C23—H23A	0.9600
C8—C9	1.354 (6)	C23—H23B	0.9600
C9—C10	1.421 (5)	C23—H23C	0.9600

C13—O1—C1	117.9 (3)	C14—C12—C11	119.7 (3)
C14—O3—C15	117.4 (3)	N1—C13—O1	109.9 (3)
C8—O4—C23	117.3 (3)	N1—C13—C12	127.2 (4)
C13—N1—H2	114 (4)	O1—C13—C12	122.9 (3)
C13—N1—H1	115 (3)	O2—C14—O3	121.9 (4)
H2—N1—H1	125 (5)	O2—C14—C12	126.8 (4)
C10—C1—O1	122.1 (3)	O3—C14—C12	111.2 (4)
C10—C1—C2	123.0 (3)	O3—C15—C16	106.5 (4)
O1—C1—C2	114.9 (3)	O3—C15—H15A	110.4
C1—C2—C3	122.9 (3)	C16—C15—H15A	110.4
C1—C2—C7	117.8 (3)	O3—C15—H15B	110.4
C3—C2—C7	119.4 (3)	C16—C15—H15B	110.4
C4—C3—C2	120.2 (4)	H15A—C15—H15B	108.6
C4—C3—H3	119.9	C15—C16—H16A	109.5
C2—C3—H3	119.9	C15—C16—H16B	109.5
C3—C4—C5	120.6 (4)	H16A—C16—H16B	109.5
C3—C4—H4	119.7	C15—C16—H16C	109.5
C5—C4—H4	119.7	H16A—C16—H16C	109.5
C6—C5—C4	120.5 (4)	H16B—C16—H16C	109.5
C6—C5—H5	119.7	C22—C17—C18	118.3 (4)
C4—C5—H5	119.7	C22—C17—C11	121.3 (4)
C5—C6—C7	121.1 (4)	C18—C17—C11	120.4 (3)
C5—C6—H6	119.4	C19—C18—C17	120.8 (4)
C7—C6—H6	119.4	C19—C18—H18	119.6
C6—C7—C2	118.1 (4)	C17—C18—H18	119.6
C6—C7—C8	123.1 (4)	C18—C19—C20	119.3 (4)
C2—C7—C8	118.8 (3)	C18—C19—H19	120.4
C9—C8—O4	125.0 (4)	C20—C19—H19	120.4
C9—C8—C7	120.8 (4)	C21—C20—C19	121.2 (4)
O4—C8—C7	114.3 (3)	C21—C20—Br1	119.8 (4)
C8—C9—C10	121.1 (4)	C19—C20—Br1	119.0 (4)
C8—C9—H9	119.5	C20—C21—C22	119.0 (4)
C10—C9—H9	119.5	C20—C21—H21	120.5
C1—C10—C9	118.5 (4)	C22—C21—H21	120.5
C1—C10—C11	121.0 (3)	C17—C22—C21	121.4 (4)
C9—C10—C11	120.4 (3)	C17—C22—H22	119.3
C10—C11—C12	110.1 (3)	C21—C22—H22	119.3
C10—C11—C17	110.4 (3)	O4—C23—H23A	109.5
C12—C11—C17	112.1 (3)	O4—C23—H23B	109.5
C10—C11—H11	108.0	H23A—C23—H23B	109.5
C12—C11—H11	108.0	O4—C23—H23C	109.5
C17—C11—H11	108.0	H23A—C23—H23C	109.5
C13—C12—C14	119.5 (4)	H23B—C23—H23C	109.5
C13—C12—C11	120.6 (3)

C13—O1—C1—C10	−17.1 (5)	C1—C10—C11—C17	−105.9 (4)
C13—O1—C1—C2	162.4 (3)	C9—C10—C11—C17	72.4 (4)
C10—C1—C2—C3	178.4 (3)	C10—C11—C12—C13	−21.7 (5)
O1—C1—C2—C3	−1.0 (5)	C17—C11—C12—C13	101.7 (4)
C10—C1—C2—C7	−1.7 (5)	C10—C11—C12—C14	164.5 (3)
O1—C1—C2—C7	178.8 (3)	C17—C11—C12—C14	−72.1 (4)
C1—C2—C3—C4	−179.5 (4)	C1—O1—C13—N1	−167.7 (3)
C7—C2—C3—C4	0.7 (5)	C1—O1—C13—C12	13.7 (5)
C2—C3—C4—C5	−1.0 (6)	C14—C12—C13—N1	2.2 (6)
C3—C4—C5—C6	0.2 (7)	C11—C12—C13—N1	−171.6 (4)
C4—C5—C6—C7	0.8 (7)	C14—C12—C13—O1	−179.5 (3)
C5—C6—C7—C2	−1.0 (6)	C11—C12—C13—O1	6.8 (5)
C5—C6—C7—C8	179.8 (4)	C15—O3—C14—O2	−3.3 (6)
C1—C2—C7—C6	−179.5 (4)	C15—O3—C14—C12	177.5 (3)
C3—C2—C7—C6	0.3 (5)	C13—C12—C14—O2	10.4 (6)
C1—C2—C7—C8	−0.4 (5)	C11—C12—C14—O2	−175.7 (3)
C3—C2—C7—C8	179.5 (3)	C13—C12—C14—O3	−170.4 (3)
C23—O4—C8—C9	−4.4 (6)	C11—C12—C14—O3	3.4 (5)
C23—O4—C8—C7	174.5 (3)	C14—O3—C15—C16	−166.9 (4)
C6—C7—C8—C9	−178.7 (4)	C10—C11—C17—C22	−111.9 (4)
C2—C7—C8—C9	2.1 (6)	C12—C11—C17—C22	125.0 (4)
C6—C7—C8—O4	2.2 (6)	C10—C11—C17—C18	66.0 (5)
C2—C7—C8—O4	−176.9 (3)	C12—C11—C17—C18	−57.2 (5)
O4—C8—C9—C10	177.0 (3)	C22—C17—C18—C19	0.2 (6)
C7—C8—C9—C10	−1.9 (6)	C11—C17—C18—C19	−177.7 (4)
O1—C1—C10—C9	−178.5 (3)	C17—C18—C19—C20	−0.5 (6)
C2—C1—C10—C9	2.1 (5)	C18—C19—C20—C21	0.4 (7)
O1—C1—C10—C11	−0.2 (5)	C18—C19—C20—Br1	178.9 (3)
C2—C1—C10—C11	−179.6 (3)	C19—C20—C21—C22	0.1 (7)
C8—C9—C10—C1	−0.2 (6)	Br1—C20—C21—C22	−178.4 (3)
C8—C9—C10—C11	−178.5 (4)	C18—C17—C22—C21	0.2 (7)
C1—C10—C11—C12	18.4 (5)	C11—C17—C22—C21	178.1 (4)
C9—C10—C11—C12	−163.3 (3)	C20—C21—C22—C17	−0.4 (7)

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the C1,C2,C7–C10, C17–C22 and C2–C7 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O2	0.88 (1)	2.09 (5)	2.744 (5)	131 (5)
N1—H1···O2ⁱ	0.88 (1)	2.22 (2)	3.075 (5)	163 (3)
N1—H2···Br1ⁱⁱ	0.88 (4)	2.76 (4)	3.547 (4)	149 (5)
C4—H4···Cg1ⁱ	0.93	2.90	3.673 (5)	142
C6—H6···Cg2ⁱⁱⁱ	0.93	2.98	3.743 (5)	140
C23—H23C···Cg3ⁱⁱⁱ	0.96	2.70	3.593 (5)	154

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y−1/2, −z+3/2; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₀BrNO₄
M_r	454.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	13.1543 (14), 16.8110 (18), 9.3672 (12)
β (°)	96.628 (10)
V (Å³)	2057.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.03
Crystal size (mm)	0.30 × 0.20 × 0.03

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.828, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12041, 4740, 2533
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.164, 1.02
No. of reflections	4740
No. of parameters	270
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.90

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the C1,C2,C7–C10, C17–C22 and C2–C7 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O2	0.876 (10)	2.09 (5)	2.744 (5)	131 (5)
N1—H1···O2ⁱ	0.878 (10)	2.223 (15)	3.075 (5)	163 (3)
N1—H2···Br1ⁱⁱ	0.88 (4)	2.76 (4)	3.547 (4)	149 (5)
C4—H4···Cg1ⁱ	0.93	2.90	3.673 (5)	142
C6—H6···Cg2ⁱⁱⁱ	0.93	2.98	3.743 (5)	140
C23—H23C···Cg3ⁱⁱⁱ	0.96	2.70	3.593 (5)	154

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y−1/2, −z+3/2; (iii) −x+1, −y+1, −z+1.

Footnotes

‡Additional correspondence author, e-mail: aamr1963@yahoo.com.

Acknowledgements

The authors are grateful for the sponsorship of the Research Center, College of Pharmacy and the Deanship of Scientific Research, King Saud University. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/12).

References

Abd-El-Aziz, A. S., El-Agrody, A. M., Bedair, A. H., Corkery, T. C. & Ata, A. (2004). Heterocycles, 63, 1793–1812. CAS Google Scholar
Abd-El-Aziz, A. S., Mohamed, H. M., Mohammed, S., Zahid, S., Ata, A., Bedair, A. H., El-Agrody, A. M. & Harvey, P. D. (2007). J. Heterocycl. Chem. 44, 1287–1301. CAS Google Scholar
Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Alvey, L., Prado, S., Saint-Joanis, B., Michel, S., Koch, M., Cole, S. T., Tillequin, F. & Janin, Y. L. (2009). Eur. J. Med. Chem. 44, 2497–2505. Web of Science CrossRef PubMed CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
El-Agrody, A. M., Al-Omar, M. A., Amr, A.-G. E., Chia, T. S. & Fun, H.-K. (2012). Acta Cryst. E68, o1803–o1804. CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kemnitzer, W., Drewe, J., Jiang, S., Zhang, H., Zhao, J., Crogan-Grundy, C., Xu, L., Lamothe, S., Gourdeau, H., Denis, R., Tseng, B., Kasibhatla, S. & Cai, S. X. (2007). J. Med. Chem. 50, 2858–2864. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 69| Part 3| March 2013| Pages o435-o436

doi:10.1107/S160053681300490X

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

Ethyl 2-amino-4-(4-bromo­phen­yl)-6-meth­­oxy-4H-benzo[h]chromene-3-carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

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organic compounds

Ethyl 2-amino-4-(4-bromophenyl)-6-methoxy-4H-benzo[h]chromene-3-carboxylate