organic compounds
Ethyl 2-amino-4-(4-bromophenyl)-6-methoxy-4H-benzo[h]chromene-3-carboxylate
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
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
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2011); cell 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
10.1107/S160053681300490X/hg5295sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681300490X/hg5295Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681300490X/hg5295Isup3.cml
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.
The C-bound H atoms were geometrically placed (C—H = 0.93–0.98 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). The N-bound-H atom was refined with the distance restraint N—H = 0.88±0.01 Å and free Uiso.
Data collection: CrysAlis PRO (Agilent, 2011); cell
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).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. |
C23H20BrNO4 | F(000) = 928 |
Mr = 454.31 | Dx = 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 |
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 | Rint = 0.054 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.6°, θmin = 2.9° |
ω scan | h = −16→17 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −21→21 |
Tmin = 0.828, Tmax = 1.000 | l = −7→12 |
12041 measured reflections |
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(Fo2) + (0.0575P)2 + 0.7996P] where P = (Fo2 + 2Fc2)/3 |
4740 reflections | (Δ/σ)max = 0.001 |
270 parameters | Δρmax = 0.91 e Å−3 |
2 restraints | Δρmin = −0.90 e Å−3 |
C23H20BrNO4 | V = 2057.6 (4) Å3 |
Mr = 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)° |
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) |
Tmin = 0.828, Tmax = 1.000 | Rint = 0.054 |
12041 measured reflections |
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 | Δρmax = 0.91 e Å−3 |
4740 reflections | Δρmin = −0.90 e Å−3 |
270 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.828, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12041, 4740, 2533 |
Rint | 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 |
Δρmax, Δρmin (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).
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
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.