organic compounds
H-chromen-3-yl)-2-methylamino-3-nitropyrano[3,2-c]chromen-5(4H)-one chloroform monosolvate
of 4-(6-bromo-4-oxo-4aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and bOrganic Chemistry Division, CSIR Central Leather Research Institute, Chennai 600 020, India
*Correspondence e-mail: raja.13nap@gmail.com
In the title compound, C22H13BrN2O7·CHCl3, the pyran ring adopts a shallow sofa conformation with the C atom bearing the bromochromene system as the flap [deviation = 0.291 (3) Å]. The dihedral angle between the pyran fused-ring system (all atoms; r.m.s. deviation = 0.032 Å) and the bromochromene ring system (r.m.s. deviation = 0.027 Å) is 87.56 (9)°. An intramolecular N—H⋯O hydrogen bond closes an S(6) ring. The Cl atoms of the solvent molecule are disordered over two sets of sites in a 0.515 (6):0.485 (6) ratio. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R22(12) loops. The packing also features C—H⋯O and very weak π–π [centroid–centroid separation = 3.960 (2) Å] interactions, which link the dimers into a three-dimensional network.
Keywords: crystal structure; chromenone; hydrogen bonding.
CCDC reference: 1416576
1. Related literature
For background to chromene derivatives, see: Ercole et al. (2009); Geen et al. (1996) Khan et al. (2010); Raj et al. (2010). For a related structure, see: Raja et al. (2015).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; 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); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
CCDC reference: 1416576
https://doi.org/10.1107/S2056989015014553/hb7473sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014553/hb7473Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015014553/hb7473Isup3.cml
4-Hydroxycoumarin (0.81 g, 5 mmol), 6-bromo-4-oxo-4H-chromene-3-carbaldehyde (0.78 g, 5 mmol) and NMSM (0.74 g, 5 mmol) were mixed in ethanol at room temperature (3 h) in the presence of TEA (triethylamine 0.1 eq), as a catalyst. Upon completion of the reaction, the mixture was filtered, and washed with ethanol to obtained desired white product in 93% yield. Colourless blocks of the title compound were recrystallised from chloroform solution.
N and C-bound H atoms were positioned geometrically (C–H = 0.93–0.98 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for all other H atoms.
Chromene derivatives are
that have a variety of industrial, biological and chemical synthesis applications (Geen et al., 1996; Ercole et al., 2009). They exhibit a number of pharmacological activities such as anti-HIV, anti-inflammatory, anti-bacterial, anti-allergic, anti-cancer, etc. (Khan et al., 2010; Raj et al., 2010). Against this background an X-ray diffraction study of the title compound and its structural aspects are presented herein.The θ = 112.7 (11) and φ = 6.7 (12)°, respectively. The atoms C10 and O3 are deviating from the mean plane of C8—C9—C11—C12 by -0.266 and -0.644 Å, respectively. The chromene ring (O2/C1—C9) and (O7/C14—C22) are almost planar and normal to one another with a dihedral angle of 88.20 (2)° between their mean planes. The nitro group is bonded to the pyran ring at CC with the torsion angle C12—C11—N1—O5 0f 3.5 (5)°, indicating a (+) syn-periplanar conformation for this group. The chromene ring attached to the pyran ring at C10 with torsion angle C11—C10—C14—C15 of 117.6 (4)°, indicating a (+) anti-clinal conformation for this group. The title compound exhibits structural similarities with already reported related structure (Raja et al., 2015).
of the title compound is shown in Fig.1. The six-membered central pyran ring is very similar to a screw boat conformation as evidenced by the puckering parameters q2 = 0.204 (4) Å,In the
the molecules are linked to form an infinite chain along [100], through N2—H···O5 hydrogen bonds, generating graph set motifs R22(12) (Fig.2). In addition, there is a N—H···O intramolecular interaction.For background to chromene derivatives, see: Ercole et al. (2009); Geen et al. (1996) Khan et al. (2010); Raj et al. (2010). For a related structure, see: Raja et al. (2015).
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title molecule, with displacement ellipsoids drawn at 30% probability level. The intramolecular hydrogen bond, which generates an S(6) ring motif, is shown as a dashed line. | |
Fig. 2. Packing diagram showing the chain motif R22(12) along the [100] direction. |
C22H13BrN2O7·CHCl3 | Z = 2 |
Mr = 616.62 | F(000) = 616 |
Triclinic, P1 | Dx = 1.643 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8816 (2) Å | Cell parameters from 3672 reflections |
b = 11.9237 (3) Å | θ = 1.8–25.0° |
c = 12.0616 (3) Å | µ = 2.02 mm−1 |
α = 80.804 (1)° | T = 293 K |
β = 68.422 (1)° | Colourless, block |
γ = 70.735 (1)° | 0.35 × 0.30 × 0.25 mm |
V = 1246.36 (5) Å3 |
Bruker SMART APEXII CCD diffractometer | 4389 independent reflections |
Radiation source: fine-focus sealed tube | 3672 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω and φ scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −11→10 |
Tmin = 0.539, Tmax = 0.632 | k = −14→14 |
17277 measured reflections | l = −14→14 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0626P)2 + 1.1978P] where P = (Fo2 + 2Fc2)/3 |
4389 reflections | (Δ/σ)max < 0.001 |
353 parameters | Δρmax = 0.63 e Å−3 |
114 restraints | Δρmin = −0.53 e Å−3 |
C22H13BrN2O7·CHCl3 | γ = 70.735 (1)° |
Mr = 616.62 | V = 1246.36 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.8816 (2) Å | Mo Kα radiation |
b = 11.9237 (3) Å | µ = 2.02 mm−1 |
c = 12.0616 (3) Å | T = 293 K |
α = 80.804 (1)° | 0.35 × 0.30 × 0.25 mm |
β = 68.422 (1)° |
Bruker SMART APEXII CCD diffractometer | 4389 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 3672 reflections with I > 2σ(I) |
Tmin = 0.539, Tmax = 0.632 | Rint = 0.019 |
17277 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 114 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.63 e Å−3 |
4389 reflections | Δρmin = −0.53 e Å−3 |
353 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 | Occ. (<1) | |
C1 | 0.6175 (4) | 0.6474 (3) | 0.0736 (4) | 0.0442 (9) | |
C2 | 0.5491 (5) | 0.6922 (3) | −0.1038 (3) | 0.0447 (9) | |
C3 | 0.5920 (6) | 0.7284 (4) | −0.2223 (4) | 0.0592 (11) | |
H3 | 0.6853 | 0.7436 | −0.2601 | 0.071* | |
C4 | 0.4958 (6) | 0.7418 (5) | −0.2839 (4) | 0.0678 (13) | |
H4 | 0.5237 | 0.7667 | −0.3640 | 0.081* | |
C5 | 0.3578 (6) | 0.7189 (5) | −0.2288 (4) | 0.0675 (13) | |
H5 | 0.2936 | 0.7283 | −0.2721 | 0.081* | |
C6 | 0.3140 (5) | 0.6820 (4) | −0.1098 (4) | 0.0545 (11) | |
H6 | 0.2211 | 0.6660 | −0.0732 | 0.065* | |
C7 | 0.4101 (4) | 0.6691 (3) | −0.0449 (3) | 0.0402 (8) | |
C8 | 0.3759 (4) | 0.6353 (3) | 0.0800 (3) | 0.0351 (8) | |
C9 | 0.4701 (4) | 0.6296 (3) | 0.1389 (3) | 0.0355 (8) | |
C10 | 0.4260 (4) | 0.6090 (3) | 0.2719 (3) | 0.0341 (8) | |
H10 | 0.5132 | 0.5529 | 0.2910 | 0.041* | |
C11 | 0.2968 (4) | 0.5549 (3) | 0.3146 (3) | 0.0362 (8) | |
C12 | 0.2024 (4) | 0.5667 (3) | 0.2490 (3) | 0.0395 (8) | |
C13 | −0.0189 (6) | 0.5523 (5) | 0.2111 (5) | 0.0758 (16) | |
H13A | −0.1049 | 0.5241 | 0.2563 | 0.114* | |
H13B | 0.0393 | 0.5076 | 0.1405 | 0.114* | |
H13C | −0.0538 | 0.6349 | 0.1888 | 0.114* | |
C14 | 0.3830 (4) | 0.7256 (3) | 0.3303 (3) | 0.0344 (8) | |
C15 | 0.4574 (4) | 0.7360 (3) | 0.3991 (3) | 0.0415 (8) | |
H15 | 0.5365 | 0.6704 | 0.4080 | 0.050* | |
C16 | 0.3129 (4) | 0.9334 (3) | 0.4428 (3) | 0.0406 (8) | |
C17 | 0.2842 (5) | 1.0337 (4) | 0.5026 (4) | 0.0530 (10) | |
H17 | 0.3397 | 1.0319 | 0.5509 | 0.064* | |
C18 | 0.1736 (5) | 1.1350 (4) | 0.4898 (4) | 0.0528 (10) | |
H18 | 0.1529 | 1.2026 | 0.5296 | 0.063* | |
C19 | 0.0923 (4) | 1.1360 (3) | 0.4165 (3) | 0.0423 (9) | |
C20 | 0.1176 (4) | 1.0372 (3) | 0.3593 (3) | 0.0396 (8) | |
H20 | 0.0607 | 1.0391 | 0.3120 | 0.047* | |
C21 | 0.2297 (4) | 0.9331 (3) | 0.3724 (3) | 0.0362 (8) | |
C22 | 0.2577 (4) | 0.8247 (3) | 0.3136 (3) | 0.0368 (8) | |
N1 | 0.2703 (4) | 0.4975 (3) | 0.4251 (3) | 0.0405 (7) | |
N2 | 0.0763 (4) | 0.5375 (3) | 0.2832 (3) | 0.0519 (9) | |
H2 | 0.0471 | 0.5069 | 0.3543 | 0.062* | |
O1 | 0.7135 (3) | 0.6371 (3) | 0.1160 (3) | 0.0648 (9) | |
O2 | 0.6502 (3) | 0.6786 (3) | −0.0456 (2) | 0.0533 (7) | |
O3 | 0.2394 (3) | 0.6112 (2) | 0.1340 (2) | 0.0408 (6) | |
O4 | 0.3527 (3) | 0.4944 (2) | 0.4837 (2) | 0.0506 (7) | |
O5 | 0.1646 (3) | 0.4491 (3) | 0.4673 (3) | 0.0514 (7) | |
O6 | 0.1798 (3) | 0.8194 (2) | 0.2569 (3) | 0.0525 (7) | |
O7 | 0.4263 (3) | 0.8351 (2) | 0.4569 (2) | 0.0498 (7) | |
Br1 | −0.05894 (5) | 1.27713 (4) | 0.39770 (4) | 0.05830 (19) | |
C23 | 0.7698 (6) | 0.9052 (8) | 0.0829 (5) | 0.146 (3) | |
H23A | 0.7777 | 0.8283 | 0.0580 | 0.175* | 0.515 (6) |
H23B | 0.7592 | 0.8259 | 0.1122 | 0.175* | 0.485 (6) |
Cl1 | 0.9143 (5) | 0.8826 (4) | 0.1496 (4) | 0.1075 (15) | 0.515 (6) |
Cl2 | 0.5958 (5) | 0.9568 (5) | 0.1863 (5) | 0.140 (2) | 0.515 (6) |
Cl3 | 0.8013 (6) | 0.9975 (5) | −0.0393 (3) | 0.131 (2) | 0.515 (6) |
Cl1' | 0.8251 (14) | 0.9193 (11) | 0.1864 (7) | 0.260 (6) | 0.485 (6) |
Cl2' | 0.5804 (9) | 0.9669 (10) | 0.0975 (13) | 0.317 (8) | 0.485 (6) |
Cl3' | 0.8819 (8) | 0.8620 (7) | −0.0529 (4) | 0.174 (3) | 0.485 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.043 (2) | 0.044 (2) | 0.046 (2) | −0.0120 (17) | −0.0174 (18) | 0.0013 (17) |
C2 | 0.052 (2) | 0.040 (2) | 0.042 (2) | −0.0108 (18) | −0.0176 (18) | −0.0028 (16) |
C3 | 0.067 (3) | 0.062 (3) | 0.044 (2) | −0.019 (2) | −0.014 (2) | −0.001 (2) |
C4 | 0.087 (4) | 0.071 (3) | 0.044 (3) | −0.020 (3) | −0.027 (3) | 0.003 (2) |
C5 | 0.086 (4) | 0.074 (3) | 0.055 (3) | −0.018 (3) | −0.046 (3) | 0.001 (2) |
C6 | 0.065 (3) | 0.058 (3) | 0.052 (3) | −0.017 (2) | −0.034 (2) | −0.001 (2) |
C7 | 0.051 (2) | 0.0308 (18) | 0.041 (2) | −0.0077 (16) | −0.0213 (18) | −0.0040 (15) |
C8 | 0.0380 (19) | 0.0290 (17) | 0.041 (2) | −0.0087 (15) | −0.0175 (16) | −0.0025 (14) |
C9 | 0.0356 (19) | 0.0303 (17) | 0.042 (2) | −0.0076 (15) | −0.0170 (16) | −0.0012 (14) |
C10 | 0.0339 (18) | 0.0322 (17) | 0.0410 (19) | −0.0075 (14) | −0.0215 (15) | 0.0021 (14) |
C11 | 0.0377 (19) | 0.0330 (18) | 0.041 (2) | −0.0105 (15) | −0.0187 (16) | 0.0043 (15) |
C12 | 0.041 (2) | 0.0343 (18) | 0.049 (2) | −0.0137 (16) | −0.0212 (17) | 0.0053 (16) |
C13 | 0.066 (3) | 0.096 (4) | 0.094 (4) | −0.045 (3) | −0.055 (3) | 0.032 (3) |
C14 | 0.0360 (19) | 0.0353 (18) | 0.0355 (18) | −0.0116 (15) | −0.0174 (15) | 0.0042 (14) |
C15 | 0.045 (2) | 0.0393 (19) | 0.045 (2) | −0.0096 (17) | −0.0255 (18) | 0.0016 (16) |
C16 | 0.045 (2) | 0.043 (2) | 0.038 (2) | −0.0138 (17) | −0.0176 (17) | −0.0001 (16) |
C17 | 0.061 (3) | 0.058 (3) | 0.051 (2) | −0.018 (2) | −0.028 (2) | −0.010 (2) |
C18 | 0.061 (3) | 0.046 (2) | 0.053 (2) | −0.019 (2) | −0.014 (2) | −0.0124 (19) |
C19 | 0.041 (2) | 0.0357 (19) | 0.044 (2) | −0.0124 (16) | −0.0075 (17) | −0.0007 (16) |
C20 | 0.039 (2) | 0.039 (2) | 0.041 (2) | −0.0134 (16) | −0.0146 (16) | 0.0035 (16) |
C21 | 0.0376 (19) | 0.0354 (18) | 0.0376 (19) | −0.0126 (15) | −0.0144 (16) | 0.0011 (15) |
C22 | 0.039 (2) | 0.0373 (19) | 0.0399 (19) | −0.0118 (16) | −0.0210 (16) | 0.0021 (15) |
N1 | 0.0407 (18) | 0.0347 (16) | 0.0451 (18) | −0.0081 (14) | −0.0186 (15) | 0.0046 (13) |
N2 | 0.048 (2) | 0.062 (2) | 0.059 (2) | −0.0286 (17) | −0.0291 (17) | 0.0172 (17) |
O1 | 0.0446 (17) | 0.098 (3) | 0.0627 (19) | −0.0300 (17) | −0.0268 (15) | 0.0082 (17) |
O2 | 0.0475 (16) | 0.0693 (19) | 0.0447 (16) | −0.0225 (14) | −0.0151 (13) | 0.0028 (14) |
O3 | 0.0430 (15) | 0.0440 (14) | 0.0461 (15) | −0.0173 (12) | −0.0265 (12) | 0.0064 (11) |
O4 | 0.0554 (17) | 0.0539 (17) | 0.0505 (16) | −0.0164 (14) | −0.0336 (14) | 0.0148 (13) |
O5 | 0.0497 (16) | 0.0521 (16) | 0.0548 (17) | −0.0239 (14) | −0.0188 (13) | 0.0133 (13) |
O6 | 0.0569 (17) | 0.0432 (15) | 0.0710 (19) | −0.0030 (13) | −0.0450 (16) | −0.0083 (13) |
O7 | 0.0592 (18) | 0.0485 (16) | 0.0545 (17) | −0.0080 (13) | −0.0388 (14) | −0.0067 (13) |
Br1 | 0.0560 (3) | 0.0359 (2) | 0.0753 (3) | −0.00750 (19) | −0.0191 (2) | −0.00208 (19) |
C23 | 0.127 (7) | 0.178 (8) | 0.117 (6) | −0.035 (6) | −0.027 (5) | −0.024 (6) |
Cl1 | 0.125 (3) | 0.100 (3) | 0.118 (4) | −0.038 (2) | −0.061 (3) | −0.005 (2) |
Cl2 | 0.107 (3) | 0.123 (4) | 0.134 (4) | −0.031 (3) | 0.019 (3) | −0.002 (3) |
Cl3 | 0.157 (4) | 0.152 (5) | 0.084 (2) | −0.078 (3) | −0.028 (2) | 0.028 (2) |
Cl1' | 0.426 (17) | 0.233 (10) | 0.126 (5) | −0.091 (11) | −0.083 (8) | −0.056 (6) |
Cl2' | 0.257 (11) | 0.154 (7) | 0.425 (19) | 0.054 (7) | −0.078 (12) | −0.041 (11) |
Cl3' | 0.214 (7) | 0.215 (8) | 0.098 (3) | −0.102 (6) | −0.032 (4) | 0.009 (4) |
C1—O1 | 1.199 (5) | C14—C15 | 1.337 (5) |
C1—O2 | 1.370 (5) | C14—C22 | 1.453 (5) |
C1—C9 | 1.446 (5) | C15—O7 | 1.358 (5) |
C2—C3 | 1.374 (6) | C15—H15 | 0.9300 |
C2—O2 | 1.374 (5) | C16—O7 | 1.367 (5) |
C2—C7 | 1.391 (6) | C16—C21 | 1.383 (5) |
C3—C4 | 1.365 (7) | C16—C17 | 1.390 (6) |
C3—H3 | 0.9300 | C17—C18 | 1.368 (6) |
C4—C5 | 1.377 (7) | C17—H17 | 0.9300 |
C4—H4 | 0.9300 | C18—C19 | 1.392 (6) |
C5—C6 | 1.381 (7) | C18—H18 | 0.9300 |
C5—H5 | 0.9300 | C19—C20 | 1.366 (5) |
C6—C7 | 1.397 (5) | C19—Br1 | 1.893 (4) |
C6—H6 | 0.9300 | C20—C21 | 1.397 (5) |
C7—C8 | 1.437 (5) | C20—H20 | 0.9300 |
C8—C9 | 1.344 (5) | C21—C22 | 1.470 (5) |
C8—O3 | 1.369 (4) | C22—O6 | 1.223 (4) |
C9—C10 | 1.501 (5) | N1—O4 | 1.248 (4) |
C10—C11 | 1.505 (5) | N1—O5 | 1.264 (4) |
C10—C14 | 1.521 (5) | N2—H2 | 0.8600 |
C10—H10 | 0.9800 | C23—Cl1' | 1.587 (7) |
C11—N1 | 1.372 (5) | C23—Cl3' | 1.653 (6) |
C11—C12 | 1.391 (5) | C23—Cl3 | 1.688 (7) |
C12—N2 | 1.307 (5) | C23—Cl2 | 1.691 (6) |
C12—O3 | 1.364 (4) | C23—Cl2' | 1.721 (7) |
C13—N2 | 1.454 (5) | C23—Cl1 | 1.812 (6) |
C13—H13A | 0.9600 | C23—H23A | 0.9800 |
C13—H13B | 0.9600 | C23—H23B | 0.9800 |
C13—H13C | 0.9600 | ||
O1—C1—O2 | 117.3 (4) | C18—C17—H17 | 120.3 |
O1—C1—C9 | 124.9 (4) | C16—C17—H17 | 120.3 |
O2—C1—C9 | 117.8 (3) | C17—C18—C19 | 119.4 (4) |
C3—C2—O2 | 117.1 (4) | C17—C18—H18 | 120.3 |
C3—C2—C7 | 121.8 (4) | C19—C18—H18 | 120.3 |
O2—C2—C7 | 121.1 (3) | C20—C19—C18 | 121.6 (4) |
C4—C3—C2 | 119.0 (5) | C20—C19—Br1 | 119.3 (3) |
C4—C3—H3 | 120.5 | C18—C19—Br1 | 119.1 (3) |
C2—C3—H3 | 120.5 | C19—C20—C21 | 119.5 (3) |
C3—C4—C5 | 120.9 (4) | C19—C20—H20 | 120.3 |
C3—C4—H4 | 119.6 | C21—C20—H20 | 120.3 |
C5—C4—H4 | 119.6 | C16—C21—C20 | 118.8 (3) |
C4—C5—C6 | 120.5 (4) | C16—C21—C22 | 120.5 (3) |
C4—C5—H5 | 119.8 | C20—C21—C22 | 120.7 (3) |
C6—C5—H5 | 119.8 | O6—C22—C14 | 123.5 (3) |
C5—C6—C7 | 119.6 (4) | O6—C22—C21 | 122.1 (3) |
C5—C6—H6 | 120.2 | C14—C22—C21 | 114.4 (3) |
C7—C6—H6 | 120.2 | O4—N1—O5 | 120.4 (3) |
C2—C7—C6 | 118.3 (4) | O4—N1—C11 | 118.6 (3) |
C2—C7—C8 | 116.7 (3) | O5—N1—C11 | 120.9 (3) |
C6—C7—C8 | 125.0 (4) | C12—N2—C13 | 125.5 (4) |
C9—C8—O3 | 122.9 (3) | C12—N2—H2 | 117.3 |
C9—C8—C7 | 122.3 (3) | C13—N2—H2 | 117.3 |
O3—C8—C7 | 114.8 (3) | C1—O2—C2 | 122.3 (3) |
C8—C9—C1 | 119.5 (3) | C12—O3—C8 | 119.7 (3) |
C8—C9—C10 | 122.2 (3) | C15—O7—C16 | 118.5 (3) |
C1—C9—C10 | 118.3 (3) | Cl1'—C23—Cl3' | 125.6 (5) |
C9—C10—C11 | 108.5 (3) | Cl1'—C23—Cl3 | 117.6 (7) |
C9—C10—C14 | 109.8 (3) | Cl3'—C23—Cl3 | 55.4 (3) |
C11—C10—C14 | 112.0 (3) | Cl1'—C23—Cl2 | 82.4 (5) |
C9—C10—H10 | 108.8 | Cl3'—C23—Cl2 | 151.9 (5) |
C11—C10—H10 | 108.8 | Cl3—C23—Cl2 | 112.8 (5) |
C14—C10—H10 | 108.8 | Cl1'—C23—Cl2' | 118.9 (5) |
N1—C11—C12 | 120.7 (3) | Cl3'—C23—Cl2' | 114.1 (5) |
N1—C11—C10 | 117.0 (3) | Cl3—C23—Cl2' | 85.0 (6) |
C12—C11—C10 | 122.3 (3) | Cl2—C23—Cl2' | 38.2 (5) |
N2—C12—O3 | 112.1 (3) | Cl1'—C23—Cl1 | 27.2 (4) |
N2—C12—C11 | 127.7 (3) | Cl3'—C23—Cl1 | 99.0 (4) |
O3—C12—C11 | 120.3 (3) | Cl3—C23—Cl1 | 109.5 (5) |
N2—C13—H13A | 109.5 | Cl2—C23—Cl1 | 109.1 (4) |
N2—C13—H13B | 109.5 | Cl2'—C23—Cl1 | 146.1 (5) |
H13A—C13—H13B | 109.5 | Cl1'—C23—H23A | 123.7 |
N2—C13—H13C | 109.5 | Cl3'—C23—H23A | 60.5 |
H13A—C13—H13C | 109.5 | Cl3—C23—H23A | 108.4 |
H13B—C13—H13C | 109.5 | Cl2—C23—H23A | 108.4 |
C15—C14—C22 | 120.1 (3) | Cl2'—C23—H23A | 94.7 |
C15—C14—C10 | 120.2 (3) | Cl1—C23—H23A | 108.4 |
C22—C14—C10 | 119.6 (3) | Cl1'—C23—H23B | 93.9 |
C14—C15—O7 | 124.9 (3) | Cl3'—C23—H23B | 93.9 |
C14—C15—H15 | 117.6 | Cl3—C23—H23B | 144.5 |
O7—C15—H15 | 117.6 | Cl2—C23—H23B | 85.5 |
O7—C16—C21 | 121.5 (3) | Cl2'—C23—H23B | 93.9 |
O7—C16—C17 | 117.2 (3) | Cl1—C23—H23B | 90.9 |
C21—C16—C17 | 121.4 (4) | H23A—C23—H23B | 36.2 |
C18—C17—C16 | 119.4 (4) | ||
O2—C2—C3—C4 | 179.3 (4) | C10—C14—C15—O7 | −178.8 (3) |
C7—C2—C3—C4 | −0.1 (7) | O7—C16—C17—C18 | 178.9 (4) |
C2—C3—C4—C5 | −0.4 (7) | C21—C16—C17—C18 | −1.4 (6) |
C3—C4—C5—C6 | 0.1 (8) | C16—C17—C18—C19 | −0.3 (7) |
C4—C5—C6—C7 | 0.6 (7) | C17—C18—C19—C20 | 1.7 (6) |
C3—C2—C7—C6 | 0.7 (6) | C17—C18—C19—Br1 | −179.2 (3) |
O2—C2—C7—C6 | −178.5 (3) | C18—C19—C20—C21 | −1.3 (6) |
C3—C2—C7—C8 | −178.1 (4) | Br1—C19—C20—C21 | 179.6 (3) |
O2—C2—C7—C8 | 2.6 (5) | O7—C16—C21—C20 | −178.6 (3) |
C5—C6—C7—C2 | −1.0 (6) | C17—C16—C21—C20 | 1.7 (6) |
C5—C6—C7—C8 | 177.8 (4) | O7—C16—C21—C22 | 2.1 (5) |
C2—C7—C8—C9 | 1.9 (5) | C17—C16—C21—C22 | −177.5 (4) |
C6—C7—C8—C9 | −176.9 (4) | C19—C20—C21—C16 | −0.4 (5) |
C2—C7—C8—O3 | −178.9 (3) | C19—C20—C21—C22 | 178.9 (3) |
C6—C7—C8—O3 | 2.3 (5) | C15—C14—C22—O6 | −176.2 (4) |
O3—C8—C9—C1 | 175.2 (3) | C10—C14—C22—O6 | 2.2 (6) |
C7—C8—C9—C1 | −5.7 (5) | C15—C14—C22—C21 | 3.0 (5) |
O3—C8—C9—C10 | −6.7 (5) | C10—C14—C22—C21 | −178.7 (3) |
C7—C8—C9—C10 | 172.4 (3) | C16—C21—C22—O6 | 175.4 (4) |
O1—C1—C9—C8 | −175.3 (4) | C20—C21—C22—O6 | −3.9 (6) |
O2—C1—C9—C8 | 4.9 (5) | C16—C21—C22—C14 | −3.8 (5) |
O1—C1—C9—C10 | 6.6 (6) | C20—C21—C22—C14 | 176.9 (3) |
O2—C1—C9—C10 | −173.2 (3) | C12—C11—N1—O4 | −176.3 (3) |
C8—C9—C10—C11 | 19.9 (4) | C10—C11—N1—O4 | 0.6 (5) |
C1—C9—C10—C11 | −162.0 (3) | C12—C11—N1—O5 | 3.5 (5) |
C8—C9—C10—C14 | −102.7 (4) | C10—C11—N1—O5 | −179.6 (3) |
C1—C9—C10—C14 | 75.4 (4) | O3—C12—N2—C13 | −1.6 (6) |
C9—C10—C11—N1 | 161.2 (3) | C11—C12—N2—C13 | 179.6 (4) |
C14—C10—C11—N1 | −77.5 (4) | O1—C1—O2—C2 | 179.6 (4) |
C9—C10—C11—C12 | −22.0 (5) | C9—C1—O2—C2 | −0.5 (5) |
C14—C10—C11—C12 | 99.3 (4) | C3—C2—O2—C1 | 177.5 (4) |
N1—C11—C12—N2 | 6.3 (6) | C7—C2—O2—C1 | −3.2 (6) |
C10—C11—C12—N2 | −170.4 (4) | N2—C12—O3—C8 | −173.6 (3) |
N1—C11—C12—O3 | −172.3 (3) | C11—C12—O3—C8 | 5.3 (5) |
C10—C11—C12—O3 | 11.0 (5) | C9—C8—O3—C12 | −7.5 (5) |
C9—C10—C14—C15 | −121.8 (4) | C7—C8—O3—C12 | 173.3 (3) |
C11—C10—C14—C15 | 117.6 (4) | C14—C15—O7—C16 | −1.5 (6) |
C9—C10—C14—C22 | 59.9 (4) | C21—C16—O7—C15 | 0.6 (5) |
C11—C10—C14—C22 | −60.7 (4) | C17—C16—O7—C15 | −179.7 (4) |
C22—C14—C15—O7 | −0.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O5 | 0.86 | 2.00 | 2.622 (5) | 128 |
N2—H2···O5i | 0.86 | 2.37 | 3.063 (5) | 138 |
C4—H4···O7ii | 0.93 | 2.59 | 3.383 (6) | 144 |
C15—H15···O4iii | 0.93 | 2.36 | 3.221 (4) | 153 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O5 | 0.86 | 2.00 | 2.622 (5) | 128 |
N2—H2···O5i | 0.86 | 2.37 | 3.063 (5) | 138 |
C4—H4···O7ii | 0.93 | 2.59 | 3.383 (6) | 144 |
C15—H15···O4iii | 0.93 | 2.36 | 3.221 (4) | 153 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1. |
Acknowledgements
The authors the thank Department of Chemistry, IIT, Chennai, India, for the data collection.
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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.
Chromene derivatives are heterocyclic compounds that have a variety of industrial, biological and chemical synthesis applications (Geen et al., 1996; Ercole et al., 2009). They exhibit a number of pharmacological activities such as anti-HIV, anti-inflammatory, anti-bacterial, anti-allergic, anti-cancer, etc. (Khan et al., 2010; Raj et al., 2010). Against this background an X-ray diffraction study of the title compound and its structural aspects are presented herein.
The asymmetric unit of the title compound is shown in Fig.1. The six-membered central pyran ring is very similar to a screw boat conformation as evidenced by the puckering parameters q2 = 0.204 (4) Å, θ = 112.7 (11) and φ = 6.7 (12)°, respectively. The atoms C10 and O3 are deviating from the mean plane of C8—C9—C11—C12 by -0.266 and -0.644 Å, respectively. The chromene ring (O2/C1—C9) and (O7/C14—C22) are almost planar and normal to one another with a dihedral angle of 88.20 (2)° between their mean planes. The nitro group is bonded to the pyran ring at CC with the torsion angle C12—C11—N1—O5 0f 3.5 (5)°, indicating a (+) syn-periplanar conformation for this group. The chromene ring attached to the pyran ring at C10 with torsion angle C11—C10—C14—C15 of 117.6 (4)°, indicating a (+) anti-clinal conformation for this group. The title compound exhibits structural similarities with already reported related structure (Raja et al., 2015).
In the crystal structure, the molecules are linked to form an infinite chain along [100], through N2—H···O5 hydrogen bonds, generating graph set motifs R22(12) (Fig.2). In addition, there is a N—H···O intramolecular interaction.