Crystal structures of two 4H-chromene derivatives: 2-amino-3-cyano-4-(3,4-di­chloro­phen­yl)-7-hy­droxy-4H-benzo[1,2-b]pyran 1,4-dioxane monosolvate and 2-amino-3-cyano-4-(2,6-di­chloro­phen­yl)-7-hy­droxy-4H-benzo[1,2-b]pyran

Silambarasan, S.; Nasser, A.J.A.; Mohandas, T.

doi:10.1107/S2056989019013197

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ISSN: 2056-9890

Volume 75| Part 10| October 2019| Pages 1568-1572

https://doi.org/10.1107/S2056989019013197

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Crystal structures of two 4H-chromene derivatives: 2-amino-3-cyano-4-(3,4-dichlorophenyl)-7-hydroxy-4H-benzo[1,2-b]pyran 1,4-dioxane monosolvate and 2-amino-3-cyano-4-(2,6-dichlorophenyl)-7-hydroxy-4H-benzo[1,2-b]pyran

S. Silambarasan,^a ^* A. Jamal Abdul Nasser ^a and T. Mohandas ^b

^aDepartment of Chemistry, Jamal Mohamed College, Tiruchirappalli 620 020, India, and ^bDepartment of Physics, K. Ramakrishnan College of Engineering, Samayapuram, Tiruchirappalli 621 115, India
^*Correspondence e-mail: ssilambu2012@gmail.com

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 3 September 2019; accepted 25 September 2019; online 27 September 2019)

In the title compounds, C₁₆H₉Cl₂N₂O₂·C₄H₈O₂ and C₁₆H₉Cl₂N₂O₂, the bicyclic 4H-chromene cores are nearly planar with maximum deviations of 0.081 (2) and 0.087 (2) Å. In both structures, the chromene derivative molecules are linked into centrosymmetric dimers by pairs of N—H⋯O hydrogen bonds, forming R²₂(16) motifs. These dimers are further linked in the 3,4-dichlorophenyl derivative by N—H⋯N hydrogen bonds into double layers parallel to (100) and in the 2,6-dichlorophenyl derivative by O—H⋯N hydrogen bonds into ribbons along the [1 $[\overline{1}]$ 0] direction. In the 3,4-dichlorophenyl derivative, the 1,4-dioxane solvent molecules are connected to the chromene molecules via O—H⋯O hydrogen bonds.

Keywords: crystal structure; 4H-chromene; π-conjugation; hydrogen bond; solvate.

CCDC references: 1865757; 1865762

1. Chemical context

Many compounds containing the heterocyclic pyran moiety exhibit diverse pharmacological activities. The pyran ring is a core unit found in benzopyrans, chromones, coumarins and flavanoids. Numerous naturally occurring compounds containing a pyran ring show therapeutic activities such as antiviral (Martínez-Grau & Marco, 1997 ), antimicrobial (Khafagy et al., 2002 ), mutagenicity (Hiramoto et al., 1997 ), sex pheromone (Bianchi & Tava, 1987 ), antitumor (Mohr et al., 1975 ), cancer therapy (Anderson et al., 2005 ), central nervous system activity (Eiden & Denk, 1991 ), antifungal (Schiller et al., 2010 ), antiproliferative (Osman et al., 2011 ), antidiabetic (Bisht et al., 2011 ), anti-inflammatory (Wang et al., 1996 ; Wang et al., 2005 ) and calcium channel antagonist activity (Shahrisa et al., 2011 ).

2-Amino-4H-benzo[1,2-b]pyrans (2-amino-4H-chromenes) act as synthetic building blocks for the design of various pyran-containing bio-active molecules (Kale et al., 2013 ; Sabry et al., 2011 ; Kidwai et al., 2010 ); among them are cytotoxic and anti-HIV preparations (Patil et al., 1993 ; Emmadi et al., 2012 ) and anticancer (Wu et al., 2003 ; Perrella et al., 1994 ), antimicrobial (Mungra et al., 2011 ) and anticoagulant agents (Cingolani et al., 1969 ).

Against this background we carried out the crystallographic studies of the title 4H-chromenes 2-amino-3-cyano-4-(3,4-dichlorophenyl)-7-hydroxy-4H-benzo[1,2-b]pyran 1,4-dioxane mono solvate (I) and 2-amino-3-cyano-4-(2,6-dichlorophenyl)-7-hydroxy-4H-benzo[1,2-b]pyran (II).

2. Structural commentary

The asymmetric units of the title compounds are illustrated in Figs. 1 and 2. The molecules of the two 4H-chromene derivatives differ only in the positions of the chlorine atoms attached to the phenyl ring, and the key bond dimensions in (I) and (II) essentially coincide. The bicyclic chromene cores in the two structures are nearly planar, with the largest deviation from the mean plane being observed for the sp³-hybridized C7 atom in both cases [0.081 (2) and 0.087 (2) Å in (I) and (II), respectively]. The interatomic distances in the pyran rings indicate a strong π-conjugation of the electron-donating atoms O2 and N2 with the cyano acceptor groups. As a result of this conjugation, the C8=C9 bonds [1.349 (3) Å in (I) and 1.354 (2) Å in (II)] are longer than the typical double bonds (Allen et al., 1987 ), whereas the C9—N2 bonds are shortened [1.335 (3) and 1.342 (2) Å for (I) and (II), respectively], thus the amino groups in the studied structures were assumed to be planar and treated with the AFIX 43 instruction. Besides this, the O—C distances in the pyran rings are asymmetric [1.393 (2) and 1.393 (2) Å for O2—C10 vs. 1.357 (3) and 1.353 (2) Å for O2—C9 in (I) and (II), respectively]. The observed planarity of the bicyclic chromene units is also a consequence of π-conjugation. The dihedral angle between the mean planes of the 4H-chromene ring system and the phenyl ring attached to C7 is 80.82 (9)° in (I) and 85.36 (8)° in (II). In (II), the o-chlorine atom Cl1 forms short intramolecular contacts with atoms C8 and C9 of the pyran ring of 3.111 (2) and 3.193 (2) Å, respectively.

Figure 1
The asymmetric unit of (I)

, with atom labelling and 50% probability displacement ellipsoids. The hydrogen bond is represented by a dashed line.

Figure 2
The molecular structure of (II)

, with atom labelling and 50% probability displacement ellipsoids.

3. Supramolecular features

As shown in Figs. 3 and 4, in both of the title structures the 4H-chromene derivative molecules are linked by pairs of N—H⋯O hydrogen bonds (Tables 1 and 2) into centrosymmetric dimers, thus forming R²₂(16) motifs. In (I), these dimers are further connected by N—H⋯N hydrogen bonds into double layers parallel to the (100) plane (Fig. 5). In (II), the dimers are linked by O—H⋯N hydrogen bonds into ribbons along the [1 $[\overline{1}]$ 0] direction. In (I), the 1,4-dioxane solvent molecules are linked to the chromene molecules via O—H⋯O hydrogen bonds. In this compound, the C—H⋯Cl contacts (Table 2) also contribute to the stability of crystal structure.

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—HO1⋯O16	0.82	1.85	2.658 (3)	167
N2—HNB⋯O1ⁱ	0.86	2.19	2.978 (3)	153
N2—HNA⋯N1ⁱⁱ	0.86	2.22	2.989 (3)	149
C4—H4⋯Cl2ⁱⁱⁱ	0.93	2.87	3.692 (3)	148
Symmetry codes: (i) -x, -y+2, -z+1; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y-1, z.

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯Cl2	0.98	2.50	3.078 (3)	117
N2—HNB⋯O1ⁱ	0.86	2.19	3.048 (2)	173
O1—HO1⋯N1ⁱⁱ	0.85 (3)	1.95 (3)	2.762 (2)	160 (3)
Symmetry codes: (i) -x+2, -y+1, -z; (ii) x+1, y-1, z.

Figure 3
A view of the hydrogen-bonding interactions in (I)

, showing the formation of centrosymmetric dimers. The C-bound hydrogen atoms are omitted for clarity. [Symmetry codes: (i) −x, 2 − y, 1 − z; (ii) −x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.]

Figure 4
A view of the hydrogen-bonding interactions in (II)

, showing the formation of centrosymmetric dimers and ribbons. The C-bound hydrogen atoms are omitted for clarity. [Symmetry codes: (i) 2 − x, 1 − y, −z; (ii) 1 + x, y − 1, z.]

Figure 5
Double layers of hydrogen-bonded molecules in (I)

. The 1,4-dioxane molecules are omitted for clarity.

4. Database survey

A search in the Cambridge Structural Database (CSD version 5.40, last update August 2019; Groom et al., 2016 ), revealed 107 structures of 4H-chromene derivatives, among them 25 containing the 2-amino-3-cyano-4H-chromene moiety. Of these, two structures, viz. 2-amino-7-hydroxy-4-(4-hydroxyphenyl)-4H-chromene-3-carbonitrile (HUPCEC; Horton et al., 2015 ) and 2-amino-4-(4-bromophenyl)-7-hydroxy-4H-chromene-3-carbonitrile (UFEKOI; Bi et al., 2017 ) are closely related to compounds (I) and (II). In the structures of both HUPCEC and UFEKOI, the molecules adopt the same conformation as in (I) and (II) and also form centrosymmetric dimers by pairs of N—H⋯O hydrogen bonds as in the title structures.

5. Synthesis and crystallization

Both studied compounds were prepared by the same procedure. Mixtures of 3,4-chlorobenzaldehyde (8.75 g, 0.05 mol) [for (I)] or 2,4-dichlorobenzaldehyde (8.75 g, 0.05 mol) [for (II)], malononitrile (3.3 ml, 0.05 mol) and resorcinol (5.5 g, 0.05 mol) in 150 ml of water were refluxed for about 10-20 minutes in 250 ml round-bottom flasks. The progress of the reaction was monitored by thin layer chromatography using silica gel-G plates. After the product had formed, the reaction mixtures were kept in the refrigerator overnight. The solid mass that settled was filtered using a suction pump, washed well with a mixture of methanol and water and dried in air. The crude products were recrystallized from methanol giving white powders. Single crystals were grown by slow evaporation of solutions in 1,4-dioxane (I) or acetonitrile (II). The melting points are 518-523 K for (I) and 513-515 K for (II).

6. Refinement

Crystal data, diffraction data and structure refinement details for (I) and (II) are summarized in Table 3. All hydrogen atoms bound to C and N were located from the difference-Fourier maps and refined isotropically using a riding model, with U_iso(H) = 1.2U_eq(C,N) and C—H = 0.98 Å for methine, 0.97 Å for methylene and 0.93 Å for aromatic C atoms, and N—H = 0.86 Å. In (I), the hydroxy H atom was constrained with AFIX 147, but its U_iso value was allowed to refine freely. In (II), the OH hydrogen atom was freely refined.

Table 3
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₆H₉Cl₂N₂O₂·C₄H₈O₂	C₁₆H₉Cl₂N₂O₂
M_r	420.25	332.15
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$
Temperature (K)	294	294
a, b, c (Å)	12.753 (9), 6.665 (4), 24.050 (14)	6.271 (3), 8.697 (5), 13.794 (7)
α, β, γ (°)	90, 102.95 (3), 90	107.06 (2), 94.269 (17), 95.00 (3)
V (Å³)	1992 (2)	712.5 (7)
Z	4	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.36	0.46
Crystal size (mm)	0.15 × 0.15 × 0.10	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Bruker Kappa APEX3 CMOS	Bruker Kappa APEX3 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2018 )	Multi-scan (SADABS; Bruker, 2018)
T_min, T_max	0.704, 0.745	0.704, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	34682, 3492, 2885	22289, 2499, 2239
R_int	0.033	0.023
(sin θ/λ)_max (Å⁻¹)	0.595	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.121, 1.11	0.033, 0.081, 1.11
No. of reflections	3492	2499
No. of parameters	256	204
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.24	0.23, −0.25
Computer programs: APEX3, SAINT and XPREP (Bruker, 2018), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2014/6 (Sheldrick, 2015b ), DIAMOND (Brandenburg, 2007 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC references: 1865757; 1865762

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989019013197/yk2126sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019013197/yk2126Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019013197/yk2126IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019013197/yk2126Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019013197/yk2126IIsup5.cml

checkCIF report

Computing details top

For both structures, data collection: APEX3 (Bruker, 2018); cell refinement: APEX3 and SAINT (Bruker, 2018); data reduction: SAINT and XPREP (Bruker, 2018); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2007) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

2-Amino-3-cyano-4-(3,4-dichlorophenyl)-7-hydroxy-4H-benzo[1,2-b]pyran 1,4-dioxane monosolvate (I) top

Crystal data top

C₁₆H₉Cl₂N₂O₂·C₄H₈O₂	D_x = 1.401 Mg m⁻³
M_r = 420.25	Melting point: 520 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.753 (9) Å	Cell parameters from 9965 reflections
b = 6.665 (4) Å	θ = 3.2–26.7°
c = 24.050 (14) Å	µ = 0.36 mm⁻¹
β = 102.95 (3)°	T = 294 K
V = 1992 (2) Å³	Block, colourless
Z = 4	0.15 × 0.15 × 0.10 mm
F(000) = 868

Data collection top

Bruker Kappa APEX3 CMOS diffractometer	3492 independent reflections
Radiation source: fine-focus sealed tube	2885 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω and φ scan	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2018)	h = −15→15
T_min = 0.704, T_max = 0.745	k = −7→7
34682 measured reflections	l = −28→26

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0541P)² + 1.1852P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
3492 reflections	Δρ_max = 0.26 e Å⁻³
256 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0174 (18)

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.60648 (5)	0.18411 (11)	0.42962 (4)	0.0702 (3)
Cl2	0.52933 (5)	0.63066 (11)	0.40894 (4)	0.0679 (3)
O1	0.12386 (15)	0.8018 (3)	0.63654 (6)	0.0519 (5)
HO1	0.1545	0.7386	0.6648	0.074 (10)*
O2	0.07140 (12)	0.8197 (2)	0.43851 (6)	0.0379 (4)
N2	0.01565 (18)	0.8571 (3)	0.34552 (8)	0.0530 (6)
HNA	0.0051	0.8207	0.3104	0.064*
HNB	−0.0032	0.9750	0.3540	0.064*
N1	0.0608 (2)	0.3924 (4)	0.28098 (9)	0.0748 (8)
C3	0.47549 (17)	0.2502 (4)	0.42953 (10)	0.0424 (6)
C4	0.40418 (19)	0.1065 (4)	0.43879 (12)	0.0512 (6)
H4	0.4266	−0.0260	0.4452	0.061*
C5	0.29931 (18)	0.1579 (3)	0.43861 (11)	0.0439 (6)
H5	0.2516	0.0592	0.4448	0.053*
C6	0.26401 (16)	0.3532 (3)	0.42946 (8)	0.0303 (5)
C7	0.14837 (15)	0.4087 (3)	0.43059 (8)	0.0305 (5)
H7	0.1068	0.2841	0.4279	0.037*
C11	0.14231 (15)	0.5105 (3)	0.48595 (8)	0.0292 (4)
C12	0.17291 (16)	0.4127 (3)	0.53832 (9)	0.0358 (5)
H12	0.1980	0.2815	0.5391	0.043*
C13	0.16731 (17)	0.5037 (4)	0.58889 (9)	0.0382 (5)
H13	0.1868	0.4337	0.6231	0.046*
C14	0.13242 (16)	0.7003 (3)	0.58846 (8)	0.0354 (5)
C10	0.10667 (15)	0.7052 (3)	0.48756 (8)	0.0291 (4)
C15	0.10195 (16)	0.8023 (3)	0.53756 (8)	0.0337 (5)
H15	0.0786	0.9346	0.5369	0.040*
C9	0.06130 (16)	0.7304 (3)	0.38688 (8)	0.0342 (5)
C8	0.09544 (16)	0.5416 (3)	0.38111 (8)	0.0347 (5)
C22	0.07678 (19)	0.4596 (4)	0.32560 (10)	0.0459 (6)
C1	0.33627 (17)	0.4972 (3)	0.42043 (9)	0.0361 (5)
H1	0.3140	0.6298	0.4143	0.043*
C2	0.44144 (17)	0.4463 (3)	0.42042 (9)	0.0380 (5)
O16	0.24114 (17)	0.6481 (4)	0.73252 (9)	0.0769 (6)
C17	0.2288 (3)	0.5035 (7)	0.77295 (16)	0.0937 (12)
H171	0.1565	0.4491	0.7630	0.112*
H172	0.2389	0.5659	0.8102	0.112*
C18	0.3066 (3)	0.3413 (7)	0.7754 (2)	0.1008 (13)
H181	0.2976	0.2450	0.8042	0.121*
H182	0.2930	0.2727	0.7389	0.121*
O19	0.4122 (2)	0.4128 (5)	0.78824 (13)	0.1129 (10)
C20	0.4249 (4)	0.5602 (9)	0.7484 (3)	0.140 (2)
H201	0.4159	0.4986	0.7111	0.169*
H202	0.4974	0.6137	0.7590	0.169*
C21	0.3484 (3)	0.7239 (7)	0.7450 (2)	0.1147 (16)
H211	0.3622	0.7957	0.7810	0.138*
H212	0.3573	0.8171	0.7154	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0349 (3)	0.0613 (5)	0.1189 (7)	0.0130 (3)	0.0268 (4)	0.0064 (4)
Cl2	0.0449 (4)	0.0492 (4)	0.1188 (7)	−0.0051 (3)	0.0379 (4)	0.0059 (4)
O1	0.0682 (12)	0.0615 (11)	0.0250 (8)	0.0233 (9)	0.0080 (8)	−0.0009 (8)
O2	0.0528 (9)	0.0356 (8)	0.0245 (7)	0.0081 (7)	0.0070 (6)	0.0006 (6)
N2	0.0766 (15)	0.0540 (13)	0.0266 (10)	0.0236 (11)	0.0079 (9)	0.0035 (9)
N1	0.100 (2)	0.0820 (18)	0.0351 (13)	0.0287 (16)	−0.0006 (12)	−0.0151 (12)
C3	0.0294 (11)	0.0424 (13)	0.0557 (14)	0.0061 (10)	0.0105 (10)	−0.0031 (11)
C4	0.0408 (13)	0.0324 (12)	0.0819 (18)	0.0077 (10)	0.0171 (12)	0.0016 (12)
C5	0.0362 (12)	0.0333 (12)	0.0634 (15)	−0.0015 (10)	0.0138 (11)	−0.0009 (11)
C6	0.0300 (10)	0.0334 (11)	0.0273 (10)	0.0020 (9)	0.0059 (8)	−0.0045 (9)
C7	0.0258 (10)	0.0325 (11)	0.0328 (11)	−0.0011 (8)	0.0062 (8)	−0.0046 (9)
C11	0.0220 (9)	0.0354 (11)	0.0305 (10)	−0.0020 (8)	0.0062 (8)	−0.0008 (9)
C12	0.0333 (11)	0.0346 (12)	0.0394 (12)	0.0048 (9)	0.0082 (9)	0.0041 (9)
C13	0.0374 (12)	0.0481 (14)	0.0285 (11)	0.0053 (10)	0.0060 (9)	0.0080 (10)
C14	0.0305 (11)	0.0481 (13)	0.0275 (11)	0.0035 (9)	0.0065 (8)	−0.0018 (9)
C10	0.0244 (9)	0.0370 (11)	0.0253 (10)	−0.0007 (8)	0.0042 (8)	0.0035 (9)
C15	0.0323 (11)	0.0377 (12)	0.0306 (11)	0.0046 (9)	0.0061 (8)	−0.0010 (9)
C9	0.0317 (11)	0.0455 (13)	0.0261 (10)	0.0020 (9)	0.0079 (8)	0.0005 (9)
C8	0.0284 (10)	0.0474 (13)	0.0274 (10)	0.0041 (9)	0.0043 (8)	−0.0054 (9)
C22	0.0459 (13)	0.0541 (15)	0.0347 (13)	0.0145 (11)	0.0028 (10)	−0.0041 (11)
C1	0.0344 (11)	0.0306 (11)	0.0450 (12)	0.0042 (9)	0.0126 (9)	−0.0021 (9)
C2	0.0320 (11)	0.0395 (12)	0.0439 (12)	−0.0026 (9)	0.0115 (9)	−0.0032 (10)
O16	0.0632 (13)	0.0935 (16)	0.0644 (13)	0.0044 (12)	−0.0062 (10)	0.0279 (12)
C17	0.067 (2)	0.126 (3)	0.091 (2)	0.018 (2)	0.0234 (18)	0.049 (2)
C18	0.082 (3)	0.096 (3)	0.126 (3)	0.008 (2)	0.027 (2)	0.042 (2)
O19	0.0663 (16)	0.131 (3)	0.137 (2)	0.0268 (17)	0.0141 (15)	0.043 (2)
C20	0.075 (3)	0.139 (4)	0.219 (6)	0.007 (3)	0.056 (3)	0.052 (5)
C21	0.079 (3)	0.108 (3)	0.141 (4)	−0.018 (3)	−0.008 (2)	0.034 (3)

Geometric parameters (Å, º) top

Cl1—C3	1.727 (2)	C12—H12	0.9300
Cl2—C2	1.727 (2)	C13—C14	1.383 (3)
O1—C14	1.365 (3)	C13—H13	0.9300
O1—HO1	0.8200	C14—C15	1.378 (3)
O2—C9	1.357 (3)	C10—C15	1.379 (3)
O2—C10	1.393 (2)	C15—H15	0.9300
N2—C9	1.335 (3)	C9—C8	1.349 (3)
N2—HNA	0.8600	C8—C22	1.413 (3)
N2—HNB	0.8600	C1—C2	1.384 (3)
N1—C22	1.138 (3)	C1—H1	0.9300
C3—C4	1.373 (3)	O16—C17	1.403 (4)
C3—C2	1.379 (3)	O16—C21	1.426 (5)
C4—C5	1.380 (3)	C17—C18	1.459 (5)
C4—H4	0.9300	C17—H171	0.9700
C5—C6	1.379 (3)	C17—H172	0.9700
C5—H5	0.9300	C18—O19	1.396 (5)
C6—C1	1.381 (3)	C18—H181	0.9700
C6—C7	1.527 (3)	C18—H182	0.9700
C7—C11	1.512 (3)	O19—C20	1.406 (5)
C7—C8	1.515 (3)	C20—C21	1.453 (7)
C7—H7	0.9800	C20—H201	0.9700
C11—C10	1.378 (3)	C20—H202	0.9700
C11—C12	1.394 (3)	C21—H211	0.9700
C12—C13	1.375 (3)	C21—H212	0.9700

C14—O1—HO1	109.5	C10—C15—H15	120.5
C9—O2—C10	118.75 (17)	N2—C9—C8	127.6 (2)
C9—N2—HNA	120.0	N2—C9—O2	109.9 (2)
C9—N2—HNB	120.0	C8—C9—O2	122.48 (19)
HNA—N2—HNB	120.0	C9—C8—C22	117.9 (2)
C4—C3—C2	119.4 (2)	C9—C8—C7	124.17 (18)
C4—C3—Cl1	119.81 (19)	C22—C8—C7	117.8 (2)
C2—C3—Cl1	120.80 (18)	N1—C22—C8	179.3 (3)
C3—C4—C5	120.2 (2)	C6—C1—C2	120.7 (2)
C3—C4—H4	119.9	C6—C1—H1	119.6
C5—C4—H4	119.9	C2—C1—H1	119.6
C6—C5—C4	121.1 (2)	C3—C2—C1	120.2 (2)
C6—C5—H5	119.4	C3—C2—Cl2	120.48 (17)
C4—C5—H5	119.4	C1—C2—Cl2	119.31 (18)
C5—C6—C1	118.41 (19)	C17—O16—C21	110.4 (3)
C5—C6—C7	120.53 (19)	O16—C17—C18	110.9 (3)
C1—C6—C7	121.05 (19)	O16—C17—H171	109.5
C11—C7—C8	109.13 (17)	C18—C17—H171	109.5
C11—C7—C6	111.39 (16)	O16—C17—H172	109.5
C8—C7—C6	112.94 (16)	C18—C17—H172	109.5
C11—C7—H7	107.7	H171—C17—H172	108.1
C8—C7—H7	107.7	O19—C18—C17	111.6 (4)
C6—C7—H7	107.7	O19—C18—H181	109.3
C10—C11—C12	116.24 (18)	C17—C18—H181	109.3
C10—C11—C7	121.97 (18)	O19—C18—H182	109.3
C12—C11—C7	121.79 (19)	C17—C18—H182	109.3
C13—C12—C11	122.2 (2)	H181—C18—H182	108.0
C13—C12—H12	118.9	C18—O19—C20	109.9 (3)
C11—C12—H12	118.9	O19—C20—C21	112.6 (4)
C12—C13—C14	119.5 (2)	O19—C20—H201	109.1
C12—C13—H13	120.3	C21—C20—H201	109.1
C14—C13—H13	120.3	O19—C20—H202	109.1
O1—C14—C15	116.6 (2)	C21—C20—H202	109.1
O1—C14—C13	123.34 (19)	H201—C20—H202	107.8
C15—C14—C13	120.01 (19)	O16—C21—C20	110.2 (4)
C11—C10—C15	123.07 (18)	O16—C21—H211	109.6
C11—C10—O2	122.57 (17)	C20—C21—H211	109.6
C15—C10—O2	114.36 (18)	O16—C21—H212	109.6
C14—C15—C10	119.0 (2)	C20—C21—H212	109.6
C14—C15—H15	120.5	H211—C21—H212	108.1

C2—C3—C4—C5	0.4 (4)	C11—C10—C15—C14	−1.1 (3)
Cl1—C3—C4—C5	−179.8 (2)	O2—C10—C15—C14	178.35 (18)
C3—C4—C5—C6	−0.3 (4)	C10—O2—C9—N2	173.17 (18)
C4—C5—C6—C1	0.0 (3)	C10—O2—C9—C8	−7.7 (3)
C4—C5—C6—C7	−178.7 (2)	N2—C9—C8—C22	−3.7 (3)
C5—C6—C7—C11	102.8 (2)	O2—C9—C8—C22	177.2 (2)
C1—C6—C7—C11	−75.9 (2)	N2—C9—C8—C7	178.9 (2)
C5—C6—C7—C8	−134.0 (2)	O2—C9—C8—C7	−0.1 (3)
C1—C6—C7—C8	47.3 (3)	C11—C7—C8—C9	7.6 (3)
C8—C7—C11—C10	−8.1 (2)	C6—C7—C8—C9	−116.9 (2)
C6—C7—C11—C10	117.2 (2)	C11—C7—C8—C22	−169.73 (19)
C8—C7—C11—C12	172.12 (18)	C6—C7—C8—C22	65.8 (2)
C6—C7—C11—C12	−62.5 (2)	C5—C6—C1—C2	0.2 (3)
C10—C11—C12—C13	0.5 (3)	C7—C6—C1—C2	178.92 (19)
C7—C11—C12—C13	−179.75 (19)	C4—C3—C2—C1	−0.2 (4)
C11—C12—C13—C14	−1.4 (3)	Cl1—C3—C2—C1	179.98 (18)
C12—C13—C14—O1	179.6 (2)	C4—C3—C2—Cl2	179.7 (2)
C12—C13—C14—C15	1.1 (3)	Cl1—C3—C2—Cl2	−0.1 (3)
C12—C11—C10—C15	0.8 (3)	C6—C1—C2—C3	−0.1 (3)
C7—C11—C10—C15	−178.98 (18)	C6—C1—C2—Cl2	179.97 (16)
C12—C11—C10—O2	−178.63 (18)	C21—O16—C17—C18	−56.6 (5)
C7—C11—C10—O2	1.6 (3)	O16—C17—C18—O19	57.7 (5)
C9—O2—C10—C11	6.9 (3)	C17—C18—O19—C20	−56.0 (5)
C9—O2—C10—C15	−172.56 (18)	C18—O19—C20—C21	55.8 (6)
O1—C14—C15—C10	−178.52 (19)	C17—O16—C21—C20	55.5 (5)
C13—C14—C15—C10	0.1 (3)	O19—C20—C21—O16	−55.7 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—HO1···O16	0.82	1.85	2.658 (3)	167
N2—HNB···O1ⁱ	0.86	2.19	2.978 (3)	153
N2—HNA···N1ⁱⁱ	0.86	2.22	2.989 (3)	149
C4—H4···Cl2ⁱⁱⁱ	0.93	2.87	3.692 (3)	148

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

2-Amino-3-cyano-4-(2,6-dichlorophenyl)-7-hydroxy-4H-\ benzo[1,2-b]pyran (II) top

Crystal data top

C₁₆H₉Cl₂N₂O₂	F(000) = 338
M_r = 332.15	D_x = 1.548 Mg m⁻³
Triclinic, P1	Melting point: 514 K
a = 6.271 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.697 (5) Å	Cell parameters from 8750 reflections
c = 13.794 (7) Å	θ = 3.1–30.4°
α = 107.06 (2)°	µ = 0.46 mm⁻¹
β = 94.269 (17)°	T = 294 K
γ = 95.00 (3)°	Block, colourless
V = 712.5 (7) Å³	0.15 × 0.15 × 0.10 mm
Z = 2

Data collection top

Bruker Kappa APEX3 CMOS diffractometer	2499 independent reflections
Radiation source: fine-focus sealed tube	2239 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω and φ scan	θ_max = 25.0°, θ_min = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2018)	h = −7→7
T_min = 0.704, T_max = 0.746	k = −10→10
22289 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0263P)² + 0.4717P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2499 reflections	Δρ_max = 0.23 e Å⁻³
204 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.080 (10)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.84692 (8)	0.84534 (6)	0.32241 (4)	0.04703 (19)
Cl2	0.10752 (8)	0.50064 (7)	0.36100 (4)	0.0536 (2)
O1	1.0482 (2)	0.15972 (18)	0.09764 (12)	0.0484 (4)
HO1	1.058 (5)	0.092 (4)	0.130 (2)	0.084 (10)*
O2	0.7394 (2)	0.62001 (14)	0.07971 (9)	0.0331 (3)
N1	0.1786 (3)	0.9314 (2)	0.18547 (15)	0.0538 (5)
N2	0.6119 (3)	0.83118 (18)	0.04811 (12)	0.0372 (4)
HNB	0.7128	0.8266	0.0087	0.045*
HNA	0.5262	0.9046	0.0540	0.045*
C14	0.8930 (3)	0.2578 (2)	0.12922 (13)	0.0314 (4)
C13	0.7476 (3)	0.2339 (2)	0.19616 (13)	0.0327 (4)
H13	0.7498	0.1452	0.2207	0.039*
C12	0.6001 (3)	0.3428 (2)	0.22588 (13)	0.0303 (4)
H12	0.5033	0.3258	0.2706	0.036*
C11	0.5912 (3)	0.47743 (19)	0.19116 (12)	0.0252 (4)
C7	0.4337 (3)	0.59914 (19)	0.22777 (12)	0.0244 (3)
H7	0.2892	0.5394	0.2131	0.029*
C6	0.4733 (3)	0.67923 (19)	0.34378 (12)	0.0256 (4)
C1	0.3324 (3)	0.6415 (2)	0.40945 (13)	0.0340 (4)
C2	0.3630 (4)	0.7086 (3)	0.51432 (15)	0.0489 (5)
H2	0.2637	0.6808	0.5549	0.059*
C3	0.5406 (4)	0.8159 (3)	0.55754 (15)	0.0545 (6)
H3	0.5623	0.8621	0.6280	0.065*
C8	0.4401 (3)	0.7173 (2)	0.16603 (12)	0.0272 (4)
C22	0.2927 (3)	0.8338 (2)	0.17803 (13)	0.0333 (4)
C9	0.5883 (3)	0.72374 (19)	0.10034 (12)	0.0270 (4)
C10	0.7341 (3)	0.49354 (19)	0.12257 (12)	0.0258 (4)
C15	0.8841 (3)	0.3873 (2)	0.09093 (13)	0.0306 (4)
H15	0.9778	0.4028	0.0446	0.037*
C4	0.6873 (4)	0.8561 (3)	0.49742 (15)	0.0482 (5)
H4	0.8094	0.9282	0.5269	0.058*
C5	0.6524 (3)	0.7886 (2)	0.39261 (13)	0.0333 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0390 (3)	0.0566 (3)	0.0404 (3)	−0.0157 (2)	0.0042 (2)	0.0129 (2)
Cl2	0.0435 (3)	0.0712 (4)	0.0448 (3)	−0.0174 (2)	0.0084 (2)	0.0216 (3)
O1	0.0615 (10)	0.0440 (8)	0.0580 (9)	0.0319 (7)	0.0295 (7)	0.0303 (7)
O2	0.0421 (7)	0.0305 (6)	0.0376 (7)	0.0150 (5)	0.0189 (5)	0.0204 (5)
N1	0.0546 (11)	0.0603 (12)	0.0685 (12)	0.0324 (10)	0.0294 (9)	0.0405 (10)
N2	0.0469 (9)	0.0356 (8)	0.0409 (9)	0.0166 (7)	0.0178 (7)	0.0231 (7)
C14	0.0388 (10)	0.0269 (8)	0.0303 (9)	0.0110 (7)	0.0057 (7)	0.0088 (7)
C13	0.0433 (10)	0.0254 (8)	0.0340 (9)	0.0057 (7)	0.0052 (8)	0.0154 (7)
C12	0.0362 (9)	0.0298 (9)	0.0276 (8)	0.0013 (7)	0.0063 (7)	0.0128 (7)
C11	0.0289 (8)	0.0243 (8)	0.0222 (8)	0.0023 (6)	0.0012 (6)	0.0071 (6)
C7	0.0235 (8)	0.0264 (8)	0.0242 (8)	0.0026 (6)	0.0033 (6)	0.0090 (6)
C6	0.0285 (8)	0.0259 (8)	0.0247 (8)	0.0063 (7)	0.0043 (6)	0.0098 (7)
C1	0.0354 (10)	0.0376 (10)	0.0314 (9)	0.0017 (8)	0.0065 (7)	0.0139 (8)
C2	0.0648 (14)	0.0541 (12)	0.0293 (10)	−0.0009 (11)	0.0165 (9)	0.0143 (9)
C3	0.0846 (17)	0.0510 (13)	0.0232 (9)	−0.0059 (12)	0.0054 (10)	0.0076 (9)
C8	0.0309 (9)	0.0284 (8)	0.0249 (8)	0.0082 (7)	0.0036 (7)	0.0107 (7)
C22	0.0358 (9)	0.0374 (10)	0.0341 (9)	0.0099 (8)	0.0097 (7)	0.0191 (8)
C9	0.0325 (9)	0.0252 (8)	0.0255 (8)	0.0085 (7)	0.0032 (7)	0.0094 (7)
C10	0.0328 (9)	0.0232 (8)	0.0248 (8)	0.0055 (7)	0.0043 (7)	0.0113 (6)
C15	0.0362 (9)	0.0304 (9)	0.0299 (9)	0.0092 (7)	0.0109 (7)	0.0130 (7)
C4	0.0604 (13)	0.0444 (11)	0.0323 (10)	−0.0108 (10)	−0.0050 (9)	0.0073 (9)
C5	0.0375 (10)	0.0336 (9)	0.0298 (9)	0.0002 (7)	0.0057 (7)	0.0118 (7)

Geometric parameters (Å, º) top

Cl1—C5	1.7383 (19)	C11—C7	1.515 (2)
Cl2—C1	1.736 (2)	C7—C8	1.515 (2)
O1—C14	1.362 (2)	C7—C6	1.538 (2)
O1—HO1	0.85 (3)	C7—H7	0.9800
O2—C9	1.353 (2)	C6—C5	1.394 (3)
O2—C10	1.392 (2)	C6—C1	1.397 (2)
N1—C22	1.144 (2)	C1—C2	1.383 (3)
N2—C9	1.342 (2)	C2—C3	1.364 (3)
N2—HNB	0.8600	C2—H2	0.9300
N2—HNA	0.8600	C3—C4	1.373 (3)
C14—C15	1.381 (2)	C3—H3	0.9300
C14—C13	1.390 (3)	C8—C9	1.354 (2)
C13—C12	1.380 (3)	C8—C22	1.413 (2)
C13—H13	0.9300	C10—C15	1.380 (2)
C12—C11	1.392 (2)	C15—H15	0.9300
C12—H12	0.9300	C4—C5	1.384 (3)
C11—C10	1.378 (2)	C4—H4	0.9300

C14—O1—HO1	112 (2)	C2—C1—Cl2	116.30 (15)
C9—O2—C10	118.64 (13)	C6—C1—Cl2	120.20 (14)
C9—N2—HNB	120.0	C3—C2—C1	119.25 (19)
C9—N2—HNA	120.0	C3—C2—H2	120.4
HNB—N2—HNA	120.0	C1—C2—H2	120.4
O1—C14—C15	116.39 (16)	C2—C3—C4	120.18 (19)
O1—C14—C13	123.88 (16)	C2—C3—H3	119.9
C15—C14—C13	119.73 (16)	C4—C3—H3	119.9
C12—C13—C14	119.48 (15)	C9—C8—C22	115.95 (15)
C12—C13—H13	120.3	C9—C8—C7	123.49 (14)
C14—C13—H13	120.3	C22—C8—C7	120.51 (15)
C13—C12—C11	122.22 (16)	N1—C22—C8	177.10 (19)
C13—C12—H12	118.9	N2—C9—O2	110.03 (14)
C11—C12—H12	118.9	N2—C9—C8	126.71 (15)
C10—C11—C12	116.26 (15)	O2—C9—C8	123.25 (15)
C10—C11—C7	122.30 (14)	C11—C10—C15	123.29 (15)
C12—C11—C7	121.44 (15)	C11—C10—O2	122.40 (14)
C11—C7—C8	109.10 (13)	C15—C10—O2	114.31 (14)
C11—C7—C6	111.28 (13)	C10—C15—C14	118.96 (16)
C8—C7—C6	114.32 (14)	C10—C15—H15	120.5
C11—C7—H7	107.3	C14—C15—H15	120.5
C8—C7—H7	107.3	C3—C4—C5	119.6 (2)
C6—C7—H7	107.3	C3—C4—H4	120.2
C5—C6—C1	114.50 (15)	C5—C4—H4	120.2
C5—C6—C7	124.05 (14)	C4—C5—C6	123.02 (17)
C1—C6—C7	121.41 (15)	C4—C5—Cl1	116.49 (15)
C2—C1—C6	123.48 (18)	C6—C5—Cl1	120.49 (13)

O1—C14—C13—C12	178.13 (17)	C10—O2—C9—N2	−176.56 (14)
C15—C14—C13—C12	−1.9 (3)	C10—O2—C9—C8	4.5 (2)
C14—C13—C12—C11	−0.1 (3)	C22—C8—C9—N2	1.8 (3)
C13—C12—C11—C10	2.0 (2)	C7—C8—C9—N2	−175.57 (16)
C13—C12—C11—C7	−177.63 (15)	C22—C8—C9—O2	−179.42 (15)
C10—C11—C7—C8	8.4 (2)	C7—C8—C9—O2	3.2 (3)
C12—C11—C7—C8	−172.08 (15)	C12—C11—C10—C15	−2.0 (2)
C10—C11—C7—C6	−118.71 (17)	C7—C11—C10—C15	177.61 (15)
C12—C11—C7—C6	60.9 (2)	C12—C11—C10—O2	178.39 (15)
C11—C7—C6—C5	70.1 (2)	C7—C11—C10—O2	−2.0 (2)
C8—C7—C6—C5	−54.1 (2)	C9—O2—C10—C11	−5.0 (2)
C11—C7—C6—C1	−107.41 (18)	C9—O2—C10—C15	175.30 (15)
C8—C7—C6—C1	128.44 (17)	C11—C10—C15—C14	0.1 (3)
C5—C6—C1—C2	1.3 (3)	O2—C10—C15—C14	179.77 (15)
C7—C6—C1—C2	179.01 (18)	O1—C14—C15—C10	−178.14 (16)
C5—C6—C1—Cl2	−177.27 (13)	C13—C14—C15—C10	1.9 (3)
C7—C6—C1—Cl2	0.4 (2)	C2—C3—C4—C5	0.9 (4)
C6—C1—C2—C3	−0.9 (3)	C3—C4—C5—C6	−0.3 (3)
Cl2—C1—C2—C3	177.78 (18)	C3—C4—C5—Cl1	−179.69 (18)
C1—C2—C3—C4	−0.3 (4)	C1—C6—C5—C4	−0.7 (3)
C11—C7—C8—C9	−9.1 (2)	C7—C6—C5—C4	−178.35 (17)
C6—C7—C8—C9	116.24 (18)	C1—C6—C5—Cl1	178.63 (13)
C11—C7—C8—C22	173.69 (15)	C7—C6—C5—Cl1	1.0 (2)
C6—C7—C8—C22	−61.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cl2	0.98	2.50	3.078 (3)	117
N2—HNB···O1ⁱ	0.86	2.19	3.048 (2)	173
O1—HO1···N1ⁱⁱ	0.85 (3)	1.95 (3)	2.762 (2)	160 (3)

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

Acknowledgements

The authors thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT Madras, Chennai, India, for the data collection.

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Volume 75| Part 10| October 2019| Pages 1568-1572

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of two 4H-chromene derivatives: 2-amino-3-cyano-4-(3,4-di­chloro­phen­yl)-7-hy­dr­oxy-4H-benzo[1,2-b]pyran 1,4-dioxane monosolvate and 2-amino-3-cyano-4-(2,6-di­chloro­phen­yl)-7-hy­dr­oxy-4H-benzo[1,2-b]pyran

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structures of two 4H-chromene derivatives: 2-amino-3-cyano-4-(3,4-dichlorophenyl)-7-hydroxy-4H-benzo[1,2-b]pyran 1,4-dioxane monosolvate and 2-amino-3-cyano-4-(2,6-dichlorophenyl)-7-hydroxy-4H-benzo[1,2-b]pyran

3. Supramolecular features