Crystal structure of 3-amino-1-(4-hy­droxy­phen­yl)-1H-benzo[f]chromene-2-carbo­nitrile

Akkurt, M.; Horton, P.N.; Younes, S.H.H.; Mohamed, S.K.; Albayati, M.R.

doi:10.1107/S2056989015012566

Crystal structure of 3-amino-1-(4-hydroxyphenyl)-1H-benzo[f]chromene-2-carbonitrile

M. Akkurt, P. N. Horton, S. H. H. Younes, S. K. Mohamed and M. R. Albayati

In the title compound, C₂₀H₁₄N₂O₂, the hydroxybenzene ring is almost perpendicular to the mean plane of the naphthalene ring system, making a dihedral angle of 85.56 (4)°. The 4H-pyran ring fused with the naphthalene ring system has a flattened boat conformation. In the crystal, O—H

N and N—H

O hydrogen bonds link the molecules into a supramolecular layer in the bc plane; N—H

π interactions also contribute to this arrangement. The layers are linked by weak by C—H

π and π–π [inter-centroid separation = 3.8713 (7) Å] interactions.

Keywords: crystal structure; aminochromenes; hydrogen bonding; N—H

π(arene) interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015012566/tk5372sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989015012566/tk5372Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015012566/tk5372Isup3.cml Supplementary material

CCDC reference: 1409621

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.034
wR factor = 0.092
Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT420_ALERT_2_C D-H Without Acceptor        N1     -   H2N    ..     Please Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          2 Note

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          5 Note
PLAT230_ALERT_2_G Hirshfeld Test Diff for    C2     --  C14     ..        8.3 su
PLAT793_ALERT_4_G The Model has Chirality at C3      (Centro SPGR)          S Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          3 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          3 Report

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

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

Comment top

During the last decade, 4H-pyrans have held a unique role in medicinal chemistry due to their biological and pharmacological activities (Elnagdi et al., 1983; Goldmann & Stoltefus, 1991). Fused pyran derivatives also exhibit a wide spectrum of biological and pharmacological properties, such as antiviral and antileishmanial (Perez-Perez et al., 1995; Fan et al., 2010), anticonvulsant and antimicrobial (Aytemir et al., 2004) and insecticidal (Uher et al., 1994). In this context we report in this study the synthesis and crystal structural determination for the title compound.

In the title compound (Fig. 1), the hydroxy-benzene ring (C15–C20) is approximately perpendicular to the naphthalene ring system [C4–C13, maximum deviation = -0.017 (1) Å at atom C13] as indicated by the dihedral angle of 85.56 (4)°. The 4H-pyran ring (O1/C1–C4/C13) in the title compound is puckered with the puckering parameters of Q_T = 0.199 (1) Å, θ = 102.9 (3) ° and φ = 354.2 (3) °. The bond lengths and angles in the title compound are within normal ranges and comparable with those reported for the similar structures (Akkurt et al., 2013; 2015).

In the crystal structure, molecules are linked by N—H···O and O—H···N hydrogen bonds (Table 1, Fig. 2), which leads to a layer in the bc plane.

Related literature top

For general biological activities of some heterocyclic derivatives containing the 4H-pyran moiety, see: Elnagdi et al. (1983); Goldmann & Stoltefus (1991); Perez-Perez et al. (1995); Fan et al. (2010); Aytemir et al. (2004); Uher et al. (1994). For similar structures, see: Akkurt et al. (2013, 2015).

Experimental top

The title compound was obtained in 95% yield from the reaction of 2-naphthol (144 mg; 1 mmol) and an equimolar amount of 4-hydroxybenzylidene-malononitrile (180 mg; 1 mmol) in absolute ethanol (10 ml ) in the presence of a catalytic amount of piperidine under reflux for 3 h. Crystallization of the crude product from ethanol gave colourless crystals of the title compound suitable for X-ray crystallography·M.pt: 521 K.

Structure description top

In the crystal structure, molecules are linked by N—H···O and O—H···N hydrogen bonds (Table 1, Fig. 2), which leads to a layer in the bc plane.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2012); cell refinement: CrystalClear-SM Expert (Rigaku, 2012); data reduction: CrystalClear-SM Expert (Rigaku, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. View of the title compound with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. View of the packing of the title compound viewing down a axis.

3-Amino-1-(4-hydroxyphenyl)-1H-benzo[f]chromene-2-carbonitrile top

Crystal data top

C₂₀H₁₄N₂O₂	F(000) = 656
M_r = 314.33	D_x = 1.302 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 12.1086 (8) Å	Cell parameters from 17749 reflections
b = 13.1418 (9) Å	θ = 2.3–27.5°
c = 10.1552 (7) Å	µ = 0.09 mm⁻¹
β = 96.992 (1)°	T = 100 K
V = 1603.97 (19) Å³	Blade, colourless
Z = 4	0.21 × 0.08 × 0.07 mm

Data collection top

Rigaku AFC12 (Right) diffractometer	3679 independent reflections
Radiation source: Rotating Anode	3251 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm^-1	R_int = 0.030
profile data from ω–scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012)	h = −15→15
T_min = 0.738, T_max = 1.000	k = −17→14
17411 measured reflections	l = −12→13

Refinement top

Refinement on F²	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0425P)² + 0.4007P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3679 reflections	Δρ_max = 0.26 e Å⁻³
229 parameters	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₀H₁₄N₂O₂	V = 1603.97 (19) Å³
M_r = 314.33	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.1086 (8) Å	µ = 0.09 mm⁻¹
b = 13.1418 (9) Å	T = 100 K
c = 10.1552 (7) Å	0.21 × 0.08 × 0.07 mm
β = 96.992 (1)°

Data collection top

Rigaku AFC12 (Right) diffractometer	3679 independent reflections
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012)	3251 reflections with I > 2σ(I)
T_min = 0.738, T_max = 1.000	R_int = 0.030
17411 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	3 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.26 e Å⁻³
3679 reflections	Δρ_min = −0.18 e Å⁻³
229 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.

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

	x	y	z	U_iso*/U_eq
C1	0.33983 (8)	0.47639 (8)	1.11802 (10)	0.0237 (2)
C2	0.31777 (8)	0.53512 (7)	1.00751 (9)	0.0225 (2)
C3	0.22804 (8)	0.50920 (7)	0.89492 (9)	0.02158 (19)
H3	0.1865	0.5730	0.8672	0.026*
C4	0.14741 (8)	0.43453 (7)	0.94430 (10)	0.0234 (2)
C5	0.04093 (8)	0.41495 (8)	0.87013 (10)	0.0261 (2)
C6	0.00288 (9)	0.46750 (8)	0.75126 (11)	0.0295 (2)
H6	0.0494	0.5170	0.7178	0.035*
C7	−0.10048 (9)	0.44795 (9)	0.68361 (12)	0.0356 (3)
H7	−0.1250	0.4847	0.6049	0.043*
C8	−0.17001 (9)	0.37399 (10)	0.73009 (13)	0.0380 (3)
H8	−0.2408	0.3603	0.6822	0.046*
C9	−0.13586 (9)	0.32188 (9)	0.84389 (13)	0.0363 (3)
H9	−0.1836	0.2722	0.8747	0.044*
C10	−0.03025 (9)	0.34047 (8)	0.91728 (11)	0.0300 (2)
C11	0.00527 (9)	0.28765 (9)	1.03649 (12)	0.0348 (3)
H11	−0.0417	0.2374	1.0675	0.042*
C12	0.10573 (9)	0.30770 (8)	1.10727 (12)	0.0325 (2)
H12	0.1287	0.2723	1.1875	0.039*
C13	0.17513 (8)	0.38188 (8)	1.05958 (10)	0.0256 (2)
C14	0.38247 (9)	0.62331 (8)	0.99791 (10)	0.0264 (2)
C15	0.27956 (8)	0.46801 (7)	0.77552 (9)	0.02106 (19)
C16	0.32470 (8)	0.37029 (7)	0.77790 (10)	0.0233 (2)
H16	0.3201	0.3280	0.8529	0.028*
C17	0.37626 (8)	0.33360 (7)	0.67264 (10)	0.0237 (2)
H17	0.4067	0.2669	0.6758	0.028*
C18	0.38308 (8)	0.39533 (8)	0.56223 (9)	0.0235 (2)
C19	0.33979 (9)	0.49308 (8)	0.55907 (10)	0.0272 (2)
H19	0.3453	0.5357	0.4846	0.033*
C20	0.28830 (8)	0.52852 (8)	0.66516 (10)	0.0255 (2)
H20	0.2585	0.5955	0.6622	0.031*
N1	0.42225 (8)	0.48875 (8)	1.21728 (9)	0.0297 (2)
N2	0.43322 (9)	0.69661 (8)	0.99112 (10)	0.0383 (2)
O1	0.27537 (6)	0.39555 (6)	1.14083 (7)	0.02776 (17)
O2	0.43199 (7)	0.36270 (6)	0.45510 (7)	0.02998 (18)
H1N	0.4259 (12)	0.4453 (10)	1.2856 (13)	0.042 (4)*
H2N	0.4767 (11)	0.5317 (10)	1.2069 (14)	0.041 (4)*
H2O	0.4737 (13)	0.3086 (11)	0.4770 (16)	0.057 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0230 (5)	0.0260 (5)	0.0232 (5)	0.0009 (4)	0.0073 (4)	−0.0010 (4)
C2	0.0224 (5)	0.0251 (5)	0.0207 (4)	−0.0014 (4)	0.0050 (3)	−0.0007 (4)
C3	0.0210 (4)	0.0223 (4)	0.0217 (4)	0.0009 (3)	0.0037 (3)	0.0003 (3)
C4	0.0221 (5)	0.0226 (5)	0.0266 (5)	0.0006 (4)	0.0074 (4)	−0.0028 (4)
C5	0.0226 (5)	0.0257 (5)	0.0312 (5)	0.0012 (4)	0.0080 (4)	−0.0073 (4)
C6	0.0246 (5)	0.0322 (5)	0.0318 (5)	0.0016 (4)	0.0040 (4)	−0.0067 (4)
C7	0.0281 (5)	0.0410 (6)	0.0370 (6)	0.0051 (5)	0.0009 (4)	−0.0108 (5)
C8	0.0223 (5)	0.0430 (7)	0.0483 (7)	0.0012 (5)	0.0022 (5)	−0.0184 (5)
C9	0.0251 (5)	0.0330 (6)	0.0529 (7)	−0.0045 (4)	0.0130 (5)	−0.0159 (5)
C10	0.0249 (5)	0.0266 (5)	0.0405 (6)	−0.0014 (4)	0.0116 (4)	−0.0089 (4)
C11	0.0317 (5)	0.0279 (5)	0.0477 (7)	−0.0057 (4)	0.0164 (5)	−0.0007 (5)
C12	0.0338 (6)	0.0287 (5)	0.0370 (6)	−0.0008 (4)	0.0119 (5)	0.0051 (4)
C13	0.0237 (5)	0.0250 (5)	0.0293 (5)	0.0004 (4)	0.0075 (4)	−0.0004 (4)
C14	0.0277 (5)	0.0328 (5)	0.0189 (4)	−0.0026 (4)	0.0035 (4)	0.0001 (4)
C15	0.0190 (4)	0.0237 (5)	0.0204 (4)	−0.0002 (3)	0.0020 (3)	−0.0005 (3)
C16	0.0251 (5)	0.0232 (5)	0.0221 (4)	−0.0006 (4)	0.0046 (4)	0.0033 (4)
C17	0.0251 (5)	0.0206 (4)	0.0258 (5)	0.0017 (4)	0.0045 (4)	0.0009 (4)
C18	0.0224 (4)	0.0285 (5)	0.0196 (4)	0.0012 (4)	0.0032 (3)	−0.0011 (4)
C19	0.0308 (5)	0.0294 (5)	0.0215 (5)	0.0051 (4)	0.0045 (4)	0.0067 (4)
C20	0.0279 (5)	0.0238 (5)	0.0249 (5)	0.0058 (4)	0.0039 (4)	0.0033 (4)
N1	0.0284 (5)	0.0386 (5)	0.0218 (4)	−0.0026 (4)	0.0020 (3)	0.0042 (4)
N2	0.0448 (6)	0.0404 (6)	0.0292 (5)	−0.0161 (5)	0.0028 (4)	0.0030 (4)
O1	0.0269 (4)	0.0280 (4)	0.0285 (4)	−0.0009 (3)	0.0036 (3)	0.0063 (3)
O2	0.0364 (4)	0.0326 (4)	0.0223 (4)	0.0095 (3)	0.0091 (3)	0.0022 (3)

Geometric parameters (Å, º) top

C1—N1	1.3393 (13)	C11—C12	1.3612 (17)
C1—O1	1.3548 (12)	C11—H11	0.9500
C1—C2	1.3614 (14)	C12—C13	1.4108 (14)
C2—C14	1.4089 (14)	C12—H12	0.9500
C2—C3	1.5171 (13)	C13—O1	1.3937 (12)
C3—C4	1.5122 (13)	C14—N2	1.1492 (14)
C3—C15	1.5286 (13)	C15—C20	1.3887 (13)
C3—H3	1.0000	C15—C16	1.3948 (13)
C4—C13	1.3661 (14)	C16—C17	1.3883 (13)
C4—C5	1.4351 (14)	C16—H16	0.9500
C5—C6	1.4180 (15)	C17—C18	1.3945 (13)
C5—C10	1.4250 (15)	C17—H17	0.9500
C6—C7	1.3765 (15)	C18—O2	1.3693 (11)
C6—H6	0.9500	C18—C19	1.3864 (14)
C7—C8	1.4047 (18)	C19—C20	1.3892 (14)
C7—H7	0.9500	C19—H19	0.9500
C8—C9	1.3636 (19)	C20—H20	0.9500
C8—H8	0.9500	N1—H1N	0.896 (12)
C9—C10	1.4207 (15)	N1—H2N	0.883 (12)
C9—H9	0.9500	O2—H2O	0.885 (13)
C10—C11	1.4162 (17)

N1—C1—O1	111.01 (9)	C12—C11—C10	121.03 (10)
N1—C1—C2	127.23 (10)	C12—C11—H11	119.5
O1—C1—C2	121.75 (9)	C10—C11—H11	119.5
C1—C2—C14	117.94 (9)	C11—C12—C13	118.93 (10)
C1—C2—C3	122.99 (9)	C11—C12—H12	120.5
C14—C2—C3	119.07 (8)	C13—C12—H12	120.5
C4—C3—C2	109.14 (8)	C4—C13—O1	123.20 (9)
C4—C3—C15	112.06 (8)	C4—C13—C12	123.35 (10)
C2—C3—C15	110.69 (8)	O1—C13—C12	113.46 (9)
C4—C3—H3	108.3	N2—C14—C2	178.35 (12)
C2—C3—H3	108.3	C20—C15—C16	118.23 (9)
C15—C3—H3	108.3	C20—C15—C3	121.06 (8)
C13—C4—C5	118.06 (9)	C16—C15—C3	120.61 (8)
C13—C4—C3	120.77 (9)	C17—C16—C15	121.23 (9)
C5—C4—C3	121.16 (9)	C17—C16—H16	119.4
C6—C5—C10	118.25 (10)	C15—C16—H16	119.4
C6—C5—C4	122.52 (10)	C16—C17—C18	119.55 (9)
C10—C5—C4	119.23 (10)	C16—C17—H17	120.2
C7—C6—C5	121.03 (11)	C18—C17—H17	120.2
C7—C6—H6	119.5	O2—C18—C19	118.08 (9)
C5—C6—H6	119.5	O2—C18—C17	122.03 (9)
C6—C7—C8	120.47 (12)	C19—C18—C17	119.90 (9)
C6—C7—H7	119.8	C18—C19—C20	119.79 (9)
C8—C7—H7	119.8	C18—C19—H19	120.1
C9—C8—C7	120.00 (11)	C20—C19—H19	120.1
C9—C8—H8	120.0	C15—C20—C19	121.29 (9)
C7—C8—H8	120.0	C15—C20—H20	119.4
C8—C9—C10	121.26 (11)	C19—C20—H20	119.4
C8—C9—H9	119.4	C1—N1—H1N	117.9 (9)
C10—C9—H9	119.4	C1—N1—H2N	119.1 (9)
C11—C10—C9	121.63 (10)	H1N—N1—H2N	122.1 (13)
C11—C10—C5	119.39 (10)	C1—O1—C13	118.57 (8)
C9—C10—C5	118.98 (11)	C18—O2—H2O	109.9 (11)

N1—C1—C2—C14	−4.87 (16)	C9—C10—C11—C12	−178.64 (10)
O1—C1—C2—C14	173.97 (9)	C5—C10—C11—C12	0.69 (16)
N1—C1—C2—C3	174.55 (9)	C10—C11—C12—C13	−0.47 (17)
O1—C1—C2—C3	−6.61 (15)	C5—C4—C13—O1	−179.02 (9)
C1—C2—C3—C4	18.81 (13)	C3—C4—C13—O1	2.51 (15)
C14—C2—C3—C4	−161.78 (9)	C5—C4—C13—C12	1.68 (15)
C1—C2—C3—C15	−104.97 (10)	C3—C4—C13—C12	−176.79 (9)
C14—C2—C3—C15	74.44 (11)	C11—C12—C13—C4	−0.76 (16)
C2—C3—C4—C13	−16.41 (12)	C11—C12—C13—O1	179.88 (9)
C15—C3—C4—C13	106.56 (10)	C4—C3—C15—C20	134.98 (10)
C2—C3—C4—C5	165.16 (8)	C2—C3—C15—C20	−102.93 (10)
C15—C3—C4—C5	−71.87 (11)	C4—C3—C15—C16	−48.65 (12)
C13—C4—C5—C6	178.20 (9)	C2—C3—C15—C16	73.44 (11)
C3—C4—C5—C6	−3.33 (14)	C20—C15—C16—C17	−0.56 (14)
C13—C4—C5—C10	−1.40 (14)	C3—C15—C16—C17	−177.04 (9)
C3—C4—C5—C10	177.07 (9)	C15—C16—C17—C18	−0.08 (15)
C10—C5—C6—C7	0.61 (15)	C16—C17—C18—O2	−179.34 (9)
C4—C5—C6—C7	−178.99 (10)	C16—C17—C18—C19	0.85 (15)
C5—C6—C7—C8	−1.03 (16)	O2—C18—C19—C20	179.21 (9)
C6—C7—C8—C9	0.84 (17)	C17—C18—C19—C20	−0.97 (16)
C7—C8—C9—C10	−0.24 (17)	C16—C15—C20—C19	0.45 (15)
C8—C9—C10—C11	179.16 (10)	C3—C15—C20—C19	176.91 (9)
C8—C9—C10—C5	−0.17 (16)	C18—C19—C20—C15	0.31 (16)
C6—C5—C10—C11	−179.35 (9)	N1—C1—O1—C13	169.17 (8)
C4—C5—C10—C11	0.26 (14)	C2—C1—O1—C13	−9.84 (14)
C6—C5—C10—C9	−0.01 (14)	C4—C13—O1—C1	12.00 (14)
C4—C5—C10—C9	179.60 (9)	C12—C13—O1—C1	−168.63 (9)

Hydrogen-bond geometry (Å, º) top

Cg3 and Cg4 are the centroids of the C5–C10 and C15–C20 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.90 (1)	2.03 (1)	2.9191 (12)	173 (1)
O2—H2O···N2ⁱⁱ	0.89 (1)	1.86 (1)	2.7403 (12)	175 (2)
N1—H2N···Cg4ⁱⁱⁱ	0.88 (1)	2.55 (1)	3.2340 (11)	135 (1)
C11—H11···Cg3^iv	0.95	2.97	3.7610 (13)	142

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