Crystal structure, DFT and Hirshfeld surface analysis of 2-amino-4-(2-chloro­phen­yl)-7-hy­droxy-4H-benzo[1,2-b]pyran-3-carbo­nitrile

The crystal and mol­ecular structures of the pyran derivative 2-amino-4-(2-chloro­phen­yl)-7-hy­droxy-4H-benzo[1,2-b]pyran-3-carbo­nitrile is reported. Hirshfeld surface analysis was performed on the mol­ecule and frontier orbitals were investigated with density functional theory calculations.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.037
• wR factor = 0.103
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT420_ALERT_2_C D-H Without Acceptor       N1       --H1B      .     Please Check
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........  <I>CG</I> Check
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........  <I>CG</I> Check
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........  <I>CG</I> Check
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -1.184 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT793_ALERT_4_G Model has Chirality at C4          (Centro SPGR)          S Verify
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2018 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          9 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          7 Info

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

   4 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
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

2-Amino-4-(2-chlorophenyl)-7-hydroxy-4H-benzo[1,2-b]pyran-3-carbonitrile

Crystal data

C16H11ClN2O2	F(000) = 616
Mr = 298.72	Dx = 1.423 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.6658 (3) Å	Cell parameters from 2115 reflections
b = 30.1600 (16) Å	θ = 2.7–26.7°
c = 7.2193 (4) Å	µ = 0.28 mm^−1
β = 106.088 (2)°	T = 296 K
V = 1394.53 (12) Å^3	Block, white crystalline
Z = 4	0.15 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEXII CCD diffractometer	2115 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
ω and φ scans	θmax = 26.7°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→8
Tmin = 0.959, Tmax = 0.973	k = −38→38
21888 measured reflections	l = −9→8
2941 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0392P)^2 + 0.5426P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.103	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.19 e Å^−3
2941 reflections	Δρmin = −0.28 e Å^−3
191 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0061 (13)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C2	0.9057 (3)	0.54802 (6)	−0.1320 (2)	0.0342 (4)
C3	1.0377 (3)	0.58264 (5)	−0.0758 (2)	0.0334 (4)
C4	1.0200 (3)	0.61567 (5)	0.0772 (2)	0.0314 (4)
H4	1.156330	0.618094	0.172872	0.038*
C5	0.8634 (3)	0.59885 (5)	0.1766 (2)	0.0314 (4)
C6	0.8329 (3)	0.62022 (6)	0.3376 (3)	0.0379 (4)
H6	0.915142	0.644648	0.387878	0.045*
C7	0.6839 (3)	0.60615 (6)	0.4248 (3)	0.0408 (4)
H7	0.665264	0.621197	0.531266	0.049*
C8	0.5627 (3)	0.56954 (6)	0.3525 (3)	0.0379 (4)
C9	0.5916 (3)	0.54711 (6)	0.1960 (3)	0.0398 (4)
H9	0.512626	0.522076	0.148322	0.048*
C10	0.7398 (3)	0.56246 (6)	0.1111 (2)	0.0335 (4)
C11	0.9601 (3)	0.66108 (5)	−0.0142 (2)	0.0322 (4)
C12	0.7556 (3)	0.66946 (6)	−0.1204 (3)	0.0400 (4)
H12	0.654979	0.647668	−0.127966	0.048*
C13	0.6976 (4)	0.70909 (7)	−0.2149 (3)	0.0539 (5)
H13	0.559727	0.713738	−0.285481	0.065*
C14	0.8442 (4)	0.74176 (7)	−0.2045 (4)	0.0621 (6)
H14	0.805563	0.768466	−0.268905	0.075*
C15	1.0465 (4)	0.73504 (7)	−0.0995 (4)	0.0600 (6)
H15	1.145714	0.757164	−0.091365	0.072*
C16	1.1027 (3)	0.69495 (6)	−0.0052 (3)	0.0446 (5)
C17	1.1869 (3)	0.58941 (6)	−0.1782 (3)	0.0402 (4)
O1	0.7539 (2)	0.53801 (4)	−0.04856 (18)	0.0420 (3)
O2	0.4103 (2)	0.55394 (5)	0.4287 (2)	0.0552 (4)
H2	0.406537	0.569128	0.521925	0.083*
Cl1	1.36070 (9)	0.68831 (2)	0.12960 (12)	0.0757 (2)
N1	0.9057 (3)	0.51897 (5)	−0.2734 (2)	0.0455 (4)
H1A	0.816166	0.497735	−0.298713	0.055*
H1B	0.995343	0.521634	−0.338516	0.055*
N2	1.3050 (3)	0.59408 (7)	−0.2655 (3)	0.0608 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0376 (10)	0.0333 (9)	0.0359 (9)	0.0032 (7)	0.0174 (8)	−0.0023 (7)
C3	0.0336 (9)	0.0322 (9)	0.0385 (10)	0.0028 (7)	0.0169 (8)	−0.0012 (7)
C4	0.0314 (9)	0.0305 (9)	0.0334 (9)	−0.0007 (7)	0.0110 (7)	−0.0026 (7)
C5	0.0339 (9)	0.0306 (9)	0.0310 (9)	0.0025 (7)	0.0113 (7)	0.0014 (7)
C6	0.0474 (11)	0.0339 (9)	0.0335 (9)	−0.0043 (8)	0.0132 (8)	−0.0054 (7)
C7	0.0556 (12)	0.0392 (10)	0.0332 (10)	0.0003 (9)	0.0215 (9)	−0.0050 (8)
C8	0.0423 (10)	0.0419 (10)	0.0349 (10)	−0.0008 (8)	0.0198 (8)	0.0007 (8)
C9	0.0442 (11)	0.0394 (10)	0.0403 (10)	−0.0071 (8)	0.0192 (9)	−0.0085 (8)
C10	0.0391 (10)	0.0340 (9)	0.0308 (9)	0.0008 (7)	0.0155 (8)	−0.0042 (7)
C11	0.0384 (10)	0.0298 (8)	0.0329 (9)	−0.0008 (7)	0.0172 (8)	−0.0043 (7)
C12	0.0434 (11)	0.0373 (10)	0.0395 (10)	−0.0014 (8)	0.0117 (9)	−0.0021 (8)
C13	0.0610 (14)	0.0490 (12)	0.0493 (12)	0.0128 (10)	0.0113 (10)	0.0079 (10)
C14	0.0862 (18)	0.0437 (12)	0.0623 (15)	0.0089 (12)	0.0303 (13)	0.0165 (11)
C15	0.0759 (16)	0.0375 (11)	0.0783 (16)	−0.0104 (11)	0.0407 (14)	0.0059 (11)
C16	0.0445 (11)	0.0405 (10)	0.0554 (12)	−0.0057 (8)	0.0248 (10)	−0.0037 (9)
C17	0.0408 (11)	0.0408 (10)	0.0433 (11)	−0.0024 (8)	0.0188 (9)	−0.0082 (8)
O1	0.0484 (8)	0.0419 (7)	0.0444 (7)	−0.0136 (6)	0.0274 (6)	−0.0159 (6)
O2	0.0659 (10)	0.0596 (9)	0.0547 (9)	−0.0182 (7)	0.0409 (8)	−0.0158 (7)
Cl1	0.0392 (3)	0.0653 (4)	0.1207 (6)	−0.0156 (3)	0.0190 (3)	−0.0037 (4)
N1	0.0532 (10)	0.0422 (9)	0.0511 (10)	−0.0077 (8)	0.0309 (8)	−0.0147 (7)
N2	0.0571 (12)	0.0748 (13)	0.0627 (12)	−0.0146 (10)	0.0368 (10)	−0.0200 (10)

Geometric parameters (Å, º)

C2—N1	1.345 (2)	C9—H9	0.9300
C2—O1	1.347 (2)	C10—O1	1.3932 (19)
C2—C3	1.353 (2)	C11—C16	1.385 (2)
C3—C17	1.408 (2)	C11—C12	1.389 (2)
C3—C4	1.516 (2)	C12—C13	1.377 (3)
C4—C5	1.509 (2)	C12—H12	0.9300
C4—C11	1.525 (2)	C13—C14	1.375 (3)
C4—H4	0.9800	C13—H13	0.9300
C5—C10	1.375 (2)	C14—C15	1.367 (3)
C5—C6	1.393 (2)	C14—H14	0.9300
C6—C7	1.382 (3)	C15—C16	1.387 (3)
C6—H6	0.9300	C15—H15	0.9300
C7—C8	1.382 (3)	C16—Cl1	1.737 (2)
C7—H7	0.9300	C17—N2	1.146 (2)
C8—O2	1.366 (2)	O2—H2	0.8200
C8—C9	1.376 (2)	N1—H1A	0.8600
C9—C10	1.379 (2)	N1—H1B	0.8600
N1—C2—O1	110.58 (15)	C5—C10—C9	123.36 (16)
N1—C2—C3	126.39 (16)	C5—C10—O1	122.36 (15)
O1—C2—C3	123.03 (15)	C9—C10—O1	114.28 (15)
C2—C3—C17	116.70 (15)	C16—C11—C12	116.58 (17)
C2—C3—C4	123.38 (15)	C16—C11—C4	123.24 (16)
C17—C3—C4	119.72 (15)	C12—C11—C4	120.11 (15)
C5—C4—C3	109.23 (13)	C13—C12—C11	121.94 (18)
C5—C4—C11	112.01 (13)	C13—C12—H12	119.0
C3—C4—C11	109.81 (13)	C11—C12—H12	119.0
C5—C4—H4	108.6	C14—C13—C12	119.8 (2)
C3—C4—H4	108.6	C14—C13—H13	120.1
C11—C4—H4	108.6	C12—C13—H13	120.1
C10—C5—C6	116.37 (15)	C15—C14—C13	120.1 (2)
C10—C5—C4	122.16 (15)	C15—C14—H14	120.0
C6—C5—C4	121.44 (15)	C13—C14—H14	120.0
C7—C6—C5	121.86 (17)	C14—C15—C16	119.5 (2)
C7—C6—H6	119.1	C14—C15—H15	120.3
C5—C6—H6	119.1	C16—C15—H15	120.3
C6—C7—C8	119.46 (16)	C11—C16—C15	122.1 (2)
C6—C7—H7	120.3	C11—C16—Cl1	120.11 (15)
C8—C7—H7	120.3	C15—C16—Cl1	117.79 (16)
O2—C8—C9	116.76 (16)	N2—C17—C3	178.0 (2)
O2—C8—C7	123.03 (16)	C2—O1—C10	118.87 (13)
C9—C8—C7	120.21 (16)	C8—O2—H2	109.5
C8—C9—C10	118.71 (17)	C2—N1—H1A	120.0
C8—C9—H9	120.6	C2—N1—H1B	120.0
C10—C9—H9	120.6	H1A—N1—H1B	120.0
N1—C2—C3—C17	1.4 (3)	C4—C5—C10—O1	1.5 (3)
O1—C2—C3—C17	−179.18 (17)	C8—C9—C10—C5	1.0 (3)
N1—C2—C3—C4	176.25 (17)	C8—C9—C10—O1	−178.75 (16)
O1—C2—C3—C4	−4.3 (3)	C5—C4—C11—C16	138.04 (17)
C2—C3—C4—C5	10.3 (2)	C3—C4—C11—C16	−100.42 (19)
C17—C3—C4—C5	−175.06 (16)	C5—C4—C11—C12	−45.1 (2)
C2—C3—C4—C11	−112.94 (19)	C3—C4—C11—C12	76.49 (19)
C17—C3—C4—C11	61.7 (2)	C16—C11—C12—C13	1.1 (3)
C3—C4—C5—C10	−8.7 (2)	C4—C11—C12—C13	−176.05 (17)
C11—C4—C5—C10	113.14 (18)	C11—C12—C13—C14	−0.3 (3)
C3—C4—C5—C6	172.89 (16)	C12—C13—C14—C15	−0.5 (3)
C11—C4—C5—C6	−65.2 (2)	C13—C14—C15—C16	0.5 (3)
C10—C5—C6—C7	−1.2 (3)	C12—C11—C16—C15	−1.0 (3)
C4—C5—C6—C7	177.30 (17)	C4—C11—C16—C15	175.98 (18)
C5—C6—C7—C8	0.8 (3)	C12—C11—C16—Cl1	178.20 (13)
C6—C7—C8—O2	−179.04 (18)	C4—C11—C16—Cl1	−4.8 (2)
C6—C7—C8—C9	0.5 (3)	C14—C15—C16—C11	0.3 (3)
O2—C8—C9—C10	178.20 (17)	C14—C15—C16—Cl1	−178.97 (18)
C7—C8—C9—C10	−1.4 (3)	N1—C2—O1—C10	175.17 (15)
C6—C5—C10—C9	0.3 (3)	C3—C2—O1—C10	−4.3 (3)
C4—C5—C10—C9	−178.19 (17)	C5—C10—O1—C2	5.7 (3)
C6—C5—C10—O1	179.99 (16)	C9—C10—O1—C2	−174.53 (16)

Hydrogen-bond geometry (Å, º)

Cg1, Cg3 and Cg4 are the centroids of the O1/C2–C5/C10 and C11–C16 rings, and the benzopyran system, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.86	2.19	3.037 (2)	167
C9—H9···O1^i	0.93	2.50	3.416 (2)	168
O2—H2···N2^ii	0.82	1.99	2.773 (2)	160
C4—H4···Cl1	0.98	2.58	3.102 (2)	113
C12—H12···Cg1	0.93	2.74	3.085 (2)	103
C12—H12···Cg4	0.93	2.83	3.291 (2)	112
C14—H14···Cg3^iii	0.93	2.85	3.494 (2)	127

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