6-Hy­droxy-2,5,7,8-tetra­methyl-3,4-dihydro-2H-1-benzopyran-2-carbonitrile, from synchrotron data

Brzezinski, K.; Baj, A.; Wałejko, P.; Witkowski, S.; Dauter, Z.

doi:10.1107/S1600536811025517

organic compounds

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Volume 67| Part 8| August 2011| Page o1901

doi:10.1107/S1600536811025517

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6-Hydroxy-2,5,7,8-tetramethyl-3,4-dihydro-2H-1-benzopyran-2-carbonitrile, from synchrotron data

Krzysztof Brzezinski,^a ^* Aneta Baj,^b Piotr Wałejko,^b Stanisław Witkowski ^b and Zbigniew Dauter ^a

^aSynchrotron Radiation Research Section, MCL, National Cancer Institute, Argonne National Laboratory, Biosciences Division, Bldg. 202, Argonne, IL 60439, USA, and ^bInstitute of Chemistry, University of Białystok, Piłsudskiego 11/4, 15-443 Białystok, Poland
^*Correspondence e-mail: kbrzezinski@anl.gov

(Received 23 June 2011; accepted 28 June 2011; online 6 July 2011)

The crystal structure of the title compound, C₁₄H₁₇NO₂, solved and refined against synchrotron diffraction data, contains one formula unit in an asymmetric unit. In the crystal, molecules form right-handed helices located at the 2₁ screw axis parallel to the a-axis direction, generated by O—H⋯N hydrogen bonding between the hydroxy group and carbonitrile group of an adjacent molecule.

Related literature

For background to the chemistry of chroman compounds and their applications as antioxidants and anti-inflammatory agents, see Cohen et al. (1989 ); van Acker et al. (1993 ); Boscoboinik et al. (1995 ). For the preparation of nitriles from primary amides, see: Campagna et al. (1977 ).

Experimental

Crystal data

C₁₄H₁₇NO₂
M_r = 231.29
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.890 (5) Å
b = 10.30 (1) Å
c = 19.710 (19) Å
V = 1195.7 (19) Å³
Z = 4
Synchrotron radiation
λ = 0.75000 Å
μ = 0.09 mm⁻¹
T = 100 K
0.1 × 0.03 × 0.01 mm

Data collection

MAR 300 CCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski et al., 2003 ) T_min = 0.991, T_max = 0.999
15411 measured reflections
1818 independent reflections
1815 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.00
1818 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O15—H15⋯N13ⁱ	0.84	2.23	3.013 (2)	155
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SER-CAT APS beamline software; cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ); data reduction: HKL-2000; program(s) used to solve structure: SHELXD (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and pyMOL (DeLano, 2002 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811025517/kp2339sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025517/kp2339Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025517/kp2339Isup3.cml

checkCIF report

Comment top

2-Substituded chromans (3,4-dihydro-2H-1-benzopyrans) are an important class of compounds possessing significant biological properties (Cohen et al., 1989). The title compound is potentially more active as an antioxidant than 6-hydroxy-2,2,5,7,8-pentamethylchroman, the model compound of α-tocopherol (Van Acker et al., 1993). Carbonitrile derivatives appear to inhibit smooth muscle cell proliferation by the non-antioxidant mechanism (Boscoboinik et al., 1995).

The asymmetric unit contains one molecule of the title compound (Fig. 1). The crystal, formed spontaneously, contains a homochiral molecule (not established experimentally). Hydrogen atoms of C14, C16 and C17 methyl groups are partially disorded and are modelled in two alternative conformations. For one conformation of the C14 methyl group, notable is a short intramolecular interaction between hydroxy H15 and H14C atoms. Such a short distance could indicate some refinement problem but on the other hand problematic hydrogen atom positions are clearly confirmed by OMIT map (Fig. 2). The hydrogen bond network is based on the interaction between hydroxy group and carbonitrile group of a subsequent molecule. Such interactions generate the right handed helices located at the 2₁ screw axis parallel to a direction (Fig. 3). A high quality diffraction data revealed a detailed electron density distribution among a molecule of the title compound. The difference Fourier synthesis indicates clearly a presence of valence electrons for most of covalent bonds (Fig. 4a). This is especially noticeable for tetrahedral deformation of electron density distribution at C2 atom and its neighbourhood (Fig. 4 b). In this case positive peaks are located on covalent bonds and correspond to valence electrons. Negative peaks are positioned in a regular and symmetrical manner indicating the electron density shift in the bond direction.

Related literature top

For background to the chemistry of chroman compounds and their applications as antioxidants and anti-inflammatory agents, see Cohen et al. (1989); van Acker et al. (1993); Boscoboinik et al. (1995). For the preparation of nitriles from primary amides, see: Campagna et al. (1977).

Experimental top

Anhydrous pyridine (26 µL, 0.32 mmol) and trifluoroacetic anhydride (25 µL, 0.18 mmol) were added dropwise to rac-6-hydroxy- 2,5,7,8-tetramethylchroman-2-carboxamide (40 mg, 0.16 mmol) solution in dry THF (2 mL) at 273 K. The reaction mixture was warmed to room temperature and further stirred for 18 h. The reaction mixture was diluted with CHCl₃, washed with water and brine. The organic layer was dried over anhydrous Na₂SO₄, filtered off and concentrated in vacuo. The crude product was purified by flash column chromatography (hexane/ethyl acetate 85:15) to give the title compound as a tan solid (15.2 mg, 41% yield). M.p. 423–425 K (from ethyl acetate/hexane v/v 1:2); ¹H NMR (400 MHz, CDCl₃): δ 4.34 (s, 1H), 2.93 (ddd, J = 17.6, 12.3 and 6.6 Hz, 1H), 2.77 (ddd, J = 17.0, 6.2 and 1.7 Hz, 1H), 2.31 (ddd, J = 13.8, 6.6 and 2.0 Hz, 1H), 2.17 (s, 3H), 2.13 (s, 6H), 1.96 (ddd, J = 13.8, 12.3 and 6.2 Hz, 1H), 1.83 (s, 6H); ¹³C NMR (100 MHz, CDCl₃): δ 146.3, 144.1, 122.9, 121.7, 120.0, 118.6, 116.5, 69.8, 32.6, 26.9, 21.2, 12.1, 11.8, 11.3; IR (KBr) ν_max/cm^-1: 3527, 2930, 2235 (–CN), 1463, 1261; ESI-MS, m/z: 254 [MNa⁺, 100%]. The crystallization was carried out at room temperature by slow evaporation of the racemic mixture of 3,4-dihydro-6-hydroxy-2,5,7,8-tetramethyl-2H-1-benzopyran-2-carbonitrile solution in acetone yielding homochiral crystals (chiral resolution).

Computing details top

Data collection: SER-CAT APS beamline software; cell refinement: HKL-2000 (Otwinowski & Minor, 1997); data reduction: HKL-2000 (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXD (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and pyMOL (DeLano, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The OMIT map at hydrogen atoms bounded to O15 and C14 (conformation occupied by H14A—C atoms) contoured at 0.21 e Å^-3 (4.5 σ level, green). Dashed line represents a short intramolecular hydrogen–hydrogen contact.
	Fig. 3. The packing diagram viewed along a axis. Dashed lines represent hydrogen bonds. For clarity, only hydrogen atoms engaged in hydrogen bond formation are shown.
	Fig. 4. The deformation of electron distribution revealed in difference Fourier synthesis; (a) The F_obs and difference syntheses for a title compound contoured at 2.27 e Å³ (2.0 σ level, blue) and ±0.13 e Å^-3 (±3.5 σ level, green and red), respectively; (b) The F_obs and difference syntheses contoured at 2.27 e Å^-3 (2.0 σ level, blue), ±0.11 e Å³ (±3.0 σ level, green and red), respectively, hydrogen atoms are omitted.

6-Hydroxy-2,5,7,8-tetramethyl-3,4-dihydro-2H-1-benzopyran-2-carbonitrile top

Crystal data top

C₁₄H₁₇NO₂	F(000) = 496
M_r = 231.29	D_x = 1.285 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Synchrotron radiation, λ = 0.75000 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1841 reflections
a = 5.890 (5) Å	θ = 2.2–30.9°
b = 10.30 (1) Å	µ = 0.09 mm⁻¹
c = 19.710 (19) Å	T = 100 K
V = 1195.7 (19) Å³	Needle, colourless
Z = 4	0.1 × 0.03 × 0.01 mm

Data collection top

MAR 300 CCD diffractometer	1818 independent reflections
Radiation source: SER-CAT 22-ID synchrotron beamline APS, USA	1815 reflections with I > 2σ(I)
Si111 double crystal monochromator	R_int = 0.031
ω scans	θ_max = 30.9°, θ_min = 2.2°
Absorption correction: multi-scan (SCALEPACK; Otwinowski et al., 2003)	h = 0→8
T_min = 0.991, T_max = 0.999	k = 0→14
15411 measured reflections	l = 0→26

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0505P)² + 0.297P] where P = (F_o² + 2F_c²)/3
1818 reflections	(Δ/σ)_max < 0.001
158 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₄H₁₇NO₂	V = 1195.7 (19) Å³
M_r = 231.29	Z = 4
Orthorhombic, P2₁2₁2₁	Synchrotron radiation, λ = 0.75000 Å
a = 5.890 (5) Å	µ = 0.09 mm⁻¹
b = 10.30 (1) Å	T = 100 K
c = 19.710 (19) Å	0.1 × 0.03 × 0.01 mm

Data collection top

MAR 300 CCD diffractometer	1818 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski et al., 2003)	1815 reflections with I > 2σ(I)
T_min = 0.991, T_max = 0.999	R_int = 0.031
15411 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.00	Δρ_max = 0.27 e Å⁻³
1818 reflections	Δρ_min = −0.20 e Å⁻³
158 parameters

Special details top

Experimental. The crystal was mounted with vaseline on a pin-attached capillary. Upon mounting, the crystal was quenched to 100 K in a nitrogen-gas stream supplied by an Oxford Cryo-Jet. Diffraction data were measured at the station 22-ID of the APS synchrotron by rotation method.

Geometry. All e.s.d.'s 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 > 2σ(F²) is used only for calculating R-factors 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.64100 (17)	0.44132 (9)	0.20022 (4)	0.0181 (2)
C2	0.5481 (2)	0.32600 (13)	0.22950 (6)	0.0185 (3)
C3	0.2980 (2)	0.31287 (15)	0.21136 (6)	0.0216 (3)
H3A	0.2131	0.3877	0.2301	0.026*
H3B	0.2363	0.2328	0.2322	0.026*
C4	0.2641 (2)	0.30738 (13)	0.13455 (6)	0.0189 (2)
H4A	0.2914	0.2176	0.1186	0.023*
H4B	0.1049	0.3302	0.1237	0.023*
C5	0.3920 (2)	0.42209 (11)	0.02739 (6)	0.0139 (2)
C6	0.5435 (2)	0.50415 (11)	−0.00586 (6)	0.0139 (2)
C7	0.7196 (2)	0.56738 (11)	0.02858 (6)	0.0146 (2)
C8	0.7490 (2)	0.54480 (11)	0.09804 (6)	0.0143 (2)
C9	0.6003 (2)	0.45959 (12)	0.13083 (5)	0.0141 (2)
C10	0.4216 (2)	0.39890 (11)	0.09736 (6)	0.0141 (2)
C11	0.5889 (3)	0.33520 (14)	0.30557 (6)	0.0246 (3)
H11A	0.5030	0.4086	0.3241	0.037*
H11B	0.7511	0.3482	0.3142	0.037*
H11C	0.5387	0.2547	0.3274	0.037*
C12	0.6795 (2)	0.21322 (13)	0.20181 (6)	0.0190 (3)
N13	0.7821 (2)	0.12765 (12)	0.18050 (6)	0.0254 (3)
C14	0.2015 (2)	0.35690 (13)	−0.01042 (6)	0.0205 (3)
H14A	0.0587	0.3702	0.0141	0.031*	0.66 (2)
H14B	0.2327	0.2637	−0.0140	0.031*	0.66 (2)
H14C	0.1891	0.3944	−0.0560	0.031*	0.66 (2)
H14D	0.2646	0.2943	−0.0428	0.031*	0.34 (2)
H14E	0.1131	0.4224	−0.0349	0.031*	0.34 (2)
H14F	0.1028	0.3115	0.0218	0.031*	0.34 (2)
O15	0.52747 (19)	0.52971 (9)	−0.07450 (4)	0.0209 (2)
H15	0.4404	0.4753	−0.0927	0.031*
C16	0.8761 (2)	0.65795 (13)	−0.00891 (7)	0.0212 (3)
H16A	0.8337	0.6602	−0.0570	0.032*	0.68 (2)
H16B	1.0328	0.6272	−0.0045	0.032*	0.68 (2)
H16C	0.8635	0.7454	0.0103	0.032*	0.68 (2)
H16D	0.7888	0.7077	−0.0423	0.032*	0.32 (2)
H16E	0.9937	0.6075	−0.0322	0.032*	0.32 (2)
H16F	0.9475	0.7177	0.0234	0.032*	0.32 (2)
C15	0.9388 (2)	0.61130 (12)	0.13588 (6)	0.0189 (2)
H17A	0.9342	0.5857	0.1837	0.028*	0.85 (3)
H17B	0.9205	0.7056	0.1323	0.028*	0.85 (3)
H17C	1.0849	0.5858	0.1162	0.028*	0.85 (3)
H17D	0.9953	0.5538	0.1717	0.028*	0.15 (3)
H17E	0.8819	0.6918	0.1562	0.028*	0.15 (3)
H17F	1.0624	0.6315	0.1043	0.028*	0.15 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0230 (4)	0.0199 (4)	0.0114 (4)	−0.0028 (4)	−0.0020 (4)	0.0008 (3)
C2	0.0221 (6)	0.0208 (6)	0.0125 (5)	0.0001 (5)	0.0020 (4)	0.0019 (4)
C3	0.0197 (6)	0.0291 (6)	0.0161 (5)	−0.0006 (6)	0.0032 (5)	0.0042 (5)
C4	0.0177 (5)	0.0226 (6)	0.0164 (5)	−0.0046 (5)	0.0003 (5)	0.0033 (4)
C5	0.0156 (5)	0.0128 (5)	0.0134 (5)	0.0006 (4)	−0.0004 (4)	−0.0012 (4)
C6	0.0186 (5)	0.0121 (5)	0.0112 (5)	0.0014 (4)	0.0005 (4)	0.0001 (4)
C7	0.0166 (6)	0.0119 (5)	0.0154 (5)	0.0001 (4)	0.0022 (4)	0.0003 (4)
C8	0.0142 (5)	0.0135 (5)	0.0154 (5)	0.0004 (4)	−0.0001 (4)	−0.0031 (4)
C9	0.0165 (5)	0.0148 (5)	0.0109 (4)	0.0018 (5)	−0.0001 (4)	−0.0006 (4)
C10	0.0145 (5)	0.0144 (5)	0.0133 (5)	0.0002 (4)	0.0011 (4)	0.0006 (4)
C11	0.0305 (7)	0.0306 (7)	0.0128 (5)	0.0027 (6)	0.0004 (5)	0.0017 (5)
C12	0.0217 (6)	0.0217 (6)	0.0136 (5)	−0.0018 (5)	0.0003 (5)	0.0024 (4)
N13	0.0292 (6)	0.0258 (6)	0.0212 (5)	0.0014 (5)	0.0015 (5)	0.0008 (4)
C14	0.0210 (6)	0.0218 (6)	0.0187 (5)	−0.0054 (5)	−0.0039 (5)	−0.0012 (5)
O15	0.0296 (5)	0.0211 (4)	0.0119 (4)	−0.0058 (4)	−0.0021 (4)	0.0021 (3)
C16	0.0224 (6)	0.0187 (5)	0.0224 (5)	−0.0052 (5)	0.0034 (5)	0.0030 (5)
C15	0.0172 (5)	0.0191 (5)	0.0205 (5)	−0.0019 (5)	−0.0023 (5)	−0.0037 (4)

Geometric parameters (Å, º) top

O1—C9	1.4011 (18)	C11—H11B	0.9800
O1—C2	1.4296 (18)	C11—H11C	0.9800
C2—C12	1.499 (2)	C12—N13	1.148 (2)
C2—C11	1.521 (2)	C14—H14A	0.9800
C2—C3	1.522 (2)	C14—H14B	0.9800
C3—C4	1.528 (2)	C14—H14C	0.9800
C3—H3A	0.9900	C14—H14D	0.9800
C3—H3B	0.9900	C14—H14E	0.9800
C4—C10	1.5121 (18)	C14—H14F	0.9800
C4—H4A	0.9900	O15—H15	0.8400
C4—H4B	0.9900	C16—H16A	0.9800
C5—C6	1.3928 (18)	C16—H16B	0.9800
C5—C10	1.4103 (19)	C16—H16C	0.9800
C5—C14	1.5050 (19)	C16—H16D	0.9800
C6—O15	1.3815 (18)	C16—H16E	0.9800
C6—C7	1.4006 (18)	C16—H16F	0.9800
C7—C8	1.400 (2)	C15—H17A	0.9800
C7—C16	1.5051 (19)	C15—H17B	0.9800
C8—C9	1.3981 (18)	C15—H17C	0.9800
C8—C15	1.5080 (19)	C15—H17D	0.9800
C9—C10	1.3909 (18)	C15—H17E	0.9800
C11—H11A	0.9800	C15—H17F	0.9800

C9—O1—C2	116.12 (10)	C5—C14—H14E	109.4
O1—C2—C12	107.40 (12)	H14A—C14—H14E	72.0
O1—C2—C11	106.61 (11)	H14B—C14—H14E	137.6
C12—C2—C11	109.00 (11)	H14C—C14—H14E	40.3
O1—C2—C3	110.46 (11)	H14D—C14—H14E	109.5
C12—C2—C3	110.22 (12)	C5—C14—H14F	109.5
C11—C2—C3	112.95 (11)	H14A—C14—H14F	40.3
C2—C3—C4	111.25 (11)	H14B—C14—H14F	72.0
C2—C3—H3A	109.4	H14C—C14—H14F	137.6
C4—C3—H3A	109.4	H14D—C14—H14F	109.5
C2—C3—H3B	109.4	H14E—C14—H14F	109.5
C4—C3—H3B	109.4	C6—O15—H15	109.5
H3A—C3—H3B	108.0	C7—C16—H16A	109.5
C10—C4—C3	112.16 (11)	C7—C16—H16B	109.5
C10—C4—H4A	109.2	H16A—C16—H16B	109.5
C3—C4—H4A	109.2	C7—C16—H16C	109.5
C10—C4—H4B	109.2	H16A—C16—H16C	109.5
C3—C4—H4B	109.2	H16B—C16—H16C	109.5
H4A—C4—H4B	107.9	C7—C16—H16D	109.4
C6—C5—C10	118.93 (11)	H16A—C16—H16D	37.3
C6—C5—C14	121.01 (12)	H16B—C16—H16D	136.3
C10—C5—C14	120.05 (11)	H16C—C16—H16D	75.0
O15—C6—C5	122.20 (11)	C7—C16—H16E	109.5
O15—C6—C7	115.88 (11)	H16A—C16—H16E	74.9
C5—C6—C7	121.92 (12)	H16B—C16—H16E	37.3
C8—C7—C6	119.24 (11)	H16C—C16—H16E	136.2
C8—C7—C16	120.50 (12)	H16D—C16—H16E	109.5
C6—C7—C16	120.26 (12)	C7—C16—H16F	109.5
C7—C8—C9	118.62 (11)	H16A—C16—H16F	136.2
C7—C8—C15	120.00 (11)	H16B—C16—H16F	75.0
C9—C8—C15	121.38 (12)	H16C—C16—H16F	37.3
C10—C9—C8	122.48 (12)	H16D—C16—H16F	109.5
C10—C9—O1	122.14 (11)	H16E—C16—H16F	109.5
C8—C9—O1	115.37 (11)	C8—C15—H17A	109.5
C9—C10—C5	118.77 (11)	C8—C15—H17B	109.5
C9—C10—C4	120.97 (11)	H17A—C15—H17B	109.5
C5—C10—C4	120.26 (11)	C8—C15—H17C	109.5
C2—C11—H11A	109.5	H17A—C15—H17C	109.5
C2—C11—H11B	109.5	H17B—C15—H17C	109.5
H11A—C11—H11B	109.5	C8—C15—H17D	109.5
C2—C11—H11C	109.5	H17A—C15—H17D	32.1
H11A—C11—H11C	109.5	H17B—C15—H17D	133.5
H11B—C11—H11C	109.5	H17C—C15—H17D	79.9
N13—C12—C2	179.29 (15)	C8—C15—H17E	109.5
C5—C14—H14A	109.5	H17A—C15—H17E	79.9
C5—C14—H14B	109.5	H17B—C15—H17E	32.1
H14A—C14—H14B	109.5	H17C—C15—H17E	133.5
C5—C14—H14C	109.5	H17D—C15—H17E	109.5
H14A—C14—H14C	109.5	C8—C15—H17F	109.5
H14B—C14—H14C	109.5	H17A—C15—H17F	133.5
C5—C14—H14D	109.5	H17B—C15—H17F	79.9
H14A—C14—H14D	137.6	H17C—C15—H17F	32.1
H14B—C14—H14D	40.3	H17D—C15—H17F	109.5
H14C—C14—H14D	72.0	H17E—C15—H17F	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O15—H15···N13ⁱ	0.84	2.23	3.013 (2)	155

Symmetry code: (i) x−1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₇NO₂
M_r	231.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	5.890 (5), 10.30 (1), 19.710 (19)
V (Å³)	1195.7 (19)
Z	4
Radiation type	Synchrotron, λ = 0.75000 Å
µ (mm⁻¹)	0.09
Crystal size (mm)	0.1 × 0.03 × 0.01

Data collection
Diffractometer	MAR 300 CCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski et al., 2003)
T_min, T_max	0.991, 0.999
No. of measured, independent and observed [I > 2σ(I)] reflections	15411, 1818, 1815
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.00
No. of reflections	1818
No. of parameters	158
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.20

Computer programs: SER-CAT APS beamline software, HKL-2000 (Otwinowski & Minor, 1997), SHELXD (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and pyMOL (DeLano, 2002).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O15—H15···N13ⁱ	0.84	2.23	3.013 (2)	155

Symmetry code: (i) x−1/2, −y+1/2, −z.

Acknowledgements

This work was supported in part by the Intramural Research Program of the NIH, National Cancer Institute, Center for Cancer Research. X-ray data were collected at Southeast Regional Collaborative Access Team (SER-CAT) 22-ID beamline at the Advanced Photon Source, Argonne National Laboratory. Use of the APS was supported by the US Department of Energy under contract No. W-31–109-Eng-38.

References

Acker van, S. A. B. E., Koymans, L. M. H. & Bast, A. (1993). Free Rad. Biol. Med. 15, 311–328. PubMed Web of Science Google Scholar
Boscoboinik, D., Özer, N., Moser, U. & Azzi, A. (1995). Arch. Biochem. Biophys. 318, 241–246. CrossRef CAS PubMed Web of Science Google Scholar
Campagna, F., Carotti, A. & Casini, G. (1977). Tetrahedron Lett. 21, 1813–1816. CrossRef Google Scholar
Cohen, N., Schaer, B., Saucy, G., Borer, R., Todaro, L. & Chiu, A. M. (1989). J. Org. Chem. 54, 3282–3292. CSD CrossRef CAS Web of Science Google Scholar
DeLano, W. L. (2002). The pyMOL Molecular Graphics System. DeLano Scientific, San Carlos, CA, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Otwinowski, Z., Borek, D., Majewski, W. & Minor, W. (2003). Acta Cryst. A59, 228–234. Web of Science CrossRef CAS IUCr Journals Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6-Hy­dr­oxy-2,5,7,8-tetra­methyl-3,4-di­hydro-2H-1-benzo­pyran-2-carbo­nitrile, from synchrotron data

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

6-Hydroxy-2,5,7,8-tetramethyl-3,4-dihydro-2H-1-benzopyran-2-carbonitrile, from synchrotron data