Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703259X/bt2428sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703259X/bt2428Isup2.hkl |
CCDC reference: 657712
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.003 Å
- R factor = 0.050
- wR factor = 0.100
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C11 = ... R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
2-naphthol (40 mmol, 5.77 g), 3-formylbenzonitrile (40 mmol, 5.25 g) and piperidine (40 mmol, 3.4 g) were added in a flask and reacted at 80 °C with stirring for one day. Then 50 ml e thanol was added to the flask and all the reactants were refluxed for five hours. After cooled to room temperature, the solution was filtered and white solid (compound I) was obtained as colorless block crystal.
H atoms bonded to O atoms were located in a difference map and refined with distance restraints of O—H = 0.84 (2) Å, and with Uiso(H) = 1.2Ueq(O). Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 times Ueq(C).
Betti-type reaction is an important method to synthesize chiral ligands and by this method many unnatural homochiral amino-phenol compounds have been obtained (Lu et al., 2002; Xu et al., 2004; Wang et al., 2005).
Molecules of the title compound have normal geometric parameters. An intramolecular O—H···N hydrogen bond stabilizes the molecule conformation. The crystal packing is characterized by helical chains of molecules linked by C—H···O hydrogen bonds.
For unnatural homochiral aminophenol compounds obtained by Betti-type reaction, see: Lu et al. (2002); Xu et al. (2004); Wang et al. (2005).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C23H22N2O | F(000) = 728 |
Mr = 342.43 | Dx = 1.199 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1875 reflections |
a = 11.9008 (13) Å | θ = 2.2–21.5° |
b = 15.0138 (17) Å | µ = 0.07 mm−1 |
c = 10.8886 (13) Å | T = 291 K |
β = 102.867 (3)° | Block, colourless |
V = 1896.7 (4) Å3 | 0.30 × 0.26 × 0.24 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 3731 independent reflections |
Radiation source: sealed tube | 2420 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −14→14 |
Tmin = 0.98, Tmax = 0.98 | k = −14→18 |
11353 measured reflections | l = −13→13 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3 |
3731 reflections | (Δ/σ)max < 0.001 |
238 parameters | Δρmax = 0.11 e Å−3 |
0 restraints | Δρmin = −0.11 e Å−3 |
C23H22N2O | V = 1896.7 (4) Å3 |
Mr = 342.43 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.9008 (13) Å | µ = 0.07 mm−1 |
b = 15.0138 (17) Å | T = 291 K |
c = 10.8886 (13) Å | 0.30 × 0.26 × 0.24 mm |
β = 102.867 (3)° |
Bruker SMART APEX CCD diffractometer | 3731 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2420 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.98 | Rint = 0.037 |
11353 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.11 e Å−3 |
3731 reflections | Δρmin = −0.11 e Å−3 |
238 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 | ||
C1 | 0.30955 (12) | 0.12699 (11) | 0.28437 (15) | 0.0403 (4) | |
C2 | 0.27607 (14) | 0.05048 (11) | 0.21554 (17) | 0.0485 (4) | |
C3 | 0.32243 (16) | 0.02771 (12) | 0.11143 (18) | 0.0553 (5) | |
H3 | 0.2952 | −0.0220 | 0.0629 | 0.066* | |
C4 | 0.40741 (16) | 0.07881 (12) | 0.08203 (18) | 0.0566 (5) | |
H4 | 0.4403 | 0.0615 | 0.0159 | 0.068* | |
C5 | 0.44673 (14) | 0.15727 (12) | 0.14922 (18) | 0.0497 (4) | |
C6 | 0.53715 (14) | 0.20855 (12) | 0.12228 (18) | 0.0518 (5) | |
H6 | 0.5736 | 0.1897 | 0.0597 | 0.062* | |
C7 | 0.57231 (16) | 0.28492 (13) | 0.18571 (19) | 0.0615 (5) | |
H7 | 0.6329 | 0.3178 | 0.1679 | 0.074* | |
C8 | 0.51596 (15) | 0.31318 (13) | 0.27803 (18) | 0.0591 (5) | |
H8 | 0.5383 | 0.3665 | 0.3199 | 0.071* | |
C9 | 0.42956 (15) | 0.26544 (13) | 0.30865 (17) | 0.0555 (5) | |
H9 | 0.3932 | 0.2869 | 0.3700 | 0.067* | |
C10 | 0.39372 (13) | 0.18291 (11) | 0.24820 (16) | 0.0436 (4) | |
C11 | 0.25970 (13) | 0.15140 (10) | 0.39746 (16) | 0.0433 (4) | |
H11 | 0.3176 | 0.1861 | 0.4564 | 0.052* | |
C12 | 0.15260 (14) | 0.20908 (11) | 0.35548 (17) | 0.0460 (4) | |
C13 | 0.06387 (15) | 0.18524 (12) | 0.25509 (19) | 0.0553 (5) | |
H13 | 0.0698 | 0.1330 | 0.2110 | 0.066* | |
C14 | −0.03407 (14) | 0.23828 (11) | 0.21927 (17) | 0.0500 (4) | |
C15 | −0.04187 (17) | 0.31443 (13) | 0.28523 (19) | 0.0644 (5) | |
H15 | −0.1075 | 0.3496 | 0.2624 | 0.077* | |
C16 | 0.04448 (15) | 0.34030 (13) | 0.38410 (19) | 0.0597 (5) | |
H16 | 0.0383 | 0.3930 | 0.4270 | 0.072* | |
C17 | 0.14176 (16) | 0.28668 (11) | 0.41951 (18) | 0.0569 (5) | |
H17 | 0.2003 | 0.3035 | 0.4873 | 0.068* | |
C18 | −0.12332 (15) | 0.21210 (11) | 0.11744 (19) | 0.0490 (4) | |
C19 | 0.17039 (16) | 0.08659 (13) | 0.56160 (19) | 0.0585 (5) | |
H19A | 0.0981 | 0.1157 | 0.5243 | 0.070* | |
H19B | 0.2148 | 0.1264 | 0.6242 | 0.070* | |
C20 | 0.14652 (16) | 0.00002 (13) | 0.6246 (2) | 0.0622 (5) | |
H20A | 0.1056 | 0.0134 | 0.6901 | 0.075* | |
H20B | 0.0974 | −0.0377 | 0.5627 | 0.075* | |
C21 | 0.25598 (17) | −0.04955 (14) | 0.68138 (19) | 0.0649 (5) | |
H21A | 0.2375 | −0.1063 | 0.7145 | 0.078* | |
H21B | 0.3018 | −0.0153 | 0.7502 | 0.078* | |
C22 | 0.32365 (16) | −0.06450 (13) | 0.58052 (19) | 0.0613 (5) | |
H22B | 0.2810 | −0.1042 | 0.5166 | 0.074* | |
H22A | 0.3968 | −0.0925 | 0.6177 | 0.074* | |
C23 | 0.34519 (14) | 0.02330 (13) | 0.52003 (19) | 0.0553 (5) | |
H23A | 0.3916 | 0.0618 | 0.5831 | 0.066* | |
H23B | 0.3876 | 0.0123 | 0.4551 | 0.066* | |
N1 | 0.23443 (10) | 0.06843 (9) | 0.46359 (14) | 0.0472 (4) | |
N2 | −0.19638 (14) | 0.19212 (12) | 0.03453 (17) | 0.0689 (5) | |
O1 | 0.19695 (11) | −0.00654 (8) | 0.24320 (13) | 0.0568 (3) | |
H1A | 0.1741 (17) | 0.0125 (14) | 0.306 (2) | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0355 (7) | 0.0412 (9) | 0.0427 (9) | 0.0043 (6) | 0.0054 (7) | 0.0003 (7) |
C2 | 0.0498 (9) | 0.0394 (9) | 0.0551 (11) | 0.0039 (8) | 0.0093 (8) | 0.0010 (8) |
C3 | 0.0623 (11) | 0.0405 (9) | 0.0615 (12) | 0.0136 (8) | 0.0106 (9) | −0.0089 (8) |
C4 | 0.0647 (11) | 0.0565 (11) | 0.0510 (11) | 0.0148 (10) | 0.0181 (9) | 0.0013 (9) |
C5 | 0.0453 (9) | 0.0527 (10) | 0.0539 (11) | 0.0040 (8) | 0.0173 (8) | 0.0041 (8) |
C6 | 0.0464 (9) | 0.0604 (12) | 0.0532 (11) | 0.0159 (9) | 0.0206 (8) | 0.0172 (9) |
C7 | 0.0581 (11) | 0.0619 (13) | 0.0633 (13) | −0.0099 (9) | 0.0109 (10) | 0.0198 (10) |
C8 | 0.0597 (11) | 0.0615 (12) | 0.0533 (12) | −0.0201 (9) | 0.0067 (9) | 0.0022 (9) |
C9 | 0.0548 (10) | 0.0633 (12) | 0.0479 (11) | −0.0189 (9) | 0.0102 (8) | 0.0013 (9) |
C10 | 0.0369 (8) | 0.0509 (10) | 0.0411 (9) | 0.0058 (7) | 0.0046 (7) | 0.0070 (7) |
C11 | 0.0395 (8) | 0.0406 (8) | 0.0499 (10) | −0.0042 (7) | 0.0098 (7) | −0.0003 (7) |
C12 | 0.0416 (8) | 0.0450 (9) | 0.0558 (11) | 0.0043 (7) | 0.0201 (8) | 0.0129 (8) |
C13 | 0.0588 (10) | 0.0454 (10) | 0.0653 (12) | −0.0003 (9) | 0.0217 (9) | −0.0090 (9) |
C14 | 0.0503 (10) | 0.0417 (9) | 0.0596 (11) | −0.0122 (8) | 0.0158 (8) | 0.0164 (8) |
C15 | 0.0689 (12) | 0.0550 (12) | 0.0592 (12) | 0.0147 (10) | −0.0073 (10) | 0.0098 (9) |
C16 | 0.0621 (11) | 0.0542 (11) | 0.0633 (13) | 0.0126 (9) | 0.0147 (10) | −0.0117 (9) |
C17 | 0.0643 (11) | 0.0423 (10) | 0.0533 (11) | −0.0030 (8) | −0.0101 (9) | 0.0094 (8) |
C18 | 0.0500 (10) | 0.0491 (10) | 0.0548 (11) | 0.0025 (8) | 0.0264 (9) | −0.0040 (8) |
C19 | 0.0560 (10) | 0.0628 (12) | 0.0614 (12) | 0.0023 (9) | 0.0234 (9) | 0.0091 (10) |
C20 | 0.0606 (11) | 0.0656 (12) | 0.0610 (12) | 0.0086 (10) | 0.0149 (9) | 0.0154 (10) |
C21 | 0.0696 (12) | 0.0693 (13) | 0.0577 (12) | 0.0199 (10) | 0.0183 (10) | 0.0159 (10) |
C22 | 0.0634 (11) | 0.0590 (11) | 0.0647 (13) | 0.0303 (10) | 0.0213 (10) | 0.0200 (10) |
C23 | 0.0429 (9) | 0.0651 (12) | 0.0584 (12) | 0.0137 (9) | 0.0120 (8) | 0.0145 (9) |
N1 | 0.0390 (7) | 0.0481 (8) | 0.0547 (9) | 0.0042 (6) | 0.0110 (6) | 0.0129 (7) |
N2 | 0.0621 (10) | 0.0778 (12) | 0.0612 (11) | 0.0263 (9) | 0.0021 (9) | 0.0027 (9) |
O1 | 0.0627 (8) | 0.0454 (7) | 0.0613 (9) | −0.0108 (6) | 0.0118 (6) | −0.0089 (6) |
C1—C2 | 1.381 (2) | C14—C15 | 1.364 (3) |
C1—C10 | 1.428 (2) | C14—C18 | 1.410 (3) |
C1—C11 | 1.526 (2) | C15—C16 | 1.369 (3) |
C2—O1 | 1.355 (2) | C15—H15 | 0.9300 |
C2—C3 | 1.409 (3) | C16—C17 | 1.392 (2) |
C3—C4 | 1.363 (3) | C16—H16 | 0.9300 |
C3—H3 | 0.9300 | C17—H17 | 0.9300 |
C4—C5 | 1.410 (3) | C18—N2 | 1.145 (2) |
C4—H4 | 0.9300 | C19—N1 | 1.468 (2) |
C5—C6 | 1.406 (2) | C19—C20 | 1.525 (3) |
C5—C10 | 1.418 (2) | C19—H19A | 0.9700 |
C6—C7 | 1.356 (3) | C19—H19B | 0.9700 |
C6—H6 | 0.9300 | C20—C21 | 1.508 (2) |
C7—C8 | 1.393 (3) | C20—H20A | 0.9700 |
C7—H7 | 0.9300 | C20—H20B | 0.9700 |
C8—C9 | 1.355 (2) | C21—C22 | 1.516 (3) |
C8—H8 | 0.9300 | C21—H21A | 0.9700 |
C9—C10 | 1.423 (2) | C21—H21B | 0.9700 |
C9—H9 | 0.9300 | C22—C23 | 1.521 (3) |
C11—N1 | 1.502 (2) | C22—H22B | 0.9700 |
C11—C12 | 1.524 (2) | C22—H22A | 0.9700 |
C11—H11 | 0.9800 | C23—N1 | 1.488 (2) |
C12—C17 | 1.378 (2) | C23—H23A | 0.9700 |
C12—C13 | 1.387 (2) | C23—H23B | 0.9700 |
C13—C14 | 1.394 (2) | O1—H1A | 0.84 (2) |
C13—H13 | 0.9300 | ||
C2—C1—C10 | 118.34 (15) | C14—C15—C16 | 121.65 (17) |
C2—C1—C11 | 121.38 (15) | C14—C15—H15 | 119.2 |
C10—C1—C11 | 120.27 (14) | C16—C15—H15 | 119.2 |
O1—C2—C1 | 122.39 (16) | C15—C16—C17 | 119.09 (17) |
O1—C2—C3 | 116.20 (15) | C15—C16—H16 | 120.5 |
C1—C2—C3 | 121.41 (16) | C17—C16—H16 | 120.5 |
C4—C3—C2 | 119.76 (17) | C12—C17—C16 | 120.96 (17) |
C4—C3—H3 | 120.1 | C12—C17—H17 | 119.5 |
C2—C3—H3 | 120.1 | C16—C17—H17 | 119.5 |
C3—C4—C5 | 121.74 (18) | N2—C18—C14 | 179.0 (2) |
C3—C4—H4 | 119.1 | N1—C19—C20 | 110.32 (16) |
C5—C4—H4 | 119.1 | N1—C19—H19A | 109.6 |
C6—C5—C4 | 122.00 (18) | C20—C19—H19A | 109.6 |
C6—C5—C10 | 120.04 (17) | N1—C19—H19B | 109.6 |
C4—C5—C10 | 117.95 (16) | C20—C19—H19B | 109.6 |
C7—C6—C5 | 121.36 (18) | H19A—C19—H19B | 108.1 |
C7—C6—H6 | 119.3 | C21—C20—C19 | 111.99 (16) |
C5—C6—H6 | 119.3 | C21—C20—H20A | 109.2 |
C6—C7—C8 | 118.79 (17) | C19—C20—H20A | 109.2 |
C6—C7—H7 | 120.6 | C21—C20—H20B | 109.2 |
C8—C7—H7 | 120.6 | C19—C20—H20B | 109.2 |
C9—C8—C7 | 122.02 (19) | H20A—C20—H20B | 107.9 |
C9—C8—H8 | 119.0 | C20—C21—C22 | 109.00 (16) |
C7—C8—H8 | 119.0 | C20—C21—H21A | 109.9 |
C8—C9—C10 | 120.84 (18) | C22—C21—H21A | 109.9 |
C8—C9—H9 | 119.6 | C20—C21—H21B | 109.9 |
C10—C9—H9 | 119.6 | C22—C21—H21B | 109.9 |
C5—C10—C9 | 116.72 (15) | H21A—C21—H21B | 108.3 |
C5—C10—C1 | 120.54 (16) | C21—C22—C23 | 110.69 (16) |
C9—C10—C1 | 122.73 (15) | C21—C22—H22B | 109.5 |
N1—C11—C12 | 111.81 (12) | C23—C22—H22B | 109.5 |
N1—C11—C1 | 110.06 (13) | C21—C22—H22A | 109.5 |
C12—C11—C1 | 110.11 (13) | C23—C22—H22A | 109.5 |
N1—C11—H11 | 108.3 | H22B—C22—H22A | 108.1 |
C12—C11—H11 | 108.3 | N1—C23—C22 | 110.76 (14) |
C1—C11—H11 | 108.3 | N1—C23—H23A | 109.5 |
C17—C12—C13 | 118.43 (15) | C22—C23—H23A | 109.5 |
C17—C12—C11 | 119.65 (16) | N1—C23—H23B | 109.5 |
C13—C12—C11 | 121.91 (15) | C22—C23—H23B | 109.5 |
C12—C13—C14 | 121.04 (16) | H23A—C23—H23B | 108.1 |
C12—C13—H13 | 119.5 | C19—N1—C23 | 109.87 (14) |
C14—C13—H13 | 119.5 | C19—N1—C11 | 112.71 (13) |
C15—C14—C13 | 118.83 (17) | C23—N1—C11 | 108.79 (12) |
C15—C14—C18 | 121.33 (16) | C2—O1—H1A | 109.5 (14) |
C13—C14—C18 | 119.83 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N1 | 0.84 (2) | 1.90 (2) | 2.598 (2) | 139.3 (19) |
C15—H15···O1i | 0.93 | 2.40 | 3.236 (2) | 149 |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C23H22N2O |
Mr | 342.43 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 291 |
a, b, c (Å) | 11.9008 (13), 15.0138 (17), 10.8886 (13) |
β (°) | 102.867 (3) |
V (Å3) | 1896.7 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.30 × 0.26 × 0.24 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.98, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11353, 3731, 2420 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.100, 1.02 |
No. of reflections | 3731 |
No. of parameters | 238 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.11, −0.11 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N1 | 0.84 (2) | 1.90 (2) | 2.598 (2) | 139.3 (19) |
C15—H15···O1i | 0.93 | 2.40 | 3.236 (2) | 149 |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Betti-type reaction is an important method to synthesize chiral ligands and by this method many unnatural homochiral amino-phenol compounds have been obtained (Lu et al., 2002; Xu et al., 2004; Wang et al., 2005).
Molecules of the title compound have normal geometric parameters. An intramolecular O—H···N hydrogen bond stabilizes the molecule conformation. The crystal packing is characterized by helical chains of molecules linked by C—H···O hydrogen bonds.