2-{[(2-Hydro­xy­phenyl)­methyl]­methyl­amino}-1-phenyl­propan-1-ol

In the title compound, C₁₇H₂₁NO₂, there are two chiral C atoms. There are two intramolecular hydrogen bonds and one intermolecular hydrogen bond. The latter intermolecular hydrogen bond links the mol­ecules in a helical fashion along the b-axis direction.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.074
• Data-to-parameter ratio = 14.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               2605
         Count of symmetry unique reflns         1557
         Completeness (_total/calc)            167.31%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1048
         Fraction of Friedel pairs measured     0.673
         Are heavy atom types Z>Si present           no
          ALERT: MoKa measured Friedel data cannot be used to
                 determine absolute structure in a light-atom
                 study EXCEPT under VERY special conditions.
                 It is preferred that Friedel data is merged in such cases.

---

S1. Comment

Ephedrine and its derivatives have been studied for a long time and the preparation of N-substituted ephedrines is common (Neelakantan, 1971). They are inexpensive and readily available in enantiomerically pure form. Therefore, with the development of stereochemistry and organometallic chemistry, they have become more and more important as a chiral ligands (Kuznetsov et al., 1999). Recently, the focus of our group has been on the organogallium complexes with chiral ligands, such as ephedrine and its derivatives. We report here the structure and relative stereochemistry of the title compound, (I), which resulted from the condensation of (-)-ephedrine with salicylic aldehyde.

The molecule looks like a camber, with the two aromatic rings located at opposite ends of the C1—C2—N1—C10 camber chain. The dihedral angle between the best planes through the aromatic rings is 39.42 (7)°. There are two chiral carbons (C1 and C2) in the molecule which are of opposite hands (1S, 2R or 1R, 2S). Two intramolecular hydrogen bonds (O2—H2a···N1 and C17—H17A···O1) and one intermolecular hydrogen bond (O1—H1a···O2 at −x + 2, y − 1/2, −z + 1/2) were found. The intermolecular hydrogen bond links the molecules into a one-dimensional helical chain (see Fig. 2).

S2. Experimental

(1R, 2S)-(-)-Ephedrine (2.5 g, 15 mmol) and salicylic aldehyde (1.6 ml, 15 mmol) were heated under reflux in benzene (20 ml) for 1 h. The calculated amount of water was then removed. The excess of benzene was abstracted by rotary evaporator and the residue recrystallized from alcohol to give the oxazolidine, a white needle-shaped crystal. To one molar equivalent of LiAlH₄ (0.5 g, 13.2 mmol) in boiling dry dioxane (20 ml), the dioxane (15 ml) solution of one mole of the oxazolidine (1.5 g, 5.54 mmol) was slowly added, and the mixture refluxed overnight. After cooling, ice and an excess of 10% sodium hydroxide solution was added, the resulting product extracted with benzene and the extract was washed with water till neutral, dried and concentrated to obtain the title compound as an oil. Crystals of (I) were obtained by recrystallization from CH₂Cl₂/hexane.

S3. Refinement

The positions of all H atoms were fixed geometrically and distances to H atoms were set by the program.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); 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.

Figures

	Fig. 1. The title compound, drawn with 50% probability displacement parameters.
	Fig. 2. Crystal packing of title compound, viewed down the a axis.

2-{[(2-Hydroxyphenyl)methyl]methylamino}-1-phenylpropan-1-ol

Crystal data

C17H21NO2	F(000) = 584
Mr = 271.35	Dx = 1.207 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3564 reflections
a = 6.004 (1) Å	θ = 2.6–24.3°
b = 10.451 (1) Å	µ = 0.08 mm^−1
c = 23.790 (3) Å	T = 293 K
V = 1492.8 (3) Å^3	Block, colorless
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2605 independent reflections
Radiation source: fine-focus sealed tube	1908 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
ϕ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: ψ scan (XPREP; Bruker, 2000)	h = −7→7
Tmin = 0.98, Tmax = 0.99	k = −9→12
7631 measured reflections	l = −26→28

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.003P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2605 reflections	Δρmax = 0.14 e Å^−3
186 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (2)

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

− 2.5865 (0.0045) x + 8.9177 (0.0049) y + 6.9893 (0.0190) z = 1.6697 (0.0054)

* 0.0012 (0.0015) C11 * 0.0035 (0.0015) C12 * −0.0048 (0.0015) C13 * 0.0014 (0.0015) C14 * 0.0033 (0.0015) C15 * −0.0046 (0.0014) C16

Rms deviation of fitted atoms = 0.0034

2.7995 (0.0050) x − 8.3604 (0.0062) y + 8.9853 (0.0201) z = 3.4770 (0.0088)

Angle to previous plane (with approximate e.s.d.) = 39.42 (0.07)

* −0.0015 (0.0016) C4 * −0.0018 (0.0016) C5 * −0.0001 (0.0017) C6 * 0.0052 (0.0019) C7 * −0.0085 (0.0017) C8 * 0.0067 (0.0016) C9

Rms deviation of fitted atoms = 0.0050

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.6882 (3)	0.17953 (16)	0.16647 (6)	0.0432 (4)
O1	0.7091 (3)	−0.03212 (14)	0.26390 (5)	0.0605 (5)
H1A	0.7976	−0.0616	0.2867	0.091*
O2	0.9930 (3)	0.35305 (15)	0.15982 (5)	0.0600 (5)
H2A	0.9148	0.2967	0.1735	0.090*
C1	0.7225 (4)	0.10431 (19)	0.26442 (8)	0.0477 (6)
H1	0.8749	0.1283	0.2541	0.057*
C2	0.5650 (3)	0.1584 (2)	0.21954 (7)	0.0475 (6)
H2	0.5186	0.2430	0.2328	0.057*
C3	0.3518 (4)	0.0804 (2)	0.21174 (9)	0.0733 (8)
H3A	0.2586	0.1213	0.1843	0.110*
H3B	0.2738	0.0752	0.2469	0.110*
H3C	0.3891	−0.0041	0.1991	0.110*
C4	0.6762 (4)	0.1575 (2)	0.32261 (8)	0.0506 (6)
C5	0.8298 (4)	0.2362 (2)	0.34798 (9)	0.0610 (7)
H5	0.9585	0.2586	0.3286	0.073*
C6	0.7969 (5)	0.2826 (2)	0.40162 (11)	0.0734 (8)
H6	0.9023	0.3359	0.4181	0.088*
C7	0.6082 (5)	0.2497 (3)	0.43038 (10)	0.0739 (8)
H7	0.5865	0.2799	0.4667	0.089*
C8	0.4503 (5)	0.1722 (2)	0.40599 (10)	0.0689 (8)
H8	0.3204	0.1518	0.4253	0.083*
C9	0.4871 (4)	0.1250 (2)	0.35228 (9)	0.0596 (7)
H9	0.3826	0.0707	0.3360	0.071*
C10	0.5666 (3)	0.2637 (2)	0.12710 (8)	0.0462 (6)
H10A	0.4851	0.3278	0.1483	0.055*
H10B	0.4597	0.2134	0.1060	0.055*
C11	0.7237 (4)	0.3292 (2)	0.08685 (8)	0.0443 (6)
C12	0.9293 (4)	0.3746 (2)	0.10531 (8)	0.0465 (6)
C13	1.0683 (4)	0.4414 (2)	0.07036 (8)	0.0523 (6)
H13A	1.2057	0.4700	0.0833	0.063*
C14	1.0029 (4)	0.4660 (2)	0.01572 (8)	0.0548 (6)
H14	1.0962	0.5120	−0.0080	0.066*
C15	0.8016 (4)	0.4230 (2)	−0.00363 (8)	0.0536 (6)
H15	0.7587	0.4401	−0.0404	0.064*
C16	0.6622 (4)	0.3543 (2)	0.03128 (8)	0.0488 (6)
H16	0.5264	0.3245	0.0177	0.059*
C17	0.7625 (4)	0.0620 (2)	0.13858 (8)	0.0602 (7)
H17A	0.8479	0.0114	0.1645	0.090*
H17B	0.8533	0.0836	0.1067	0.090*
H17C	0.6352	0.0141	0.1263	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0464 (11)	0.0435 (10)	0.0397 (9)	0.0056 (10)	0.0008 (9)	0.0033 (8)
O1	0.0741 (12)	0.0502 (10)	0.0572 (9)	0.0075 (10)	−0.0125 (9)	0.0026 (8)
O2	0.0656 (12)	0.0664 (12)	0.0479 (9)	−0.0186 (10)	−0.0132 (8)	0.0086 (8)
C1	0.0497 (15)	0.0465 (14)	0.0468 (12)	0.0019 (12)	−0.0002 (11)	0.0057 (11)
C2	0.0470 (14)	0.0495 (14)	0.0459 (12)	0.0048 (12)	0.0017 (11)	0.0069 (11)
C3	0.0485 (16)	0.098 (2)	0.0738 (15)	−0.0094 (15)	−0.0066 (13)	0.0268 (15)
C4	0.0590 (17)	0.0450 (14)	0.0477 (13)	0.0027 (14)	0.0005 (12)	0.0065 (11)
C5	0.0745 (19)	0.0522 (15)	0.0564 (15)	−0.0023 (14)	0.0010 (14)	0.0020 (12)
C6	0.095 (2)	0.0584 (17)	0.0671 (17)	−0.0022 (17)	−0.0017 (17)	−0.0067 (14)
C7	0.099 (2)	0.0604 (19)	0.0620 (17)	0.0122 (18)	0.0075 (17)	−0.0050 (15)
C8	0.083 (2)	0.0606 (18)	0.0628 (16)	0.0101 (17)	0.0138 (16)	0.0052 (15)
C9	0.0691 (18)	0.0539 (16)	0.0557 (14)	0.0020 (14)	0.0065 (14)	0.0044 (12)
C10	0.0489 (14)	0.0442 (14)	0.0456 (12)	0.0022 (11)	−0.0019 (12)	0.0020 (11)
C11	0.0512 (15)	0.0404 (13)	0.0414 (12)	0.0016 (12)	−0.0009 (11)	0.0014 (10)
C12	0.0547 (16)	0.0431 (14)	0.0417 (12)	−0.0009 (12)	−0.0006 (11)	0.0022 (11)
C13	0.0579 (17)	0.0458 (15)	0.0532 (13)	−0.0014 (13)	0.0042 (12)	0.0031 (12)
C14	0.0664 (18)	0.0481 (14)	0.0499 (14)	0.0029 (15)	0.0122 (13)	0.0043 (12)
C15	0.0694 (18)	0.0490 (15)	0.0424 (12)	0.0080 (14)	0.0008 (13)	0.0034 (11)
C16	0.0585 (16)	0.0447 (14)	0.0432 (12)	0.0048 (13)	−0.0040 (11)	−0.0002 (11)
C17	0.0704 (17)	0.0536 (15)	0.0567 (13)	0.0068 (14)	−0.0017 (13)	−0.0040 (12)

Geometric parameters (Å, º)

N1—C17	1.466 (2)	C7—C8	1.375 (3)
N1—C10	1.478 (2)	C7—H7	0.9300
N1—C2	1.480 (2)	C8—C9	1.387 (3)
O1—C1	1.428 (2)	C8—H8	0.9300
O1—H1A	0.8200	C9—H9	0.9300
O2—C12	1.371 (2)	C10—C11	1.508 (3)
O2—H2A	0.8200	C10—H10A	0.9700
C1—C4	1.517 (3)	C10—H10B	0.9700
C1—C2	1.534 (3)	C11—C12	1.393 (3)
C1—H1	0.9800	C11—C16	1.397 (3)
C2—C3	1.528 (3)	C12—C13	1.369 (3)
C2—H2	0.9800	C13—C14	1.382 (3)
C3—H3A	0.9600	C13—H13A	0.9300
C3—H3B	0.9600	C14—C15	1.369 (3)
C3—H3C	0.9600	C14—H14	0.9300
C4—C5	1.375 (3)	C15—C16	1.381 (3)
C4—C9	1.380 (3)	C15—H15	0.9300
C5—C6	1.379 (3)	C16—H16	0.9300
C5—H5	0.9300	C17—H17A	0.9600
C6—C7	1.368 (4)	C17—H17B	0.9600
C6—H6	0.9300	C17—H17C	0.9600
C17—N1—C10	111.25 (15)	C7—C8—H8	120.4
C17—N1—C2	114.41 (16)	C9—C8—H8	120.4
C10—N1—C2	112.48 (16)	C4—C9—C8	121.0 (2)
C1—O1—H1A	109.5	C4—C9—H9	119.5
C12—O2—H2A	109.5	C8—C9—H9	119.5
O1—C1—C4	111.29 (16)	N1—C10—C11	111.31 (16)
O1—C1—C2	109.07 (18)	N1—C10—H10A	109.4
C4—C1—C2	112.79 (18)	C11—C10—H10A	109.4
O1—C1—H1	107.8	N1—C10—H10B	109.4
C4—C1—H1	107.8	C11—C10—H10B	109.4
C2—C1—H1	107.8	H10A—C10—H10B	108.0
N1—C2—C3	113.26 (17)	C12—C11—C16	117.9 (2)
N1—C2—C1	109.90 (16)	C12—C11—C10	120.55 (17)
C3—C2—C1	113.86 (18)	C16—C11—C10	121.4 (2)
N1—C2—H2	106.4	C13—C12—O2	119.2 (2)
C3—C2—H2	106.4	C13—C12—C11	121.5 (2)
C1—C2—H2	106.4	O2—C12—C11	119.31 (19)
C2—C3—H3A	109.5	C12—C13—C14	119.5 (2)
C2—C3—H3B	109.5	C12—C13—H13A	120.2
H3A—C3—H3B	109.5	C14—C13—H13A	120.2
C2—C3—H3C	109.5	C15—C14—C13	120.4 (2)
H3A—C3—H3C	109.5	C15—C14—H14	119.8
H3B—C3—H3C	109.5	C13—C14—H14	119.8
C5—C4—C9	118.3 (2)	C14—C15—C16	120.3 (2)
C5—C4—C1	119.8 (2)	C14—C15—H15	119.9
C9—C4—C1	121.9 (2)	C16—C15—H15	119.9
C4—C5—C6	121.4 (3)	C15—C16—C11	120.4 (2)
C4—C5—H5	119.3	C15—C16—H16	119.8
C6—C5—H5	119.3	C11—C16—H16	119.8
C7—C6—C5	119.5 (3)	N1—C17—H17A	109.5
C7—C6—H6	120.2	N1—C17—H17B	109.5
C5—C6—H6	120.2	H17A—C17—H17B	109.5
C6—C7—C8	120.6 (2)	N1—C17—H17C	109.5
C6—C7—H7	119.7	H17A—C17—H17C	109.5
C8—C7—H7	119.7	H17B—C17—H17C	109.5
C7—C8—C9	119.2 (3)
C17—N1—C2—C3	−60.7 (2)	C1—C4—C9—C8	178.5 (2)
C10—N1—C2—C3	67.5 (2)	C7—C8—C9—C4	−1.8 (3)
C17—N1—C2—C1	67.9 (2)	C17—N1—C10—C11	−74.7 (2)
C10—N1—C2—C1	−163.87 (17)	C2—N1—C10—C11	155.47 (17)
O1—C1—C2—N1	−93.8 (2)	N1—C10—C11—C12	−39.5 (3)
C4—C1—C2—N1	142.02 (19)	N1—C10—C11—C16	145.10 (19)
O1—C1—C2—C3	34.5 (2)	C16—C11—C12—C13	−0.2 (3)
C4—C1—C2—C3	−89.7 (2)	C10—C11—C12—C13	−175.83 (19)
O1—C1—C4—C5	124.5 (2)	C16—C11—C12—O2	179.13 (19)
C2—C1—C4—C5	−112.5 (2)	C10—C11—C12—O2	3.5 (3)
O1—C1—C4—C9	−52.8 (3)	O2—C12—C13—C14	−178.6 (2)
C2—C1—C4—C9	70.2 (3)	C11—C12—C13—C14	0.8 (3)
C9—C4—C5—C6	−0.3 (3)	C12—C13—C14—C15	−0.6 (3)
C1—C4—C5—C6	−177.7 (2)	C13—C14—C15—C16	−0.2 (3)
C4—C5—C6—C7	0.2 (4)	C14—C15—C16—C11	0.8 (3)
C5—C6—C7—C8	−0.8 (4)	C12—C11—C16—C15	−0.5 (3)
C6—C7—C8—C9	1.6 (4)	C10—C11—C16—C15	175.00 (19)
C5—C4—C9—C8	1.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2^i	0.82	2.00	2.8165 (19)	176
O2—H2A···N1	0.82	1.84	2.581 (2)	150
C17—H17A···O1	0.96	2.55	3.156 (2)	121

Symmetry code: (i) −x+2, y−1/2, −z+1/2.