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Hydrolysis of the methyl ester (±)-threo-methyl phenidate afforded the free acid in 40% yield, viz. (±)-threo-ritalinic acid, C13H17NO2. Hydrolysis and subsequent crystallization were accomplished at pH values between 5 and 7 to yield colourless prisms which were analysed by X-ray crystallography. Crystals of (±)-threo-ritalinic acid belong to the P21/n space group and form intermolecular hydrogen bonds. An antiperiplanar disposition of the H atoms of the (HOOC-)CH-CHpy group (py is pyridine) was found in both the solid (diffraction analysis) and solution state (NMR analysis). It was also determined that (±)-threo-ritalinic acid conforms to the minimization of negative gauche+-gauche- interactions.
Supporting information
CCDC reference: 936328
Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and ORTEPIII (Johnson & Burnett, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
(
R,
R)-2-Phenyl-2-(piperidin-2-yl)acetic acid
top
Crystal data top
C13H17NO2 | F(000) = 472 |
Mr = 219.28 | Dx = 1.292 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 895 reflections |
a = 13.495 (3) Å | θ = 3.2–24.3° |
b = 5.6335 (12) Å | µ = 0.09 mm−1 |
c = 15.721 (4) Å | T = 100 K |
β = 109.368 (8)° | Rod, colourless |
V = 1127.5 (4) Å3 | 0.14 × 0.05 × 0.02 mm |
Z = 4 | |
Data collection top
Bruker APEXII CCD diffractometer | 2603 independent reflections |
Radiation source: fine-focus sealed tube | 1482 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.097 |
φ and ω scans | θmax = 27.6°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −17→17 |
Tmin = 0.988, Tmax = 0.998 | k = −7→6 |
10280 measured reflections | l = −20→20 |
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)] = 0.065 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.143 | All H-atom parameters refined |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0513P)2] where P = (Fo2 + 2Fc2)/3 |
2603 reflections | (Δ/σ)max = 0.007 |
213 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
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. |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 1.10921 (14) | 0.2562 (3) | 0.61033 (13) | 0.0188 (5) | |
O2 | 0.99451 (14) | −0.0390 (3) | 0.59486 (12) | 0.0173 (5) | |
N1 | 0.84435 (17) | 0.3000 (4) | 0.42549 (15) | 0.0149 (5) | |
H1A | 0.867 (2) | 0.458 (6) | 0.418 (2) | 0.037 (9)* | |
H1B | 0.903 (3) | 0.195 (6) | 0.423 (2) | 0.049 (10)* | |
C2 | 0.8278 (2) | 0.2914 (5) | 0.51527 (18) | 0.0162 (6) | |
H2 | 0.803 (2) | 0.131 (5) | 0.5193 (18) | 0.017 (7)* | |
C3 | 0.7376 (2) | 0.4585 (6) | 0.5116 (2) | 0.0238 (7) | |
H3A | 0.725 (2) | 0.446 (5) | 0.573 (2) | 0.031 (8)* | |
H3B | 0.759 (2) | 0.623 (6) | 0.507 (2) | 0.025 (8)* | |
C4 | 0.6384 (2) | 0.3989 (6) | 0.4352 (2) | 0.0265 (7) | |
H4A | 0.615 (2) | 0.235 (6) | 0.449 (2) | 0.035 (9)* | |
H4B | 0.579 (2) | 0.509 (5) | 0.4344 (19) | 0.030 (8)* | |
C5 | 0.6590 (2) | 0.4042 (6) | 0.34566 (19) | 0.0214 (7) | |
H5A | 0.599 (2) | 0.345 (5) | 0.300 (2) | 0.021 (8)* | |
H5B | 0.676 (2) | 0.569 (5) | 0.3305 (19) | 0.024 (8)* | |
C6 | 0.7487 (2) | 0.2388 (5) | 0.3486 (2) | 0.0197 (6) | |
H6A | 0.766 (2) | 0.254 (5) | 0.295 (2) | 0.021 (8)* | |
H6B | 0.731 (2) | 0.075 (5) | 0.3593 (19) | 0.024 (8)* | |
C7 | 0.9294 (2) | 0.3550 (5) | 0.58976 (18) | 0.0160 (6) | |
H7 | 0.948 (2) | 0.514 (5) | 0.5718 (18) | 0.017 (7)* | |
C8 | 0.9128 (2) | 0.3658 (4) | 0.68055 (18) | 0.0147 (6) | |
C9 | 0.8648 (2) | 0.1789 (5) | 0.71042 (19) | 0.0187 (6) | |
H9 | 0.837 (2) | 0.043 (5) | 0.6660 (18) | 0.019 (7)* | |
C10 | 0.8501 (2) | 0.1864 (5) | 0.7927 (2) | 0.0202 (6) | |
H10 | 0.814 (2) | 0.046 (6) | 0.814 (2) | 0.038 (9)* | |
C11 | 0.8852 (2) | 0.3802 (5) | 0.8488 (2) | 0.0222 (7) | |
H11 | 0.877 (2) | 0.380 (5) | 0.907 (2) | 0.038 (9)* | |
C12 | 0.9339 (2) | 0.5657 (5) | 0.82067 (19) | 0.0228 (7) | |
H12 | 0.958 (2) | 0.705 (5) | 0.858 (2) | 0.023 (8)* | |
C13 | 0.9474 (2) | 0.5600 (5) | 0.73721 (19) | 0.0189 (6) | |
H13 | 0.977 (2) | 0.698 (5) | 0.712 (2) | 0.036 (9)* | |
C14 | 1.0181 (2) | 0.1778 (5) | 0.59797 (17) | 0.0144 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0162 (10) | 0.0149 (10) | 0.0247 (11) | −0.0001 (8) | 0.0061 (8) | 0.0016 (8) |
O2 | 0.0217 (10) | 0.0107 (9) | 0.0200 (11) | −0.0004 (8) | 0.0076 (8) | 0.0008 (8) |
N1 | 0.0172 (12) | 0.0129 (12) | 0.0143 (12) | −0.0006 (10) | 0.0050 (10) | 0.0001 (9) |
C2 | 0.0154 (14) | 0.0159 (14) | 0.0182 (15) | 0.0004 (12) | 0.0067 (12) | 0.0027 (11) |
C3 | 0.0189 (16) | 0.0322 (18) | 0.0205 (17) | 0.0060 (14) | 0.0068 (13) | −0.0013 (14) |
C4 | 0.0204 (17) | 0.036 (2) | 0.0229 (17) | 0.0062 (15) | 0.0062 (13) | 0.0031 (14) |
C5 | 0.0198 (16) | 0.0242 (17) | 0.0154 (15) | 0.0022 (13) | −0.0007 (13) | 0.0010 (12) |
C6 | 0.0222 (16) | 0.0194 (16) | 0.0148 (15) | −0.0038 (13) | 0.0024 (12) | −0.0057 (12) |
C7 | 0.0186 (14) | 0.0115 (14) | 0.0193 (15) | −0.0013 (12) | 0.0083 (12) | 0.0002 (11) |
C8 | 0.0124 (13) | 0.0139 (14) | 0.0155 (14) | 0.0024 (11) | 0.0016 (11) | 0.0014 (11) |
C9 | 0.0200 (15) | 0.0180 (15) | 0.0177 (15) | 0.0010 (12) | 0.0057 (12) | 0.0008 (12) |
C10 | 0.0186 (15) | 0.0230 (15) | 0.0193 (16) | 0.0016 (13) | 0.0068 (12) | 0.0050 (13) |
C11 | 0.0256 (16) | 0.0267 (17) | 0.0146 (15) | 0.0067 (13) | 0.0071 (13) | 0.0043 (13) |
C12 | 0.0271 (17) | 0.0225 (16) | 0.0165 (15) | 0.0013 (14) | 0.0044 (13) | −0.0044 (13) |
C13 | 0.0194 (15) | 0.0155 (14) | 0.0203 (15) | 0.0040 (12) | 0.0044 (12) | 0.0023 (12) |
C14 | 0.0199 (15) | 0.0130 (14) | 0.0120 (14) | −0.0015 (11) | 0.0075 (12) | 0.0003 (11) |
Geometric parameters (Å, º) top
O1—C14 | 1.260 (3) | C5—C6 | 1.517 (4) |
O2—C14 | 1.259 (3) | C6—H6A | 0.95 (3) |
N1—H1A | 0.96 (3) | C6—H6B | 0.98 (3) |
N1—H1B | 1.00 (4) | C7—H7 | 0.99 (3) |
N1—C2 | 1.501 (3) | C7—C8 | 1.518 (4) |
N1—C6 | 1.487 (3) | C7—C14 | 1.530 (4) |
C2—H2 | 0.97 (3) | C8—C9 | 1.397 (4) |
C2—C3 | 1.524 (4) | C8—C13 | 1.390 (4) |
C2—C7 | 1.522 (4) | C9—H9 | 1.02 (3) |
C3—H3A | 1.04 (3) | C9—C10 | 1.373 (4) |
C3—H3B | 0.98 (3) | C10—H10 | 1.04 (3) |
C3—C4 | 1.511 (4) | C10—C11 | 1.385 (4) |
C4—H4A | 1.02 (3) | C11—H11 | 0.95 (3) |
C4—H4B | 1.01 (3) | C11—C12 | 1.382 (4) |
C4—C5 | 1.522 (4) | C12—H12 | 0.97 (3) |
C5—H5A | 0.95 (3) | C12—C13 | 1.384 (4) |
C5—H5B | 1.00 (3) | C13—H13 | 1.01 (3) |
| | | |
H1A—N1—H1B | 105 (3) | N1—C6—H6B | 105.9 (16) |
C2—N1—H1A | 107.4 (19) | C5—C6—H6A | 110.3 (16) |
C2—N1—H1B | 113 (2) | C5—C6—H6B | 110.3 (16) |
C6—N1—H1A | 109.6 (19) | H6A—C6—H6B | 113 (2) |
C6—N1—H1B | 108 (2) | C2—C7—H7 | 103.7 (16) |
C6—N1—C2 | 113.4 (2) | C2—C7—C14 | 113.1 (2) |
N1—C2—H2 | 104.6 (16) | C8—C7—C2 | 110.9 (2) |
N1—C2—C3 | 108.1 (2) | C8—C7—H7 | 111.0 (15) |
N1—C2—C7 | 109.8 (2) | C8—C7—C14 | 107.6 (2) |
C3—C2—H2 | 106.8 (16) | C14—C7—H7 | 110.7 (15) |
C7—C2—H2 | 114.2 (16) | C9—C8—C7 | 121.0 (2) |
C7—C2—C3 | 112.9 (2) | C13—C8—C7 | 120.8 (2) |
C2—C3—H3A | 107.3 (16) | C13—C8—C9 | 118.2 (3) |
C2—C3—H3B | 109.3 (17) | C8—C9—H9 | 116.1 (15) |
H3A—C3—H3B | 106 (2) | C10—C9—C8 | 121.4 (3) |
C4—C3—C2 | 112.2 (3) | C10—C9—H9 | 122.3 (15) |
C4—C3—H3A | 110.6 (16) | C9—C10—H10 | 120.5 (18) |
C4—C3—H3B | 110.8 (18) | C9—C10—C11 | 119.9 (3) |
C3—C4—H4A | 106.6 (18) | C11—C10—H10 | 119.6 (17) |
C3—C4—H4B | 111.3 (17) | C10—C11—H11 | 119.0 (19) |
C3—C4—C5 | 110.2 (3) | C12—C11—C10 | 119.4 (3) |
H4A—C4—H4B | 105 (2) | C12—C11—H11 | 121.6 (19) |
C5—C4—H4A | 112.1 (17) | C11—C12—H12 | 121.0 (16) |
C5—C4—H4B | 111.3 (17) | C11—C12—C13 | 120.8 (3) |
C4—C5—H5A | 108.8 (17) | C13—C12—H12 | 118.2 (17) |
C4—C5—H5B | 111.4 (16) | C8—C13—H13 | 116.6 (17) |
H5A—C5—H5B | 110 (2) | C12—C13—C8 | 120.3 (3) |
C6—C5—C4 | 110.4 (3) | C12—C13—H13 | 123.0 (17) |
C6—C5—H5A | 106.3 (16) | O1—C14—O2 | 124.6 (2) |
C6—C5—H5B | 109.4 (16) | O1—C14—C7 | 118.7 (2) |
N1—C6—C5 | 110.6 (2) | O2—C14—C7 | 116.7 (2) |
N1—C6—H6A | 107.1 (17) | | |
| | | |
N1—C2—C3—C4 | 56.2 (3) | C6—N1—C2—C7 | 179.7 (2) |
N1—C2—C7—C8 | 175.7 (2) | C7—C2—C3—C4 | 177.8 (3) |
N1—C2—C7—C14 | −63.3 (3) | C7—C8—C9—C10 | 179.6 (3) |
C2—N1—C6—C5 | 57.8 (3) | C7—C8—C13—C12 | −178.6 (3) |
C2—C3—C4—C5 | −57.1 (4) | C8—C7—C14—O1 | −99.4 (3) |
C2—C7—C8—C9 | 51.1 (3) | C8—C7—C14—O2 | 78.2 (3) |
C2—C7—C8—C13 | −130.5 (3) | C8—C9—C10—C11 | −1.4 (4) |
C2—C7—C14—O1 | 137.8 (2) | C9—C8—C13—C12 | −0.1 (4) |
C2—C7—C14—O2 | −44.6 (3) | C9—C10—C11—C12 | 0.7 (4) |
C3—C2—C7—C8 | 55.1 (3) | C10—C11—C12—C13 | 0.3 (4) |
C3—C2—C7—C14 | 176.0 (2) | C11—C12—C13—C8 | −0.5 (4) |
C3—C4—C5—C6 | 55.6 (4) | C13—C8—C9—C10 | 1.1 (4) |
C4—C5—C6—N1 | −55.7 (4) | C14—C7—C8—C9 | −73.0 (3) |
C6—N1—C2—C3 | −56.8 (3) | C14—C7—C8—C13 | 105.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.96 (3) | 1.73 (3) | 2.682 (3) | 172 (2) |
N1—H1B···O2ii | 1.00 (4) | 1.74 (3) | 2.730 (3) | 171 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+1. |
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