N-(2-Hydro­xy­naphthyl­methyl)-(S)-proline methyl ester

The title compound, C₁₆H₁₇NO₃, a new derivative of L-proline, was synthesized via a Mannich reaction. The X-ray crystal analysis revealed that the pyrrolidine ring adopts an envelope conformation, with the N atom deviating by 0.515 (5) Å from the mean plane through the four C atoms. The 2-hydroxy­naphthyl­methyl moiety, which is trans to the methoxy­carbonyl group, adopts a pseudo-equatorial direction.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.053
• wR factor = 0.119
• Data-to-parameter ratio = 7.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.99

Alert level C
REFNR01_ALERT_3_C  Ratio of reflections to parameters is < 8 for a
            non-centrosymmetric structure, where ZMAX < 18
            sine(theta)/lambda               -0.1583
            Proportion of unique data used    1.0000
            Ratio reflections to parameters   7.8021
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.80
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....         C2
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         C5
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.02
           From the CIF: _reflns_number_total               1498
           Count of symmetry unique reflns         1517
           Completeness (_total/calc)             98.75%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present           no

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 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
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997) and SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

N-(2-Hydroxynaphthylmethyl)-(L)-proline Methyl Ester

Crystal data

C17H19NO3	F(000) = 608
Mr = 285.33	Dx = 1.274 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 744 reflections
a = 9.427 (6) Å	θ = 2.3–19.7°
b = 11.692 (7) Å	µ = 0.09 mm^−1
c = 13.501 (8) Å	T = 293 K
V = 1488.0 (15) Å^3	Columnar, colourless
Z = 4	0.40 × 0.35 × 0.10 mm

Data collection

CCD area detector diffractometer	1498 independent reflections
Radiation source: fine-focus sealed tube	917 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→11
Tmin = 0.966, Tmax = 0.991	k = −12→13
5521 measured reflections	l = −15→16

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0458P)^2 + ] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.053	(Δ/σ)max = 0.017
wR(F^2) = 0.119	Δρmax = 0.12 e Å^−3
S = 1.10	Δρmin = −0.14 e Å^−3
1498 reflections	Extinction correction: SHELXL
192 parameters	Extinction coefficient: 0.016 (4)
0 restraints

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.

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(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
O1	0.0994 (4)	0.1462 (3)	−0.2105 (2)	0.1034 (11)
O2	0.1685 (4)	0.2951 (3)	−0.1213 (2)	0.1141 (13)
O3	0.2993 (4)	0.3793 (2)	0.0745 (2)	0.0967 (10)
H3	0.2849	0.3188	0.0411	0.145*
N1	0.2184 (3)	0.1600 (3)	0.0423 (2)	0.0699 (9)
C1	0.3023 (6)	0.0753 (4)	0.0960 (4)	0.1018 (16)
H1A	0.2415	0.0211	0.1300	0.122*
H1B	0.3641	0.1118	0.1440	0.122*
C2	0.3875 (7)	0.0168 (5)	0.0160 (4)	0.126 (2)
H2A	0.4822	0.0490	0.0129	0.151*
H2B	0.3953	−0.0643	0.0298	0.151*
C3	0.3118 (6)	0.0355 (4)	−0.0794 (4)	0.1086 (17)
H3A	0.2833	−0.0368	−0.1084	0.130*
H3B	0.3717	0.0760	−0.1261	0.130*
C4	0.1815 (5)	0.1078 (3)	−0.0515 (3)	0.0770 (12)
H4	0.0992	0.0576	−0.0425	0.092*
C5	0.1495 (5)	0.1946 (4)	−0.1292 (3)	0.0819 (13)
C6	0.0624 (7)	0.2219 (5)	−0.2914 (3)	0.1217 (19)
H6A	0.0002	0.2808	−0.2676	0.183*
H6B	0.0156	0.1791	−0.3425	0.183*
H6C	0.1471	0.2561	−0.3177	0.183*
C7	0.0951 (5)	0.2004 (4)	0.0981 (3)	0.0749 (11)
H7A	0.0456	0.1351	0.1260	0.090*
H7B	0.0306	0.2392	0.0534	0.090*
C8	0.1362 (4)	0.2813 (3)	0.1810 (3)	0.0628 (10)
C9	0.0714 (4)	0.2758 (3)	0.2764 (3)	0.0642 (10)
C10	−0.0328 (4)	0.1937 (4)	0.3016 (3)	0.0780 (13)
H10	−0.0599	0.1394	0.2549	0.094*
C11	−0.0942 (5)	0.1930 (4)	0.3930 (3)	0.0916 (14)
H11	−0.1619	0.1376	0.4076	0.110*
C12	−0.0587 (6)	0.2720 (5)	0.4642 (4)	0.1030 (16)
H12	−0.1034	0.2709	0.5256	0.124*
C13	0.0412 (6)	0.3511 (5)	0.4445 (4)	0.0958 (16)
H13	0.0666	0.4034	0.4932	0.115*
C14	0.1082 (4)	0.3559 (4)	0.3508 (3)	0.0749 (12)
C15	0.2102 (6)	0.4398 (4)	0.3283 (4)	0.0916 (15)
H15	0.2360	0.4927	0.3765	0.110*
C16	0.2709 (5)	0.4449 (3)	0.2385 (4)	0.0866 (14)
H16	0.3379	0.5012	0.2252	0.104*
C17	0.2342 (4)	0.3659 (4)	0.1644 (3)	0.0746 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.120 (3)	0.118 (2)	0.071 (2)	−0.030 (2)	0.0040 (19)	−0.011 (2)
O2	0.168 (4)	0.089 (2)	0.085 (2)	−0.030 (2)	−0.001 (2)	0.0042 (19)
O3	0.101 (2)	0.0865 (19)	0.102 (2)	−0.0273 (17)	0.012 (2)	−0.0049 (17)
N1	0.0676 (19)	0.0709 (18)	0.071 (2)	−0.0013 (17)	0.0055 (18)	−0.0092 (19)
C1	0.116 (4)	0.085 (3)	0.104 (4)	0.014 (3)	−0.009 (3)	−0.002 (3)
C2	0.149 (5)	0.101 (4)	0.127 (5)	0.043 (4)	0.011 (5)	−0.014 (4)
C3	0.120 (4)	0.097 (3)	0.108 (4)	−0.001 (3)	0.017 (4)	−0.025 (3)
C4	0.085 (3)	0.073 (2)	0.074 (3)	−0.019 (2)	0.015 (3)	−0.014 (2)
C5	0.086 (3)	0.091 (3)	0.069 (3)	−0.024 (3)	0.017 (2)	−0.004 (3)
C6	0.146 (5)	0.154 (5)	0.065 (3)	−0.029 (4)	0.000 (3)	0.019 (3)
C7	0.071 (3)	0.083 (3)	0.070 (3)	−0.013 (2)	0.004 (2)	−0.005 (2)
C8	0.059 (2)	0.065 (2)	0.065 (2)	−0.001 (2)	−0.005 (2)	−0.0043 (19)
C9	0.057 (2)	0.068 (2)	0.068 (3)	0.015 (2)	−0.014 (2)	−0.003 (2)
C10	0.071 (3)	0.097 (3)	0.066 (3)	0.004 (3)	−0.004 (2)	−0.003 (2)
C11	0.079 (3)	0.122 (4)	0.074 (3)	0.014 (3)	0.002 (3)	0.008 (3)
C12	0.100 (4)	0.141 (5)	0.068 (3)	0.042 (4)	−0.004 (3)	−0.005 (4)
C13	0.100 (4)	0.113 (4)	0.075 (3)	0.043 (3)	−0.022 (3)	−0.023 (3)
C14	0.069 (3)	0.074 (3)	0.082 (3)	0.028 (3)	−0.018 (3)	−0.014 (2)
C15	0.094 (4)	0.079 (3)	0.102 (4)	0.023 (3)	−0.032 (3)	−0.030 (3)
C16	0.085 (3)	0.059 (2)	0.116 (4)	−0.002 (2)	−0.014 (3)	−0.018 (3)
C17	0.072 (3)	0.066 (3)	0.086 (3)	0.002 (2)	0.003 (3)	−0.002 (2)

Geometric parameters (Å, º)

O1—C5	1.323 (5)	C6—H6C	0.9600
O1—C6	1.448 (6)	C7—C8	1.515 (5)
O2—C5	1.194 (5)	C7—H7A	0.9700
O3—C17	1.369 (5)	C7—H7B	0.9700
O3—H3	0.8500	C8—C17	1.372 (5)
N1—C4	1.449 (5)	C8—C9	1.427 (5)
N1—C1	1.460 (5)	C9—C10	1.415 (5)
N1—C7	1.464 (5)	C9—C14	1.416 (5)
C1—C2	1.508 (7)	C10—C11	1.363 (6)
C1—H1A	0.9700	C10—H10	0.9300
C1—H1B	0.9700	C11—C12	1.375 (7)
C2—C3	1.488 (7)	C11—H11	0.9300
C2—H2A	0.9700	C12—C13	1.346 (7)
C2—H2B	0.9700	C12—H12	0.9300
C3—C4	1.538 (6)	C13—C14	1.415 (6)
C3—H3A	0.9700	C13—H13	0.9300
C3—H3B	0.9700	C14—C15	1.407 (6)
C4—C5	1.490 (6)	C15—C16	1.342 (6)
C4—H4	0.9800	C15—H15	0.9300
C6—H6A	0.9600	C16—C17	1.405 (6)
C6—H6B	0.9600	C16—H16	0.9300
C5—O1—C6	116.7 (4)	H6B—C6—H6C	109.5
C17—O3—H3	107.7	N1—C7—C8	112.2 (3)
C4—N1—C1	106.2 (3)	N1—C7—H7A	109.2
C4—N1—C7	113.3 (3)	C8—C7—H7A	109.2
C1—N1—C7	113.2 (3)	N1—C7—H7B	109.2
N1—C1—C2	103.9 (4)	C8—C7—H7B	109.2
N1—C1—H1A	111.0	H7A—C7—H7B	107.9
C2—C1—H1A	111.0	C17—C8—C9	117.9 (4)
N1—C1—H1B	111.0	C17—C8—C7	120.1 (3)
C2—C1—H1B	111.0	C9—C8—C7	122.0 (3)
H1A—C1—H1B	109.0	C10—C9—C14	116.6 (4)
C3—C2—C1	107.3 (4)	C10—C9—C8	122.9 (4)
C3—C2—H2A	110.2	C14—C9—C8	120.4 (4)
C1—C2—H2A	110.2	C11—C10—C9	121.1 (4)
C3—C2—H2B	110.2	C11—C10—H10	119.4
C1—C2—H2B	110.2	C9—C10—H10	119.4
H2A—C2—H2B	108.5	C10—C11—C12	121.7 (5)
C2—C3—C4	104.6 (4)	C10—C11—H11	119.2
C2—C3—H3A	110.8	C12—C11—H11	119.2
C4—C3—H3A	110.8	C13—C12—C11	119.6 (5)
C2—C3—H3B	110.8	C13—C12—H12	120.2
C4—C3—H3B	110.8	C11—C12—H12	120.2
H3A—C3—H3B	108.9	C12—C13—C14	121.1 (5)
N1—C4—C5	112.2 (3)	C12—C13—H13	119.4
N1—C4—C3	104.7 (4)	C14—C13—H13	119.4
C5—C4—C3	111.3 (4)	C15—C14—C13	121.7 (5)
N1—C4—H4	109.5	C15—C14—C9	118.4 (4)
C5—C4—H4	109.5	C13—C14—C9	119.9 (5)
C3—C4—H4	109.5	C16—C15—C14	121.1 (4)
O2—C5—O1	123.3 (5)	C16—C15—H15	119.4
O2—C5—C4	125.2 (5)	C14—C15—H15	119.4
O1—C5—C4	111.4 (4)	C15—C16—C17	120.6 (4)
O1—C6—H6A	109.5	C15—C16—H16	119.7
O1—C6—H6B	109.5	C17—C16—H16	119.7
H6A—C6—H6B	109.5	O3—C17—C8	122.0 (4)
O1—C6—H6C	109.5	O3—C17—C16	116.5 (4)
H6A—C6—H6C	109.5	C8—C17—C16	121.6 (4)
C4—N1—C1—C2	35.9 (5)	C17—C8—C9—C14	0.1 (5)
C7—N1—C1—C2	160.7 (4)	C7—C8—C9—C14	−177.3 (3)
N1—C1—C2—C3	−21.8 (6)	C14—C9—C10—C11	0.2 (5)
C1—C2—C3—C4	0.6 (6)	C8—C9—C10—C11	−178.6 (4)
C1—N1—C4—C5	−156.5 (4)	C9—C10—C11—C12	0.5 (7)
C7—N1—C4—C5	78.7 (4)	C10—C11—C12—C13	−1.3 (7)
C1—N1—C4—C3	−35.7 (5)	C11—C12—C13—C14	1.4 (7)
C7—N1—C4—C3	−160.5 (3)	C12—C13—C14—C15	178.4 (4)
C2—C3—C4—N1	21.0 (5)	C12—C13—C14—C9	−0.7 (6)
C2—C3—C4—C5	142.4 (4)	C10—C9—C14—C15	−179.2 (3)
C6—O1—C5—O2	−2.1 (7)	C8—C9—C14—C15	−0.4 (5)
C6—O1—C5—C4	179.3 (4)	C10—C9—C14—C13	−0.1 (5)
N1—C4—C5—O2	9.1 (7)	C8—C9—C14—C13	178.7 (4)
C3—C4—C5—O2	−107.8 (6)	C13—C14—C15—C16	−178.7 (4)
N1—C4—C5—O1	−172.3 (3)	C9—C14—C15—C16	0.5 (6)
C3—C4—C5—O1	70.8 (5)	C14—C15—C16—C17	−0.2 (7)
C4—N1—C7—C8	−164.8 (3)	C9—C8—C17—O3	−178.5 (4)
C1—N1—C7—C8	74.3 (4)	C7—C8—C17—O3	−1.1 (6)
N1—C7—C8—C17	44.0 (5)	C9—C8—C17—C16	0.2 (6)
N1—C7—C8—C9	−138.7 (4)	C7—C8—C17—C16	177.7 (4)
C17—C8—C9—C10	178.8 (4)	C15—C16—C17—O3	178.6 (4)
C7—C8—C9—C10	1.4 (5)	C15—C16—C17—C8	−0.2 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1	0.85	1.96	2.710 (5)	147
O3—H3···O2	0.85	2.47	3.078 (5)	130