N-(2-Hydr­oxy-1-naphthyl­meth­yl)-(S)-proline

The title compound [systematic name: (2S)-1-(2-hydroxy-1-naphthyl­meth­yl)pyrrolidinio-2-carboxyl­ate], C₁₆H₁₇NO₃, a derivative of L-proline, was synthesized via the Mannich reaction. The X-ray crystal analysis reveals that the pyrrolidine ring adopts an envelope conformation, with the flap C atom deviating by 0.631 (9) Å from the plane defined by the other four atoms.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.039
• wR factor = 0.113
• Data-to-parameter ratio = 10.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT199_ALERT_1_C Check the Reported cell_measurement_temperature         293
PLAT200_ALERT_1_C Check the Reported cell_ambient_temperature ....        293
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.16 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.40 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C15    -   C16     ..       6.36 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C4
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C16
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6
PLAT731_ALERT_1_C Bond    Calc     0.86(3), Rep   0.860(10) ......       3.00 su-Rat
              O3   -H3      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(3), Rep   0.860(10) ......       3.00 su-Rat
              O3   -H3      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.73(3), Rep   1.731(12) ......       2.50 su-Rat
              H3   -O2      1.555   3.656

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           27.97
           From the CIF: _reflns_number_total               1980
           Count of symmetry unique reflns         1980
           Completeness (_total/calc)            100.00%
           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
   0 ALERT level B = Potentially serious problem
  12 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

(2S)-1-(2-Hydroxy-1-naphthylmethyl)pyrrolidinio-2-carboxylate

Crystal data

C16H17NO3	F(000) = 576
Mr = 271.31	Dx = 1.278 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1714 reflections
a = 5.8037 (7) Å	θ = 2.6–22.2°
b = 12.0508 (15) Å	µ = 0.09 mm^−1
c = 20.160 (3) Å	T = 293 K
V = 1410.0 (3) Å^3	Block, colourless
Z = 4	0.24 × 0.16 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1980 independent reflections
Radiation source: fine-focus sealed tube	1329 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 28.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −7→7
Tmin = 0.964, Tmax = 0.988	k = −15→15
9621 measured reflections	l = −26→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0446P)^2 + 0.1866P] where P = (Fo^2 + 2Fc^2)/3
1980 reflections	(Δ/σ)max = 0.001
188 parameters	Δρmax = 0.18 e Å^−3
14 restraints	Δρmin = −0.15 e Å^−3

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 > 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	0.0132 (3)	0.23124 (15)	0.70192 (11)	0.0504 (5)
H1	0.159 (2)	0.2567 (18)	0.7068 (12)	0.053 (7)*
O1	0.4361 (3)	0.16119 (16)	0.69549 (13)	0.0833 (7)
O2	0.3504 (4)	−0.01668 (17)	0.68613 (17)	0.1076 (10)
O3	0.2728 (3)	0.37754 (15)	0.78763 (11)	0.0686 (5)
H3	0.393 (4)	0.416 (3)	0.7972 (18)	0.103*
C1	0.3025 (4)	0.0831 (2)	0.69123 (15)	0.0608 (7)
C2	0.0445 (4)	0.10908 (18)	0.68787 (12)	0.0474 (6)
H2	−0.0401	0.0645	0.7205	0.057*
C3	−0.0552 (5)	0.0922 (2)	0.61914 (14)	0.0648 (7)
H3A	−0.2151	0.0690	0.6214	0.078*
H3B	0.0320	0.0372	0.5945	0.078*
C4	−0.0333 (7)	0.2066 (3)	0.58757 (16)	0.0861 (10)
H4A	0.1234	0.2208	0.5732	0.103*
H4B	−0.1366	0.2145	0.5500	0.103*
C5	−0.1011 (6)	0.2820 (2)	0.64328 (15)	0.0716 (9)
H5A	−0.0458	0.3569	0.6357	0.086*
H5B	−0.2671	0.2838	0.6488	0.086*
C6	−0.1087 (4)	0.2593 (2)	0.76545 (13)	0.0592 (7)
H6A	−0.1476	0.3376	0.7655	0.071*
H6B	−0.2511	0.2174	0.7680	0.071*
C7	0.0349 (5)	0.2340 (2)	0.82431 (13)	0.0558 (6)
C8	0.2267 (5)	0.2995 (2)	0.83358 (15)	0.0602 (7)
C9	0.3704 (7)	0.2858 (3)	0.88968 (19)	0.0868 (11)
H9	0.4994	0.3305	0.8955	0.104*
C10	0.3175 (10)	0.2068 (4)	0.93467 (19)	0.1061 (15)
H10	0.4104	0.1991	0.9720	0.127*
C11	0.1295 (9)	0.1366 (3)	0.92729 (17)	0.0960 (14)
C12	−0.0173 (6)	0.1493 (2)	0.87105 (16)	0.0733 (9)
C13	−0.2108 (7)	0.0785 (3)	0.8648 (2)	0.0992 (13)
H13	−0.3074	0.0847	0.8282	0.119*
C14	−0.2566 (11)	−0.0004 (4)	0.9135 (4)	0.137 (2)
H14	−0.3857	−0.0458	0.9099	0.164*
C15	−0.1118 (14)	−0.0114 (5)	0.9668 (3)	0.150 (3)
H15	−0.1438	−0.0656	0.9983	0.180*
C16	0.0740 (13)	0.0530 (4)	0.9752 (2)	0.141 (2)
H16	0.1673	0.0434	1.0123	0.169*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0374 (9)	0.0417 (9)	0.0720 (13)	−0.0060 (8)	−0.0070 (11)	0.0037 (9)
O1	0.0394 (9)	0.0697 (12)	0.141 (2)	−0.0114 (9)	0.0017 (12)	−0.0181 (13)
O2	0.0498 (10)	0.0566 (11)	0.216 (3)	0.0081 (10)	−0.0158 (16)	0.0136 (15)
O3	0.0487 (10)	0.0552 (10)	0.1020 (15)	−0.0087 (9)	−0.0097 (11)	−0.0106 (11)
C1	0.0373 (12)	0.0529 (14)	0.092 (2)	0.0004 (11)	−0.0058 (14)	0.0053 (14)
C2	0.0380 (11)	0.0399 (11)	0.0643 (15)	−0.0073 (9)	−0.0042 (11)	0.0021 (11)
C3	0.0602 (17)	0.0639 (16)	0.0705 (17)	−0.0014 (14)	−0.0103 (15)	−0.0056 (13)
C4	0.092 (2)	0.092 (2)	0.074 (2)	−0.013 (2)	−0.017 (2)	0.0204 (18)
C5	0.0700 (19)	0.0546 (15)	0.090 (2)	−0.0071 (15)	−0.0170 (17)	0.0217 (15)
C6	0.0366 (12)	0.0527 (14)	0.088 (2)	0.0007 (12)	0.0019 (13)	−0.0123 (14)
C7	0.0496 (13)	0.0491 (12)	0.0688 (16)	0.0077 (12)	0.0067 (13)	−0.0095 (12)
C8	0.0563 (15)	0.0502 (14)	0.0743 (17)	0.0093 (12)	−0.0031 (15)	−0.0180 (13)
C9	0.092 (2)	0.080 (2)	0.088 (2)	0.025 (2)	−0.032 (2)	−0.0338 (19)
C10	0.157 (4)	0.095 (3)	0.066 (2)	0.050 (3)	−0.029 (3)	−0.030 (2)
C11	0.158 (4)	0.074 (2)	0.057 (2)	0.044 (3)	0.021 (2)	−0.0084 (18)
C12	0.083 (2)	0.0533 (15)	0.084 (2)	0.0153 (16)	0.0335 (19)	−0.0103 (14)
C13	0.093 (3)	0.0634 (17)	0.141 (3)	0.0041 (18)	0.066 (3)	0.000 (2)
C14	0.146 (4)	0.071 (2)	0.193 (5)	0.013 (3)	0.104 (5)	0.004 (3)
C15	0.221 (7)	0.104 (4)	0.126 (4)	0.030 (5)	0.098 (5)	0.000 (3)
C16	0.257 (8)	0.097 (3)	0.070 (2)	0.065 (4)	0.048 (4)	−0.004 (2)

Geometric parameters (Å, º)

N1—C5	1.487 (3)	C6—H6A	0.97
N1—C6	1.502 (3)	C6—H6B	0.97
N1—C2	1.510 (3)	C7—C8	1.378 (4)
N1—H1	0.90 (1)	C7—C12	1.421 (4)
O1—C1	1.222 (3)	C8—C9	1.415 (4)
O2—C1	1.239 (3)	C9—C10	1.351 (5)
O3—C8	1.347 (3)	C9—H9	0.93
O3—H3	0.86 (1)	C10—C11	1.389 (6)
C1—C2	1.531 (3)	C10—H10	0.93
C2—C3	1.515 (4)	C11—C12	1.427 (5)
C2—H2	0.98	C11—C16	1.432 (6)
C3—C4	1.524 (4)	C12—C13	1.416 (5)
C3—H3A	0.97	C13—C14	1.393 (6)
C3—H3B	0.97	C13—H13	0.93
C4—C5	1.498 (4)	C14—C15	1.370 (8)
C4—H4A	0.97	C14—H14	0.93
C4—H4B	0.97	C15—C16	1.339 (8)
C5—H5A	0.97	C15—H15	0.93
C5—H5B	0.97	C16—H16	0.93
C6—C7	1.482 (4)
C5—N1—C6	112.1 (2)	C7—C6—H6A	109.3
C5—N1—C2	107.8 (2)	N1—C6—H6A	109.3
C6—N1—C2	115.84 (19)	C7—C6—H6B	109.3
C5—N1—H1	111.3 (16)	N1—C6—H6B	109.3
C6—N1—H1	105.7 (16)	H6A—C6—H6B	107.9
C2—N1—H1	103.8 (15)	C8—C7—C12	119.6 (3)
C8—O3—H3	112 (2)	C8—C7—C6	116.4 (2)
O1—C1—O2	127.6 (3)	C12—C7—C6	124.0 (3)
O1—C1—C2	117.8 (2)	O3—C8—C7	117.9 (3)
O2—C1—C2	114.5 (2)	O3—C8—C9	121.0 (3)
N1—C2—C3	104.87 (19)	C7—C8—C9	121.2 (3)
N1—C2—C1	107.96 (18)	C10—C9—C8	119.0 (4)
C3—C2—C1	112.7 (2)	C10—C9—H9	120.5
N1—C2—H2	110.4	C8—C9—H9	120.5
C3—C2—H2	110.4	C9—C10—C11	122.4 (4)
C1—C2—H2	110.4	C9—C10—H10	118.8
C2—C3—C4	103.2 (2)	C11—C10—H10	118.8
C2—C3—H3A	111.1	C10—C11—C12	119.3 (3)
C4—C3—H3A	111.1	C10—C11—C16	122.2 (5)
C2—C3—H3B	111.1	C12—C11—C16	118.5 (5)
C4—C3—H3B	111.1	C13—C12—C7	122.9 (3)
H3A—C3—H3B	109.1	C13—C12—C11	118.6 (4)
C5—C4—C3	102.4 (2)	C7—C12—C11	118.5 (3)
C5—C4—H4A	111.3	C14—C13—C12	120.0 (5)
C3—C4—H4A	111.3	C14—C13—H13	120.0
C5—C4—H4B	111.3	C12—C13—H13	120.0
C3—C4—H4B	111.3	C15—C14—C13	120.1 (6)
H4A—C4—H4B	109.2	C15—C14—H14	119.9
N1—C5—C4	103.3 (2)	C13—C14—H14	119.9
N1—C5—H5A	111.1	C16—C15—C14	122.5 (6)
C4—C5—H5A	111.1	C16—C15—H15	118.7
N1—C5—H5B	111.1	C14—C15—H15	118.7
C4—C5—H5B	111.1	C15—C16—C11	120.2 (6)
H5A—C5—H5B	109.1	C15—C16—H16	119.9
C7—C6—N1	111.8 (2)	C11—C16—H16	119.9
C5—N1—C2—C3	0.2 (3)	C6—C7—C8—C9	177.2 (2)
C6—N1—C2—C3	126.6 (2)	O3—C8—C9—C10	179.8 (3)
C5—N1—C2—C1	120.6 (2)	C7—C8—C9—C10	0.1 (4)
C6—N1—C2—C1	−113.0 (2)	C8—C9—C10—C11	1.4 (5)
O1—C1—C2—N1	−9.0 (4)	C9—C10—C11—C12	−1.5 (5)
O2—C1—C2—N1	174.2 (3)	C9—C10—C11—C16	−179.9 (4)
O1—C1—C2—C3	106.4 (3)	C8—C7—C12—C13	−179.8 (2)
O2—C1—C2—C3	−70.5 (3)	C6—C7—C12—C13	1.7 (4)
N1—C2—C3—C4	25.1 (3)	C8—C7—C12—C11	1.3 (4)
C1—C2—C3—C4	−92.1 (3)	C6—C7—C12—C11	−177.2 (2)
C2—C3—C4—C5	−41.2 (3)	C10—C11—C12—C13	−178.9 (3)
C6—N1—C5—C4	−154.4 (2)	C16—C11—C12—C13	−0.4 (4)
C2—N1—C5—C4	−25.8 (3)	C10—C11—C12—C7	0.1 (4)
C3—C4—C5—N1	41.1 (3)	C16—C11—C12—C7	178.6 (3)
C5—N1—C6—C7	−165.4 (2)	C7—C12—C13—C14	−177.9 (3)
C2—N1—C6—C7	70.4 (3)	C11—C12—C13—C14	1.0 (4)
N1—C6—C7—C8	68.8 (3)	C12—C13—C14—C15	−1.5 (6)
N1—C6—C7—C12	−112.7 (3)	C13—C14—C15—C16	1.3 (8)
C12—C7—C8—O3	178.9 (2)	C14—C15—C16—C11	−0.6 (8)
C6—C7—C8—O3	−2.5 (3)	C10—C11—C16—C15	178.6 (4)
C12—C7—C8—C9	−1.4 (4)	C12—C11—C16—C15	0.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.90 (1)	1.99 (2)	2.599 (3)	123 (2)
N1—H1···O3	0.90 (1)	2.28 (2)	2.892 (3)	124 (2)
O3—H3···O2^i	0.86 (1)	1.73 (1)	2.586 (3)	175 (4)

Symmetry code: (i) −x+1, y+1/2, −z+3/2.