Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103013349/ga1021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103013349/ga1021Isup2.hkl |
CCDC reference: 219588
(1R,3S)-1-Monoamide-camphoric acid was synthesized successfully from D-(+)-camphoric imide via a simplified version of the method reported by Noyes (1894). Treatment of D-(+)-camphoric imide (1.81 g, 10 mmol) with sodium hydroxide (2.0 g, 50 mmol) in water under reflux for 2 h gave a solution of the sodium salt of (1R,3S)-1-monoamide-camphoric acid. After being cooled to room temperature, the mixture was carefully acidified with hydrochloric acid (2 mol l−1), and the resulting white precipitates [(1R,3S)-1-monoamide-camphoric acid] were collected and recrystallized in ethanol/water (yield 1.22 g, 61.3%; m.p. 452–454 K. Analysis calculated for C10H17NO3: C 60.28, H 8.60, N 7.03; found: C 59.91, H 8.60, N 6.93. Main FT–IR (KBr plates, cm−1): 3475, 3415, 3224, 3235, 3195, 2982, 2971, 1709, 1693, 1644 and 1389 (all strong peaks); 1H NMR (d6-DMSO): δ 0.74 (s, 3H, Me), 1.08 (s, 3H, Me), 1.18 (s, 3H, Me), 1.43 (m, 1H, CH2), 1.65 (m, 1H, CH2), 1.98 (t, 1H, CH2), 2.39 (t, 1H, CH2), 2.63 (t, 1H, CH), 3.29 (s, 2H, CONH2), 6.65 (s, 1H, COOH); 13C NMR (d6-DMSO): δ 26.36, 26.94, 27.68, 28.48, 37.86, 51.39, 57.70, 60.77, 180.83, 182.85; Es-ms: m/z [C10H17NO3H]+ 200 (100%). [α]D20 = + 73.3° (C = 1 g/100 mL, C2H5OH). Elemental analysis was performed with a Perkin-Elmer 1400 C analyzer, IR spectra (4000–400 cm−1) were recorded on a Nicolet FT–IR 170X spectrophotometer, NMR spectra were obtained with a Bruker 500 MHz NMR spectrometer, electrospray ionization mass spectra were obtained with a Finnigan MAT SSQ 710 mass spectrometer in a scan range 300–1200 a.m.u. and the optical rotation values were determined via a WZZ-115 digital auto-polarimeter.
The positions of all H atoms were fixed geometrically with C—H distances of 0.96 Å, N—H distances of 0.86 Å and O—H distances of 0.85 Å.
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.
C10H17NO3 | F(000) = 864 |
Mr = 199.25 | Dx = 1.242 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 871 reflections |
a = 10.400 (2) Å | θ = 2.8–20.1° |
b = 12.810 (3) Å | µ = 0.09 mm−1 |
c = 16.000 (3) Å | T = 293 K |
V = 2131.6 (8) Å3 | Slab, colorless |
Z = 8 | 0.40 × 0.30 × 0.20 mm |
Bruker CCD area-detector diffractometer | 2873 independent reflections |
Radiation source: fine-focus sealed tube | 1653 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
ϕ and ω scans | θmax = 28.1°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −13→13 |
Tmin = 0.968, Tmax = 0.982 | k = −16→16 |
12841 measured reflections | l = −14→20 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 0.87 | w = 1/[σ2(Fo2) + (0.0396P)2] where P = (Fo2 + 2Fc2)/3 |
2873 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C10H17NO3 | V = 2131.6 (8) Å3 |
Mr = 199.25 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.400 (2) Å | µ = 0.09 mm−1 |
b = 12.810 (3) Å | T = 293 K |
c = 16.000 (3) Å | 0.40 × 0.30 × 0.20 mm |
Bruker CCD area-detector diffractometer | 2873 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1653 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.982 | Rint = 0.078 |
12841 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.16 e Å−3 |
2873 reflections | Δρmin = −0.19 e Å−3 |
253 parameters |
Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses. |
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 | 0.7058 (2) | 0.3940 (2) | 0.84114 (15) | 0.0354 (6) | |
C2 | 0.7895 (2) | 0.4071 (2) | 0.92181 (15) | 0.0335 (6) | |
C3 | 0.7271 (2) | 0.3249 (2) | 0.98221 (15) | 0.0374 (7) | |
H3A | 0.7711 | 0.2583 | 0.9727 | 0.045* | |
C4 | 0.5875 (3) | 0.3111 (2) | 0.95373 (16) | 0.0511 (8) | |
H4A | 0.5710 | 0.2388 | 0.9392 | 0.061* | |
H4B | 0.5287 | 0.3315 | 0.9979 | 0.061* | |
C5 | 0.5703 (3) | 0.3810 (3) | 0.87756 (16) | 0.0481 (8) | |
H5A | 0.5348 | 0.4481 | 0.8936 | 0.058* | |
H5B | 0.5134 | 0.3487 | 0.8371 | 0.058* | |
C6 | 0.7469 (2) | 0.3530 (2) | 1.07212 (17) | 0.0350 (7) | |
C7 | 0.7197 (3) | 0.4848 (2) | 0.78110 (16) | 0.0359 (7) | |
C8 | 0.7417 (3) | 0.2972 (3) | 0.79094 (19) | 0.0640 (10) | |
H8A | 0.6879 | 0.2927 | 0.7424 | 0.096* | |
H8B | 0.7299 | 0.2362 | 0.8249 | 0.096* | |
H8C | 0.8301 | 0.3019 | 0.7740 | 0.096* | |
C9 | 0.7768 (3) | 0.5183 (2) | 0.95574 (17) | 0.0504 (8) | |
H9A | 0.8158 | 0.5663 | 0.9173 | 0.076* | |
H9B | 0.8191 | 0.5230 | 1.0089 | 0.076* | |
H9C | 0.6874 | 0.5353 | 0.9623 | 0.076* | |
C10 | 0.9322 (2) | 0.3846 (3) | 0.91017 (17) | 0.0612 (10) | |
H10A | 0.9688 | 0.4355 | 0.8732 | 0.092* | |
H10B | 0.9429 | 0.3162 | 0.8867 | 0.092* | |
H10C | 0.9748 | 0.3879 | 0.9633 | 0.092* | |
C11 | 0.2475 (2) | 0.3869 (2) | 0.66828 (16) | 0.0384 (7) | |
C12 | 0.1953 (2) | 0.4103 (2) | 0.57783 (15) | 0.0352 (7) | |
C13 | 0.2649 (2) | 0.3239 (2) | 0.52581 (15) | 0.0359 (7) | |
H13A | 0.2126 | 0.2604 | 0.5290 | 0.043* | |
C14 | 0.3926 (3) | 0.3016 (2) | 0.56983 (17) | 0.0531 (9) | |
H14A | 0.4019 | 0.2274 | 0.5805 | 0.064* | |
H14B | 0.4642 | 0.3246 | 0.5357 | 0.064* | |
C15 | 0.3884 (3) | 0.3622 (3) | 0.65165 (17) | 0.0618 (10) | |
H15A | 0.4380 | 0.4261 | 0.6470 | 0.074* | |
H15B | 0.4238 | 0.3206 | 0.6968 | 0.074* | |
C16 | 0.2799 (3) | 0.3517 (2) | 0.43490 (18) | 0.0416 (7) | |
C17 | 0.2343 (3) | 0.4803 (2) | 0.72694 (16) | 0.0376 (7) | |
C18 | 0.1822 (3) | 0.2933 (2) | 0.70927 (19) | 0.0694 (11) | |
H18A | 0.2178 | 0.2824 | 0.7639 | 0.104* | |
H18B | 0.1961 | 0.2322 | 0.6757 | 0.104* | |
H18C | 0.0916 | 0.3064 | 0.7139 | 0.104* | |
C19 | 0.2370 (3) | 0.5190 (2) | 0.55021 (19) | 0.0628 (10) | |
H19A | 0.2044 | 0.5327 | 0.4952 | 0.094* | |
H19B | 0.3291 | 0.5227 | 0.5496 | 0.094* | |
H19C | 0.2036 | 0.5699 | 0.5885 | 0.094* | |
C20 | 0.0497 (2) | 0.4005 (3) | 0.56911 (17) | 0.0626 (10) | |
H20A | 0.0251 | 0.4158 | 0.5126 | 0.094* | |
H20B | 0.0085 | 0.4487 | 0.6063 | 0.094* | |
H20D | 0.0239 | 0.3306 | 0.5829 | 0.094* | |
N1 | 0.6154 (2) | 0.53641 (19) | 0.75811 (14) | 0.0482 (7) | |
H1A | 0.6212 | 0.5866 | 0.7226 | 0.058* | |
H1B | 0.5418 | 0.5198 | 0.7786 | 0.058* | |
N2 | 0.1173 (2) | 0.5117 (2) | 0.74708 (13) | 0.0510 (7) | |
H2A | 0.1071 | 0.5627 | 0.7815 | 0.061* | |
H2B | 0.0513 | 0.4813 | 0.7258 | 0.061* | |
O1 | 0.84661 (18) | 0.33983 (17) | 1.10820 (11) | 0.0574 (6) | |
O2 | 0.64617 (17) | 0.39390 (17) | 1.10895 (11) | 0.0541 (6) | |
H1 | 0.6646 | 0.4076 | 1.1595 | 0.081* | |
O3 | 0.82536 (17) | 0.50865 (16) | 0.75165 (11) | 0.0486 (5) | |
O4 | 0.38118 (19) | 0.36362 (19) | 0.39985 (12) | 0.0630 (7) | |
O5 | 0.16833 (18) | 0.36150 (17) | 0.39614 (11) | 0.0539 (6) | |
H2 | 0.1765 | 0.3977 | 0.3431 | 0.081* | |
O6 | 0.32943 (17) | 0.52418 (16) | 0.75759 (12) | 0.0497 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0440 (16) | 0.0342 (17) | 0.0280 (15) | −0.0040 (14) | −0.0026 (12) | 0.0026 (13) |
C2 | 0.0344 (14) | 0.0385 (17) | 0.0277 (14) | −0.0019 (13) | −0.0018 (11) | 0.0048 (13) |
C3 | 0.0518 (17) | 0.0318 (17) | 0.0287 (16) | −0.0001 (14) | −0.0006 (13) | −0.0002 (13) |
C4 | 0.0604 (19) | 0.059 (2) | 0.0339 (17) | −0.0238 (16) | −0.0050 (15) | 0.0088 (15) |
C5 | 0.0455 (17) | 0.064 (2) | 0.0350 (16) | −0.0162 (15) | −0.0077 (13) | 0.0071 (16) |
C6 | 0.0405 (17) | 0.0363 (17) | 0.0282 (15) | 0.0056 (13) | 0.0031 (12) | 0.0040 (13) |
C7 | 0.0360 (16) | 0.0434 (19) | 0.0282 (15) | −0.0002 (14) | −0.0047 (13) | 0.0017 (13) |
C8 | 0.107 (3) | 0.049 (2) | 0.0361 (19) | 0.001 (2) | −0.0041 (18) | −0.0085 (16) |
C9 | 0.074 (2) | 0.0398 (19) | 0.0368 (17) | −0.0102 (17) | −0.0079 (15) | 0.0034 (15) |
C10 | 0.0464 (18) | 0.087 (3) | 0.050 (2) | 0.0061 (18) | 0.0009 (15) | 0.025 (2) |
C11 | 0.0441 (16) | 0.0428 (19) | 0.0282 (15) | 0.0043 (14) | −0.0067 (12) | 0.0004 (14) |
C12 | 0.0404 (16) | 0.0363 (17) | 0.0290 (15) | 0.0038 (14) | −0.0056 (12) | 0.0000 (13) |
C13 | 0.0447 (16) | 0.0342 (17) | 0.0289 (16) | 0.0015 (13) | −0.0022 (13) | 0.0002 (13) |
C14 | 0.0571 (19) | 0.064 (2) | 0.0380 (18) | 0.0246 (17) | −0.0072 (15) | −0.0107 (16) |
C15 | 0.0570 (19) | 0.090 (3) | 0.0385 (18) | 0.0332 (19) | −0.0135 (15) | −0.0216 (18) |
C16 | 0.0506 (18) | 0.0396 (19) | 0.0348 (17) | 0.0026 (15) | −0.0048 (15) | −0.0048 (14) |
C17 | 0.0422 (17) | 0.047 (2) | 0.0235 (15) | 0.0072 (15) | 0.0010 (13) | −0.0024 (14) |
C18 | 0.121 (3) | 0.044 (2) | 0.043 (2) | 0.004 (2) | 0.012 (2) | 0.0063 (16) |
C19 | 0.103 (3) | 0.040 (2) | 0.0451 (19) | −0.0003 (19) | 0.0040 (18) | 0.0027 (16) |
C20 | 0.0474 (18) | 0.091 (3) | 0.0496 (19) | 0.0116 (19) | −0.0103 (14) | −0.022 (2) |
N1 | 0.0389 (13) | 0.0588 (17) | 0.0470 (16) | −0.0003 (12) | 0.0052 (12) | 0.0212 (13) |
N2 | 0.0390 (14) | 0.0676 (18) | 0.0464 (15) | −0.0016 (13) | −0.0006 (11) | −0.0219 (15) |
O1 | 0.0494 (13) | 0.0886 (17) | 0.0343 (12) | 0.0252 (12) | −0.0067 (10) | −0.0116 (12) |
O2 | 0.0485 (12) | 0.0762 (16) | 0.0377 (12) | 0.0144 (12) | −0.0054 (9) | −0.0156 (12) |
O3 | 0.0358 (11) | 0.0708 (15) | 0.0393 (12) | 0.0001 (10) | 0.0023 (9) | 0.0204 (11) |
O4 | 0.0512 (13) | 0.0928 (18) | 0.0449 (13) | 0.0071 (12) | 0.0094 (10) | 0.0161 (12) |
O5 | 0.0492 (12) | 0.0808 (16) | 0.0319 (11) | −0.0081 (11) | −0.0070 (10) | 0.0078 (11) |
O6 | 0.0375 (11) | 0.0653 (14) | 0.0462 (13) | −0.0050 (10) | −0.0006 (10) | −0.0193 (12) |
C1—C7 | 1.516 (4) | C11—C12 | 1.575 (3) |
C1—C8 | 1.524 (4) | C12—C19 | 1.523 (4) |
C1—C5 | 1.534 (4) | C12—C20 | 1.525 (4) |
C1—C2 | 1.566 (3) | C12—C13 | 1.563 (4) |
C2—C10 | 1.523 (4) | C13—C16 | 1.506 (4) |
C2—C9 | 1.530 (4) | C13—C14 | 1.530 (3) |
C2—C3 | 1.569 (4) | C13—H13A | 0.9800 |
C3—C6 | 1.497 (4) | C14—C15 | 1.522 (4) |
C3—C4 | 1.532 (4) | C14—H14A | 0.9700 |
C3—H3A | 0.9800 | C14—H14B | 0.9700 |
C4—C5 | 1.523 (4) | C15—H15A | 0.9700 |
C4—H4A | 0.9700 | C15—H15B | 0.9700 |
C4—H4B | 0.9700 | C16—O4 | 1.203 (3) |
C5—H5A | 0.9700 | C16—O5 | 1.322 (3) |
C5—H5B | 0.9700 | C17—O6 | 1.239 (3) |
C6—O1 | 1.199 (3) | C17—N2 | 1.322 (3) |
C6—O2 | 1.311 (3) | C18—H18A | 0.9600 |
C7—O3 | 1.234 (3) | C18—H18B | 0.9600 |
C7—N1 | 1.323 (3) | C18—H18C | 0.9600 |
C8—H8A | 0.9600 | C19—H19A | 0.9600 |
C8—H8B | 0.9600 | C19—H19B | 0.9600 |
C8—H8C | 0.9600 | C19—H19C | 0.9600 |
C9—H9A | 0.9600 | C20—H20A | 0.9600 |
C9—H9B | 0.9600 | C20—H20B | 0.9600 |
C9—H9C | 0.9600 | C20—H20D | 0.9600 |
C10—H10A | 0.9600 | N1—H1A | 0.8600 |
C10—H10B | 0.9600 | N1—H1B | 0.8600 |
C10—H10C | 0.9600 | N2—H2A | 0.8600 |
C11—C15 | 1.523 (4) | N2—H2B | 0.8600 |
C11—C18 | 1.526 (4) | O2—H1 | 0.8500 |
C11—C17 | 1.527 (4) | O5—H2 | 0.9711 |
C7—C1—C8 | 105.5 (2) | C18—C11—C12 | 113.0 (2) |
C7—C1—C5 | 114.3 (2) | C17—C11—C12 | 112.6 (2) |
C8—C1—C5 | 109.7 (2) | C19—C12—C20 | 109.4 (2) |
C7—C1—C2 | 112.8 (2) | C19—C12—C13 | 111.2 (2) |
C8—C1—C2 | 112.7 (2) | C20—C12—C13 | 110.6 (2) |
C5—C1—C2 | 102.1 (2) | C19—C12—C11 | 110.0 (2) |
C10—C2—C9 | 107.7 (2) | C20—C12—C11 | 114.3 (2) |
C10—C2—C1 | 114.9 (2) | C13—C12—C11 | 101.2 (2) |
C9—C2—C1 | 110.1 (2) | C16—C13—C14 | 113.5 (2) |
C10—C2—C3 | 110.5 (2) | C16—C13—C12 | 113.3 (2) |
C9—C2—C3 | 111.7 (2) | C14—C13—C12 | 106.8 (2) |
C1—C2—C3 | 101.9 (2) | C16—C13—H13A | 107.7 |
C6—C3—C4 | 116.4 (2) | C14—C13—H13A | 107.7 |
C6—C3—C2 | 111.9 (2) | C12—C13—H13A | 107.7 |
C4—C3—C2 | 106.6 (2) | C15—C14—C13 | 106.0 (2) |
C6—C3—H3A | 107.2 | C15—C14—H14A | 110.5 |
C4—C3—H3A | 107.2 | C13—C14—H14A | 110.5 |
C2—C3—H3A | 107.2 | C15—C14—H14B | 110.5 |
C5—C4—C3 | 106.3 (2) | C13—C14—H14B | 110.5 |
C5—C4—H4A | 110.5 | H14A—C14—H14B | 108.7 |
C3—C4—H4A | 110.5 | C14—C15—C11 | 106.5 (2) |
C5—C4—H4B | 110.5 | C14—C15—H15A | 110.4 |
C3—C4—H4B | 110.5 | C11—C15—H15A | 110.4 |
H4A—C4—H4B | 108.7 | C14—C15—H15B | 110.4 |
C4—C5—C1 | 105.1 (2) | C11—C15—H15B | 110.4 |
C4—C5—H5A | 110.7 | H15A—C15—H15B | 108.6 |
C1—C5—H5A | 110.7 | O4—C16—O5 | 122.5 (3) |
C4—C5—H5B | 110.7 | O4—C16—C13 | 124.8 (3) |
C1—C5—H5B | 110.7 | O5—C16—C13 | 112.6 (3) |
H5A—C5—H5B | 108.8 | O6—C17—N2 | 120.0 (3) |
O1—C6—O2 | 122.1 (3) | O6—C17—C11 | 121.8 (2) |
O1—C6—C3 | 123.2 (2) | N2—C17—C11 | 118.1 (3) |
O2—C6—C3 | 114.7 (2) | C11—C18—H18A | 109.5 |
O3—C7—N1 | 120.0 (2) | C11—C18—H18B | 109.5 |
O3—C7—C1 | 121.1 (2) | H18A—C18—H18B | 109.5 |
N1—C7—C1 | 118.8 (2) | C11—C18—H18C | 109.5 |
C1—C8—H8A | 109.5 | H18A—C18—H18C | 109.5 |
C1—C8—H8B | 109.5 | H18B—C18—H18C | 109.5 |
H8A—C8—H8B | 109.5 | C12—C19—H19A | 109.5 |
C1—C8—H8C | 109.5 | C12—C19—H19B | 109.5 |
H8A—C8—H8C | 109.5 | H19A—C19—H19B | 109.5 |
H8B—C8—H8C | 109.5 | C12—C19—H19C | 109.5 |
C2—C9—H9A | 109.5 | H19A—C19—H19C | 109.5 |
C2—C9—H9B | 109.5 | H19B—C19—H19C | 109.5 |
H9A—C9—H9B | 109.5 | C12—C20—H20A | 109.5 |
C2—C9—H9C | 109.5 | C12—C20—H20B | 109.5 |
H9A—C9—H9C | 109.5 | H20A—C20—H20B | 109.5 |
H9B—C9—H9C | 109.5 | C12—C20—H20D | 109.5 |
C2—C10—H10A | 109.5 | H20A—C20—H20D | 109.5 |
C2—C10—H10B | 109.5 | H20B—C20—H20D | 109.5 |
H10A—C10—H10B | 109.5 | C7—N1—H1A | 120.0 |
C2—C10—H10C | 109.5 | C7—N1—H1B | 120.0 |
H10A—C10—H10C | 109.5 | H1A—N1—H1B | 120.0 |
H10B—C10—H10C | 109.5 | C17—N2—H2A | 120.0 |
C15—C11—C18 | 109.9 (3) | C17—N2—H2B | 120.0 |
C15—C11—C17 | 110.9 (2) | H2A—N2—H2B | 120.0 |
C18—C11—C17 | 108.1 (2) | C6—O2—H1 | 109.2 |
C15—C11—C12 | 102.2 (2) | C16—O5—H2 | 112.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O3i | 0.85 | 1.83 | 2.619 (3) | 155 |
N1—H1A···O1ii | 0.86 | 2.09 | 2.902 (3) | 158 |
N1—H1B···O6 | 0.86 | 2.23 | 2.978 (3) | 145 |
O5—H2···O6iii | 0.97 | 1.70 | 2.657 (3) | 170 |
N2—H2A···O4iv | 0.86 | 2.12 | 2.920 (3) | 155 |
N2—H2B···O3v | 0.86 | 2.41 | 3.037 (3) | 130 |
C4—H4B···O2 | 0.97 | 2.30 | 2.769 (3) | 109 |
C14—H14B···O4 | 0.97 | 2.39 | 2.836 (4) | 107 |
C20—H20A···O5 | 0.96 | 2.48 | 3.071 (3) | 119 |
C20—H20B···O2iii | 0.96 | 2.58 | 3.391 (4) | 142 |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+3/2, −y+1, z−1/2; (iii) −x+1/2, −y+1, z−1/2; (iv) −x+1/2, −y+1, z+1/2; (v) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C10H17NO3 |
Mr | 199.25 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 10.400 (2), 12.810 (3), 16.000 (3) |
V (Å3) | 2131.6 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.968, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12841, 2873, 1653 |
Rint | 0.078 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.096, 0.87 |
No. of reflections | 2873 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.19 |
Computer programs: SMART (Bruker 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
C1—C2 | 1.566 (3) | C6—O2 | 1.311 (3) |
C2—C3 | 1.569 (4) | C7—O3 | 1.234 (3) |
C6—O1 | 1.199 (3) | C7—N1 | 1.323 (3) |
C1—C2—C3 | 101.9 (2) | O3—C7—N1 | 120.0 (2) |
O1—C6—O2 | 122.1 (3) | O3—C7—C1 | 121.1 (2) |
O1—C6—C3 | 123.2 (2) | N1—C7—C1 | 118.8 (2) |
O2—C6—C3 | 114.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O3i | 0.85 | 1.83 | 2.619 (3) | 155 |
N1—H1A···O1ii | 0.86 | 2.09 | 2.902 (3) | 158 |
N1—H1B···O6 | 0.86 | 2.23 | 2.978 (3) | 145 |
O5—H2···O6iii | 0.97 | 1.70 | 2.657 (3) | 170 |
N2—H2A···O4iv | 0.86 | 2.12 | 2.920 (3) | 155 |
N2—H2B···O3v | 0.86 | 2.41 | 3.037 (3) | 130 |
C4—H4B···O2 | 0.97 | 2.30 | 2.769 (3) | 109 |
C14—H14B···O4 | 0.97 | 2.39 | 2.836 (4) | 107 |
C20—H20A···O5 | 0.96 | 2.48 | 3.071 (3) | 119 |
C20—H20B···O2iii | 0.96 | 2.58 | 3.391 (4) | 142 |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+3/2, −y+1, z−1/2; (iii) −x+1/2, −y+1, z−1/2; (iv) −x+1/2, −y+1, z+1/2; (v) x−1, y, z. |
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Camphoric acids and their derivatives, especially those having specific absolute configurations, are very useful intermediates in organic synthesis (Nieto et al., 1998), and can be used as building blocks in self-assembly studies via coordinative and hydrogen bonds, thus generating interesting topologies and functions. For example, D-(+)-camphoric acid has been used in self-assembly with certain organic acids (Hu et al., 2001) or polyamines (Goswami et al., 2000; Zakaria et al., 2003) by means of hydrogen-bonding interactions.
While racemic 3-monoamidocamphoric acid can be obtained from camphoric anhydride, racemic 1-monoamidocamphoric acid can be prepared from camphoric imide (Noyes, 1894) by a method which has been improved, simplified and further characterized in our experiments. The crystallographic data of the title compound, (I) [also known as (1R,3S)-β-camphoramic acid] is different to that of (1R,3S)-3-monoamidocamphoric acid [or (1R,3S)-α-camphoramic acid], synthesized via an alternative method from (1R,3S)-camphoric acid (Nie et al., 2002). The results of the IR, microanalytical, ES–MS, 1H NMR and 13C NMR analyses of (1R,3S)-β-camphoramic acid and its optical rotation value confirm the formulation and absolute configuration.
The atom-numbering scheme for (I) is shown in Fig. 1, while selected bond distances and angles are given in Table 1. There are two crystallographically independent molecules per asymmetric unit in the orthorhombic chiral space group P212121. The absolute configuration shown is that determined by its optical rotation value [α]D20 = + 73.3° (C = 1, C2H5OH), which is consistent with the value in the literature (CRC Handbook of Chemistry and Physics, 1988–1989). The ring geometies are similar to those of (1R,3S)-3-monoamidocamphoric acid reported by Nie et al. (2002), with elongations of the C—C bonds and C—C—C bond-angle contractions of the `flap' quaternary atoms in the five-membered rings (C2 and C12). Bond lengths related to the carboxylic acid groups also exhibit electron-delocalization because of their conjugate interactions. Changing the positions of the carboxylic acid group and the acylamino group leads to higher values of R1 and wR2 (0.065 and 0.146, respectively) and of the displacement parameters, thus confirming the (1R,3S)-1-monoamidocamphoric acid formulation.
The crystal packing involves three kinds of traditional hydrogen-bonding interactions, as well as weak C—H···O interactions(Table 2). Hydrogen-bonding interactions between the carboxyl and acylamide groups (O2—H1···O3, O5—H2···O6 and N1—H1A···O1, N2—H2A···O4) form eight-membered rings along the c axis. Hydrogen bonds associated with the N and O atoms of adjacent acylamides (N1—H1B···O6 and N2—H2B···O3) along the a axis are also observed. The resulting two-dimensional layers formed are not planar, but form a ripple along the c direction. This is different from the crystal packing of (1R,3S)-3-monoamid-camphoric acid in which a three-dimensional hydrogen-bond-supported framework is found.