The title compound, C14H18ClF2NO2, crystallizes as a single enantiomer, and the absolute configuration for the chiral C atom was confirmed as S. The molecules are efficiently stacked, with no residual void for solvent inclusion.
Supporting information
CCDC reference: 613573
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.004 Å
- R factor = 0.038
- wR factor = 0.091
- Data-to-parameter ratio = 17.6
checkCIF/PLATON results
No syntax errors found
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 27.49
From the CIF: _reflns_number_total 3178
Count of symmetry unique reflns 1974
Completeness (_total/calc) 160.99%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1204
Fraction of Friedel pairs measured 0.610
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
0 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: COLLECT and KappaCCD Server Software (Nonius, 1997–2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2003); software used to prepare material for publication: PLATON and ACD/Labs
(Advanced Chemistry Development, 1994–2004).
tert-Butyl[(1
S)-3-chloro-1-(3,5-difluorophenyl)propyl]carbamate
top
Crystal data top
C14H18ClF2NO2 | F(000) = 640 |
Mr = 305.74 | Dx = 1.386 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 17273 reflections |
a = 5.2216 (2) Å | θ = 1.0–27.5° |
b = 14.3035 (6) Å | µ = 0.28 mm−1 |
c = 19.6163 (8) Å | T = 200 K |
V = 1465.09 (10) Å3 | Needle, colourless |
Z = 4 | 0.60 × 0.03 × 0.03 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1724 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.055 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
φ and ω scans with κ offsets | h = −6→6 |
17273 measured reflections | k = −18→18 |
3178 independent reflections | l = −24→23 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0453P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.85 | (Δ/σ)max < 0.001 |
3178 reflections | Δρmax = 0.15 e Å−3 |
181 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 1268 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.06 (8) |
Special details top
Experimental. Crystals were crystallized from diethyl ether/hexane (1:3) Number of collected
frames: 303 Number of repeats: 1 Crystal-Detector distance (mm): 30 Exposure
time (sec) per frame: 40 Phi-rotation step: 1 |
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user
for potential systematic errors. Weighted R-factors wR and all
goodnesses of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The observed criterion of F2 > σ(F2)
is used only for calculating -R-factor-obs etc. and is not
relevant to the choice of reflections for refinement. R-factors based
on F2are 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 | |
Cl1 | 0.42779 (16) | −0.20447 (5) | 0.34454 (4) | 0.0525 (3) | |
F11 | 0.8635 (3) | 0.32196 (11) | 0.32064 (8) | 0.0612 (6) | |
F12 | 0.1426 (3) | 0.23604 (12) | 0.44816 (8) | 0.0664 (7) | |
O15 | 0.1001 (4) | 0.04220 (13) | 0.19638 (9) | 0.0426 (7) | |
O16 | 0.3947 (3) | 0.04197 (12) | 0.10971 (9) | 0.0395 (6) | |
N13 | 0.5248 (4) | 0.01423 (15) | 0.21448 (10) | 0.0362 (8) | |
C2 | 0.6968 (6) | −0.15215 (19) | 0.30147 (14) | 0.0446 (10) | |
C3 | 0.7177 (5) | −0.04925 (18) | 0.31808 (14) | 0.0385 (9) | |
C4 | 0.5018 (5) | 0.01091 (18) | 0.28888 (12) | 0.0354 (9) | |
C5 | 0.5008 (5) | 0.1071 (2) | 0.32173 (12) | 0.0374 (9) | |
C6 | 0.6884 (6) | 0.17224 (19) | 0.30540 (14) | 0.0415 (10) | |
C7 | 0.6816 (6) | 0.2581 (2) | 0.33760 (15) | 0.0449 (10) | |
C8 | 0.5027 (6) | 0.2829 (2) | 0.38531 (14) | 0.0474 (11) | |
C9 | 0.3249 (6) | 0.2155 (2) | 0.40091 (13) | 0.0465 (10) | |
C10 | 0.3175 (6) | 0.1293 (2) | 0.37007 (13) | 0.0428 (10) | |
C14 | 0.3197 (6) | 0.03449 (18) | 0.17535 (14) | 0.0359 (10) | |
C17 | 0.2055 (5) | 0.0592 (2) | 0.05433 (14) | 0.0394 (10) | |
C18 | 0.0624 (6) | 0.14954 (19) | 0.06702 (14) | 0.0530 (11) | |
C19 | 0.0312 (6) | −0.0245 (2) | 0.04703 (15) | 0.0494 (10) | |
C20 | 0.3822 (6) | 0.0684 (2) | −0.00697 (14) | 0.0563 (11) | |
H2A | 0.67470 | −0.16000 | 0.25320 | 0.0540* | |
H2B | 0.85030 | −0.18350 | 0.31570 | 0.0540* | |
H3A | 0.71500 | −0.04080 | 0.36660 | 0.0460* | |
H3B | 0.87530 | −0.02500 | 0.30000 | 0.0460* | |
H4 | 0.34020 | −0.01760 | 0.29940 | 0.0430* | |
H6 | 0.81720 | 0.15730 | 0.27220 | 0.0500* | |
H8 | 0.50980 | 0.34390 | 0.40570 | 0.0570* | |
H10 | 0.18980 | 0.08340 | 0.38120 | 0.0510* | |
H13 | 0.67480 | 0.01780 | 0.19790 | 0.0430* | |
H18A | −0.05890 | 0.16010 | 0.03110 | 0.0640* | |
H18B | 0.18300 | 0.20010 | 0.06830 | 0.0640* | |
H18C | −0.02620 | 0.14590 | 0.10980 | 0.0640* | |
H19A | −0.08990 | −0.01300 | 0.01110 | 0.0590* | |
H19B | −0.05870 | −0.03450 | 0.08910 | 0.0590* | |
H19C | 0.13050 | −0.07900 | 0.03620 | 0.0590* | |
H20A | 0.28220 | 0.08000 | −0.04710 | 0.0670* | |
H20B | 0.47810 | 0.01170 | −0.01270 | 0.0670* | |
H20C | 0.49800 | 0.11960 | 0.00030 | 0.0670* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0527 (5) | 0.0471 (4) | 0.0578 (5) | −0.0044 (4) | 0.0068 (4) | 0.0038 (4) |
F11 | 0.0586 (12) | 0.0498 (10) | 0.0751 (11) | −0.0145 (9) | 0.0071 (10) | −0.0036 (9) |
F12 | 0.0638 (12) | 0.0783 (14) | 0.0571 (10) | 0.0065 (10) | 0.0163 (10) | −0.0163 (9) |
O15 | 0.0300 (11) | 0.0549 (12) | 0.0429 (11) | 0.0059 (10) | 0.0007 (10) | −0.0002 (9) |
O16 | 0.0327 (10) | 0.0576 (12) | 0.0281 (10) | 0.0057 (10) | −0.0040 (9) | 0.0043 (8) |
N13 | 0.0272 (13) | 0.0501 (14) | 0.0313 (13) | 0.0014 (11) | −0.0012 (10) | −0.0002 (10) |
C2 | 0.0380 (17) | 0.0484 (19) | 0.0475 (18) | 0.0027 (15) | 0.0056 (15) | 0.0067 (15) |
C3 | 0.0327 (15) | 0.0476 (18) | 0.0353 (16) | 0.0008 (14) | −0.0025 (13) | 0.0057 (13) |
C4 | 0.0322 (16) | 0.0417 (16) | 0.0324 (15) | 0.0016 (13) | 0.0004 (12) | 0.0022 (12) |
C5 | 0.0370 (17) | 0.0465 (17) | 0.0288 (14) | 0.0007 (14) | −0.0063 (14) | 0.0052 (12) |
C6 | 0.0391 (17) | 0.0474 (19) | 0.0379 (16) | 0.0019 (15) | 0.0042 (14) | 0.0047 (14) |
C7 | 0.0408 (17) | 0.0455 (19) | 0.0483 (18) | −0.0074 (16) | 0.0008 (16) | 0.0043 (15) |
C8 | 0.0527 (19) | 0.0458 (19) | 0.0436 (17) | 0.0015 (17) | −0.0031 (16) | −0.0046 (15) |
C9 | 0.0410 (17) | 0.064 (2) | 0.0345 (17) | 0.0104 (18) | 0.0030 (15) | −0.0050 (16) |
C10 | 0.0445 (18) | 0.0489 (19) | 0.0351 (17) | −0.0005 (15) | 0.0025 (15) | 0.0043 (13) |
C14 | 0.0359 (18) | 0.0345 (16) | 0.0372 (17) | 0.0004 (14) | −0.0004 (14) | 0.0003 (12) |
C17 | 0.0332 (15) | 0.0476 (19) | 0.0375 (16) | 0.0032 (15) | −0.0082 (15) | 0.0026 (14) |
C18 | 0.0526 (19) | 0.0477 (19) | 0.0587 (19) | 0.0086 (17) | −0.0131 (18) | 0.0039 (15) |
C19 | 0.0416 (17) | 0.060 (2) | 0.0466 (17) | 0.0025 (16) | −0.0106 (15) | −0.0026 (14) |
C20 | 0.055 (2) | 0.080 (2) | 0.0338 (17) | −0.0002 (18) | −0.0053 (17) | 0.0052 (15) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.802 (3) | C17—C20 | 1.521 (4) |
F11—C7 | 1.359 (3) | C17—C18 | 1.513 (4) |
F12—C9 | 1.361 (3) | C2—H2A | 0.9605 |
O15—C14 | 1.224 (4) | C2—H2B | 0.9599 |
O16—C14 | 1.350 (3) | C3—H3A | 0.9595 |
O16—C17 | 1.489 (3) | C3—H3B | 0.9609 |
N13—C4 | 1.465 (3) | C4—H4 | 0.9596 |
N13—C14 | 1.349 (4) | C6—H6 | 0.9603 |
N13—H13 | 0.8496 | C8—H8 | 0.9605 |
C2—C3 | 1.511 (4) | C10—H10 | 0.9609 |
C3—C4 | 1.530 (4) | C18—H18A | 0.9594 |
C4—C5 | 1.519 (4) | C18—H18B | 0.9593 |
C5—C6 | 1.389 (4) | C18—H18C | 0.9597 |
C5—C10 | 1.384 (4) | C19—H19A | 0.9611 |
C6—C7 | 1.381 (4) | C19—H19B | 0.9601 |
C7—C8 | 1.369 (4) | C19—H19C | 0.9600 |
C8—C9 | 1.373 (4) | C20—H20A | 0.9591 |
C9—C10 | 1.374 (4) | C20—H20B | 0.9598 |
C17—C19 | 1.511 (4) | C20—H20C | 0.9604 |
| | | |
Cl1···C6i | 3.483 (3) | C14···H18C | 2.7304 |
Cl1···H4 | 2.8527 | C14···H19B | 2.7821 |
Cl1···H20Aii | 2.9816 | C20···H19Av | 3.0132 |
Cl1···H2Biii | 3.0827 | H2A···N13 | 2.7203 |
Cl1···H18Bi | 2.9861 | H2A···F11ix | 2.8247 |
Cl1···H18Civ | 3.1273 | H2A···C7i | 2.8295 |
F11···C9v | 3.256 (3) | H2A···C8i | 2.9845 |
F11···O15vi | 3.174 (2) | H2B···Cl1v | 3.0827 |
F11···C2vii | 3.339 (3) | H3B···O15v | 2.5364 |
F11···C14vi | 3.188 (3) | H3B···C6 | 2.9871 |
F12···C7iii | 3.255 (3) | H3B···H4v | 2.4299 |
F12···C8viii | 3.358 (3) | H3B···H13 | 2.3414 |
F11···H2Avii | 2.8247 | H4···Cl1 | 2.8527 |
O15···N13iii | 3.051 (3) | H4···O15 | 2.5273 |
O15···C3iii | 3.376 (3) | H4···H3Biii | 2.4299 |
O15···C5 | 3.359 (3) | H4···H10 | 2.2975 |
O15···C18 | 2.972 (3) | H6···O15v | 2.6654 |
O15···C19 | 3.102 (3) | H6···N13 | 2.7930 |
O15···F11i | 3.174 (2) | H6···H13 | 2.5804 |
O15···H4 | 2.5273 | H8···O16vi | 2.8925 |
O15···H6iii | 2.6654 | H8···H19Cvi | 2.4582 |
O15···H3Biii | 2.5364 | H10···H4 | 2.2975 |
O15···H18C | 2.3494 | H13···O15v | 2.2482 |
O15···H19B | 2.5139 | H13···C6 | 3.0548 |
O15···H13iii | 2.2482 | H13···H3B | 2.3414 |
O16···H8i | 2.8925 | H13···H6 | 2.5804 |
N13···O15v | 3.051 (3) | H18A···H19A | 2.5120 |
N13···H2A | 2.7203 | H18A···H20Ciii | 2.4604 |
N13···H6 | 2.7930 | H18B···H20C | 2.4105 |
C2···F11ix | 3.339 (3) | H18B···Cl1vi | 2.9861 |
C3···O15v | 3.376 (3) | H18C···O15 | 2.3494 |
C5···O15 | 3.359 (3) | H18C···C14 | 2.7304 |
C6···C10v | 3.575 (4) | H18C···Cl1xi | 3.1273 |
C6···Cl1vi | 3.483 (3) | H19A···C20iii | 3.0132 |
C7···F12v | 3.255 (3) | H19A···H18A | 2.5120 |
C8···F12x | 3.358 (3) | H19A···H20Biii | 2.3305 |
C9···F11iii | 3.256 (3) | H19B···O15 | 2.5139 |
C10···C6iii | 3.575 (4) | H19B···C14 | 2.7821 |
C14···F11i | 3.188 (3) | H19C···H20B | 2.4285 |
C18···O15 | 2.972 (3) | H19C···H8i | 2.4582 |
C19···O15 | 3.102 (3) | H20A···Cl1xii | 2.9816 |
C6···H3B | 2.9871 | H20B···H19Av | 2.3305 |
C6···H13 | 3.0548 | H20B···H19C | 2.4285 |
C7···H2Avi | 2.8295 | H20C···H18Av | 2.4604 |
C8···H2Avi | 2.9845 | H20C···H18B | 2.4105 |
| | | |
C14—O16—C17 | 121.1 (2) | H2A—C2—H2B | 109.41 |
C4—N13—C14 | 120.6 (2) | C2—C3—H3A | 109.60 |
C4—N13—H13 | 117.31 | C2—C3—H3B | 109.50 |
C14—N13—H13 | 120.07 | C4—C3—H3A | 106.84 |
Cl1—C2—C3 | 111.1 (2) | C4—C3—H3B | 106.85 |
C2—C3—C4 | 114.5 (2) | H3A—C3—H3B | 109.47 |
N13—C4—C5 | 113.2 (2) | N13—C4—H4 | 107.46 |
N13—C4—C3 | 109.3 (2) | C3—C4—H4 | 109.18 |
C3—C4—C5 | 110.7 (2) | C5—C4—H4 | 106.89 |
C4—C5—C10 | 120.0 (2) | C5—C6—H6 | 120.06 |
C6—C5—C10 | 119.4 (3) | C7—C6—H6 | 121.73 |
C4—C5—C6 | 120.5 (2) | C7—C8—H8 | 119.58 |
C5—C6—C7 | 118.2 (3) | C9—C8—H8 | 124.83 |
F11—C7—C8 | 118.0 (2) | C5—C10—H10 | 118.60 |
F11—C7—C6 | 117.9 (3) | C9—C10—H10 | 122.18 |
C6—C7—C8 | 124.1 (3) | C17—C18—H18A | 109.85 |
C7—C8—C9 | 115.6 (3) | C17—C18—H18B | 108.90 |
F12—C9—C10 | 118.3 (3) | C17—C18—H18C | 109.61 |
C8—C9—C10 | 123.4 (3) | H18A—C18—H18B | 109.51 |
F12—C9—C8 | 118.2 (2) | H18A—C18—H18C | 109.42 |
C5—C10—C9 | 119.2 (3) | H18B—C18—H18C | 109.54 |
O15—C14—N13 | 124.9 (2) | C17—C19—H19A | 109.28 |
O15—C14—O16 | 125.9 (3) | C17—C19—H19B | 109.34 |
O16—C14—N13 | 109.2 (2) | C17—C19—H19C | 109.82 |
O16—C17—C19 | 109.7 (2) | H19A—C19—H19B | 109.52 |
O16—C17—C20 | 100.9 (2) | H19A—C19—H19C | 109.39 |
C18—C17—C20 | 110.8 (2) | H19B—C19—H19C | 109.47 |
C19—C17—C20 | 111.0 (2) | C17—C20—H20A | 109.48 |
C18—C17—C19 | 113.3 (2) | C17—C20—H20B | 109.63 |
O16—C17—C18 | 110.4 (2) | C17—C20—H20C | 109.30 |
Cl1—C2—H2A | 108.66 | H20A—C20—H20B | 109.52 |
Cl1—C2—H2B | 108.70 | H20A—C20—H20C | 109.44 |
C3—C2—H2A | 109.58 | H20B—C20—H20C | 109.47 |
C3—C2—H2B | 109.39 | | |
| | | |
C17—O16—C14—O15 | −1.3 (4) | C3—C4—C5—C10 | −104.7 (3) |
C17—O16—C14—N13 | 176.8 (2) | N13—C4—C5—C10 | 132.2 (3) |
C14—O16—C17—C18 | 59.1 (3) | C6—C5—C10—C9 | 0.0 (4) |
C14—O16—C17—C19 | −66.5 (3) | C4—C5—C10—C9 | 177.8 (2) |
C14—O16—C17—C20 | 176.3 (2) | C4—C5—C6—C7 | −178.9 (2) |
C14—N13—C4—C3 | 157.5 (2) | C10—C5—C6—C7 | −1.1 (4) |
C14—N13—C4—C5 | −78.6 (3) | C5—C6—C7—F11 | −179.1 (2) |
C4—N13—C14—O15 | −7.6 (4) | C5—C6—C7—C8 | 0.7 (5) |
C4—N13—C14—O16 | 174.2 (2) | C6—C7—C8—C9 | 0.7 (4) |
Cl1—C2—C3—C4 | −68.3 (3) | F11—C7—C8—C9 | −179.5 (2) |
C2—C3—C4—C5 | 166.1 (2) | C7—C8—C9—F12 | 179.8 (2) |
C2—C3—C4—N13 | −68.5 (3) | C7—C8—C9—C10 | −1.9 (4) |
N13—C4—C5—C6 | −50.1 (3) | C8—C9—C10—C5 | 1.5 (4) |
C3—C4—C5—C6 | 73.0 (3) | F12—C9—C10—C5 | 179.8 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1/2, −y, z+1/2; (iii) x−1, y, z; (iv) −x, y−1/2, −z+1/2; (v) x+1, y, z; (vi) −x+1, y+1/2, −z+1/2; (vii) −x+2, y+1/2, −z+1/2; (viii) x−1/2, −y+1/2, −z+1; (ix) −x+2, y−1/2, −z+1/2; (x) x+1/2, −y+1/2, −z+1; (xi) −x, y+1/2, −z+1/2; (xii) −x+1/2, −y, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O15v | 0.85 | 2.25 | 3.051 (3) | 158 |
C3—H3B···O15v | 0.96 | 2.54 | 3.376 (3) | 146 |
C18—H18C···O15 | 0.96 | 2.35 | 2.972 (3) | 122 |
C19—H19B···O15 | 0.96 | 2.51 | 3.102 (3) | 120 |
Symmetry code: (v) x+1, y, z. |