(1S)-tert-But­yl [3-chloro-1-(3,5-difluoro­phen­yl)prop­yl]carbamate: structure and absolute configuration

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.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](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

---

Computing details

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[(1S)-3-chloro-1-(3,5-difluorophenyl)propyl]carbamate

Crystal data

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) Å^3	Needle, colourless
Z = 4	0.60 × 0.03 × 0.03 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.091	w = 1/[σ^2(Fo^2) + (0.0453P)^2] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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···C6^i	3.483 (3)	C14···H18C	2.7304
Cl1···H4	2.8527	C14···H19B	2.7821
Cl1···H20A^ii	2.9816	C20···H19A^v	3.0132
Cl1···H2B^iii	3.0827	H2A···N13	2.7203
Cl1···H18B^i	2.9861	H2A···F11^ix	2.8247
Cl1···H18C^iv	3.1273	H2A···C7^i	2.8295
F11···C9^v	3.256 (3)	H2A···C8^i	2.9845
F11···O15^vi	3.174 (2)	H2B···Cl1^v	3.0827
F11···C2^vii	3.339 (3)	H3B···O15^v	2.5364
F11···C14^vi	3.188 (3)	H3B···C6	2.9871
F12···C7^iii	3.255 (3)	H3B···H4^v	2.4299
F12···C8^viii	3.358 (3)	H3B···H13	2.3414
F11···H2A^vii	2.8247	H4···Cl1	2.8527
O15···N13^iii	3.051 (3)	H4···O15	2.5273
O15···C3^iii	3.376 (3)	H4···H3B^iii	2.4299
O15···C5	3.359 (3)	H4···H10	2.2975
O15···C18	2.972 (3)	H6···O15^v	2.6654
O15···C19	3.102 (3)	H6···N13	2.7930
O15···F11^i	3.174 (2)	H6···H13	2.5804
O15···H4	2.5273	H8···O16^vi	2.8925
O15···H6^iii	2.6654	H8···H19C^vi	2.4582
O15···H3B^iii	2.5364	H10···H4	2.2975
O15···H18C	2.3494	H13···O15^v	2.2482
O15···H19B	2.5139	H13···C6	3.0548
O15···H13^iii	2.2482	H13···H3B	2.3414
O16···H8^i	2.8925	H13···H6	2.5804
N13···O15^v	3.051 (3)	H18A···H19A	2.5120
N13···H2A	2.7203	H18A···H20C^iii	2.4604
N13···H6	2.7930	H18B···H20C	2.4105
C2···F11^ix	3.339 (3)	H18B···Cl1^vi	2.9861
C3···O15^v	3.376 (3)	H18C···O15	2.3494
C5···O15	3.359 (3)	H18C···C14	2.7304
C6···C10^v	3.575 (4)	H18C···Cl1^xi	3.1273
C6···Cl1^vi	3.483 (3)	H19A···C20^iii	3.0132
C7···F12^v	3.255 (3)	H19A···H18A	2.5120
C8···F12^x	3.358 (3)	H19A···H20B^iii	2.3305
C9···F11^iii	3.256 (3)	H19B···O15	2.5139
C10···C6^iii	3.575 (4)	H19B···C14	2.7821
C14···F11^i	3.188 (3)	H19C···H20B	2.4285
C18···O15	2.972 (3)	H19C···H8^i	2.4582
C19···O15	3.102 (3)	H20A···Cl1^xii	2.9816
C6···H3B	2.9871	H20B···H19A^v	2.3305
C6···H13	3.0548	H20B···H19C	2.4285
C7···H2A^vi	2.8295	H20C···H18A^v	2.4604
C8···H2A^vi	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)

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13···O15^v	0.85	2.25	3.051 (3)	158
C3—H3B···O15^v	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.