Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035015/bg2075sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035015/bg2075Isup2.hkl |
CCDC reference: 657827
Key indicators
- Single-crystal X-ray study
- T = 90 K
- Mean (C-C) = 0.002 Å
- R factor = 0.036
- wR factor = 0.083
- Data-to-parameter ratio = 20.3
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for S1 - C12 .. 7.30 su
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 27.48 From the CIF: _reflns_number_total 3181 Count of symmetry unique reflns 1705 Completeness (_total/calc) 186.57% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1476 Fraction of Friedel pairs measured 0.866 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C11 = . R PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
In a 50-ml round-bottom flask under N2 was placed dicyclohexylcarbodiimide (0.72 g, 3.50 mmol), carbon disulfide (1.5 ml, 24.9 mmol), and THF (20 ml). The solution was cooled to -5 °C. To this was added a solution of tert-butyl (1R,2R)-2-aminocyclohexylcarbamate (0.75 g, 3.50 mmol) in THF (10 ml) over a period of 30 min. This mixture was allowed to stir at ambient temperature overnight. THF was removed under reduced pressure, and the resulting white solid was resuspended in diethyl ether (20 ml) and filtered. The filtrate was concentrated to give a white solid which was further purified by flash chromatography (hexanes/ethyl acetate, 3:1) to afford 0.70 g of a white crystalline material (78%) (Smith, et al., 1996).
H atoms were found in difference Fourier maps and subsequently placed in idealized positions with constrained C—H distances of 0.98 Å (CH3), 0.99 Å (CH2), 1.00 Å (CH1), and 0.88 Å (N—H). Uiso(H) values were set to either 1.5Ueq of the attached C atom (CH3) or 1.2Ueq for all other H atoms.
Isothiocyanates are important linkers for the facile synthesis of thioureas. The title compound (I), C12H20N2O2S, is a chiral isothiocyanate which can form a thiourea bond with another amine (Drobnica, et al., 1977; and Smith, et al., 1996).
The asymmetric unit of (I), (Fig. 1), contains one molecule and the bond lengths and angles are within normal ranges (Allen et al., 1987). In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) exist bewteen the NH of the carbamate of one molecule and the carbonyl O of the carbamate of another molecule. The molecules form one-dimensional chains along the [100] direction, based on a C(4) (Etter, 1990) hydrogen bonding motif (Fig. 2).
For related literature, see: Allen et al. (1987); Drobnica et al. (1977); Etter (1990); Smith et al. (1996).
Data collection: COLLECT (Nonius, 2002); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 and local procedures.
C12H20N2O2S | F(000) = 276 |
Mr = 256.36 | Dx = 1.216 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1710 reflections |
a = 5.1684 (2) Å | θ = 1.0–27.5° |
b = 8.5494 (3) Å | µ = 0.23 mm−1 |
c = 15.9227 (5) Å | T = 90 K |
β = 95.518 (2)° | Thick plate, colourless |
V = 700.31 (4) Å3 | 0.40 × 0.25 × 0.10 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 3181 independent reflections |
Radiation source: fine-focus sealed tube | 2852 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 18 pixels mm-1 | θmax = 27.5°, θmin = 1.3° |
ω scans at fixed χ = 55° | h = −6→6 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −11→11 |
Tmin = 0.92, Tmax = 0.98 | l = −20→20 |
12160 measured reflections |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0358P)2 + 0.1871P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
3181 reflections | Δρmax = 0.19 e Å−3 |
157 parameters | Δρmin = −0.20 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (6) |
C12H20N2O2S | V = 700.31 (4) Å3 |
Mr = 256.36 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.1684 (2) Å | µ = 0.23 mm−1 |
b = 8.5494 (3) Å | T = 90 K |
c = 15.9227 (5) Å | 0.40 × 0.25 × 0.10 mm |
β = 95.518 (2)° |
Nonius KappaCCD diffractometer | 3181 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 2852 reflections with I > 2σ(I) |
Tmin = 0.92, Tmax = 0.98 | Rint = 0.044 |
12160 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.083 | Δρmax = 0.19 e Å−3 |
S = 1.07 | Δρmin = −0.20 e Å−3 |
3181 reflections | Absolute structure: Flack (1983) |
157 parameters | Absolute structure parameter: 0.04 (6) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.5682 (3) | 0.9658 (2) | 0.04080 (13) | 0.0298 (4) | |
H1A | 0.4673 | 0.9113 | −0.0055 | 0.045* | |
H1B | 0.6622 | 1.0534 | 0.0182 | 0.045* | |
H1C | 0.4506 | 1.0056 | 0.0806 | 0.045* | |
C2 | 0.9247 (3) | 0.7762 (2) | 0.02368 (11) | 0.0241 (4) | |
H2A | 1.0591 | 0.7118 | 0.0545 | 0.036* | |
H2B | 1.0073 | 0.8567 | −0.0085 | 0.036* | |
H2C | 0.8142 | 0.7099 | −0.0151 | 0.036* | |
C3 | 0.9231 (3) | 0.9369 (2) | 0.15731 (11) | 0.0257 (4) | |
H3A | 0.8100 | 0.9727 | 0.1994 | 0.038* | |
H3B | 1.0108 | 1.0270 | 0.1347 | 0.038* | |
H3C | 1.0532 | 0.8643 | 0.1838 | 0.038* | |
C4 | 0.7601 (3) | 0.8538 (2) | 0.08578 (10) | 0.0188 (3) | |
C5 | 0.6834 (3) | 0.6210 (2) | 0.17045 (10) | 0.0186 (3) | |
C6 | 0.5257 (3) | 0.4216 (2) | 0.26417 (10) | 0.0185 (3) | |
H6 | 0.7153 | 0.3958 | 0.2719 | 0.022* | |
C7 | 0.3768 (3) | 0.2729 (2) | 0.23807 (10) | 0.0219 (4) | |
H7A | 0.4390 | 0.2317 | 0.1855 | 0.026* | |
H7B | 0.1897 | 0.2977 | 0.2264 | 0.026* | |
C8 | 0.4121 (4) | 0.1481 (2) | 0.30674 (12) | 0.0274 (4) | |
H8A | 0.3076 | 0.0548 | 0.2888 | 0.033* | |
H8B | 0.5970 | 0.1164 | 0.3148 | 0.033* | |
C9 | 0.3281 (4) | 0.2087 (2) | 0.38992 (12) | 0.0279 (4) | |
H9A | 0.1396 | 0.2320 | 0.3832 | 0.033* | |
H9B | 0.3595 | 0.1272 | 0.4339 | 0.033* | |
C10 | 0.4781 (4) | 0.3554 (3) | 0.41734 (11) | 0.0286 (4) | |
H10A | 0.6649 | 0.3298 | 0.4291 | 0.034* | |
H10B | 0.4155 | 0.3960 | 0.4700 | 0.034* | |
C11 | 0.4441 (3) | 0.4810 (2) | 0.34895 (11) | 0.0229 (4) | |
H11 | 0.2564 | 0.5112 | 0.3409 | 0.028* | |
C12 | 0.7622 (3) | 0.7085 (2) | 0.38407 (11) | 0.0244 (4) | |
N1 | 0.4866 (3) | 0.54204 (18) | 0.20018 (9) | 0.0212 (3) | |
H1 | 0.3265 | 0.5645 | 0.1798 | 0.025* | |
N2 | 0.5948 (3) | 0.6181 (2) | 0.37449 (11) | 0.0332 (4) | |
O1 | 0.5876 (2) | 0.73878 (14) | 0.12093 (7) | 0.0202 (3) | |
O2 | 0.9141 (2) | 0.58898 (16) | 0.18584 (8) | 0.0231 (3) | |
S1 | 0.98280 (9) | 0.83806 (6) | 0.40018 (3) | 0.03501 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0189 (8) | 0.0283 (11) | 0.0429 (11) | 0.0002 (8) | 0.0064 (8) | 0.0156 (9) |
C2 | 0.0187 (8) | 0.0296 (10) | 0.0248 (9) | −0.0032 (7) | 0.0064 (7) | −0.0024 (8) |
C3 | 0.0248 (9) | 0.0263 (10) | 0.0265 (9) | −0.0074 (8) | 0.0057 (7) | −0.0034 (8) |
C4 | 0.0116 (6) | 0.0208 (9) | 0.0246 (8) | −0.0029 (7) | 0.0043 (6) | 0.0024 (8) |
C5 | 0.0154 (7) | 0.0204 (9) | 0.0203 (8) | −0.0007 (7) | 0.0029 (6) | −0.0011 (7) |
C6 | 0.0142 (7) | 0.0201 (9) | 0.0215 (8) | 0.0009 (7) | 0.0022 (6) | 0.0022 (7) |
C7 | 0.0235 (8) | 0.0219 (9) | 0.0202 (9) | −0.0007 (7) | 0.0014 (7) | −0.0005 (7) |
C8 | 0.0309 (10) | 0.0209 (10) | 0.0299 (10) | −0.0027 (8) | 0.0008 (8) | 0.0009 (8) |
C9 | 0.0298 (9) | 0.0305 (11) | 0.0234 (9) | −0.0069 (8) | 0.0025 (7) | 0.0052 (8) |
C10 | 0.0329 (9) | 0.0336 (11) | 0.0194 (8) | −0.0105 (9) | 0.0033 (7) | −0.0009 (8) |
C11 | 0.0209 (8) | 0.0210 (9) | 0.0276 (9) | −0.0064 (7) | 0.0055 (7) | −0.0038 (7) |
C12 | 0.0250 (9) | 0.0270 (10) | 0.0212 (8) | −0.0002 (8) | 0.0022 (7) | −0.0001 (8) |
N1 | 0.0104 (6) | 0.0259 (9) | 0.0272 (8) | 0.0013 (6) | 0.0016 (5) | 0.0074 (6) |
N2 | 0.0367 (9) | 0.0285 (10) | 0.0350 (9) | −0.0117 (8) | 0.0070 (7) | −0.0077 (7) |
O1 | 0.0117 (5) | 0.0216 (7) | 0.0278 (6) | −0.0004 (5) | 0.0033 (4) | 0.0067 (5) |
O2 | 0.0115 (5) | 0.0263 (7) | 0.0317 (7) | 0.0015 (5) | 0.0025 (5) | 0.0060 (6) |
S1 | 0.0318 (2) | 0.0396 (3) | 0.0333 (3) | −0.0163 (2) | 0.00155 (19) | −0.0024 (2) |
C1—C4 | 1.509 (2) | C6—H6 | 1.0000 |
C1—H1A | 0.9800 | C7—C8 | 1.526 (3) |
C1—H1B | 0.9800 | C7—H7A | 0.9900 |
C1—H1C | 0.9800 | C7—H7B | 0.9900 |
C2—C4 | 1.518 (2) | C8—C9 | 1.524 (3) |
C2—H2A | 0.9800 | C8—H8A | 0.9900 |
C2—H2B | 0.9800 | C8—H8B | 0.9900 |
C2—H2C | 0.9800 | C9—C10 | 1.517 (3) |
C3—C4 | 1.526 (2) | C9—H9A | 0.9900 |
C3—H3A | 0.9800 | C9—H9B | 0.9900 |
C3—H3B | 0.9800 | C10—C11 | 1.527 (3) |
C3—H3C | 0.9800 | C10—H10A | 0.9900 |
C4—O1 | 1.473 (2) | C10—H10B | 0.9900 |
C5—O2 | 1.2247 (19) | C11—N2 | 1.444 (2) |
C5—O1 | 1.344 (2) | C11—H11 | 1.0000 |
C5—N1 | 1.344 (2) | C12—N2 | 1.159 (2) |
C6—N1 | 1.449 (2) | C12—S1 | 1.5927 (19) |
C6—C7 | 1.524 (2) | N1—H1 | 0.8800 |
C6—C11 | 1.539 (2) | ||
C4—C1—H1A | 109.5 | C8—C7—H7A | 109.3 |
C4—C1—H1B | 109.5 | C6—C7—H7B | 109.3 |
H1A—C1—H1B | 109.5 | C8—C7—H7B | 109.3 |
C4—C1—H1C | 109.5 | H7A—C7—H7B | 108.0 |
H1A—C1—H1C | 109.5 | C9—C8—C7 | 111.17 (16) |
H1B—C1—H1C | 109.5 | C9—C8—H8A | 109.4 |
C4—C2—H2A | 109.5 | C7—C8—H8A | 109.4 |
C4—C2—H2B | 109.5 | C9—C8—H8B | 109.4 |
H2A—C2—H2B | 109.5 | C7—C8—H8B | 109.4 |
C4—C2—H2C | 109.5 | H8A—C8—H8B | 108.0 |
H2A—C2—H2C | 109.5 | C10—C9—C8 | 110.54 (15) |
H2B—C2—H2C | 109.5 | C10—C9—H9A | 109.5 |
C4—C3—H3A | 109.5 | C8—C9—H9A | 109.5 |
C4—C3—H3B | 109.5 | C10—C9—H9B | 109.5 |
H3A—C3—H3B | 109.5 | C8—C9—H9B | 109.5 |
C4—C3—H3C | 109.5 | H9A—C9—H9B | 108.1 |
H3A—C3—H3C | 109.5 | C9—C10—C11 | 110.82 (14) |
H3B—C3—H3C | 109.5 | C9—C10—H10A | 109.5 |
O1—C4—C1 | 102.12 (12) | C11—C10—H10A | 109.5 |
O1—C4—C2 | 110.70 (14) | C9—C10—H10B | 109.5 |
C1—C4—C2 | 110.63 (14) | C11—C10—H10B | 109.5 |
O1—C4—C3 | 109.76 (13) | H10A—C10—H10B | 108.1 |
C1—C4—C3 | 110.44 (16) | N2—C11—C10 | 110.33 (15) |
C2—C4—C3 | 112.70 (13) | N2—C11—C6 | 109.17 (14) |
O2—C5—O1 | 125.56 (15) | C10—C11—C6 | 111.81 (16) |
O2—C5—N1 | 124.94 (16) | N2—C11—H11 | 108.5 |
O1—C5—N1 | 109.50 (13) | C10—C11—H11 | 108.5 |
N1—C6—C7 | 111.61 (13) | C6—C11—H11 | 108.5 |
N1—C6—C11 | 110.57 (15) | N2—C12—S1 | 176.98 (18) |
C7—C6—C11 | 109.91 (13) | C5—N1—C6 | 123.01 (14) |
N1—C6—H6 | 108.2 | C5—N1—H1 | 118.5 |
C7—C6—H6 | 108.2 | C6—N1—H1 | 118.5 |
C11—C6—H6 | 108.2 | C12—N2—C11 | 162.54 (19) |
C6—C7—C8 | 111.45 (14) | C5—O1—C4 | 121.36 (12) |
C6—C7—H7A | 109.3 | ||
N1—C6—C7—C8 | −178.30 (14) | O2—C5—N1—C6 | 9.0 (3) |
C11—C6—C7—C8 | −55.25 (18) | O1—C5—N1—C6 | −171.51 (14) |
C6—C7—C8—C9 | 56.88 (19) | C7—C6—N1—C5 | −130.07 (17) |
C7—C8—C9—C10 | −57.0 (2) | C11—C6—N1—C5 | 107.26 (18) |
C8—C9—C10—C11 | 56.5 (2) | C10—C11—N2—C12 | 92.0 (7) |
C9—C10—C11—N2 | −178.01 (14) | C6—C11—N2—C12 | −31.2 (7) |
C9—C10—C11—C6 | −56.31 (19) | O2—C5—O1—C4 | −6.1 (3) |
N1—C6—C11—N2 | −58.75 (18) | N1—C5—O1—C4 | 174.42 (14) |
C7—C6—C11—N2 | 177.59 (15) | C1—C4—O1—C5 | −176.42 (15) |
N1—C6—C11—C10 | 178.88 (14) | C2—C4—O1—C5 | 65.79 (18) |
C7—C6—C11—C10 | 55.22 (17) | C3—C4—O1—C5 | −59.24 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.88 | 2.15 | 2.9727 (17) | 155 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C12H20N2O2S |
Mr | 256.36 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 90 |
a, b, c (Å) | 5.1684 (2), 8.5494 (3), 15.9227 (5) |
β (°) | 95.518 (2) |
V (Å3) | 700.31 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.40 × 0.25 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.92, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12160, 3181, 2852 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.083, 1.07 |
No. of reflections | 3181 |
No. of parameters | 157 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.20 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.04 (6) |
Computer programs: COLLECT (Nonius, 2002), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1995), SHELXL97 and local procedures.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.88 | 2.15 | 2.9727 (17) | 154.7 |
Symmetry code: (i) x−1, y, z. |
Isothiocyanates are important linkers for the facile synthesis of thioureas. The title compound (I), C12H20N2O2S, is a chiral isothiocyanate which can form a thiourea bond with another amine (Drobnica, et al., 1977; and Smith, et al., 1996).
The asymmetric unit of (I), (Fig. 1), contains one molecule and the bond lengths and angles are within normal ranges (Allen et al., 1987). In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) exist bewteen the NH of the carbamate of one molecule and the carbonyl O of the carbamate of another molecule. The molecules form one-dimensional chains along the [100] direction, based on a C(4) (Etter, 1990) hydrogen bonding motif (Fig. 2).