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In the crystal structure of the title compound, C12H20N2O2S, the mol­ecules form one-dimensional chains along the [100] direction, based on a C(4) hydrogen-bonding motif between the carbamate NH group of one mol­ecule and the carbamate C=O group of a neighbouring mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035015/bg2075sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035015/bg2075Isup2.hkl
Contains datablock I

CCDC reference: 657827

Key indicators

  • Single-crystal X-ray study
  • T = 90 K
  • Mean [sigma](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

Comment top

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).

Related literature top

For related literature, see: Allen et al. (1987); Drobnica et al. (1977); Etter (1990); Smith et al. (1996).

Experimental top

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).

Refinement top

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.

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram of (I) viewed along the b axis. In broken lines, the H bonds defining the [100] chains.
tert-Butyl N-[(1R,2R)-2-(isothiocyanato)cyclohexyl]carbamate top
Crystal data top
C12H20N2O2SF(000) = 276
Mr = 256.36Dx = 1.216 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1710 reflections
a = 5.1684 (2) Åθ = 1.0–27.5°
b = 8.5494 (3) ŵ = 0.23 mm1
c = 15.9227 (5) ÅT = 90 K
β = 95.518 (2)°Thick plate, colourless
V = 700.31 (4) Å30.40 × 0.25 × 0.10 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer
3181 independent reflections
Radiation source: fine-focus sealed tube2852 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 18 pixels mm-1θmax = 27.5°, θmin = 1.3°
ω scans at fixed χ = 55°h = 66
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
k = 1111
Tmin = 0.92, Tmax = 0.98l = 2020
12160 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-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 reflectionsΔρmax = 0.19 e Å3
157 parametersΔρmin = 0.20 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.04 (6)
Crystal data top
C12H20N2O2SV = 700.31 (4) Å3
Mr = 256.36Z = 2
Monoclinic, P21Mo Kα radiation
a = 5.1684 (2) ŵ = 0.23 mm1
b = 8.5494 (3) ÅT = 90 K
c = 15.9227 (5) Å0.40 × 0.25 × 0.10 mm
β = 95.518 (2)°
Data collection top
Nonius KappaCCD
diffractometer
3181 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
2852 reflections with I > 2σ(I)
Tmin = 0.92, Tmax = 0.98Rint = 0.044
12160 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.083Δρmax = 0.19 e Å3
S = 1.07Δρmin = 0.20 e Å3
3181 reflectionsAbsolute structure: Flack (1983)
157 parametersAbsolute structure parameter: 0.04 (6)
1 restraint
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.5682 (3)0.9658 (2)0.04080 (13)0.0298 (4)
H1A0.46730.91130.00550.045*
H1B0.66221.05340.01820.045*
H1C0.45061.00560.08060.045*
C20.9247 (3)0.7762 (2)0.02368 (11)0.0241 (4)
H2A1.05910.71180.05450.036*
H2B1.00730.85670.00850.036*
H2C0.81420.70990.01510.036*
C30.9231 (3)0.9369 (2)0.15731 (11)0.0257 (4)
H3A0.81000.97270.19940.038*
H3B1.01081.02700.13470.038*
H3C1.05320.86430.18380.038*
C40.7601 (3)0.8538 (2)0.08578 (10)0.0188 (3)
C50.6834 (3)0.6210 (2)0.17045 (10)0.0186 (3)
C60.5257 (3)0.4216 (2)0.26417 (10)0.0185 (3)
H60.71530.39580.27190.022*
C70.3768 (3)0.2729 (2)0.23807 (10)0.0219 (4)
H7A0.43900.23170.18550.026*
H7B0.18970.29770.22640.026*
C80.4121 (4)0.1481 (2)0.30674 (12)0.0274 (4)
H8A0.30760.05480.28880.033*
H8B0.59700.11640.31480.033*
C90.3281 (4)0.2087 (2)0.38992 (12)0.0279 (4)
H9A0.13960.23200.38320.033*
H9B0.35950.12720.43390.033*
C100.4781 (4)0.3554 (3)0.41734 (11)0.0286 (4)
H10A0.66490.32980.42910.034*
H10B0.41550.39600.47000.034*
C110.4441 (3)0.4810 (2)0.34895 (11)0.0229 (4)
H110.25640.51120.34090.028*
C120.7622 (3)0.7085 (2)0.38407 (11)0.0244 (4)
N10.4866 (3)0.54204 (18)0.20018 (9)0.0212 (3)
H10.32650.56450.17980.025*
N20.5948 (3)0.6181 (2)0.37449 (11)0.0332 (4)
O10.5876 (2)0.73878 (14)0.12093 (7)0.0202 (3)
O20.9141 (2)0.58898 (16)0.18584 (8)0.0231 (3)
S10.98280 (9)0.83806 (6)0.40018 (3)0.03501 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0189 (8)0.0283 (11)0.0429 (11)0.0002 (8)0.0064 (8)0.0156 (9)
C20.0187 (8)0.0296 (10)0.0248 (9)0.0032 (7)0.0064 (7)0.0024 (8)
C30.0248 (9)0.0263 (10)0.0265 (9)0.0074 (8)0.0057 (7)0.0034 (8)
C40.0116 (6)0.0208 (9)0.0246 (8)0.0029 (7)0.0043 (6)0.0024 (8)
C50.0154 (7)0.0204 (9)0.0203 (8)0.0007 (7)0.0029 (6)0.0011 (7)
C60.0142 (7)0.0201 (9)0.0215 (8)0.0009 (7)0.0022 (6)0.0022 (7)
C70.0235 (8)0.0219 (9)0.0202 (9)0.0007 (7)0.0014 (7)0.0005 (7)
C80.0309 (10)0.0209 (10)0.0299 (10)0.0027 (8)0.0008 (8)0.0009 (8)
C90.0298 (9)0.0305 (11)0.0234 (9)0.0069 (8)0.0025 (7)0.0052 (8)
C100.0329 (9)0.0336 (11)0.0194 (8)0.0105 (9)0.0033 (7)0.0009 (8)
C110.0209 (8)0.0210 (9)0.0276 (9)0.0064 (7)0.0055 (7)0.0038 (7)
C120.0250 (9)0.0270 (10)0.0212 (8)0.0002 (8)0.0022 (7)0.0001 (8)
N10.0104 (6)0.0259 (9)0.0272 (8)0.0013 (6)0.0016 (5)0.0074 (6)
N20.0367 (9)0.0285 (10)0.0350 (9)0.0117 (8)0.0070 (7)0.0077 (7)
O10.0117 (5)0.0216 (7)0.0278 (6)0.0004 (5)0.0033 (4)0.0067 (5)
O20.0115 (5)0.0263 (7)0.0317 (7)0.0015 (5)0.0025 (5)0.0060 (6)
S10.0318 (2)0.0396 (3)0.0333 (3)0.0163 (2)0.00155 (19)0.0024 (2)
Geometric parameters (Å, º) top
C1—C41.509 (2)C6—H61.0000
C1—H1A0.9800C7—C81.526 (3)
C1—H1B0.9800C7—H7A0.9900
C1—H1C0.9800C7—H7B0.9900
C2—C41.518 (2)C8—C91.524 (3)
C2—H2A0.9800C8—H8A0.9900
C2—H2B0.9800C8—H8B0.9900
C2—H2C0.9800C9—C101.517 (3)
C3—C41.526 (2)C9—H9A0.9900
C3—H3A0.9800C9—H9B0.9900
C3—H3B0.9800C10—C111.527 (3)
C3—H3C0.9800C10—H10A0.9900
C4—O11.473 (2)C10—H10B0.9900
C5—O21.2247 (19)C11—N21.444 (2)
C5—O11.344 (2)C11—H111.0000
C5—N11.344 (2)C12—N21.159 (2)
C6—N11.449 (2)C12—S11.5927 (19)
C6—C71.524 (2)N1—H10.8800
C6—C111.539 (2)
C4—C1—H1A109.5C8—C7—H7A109.3
C4—C1—H1B109.5C6—C7—H7B109.3
H1A—C1—H1B109.5C8—C7—H7B109.3
C4—C1—H1C109.5H7A—C7—H7B108.0
H1A—C1—H1C109.5C9—C8—C7111.17 (16)
H1B—C1—H1C109.5C9—C8—H8A109.4
C4—C2—H2A109.5C7—C8—H8A109.4
C4—C2—H2B109.5C9—C8—H8B109.4
H2A—C2—H2B109.5C7—C8—H8B109.4
C4—C2—H2C109.5H8A—C8—H8B108.0
H2A—C2—H2C109.5C10—C9—C8110.54 (15)
H2B—C2—H2C109.5C10—C9—H9A109.5
C4—C3—H3A109.5C8—C9—H9A109.5
C4—C3—H3B109.5C10—C9—H9B109.5
H3A—C3—H3B109.5C8—C9—H9B109.5
C4—C3—H3C109.5H9A—C9—H9B108.1
H3A—C3—H3C109.5C9—C10—C11110.82 (14)
H3B—C3—H3C109.5C9—C10—H10A109.5
O1—C4—C1102.12 (12)C11—C10—H10A109.5
O1—C4—C2110.70 (14)C9—C10—H10B109.5
C1—C4—C2110.63 (14)C11—C10—H10B109.5
O1—C4—C3109.76 (13)H10A—C10—H10B108.1
C1—C4—C3110.44 (16)N2—C11—C10110.33 (15)
C2—C4—C3112.70 (13)N2—C11—C6109.17 (14)
O2—C5—O1125.56 (15)C10—C11—C6111.81 (16)
O2—C5—N1124.94 (16)N2—C11—H11108.5
O1—C5—N1109.50 (13)C10—C11—H11108.5
N1—C6—C7111.61 (13)C6—C11—H11108.5
N1—C6—C11110.57 (15)N2—C12—S1176.98 (18)
C7—C6—C11109.91 (13)C5—N1—C6123.01 (14)
N1—C6—H6108.2C5—N1—H1118.5
C7—C6—H6108.2C6—N1—H1118.5
C11—C6—H6108.2C12—N2—C11162.54 (19)
C6—C7—C8111.45 (14)C5—O1—C4121.36 (12)
C6—C7—H7A109.3
N1—C6—C7—C8178.30 (14)O2—C5—N1—C69.0 (3)
C11—C6—C7—C855.25 (18)O1—C5—N1—C6171.51 (14)
C6—C7—C8—C956.88 (19)C7—C6—N1—C5130.07 (17)
C7—C8—C9—C1057.0 (2)C11—C6—N1—C5107.26 (18)
C8—C9—C10—C1156.5 (2)C10—C11—N2—C1292.0 (7)
C9—C10—C11—N2178.01 (14)C6—C11—N2—C1231.2 (7)
C9—C10—C11—C656.31 (19)O2—C5—O1—C46.1 (3)
N1—C6—C11—N258.75 (18)N1—C5—O1—C4174.42 (14)
C7—C6—C11—N2177.59 (15)C1—C4—O1—C5176.42 (15)
N1—C6—C11—C10178.88 (14)C2—C4—O1—C565.79 (18)
C7—C6—C11—C1055.22 (17)C3—C4—O1—C559.24 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.882.152.9727 (17)155
Symmetry code: (i) x1, y, z.

Experimental details

Crystal data
Chemical formulaC12H20N2O2S
Mr256.36
Crystal system, space groupMonoclinic, P21
Temperature (K)90
a, b, c (Å)5.1684 (2), 8.5494 (3), 15.9227 (5)
β (°) 95.518 (2)
V3)700.31 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.23
Crystal size (mm)0.40 × 0.25 × 0.10
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.92, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
12160, 3181, 2852
Rint0.044
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.083, 1.07
No. of reflections3181
No. of parameters157
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.20
Absolute structureFlack (1983)
Absolute structure parameter0.04 (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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.882.152.9727 (17)154.7
Symmetry code: (i) x1, y, z.
 

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