4-Methyl-2-thio­xo-2,3-di­hydro­thia­zol-3-yl 4-methyl­phenyl carbonate

The p-cresyl substituent is inclined by -69.5 (10)° and the heterocyclic subunit is tilted by 88.4 (7)° with respect to the bridging carbonate functionality in the title compound, C₁₂H₁₁NO₃S₂.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.071
• wR factor = 0.150
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level A
TYPE032_ALERT_1_A  _cell_measurement_reflns_used is not of type numb.

Author Response: At least 50 reflections with I/s(I) > 6 taken from each frame were used to calculate the decay. None decay was observed.

DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.

Author Response: Please refer to the arguments given above at _vrf_TYPE032_I

PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............      24.22 Deg.

Author Response: We wish to point out that the theta range used for the analysis of (I) is lower than meanwhile required by the Union of Crystallography. The compound was prepared in a project that ended some time ago. The title compound is prone to thermal and photochemical decomposition. It is therefore hard to purify and to crystallize and, unfortunately, is no longer available in our laboratory. In view of the fact that the structure is an organic compound, which scatters with little intensity at high theta values we feel that the presented structural information on this compound is reliable enough in order to merit publication in Acta Crystallograhica E.

PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.92

Author Response: Please refer to the arguments given above at _vrf_PLAT027_I

PLAT035_ALERT_1_A No _chemical_absolute_configuration info given .          ?

Author Response: is corrected 'P'

Alert level B
RINTA01_ALERT_3_B  The value of Rint is greater than 0.15
            Rint given   0.156
PLAT020_ALERT_3_B The value of Rint is greater than 0.10 .........       0.16
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O3
PLAT340_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ...         11

Alert level C
THETM01_ALERT_3_C  The value of sine(theta_max)/wavelength is less than 0.590
            Calculated sin(theta_max)/wavelength =    0.5772
PLAT023_ALERT_3_C Resolution (too) Low [sin(th)/Lambda < 0.6].....      24.22 Deg.
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6B    ..  S2      ..       2.99 Ang.

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           24.22
           From the CIF: _reflns_number_total               2015
           Count of symmetry unique reflns         1159
           Completeness (_total/calc)            173.86%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       856
           Fraction of Friedel pairs measured     0.739
           Are heavy atom types Z>Si present          yes

   5 ALERT level A = In general: serious problem
   4 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   7 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: EXPOSE (Stoe & Cie, 1998); cell refinement: CELL (Stoe & Cie, 1998); data reduction: INTEGRATE (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1994); software used to prepare material for publication: SHELXTL-Plus.

4-Methyl-2-thioxo-2,3-dihydrothiazol-3-yl 4-methylphenyl carbonate

Crystal data

C12H11NO3S2	Dx = 1.374 Mg m^−3
Mr = 281.34	Melting point: 358 K
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.1730 (14) Å	Cell parameters from 6004 reflections selected from the whole data set with the program SELECT (STOE, 1998) reflections
b = 12.267 (3) Å	θ = 2.6–24.1°
c = 7.8680 (16) Å	µ = 0.39 mm^−1
β = 100.75 (3)°	T = 293 K
V = 680.2 (2) Å^3	Prism, yellow
Z = 2	0.45 × 0.30 × 0.20 mm
F(000) = 292

Data collection

STOE-IPDS- diffractometer	1299 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.156
Graphite monochromator	θmax = 24.2°, θmin = 2.6°
171 exposures were taken in the 0–290.7 phi range with a crystal to detector distance of 80 mm and an exposure time of 3.00 minutes. Dynamic profiles (17–21 pixels) were used for integration. scans	h = −7→7
6164 measured reflections	k = −14→14
2015 independent reflections	l = −9→8

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.071	w = 1/[σ^2(Fo^2) + (0.0152P)^2 + 0.158P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.150	(Δ/σ)max < 0.001
S = 1.14	Δρmax = 0.16 e Å^−3
2015 reflections	Δρmin = −0.23 e Å^−3
166 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.053 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.28 (17)

Special details

Experimental. 6004 reflections selected from the whole data set with the program SELECT (Stoe, 1998)

171 exposures were taken in the 0–290.7 phi range with a crystal to detector distance of 80 mm and an exposure time of 3.00 minutes. Dynamic profiles (17–21 pixels) were used for integration.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.4754 (3)	0.46004 (14)	0.9502 (3)	0.1110 (7)
S2	0.5453 (4)	0.23638 (15)	0.8123 (4)	0.1307 (10)
O1	0.1286 (8)	0.2735 (3)	0.6617 (6)	0.1044 (17)
O2	0.0694 (7)	0.1739 (3)	0.8892 (7)	0.0923 (14)
O3	0.0015 (9)	0.1195 (4)	0.6100 (7)	0.125 (2)
N3	0.2228 (9)	0.3492 (4)	0.7822 (8)	0.0870 (16)
C2	0.4086 (10)	0.3407 (4)	0.8385 (10)	0.088 (2)
C4	0.1247 (10)	0.4435 (5)	0.8138 (10)	0.090 (2)
C5	0.2492 (11)	0.5116 (5)	0.9058 (11)	0.104 (2)
H5	0.2168	0.5800	0.9422	0.125*
C6	−0.0809 (11)	0.4548 (7)	0.7530 (12)	0.124 (3)
H6A	−0.1209	0.5258	0.7831	0.185*
H6B	−0.1463	0.4001	0.8066	0.185*
H6C	−0.1100	0.4460	0.6297	0.185*
C7	0.0705 (11)	0.1842 (5)	0.7455 (11)	0.091 (2)
C8	−0.0951 (13)	0.0227 (5)	0.6460 (10)	0.097 (2)
C9	0.0026 (12)	−0.0618 (6)	0.7355 (11)	0.107 (2)
H9	0.1315	−0.0562	0.7814	0.129*
C10	−0.0970 (12)	−0.1553 (5)	0.7550 (11)	0.101 (2)
H10	−0.0329	−0.2139	0.8143	0.121*
C11	−0.2838 (12)	−0.1652 (5)	0.6914 (11)	0.099 (2)
C12	−0.3795 (13)	−0.0790 (5)	0.6050 (11)	0.107 (2)
H12	−0.5091	−0.0840	0.5617	0.128*
C13	−0.2816 (13)	0.0153 (6)	0.5828 (11)	0.107 (2)
H13	−0.3455	0.0740	0.5236	0.128*
C14	−0.3887 (14)	−0.2679 (6)	0.7120 (12)	0.140 (4)
H14A	−0.3543	−0.3229	0.6366	0.210*
H14B	−0.5228	−0.2546	0.6828	0.210*
H14C	−0.3566	−0.2924	0.8297	0.210*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0980 (14)	0.0876 (11)	0.1469 (19)	−0.0170 (11)	0.0215 (12)	−0.0006 (12)
S2	0.129 (2)	0.0919 (11)	0.183 (3)	0.0365 (12)	0.0599 (18)	0.0286 (14)
O1	0.149 (5)	0.074 (2)	0.091 (3)	−0.028 (3)	0.024 (3)	−0.001 (2)
O2	0.121 (4)	0.066 (2)	0.094 (3)	−0.018 (2)	0.030 (3)	−0.003 (2)
O3	0.200 (6)	0.082 (3)	0.096 (4)	−0.050 (3)	0.039 (4)	−0.016 (3)
N3	0.097 (5)	0.059 (2)	0.109 (5)	−0.004 (3)	0.031 (3)	−0.002 (3)
C2	0.075 (5)	0.064 (3)	0.129 (6)	0.001 (3)	0.032 (4)	0.006 (3)
C4	0.088 (5)	0.069 (4)	0.122 (6)	0.005 (3)	0.040 (4)	0.016 (4)
C5	0.114 (6)	0.067 (3)	0.140 (7)	−0.001 (4)	0.043 (5)	−0.008 (4)
C6	0.089 (5)	0.115 (5)	0.172 (9)	0.013 (5)	0.039 (5)	0.026 (6)
C7	0.104 (6)	0.067 (3)	0.107 (6)	−0.011 (3)	0.034 (5)	0.004 (4)
C8	0.135 (7)	0.059 (4)	0.099 (5)	−0.021 (4)	0.028 (5)	−0.006 (3)
C9	0.113 (6)	0.087 (5)	0.116 (6)	−0.005 (4)	0.007 (5)	−0.004 (4)
C10	0.119 (7)	0.069 (4)	0.111 (6)	−0.005 (4)	0.014 (5)	0.001 (3)
C11	0.117 (7)	0.077 (4)	0.107 (6)	−0.015 (4)	0.031 (5)	−0.013 (4)
C12	0.111 (6)	0.086 (4)	0.125 (7)	−0.007 (4)	0.028 (5)	−0.008 (4)
C13	0.122 (7)	0.072 (4)	0.124 (6)	0.013 (4)	0.017 (5)	−0.005 (4)
C14	0.188 (10)	0.091 (4)	0.137 (8)	−0.065 (6)	0.022 (7)	−0.015 (5)

Geometric parameters (Å, º)

S1—C5	1.715 (8)	C6—H6C	0.9600
S1—C2	1.729 (7)	C8—C13	1.341 (11)
S2—C2	1.648 (6)	C8—C9	1.371 (10)
O1—C7	1.383 (8)	C9—C10	1.375 (10)
O1—N3	1.407 (7)	C9—H9	0.9300
O2—C7	1.139 (8)	C10—C11	1.345 (11)
O3—C7	1.347 (9)	C10—H10	0.9300
O3—C8	1.429 (8)	C11—C12	1.370 (10)
N3—C2	1.327 (9)	C11—C14	1.492 (9)
N3—C4	1.400 (8)	C12—C13	1.381 (9)
C4—C5	1.334 (9)	C12—H12	0.9300
C4—C6	1.470 (10)	C13—H13	0.9300
C5—H5	0.9300	C14—H14A	0.9600
C6—H6A	0.9600	C14—H14B	0.9600
C6—H6B	0.9600	C14—H14C	0.9600
C5—S1—C2	92.7 (3)	C13—C8—C9	121.2 (7)
C7—O1—N3	110.6 (5)	C13—C8—O3	118.0 (7)
C7—O3—C8	116.9 (6)	C9—C8—O3	120.7 (8)
C2—N3—C4	120.8 (6)	C8—C9—C10	117.5 (8)
C2—N3—O1	119.9 (5)	C8—C9—H9	121.3
C4—N3—O1	118.1 (6)	C10—C9—H9	121.3
N3—C2—S2	127.1 (5)	C11—C10—C9	122.4 (7)
N3—C2—S1	105.6 (4)	C11—C10—H10	118.8
S2—C2—S1	127.3 (5)	C9—C10—H10	118.8
C5—C4—N3	107.8 (6)	C10—C11—C12	119.2 (7)
C5—C4—C6	130.3 (6)	C10—C11—C14	121.5 (8)
N3—C4—C6	121.9 (7)	C12—C11—C14	119.3 (8)
C4—C5—S1	113.0 (5)	C11—C12—C13	119.3 (8)
C4—C5—H5	123.5	C11—C12—H12	120.3
S1—C5—H5	123.5	C13—C12—H12	120.3
C4—C6—H6A	109.5	C8—C13—C12	120.4 (8)
C4—C6—H6B	109.5	C8—C13—H13	119.8
H6A—C6—H6B	109.5	C12—C13—H13	119.8
C4—C6—H6C	109.5	C11—C14—H14A	109.5
H6A—C6—H6C	109.5	C11—C14—H14B	109.5
H6B—C6—H6C	109.5	H14A—C14—H14B	109.5
O2—C7—O3	130.6 (6)	C11—C14—H14C	109.5
O2—C7—O1	128.3 (7)	H14A—C14—H14C	109.5
O3—C7—O1	100.9 (6)	H14B—C14—H14C	109.5
C7—O1—N3—C2	88.4 (7)	C8—O3—C7—O1	−172.3 (7)
C7—O1—N3—C4	−103.9 (7)	N3—O1—C7—O2	10.6 (11)
C4—N3—C2—S2	−179.8 (6)	N3—O1—C7—O3	−174.7 (6)
O1—N3—C2—S2	−12.4 (10)	C7—O3—C8—C13	113.6 (8)
C4—N3—C2—S1	2.0 (8)	C7—O3—C8—C9	−69.5 (10)
O1—N3—C2—S1	169.3 (4)	C13—C8—C9—C10	1.3 (12)
C5—S1—C2—N3	−1.6 (6)	O3—C8—C9—C10	−175.6 (7)
C5—S1—C2—S2	−179.8 (6)	C8—C9—C10—C11	−0.7 (13)
C2—N3—C4—C5	−1.3 (9)	C9—C10—C11—C12	−0.5 (13)
O1—N3—C4—C5	−168.9 (6)	C9—C10—C11—C14	179.2 (8)
C2—N3—C4—C6	−179.9 (7)	C10—C11—C12—C13	1.0 (12)
O1—N3—C4—C6	12.4 (10)	C14—C11—C12—C13	−178.7 (8)
N3—C4—C5—S1	−0.1 (8)	C9—C8—C13—C12	−0.8 (12)
C6—C4—C5—S1	178.4 (7)	O3—C8—C13—C12	176.2 (6)
C2—S1—C5—C4	1.0 (7)	C11—C12—C13—C8	−0.4 (12)
C8—O3—C7—O2	2.1 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···S2^i	0.96	2.99	3.880 (9)	154

Symmetry code: (i) x−1, y, z.