Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001982/bt6012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001982/bt6012Isup2.hkl |
CCDC reference: 159840
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å
- R factor = 0.041
- wR factor = 0.116
- Data-to-parameter ratio = 18.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound, (I), was prepared by Spa Contract Synthesis. Crystals of (I) were grown from an ethanol solution.
All H atoms were included in the refinement, at calculated positions, as riding models with C—H set to 0.95 Å (Ar—H), 0.98 Å (CH3) and 0.99 Å (CH2). The methyl group was allowed to rotate about its local threefold axis.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular configuration and atom-numbering scheme for (I) showing 50% probability ellipsoids. |
C10H14ClN3S | Dx = 1.417 Mg m−3 |
Mr = 243.75 | Melting point: 356-358 K K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 13.189 (3) Å | Cell parameters from 15006 reflections |
b = 8.577 (2) Å | θ = 2.9–30.5° |
c = 20.195 (4) Å | µ = 0.49 mm−1 |
V = 2284.4 (8) Å3 | T = 150 K |
Z = 8 | Block, colourless |
F(000) = 1024 | 0.40 × 0.40 × 0.36 mm |
Enraf Nonius KappaCCD area-detector diffractometer | 2580 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 2124 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −17→17 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −11→10 |
Tmin = 0.829, Tmax = 0.844 | l = −26→26 |
11709 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0691P)2 + 0.3268P] where P = (Fo2 + 2Fc2)/3 |
2580 reflections | (Δ/σ)max < 0.001 |
137 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C10H14ClN3S | V = 2284.4 (8) Å3 |
Mr = 243.75 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.189 (3) Å | µ = 0.49 mm−1 |
b = 8.577 (2) Å | T = 150 K |
c = 20.195 (4) Å | 0.40 × 0.40 × 0.36 mm |
Enraf Nonius KappaCCD area-detector diffractometer | 2580 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 2124 reflections with I > 2σ(I) |
Tmin = 0.829, Tmax = 0.844 | Rint = 0.070 |
11709 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.29 e Å−3 |
2580 reflections | Δρmin = −0.36 e Å−3 |
137 parameters |
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.40565 (10) | −0.13958 (15) | 0.41858 (7) | 0.0247 (3) | |
C2 | 0.36235 (12) | −0.08692 (18) | 0.47313 (8) | 0.0242 (3) | |
S2 | 0.25591 (3) | 0.03635 (5) | 0.46554 (2) | 0.02906 (16) | |
C21 | 0.23515 (14) | 0.0312 (2) | 0.37775 (9) | 0.0352 (5) | |
H21 | 0.2952 | 0.0714 | 0.3549 | 0.044* | |
H22 | 0.1763 | 0.0958 | 0.3666 | 0.044* | |
H23 | 0.2226 | −0.0766 | 0.3638 | 0.044* | |
N3 | 0.38882 (11) | −0.11320 (16) | 0.53622 (7) | 0.0269 (3) | |
C4 | 0.46762 (14) | −0.20955 (19) | 0.54096 (8) | 0.0254 (4) | |
Cl4 | 0.50641 (4) | −0.25289 (5) | 0.62175 (2) | 0.03458 (17) | |
C5 | 0.52051 (13) | −0.27526 (18) | 0.48988 (9) | 0.0263 (4) | |
H5 | 0.5758 | −0.3443 | 0.4970 | 0.033* | |
C6 | 0.48734 (13) | −0.23358 (19) | 0.42617 (9) | 0.0245 (4) | |
N61 | 0.53176 (13) | −0.28667 (19) | 0.36979 (7) | 0.0322 (4) | |
C62 | 0.62913 (15) | −0.3687 (2) | 0.36993 (9) | 0.0361 (4) | |
H621 | 0.6263 | −0.4571 | 0.3384 | 0.045* | |
H622 | 0.6423 | −0.4113 | 0.4147 | 0.045* | |
C63 | 0.71465 (15) | −0.2595 (2) | 0.35043 (10) | 0.0382 (5) | |
H631 | 0.7217 | −0.1764 | 0.3841 | 0.048* | |
H632 | 0.7792 | −0.3181 | 0.3486 | 0.048* | |
C64 | 0.69324 (15) | −0.1868 (2) | 0.28338 (9) | 0.0368 (4) | |
H641 | 0.6953 | −0.2686 | 0.2488 | 0.046* | |
H642 | 0.7463 | −0.1089 | 0.2731 | 0.046* | |
C65 | 0.58996 (15) | −0.1084 (2) | 0.28281 (9) | 0.0335 (4) | |
H651 | 0.5912 | −0.0169 | 0.3127 | 0.042* | |
H652 | 0.5748 | −0.0710 | 0.2375 | 0.042* | |
C66 | 0.50718 (14) | −0.2200 (2) | 0.30501 (9) | 0.0326 (4) | |
H661 | 0.4418 | −0.1636 | 0.3077 | 0.041* | |
H662 | 0.4999 | −0.3047 | 0.2721 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0219 (7) | 0.0245 (6) | 0.0276 (7) | −0.0012 (5) | −0.0001 (5) | 0.0001 (5) |
C2 | 0.0221 (8) | 0.0206 (7) | 0.0299 (8) | −0.0014 (6) | −0.0010 (6) | −0.0008 (6) |
S2 | 0.0269 (3) | 0.0295 (3) | 0.0308 (3) | 0.00478 (17) | −0.00029 (16) | −0.00190 (17) |
C21 | 0.0332 (11) | 0.0412 (11) | 0.0313 (10) | 0.0100 (8) | −0.0053 (7) | 0.0003 (7) |
N3 | 0.0275 (8) | 0.0266 (7) | 0.0267 (7) | −0.0008 (6) | 0.0003 (5) | −0.0004 (5) |
C4 | 0.0272 (9) | 0.0257 (8) | 0.0233 (8) | −0.0045 (7) | −0.0013 (7) | 0.0024 (6) |
Cl4 | 0.0401 (3) | 0.0392 (3) | 0.0245 (3) | 0.00439 (19) | −0.00355 (17) | 0.00434 (17) |
C5 | 0.0258 (9) | 0.0243 (8) | 0.0288 (9) | 0.0006 (6) | −0.0001 (7) | 0.0028 (7) |
C6 | 0.0235 (9) | 0.0227 (8) | 0.0273 (9) | −0.0037 (6) | 0.0024 (6) | −0.0012 (6) |
N61 | 0.0301 (9) | 0.0389 (9) | 0.0277 (8) | 0.0078 (7) | 0.0033 (6) | 0.0019 (6) |
C62 | 0.0378 (11) | 0.0374 (10) | 0.0331 (9) | 0.0143 (8) | 0.0062 (7) | 0.0011 (7) |
C63 | 0.0303 (10) | 0.0520 (11) | 0.0324 (10) | 0.0071 (9) | −0.0017 (8) | −0.0063 (8) |
C64 | 0.0338 (10) | 0.0444 (10) | 0.0321 (9) | −0.0048 (9) | 0.0039 (8) | −0.0038 (8) |
C65 | 0.0436 (11) | 0.0320 (9) | 0.0249 (8) | 0.0019 (8) | −0.0006 (7) | −0.0025 (7) |
C66 | 0.0307 (10) | 0.0444 (11) | 0.0227 (9) | 0.0036 (7) | −0.0005 (7) | −0.0030 (7) |
N1—C2 | 1.320 (2) | N61—C66 | 1.464 (2) |
N1—C6 | 1.354 (2) | C62—C63 | 1.518 (3) |
C2—N3 | 1.340 (2) | C62—H621 | 0.99 |
C2—S2 | 1.7641 (17) | C62—H622 | 0.99 |
S2—C21 | 1.7944 (18) | C63—C64 | 1.517 (3) |
C21—H21 | 0.98 | C63—H631 | 0.99 |
C21—H22 | 0.98 | C63—H632 | 0.99 |
C21—H23 | 0.98 | C64—C65 | 1.519 (3) |
N3—C4 | 1.331 (2) | C64—H641 | 0.99 |
C4—C5 | 1.367 (2) | C64—H642 | 0.99 |
C4—Cl4 | 1.7499 (17) | C65—C66 | 1.519 (3) |
C5—C6 | 1.405 (2) | C65—H651 | 0.99 |
C5—H5 | 0.95 | C65—H652 | 0.99 |
C6—N61 | 1.359 (2) | C66—H661 | 0.99 |
N61—C62 | 1.464 (2) | C66—H662 | 0.99 |
C2—N1—C6 | 116.95 (14) | N61—C62—H622 | 109.5 |
N1—C2—N3 | 128.54 (15) | C63—C62—H622 | 109.5 |
N1—C2—S2 | 118.47 (12) | H621—C62—H622 | 108.1 |
N3—C2—S2 | 112.99 (12) | C64—C63—C62 | 110.28 (16) |
C2—S2—C21 | 101.09 (8) | C64—C63—H631 | 109.6 |
S2—C21—H21 | 109.5 | C62—C63—H631 | 109.6 |
S2—C21—H22 | 109.5 | C64—C63—H632 | 109.6 |
H21—C21—H22 | 109.5 | C62—C63—H632 | 109.6 |
S2—C21—H23 | 109.5 | H631—C63—H632 | 108.1 |
H21—C21—H23 | 109.5 | C63—C64—C65 | 110.83 (15) |
H22—C21—H23 | 109.5 | C63—C64—H641 | 109.5 |
C4—N3—C2 | 112.08 (14) | C65—C64—H641 | 109.5 |
N3—C4—C5 | 126.88 (15) | C63—C64—H642 | 109.5 |
N3—C4—Cl4 | 115.28 (12) | C65—C64—H642 | 109.5 |
C5—C4—Cl4 | 117.83 (14) | H641—C64—H642 | 108.1 |
C4—C5—C6 | 115.29 (16) | C66—C65—C64 | 111.30 (15) |
C4—C5—H5 | 122.4 | C66—C65—H651 | 109.4 |
C6—C5—H5 | 122.4 | C64—C65—H651 | 109.4 |
N1—C6—N61 | 116.59 (15) | C66—C65—H652 | 109.4 |
N1—C6—C5 | 120.18 (15) | C64—C65—H652 | 109.4 |
N61—C6—C5 | 123.21 (16) | H651—C65—H652 | 108.0 |
C6—N61—C62 | 122.50 (14) | N61—C66—C65 | 110.52 (15) |
C6—N61—C66 | 121.48 (16) | N61—C66—H661 | 109.5 |
C62—N61—C66 | 112.57 (14) | C65—C66—H661 | 109.5 |
N61—C62—C63 | 110.75 (16) | N61—C66—H662 | 109.5 |
N61—C62—H621 | 109.5 | C65—C66—H662 | 109.5 |
C63—C62—H621 | 109.5 | H661—C66—H662 | 108.1 |
C6—N1—C2—N3 | 0.5 (3) | C4—C5—C6—N61 | 179.32 (16) |
C6—N1—C2—S2 | 179.83 (11) | N1—C6—N61—C62 | 170.32 (16) |
N1—C2—S2—C21 | 5.7 (2) | C5—C6—N61—C62 | −11.5 (3) |
N3—C2—S2—C21 | −174.86 (13) | N1—C6—N61—C66 | 12.8 (3) |
N1—C2—N3—C4 | −2.2 (2) | C5—C6—N61—C66 | −168.99 (16) |
S2—C2—N3—C4 | 178.40 (11) | C6—N61—C62—C63 | −100.3 (2) |
C2—N3—C4—C5 | 1.5 (2) | C66—N61—C62—C63 | 59.0 (2) |
C2—N3—C4—Cl4 | −179.11 (11) | N61—C62—C63—C64 | −56.4 (2) |
N3—C4—C5—C6 | 0.7 (3) | C62—C63—C64—C65 | 54.1 (2) |
Cl4—C4—C5—C6 | −178.66 (12) | C63—C64—C65—C66 | −53.5 (2) |
C2—N1—C6—N61 | −179.69 (14) | C6—N61—C66—C65 | 101.77 (19) |
C2—N1—C6—C5 | 2.1 (2) | C62—N61—C66—C65 | −57.7 (2) |
C4—C5—C6—N1 | −2.6 (2) | C64—C65—C66—N61 | 54.58 (19) |
Experimental details
Crystal data | |
Chemical formula | C10H14ClN3S |
Mr | 243.75 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 150 |
a, b, c (Å) | 13.189 (3), 8.577 (2), 20.195 (4) |
V (Å3) | 2284.4 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.49 |
Crystal size (mm) | 0.40 × 0.40 × 0.36 |
Data collection | |
Diffractometer | Enraf Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.829, 0.844 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11709, 2580, 2124 |
Rint | 0.070 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.117, 1.06 |
No. of reflections | 2580 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.36 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
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The title compound, (I), was prepared from 4,6-dichloro-2-methylthiopyrimidine. Both Cl atoms can be displaced by nucleophiles before the methylthio group but the reactivity of the second Cl atom is much less than the first. This difference in reaction rate can be used to prepare unsymmetrical 4,6-substituted 2-methylthiopyrimidines because the product of the loss of the first Cl atom can be separated in large yield, e.g. compound (I). An interesting feature of the structure of 4,6-dichloro-2-methylthiopyrimidine is that there are six unique molecules in the asymmetric unit (Lynch & McClenaghan, 2000); differences arising due to the out-of-plane twist the methylthio bond makes with respect to the pyrimidine ring. The structure determination of the title compound was undertaken within a study of the effects that different substituents of 2-methylthiopyrimidines have on the pyrimidine–methylthio torsion angle.