The title compound, C
12H
18O
4S
2, exhibits fungicidal activity. A short S
S intermolecular contact [3.576 (3)Å] is observed in the crystal structure, which is further stabilized by C—H
O intermolecular interactions, forming molecular chains along the
b axis.
Supporting information
CCDC reference: 262421
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.010 Å
- R factor = 0.090
- wR factor = 0.205
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT220_ALERT_2_A Large Non-Solvent C Ueq(max)/Ueq(min) ... 4.54 Ratio
| Author Response:
The carbon atoms C7 and C8 of the isopropyl group have large thermal
parameters compared to the riding hydrogen and hence the ratio
Ueq(max)/Ueq(min) has a large value.
|
PLAT222_ALERT_3_A Large Non-Solvent H Ueq(max)/Ueq(min) ... 6.68 Ratio
| Author Response: The carbon atoms C7 and C8 of the isopropyl group have large
thermal
parameters compared to the riding hydrogen and hence the ratio
Ueq(max)/Ueq(min) has a large value.
|
PLAT242_ALERT_2_A Check Low Ueq as Compared to Neighbors for C9
| Author Response: In the isopropyl group, the thermal parameters of carbon atoms
C7 and C8 is greater than that of C9 to which these are connected.
This is due to greater vibrational freedom of the carbon atoms C7 and
C8 compared to C9.
|
Alert level C
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C5
| Author Response: In the isopropyl group, the thermal parameters of carbon atoms
C7 and C8 is greater than that of C9 to which these are connected.
This is due to greater vibrational freedom of the carbon atoms C7 and
C8 compared to C9.
|
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C10
| Author Response: In the isopropyl group, the thermal parameters of carbon atoms
C7 and C8 is greater than that of C9 to which these are connected.
This is due to greater vibrational freedom of the carbon atoms C7 and
C8 compared to C9.
|
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 10
PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C7 - C9 ... 1.40 Ang.
3 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
5 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 1990).
diisopropyl (1,3-dithiolan-2-ylidene)malonate
top
Crystal data top
C12H18O4S2 | F(000) = 1232 |
Mr = 290.40 | Dx = 1.268 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 675 reflections |
a = 10.400 (7) Å | θ = 1.9–24.4° |
b = 9.117 (6) Å | µ = 0.35 mm−1 |
c = 32.09 (2) Å | T = 293 K |
V = 3043 (3) Å3 | Block, colorless |
Z = 8 | 0.23 × 0.11 × 0.02 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2681 independent reflections |
Radiation source: fine-focus sealed tube | 1925 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
φ and ω scans | θmax = 25.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→11 |
Tmin = 0.943, Tmax = 0.993 | k = −10→10 |
20345 measured reflections | l = −38→34 |
Refinement top
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)] = 0.090 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.205 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.22 | w = 1/[σ2(Fo2) + (0.0874P)2 + 1.215P] where P = (Fo2 + 2Fc2)/3 |
2681 reflections | (Δ/σ)max = 0.001 |
191 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
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 >
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 (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.74652 (12) | 0.09080 (16) | 0.59790 (4) | 0.0777 (5) | |
S2 | 0.92128 (11) | 0.14398 (13) | 0.52795 (4) | 0.0653 (4) | |
O1 | 0.8733 (5) | 0.1781 (6) | 0.67037 (13) | 0.1322 (19) | |
O2 | 1.1185 (3) | 0.3271 (4) | 0.55557 (11) | 0.0825 (11) | |
O3 | 1.1891 (3) | 0.2926 (4) | 0.62048 (10) | 0.0712 (9) | |
O4 | 0.9837 (4) | 0.3851 (4) | 0.66638 (11) | 0.0886 (11) | |
C1 | 0.7926 (5) | 0.0139 (6) | 0.5189 (2) | 0.0733 (14) | |
C2 | 0.6832 (5) | 0.0569 (6) | 0.54649 (19) | 0.0737 (15) | |
C3 | 0.8923 (4) | 0.1680 (4) | 0.58113 (15) | 0.0572 (12) | |
C4 | 0.9743 (4) | 0.2402 (5) | 0.60720 (14) | 0.0563 (11) | |
C5 | 0.9391 (5) | 0.2614 (6) | 0.65102 (16) | 0.0734 (14) | |
C6 | 1.0992 (4) | 0.2917 (5) | 0.59100 (16) | 0.0580 (11) | |
C7 | 0.8881 (12) | 0.5431 (16) | 0.7129 (3) | 0.254 (8) | |
C8 | 1.0887 (11) | 0.4374 (17) | 0.7311 (3) | 0.225 (6) | |
C9 | 0.9611 (8) | 0.4148 (10) | 0.7112 (2) | 0.111 (2) | |
C10 | 1.3179 (5) | 0.3493 (7) | 0.61023 (19) | 0.0764 (15) | |
C11 | 1.3952 (6) | 0.2307 (9) | 0.5908 (2) | 0.121 (2) | |
C12 | 1.3727 (6) | 0.4053 (8) | 0.6509 (2) | 0.115 (2) | |
H1A | 0.773 (5) | 0.014 (6) | 0.4896 (19) | 0.096 (19)* | |
H1B | 0.830 (5) | −0.084 (6) | 0.5265 (15) | 0.086 (15)* | |
H2A | 0.621 (5) | −0.014 (5) | 0.5489 (13) | 0.067 (13)* | |
H2B | 0.641 (5) | 0.147 (5) | 0.5367 (14) | 0.075 (14)* | |
H7A | 0.9330 | 0.6207 | 0.6989 | 0.381* | |
H7B | 0.8743 | 0.5700 | 0.7415 | 0.381* | |
H7C | 0.8067 | 0.5270 | 0.6996 | 0.381* | |
H8A | 1.1280 | 0.5243 | 0.7200 | 0.337* | |
H8B | 1.1428 | 0.3543 | 0.7256 | 0.337* | |
H8C | 1.0777 | 0.4483 | 0.7607 | 0.337* | |
H9 | 0.941 (5) | 0.326 (6) | 0.7277 (17) | 0.089 (18)* | |
H10 | 1.316 (4) | 0.434 (5) | 0.5952 (13) | 0.057 (13)* | |
H11A | 1.3983 | 0.1479 | 0.6093 | 0.182* | |
H11B | 1.4808 | 0.2655 | 0.5857 | 0.182* | |
H11C | 1.3563 | 0.2021 | 0.5649 | 0.182* | |
H12A | 1.3217 | 0.4861 | 0.6607 | 0.173* | |
H12B | 1.4596 | 0.4375 | 0.6466 | 0.173* | |
H12C | 1.3715 | 0.3281 | 0.6712 | 0.173* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0608 (8) | 0.0879 (10) | 0.0843 (10) | −0.0183 (7) | 0.0118 (7) | 0.0085 (7) |
S2 | 0.0597 (7) | 0.0664 (8) | 0.0697 (8) | −0.0022 (6) | 0.0093 (6) | −0.0093 (6) |
O1 | 0.167 (4) | 0.150 (4) | 0.079 (3) | −0.082 (4) | 0.039 (3) | −0.002 (3) |
O2 | 0.066 (2) | 0.120 (3) | 0.062 (2) | −0.025 (2) | 0.0046 (17) | 0.014 (2) |
O3 | 0.0538 (18) | 0.087 (2) | 0.073 (2) | −0.0062 (16) | −0.0018 (16) | 0.0172 (18) |
O4 | 0.109 (3) | 0.092 (3) | 0.064 (2) | −0.021 (2) | 0.024 (2) | −0.0106 (19) |
C1 | 0.067 (3) | 0.061 (3) | 0.093 (4) | −0.001 (3) | −0.003 (3) | −0.010 (3) |
C2 | 0.054 (3) | 0.057 (3) | 0.110 (4) | −0.009 (3) | −0.004 (3) | 0.003 (3) |
C3 | 0.051 (2) | 0.049 (3) | 0.071 (3) | 0.008 (2) | 0.009 (2) | 0.013 (2) |
C4 | 0.053 (3) | 0.057 (3) | 0.058 (3) | −0.001 (2) | 0.004 (2) | 0.005 (2) |
C5 | 0.065 (3) | 0.085 (4) | 0.070 (3) | −0.015 (3) | 0.006 (3) | 0.007 (3) |
C6 | 0.055 (3) | 0.058 (3) | 0.061 (3) | −0.003 (2) | 0.003 (2) | 0.004 (2) |
C7 | 0.286 (14) | 0.375 (18) | 0.100 (6) | 0.226 (14) | −0.019 (8) | −0.047 (9) |
C8 | 0.191 (11) | 0.380 (18) | 0.104 (7) | 0.054 (11) | −0.029 (7) | −0.059 (9) |
C9 | 0.127 (6) | 0.129 (6) | 0.076 (5) | −0.017 (5) | 0.019 (4) | −0.017 (4) |
C10 | 0.057 (3) | 0.081 (4) | 0.091 (4) | −0.012 (3) | 0.000 (3) | 0.016 (3) |
C11 | 0.064 (4) | 0.134 (6) | 0.167 (7) | 0.007 (4) | 0.010 (4) | −0.018 (5) |
C12 | 0.097 (5) | 0.129 (6) | 0.120 (6) | −0.031 (4) | −0.024 (4) | 0.002 (4) |
Geometric parameters (Å, º) top
C1—C2 | 1.494 (8) | C9—C7 | 1.396 (12) |
C1—H1A | 0.96 (6) | C9—C8 | 1.488 (12) |
C1—H1B | 1.01 (5) | C9—H9 | 0.99 (5) |
S1—C2 | 1.803 (6) | C8—H8A | 0.9600 |
S1—C3 | 1.756 (4) | C8—H8B | 0.9600 |
S2—C1 | 1.811 (5) | C8—H8C | 0.9600 |
S2—C3 | 1.747 (5) | C10—C11 | 1.484 (8) |
C3—C4 | 1.364 (6) | C10—C12 | 1.512 (8) |
C4—C5 | 1.466 (7) | C10—H10 | 0.91 (4) |
C6—C4 | 1.477 (6) | C11—H11A | 0.9600 |
O2—C6 | 1.199 (5) | C11—H11B | 0.9600 |
O3—C6 | 1.330 (5) | C11—H11C | 0.9600 |
C5—O1 | 1.196 (6) | C12—H12A | 0.9600 |
O4—C5 | 1.315 (6) | C12—H12B | 0.9600 |
O3—C10 | 1.473 (6) | C12—H12C | 0.9600 |
O4—C9 | 1.481 (7) | C7—H7A | 0.9600 |
C2—H2A | 0.92 (5) | C7—H7B | 0.9600 |
C2—H2B | 0.98 (5) | C7—H7C | 0.9600 |
| | | |
C3—S1—C2 | 96.0 (2) | O4—C9—H9 | 114 (3) |
C3—S2—C1 | 96.4 (3) | C8—C9—H9 | 94 (3) |
C4—C3—S1 | 123.0 (4) | C9—C8—H8A | 109.5 |
C4—C3—S2 | 123.5 (3) | C9—C8—H8B | 109.5 |
C3—C4—C5 | 119.7 (4) | H8A—C8—H8B | 109.5 |
C3—C4—C6 | 119.2 (4) | C9—C8—H8C | 109.5 |
C5—C4—C6 | 121.0 (4) | H8A—C8—H8C | 109.5 |
C6—O3—C10 | 118.8 (4) | H8B—C8—H8C | 109.5 |
O2—C6—O3 | 123.8 (4) | O3—C10—C11 | 109.3 (5) |
O2—C6—C4 | 124.5 (4) | O3—C10—C12 | 105.6 (5) |
O3—C6—C4 | 111.7 (4) | C11—C10—C12 | 113.8 (6) |
C2—C1—S2 | 107.2 (4) | O3—C10—H10 | 113 (3) |
C2—C1—H1A | 115 (3) | C11—C10—H10 | 114 (3) |
S2—C1—H1A | 108 (3) | C12—C10—H10 | 100 (3) |
C2—C1—H1B | 113 (3) | C10—C11—H11A | 109.5 |
S2—C1—H1B | 105 (3) | C10—C11—H11B | 109.5 |
H1A—C1—H1B | 109 (4) | H11A—C11—H11B | 109.5 |
S2—C3—S1 | 113.5 (3) | C10—C11—H11C | 109.5 |
C5—O4—C9 | 117.7 (5) | H11A—C11—H11C | 109.5 |
O1—C5—O4 | 123.5 (5) | H11B—C11—H11C | 109.5 |
O1—C5—C4 | 123.8 (5) | C10—C12—H12A | 109.5 |
O4—C5—C4 | 112.6 (4) | C10—C12—H12B | 109.5 |
C1—C2—S1 | 108.0 (4) | H12A—C12—H12B | 109.5 |
C1—C2—H2A | 114 (3) | C10—C12—H12C | 109.5 |
S1—C2—H2A | 107 (3) | H12A—C12—H12C | 109.5 |
C1—C2—H2B | 112 (3) | H12B—C12—H12C | 109.5 |
S1—C2—H2B | 108 (3) | C9—C7—H7A | 109.5 |
H2A—C2—H2B | 107 (4) | C9—C7—H7B | 109.5 |
C7—C9—O4 | 106.2 (7) | H7A—C7—H7B | 109.5 |
C7—C9—C8 | 110.6 (10) | C9—C7—H7C | 109.5 |
O4—C9—C8 | 107.6 (6) | H7A—C7—H7C | 109.5 |
C7—C9—H9 | 123 (3) | H7B—C7—H7C | 109.5 |
| | | |
C10—O3—C6—O2 | 4.3 (7) | O3—C6—C4—C5 | 28.7 (6) |
C10—O3—C6—C4 | −176.5 (4) | C9—O4—C5—O1 | 6.0 (9) |
C3—S2—C1—C2 | 35.1 (5) | C9—O4—C5—C4 | −176.4 (5) |
C1—S2—C3—C4 | 169.4 (4) | C3—C4—C5—O1 | 30.4 (8) |
C1—S2—C3—S1 | −10.8 (3) | C6—C4—C5—O1 | −147.7 (6) |
C2—S1—C3—C4 | 168.1 (4) | C3—C4—C5—O4 | −147.1 (4) |
C2—S1—C3—S2 | −11.6 (3) | C6—C4—C5—O4 | 34.8 (6) |
S2—C3—C4—C5 | 177.0 (3) | S2—C1—C2—S1 | −46.9 (5) |
S1—C3—C4—C5 | −2.7 (6) | C3—S1—C2—C1 | 35.9 (4) |
S2—C3—C4—C6 | −4.9 (6) | C5—O4—C9—C7 | −119.0 (9) |
S1—C3—C4—C6 | 175.4 (3) | C5—O4—C9—C8 | 122.6 (9) |
O2—C6—C4—C3 | 29.8 (7) | C6—O3—C10—C11 | −84.3 (6) |
O3—C6—C4—C3 | −149.4 (4) | C6—O3—C10—C12 | 152.9 (5) |
O2—C6—C4—C5 | −152.1 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7C···O1i | 0.96 | 2.51 | 3.281 (19) | 138 (1) |
Symmetry code: (i) −x+3/2, y+1/2, z. |