In the title compound, C
22H
28N
2O
2S, the carbonyl group closer to the thiol group is almost perpendicular to the attached benzene ring. The crystal packing is stabilized by intermolecular N—H
O and C—H
O hydrogen bonds.
Supporting information
CCDC reference: 270280
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.060
- wR factor = 0.176
- Data-to-parameter ratio = 17.5
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 47 Perc.
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.96 Ratio
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.09 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for O1 - C1 .. 5.74 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C10
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT414_ALERT_2_C Short Intra D-H..H-X H2 .. H16 .. 1.99 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor S1 - H1 ... ?
PLAT721_ALERT_1_C Bond Calc 1.01697, Rep 1.00000 Dev... 0.02 Ang.
S1 -H1 1.555 1.555
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
10 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 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
3 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
1-
tert-Butyl-2-(4-ethylbenzoyl)-1-(2-mercapto-3,5-dimethylbenzoyl)hydrazine
top
Crystal data top
C22H28N2O2S | F(000) = 824 |
Mr = 384.52 | Dx = 1.181 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.656 (3) Å | Cell parameters from 1021 reflections |
b = 9.960 (3) Å | θ = 3.0–21.6° |
c = 18.796 (5) Å | µ = 0.17 mm−1 |
β = 97.776 (5)° | T = 293 K |
V = 2162.1 (10) Å3 | Granular, colourless |
Z = 4 | 0.30 × 0.24 × 0.18 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4433 independent reflections |
Radiation source: fine-focus sealed tube | 2103 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
φ and ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −14→14 |
Tmin = 0.938, Tmax = 0.970 | k = −12→4 |
12135 measured reflections | l = −23→23 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.176 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.083P)2 + 0.0808P] where P = (Fo2 + 2Fc2)/3 |
4433 reflections | (Δ/σ)max = 0.001 |
254 parameters | Δρmax = 0.41 e Å−3 |
2 restraints | Δρmin = −0.27 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 | 0.43437 (8) | 0.50344 (10) | 0.21838 (4) | 0.0717 (3) | |
H1 | 0.4146 | 0.4200 | 0.1880 | 0.108* | |
O1 | 0.21414 (16) | 0.3035 (2) | 0.23290 (10) | 0.0575 (6) | |
O2 | 0.0933 (2) | 0.4731 (2) | 0.41760 (11) | 0.0720 (7) | |
N1 | 0.1483 (2) | 0.4875 (2) | 0.28455 (11) | 0.0467 (6) | |
N2 | 0.1754 (2) | 0.5877 (3) | 0.33535 (12) | 0.0478 (6) | |
H2 | 0.206 (2) | 0.6628 (18) | 0.3231 (14) | 0.067 (10)* | |
C1 | 0.2287 (2) | 0.3927 (3) | 0.27809 (15) | 0.0481 (7) | |
C2 | 0.3404 (2) | 0.3997 (3) | 0.32907 (15) | 0.0497 (7) | |
C3 | 0.4413 (3) | 0.4426 (3) | 0.30521 (16) | 0.0571 (8) | |
C4 | 0.5470 (3) | 0.4357 (4) | 0.34899 (19) | 0.0668 (9) | |
C5 | 0.5484 (3) | 0.3821 (4) | 0.41679 (19) | 0.0746 (10) | |
H5 | 0.6188 | 0.3758 | 0.4465 | 0.090* | |
C6 | 0.4488 (3) | 0.3371 (3) | 0.44259 (16) | 0.0662 (9) | |
C7 | 0.3447 (3) | 0.3473 (3) | 0.39758 (16) | 0.0591 (9) | |
H7 | 0.2768 | 0.3186 | 0.4137 | 0.071* | |
C8 | 0.6583 (3) | 0.4822 (5) | 0.3237 (2) | 0.1029 (14) | |
H8A | 0.7187 | 0.4861 | 0.3638 | 0.154* | |
H8B | 0.6470 | 0.5697 | 0.3025 | 0.154* | |
H8C | 0.6798 | 0.4202 | 0.2887 | 0.154* | |
C9 | 0.4552 (4) | 0.2751 (4) | 0.51625 (18) | 0.0947 (13) | |
H9A | 0.4721 | 0.1810 | 0.5134 | 0.142* | |
H9B | 0.3824 | 0.2866 | 0.5340 | 0.142* | |
H9C | 0.5153 | 0.3181 | 0.5483 | 0.142* | |
C10 | 0.0323 (2) | 0.4921 (3) | 0.23757 (15) | 0.0516 (8) | |
C11 | −0.0310 (3) | 0.3610 (4) | 0.24578 (19) | 0.0747 (10) | |
H11A | 0.0106 | 0.2885 | 0.2273 | 0.112* | |
H11B | −0.1076 | 0.3660 | 0.2196 | 0.112* | |
H11C | −0.0362 | 0.3454 | 0.2957 | 0.112* | |
C12 | 0.0532 (3) | 0.5152 (4) | 0.16048 (16) | 0.0762 (10) | |
H12A | 0.0992 | 0.5946 | 0.1580 | 0.114* | |
H12B | −0.0197 | 0.5263 | 0.1305 | 0.114* | |
H12C | 0.0932 | 0.4394 | 0.1442 | 0.114* | |
C13 | −0.0387 (3) | 0.6078 (4) | 0.26055 (19) | 0.0819 (11) | |
H13A | −0.0538 | 0.5935 | 0.3089 | 0.123* | |
H13B | −0.1108 | 0.6132 | 0.2292 | 0.123* | |
H13C | 0.0033 | 0.6902 | 0.2581 | 0.123* | |
C14 | 0.1402 (2) | 0.5754 (3) | 0.40142 (15) | 0.0519 (8) | |
C15 | 0.1607 (2) | 0.6919 (3) | 0.45014 (13) | 0.0467 (7) | |
C16 | 0.2196 (3) | 0.8064 (3) | 0.43483 (16) | 0.0631 (9) | |
H16 | 0.2505 | 0.8122 | 0.3918 | 0.076* | |
C17 | 0.2331 (3) | 0.9117 (4) | 0.48231 (16) | 0.0739 (10) | |
H17 | 0.2731 | 0.9876 | 0.4707 | 0.089* | |
C18 | 0.1891 (3) | 0.9079 (4) | 0.54654 (16) | 0.0683 (10) | |
C19 | 0.1303 (3) | 0.7942 (4) | 0.56147 (16) | 0.0751 (10) | |
H19 | 0.0992 | 0.7891 | 0.6044 | 0.090* | |
C20 | 0.1162 (3) | 0.6875 (4) | 0.51452 (16) | 0.0647 (9) | |
H20 | 0.0763 | 0.6116 | 0.5263 | 0.078* | |
C21 | 0.2038 (4) | 1.0247 (5) | 0.59777 (19) | 0.0969 (13) | |
H21A | 0.1882 | 0.9951 | 0.6447 | 0.116* | |
H21B | 0.2834 | 1.0553 | 0.6026 | 0.116* | |
C22 | 0.1272 (4) | 1.1365 (5) | 0.5741 (3) | 0.138 (2) | |
H22A | 0.1376 | 1.1614 | 0.5261 | 0.207* | |
H22B | 0.1453 | 1.2117 | 0.6056 | 0.207* | |
H22C | 0.0482 | 1.1101 | 0.5752 | 0.207* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0753 (6) | 0.0771 (7) | 0.0665 (6) | −0.0105 (5) | 0.0225 (4) | 0.0025 (5) |
O1 | 0.0626 (13) | 0.0531 (13) | 0.0573 (12) | 0.0026 (11) | 0.0101 (10) | −0.0166 (11) |
O2 | 0.0869 (16) | 0.0603 (15) | 0.0760 (15) | −0.0176 (13) | 0.0375 (13) | 0.0017 (12) |
N1 | 0.0465 (13) | 0.0456 (15) | 0.0488 (13) | −0.0010 (13) | 0.0095 (11) | −0.0086 (12) |
N2 | 0.0570 (15) | 0.0415 (16) | 0.0477 (14) | −0.0069 (14) | 0.0173 (12) | −0.0056 (13) |
C1 | 0.0503 (18) | 0.0471 (19) | 0.0501 (16) | −0.0012 (16) | 0.0188 (14) | 0.0025 (16) |
C2 | 0.0511 (17) | 0.0462 (18) | 0.0525 (17) | 0.0036 (15) | 0.0094 (14) | −0.0051 (15) |
C3 | 0.0566 (19) | 0.054 (2) | 0.0623 (19) | 0.0004 (17) | 0.0133 (16) | −0.0056 (16) |
C4 | 0.055 (2) | 0.068 (2) | 0.079 (2) | 0.0013 (18) | 0.0103 (18) | −0.005 (2) |
C5 | 0.061 (2) | 0.082 (3) | 0.075 (2) | 0.001 (2) | −0.0098 (18) | −0.005 (2) |
C6 | 0.073 (2) | 0.066 (2) | 0.0571 (19) | 0.007 (2) | −0.0001 (18) | −0.0055 (17) |
C7 | 0.061 (2) | 0.060 (2) | 0.0574 (19) | 0.0027 (17) | 0.0119 (16) | −0.0010 (17) |
C8 | 0.052 (2) | 0.129 (4) | 0.128 (3) | −0.012 (2) | 0.013 (2) | 0.010 (3) |
C9 | 0.107 (3) | 0.102 (3) | 0.070 (2) | 0.002 (3) | −0.008 (2) | 0.014 (2) |
C10 | 0.0479 (17) | 0.051 (2) | 0.0551 (17) | 0.0004 (16) | 0.0035 (14) | 0.0017 (16) |
C11 | 0.058 (2) | 0.068 (2) | 0.096 (3) | −0.0148 (19) | 0.0022 (18) | 0.014 (2) |
C12 | 0.074 (2) | 0.089 (3) | 0.065 (2) | −0.001 (2) | 0.0050 (17) | 0.015 (2) |
C13 | 0.063 (2) | 0.081 (3) | 0.099 (3) | 0.021 (2) | 0.0014 (19) | −0.011 (2) |
C14 | 0.0525 (18) | 0.052 (2) | 0.0549 (18) | 0.0004 (16) | 0.0196 (14) | 0.0045 (17) |
C15 | 0.0476 (17) | 0.054 (2) | 0.0403 (15) | 0.0012 (15) | 0.0138 (13) | 0.0010 (15) |
C16 | 0.077 (2) | 0.069 (2) | 0.0475 (17) | −0.0116 (19) | 0.0233 (16) | −0.0126 (18) |
C17 | 0.094 (3) | 0.075 (3) | 0.0554 (19) | −0.023 (2) | 0.0218 (18) | −0.0137 (19) |
C18 | 0.074 (2) | 0.081 (3) | 0.0502 (19) | 0.000 (2) | 0.0115 (16) | −0.0156 (19) |
C19 | 0.086 (3) | 0.099 (3) | 0.0452 (18) | −0.002 (2) | 0.0252 (17) | −0.009 (2) |
C20 | 0.072 (2) | 0.072 (2) | 0.0542 (18) | −0.0052 (19) | 0.0220 (16) | 0.0033 (19) |
C21 | 0.097 (3) | 0.123 (4) | 0.069 (2) | 0.006 (3) | 0.006 (2) | −0.035 (3) |
C22 | 0.134 (4) | 0.149 (5) | 0.127 (4) | 0.048 (4) | 0.003 (3) | −0.057 (4) |
Geometric parameters (Å, º) top
S1—C3 | 1.733 (3) | C10—C12 | 1.519 (4) |
S1—H1 | 1.0 | C11—H11A | 0.9600 |
O1—C1 | 1.225 (3) | C11—H11B | 0.9600 |
O2—C14 | 1.215 (3) | C11—H11C | 0.9600 |
N1—C1 | 1.347 (3) | C12—H12A | 0.9600 |
N1—N2 | 1.388 (3) | C12—H12B | 0.9600 |
N1—C10 | 1.512 (4) | C12—H12C | 0.9600 |
N2—C14 | 1.365 (3) | C13—H13A | 0.9600 |
N2—H2 | 0.87 (1) | C13—H13B | 0.9600 |
C1—C2 | 1.510 (4) | C13—H13C | 0.9600 |
C2—C3 | 1.383 (4) | C14—C15 | 1.477 (4) |
C2—C7 | 1.384 (4) | C15—C20 | 1.380 (4) |
C3—C4 | 1.388 (4) | C15—C16 | 1.381 (4) |
C4—C5 | 1.380 (4) | C16—C17 | 1.372 (4) |
C4—C8 | 1.513 (5) | C16—H16 | 0.9300 |
C5—C6 | 1.391 (5) | C17—C18 | 1.374 (4) |
C5—H5 | 0.9300 | C17—H17 | 0.9300 |
C6—C7 | 1.386 (4) | C18—C19 | 1.372 (5) |
C6—C9 | 1.509 (5) | C18—C21 | 1.505 (5) |
C7—H7 | 0.9300 | C19—C20 | 1.377 (4) |
C8—H8A | 0.9600 | C19—H19 | 0.9300 |
C8—H8B | 0.9600 | C20—H20 | 0.9300 |
C8—H8C | 0.9600 | C21—C22 | 1.458 (5) |
C9—H9A | 0.9600 | C21—H21A | 0.9700 |
C9—H9B | 0.9600 | C21—H21B | 0.9700 |
C9—H9C | 0.9600 | C22—H22A | 0.9600 |
C10—C13 | 1.516 (4) | C22—H22B | 0.9600 |
C10—C11 | 1.519 (4) | C22—H22C | 0.9600 |
| | | |
C3—S1—H1 | 102.8 | C10—C11—H11C | 109.5 |
C1—N1—N2 | 118.0 (2) | H11A—C11—H11C | 109.5 |
C1—N1—C10 | 123.1 (2) | H11B—C11—H11C | 109.5 |
N2—N1—C10 | 118.8 (2) | C10—C12—H12A | 109.5 |
C14—N2—N1 | 119.6 (2) | C10—C12—H12B | 109.5 |
C14—N2—H2 | 120.0 (19) | H12A—C12—H12B | 109.5 |
N1—N2—H2 | 119.9 (19) | C10—C12—H12C | 109.5 |
O1—C1—N1 | 122.6 (3) | H12A—C12—H12C | 109.5 |
O1—C1—C2 | 120.0 (3) | H12B—C12—H12C | 109.5 |
N1—C1—C2 | 117.5 (3) | C10—C13—H13A | 109.5 |
C3—C2—C7 | 119.5 (3) | C10—C13—H13B | 109.5 |
C3—C2—C1 | 120.5 (2) | H13A—C13—H13B | 109.5 |
C7—C2—C1 | 119.6 (3) | C10—C13—H13C | 109.5 |
C2—C3—C4 | 121.2 (3) | H13A—C13—H13C | 109.5 |
C2—C3—S1 | 118.7 (2) | H13B—C13—H13C | 109.5 |
C4—C3—S1 | 120.0 (2) | O2—C14—N2 | 120.2 (3) |
C5—C4—C3 | 117.7 (3) | O2—C14—C15 | 123.0 (3) |
C5—C4—C8 | 120.4 (3) | N2—C14—C15 | 116.8 (3) |
C3—C4—C8 | 121.9 (3) | C20—C15—C16 | 117.7 (3) |
C4—C5—C6 | 122.7 (3) | C20—C15—C14 | 118.0 (3) |
C4—C5—H5 | 118.6 | C16—C15—C14 | 124.2 (2) |
C6—C5—H5 | 118.6 | C17—C16—C15 | 120.8 (3) |
C7—C6—C5 | 117.8 (3) | C17—C16—H16 | 119.6 |
C7—C6—C9 | 121.4 (3) | C15—C16—H16 | 119.6 |
C5—C6—C9 | 120.8 (3) | C16—C17—C18 | 121.8 (3) |
C2—C7—C6 | 121.0 (3) | C16—C17—H17 | 119.1 |
C2—C7—H7 | 119.5 | C18—C17—H17 | 119.1 |
C6—C7—H7 | 119.5 | C19—C18—C17 | 117.3 (3) |
C4—C8—H8A | 109.5 | C19—C18—C21 | 121.6 (3) |
C4—C8—H8B | 109.5 | C17—C18—C21 | 121.2 (4) |
H8A—C8—H8B | 109.5 | C18—C19—C20 | 121.7 (3) |
C4—C8—H8C | 109.5 | C18—C19—H19 | 119.1 |
H8A—C8—H8C | 109.5 | C20—C19—H19 | 119.1 |
H8B—C8—H8C | 109.5 | C19—C20—C15 | 120.7 (3) |
C6—C9—H9A | 109.5 | C19—C20—H20 | 119.6 |
C6—C9—H9B | 109.5 | C15—C20—H20 | 119.6 |
H9A—C9—H9B | 109.5 | C22—C21—C18 | 112.6 (3) |
C6—C9—H9C | 109.5 | C22—C21—H21A | 109.1 |
H9A—C9—H9C | 109.5 | C18—C21—H21A | 109.1 |
H9B—C9—H9C | 109.5 | C22—C21—H21B | 109.1 |
N1—C10—C13 | 109.7 (2) | C18—C21—H21B | 109.1 |
N1—C10—C11 | 108.8 (2) | H21A—C21—H21B | 107.8 |
C13—C10—C11 | 109.5 (3) | C21—C22—H22A | 109.5 |
N1—C10—C12 | 108.4 (2) | C21—C22—H22B | 109.5 |
C13—C10—C12 | 108.7 (3) | H22A—C22—H22B | 109.5 |
C11—C10—C12 | 111.7 (3) | C21—C22—H22C | 109.5 |
C10—C11—H11A | 109.5 | H22A—C22—H22C | 109.5 |
C10—C11—H11B | 109.5 | H22B—C22—H22C | 109.5 |
H11A—C11—H11B | 109.5 | | |
| | | |
C1—N1—N2—C14 | −96.5 (3) | C9—C6—C7—C2 | −177.5 (3) |
C10—N1—N2—C14 | 85.6 (3) | C1—N1—C10—C13 | 178.0 (3) |
N2—N1—C1—O1 | −177.1 (2) | N2—N1—C10—C13 | −4.1 (3) |
C10—N1—C1—O1 | 0.7 (4) | C1—N1—C10—C11 | 58.3 (3) |
N2—N1—C1—C2 | 2.6 (3) | N2—N1—C10—C11 | −123.8 (3) |
C10—N1—C1—C2 | −179.5 (2) | C1—N1—C10—C12 | −63.4 (3) |
O1—C1—C2—C3 | 73.7 (4) | N2—N1—C10—C12 | 114.5 (3) |
N1—C1—C2—C3 | −106.1 (3) | N1—N2—C14—O2 | 5.6 (4) |
O1—C1—C2—C7 | −98.4 (3) | N1—N2—C14—C15 | −173.5 (2) |
N1—C1—C2—C7 | 81.9 (3) | O2—C14—C15—C20 | −5.2 (4) |
C7—C2—C3—C4 | −0.7 (5) | N2—C14—C15—C20 | 173.9 (3) |
C1—C2—C3—C4 | −172.8 (3) | O2—C14—C15—C16 | 176.2 (3) |
C7—C2—C3—S1 | 178.2 (2) | N2—C14—C15—C16 | −4.7 (4) |
C1—C2—C3—S1 | 6.2 (4) | C20—C15—C16—C17 | 0.0 (5) |
C2—C3—C4—C5 | 1.2 (5) | C14—C15—C16—C17 | 178.6 (3) |
S1—C3—C4—C5 | −177.8 (3) | C15—C16—C17—C18 | 0.0 (6) |
C2—C3—C4—C8 | 180.0 (3) | C16—C17—C18—C19 | −0.3 (5) |
S1—C3—C4—C8 | 1.0 (5) | C16—C17—C18—C21 | −179.5 (3) |
C3—C4—C5—C6 | −0.8 (5) | C17—C18—C19—C20 | 0.4 (5) |
C8—C4—C5—C6 | −179.6 (3) | C21—C18—C19—C20 | 179.6 (3) |
C4—C5—C6—C7 | 0.0 (5) | C18—C19—C20—C15 | −0.4 (5) |
C4—C5—C6—C9 | 178.0 (3) | C16—C15—C20—C19 | 0.2 (5) |
C3—C2—C7—C6 | −0.1 (5) | C14—C15—C20—C19 | −178.6 (3) |
C1—C2—C7—C6 | 172.0 (3) | C19—C18—C21—C22 | −103.9 (5) |
C5—C6—C7—C2 | 0.5 (5) | C17—C18—C21—C22 | 75.2 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.87 (1) | 2.05 (1) | 2.893 (3) | 162 (3) |
C16—H16···O1i | 0.93 | 2.44 | 3.346 (3) | 166 |
C20—H20···O2ii | 0.93 | 2.51 | 3.315 (4) | 145 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1. |