A series of bidentate nitrogen–sulfur pro-ligands has been designed and synthesized with the purpose of introducing a structural modification that favours the tetrahedral site distortions of metalloprotein systems with metallic centers surrounded by ligands containing two N atoms and two S atoms as donor groups. Some of these new pro-ligands were obtained only as powders. Here we present the molecular and crystalline structure of cycloheptanespiro-3′(4′
H)-6′,7′,8′,9′-tetrahydrocyclohexa[
b][1,4]thiazole-2′(5′
H)-thione (I) solved and refined from powder synchrotron X-ray diffraction data. Two independent molecules comprising a total of 36 non-H atoms were obtained from the direct-methods solution and refined against the powder X-ray diffraction data using the Rietveld method. The molecular conformations of the heterocyclic benzothiazine ring, the fused heptenyl ring and the heptanyl spiro ring are thoroughly discussed and compared with VASP theoretical calculations and other related structures. The packing of molecules in (I) is based on hydrogen bonds of the type N—H
S and hydrophobic C—H interactions.
Supporting information
CCDC reference: 685154
Program(s) used to solve structure: EXPO2004 (Altomare, et al., 2004; program(s) used to refine structure: GSAS (von Dreele, 2004); molecular graphics: PLATON (Spek, 1999) and DIAMOND 2.1 (Brandenburg, 2001)'; software used to prepare material for publication: GSAS2CIF (von Dreele, 2004), PLATON (Spek, 1999) and publCIF (Westrip, 2007).
2-spiro(cycloheptane)-4-thiono-[5,6,7,8]-tetrahydro-(1
H,4H)-3,1-
cyclo- heptatiazine
top
Crystal data top
C15H23NS2 | F(000) = 1216.0 |
Mr = 281.48 | Dx = 1.245 Mg m−3 |
Monoclinic, P21/c | Melting point: 473 K |
Hall symbol: -P 2ybc | Synchrotron radiation, λ = 1.25248 Å |
a = 13.11563 (4) Å | µ = 1.99 mm−1 |
b = 21.32201 (6) Å | T = 298 K |
c = 11.75591 (3) Å | Particle morphology: thin powder |
β = 113.9899 (1)° | yellow |
V = 3003.57 (2) Å3 | cylinder, 40.0 × 1.5 mm |
Z = 8 | Specimen preparation: Prepared at 298 K |
Data collection top
High Resolution Diffractometer | Specimen mounting: borosilicate glass capillary |
Radiation source: synchrotron, Beamline ID31 | Data collection mode: transmission |
Double crystal Si 111 monochromator | Scan method: continuous |
Refinement top
Refinement on Inet | Profile function: CW Profile function number 4 with 21 terms
Pseudovoigt profile coefficients as parameterized in
P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83.
Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994).
J. Appl. Cryst.,27,892-900.
Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289.
#1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.021
#4(GP) = 0.000 #5(LX) = 0.533 #6(ptec) = 0.26
#7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00
#10(S/L) = 0.0030 #11(H/L) = 0.0025 #12(eta) = 0.0000
#13(S400 ) = 3.3E-04 #14(S040 ) = 1.0E-05 #15(S004 ) = 3.3E-04
#16(S220 ) = 3.6E-05 #17(S202 ) = 4.3E-05 #18(S022 ) = 3.6E-05
#19(S301 ) = 2.3E-04 #20(S103 ) = 1.2E-04 #21(S121 ) = 2.1E-05
Peak tails are ignored where the intensity is below 0.0010 times the peak
Aniso. broadening axis 0.0 0.0 1.0 |
Least-squares matrix: full | 293 parameters |
Rp = 0.050 | 252 restraints |
Rwp = 0.061 | 6 constraints |
Rexp = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
RBragg = 0.153 | Weighting scheme based on measured s.u.'s wi = 1/σi2 |
R(F2) = 0.15339 | (Δ/σ)max = 0.07 |
χ2 = 6.300 | Background function: GSAS Background function number 1 with 20 terms.
Shifted Chebyshev function of 1st kind
1: 1420.43 2: -362.944 3: 112.717 4: -99.9419
5: 101.466 6: -204.596 7: 147.588 8: -117.114
9: 35.1087 10: 59.3425 11: -57.1978 12: -16.0827
13: 40.9099 14: -34.6154 15: 4.09785 16: 8.43750
17: -24.0855 18: 11.1225 19: 13.3442 20: -17.9072 |
20986 data points | Preferred orientation correction: none |
Excluded region(s): none | |
Crystal data top
C15H23NS2 | V = 3003.57 (2) Å3 |
Mr = 281.48 | Z = 8 |
Monoclinic, P21/c | Synchrotron radiation, λ = 1.25248 Å |
a = 13.11563 (4) Å | µ = 1.99 mm−1 |
b = 21.32201 (6) Å | T = 298 K |
c = 11.75591 (3) Å | cylinder, 40.0 × 1.5 mm |
β = 113.9899 (1)° | |
Data collection top
High Resolution Diffractometer | Data collection mode: transmission |
Specimen mounting: borosilicate glass capillary | Scan method: continuous |
Refinement top
Rp = 0.050 | χ2 = 6.300 |
Rwp = 0.061 | 20986 data points |
Rexp = 0.025 | 293 parameters |
RBragg = 0.153 | 252 restraints |
R(F2) = 0.15339 | H atoms treated by a mixture of independent and constrained refinement |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.0766 (2) | 0.19343 (12) | 1.0006 (3) | 0.0287 (7)* | |
S2 | 0.2063 (2) | 0.21857 (13) | 0.8572 (3) | 0.0287 (7)* | |
N1 | 0.3894 (5) | 0.1441 (3) | 0.9288 (6) | 0.0287 (7)* | |
H1 | 0.4581 (16) | 0.1484 (14) | 0.9406 (17) | 0.0294 (8)* | |
C1 | 0.1898 (5) | 0.1754 (3) | 0.9723 (7) | 0.0287 (7)* | |
C2 | 0.2606 (6) | 0.1214 (3) | 1.0243 (8) | 0.0287 (7)* | |
C3 | 0.3618 (6) | 0.1141 (4) | 1.0156 (8) | 0.0287 (7)* | |
C4 | 0.4487 (6) | 0.0673 (4) | 1.0966 (7) | 0.0471 (19)* | |
H41 | 0.4163 (17) | 0.0257 (5) | 1.0891 (19) | 0.052 (2)* | |
H42 | 0.5123 (13) | 0.0640 (11) | 1.0749 (19) | 0.052 (2)* | |
C5 | 0.4816 (7) | 0.0889 (4) | 1.2288 (7) | 0.0471 (19)* | |
H51 | 0.470 (2) | 0.1338 (5) | 1.220 (2) | 0.052 (2)* | |
H52 | 0.5609 (8) | 0.0828 (13) | 1.2763 (17) | 0.052 (2)* | |
C6 | 0.4156 (6) | 0.0673 (4) | 1.3024 (7) | 0.0471 (19)* | |
H61 | 0.4123 (15) | 0.0220 (5) | 1.300 (3) | 0.052 (2)* | |
H62 | 0.4536 (14) | 0.0803 (12) | 1.3882 (10) | 0.052 (2)* | |
C7 | 0.2957 (6) | 0.0883 (4) | 1.2507 (7) | 0.0471 (19)* | |
H71 | 0.2900 (18) | 0.1327 (6) | 1.2655 (18) | 0.052 (2)* | |
H72 | 0.2560 (15) | 0.0641 (11) | 1.2893 (17) | 0.052 (2)* | |
C8 | 0.2398 (6) | 0.0766 (4) | 1.1138 (7) | 0.0471 (19)* | |
H81 | 0.264 (2) | 0.0344 (5) | 1.105 (2) | 0.052 (2)* | |
H82 | 0.1605 (8) | 0.0747 (12) | 1.094 (2) | 0.052 (2)* | |
C9 | 0.3001 (5) | 0.1683 (3) | 0.8174 (6) | 0.0287 (7)* | |
C10 | 0.3528 (6) | 0.2182 (3) | 0.7587 (7) | 0.0405 (16)* | |
H101 | 0.2926 (12) | 0.2441 (9) | 0.703 (2) | 0.044 (2)* | |
H102 | 0.4021 (15) | 0.2446 (10) | 0.8256 (17) | 0.044 (2)* | |
C11 | 0.4198 (6) | 0.1935 (4) | 0.6879 (7) | 0.0405 (16)* | |
H111 | 0.440 (2) | 0.2310 (6) | 0.655 (2) | 0.044 (2)* | |
H112 | 0.4872 (14) | 0.1747 (12) | 0.7492 (15) | 0.044 (2)* | |
C12 | 0.3745 (7) | 0.1474 (3) | 0.5813 (7) | 0.0405 (16)* | |
H121 | 0.3032 (13) | 0.1614 (9) | 0.5191 (18) | 0.044 (2)* | |
H122 | 0.4261 (19) | 0.1452 (9) | 0.542 (2) | 0.044 (2)* | |
C13 | 0.3608 (7) | 0.0827 (3) | 0.6179 (8) | 0.0405 (16)* | |
H131 | 0.4345 (11) | 0.0639 (9) | 0.652 (3) | 0.044 (2)* | |
H132 | 0.3153 (18) | 0.0610 (10) | 0.5419 (13) | 0.044 (2)* | |
C14 | 0.3094 (7) | 0.0696 (3) | 0.7083 (7) | 0.0405 (16)* | |
H141 | 0.3704 (14) | 0.0614 (12) | 0.7877 (12) | 0.044 (2)* | |
H142 | 0.2672 (14) | 0.0311 (6) | 0.679 (3) | 0.044 (2)* | |
C15 | 0.2294 (6) | 0.1171 (3) | 0.7249 (7) | 0.0405 (16)* | |
H151 | 0.1809 (16) | 0.0966 (8) | 0.758 (2) | 0.044 (2)* | |
H152 | 0.1806 (16) | 0.1351 (9) | 0.6458 (11) | 0.044 (2)* | |
S3 | −0.3518 (2) | 0.40433 (13) | 0.4523 (3) | 0.0294 (7)* | |
S4 | −0.3199 (2) | 0.28822 (13) | 0.5887 (3) | 0.0294 (7)* | |
N2 | −0.1036 (6) | 0.2751 (3) | 0.7481 (6) | 0.0294 (7)* | |
H2 | −0.072 (4) | 0.2610 (12) | 0.8227 (15) | 0.0303 (8)* | |
C16 | −0.2623 (5) | 0.3525 (3) | 0.5475 (7) | 0.0294 (7)* | |
C17 | −0.1464 (5) | 0.3672 (3) | 0.6113 (7) | 0.0294 (7)* | |
C18 | −0.0793 (7) | 0.3344 (3) | 0.7180 (6) | 0.0294 (7)* | |
C19 | 0.0256 (6) | 0.3592 (3) | 0.8217 (7) | 0.0408 (18)* | |
H191 | 0.0790 (16) | 0.3630 (10) | 0.785 (2) | 0.044 (2)* | |
H192 | 0.0548 (19) | 0.3280 (7) | 0.8873 (13) | 0.044 (2)* | |
C20 | 0.0148 (7) | 0.4228 (3) | 0.8785 (7) | 0.0408 (18)* | |
H201 | −0.0439 (18) | 0.4201 (9) | 0.908 (3) | 0.044 (2)* | |
H202 | 0.0826 (14) | 0.4345 (8) | 0.9494 (16) | 0.044 (2)* | |
C21 | −0.0169 (7) | 0.4773 (3) | 0.7887 (7) | 0.0408 (18)* | |
H211 | −0.038 (3) | 0.5104 (8) | 0.8318 (17) | 0.044 (2)* | |
H212 | 0.0526 (12) | 0.4912 (13) | 0.786 (2) | 0.044 (2)* | |
C22 | −0.1002 (7) | 0.4808 (3) | 0.6562 (7) | 0.0408 (18)* | |
H221 | −0.085 (2) | 0.5193 (6) | 0.6229 (18) | 0.044 (2)* | |
H222 | −0.1733 (11) | 0.4833 (11) | 0.658 (2) | 0.044 (2)* | |
C23 | −0.0972 (6) | 0.4233 (3) | 0.5807 (7) | 0.0408 (18)* | |
H231 | −0.1376 (19) | 0.4316 (9) | 0.4928 (9) | 0.044 (2)* | |
H232 | −0.0217 (10) | 0.4133 (8) | 0.592 (3) | 0.044 (2)* | |
C24 | −0.1943 (5) | 0.2388 (3) | 0.6573 (7) | 0.0294 (7)* | |
C25 | −0.2157 (7) | 0.1882 (4) | 0.7403 (7) | 0.078 (2)* | |
H251 | −0.1439 (11) | 0.1698 (8) | 0.792 (2) | 0.089 (3)* | |
H252 | −0.245 (2) | 0.2085 (9) | 0.794 (2) | 0.089 (3)* | |
C26 | −0.2937 (7) | 0.1342 (4) | 0.6750 (8) | 0.078 (2)* | |
H261 | −0.323 (2) | 0.1192 (9) | 0.733 (2) | 0.089 (3)* | |
H262 | −0.3567 (16) | 0.1524 (9) | 0.6067 (17) | 0.089 (3)* | |
C27 | −0.2514 (8) | 0.0788 (4) | 0.6243 (8) | 0.078 (2)* | |
H271 | −0.3129 (14) | 0.0499 (9) | 0.585 (3) | 0.089 (3)* | |
H272 | −0.1946 (17) | 0.0561 (11) | 0.6923 (17) | 0.089 (3)* | |
C28 | −0.2032 (7) | 0.0954 (4) | 0.5304 (9) | 0.078 (2)* | |
H281 | −0.230 (2) | 0.0657 (8) | 0.4620 (17) | 0.089 (3)* | |
H282 | −0.1225 (9) | 0.0913 (12) | 0.573 (3) | 0.089 (3)* | |
C29 | −0.2228 (7) | 0.1611 (4) | 0.4722 (8) | 0.078 (2)* | |
H291 | −0.203 (2) | 0.1594 (9) | 0.4006 (16) | 0.089 (3)* | |
H292 | −0.3013 (9) | 0.1717 (9) | 0.442 (3) | 0.089 (3)* | |
C30 | −0.1475 (7) | 0.2078 (4) | 0.5673 (8) | 0.078 (2)* | |
H301 | −0.133 (2) | 0.2405 (7) | 0.519 (2) | 0.089 (3)* | |
H302 | −0.0778 (13) | 0.1855 (11) | 0.6124 (18) | 0.089 (3)* | |
Geometric parameters (Å, º) top
S1—C1 | 1.693 (8) | C13—H132 | 0.967 (18) |
S2—C1 | 1.721 (8) | C13—H131 | 0.97 (2) |
S2—C9 | 1.830 (7) | C14—H141 | 0.967 (17) |
S3—C16 | 1.668 (8) | C14—H142 | 0.972 (19) |
S4—C16 | 1.727 (7) | C15—H152 | 0.968 (16) |
S4—C24 | 1.842 (8) | C15—H151 | 0.97 (2) |
N1—C3 | 1.372 (11) | C16—C17 | 1.430 (10) |
N1—C9 | 1.451 (9) | C17—C23 | 1.472 (10) |
N1—H1 | 0.86 (2) | C17—C18 | 1.393 (10) |
N2—C18 | 1.385 (10) | C18—C19 | 1.515 (11) |
N2—C24 | 1.456 (10) | C19—C20 | 1.543 (10) |
N2—H2 | 0.858 (19) | C20—C21 | 1.510 (10) |
C1—C2 | 1.449 (10) | C21—C22 | 1.497 (11) |
C2—C8 | 1.526 (11) | C22—C23 | 1.523 (10) |
C2—C3 | 1.381 (12) | C24—C30 | 1.569 (12) |
C3—C4 | 1.523 (11) | C24—C25 | 1.555 (11) |
C4—C5 | 1.506 (11) | C25—C26 | 1.524 (12) |
C5—C6 | 1.523 (12) | C26—C27 | 1.526 (12) |
C6—C7 | 1.505 (12) | C27—C28 | 1.520 (14) |
C7—C8 | 1.494 (11) | C28—C29 | 1.534 (12) |
C9—C10 | 1.573 (10) | C29—C30 | 1.523 (12) |
C9—C15 | 1.554 (10) | C19—H191 | 0.96 (2) |
C10—C11 | 1.529 (11) | C19—H192 | 0.972 (16) |
C11—C12 | 1.511 (10) | C20—H201 | 0.97 (3) |
C12—C13 | 1.478 (10) | C20—H202 | 0.97 (2) |
C13—C14 | 1.498 (13) | C21—H211 | 0.97 (2) |
C14—C15 | 1.527 (11) | C21—H212 | 0.97 (2) |
C4—H41 | 0.972 (15) | C22—H221 | 0.965 (18) |
C4—H42 | 0.97 (2) | C22—H222 | 0.97 (2) |
C5—H51 | 0.968 (14) | C23—H231 | 0.967 (13) |
C5—H52 | 0.969 (18) | C23—H232 | 0.97 (2) |
C6—H62 | 0.966 (15) | C25—H251 | 0.97 (2) |
C6—H61 | 0.967 (14) | C25—H252 | 0.97 (3) |
C7—H71 | 0.971 (16) | C26—H261 | 0.96 (3) |
C7—H72 | 0.97 (2) | C26—H262 | 0.97 (2) |
C8—H81 | 0.974 (17) | C27—H271 | 0.97 (3) |
C8—H82 | 0.970 (17) | C27—H272 | 0.97 (2) |
C10—H102 | 0.97 (2) | C28—H281 | 0.97 (2) |
C10—H101 | 0.97 (2) | C28—H282 | 0.97 (2) |
C11—H111 | 0.971 (19) | C29—H291 | 0.98 (2) |
C11—H112 | 0.97 (2) | C29—H292 | 0.970 (19) |
C12—H121 | 0.97 (2) | C30—H301 | 0.97 (2) |
C12—H122 | 0.96 (3) | C30—H302 | 0.97 (2) |
| | | |
C1—S2—C9 | 101.6 (3) | H151—C15—H152 | 106 (2) |
C16—S4—C24 | 99.3 (4) | C9—C15—H151 | 109.7 (13) |
C3—N1—C9 | 118.5 (7) | C14—C15—H151 | 110.4 (13) |
C9—N1—H1 | 121.1 (16) | C14—C15—H152 | 111.1 (13) |
C3—N1—H1 | 120.4 (16) | S3—C16—S4 | 116.4 (4) |
C18—N2—C24 | 120.2 (6) | S3—C16—C17 | 121.0 (5) |
C18—N2—H2 | 121 (2) | S4—C16—C17 | 121.3 (5) |
C24—N2—H2 | 118 (2) | C16—C17—C18 | 120.7 (7) |
S1—C1—C2 | 124.1 (6) | C18—C17—C23 | 116.7 (7) |
S2—C1—C2 | 119.5 (6) | C16—C17—C23 | 121.9 (6) |
S1—C1—S2 | 115.7 (4) | N2—C18—C19 | 110.0 (6) |
C1—C2—C8 | 121.7 (7) | N2—C18—C17 | 124.2 (7) |
C3—C2—C8 | 115.3 (7) | C17—C18—C19 | 125.7 (6) |
C1—C2—C3 | 121.9 (7) | C18—C19—C20 | 116.2 (7) |
C2—C3—C4 | 121.7 (7) | C19—C20—C21 | 114.9 (6) |
N1—C3—C4 | 114.5 (7) | C20—C21—C22 | 130.0 (6) |
N1—C3—C2 | 123.7 (8) | C21—C22—C23 | 112.7 (6) |
C3—C4—C5 | 105.8 (6) | C17—C23—C22 | 113.2 (7) |
C4—C5—C6 | 120.2 (7) | S4—C24—C25 | 108.3 (5) |
C5—C6—C7 | 115.0 (7) | S4—C24—N2 | 109.6 (5) |
C6—C7—C8 | 111.1 (7) | N2—C24—C30 | 106.9 (6) |
C2—C8—C7 | 119.4 (7) | S4—C24—C30 | 118.1 (6) |
S2—C9—C15 | 108.6 (5) | N2—C24—C25 | 102.2 (6) |
S2—C9—C10 | 100.2 (4) | C25—C24—C30 | 110.5 (6) |
N1—C9—C15 | 114.5 (5) | C24—C25—C26 | 117.6 (6) |
C10—C9—C15 | 114.3 (6) | C25—C26—C27 | 120.4 (8) |
S2—C9—N1 | 110.9 (5) | C26—C27—C28 | 115.4 (6) |
N1—C9—C10 | 107.4 (6) | C27—C28—C29 | 119.5 (8) |
C9—C10—C11 | 117.3 (5) | C28—C29—C30 | 109.2 (7) |
C10—C11—C12 | 123.8 (7) | C24—C30—C29 | 117.1 (8) |
C11—C12—C13 | 114.8 (6) | C18—C19—H191 | 104.9 (15) |
C12—C13—C14 | 121.6 (7) | C18—C19—H192 | 109.6 (13) |
C13—C14—C15 | 119.9 (6) | C20—C19—H191 | 109.3 (14) |
C9—C15—C14 | 108.1 (6) | C20—C19—H192 | 109.5 (11) |
C3—C4—H42 | 112.9 (15) | H191—C19—H192 | 107 (2) |
H41—C4—H42 | 108 (2) | C19—C20—H201 | 109.3 (13) |
C3—C4—H41 | 110.7 (15) | C19—C20—H202 | 112.6 (13) |
C5—C4—H42 | 112.2 (14) | C21—C20—H201 | 105.3 (14) |
C5—C4—H41 | 107.7 (14) | C21—C20—H202 | 107.3 (12) |
C6—C5—H52 | 110.9 (13) | H201—C20—H202 | 107.0 (19) |
C6—C5—H51 | 105.0 (18) | C20—C21—H211 | 104.5 (13) |
C4—C5—H52 | 110.1 (14) | C20—C21—H212 | 105.2 (16) |
C4—C5—H51 | 103.0 (14) | C22—C21—H211 | 105.3 (14) |
H51—C5—H52 | 106 (2) | C22—C21—H212 | 104.4 (15) |
C7—C6—H61 | 105.0 (15) | H211—C21—H212 | 105 (2) |
C5—C6—H61 | 108.3 (15) | C21—C22—H221 | 106.3 (14) |
C5—C6—H62 | 109.6 (14) | C21—C22—H222 | 106.9 (15) |
H61—C6—H62 | 108 (2) | C23—C22—H221 | 113.0 (14) |
C7—C6—H62 | 110.3 (14) | C23—C22—H222 | 108.5 (15) |
C6—C7—H72 | 109.0 (14) | H221—C22—H222 | 109 (2) |
H71—C7—H72 | 110 (2) | C17—C23—H231 | 107.8 (14) |
C6—C7—H71 | 111.2 (16) | C17—C23—H232 | 108.3 (13) |
C8—C7—H72 | 107.1 (13) | C22—C23—H231 | 110.0 (13) |
C8—C7—H71 | 108.4 (13) | C22—C23—H232 | 111.4 (16) |
C7—C8—H82 | 105.9 (15) | H231—C23—H232 | 106 (3) |
C7—C8—H81 | 103.3 (14) | C24—C25—H251 | 107.2 (13) |
H81—C8—H82 | 108 (2) | C24—C25—H252 | 108.7 (14) |
C2—C8—H81 | 110.4 (15) | C26—C25—H251 | 106.9 (13) |
C2—C8—H82 | 109.6 (15) | C26—C25—H252 | 107.7 (17) |
H101—C10—H102 | 108.0 (18) | H251—C25—H252 | 108 (2) |
C11—C10—H101 | 108.6 (14) | C25—C26—H261 | 105.9 (15) |
C11—C10—H102 | 107.5 (14) | C25—C26—H262 | 106.7 (14) |
C9—C10—H102 | 107.7 (13) | C27—C26—H261 | 109.4 (14) |
C9—C10—H101 | 107.4 (13) | C27—C26—H262 | 108.0 (14) |
C12—C11—H111 | 106.5 (14) | H261—C26—H262 | 106 (2) |
C10—C11—H112 | 106.8 (13) | C26—C27—H271 | 108.3 (16) |
C10—C11—H111 | 104.1 (15) | C26—C27—H272 | 110.1 (15) |
H111—C11—H112 | 109 (2) | C28—C27—H271 | 108.2 (19) |
C12—C11—H112 | 106.2 (15) | C28—C27—H272 | 107.9 (16) |
C11—C12—H122 | 108.3 (15) | H271—C27—H272 | 107 (2) |
H121—C12—H122 | 107.7 (19) | C27—C28—H281 | 109.4 (16) |
C11—C12—H121 | 111.0 (13) | C27—C28—H282 | 107.0 (19) |
C13—C12—H121 | 108.2 (14) | C29—C28—H281 | 106.7 (13) |
C13—C12—H122 | 106.7 (13) | C29—C28—H282 | 105.2 (17) |
H131—C13—H132 | 109 (2) | H281—C28—H282 | 109 (2) |
C14—C13—H131 | 106.9 (18) | C28—C29—H291 | 107.2 (14) |
C14—C13—H132 | 106.2 (16) | C28—C29—H292 | 109.7 (14) |
C12—C13—H131 | 106.7 (14) | C30—C29—H291 | 109.7 (15) |
C12—C13—H132 | 106.3 (14) | C30—C29—H292 | 113.1 (14) |
C15—C14—H141 | 109.8 (14) | H291—C29—H292 | 108 (2) |
C13—C14—H142 | 105.2 (18) | C24—C30—H301 | 108.5 (14) |
C13—C14—H141 | 106.5 (14) | C24—C30—H302 | 112.1 (14) |
H141—C14—H142 | 109 (2) | C29—C30—H301 | 105.3 (14) |
C15—C14—H142 | 106.5 (15) | C29—C30—H302 | 105.4 (15) |
C9—C15—H152 | 111.5 (12) | H301—C30—H302 | 108 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S3 | 0.86 (2) | 2.69 (2) | 3.450 (8) | 149 (3) |
N2—H2···S1 | 0.858 (19) | 2.63 (3) | 3.424 (7) | 154 (4) |
C4—H41···S3i | 0.972 (15) | 2.705 (13) | 3.664 (7) | 169.4 (19) |
C4—H42···S3 | 0.97 (2) | 2.79 (2) | 3.701 (9) | 156.5 (18) |
C8—H82···S1 | 0.970 (17) | 2.80 (2) | 3.200 (9) | 105.6 (17) |
C14—H141···N1 | 0.967 (17) | 2.36 (2) | 2.852 (10) | 110.6 (18) |
C23—H231···S3 | 0.967 (13) | 2.72 (2) | 3.081 (9) | 103.1 (17) |
C26—H261···S3 | 0.96 (3) | 2.80 (2) | 3.729 (10) | 162.5 (19) |
Symmetry code: (i) −x, y−1/2, −z+3/2. |
Experimental details
Crystal data |
Chemical formula | C15H23NS2 |
Mr | 281.48 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 13.11563 (4), 21.32201 (6), 11.75591 (3) |
β (°) | 113.9899 (1) |
V (Å3) | 3003.57 (2) |
Z | 8 |
Radiation type | Synchrotron, λ = 1.25248 Å |
µ (mm−1) | 1.99 |
Specimen shape, size (mm) | Cylinder, 40.0 × 1.5 |
|
Data collection |
Diffractometer | High Resolution Diffractometer |
Specimen mounting | Borosilicate glass capillary |
Data collection mode | Transmission |
Scan method | Continuous |
2θ values (°) | 2θmin = ? 2θmax = ? 2θstep = ? |
|
Refinement |
R factors and goodness of fit | Rp = 0.050, Rwp = 0.061, Rexp = 0.025, RBragg = 0.153, R(F2) = 0.15339, χ2 = 6.300 |
No. of data points | 20986 |
No. of parameters | 293 |
No. of restraints | 252 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Selected geometric parameters (Å, º) topS1—C1 | 1.693 (8) | C10—C11 | 1.529 (11) |
S2—C1 | 1.721 (8) | C11—C12 | 1.511 (10) |
S2—C9 | 1.830 (7) | C12—C13 | 1.478 (10) |
S3—C16 | 1.668 (8) | C13—C14 | 1.498 (13) |
S4—C16 | 1.727 (7) | C14—C15 | 1.527 (11) |
S4—C24 | 1.842 (8) | C16—C17 | 1.430 (10) |
N1—C3 | 1.372 (11) | C17—C23 | 1.472 (10) |
N1—C9 | 1.451 (9) | C17—C18 | 1.393 (10) |
N2—C18 | 1.385 (10) | C18—C19 | 1.515 (11) |
N2—C24 | 1.456 (10) | C19—C20 | 1.543 (10) |
C1—C2 | 1.449 (10) | C20—C21 | 1.510 (10) |
C2—C8 | 1.526 (11) | C21—C22 | 1.497 (11) |
C2—C3 | 1.381 (12) | C22—C23 | 1.523 (10) |
C3—C4 | 1.523 (11) | C24—C30 | 1.569 (12) |
C4—C5 | 1.506 (11) | C24—C25 | 1.555 (11) |
C5—C6 | 1.523 (12) | C25—C26 | 1.524 (12) |
C6—C7 | 1.505 (12) | C26—C27 | 1.526 (12) |
C7—C8 | 1.494 (11) | C27—C28 | 1.520 (14) |
C9—C10 | 1.573 (10) | C28—C29 | 1.534 (12) |
C9—C15 | 1.554 (10) | C29—C30 | 1.523 (12) |
| | | |
C1—S2—C9 | 101.6 (3) | S2—C9—N1 | 110.9 (5) |
C16—S4—C24 | 99.3 (4) | N1—C9—C10 | 107.4 (6) |
C3—N1—C9 | 118.5 (7) | S3—C16—S4 | 116.4 (4) |
C18—N2—C24 | 120.2 (6) | S3—C16—C17 | 121.0 (5) |
S1—C1—C2 | 124.1 (6) | S4—C16—C17 | 121.3 (5) |
S2—C1—C2 | 119.5 (6) | N2—C18—C19 | 110.0 (6) |
S1—C1—S2 | 115.7 (4) | N2—C18—C17 | 124.2 (7) |
N1—C3—C4 | 114.5 (7) | S4—C24—C25 | 108.3 (5) |
N1—C3—C2 | 123.7 (8) | S4—C24—N2 | 109.6 (5) |
S2—C9—C15 | 108.6 (5) | N2—C24—C30 | 106.9 (6) |
S2—C9—C10 | 100.2 (4) | S4—C24—C30 | 118.1 (6) |
N1—C9—C15 | 114.5 (5) | N2—C24—C25 | 102.2 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S3 | 0.86 (2) | 2.69 (2) | 3.450 (8) | 149 (3) |
N2—H2···S1 | 0.858 (19) | 2.63 (3) | 3.424 (7) | 154 (4) |
C4—H41···S3i | 0.972 (15) | 2.705 (13) | 3.664 (7) | 169.4 (19) |
C4—H42···S3 | 0.97 (2) | 2.79 (2) | 3.701 (9) | 156.5 (18) |
C8—H82···S1 | 0.970 (17) | 2.80 (2) | 3.200 (9) | 105.6 (17) |
C14—H141···N1 | 0.967 (17) | 2.36 (2) | 2.852 (10) | 110.6 (18) |
C23—H231···S3 | 0.967 (13) | 2.72 (2) | 3.081 (9) | 103.1 (17) |
C26—H261···S3 | 0.96 (3) | 2.80 (2) | 3.729 (10) | 162.5 (19) |
Symmetry code: (i) −x, y−1/2, −z+3/2. |