Molecular and crystalline structure of cyclo­heptanespiro-3′(4′H)-6′,7′,8′,9′-tetrahydrocyclo­hexa[b][1,4]thiazole-2′(5′H)-thione from powder synchrotron X-ray diffraction data

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.

Computing details

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).

Figures

2-spiro(cycloheptane)-4-thiono-[5,6,7,8]-tetrahydro-(1H,4H)-3,1-cyclo- heptatiazine

Crystal data

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) Å^3	cylinder, 40.0 × 1.5 mm
Z = 8	Specimen preparation: Prepared at 298 K

Data collection

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

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/σi^2
R(F^2) = 0.15339	(Δ/σ)max = 0.07
χ^2 = 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

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

	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)

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)

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···S3^i	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.