Four cyclo­alkane­spiro-4′-imidazolidine-2′,5′-dithiones

The crystal structures of four cyclo­alkane­spiro-4′-imidazolidine-2′,5′-dithiones, namely cyclo­pentane­spiro-4′-imidazolidine-2′,5′-dithione {systematic name: 1,3-diaza­spiro­[4.4]­nonane-2,4-dithione}, C₇H₁₀N₂S₂, cyclo­hexane­spiro-4′-imidazolidine-2′,5′-dithione {systematic name: 1,3-diaza­spiro­[4.5]decane-2,4-dithione}, C₈H₁₂N₂S₂, cyclo­heptane­spiro-4′-imidazolidine-2′,5′-dithione {systematic name: 1,3-diaza­spiro­[4.6]undecane-2,4-dithione}, C₉H₁₄N₂S₂, and cyclo­octane­spiro-4′-imidazolidine-2′,5′-dithione {systematic name: 1,3-di­aza­spiro­[4.7]dodecane-2,4-dithione}, C₁₀H₁₆N₂S₂, have been determined. The three-dimensional packing in all of the structures is based on closely similar chains, in which hydantoin moieties are linked through N—H...S hydrogen bonding. The size of the cyclo­alkane moiety influences the degree of its deformation. In the cyclo­octane compound, the cyclo­octane ring assumes both boat–chair and boat–boat conformations.

S1. Comment

##AUTHOR: I cannot find any evidence in the literature for significant C—H···S interactions, so I have removed all such references. Please approve the changes.

The structural characteristics of spirohydantoins are interesting because of their potential biological activities (Somsak et al., 2005). Recently, we began a structural and biological investigation of new hydantoin derivatives and their organo-metallic complexes (Shivachev et al., 2005). As a part of this study, we report for the first time the crystal structures of four cycloalkanespirohydantoindithiones derivatives, namely the pentyl, (I), hexyl, (II), heptyl, (III), and octyl, (IV), compounds (Fig. 1). The synthesis and spectroscopic and theoretical ab-initio calculations for compounds (I)–(IV) were described elsewhere (Marinov et al., 2005).

For all of the structures, only one independent molecule is present in the asymmetric unit. The hydantoin moieties are almost planar, with r.m.s. deviations of 0.017, 0.066, 0.014 and 0.004 Å for the molecules of (I)–(IV), respectively. The bond distances and angles in the hydantoin moieties are comparable to those observed in other spiro hydantoins (Gauthier et al., 1997; Shivachev et al., 2005). In (I), the cyclopentane ring adopts an envelope (C5) conformation, in (II) the cyclohexane adopts a chair conformation, while in (III) the cycloheptane is in a twist-chair conformation (Allen et al., 1993) The cyclooctane ring in (IV) assumes either a boat–chair (62%) or a boat–boat (38%) conformation (Perez et al., 2005).

The geometrical parameters for compounds (I)–(IV) derived from the refined crystal structures and ab-initio calculated gas-phase molecular structures correspond in general (Tables 1, 3, 5 and 7). The bond distances calculated at the HF/3–21G* level in the theoretical models are slightly longer than the those obtained from crystal structure determination. The largest discrepancy is for the C2—N1 bond, where the average discrepancy is 0.02 Å. The only exception is the C2—S1 bond length, which is slightly shorter in all theoretical models, which we attribute to the absence of hydrogen bonding in the theoretical models. Experimental confirmation of the difference between C2═S1 and C4═S2 observed in the computational model shows that the elongation of the C═S bond at the 2'-position is a fundamental feature of the spirohydantoin molecular structure. Another tendency suggested by the theoretical model is a relationship between the C5—C4 bond length [1.526, 1.535, 1.539 and 1.542 Å for (I)–(IV), respectively] and the size of the cycloalkane derivative. The values of the corresponding experimental bond lengths are 1.519 (4), 1.520 (2), 1.530 (2) and 1.525 (4) Å. Taking into account the standard uncertainties, the apparent differences between the experimental bond lengths were shown to be insignificant.

The molecular packing in (I)–(IV) is mainly governed by two factors, namely the hydrogen-bonding properties of the hydantoin moiety and the size of the cycloalkane ring. In all structures the organic molecules are arranged in chains in which hydantoin moieties are linked through hydrogen-bonded rings involving atom S1 (Tables 2, 4, 6 and 8). In compounds (I) and (IV), these rings are generated by a screw axis and have one H1 atom and one H3 atom in each ring. Thus, the chains for these compounds can be described by the graph-set notation C(4)[R₂²(8)] (Etter et al., 1990). A search of the Cambridge Structural Database performed by Yu et al. (2004) showed that six of the hydantoin structures are built up of similar chains, where one O atom analogous to S1 accepts two hydrogen bonds. In contrast, the extended structures of (II) and (III) comprise C(6)[R₂²(8)] chains where the R₂²(8) rings are generated by inversion and have two H1 atoms and two H3 atoms in successive rings. It is interesting to note that the same chains of rings involving atom S1 are formed in two different ways. It appears that this arrangement is common for this type of molecule and further investigations will show if the reason is steric (because S1 is more accessible than S2, which lies adjacent to a cycloalkyl ring); another factor could be different charges on S1 and S2. The similarity of the chain structures imparts almost the same values to the cell directions along which the chains propagate [specify the direction and distance for each structure] (Figs. 2–5). While the hydantoin moiety is responsible for the chain-like arrangement of the organic molecules, the cycloalkane moiety determines the three-dimensional arrangement of these chains.

S2. Experimental

Compounds (I)–(IV) were prepared according to the method described by Marinov et al. (2005). Crystals suitable for X-ray diffraction were obtained by slow evaporation from a methanol solution at 277 K.

S3. Refinement

H atoms were placed in idealized positions (C—H = 0.97 and N—H = 0.86 Å), and were constrained to ride on their parent atoms, with U_iso(H) values of 1.2U_eq(C,N). Disorder of atom C10 in the cyclooctane ring in (IV) was modelled by competitive refinement of two alternative sites. The major [0.622 (8)] and minor [0.378 (2)] occupancies correspond to the boat–chair and boat–boat conformations, respectively.

Computing details

For all compounds, data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury 1.4 (Bruno et al., 2002) for (I), (II), (III); ORTEP-3 for Windows (Farrugia, 1997) and Mercury 1.4 (Bruno et al., 2002)' for (IV). For all compounds, software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

##AUTHOR: Orientation of Scheme should be rotated to match Figures. ##AUTHOR: All reference to C—H···S hydrogen bonds removed. Fig. 1. A view of the structure and the atom-numbering scheme of the independent molecule in (a) (I), (b) (II), (c) (III) and (d) (IV), showing 50% probability displacement ellipsoids. For compound (IV), only the major (62%) disorder component is represented, the minor (38%) component being omitted for clarity (see text). Fig. 2. A partial view of the molecular packing in (I). Dotted lines represent N—H···S1 hydrogen bonds. [Symmetry codes: (i) −x, y − 1/2, −z + 3/2; (ii) −x, y + 1/2, −z + 3/2.] Fig. 3. A partial view of the molecular packing in (II). Dotted lines represent N—H···S1 hydrogen bonds. [Symmetry codes: (i) −x, −y + 1, −z; (ii) −x + 1, −y + 1, −z.] Fig. 4. A partial view of the molecular packing in (III). Hydrogen bonds are indicated by dotted lines. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + 1, −y + 1, −z.] Fig. 5. A partial view of the molecular packing in (IV). Hydrogen bonds are indicated by dotted lines. [Symmetry codes: (i) x + 1/2, −y + 1/2, −z + 1; (ii) x − 1/2, −y + 1/2, −z + 1.]

(I) 1,3-diazaspiro[4.4]nonane-2,4-dithione

Crystal data

C7H10N2S2	Dx = 1.363 Mg m^−3
Mr = 186.29	Melting point: 495 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 22 reflections
a = 7.898 (5) Å	θ = 20.3–20.7°
b = 8.4607 (19) Å	µ = 0.52 mm^−1
c = 13.587 (2) Å	T = 290 K
V = 907.9 (6) Å^3	Square prism, orange
Z = 4	0.24 × 0.20 × 0.20 mm
F(000) = 392

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.056
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 2.8°
Graphite monochromator	h = 0→10
non–profiled ω/2θ scans	k = 0→11
2483 measured reflections	l = −17→17
2198 independent reflections	3 standard reflections every 120 min
1629 reflections with I > 2σ(I)	intensity decay: 2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0446P)^2 + 0.3808P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2198 reflections	Δρmax = 0.26 e Å^−3
100 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Absolute structure: Flack (1983), 911 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (16)

Special details

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.

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

	x	y	z	Uiso*/Ueq
S1	−0.08105 (12)	0.14147 (10)	0.73014 (7)	0.0490 (3)
S2	0.42294 (17)	0.36691 (13)	0.95075 (10)	0.0758 (4)
N1	0.1853 (4)	0.0174 (3)	0.8266 (2)	0.0445 (8)
H1	0.1597	−0.0787	0.8125	0.053*
N3	0.1704 (4)	0.2716 (3)	0.8361 (2)	0.0364 (6)
H3	0.1335	0.3658	0.8258	0.044*
C2	0.0955 (4)	0.1392 (4)	0.7984 (2)	0.0338 (6)
C4	0.3087 (4)	0.2393 (4)	0.8914 (3)	0.0411 (8)
C5	0.3338 (4)	0.0617 (4)	0.8848 (3)	0.0366 (7)
C6	0.4999 (5)	0.0135 (5)	0.8350 (3)	0.0583 (11)
H6A	0.4864	0.0103	0.7640	0.070*
H6B	0.5893	0.0878	0.8510	0.070*
C7	0.5410 (7)	−0.1478 (6)	0.8742 (4)	0.0899 (17)
H7A	0.5127	−0.2278	0.8258	0.108*
H7B	0.6610	−0.1554	0.8887	0.108*
C8	0.4421 (7)	−0.1716 (6)	0.9636 (3)	0.0804 (15)
H8A	0.5170	−0.1934	1.0185	0.096*
H8B	0.3670	−0.2614	0.9553	0.096*
C9	0.3411 (5)	−0.0266 (4)	0.9840 (3)	0.0465 (9)
H9A	0.3957	0.0378	1.0338	0.056*
H9B	0.2282	−0.0538	1.0064	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0486 (5)	0.0299 (4)	0.0686 (6)	0.0001 (5)	−0.0247 (4)	−0.0010 (4)
S2	0.0832 (8)	0.0430 (5)	0.1014 (9)	−0.0149 (7)	−0.0503 (7)	−0.0013 (6)
N1	0.0463 (19)	0.0266 (14)	0.061 (2)	0.0025 (13)	−0.0171 (16)	−0.0035 (13)
N3	0.0395 (16)	0.0238 (12)	0.0460 (15)	−0.0011 (11)	−0.0064 (13)	−0.0004 (12)
C2	0.0351 (15)	0.0288 (14)	0.0376 (16)	−0.0035 (17)	−0.0030 (13)	0.0001 (14)
C4	0.0425 (19)	0.0331 (16)	0.0476 (19)	−0.0061 (14)	−0.0060 (19)	0.0056 (18)
C5	0.0330 (16)	0.0325 (15)	0.0442 (19)	0.0004 (13)	−0.0074 (18)	0.0022 (16)
C6	0.047 (2)	0.064 (3)	0.065 (2)	0.012 (2)	0.010 (2)	0.008 (2)
C7	0.090 (4)	0.075 (3)	0.105 (4)	0.046 (3)	0.026 (3)	0.015 (3)
C8	0.105 (4)	0.063 (3)	0.073 (3)	0.044 (3)	0.015 (3)	0.016 (2)
C9	0.054 (2)	0.0419 (19)	0.044 (2)	0.0103 (18)	−0.0008 (18)	0.0049 (16)

Geometric parameters (Å, º)

C2—N1	1.309 (4)	C6—H6B	0.9700
C2—N3	1.366 (4)	C7—C8	1.458 (6)
C2—S1	1.674 (3)	C7—H7A	0.9700
C4—N3	1.353 (4)	C7—H7B	0.9700
C4—C5	1.519 (4)	C8—C9	1.490 (5)
C4—S2	1.622 (4)	C8—H8A	0.9700
C5—N1	1.463 (4)	C8—H8B	0.9700
C5—C6	1.532 (5)	C9—H9A	0.9700
C5—C9	1.543 (5)	C9—H9B	0.9700
C6—C7	1.500 (6)	N1—H1	0.8600
C6—H6A	0.9700	N3—H3	0.8600
N1—C2—N3	107.5 (3)	C8—C7—H7B	110.1
N1—C2—S1	128.5 (3)	C6—C7—H7B	110.1
N3—C2—S1	124.0 (2)	H7A—C7—H7B	108.5
N3—C4—C5	105.8 (3)	C7—C8—C9	109.2 (4)
N3—C4—S2	126.2 (3)	C7—C8—H8A	109.8
C5—C4—S2	128.0 (3)	C9—C8—H8A	109.8
N1—C5—C4	100.4 (3)	C7—C8—H8B	109.8
N1—C5—C6	112.3 (3)	C9—C8—H8B	109.8
C4—C5—C6	113.7 (3)	H8A—C8—H8B	108.3
N1—C5—C9	112.2 (3)	C8—C9—C5	104.8 (3)
C4—C5—C9	115.6 (3)	C8—C9—H9A	110.8
C6—C5—C9	103.0 (3)	C5—C9—H9A	110.8
C7—C6—C5	105.7 (4)	C8—C9—H9B	110.8
C7—C6—H6A	110.6	C5—C9—H9B	110.8
C5—C6—H6A	110.6	H9A—C9—H9B	108.9
C7—C6—H6B	110.6	C2—N1—C5	113.0 (3)
C5—C6—H6B	110.6	C2—N1—H1	123.5
H6A—C6—H6B	108.7	C5—N1—H1	123.5
C8—C7—C6	107.8 (4)	C4—N3—C2	113.1 (3)
C8—C7—H7A	110.1	C4—N3—H3	123.4
C6—C7—H7A	110.1	C2—N3—H3	123.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.86	2.51	3.375 (3)	179
N3—H3···S1^ii	0.86	2.49	3.332 (3)	167

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2.

(II) 1,3-diazaspiro[4.5]decane-2,4-dithione

Crystal data

C8H12N2S2	F(000) = 424
Mr = 200.32	Dx = 1.356 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 22 reflections
a = 8.6896 (10) Å	θ = 20.5–21.5°
b = 12.2674 (15) Å	µ = 0.49 mm^−1
c = 9.7864 (10) Å	T = 290 K
β = 109.86 (9)°	Cube, yellow
V = 981.2 (6) Å^3	0.45 × 0.45 × 0.45 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.023
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 2.7°
Graphite monochromator	h = 0→11
non–profiled ω/2θ scans	k = −16→16
4892 measured reflections	l = −12→12
2356 independent reflections	3 standard reflections every 120 min
2036 reflections with I > 2σ(I)	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.060P)^2 + 0.2697P] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
2356 reflections	Δρmax = 0.41 e Å^−3
110 parameters	Δρmin = −0.45 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.097 (6)

Special details

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.

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

	x	y	z	Uiso*/Ueq
S1	0.21807 (5)	0.51835 (4)	−0.08084 (4)	0.04149 (16)
S2	0.61596 (6)	0.28711 (5)	0.36038 (5)	0.0625 (2)
N1	0.19152 (15)	0.41895 (10)	0.15650 (13)	0.0347 (3)
H1	0.0904	0.4361	0.1377	0.042*
N3	0.43244 (16)	0.40577 (11)	0.13720 (14)	0.0395 (3)
H3	0.5100	0.4151	0.1024	0.047*
C2	0.27670 (17)	0.44725 (12)	0.07349 (15)	0.0328 (3)
C4	0.45042 (19)	0.34889 (13)	0.26005 (16)	0.0380 (3)
C5	0.28705 (17)	0.35503 (12)	0.28466 (15)	0.0332 (3)
C6	0.2121 (2)	0.24228 (14)	0.28581 (19)	0.0449 (4)
H6A	0.1900	0.2082	0.1916	0.054*
H6B	0.2902	0.1969	0.3578	0.054*
C7	0.0540 (2)	0.24876 (17)	0.3202 (2)	0.0547 (5)
H7A	−0.0287	0.2859	0.2416	0.066*
H7B	0.0150	0.1756	0.3272	0.066*
C8	0.0784 (2)	0.3090 (2)	0.4615 (2)	0.0584 (5)
H8A	−0.0256	0.3151	0.4772	0.070*
H8B	0.1525	0.2679	0.5417	0.070*
C9	0.1480 (2)	0.42187 (18)	0.4581 (2)	0.0523 (5)
H9A	0.1678	0.4571	0.5513	0.063*
H9B	0.0688	0.4653	0.3844	0.063*
C10	0.30657 (19)	0.41673 (15)	0.42555 (17)	0.0409 (4)
H10A	0.3895	0.3810	0.5055	0.049*
H10B	0.3438	0.4903	0.4179	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0345 (2)	0.0507 (3)	0.0390 (2)	0.00483 (16)	0.01217 (16)	0.01622 (16)
S2	0.0474 (3)	0.0923 (4)	0.0497 (3)	0.0355 (3)	0.0190 (2)	0.0276 (2)
N3	0.0326 (6)	0.0501 (8)	0.0390 (7)	0.0109 (5)	0.0165 (5)	0.0119 (6)
N1	0.0282 (6)	0.0420 (7)	0.0336 (6)	0.0046 (5)	0.0102 (5)	0.0088 (5)
C4	0.0362 (7)	0.0443 (8)	0.0348 (7)	0.0108 (6)	0.0136 (6)	0.0051 (6)
C2	0.0310 (7)	0.0330 (7)	0.0336 (7)	0.0021 (5)	0.0100 (6)	0.0021 (5)
C5	0.0306 (7)	0.0387 (7)	0.0296 (7)	0.0052 (6)	0.0091 (5)	0.0057 (6)
C6	0.0555 (10)	0.0377 (8)	0.0387 (8)	−0.0021 (7)	0.0126 (7)	0.0059 (7)
C7	0.0456 (9)	0.0591 (11)	0.0522 (10)	−0.0124 (9)	0.0072 (8)	0.0173 (9)
C8	0.0408 (9)	0.0881 (15)	0.0512 (10)	0.0036 (9)	0.0221 (8)	0.0191 (10)
C9	0.0422 (9)	0.0746 (13)	0.0439 (9)	0.0107 (9)	0.0196 (7)	−0.0023 (9)
C10	0.0347 (7)	0.0525 (9)	0.0348 (7)	0.0024 (7)	0.0110 (6)	−0.0041 (7)

Geometric parameters (Å, º)

S1—C2	1.6669 (16)	C6—H6B	0.9700
S2—C4	1.627 (2)	C7—C8	1.518 (3)
N3—C4	1.3524 (19)	C7—H7A	0.9700
N3—C2	1.380 (2)	C7—H7B	0.9700
N3—H3	0.8600	C8—C9	1.515 (3)
N1—C2	1.318 (2)	C8—H8A	0.9700
N1—C5	1.473 (2)	C8—H8B	0.9700
N1—H1	0.8600	C9—C10	1.518 (2)
C4—C5	1.520 (2)	C9—H9A	0.9700
C5—C6	1.530 (2)	C9—H9B	0.9700
C5—C10	1.531 (2)	C10—H10A	0.9700
C6—C7	1.524 (3)	C10—H10B	0.9700
C6—H6A	0.9700
C4—N3—C2	113.03 (14)	C8—C7—C6	111.67 (17)
C4—N3—H3	123.5	C8—C7—H7A	109.3
C2—N3—H3	123.5	C6—C7—H7A	109.3
C2—N1—C5	113.14 (12)	C8—C7—H7B	109.3
C2—N1—H1	123.4	C6—C7—H7B	109.3
C5—N1—H1	123.4	H7A—C7—H7B	107.9
N3—C4—C5	106.45 (14)	C9—C8—C7	110.98 (15)
N3—C4—S2	126.03 (13)	C9—C8—H8A	109.4
C5—C4—S2	127.52 (12)	C7—C8—H8A	109.4
N1—C2—N3	107.11 (13)	C9—C8—H8B	109.4
N1—C2—S1	129.31 (12)	C7—C8—H8B	109.4
N3—C2—S1	123.58 (13)	H8A—C8—H8B	108.0
N1—C5—C4	100.25 (12)	C8—C9—C10	111.35 (16)
N1—C5—C6	111.68 (13)	C8—C9—H9A	109.4
C4—C5—C6	112.26 (13)	C10—C9—H9A	109.4
N1—C5—C10	111.20 (13)	C8—C9—H9B	109.4
C4—C5—C10	110.09 (14)	C10—C9—H9B	109.4
C6—C5—C10	110.95 (13)	H9A—C9—H9B	108.0
C7—C6—C5	111.85 (15)	C9—C10—C5	112.27 (15)
C7—C6—H6A	109.2	C9—C10—H10A	109.2
C5—C6—H6A	109.2	C5—C10—H10A	109.2
C7—C6—H6B	109.2	C9—C10—H10B	109.2
C5—C6—H6B	109.2	C5—C10—H10B	109.2
H6A—C6—H6B	107.9	H10A—C10—H10B	107.9
C5—C6—C7—C8	−54.66 (19)	C7—C8—C9—C10	−56.0 (2)
C6—C7—C8—C9	56.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.86	2.61	3.4665 (17)	178
N3—H3···S1^ii	0.86	2.58	3.3959 (16)	160

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z.

(III) 1,3-diazaspiro[4.6]undecane-2,4-dithione

Crystal data

C9H14N2S2	F(000) = 456
Mr = 214.34	Dx = 1.325 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 22 reflections
a = 7.4041 (14) Å	θ = 18.4–19.8°
b = 17.859 (4) Å	µ = 0.45 mm^−1
c = 8.4491 (14) Å	T = 290 K
β = 105.848 (19)°	Cube, yellow
V = 1074.7 (4) Å^3	0.33 × 0.33 × 0.33 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.023
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 2.3°
Graphite monochromator	h = 0→9
non–profiled ω/2θ scans	k = −23→23
5464 measured reflections	l = −11→10
2591 independent reflections	3 standard reflections every 500 reflections
2042 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0458P)^2 + 0.254P] where P = (Fo^2 + 2Fc^2)/3
2591 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
S1	0.54858 (6)	0.45898 (3)	0.26027 (5)	0.04001 (13)
S2	−0.00067 (7)	0.63319 (3)	−0.09273 (5)	0.05107 (16)
N1	0.29715 (19)	0.55459 (8)	0.32787 (15)	0.0346 (3)
H1	0.3315	0.5462	0.4321	0.042*
N3	0.2837 (2)	0.54828 (8)	0.06919 (15)	0.0351 (3)
H3	0.3135	0.5355	−0.0186	0.042*
C2	0.3755 (2)	0.52184 (8)	0.22362 (18)	0.0305 (3)
C4	0.1426 (2)	0.59606 (9)	0.06924 (18)	0.0319 (3)
C5	0.1453 (2)	0.60684 (8)	0.24953 (17)	0.0295 (3)
C6	0.2080 (2)	0.68680 (9)	0.3080 (2)	0.0400 (4)
H6A	0.2752	0.6845	0.4239	0.048*
H6B	0.2962	0.7038	0.2493	0.048*
C7	0.0543 (3)	0.74498 (10)	0.2863 (3)	0.0530 (5)
H7A	−0.0421	0.7345	0.1852	0.064*
H7B	0.1065	0.7939	0.2750	0.064*
C8	−0.0363 (3)	0.74755 (12)	0.4289 (3)	0.0626 (6)
H8A	0.0627	0.7506	0.5312	0.075*
H8B	−0.1099	0.7931	0.4192	0.075*
C9	−0.1618 (3)	0.68186 (12)	0.4400 (3)	0.0576 (5)
H9A	−0.2727	0.6841	0.3470	0.069*
H9B	−0.2026	0.6874	0.5391	0.069*
C10	−0.0725 (3)	0.60469 (11)	0.4424 (2)	0.0464 (4)
H10A	−0.1526	0.5677	0.4735	0.056*
H10B	0.0473	0.6043	0.5256	0.056*
C11	−0.0414 (2)	0.58219 (9)	0.2773 (2)	0.0361 (4)
H11A	−0.1425	0.6031	0.1901	0.043*
H11B	−0.0500	0.5281	0.2677	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0452 (3)	0.0481 (3)	0.0278 (2)	0.01627 (19)	0.01183 (17)	0.00268 (16)
S2	0.0536 (3)	0.0663 (3)	0.0295 (2)	0.0192 (2)	0.00480 (19)	0.0103 (2)
N1	0.0402 (8)	0.0432 (7)	0.0204 (6)	0.0115 (6)	0.0083 (5)	0.0017 (5)
N3	0.0403 (7)	0.0456 (8)	0.0209 (6)	0.0089 (6)	0.0108 (5)	0.0020 (5)
C2	0.0347 (8)	0.0334 (7)	0.0241 (7)	0.0000 (6)	0.0092 (6)	−0.0005 (5)
C4	0.0351 (8)	0.0343 (8)	0.0267 (7)	0.0002 (6)	0.0092 (6)	0.0017 (6)
C5	0.0333 (8)	0.0319 (7)	0.0231 (6)	0.0027 (6)	0.0074 (6)	0.0003 (6)
C6	0.0386 (9)	0.0365 (8)	0.0457 (9)	−0.0045 (7)	0.0129 (7)	−0.0076 (7)
C7	0.0595 (12)	0.0335 (9)	0.0691 (13)	0.0026 (8)	0.0230 (10)	−0.0004 (9)
C8	0.0683 (14)	0.0515 (12)	0.0734 (15)	0.0134 (10)	0.0289 (12)	−0.0165 (10)
C9	0.0592 (13)	0.0692 (13)	0.0531 (11)	0.0139 (11)	0.0301 (10)	−0.0058 (10)
C10	0.0535 (11)	0.0538 (11)	0.0387 (9)	0.0004 (9)	0.0242 (8)	0.0021 (8)
C11	0.0389 (9)	0.0367 (9)	0.0350 (8)	−0.0018 (7)	0.0140 (7)	−0.0009 (6)

Geometric parameters (Å, º)

S1—C2	1.6676 (16)	C7—C8	1.532 (3)
S2—C4	1.6263 (16)	C7—H7A	0.9700
N1—C2	1.3169 (19)	C7—H7B	0.9700
N1—C5	1.4717 (19)	C8—C9	1.515 (3)
N1—H1	0.8600	C8—H8A	0.9700
N3—C4	1.349 (2)	C8—H8B	0.9700
N3—C2	1.3795 (19)	C9—C10	1.526 (3)
N3—H3	0.8600	C9—H9A	0.9700
C4—C5	1.530 (2)	C9—H9B	0.9700
C5—C11	1.529 (2)	C10—C11	1.528 (2)
C5—C6	1.541 (2)	C10—H10A	0.9700
C6—C7	1.515 (2)	C10—H10B	0.9700
C6—H6A	0.9700	C11—H11A	0.9700
C6—H6B	0.9700	C11—H11B	0.9700
C2—N1—C5	113.75 (12)	C6—C7—H7B	108.8
C2—N1—H1	123.1	C8—C7—H7B	108.8
C5—N1—H1	123.1	H7A—C7—H7B	107.7
C4—N3—C2	113.45 (13)	C9—C8—C7	115.66 (17)
C4—N3—H3	123.3	C9—C8—H8A	108.4
C2—N3—H3	123.3	C7—C8—H8A	108.4
N3—C4—C5	106.27 (12)	C9—C8—H8B	108.4
N3—C4—S2	125.79 (12)	C7—C8—H8B	108.4
C5—C4—S2	127.93 (12)	H8A—C8—H8B	107.4
N1—C2—N3	106.69 (13)	C8—C9—C10	115.44 (17)
N1—C2—S1	129.15 (12)	C8—C9—H9A	108.4
N3—C2—S1	124.15 (11)	C10—C9—H9A	108.4
N1—C5—C11	111.11 (13)	C8—C9—H9B	108.4
N1—C5—C4	99.72 (12)	C10—C9—H9B	108.4
C11—C5—C4	110.48 (13)	H9A—C9—H9B	107.5
N1—C5—C6	108.49 (13)	C9—C10—C11	113.44 (15)
C11—C5—C6	115.05 (13)	C9—C10—H10A	108.9
C4—C5—C6	110.91 (13)	C11—C10—H10A	108.9
C7—C6—C5	116.51 (14)	C9—C10—H10B	108.9
C7—C6—H6A	108.2	C11—C10—H10B	108.9
C5—C6—H6A	108.2	H10A—C10—H10B	107.7
C7—C6—H6B	108.2	C10—C11—C5	115.62 (14)
C5—C6—H6B	108.2	C10—C11—H11A	108.4
H6A—C6—H6B	107.3	C5—C11—H11A	108.4
C6—C7—C8	113.66 (17)	C10—C11—H11B	108.4
C6—C7—H7A	108.8	C5—C11—H11B	108.4
C8—C7—H7A	108.8	H11A—C11—H11B	107.4
C5—C6—C7—C8	86.0 (2)	C7—C8—C9—C10	53.5 (3)
C6—C7—C8—C9	−71.7 (3)	C8—C9—C10—C11	−70.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.86	2.51	3.3618 (14)	172
N3—H3···S1^ii	0.86	2.52	3.3460 (15)	161

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z.

(IV) 1,3-diazaspiro[4.7]dodecane-2,4-dithione

Crystal data

C10H16N2S2	F(000) = 976
Mr = 228.37	Dx = 1.296 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 22 reflections
a = 8.484 (2) Å	θ = 17.9–19.1°
b = 11.5018 (18) Å	µ = 0.42 mm^−1
c = 23.992 (10) Å	T = 290 K
V = 2341.2 (12) Å^3	Square prism, yellow
Z = 8	0.40 × 0.38 × 0.36 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.061
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 1.7°
Graphite monochromator	h = 0→11
non–profiled ω/2θ scans	k = −15→15
10820 measured reflections	l = −31→31
2812 independent reflections	3 standard reflections every 120 min
1730 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.174	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0826P)^2 + 1.361P] where P = (Fo^2 + 2Fc^2)/3
2812 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

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. # start RESPONSE (PLAT301) "Normal" structure refinement (Npar = 127) finished at R1 = 0.063, wR2 = 0.1972, S = 1.021. Introducing 2 atomic positions for C10 we got the final model (Npar = 136) of the disordered molecule." # end RESPONSE PLAT301

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.9007 (3)	0.3404 (2)	0.55765 (10)	0.0476 (6)
H1	0.9930	0.3099	0.5553	0.057*
N3	0.6569 (3)	0.3784 (2)	0.54033 (11)	0.0540 (7)
H3	0.5666	0.3754	0.5241	0.065*
S1	0.78194 (9)	0.21329 (8)	0.47347 (4)	0.0576 (3)
S2	0.56062 (11)	0.53474 (10)	0.61389 (5)	0.0818 (4)
C2	0.7837 (3)	0.3117 (3)	0.52427 (12)	0.0455 (7)
C4	0.6874 (3)	0.4488 (3)	0.58401 (14)	0.0522 (7)
C5	0.8598 (3)	0.4289 (3)	0.59923 (12)	0.0442 (7)
C6	0.9603 (4)	0.5383 (3)	0.58883 (14)	0.0544 (8)
H6A	1.0686	0.5136	0.5834	0.065*
H6B	0.9254	0.5731	0.5541	0.065*
C7	0.9597 (5)	0.6322 (3)	0.6330 (2)	0.0774 (11)
H7A	0.8638	0.6250	0.6547	0.093*
H7B	0.9572	0.7074	0.6147	0.093*
C8	1.1020 (8)	0.6293 (5)	0.6732 (2)	0.121 (2)
H8A	1.1958	0.6365	0.6503	0.145*
H8B	1.0960	0.6993	0.6956	0.145*
C9	1.1285 (8)	0.5374 (5)	0.7098 (2)	0.120 (2)
H9A	1.0354	0.5280	0.7328	0.144*
H9B	1.2148	0.5587	0.7342	0.144*
C10	1.1667 (9)	0.4217 (7)	0.6837 (4)	0.0784 (18)	0.62
H10A	1.2479	0.3848	0.7060	0.094*	0.62
H10B	1.2113	0.4360	0.6471	0.094*	0.62
C101	1.1092 (18)	0.4142 (12)	0.7190 (5)	0.088 (4)	0.38
H10C	1.0508	0.4056	0.7535	0.105*	0.38
H10D	1.2135	0.3827	0.7257	0.105*	0.38
C11	1.0316 (5)	0.3359 (4)	0.67705 (17)	0.0783 (12)
H11A	1.0663	0.2767	0.6510	0.094*
H11B	1.0174	0.2978	0.7128	0.094*
C12	0.8699 (4)	0.3769 (3)	0.65781 (13)	0.0586 (8)
H12A	0.8324	0.4346	0.6841	0.070*
H12B	0.7982	0.3113	0.6596	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0265 (11)	0.0625 (15)	0.0540 (14)	0.0049 (11)	−0.0022 (10)	−0.0135 (12)
N3	0.0252 (11)	0.0704 (17)	0.0665 (17)	0.0039 (11)	−0.0033 (11)	−0.0144 (14)
S1	0.0307 (4)	0.0809 (6)	0.0611 (5)	−0.0017 (4)	0.0000 (3)	−0.0244 (4)
S2	0.0446 (5)	0.0897 (8)	0.1112 (9)	0.0120 (4)	0.0123 (5)	−0.0378 (6)
C2	0.0293 (12)	0.0595 (17)	0.0477 (15)	−0.0046 (12)	0.0044 (11)	−0.0043 (13)
C4	0.0342 (14)	0.0606 (18)	0.0617 (19)	−0.0008 (13)	0.0056 (13)	−0.0088 (15)
C5	0.0323 (13)	0.0523 (16)	0.0481 (16)	−0.0002 (12)	0.0022 (11)	−0.0063 (13)
C6	0.0472 (17)	0.0610 (19)	0.0550 (18)	−0.0025 (14)	0.0010 (14)	0.0031 (15)
C7	0.067 (2)	0.060 (2)	0.106 (3)	−0.0034 (18)	0.013 (2)	−0.008 (2)
C8	0.146 (5)	0.109 (4)	0.108 (4)	−0.031 (4)	−0.045 (4)	−0.021 (3)
C9	0.145 (5)	0.107 (4)	0.107 (4)	−0.020 (4)	−0.066 (4)	−0.017 (3)
C10	0.066 (4)	0.088 (5)	0.081 (5)	0.009 (4)	−0.025 (4)	0.000 (4)
C101	0.099 (10)	0.109 (10)	0.055 (6)	0.000 (8)	−0.023 (7)	−0.010 (7)
C11	0.102 (3)	0.070 (2)	0.063 (2)	0.010 (2)	−0.023 (2)	0.0038 (19)
C12	0.066 (2)	0.0577 (19)	0.0520 (18)	−0.0127 (17)	0.0064 (15)	0.0003 (15)

Geometric parameters (Å, º)

N1—C2	1.317 (3)	C8—H8A	0.9700
N1—C5	1.467 (4)	C8—H8B	0.9700
N1—H1	0.8600	C12—C11	1.522 (5)
N3—C4	1.350 (4)	C12—H12A	0.9700
N3—C2	1.376 (4)	C12—H12B	0.9700
N3—H3	0.8600	C9—C10	1.507 (9)
S1—C2	1.664 (3)	C9—C101	1.444 (15)
S2—C4	1.627 (3)	C9—H9A	0.9700
C4—C5	1.525 (4)	C9—H9B	0.9700
C5—C12	1.530 (4)	C11—C10	1.520 (9)
C5—C6	1.540 (4)	C11—C101	1.501 (12)
C6—C7	1.513 (5)	C11—H11A	0.9700
C6—H6A	0.9700	C11—H11B	0.9700
C6—H6B	0.9700	C10—H10A	0.9700
C7—C8	1.544 (6)	C10—H10B	0.9700
C7—H7A	0.9700	C101—H10C	0.9700
C7—H7B	0.9700	C101—H10D	0.9700
C8—C9	1.392 (7)
C2—N1—C5	114.1 (2)	C11—C12—C5	116.7 (3)
C2—N1—H1	122.9	C11—C12—H12A	108.1
C5—N1—H1	122.9	C5—C12—H12A	108.1
C4—N3—C2	113.7 (2)	C11—C12—H12B	108.1
C4—N3—H3	123.2	C5—C12—H12B	108.1
C2—N3—H3	123.2	H12A—C12—H12B	107.3
N1—C2—N3	106.2 (2)	C8—C9—C101	145.4 (6)
N1—C2—S1	128.5 (2)	C8—C9—C10	116.3 (6)
N3—C2—S1	125.2 (2)	C8—C9—H9A	108.2
N3—C4—C5	106.3 (2)	C101—C9—H9A	73.2
N3—C4—S2	125.4 (2)	C10—C9—H9A	108.2
C5—C4—S2	128.3 (2)	C8—C9—H9B	108.2
N1—C5—C4	99.7 (2)	C101—C9—H9B	103.9
N1—C5—C12	109.9 (2)	C10—C9—H9B	108.2
C4—C5—C12	109.4 (2)	H9A—C9—H9B	107.4
N1—C5—C6	109.0 (2)	C101—C11—C12	114.4 (6)
C4—C5—C6	111.7 (3)	C12—C11—C10	120.7 (4)
C12—C5—C6	116.0 (3)	C101—C11—H11A	136.0
C7—C6—C5	117.9 (3)	C12—C11—H11A	107.2
C7—C6—H6A	107.8	C10—C11—H11A	107.2
C5—C6—H6A	107.8	C101—C11—H11B	74.6
C7—C6—H6B	107.8	C12—C11—H11B	107.2
C5—C6—H6B	107.8	C10—C11—H11B	107.2
H6A—C6—H6B	107.2	H11A—C11—H11B	106.8
C6—C7—C8	114.7 (4)	C9—C10—C11	117.1 (6)
C6—C7—H7A	108.6	C9—C10—H10A	108.0
C8—C7—H7A	108.6	C11—C10—H10A	108.0
C6—C7—H7B	108.6	C9—C10—H10B	108.0
C8—C7—H7B	108.6	C11—C10—H10B	108.0
H7A—C7—H7B	107.6	H10A—C10—H10B	107.3
C9—C8—C7	122.4 (5)	C9—C101—C11	122.4 (9)
C9—C8—H8A	106.7	C9—C101—H10C	106.7
C7—C8—H8A	106.7	C11—C101—H10C	106.7
C9—C8—H8B	106.7	C9—C101—H10D	106.7
C7—C8—H8B	106.7	C11—C101—H10D	106.7
H8A—C8—H8B	106.6	H10C—C101—H10D	106.6
C5—C6—C7—C8	98.5 (4)	C8—C9—C10—C11	−97.4 (8)
C6—C7—C8—C9	−64.9 (7)	C9—C10—C11—C12	41.5 (8)
C7—C8—C9—C10	65.9 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.86	2.56	3.376 (2)	159
N3—H3···S1^ii	0.86	2.62	3.367 (3)	146

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, −z+1.