Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035374/hj3049sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035374/hj3049Isup2.hkl |
CCDC reference: 657832
The title compound I was synthesized according to Hurd et al. (1961). crystals were obtained by recrystallization from a chloroform-petrol ether (1:1) solution.
Hydrogen atoms were localized from the difference Fourier map and idealized by the well known "riding-model technique" with distances to the parent atoms of of 0.96 to 0.98 Å. The best refinement was obtained with the psi-scan (North et al., 1968) absorption correction performed by XSCANS (Siemens, 1989).
Secondary dithioxamides behave as binucleating ligands both in N,S–N,S (Veit et al., 1984; Ye et al., 1991; Lanza et al. 2002) and in N,N–S,S modes (Lanza et al., 2000; 2003; 2005) (Scheme 1). It has been already observed (Lanza et al., 2005) that in the trimetallic complexes [Pt{{µ-S2C2(NR)2}MLn}2] (µ-S2C2(NR)2 = bridging dianionic dithioxamidate; MLn+= positively charged metal fragment) there is an electron removal from platinum to MLn+ via the π* system in the N—C—S fragments (Lanza et al. 2005). The possibility of a π donation from the bridged dithioxamide to the platinum d orbitals has been ruled out, since this latter circumstance would require a C—C double bond connecting the two N—C—S frames. In order to asses factors affecting electronic transmission between metals in polymetallic chains through binucleating dithioxamides, we think it is important to gain as much structural information as possible about free and coordinated H2S2C2(NR)2 ligands
The asymmetric unit of (I) contains one half of the symmetric molecule with the other half generated by inversion (Fig. 1). The thioamide moiety is planar [maximum deviation from the mean plane for the C1 = 0.001 (1) Å]; the trans conformation is also stabilized by the intramolecular interaction N—H···S [N1—H1 = 0.860 (1), N1···S1i = 2.945 (1) Å, N1—H1···S1i = 117.6 (1)°; symmetry code (i) -x + 1, -y + 1, -z], moreover the first C atom of the N-attached alkyl chain keeps the planarity of the core atoms [maximum deviation of C2 = 0.005 (2) Å]. On the other hand the features of the sp3 hybridized C atoms mean that the side aliphatic chains are above and below with respect to the core planar fragment. The thioamide geometrical parameters in the table are in accord with those found for similar crystal structures (Shimanouchi & Sasada, 1979; Bermejo et al., 1998; Perec et al., 1995; Jean 1994; Simonov et al. 2003).
The crystal lattice is mainly supported by intermolecular N—H···S interactions [N1—H1 = 0.860 (1), N1···S1ii = 3.425 (2) Å, N1—H1···S1ii = 131.3 (1)°; symmetry code (ii) x, y + 1, z] together with a much weaker C—H···S hydrogen bond [C2—H2B = 0.970 (2), C1···S1ii = 3.499 (2) Å, C2—H2B···S1ii = 114.1 (1)°]. The interaction N—H···S doubled by the crystallographic inversion centre leads to the "chain of rings" C(3)R22(10) motif (Bernstein et al., 1995). The resulting one-dimensional-array of molecules along the b crystallographic axis looks like a planar strand because of the directional self-recognition (Fig. 2). The thioamidic group also develops vertical π-π interactions [distance from the mean thioxamidic planes 3.6595 (5) Å; symmetry code for the π stacked equivalent is x + 1, y, z] generating a ladder like disposition of the planar strands running along the a crystallographic axis (Fig. 3). The non-polar nature of the alkylic chain means that very weak interactions complete the third dimension of the crystal packing. Compounds with similar structure can be regarded as forerunners of metallomesogens; actually mesophases are observed when the R groups are aryl substituents bearing long hydrocarbon chains (Aversa et al., 2000; 1997).
For related literature, see: Aversa et al. (1997, 2000); Bermejo et al. (1998); Cremer & Pople (1975); Desseyn et al. (1978); Hurd et al. (1961); Jean (1994); Lanza et al. (2000, 2002, 2003, 2005); Perec et al. (1995); Shimanouchi & Sasada (1979); Simonov et al. (2003); Veit et al. (1984); Ye et al. (1991).
Data collection: XSCANS (Siemens, 1989); cell refinement: XSCANS; data reduction: XPREP (Bruker, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPREP; software used to prepare material for publication: PARST95 (Nardelli, 1995) and WinGX-PC (Farrugia, 1999).
C12H24N2S2 | Z = 1 |
Mr = 260.45 | F(000) = 142 |
Triclinic, P1 | Dx = 1.112 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.7658 (9) Å | Cell parameters from 66 reflections |
b = 6.0323 (9) Å | θ = 4.8–22.5° |
c = 14.470 (2) Å | µ = 0.32 mm−1 |
α = 83.082 (14)° | T = 571 K |
β = 85.919 (15)° | Irregular, yellow |
γ = 70.427 (15)° | 0.58 × 0.44 × 0.24 mm |
V = 388.90 (11) Å3 |
Bruker P4 diffractometer | Rint = 0.011 |
2θ/ω scans | θmax = 26.0°, θmin = 2.8° |
Absorption correction: ψ scan (North et al., 1968) | h = −1→5 |
Tmin = 0.825, Tmax = 0.924 | k = −7→7 |
2093 measured reflections | l = −17→17 |
1523 independent reflections | 3 standard reflections every 197 reflections |
1344 reflections with I > 2σ(I) | intensity decay: 2% |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.034 | w = 1/[σ2(Fo2) + (0.0509P)2 + 0.0753P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.098 | (Δ/σ)max < 0.001 |
S = 1.12 | Δρmax = 0.23 e Å−3 |
1523 reflections | Δρmin = −0.17 e Å−3 |
74 parameters |
C12H24N2S2 | γ = 70.427 (15)° |
Mr = 260.45 | V = 388.90 (11) Å3 |
Triclinic, P1 | Z = 1 |
a = 4.7658 (9) Å | Mo Kα radiation |
b = 6.0323 (9) Å | µ = 0.32 mm−1 |
c = 14.470 (2) Å | T = 571 K |
α = 83.082 (14)° | 0.58 × 0.44 × 0.24 mm |
β = 85.919 (15)° |
Bruker P4 diffractometer | 1344 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.011 |
Tmin = 0.825, Tmax = 0.924 | 3 standard reflections every 197 reflections |
2093 measured reflections | intensity decay: 2% |
1523 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.23 e Å−3 |
1523 reflections | Δρmin = −0.17 e Å−3 |
74 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.30375 (11) | 0.27375 (7) | 0.08976 (3) | 0.05646 (19) | |
N1 | 0.2847 (3) | 0.7182 (2) | 0.07141 (9) | 0.0431 (3) | |
H1 | 0.3425 | 0.8287 | 0.042 | 0.052* | |
C1 | 0.3922 (3) | 0.5069 (2) | 0.04182 (10) | 0.0384 (3) | |
C2 | 0.0759 (4) | 0.7793 (3) | 0.15000 (11) | 0.0475 (4) | |
H2A | −0.0553 | 0.6852 | 0.1543 | 0.057* | |
H2B | −0.0457 | 0.9446 | 0.1398 | 0.057* | |
C3 | 0.2347 (4) | 0.7371 (3) | 0.24076 (12) | 0.0534 (4) | |
H3A | 0.3617 | 0.8346 | 0.2365 | 0.064* | |
H3B | 0.3618 | 0.5731 | 0.2493 | 0.064* | |
C4 | 0.0254 (5) | 0.7911 (4) | 0.32571 (13) | 0.0641 (5) | |
H4 | −0.117 | 0.706 | 0.325 | 0.077* | |
C5 | −0.1497 (7) | 1.0529 (5) | 0.32366 (19) | 0.0993 (9) | |
H5A | −0.256 | 1.1057 | 0.2669 | 0.149* | |
H5B | −0.0152 | 1.1396 | 0.327 | 0.149* | |
H5C | −0.2888 | 1.0791 | 0.3758 | 0.149* | |
C6 | 0.1984 (7) | 0.7021 (6) | 0.41444 (15) | 0.1009 (9) | |
H6A | 0.3081 | 0.5365 | 0.4142 | 0.151* | |
H6B | 0.0623 | 0.7259 | 0.4674 | 0.151* | |
H6C | 0.3343 | 0.7875 | 0.4179 | 0.151* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0758 (3) | 0.0383 (2) | 0.0581 (3) | −0.0242 (2) | 0.0082 (2) | −0.00594 (18) |
N1 | 0.0514 (8) | 0.0345 (6) | 0.0446 (7) | −0.0147 (5) | −0.0004 (6) | −0.0075 (5) |
C1 | 0.0432 (8) | 0.0345 (7) | 0.0376 (7) | −0.0117 (6) | −0.0091 (6) | −0.0036 (6) |
C2 | 0.0481 (9) | 0.0436 (8) | 0.0490 (9) | −0.0110 (7) | 0.0013 (7) | −0.0111 (7) |
C3 | 0.0535 (10) | 0.0558 (10) | 0.0473 (9) | −0.0123 (8) | −0.0010 (7) | −0.0085 (7) |
C4 | 0.0661 (12) | 0.0776 (13) | 0.0496 (10) | −0.0238 (10) | 0.0056 (9) | −0.0142 (9) |
C5 | 0.108 (2) | 0.0939 (19) | 0.0741 (15) | 0.0040 (15) | 0.0068 (14) | −0.0387 (14) |
C6 | 0.119 (2) | 0.126 (2) | 0.0466 (12) | −0.0267 (19) | 0.0001 (13) | −0.0040 (13) |
S1—C1 | 1.6606 (15) | C3—H3B | 0.97 |
N1—C1 | 1.3165 (19) | C4—C5 | 1.517 (3) |
N1—C2 | 1.454 (2) | C4—C6 | 1.518 (3) |
N1—H1 | 0.86 | C4—H4 | 0.98 |
C1—C1i | 1.522 (3) | C5—H5A | 0.96 |
C2—C3 | 1.515 (2) | C5—H5B | 0.96 |
C2—H2A | 0.97 | C5—H5C | 0.96 |
C2—H2B | 0.97 | C6—H6A | 0.96 |
C3—C4 | 1.522 (2) | C6—H6B | 0.96 |
C3—H3A | 0.97 | C6—H6C | 0.96 |
C1—N1—C2 | 125.09 (14) | C5—C4—C6 | 110.9 (2) |
C1—N1—H1 | 117.5 | C5—C4—C3 | 111.70 (19) |
C2—N1—H1 | 117.5 | C6—C4—C3 | 110.33 (18) |
N1—C1—C1i | 113.92 (16) | C5—C4—H4 | 107.9 |
N1—C1—S1 | 124.00 (12) | C6—C4—H4 | 107.9 |
C1i—C1—S1 | 122.08 (14) | C3—C4—H4 | 107.9 |
N1—C2—C3 | 111.77 (13) | C4—C5—H5A | 109.5 |
N1—C2—H2A | 109.3 | C4—C5—H5B | 109.5 |
C3—C2—H2A | 109.3 | H5A—C5—H5B | 109.5 |
N1—C2—H2B | 109.3 | C4—C5—H5C | 109.5 |
C3—C2—H2B | 109.3 | H5A—C5—H5C | 109.5 |
H2A—C2—H2B | 107.9 | H5B—C5—H5C | 109.5 |
C2—C3—C4 | 113.83 (15) | C4—C6—H6A | 109.5 |
C2—C3—H3A | 108.8 | C4—C6—H6B | 109.5 |
C4—C3—H3A | 108.8 | H6A—C6—H6B | 109.5 |
C2—C3—H3B | 108.8 | C4—C6—H6C | 109.5 |
C4—C3—H3B | 108.8 | H6A—C6—H6C | 109.5 |
H3A—C3—H3B | 107.7 | H6B—C6—H6C | 109.5 |
C2—N1—C1—C1i | −179.80 (15) | N1—C2—C3—C4 | −178.18 (15) |
C2—N1—C1—S1 | 0.4 (2) | C2—C3—C4—C5 | −66.7 (2) |
C1—N1—C2—C3 | 88.31 (19) | C2—C3—C4—C6 | 169.55 (19) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.86 | 2.45 | 2.9452 (15) | 118 |
N1—H1···S1ii | 0.86 | 2.80 | 3.4251 (14) | 131 |
C2—H2B···S1ii | 0.97 | 2.99 | 3.4991 (18) | 114 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C12H24N2S2 |
Mr | 260.45 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 571 |
a, b, c (Å) | 4.7658 (9), 6.0323 (9), 14.470 (2) |
α, β, γ (°) | 83.082 (14), 85.919 (15), 70.427 (15) |
V (Å3) | 388.90 (11) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.58 × 0.44 × 0.24 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.825, 0.924 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2093, 1523, 1344 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.098, 1.12 |
No. of reflections | 1523 |
No. of parameters | 74 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.17 |
Computer programs: XSCANS (Siemens, 1989), XSCANS, XPREP (Bruker, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 1997), XPREP, PARST95 (Nardelli, 1995) and WinGX-PC (Farrugia, 1999).
S1—C1 | 1.6606 (15) | N1—C2 | 1.454 (2) |
N1—C1 | 1.3165 (19) | C1—C1i | 1.522 (3) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.86 | 2.45 | 2.9452 (15) | 117.6 |
N1—H1···S1ii | 0.86 | 2.80 | 3.4251 (14) | 131.3 |
C2—H2B···S1ii | 0.97 | 2.99 | 3.4991 (18) | 114.1 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z. |
Secondary dithioxamides behave as binucleating ligands both in N,S–N,S (Veit et al., 1984; Ye et al., 1991; Lanza et al. 2002) and in N,N–S,S modes (Lanza et al., 2000; 2003; 2005) (Scheme 1). It has been already observed (Lanza et al., 2005) that in the trimetallic complexes [Pt{{µ-S2C2(NR)2}MLn}2] (µ-S2C2(NR)2 = bridging dianionic dithioxamidate; MLn+= positively charged metal fragment) there is an electron removal from platinum to MLn+ via the π* system in the N—C—S fragments (Lanza et al. 2005). The possibility of a π donation from the bridged dithioxamide to the platinum d orbitals has been ruled out, since this latter circumstance would require a C—C double bond connecting the two N—C—S frames. In order to asses factors affecting electronic transmission between metals in polymetallic chains through binucleating dithioxamides, we think it is important to gain as much structural information as possible about free and coordinated H2S2C2(NR)2 ligands
The asymmetric unit of (I) contains one half of the symmetric molecule with the other half generated by inversion (Fig. 1). The thioamide moiety is planar [maximum deviation from the mean plane for the C1 = 0.001 (1) Å]; the trans conformation is also stabilized by the intramolecular interaction N—H···S [N1—H1 = 0.860 (1), N1···S1i = 2.945 (1) Å, N1—H1···S1i = 117.6 (1)°; symmetry code (i) -x + 1, -y + 1, -z], moreover the first C atom of the N-attached alkyl chain keeps the planarity of the core atoms [maximum deviation of C2 = 0.005 (2) Å]. On the other hand the features of the sp3 hybridized C atoms mean that the side aliphatic chains are above and below with respect to the core planar fragment. The thioamide geometrical parameters in the table are in accord with those found for similar crystal structures (Shimanouchi & Sasada, 1979; Bermejo et al., 1998; Perec et al., 1995; Jean 1994; Simonov et al. 2003).
The crystal lattice is mainly supported by intermolecular N—H···S interactions [N1—H1 = 0.860 (1), N1···S1ii = 3.425 (2) Å, N1—H1···S1ii = 131.3 (1)°; symmetry code (ii) x, y + 1, z] together with a much weaker C—H···S hydrogen bond [C2—H2B = 0.970 (2), C1···S1ii = 3.499 (2) Å, C2—H2B···S1ii = 114.1 (1)°]. The interaction N—H···S doubled by the crystallographic inversion centre leads to the "chain of rings" C(3)R22(10) motif (Bernstein et al., 1995). The resulting one-dimensional-array of molecules along the b crystallographic axis looks like a planar strand because of the directional self-recognition (Fig. 2). The thioamidic group also develops vertical π-π interactions [distance from the mean thioxamidic planes 3.6595 (5) Å; symmetry code for the π stacked equivalent is x + 1, y, z] generating a ladder like disposition of the planar strands running along the a crystallographic axis (Fig. 3). The non-polar nature of the alkylic chain means that very weak interactions complete the third dimension of the crystal packing. Compounds with similar structure can be regarded as forerunners of metallomesogens; actually mesophases are observed when the R groups are aryl substituents bearing long hydrocarbon chains (Aversa et al., 2000; 1997).