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The crystal structure of bis(thiourea) pyridinium iodide (T2PyI) was previously determined at 295 and 110 K [Prout, Heyes, Dobson, McDaid, Maris, Mueller & Seaman (2000). Chem. Mater. 12, 3561–3569] and the two phases were described in the space groups Cmcm and P21cn, respectively. Because differential scanning calorimetry revealed two phase transitions, at 161 and 141 K, a redetermination of the structure of T2pyI at 295, 155 and 110 K has been undertaken, and the following sequence of space groups obtained: Cmcm (I) → C2cm (II) → P21cn (III). The high- (I) and low-temperature (III) phases confirmed the results reported in the previous study. In the new intermediate phase II, the mirror plane perpendicular to the x axis vanishes and the crystal structure loses the centre of symmetry. In phases I and II the pyridinium cations are strongly dynamically disordered, while in the low-temperature phase III the cations are well ordered. In all three phases the thiourea–iodine hydrogen-bonded sublattice is very well ordered. Dielectric measurements show that the intermediate and low-temperature phases are ferroelectric and that 161 K is the Curie point of a new ferroelectric crystal.
Supporting information
CCDC references: 705580; 705581; 705582
For all compounds, data collection: KUMA KM-4; cell refinement: KUMA KM-4; data reduction: KUMA KM-4 Data reduction program; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
(I) bis-thiourea pyridinium iodide
top
Crystal data top
C7H14IN5S2 | Dx = 1.587 Mg m−3 |
Mr = 359.25 | Melting point: 2[SC(NH2)2] [C5H6N]+ [I]- K |
Orthorhombic, Cmcm | Mo Kαlpha radiation, λ = 0.71073 Å |
a = 15.180 (3) Å | Cell parameters from 34 reflections |
b = 11.827 (2) Å | θ = 7.0–12.5° |
c = 8.375 (2) Å | µ = 2.39 mm−1 |
V = 1503.6 (5) Å3 | T = 295 K |
Z = 4 | Needle, colourless |
F(000) = 704 | 0.6 × 0.1 × 0.1 mm |
Data collection top
KUMA KM-4 diffractometer | 965 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 30.0°, θmin = 2.2° |
ω – 2θ scans | h = 0→21 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→15 |
Tmin = 0.51, Tmax = 0.56 | l = −11→0 |
2244 measured reflections | 2 standard reflections every 100 reflections |
1158 independent reflections | |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 0.74 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
1158 reflections | (Δ/σ)max = 0.135 |
50 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.92 e Å−3 |
Crystal data top
C7H14IN5S2 | V = 1503.6 (5) Å3 |
Mr = 359.25 | Z = 4 |
Orthorhombic, Cmcm | Mo Kαlpha radiation |
a = 15.180 (3) Å | µ = 2.39 mm−1 |
b = 11.827 (2) Å | T = 295 K |
c = 8.375 (2) Å | 0.6 × 0.1 × 0.1 mm |
Data collection top
KUMA KM-4 diffractometer | 1158 independent reflections |
Absorption correction: ψ scan (North et al., 1968) | 965 reflections with I > 2σ(I) |
Tmin = 0.51, Tmax = 0.56 | Rint = 0.024 |
2244 measured reflections | 2 standard reflections every 100 reflections |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 0.74 | (Δ/σ)max = 0.135 |
1158 reflections | Δρmax = 0.67 e Å−3 |
50 parameters | Δρmin = −0.92 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 | Occ. (<1) |
I1 | 0.0000 | 0.40856 (3) | 0.2500 | 0.03794 (14) | |
S1 | 0.22815 (11) | 0.27706 (18) | 0.2500 | 0.0843 (6) | |
C11 | 0.3118 (3) | 0.1785 (4) | 0.2500 | 0.0518 (11) | |
N11 | 0.3458 (2) | 0.1386 (3) | 0.1146 (3) | 0.0668 (10) | |
H11A | 0.3221 | 0.1674 | 0.0068 | 0.080* | |
H11B | 0.3957 | 0.0796 | 0.1172 | 0.080* | |
C2 | 0.435 (2) | 0.424 (3) | −0.054 (4) | 0.145 (13) | 0.50 |
C3 | 0.4206 (19) | 0.458 (3) | 0.032 (4) | 0.142 (11) | 0.50 |
C1 | 0.5000 | 0.3829 (16) | −0.027 (3) | 0.178 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.03287 (18) | 0.0397 (2) | 0.0413 (2) | 0.000 | 0.000 | 0.000 |
S1 | 0.0916 (10) | 0.1316 (14) | 0.0297 (5) | 0.0793 (10) | 0.000 | 0.000 |
C11 | 0.057 (2) | 0.068 (3) | 0.0309 (16) | 0.026 (2) | 0.000 | 0.000 |
N11 | 0.080 (2) | 0.091 (2) | 0.0296 (11) | 0.0498 (19) | 0.0027 (13) | −0.0013 (13) |
C2 | 0.17 (3) | 0.15 (3) | 0.114 (16) | −0.07 (2) | −0.02 (2) | 0.030 (18) |
C3 | 0.116 (13) | 0.18 (3) | 0.125 (17) | −0.041 (16) | −0.001 (14) | 0.021 (16) |
C1 | 0.26 (3) | 0.100 (8) | 0.17 (2) | 0.000 | 0.000 | −0.024 (11) |
Geometric parameters (Å, º) top
S1—C11 | 1.724 (4) | C2—C1 | 1.13 (4) |
C11—N11 | 1.333 (3) | C2—C3ii | 1.42 (4) |
C11—N11i | 1.333 (3) | C3—C1 | 1.58 (4) |
| | | |
N11—C11—N11i | 116.7 (4) | C1—C2—C3ii | 122 (4) |
N11—C11—S1 | 121.7 (2) | C2ii—C3—C1 | 118 (3) |
N11i—C11—S1 | 121.7 (2) | C2iii—C1—C3 | 119 (2) |
Symmetry codes: (i) x, y, −z+1/2; (ii) x, −y+1, −z; (iii) −x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···S1iv | 1.03 | 2.37 | 3.403 (3) | 176 |
N11—H11B···I1v | 1.03 | 2.80 | 3.763 (3) | 156 |
Symmetry codes: (iv) −x+1/2, −y+1/2, −z; (v) x+1/2, y−1/2, z. |
(II) bis-thiourea pyridinium iodide
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Crystal data top
2[SC(NH2)2][C5H6N]+[I]− | Dx = 1.696 Mg m−3 |
Mr = 359.25 | Mo Kαlpha radiation, λ = 0.71073 Å |
Orthorhombic, C2cm | Cell parameters from 23 reflections |
a = 15.022 (3) Å | θ = 7.5–14.5° |
b = 11.227 (2) Å | µ = 2.55 mm−1 |
c = 8.3410 (17) Å | T = 155 K |
V = 1406.7 (5) Å3 | Needle, colourless |
Z = 4 | 0.6 × 0.1 × 0.05 mm |
F(000) = 704 | |
Data collection top
KUMA KM-4 diffractometer | 920 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 30.1°, θmin = 2.3° |
ω – 2θ scans | h = −19→0 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→14 |
Tmin = 0.55, Tmax = 0.62 | l = −11→0 |
1960 measured reflections | 2 standard reflections every 100 reflections |
1010 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0422P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.148 |
1010 reflections | Δρmax = 0.76 e Å−3 |
104 parameters | Δρmin = −0.69 e Å−3 |
1 restraint | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.35 (10) |
Crystal data top
2[SC(NH2)2][C5H6N]+[I]− | V = 1406.7 (5) Å3 |
Mr = 359.25 | Z = 4 |
Orthorhombic, C2cm | Mo Kαlpha radiation |
a = 15.022 (3) Å | µ = 2.55 mm−1 |
b = 11.227 (2) Å | T = 155 K |
c = 8.3410 (17) Å | 0.6 × 0.1 × 0.05 mm |
Data collection top
KUMA KM-4 diffractometer | 1010 independent reflections |
Absorption correction: ψ scan (North et al., 1968) | 920 reflections with I > 2σ(I) |
Tmin = 0.55, Tmax = 0.62 | Rint = 0.027 |
1960 measured reflections | 2 standard reflections every 100 reflections |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.058 | (Δ/σ)max = 0.148 |
S = 1.01 | Δρmax = 0.76 e Å−3 |
1010 reflections | Δρmin = −0.69 e Å−3 |
104 parameters | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
1 restraint | Absolute structure parameter: 0.35 (10) |
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 | Occ. (<1) |
I1 | 0.22848 (7) | 0.40864 (2) | 0.2500 | 0.01881 (10) | |
S1 | 0.0145 (2) | 0.2562 (3) | 0.2500 | 0.0452 (7) | |
S2 | −0.0319 (2) | −0.2031 (3) | 0.2500 | 0.0471 (8) | |
C11 | −0.0788 (7) | 0.1692 (11) | 0.2500 | 0.032 (2) | |
C21 | 0.0451 (8) | −0.3145 (10) | 0.2500 | 0.029 (2) | |
N11 | −0.1154 (5) | 0.1348 (7) | 0.1139 (7) | 0.0355 (17) | |
H11A | −0.0874 | 0.1592 | 0.0061 | 0.043* | |
H11B | −0.1721 | 0.0833 | 0.1157 | 0.043* | |
N21 | 0.0771 (6) | −0.3569 (7) | 0.1119 (7) | 0.0367 (16) | |
H21A | 0.0554 | −0.3210 | 0.0052 | 0.044* | |
H21B | 0.1234 | −0.4246 | 0.1115 | 0.044* | |
C4 | 0.268 (4) | −0.119 (4) | −0.038 (7) | 0.11 (2) | 0.50 |
C1 | 0.1546 (18) | −0.026 (3) | 0.051 (3) | 0.084 (9) | 0.50 |
C3 | 0.223 (4) | −0.109 (3) | −0.006 (5) | 0.085 (14) | 0.50 |
C2 | 0.172 (4) | −0.090 (3) | −0.058 (5) | 0.094 (17) | 0.50 |
C5 | 0.286 (5) | −0.068 (4) | −0.060 (7) | 0.11 (2) | 0.50 |
C6 | 0.320 (3) | −0.054 (3) | 0.028 (4) | 0.079 (9) | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.01728 (15) | 0.01789 (15) | 0.02127 (13) | −0.0010 (3) | 0.000 | 0.000 |
S1 | 0.0492 (13) | 0.0691 (16) | 0.0174 (8) | −0.0432 (13) | 0.000 | 0.000 |
S2 | 0.0621 (17) | 0.0637 (15) | 0.0154 (7) | 0.0471 (14) | 0.000 | 0.000 |
C11 | 0.027 (4) | 0.046 (6) | 0.023 (4) | −0.023 (4) | 0.000 | 0.000 |
C21 | 0.042 (5) | 0.035 (4) | 0.011 (3) | 0.014 (4) | 0.000 | 0.000 |
N11 | 0.043 (3) | 0.049 (4) | 0.015 (2) | −0.034 (4) | −0.003 (2) | 0.002 (3) |
N21 | 0.048 (4) | 0.046 (4) | 0.017 (3) | 0.023 (4) | 0.001 (3) | −0.002 (3) |
C4 | 0.15 (5) | 0.06 (2) | 0.12 (3) | 0.07 (3) | −0.04 (3) | 0.00 (3) |
C1 | 0.071 (13) | 0.10 (2) | 0.077 (13) | −0.041 (14) | 0.015 (9) | −0.035 (15) |
C3 | 0.11 (3) | 0.043 (13) | 0.102 (18) | −0.054 (16) | −0.01 (2) | −0.010 (12) |
C2 | 0.13 (4) | 0.08 (3) | 0.068 (18) | −0.04 (2) | −0.05 (2) | 0.041 (15) |
C5 | 0.16 (5) | 0.06 (2) | 0.10 (3) | 0.09 (3) | 0.05 (3) | 0.03 (2) |
C6 | 0.079 (18) | 0.075 (17) | 0.08 (2) | 0.030 (14) | −0.005 (14) | 0.010 (15) |
Geometric parameters (Å, º) top
S1—C11 | 1.708 (10) | C4—C2 | 1.49 (8) |
S2—C21 | 1.705 (11) | C4—C6 | 1.20 (7) |
C11—N11 | 1.319 (7) | C1—C3 | 1.47 (7) |
C11—N11i | 1.319 (7) | C1—C2ii | 1.33 (4) |
C21—N21i | 1.336 (7) | C3—C5 | 1.15 (10) |
C21—N21 | 1.336 (7) | C5—C6ii | 1.49 (7) |
| | | |
N11—C11—N11i | 118.8 (9) | C2—C4—C6 | 124 (5) |
N11—C11—S1 | 120.6 (4) | C3—C1—C2ii | 120 (3) |
N11i—C11—S1 | 120.6 (4) | C1—C3—C5 | 117 (3) |
N21i—C21—N21 | 119.2 (10) | C4—C2—C1ii | 113 (4) |
N21i—C21—S2 | 120.4 (5) | C6ii—C5—C3 | 126 (4) |
N21—C21—S2 | 120.4 (5) | C5ii—C6—C4 | 114 (4) |
Symmetry codes: (i) x, y, −z+1/2; (ii) x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···S2iii | 1.03 | 2.34 | 3.372 (7) | 175 |
N11—H11B···I1iv | 1.03 | 2.71 | 3.638 (7) | 150 |
N21—H21A···S1iii | 1.03 | 2.33 | 3.358 (7) | 174 |
N21—H21B···I1v | 1.03 | 2.71 | 3.664 (8) | 155 |
Symmetry codes: (iii) x, −y, z−1/2; (iv) x−1/2, y−1/2, z; (v) x, y−1, z. |
(III) bis-thiourea pyridinium iodide
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Crystal data top
2[SC(NH2)2][C5H6N]+[I]− | Dx = 1.712 Mg m−3 |
Mr = 359.25 | Mo Kαlpha radiation, λ = 0.71030 Å |
Orthorhombic, P21cn | Cell parameters from 23 reflections |
a = 14.860 (1) Å | θ = 7.0–14.5° |
b = 11.291 (1) Å | µ = 2.58 mm−1 |
c = 8.307 (2) Å | T = 110 K |
V = 1393.8 (4) Å3 | Needle, colourless |
Z = 4 | 0.6 × 0.1 × 0.05 mm |
F(000) = 704 | |
Data collection top
KUMA KM-4 diffractometer | 1223 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 30.1°, θmin = 2.3° |
ω – 2θ scans | h = 0→20 |
Absorption correction: ψ scan (North et al.1968) | k = −14→15 |
Tmin = 0.539, Tmax = 0.596 | l = −11→0 |
4104 measured reflections | 2 standard reflections every 100 reflections |
2116 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0417P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
2116 reflections | Δρmax = 2.14 e Å−3 |
137 parameters | Δρmin = −1.10 e Å−3 |
1 restraint | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.46 (7) |
Crystal data top
2[SC(NH2)2][C5H6N]+[I]− | V = 1393.8 (4) Å3 |
Mr = 359.25 | Z = 4 |
Orthorhombic, P21cn | Mo Kαlpha radiation |
a = 14.860 (1) Å | µ = 2.58 mm−1 |
b = 11.291 (1) Å | T = 110 K |
c = 8.307 (2) Å | 0.6 × 0.1 × 0.05 mm |
Data collection top
KUMA KM-4 diffractometer | 2116 independent reflections |
Absorption correction: ψ scan (North et al.1968) | 1223 reflections with I > 2σ(I) |
Tmin = 0.539, Tmax = 0.596 | Rint = 0.036 |
4104 measured reflections | 2 standard reflections every 100 reflections |
Refinement top
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.075 | Δρmax = 2.14 e Å−3 |
S = 0.99 | Δρmin = −1.10 e Å−3 |
2116 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
137 parameters | Absolute structure parameter: 0.46 (7) |
1 restraint | |
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 | |
I1 | 0.490481 (19) | 0.840315 (19) | 0.25345 (5) | 0.01326 (8) | |
S1 | 0.24542 (17) | 0.94624 (17) | 0.2493 (3) | 0.0309 (4) | |
S2 | 0.19436 (14) | 0.50790 (13) | 0.2490 (2) | 0.0213 (3) | |
N21 | 0.3328 (7) | 0.6158 (7) | 0.1108 (8) | 0.023 (2) | |
H21A | 0.3051 | 0.5884 | 0.0035 | 0.027* | |
H21B | 0.3916 | 0.6643 | 0.1111 | 0.027* | |
N22 | 0.3289 (7) | 0.6241 (7) | 0.3860 (8) | 0.025 (2) | |
H22A | 0.2994 | 0.6035 | 0.4947 | 0.030* | |
H22B | 0.3876 | 0.6725 | 0.3831 | 0.030* | |
N11 | 0.1400 (7) | 1.1030 (8) | 0.1102 (7) | 0.026 (2) | |
H11A | 0.1628 | 1.0681 | 0.0032 | 0.031* | |
H11B | 0.0941 | 1.1714 | 0.1097 | 0.031* | |
N12 | 0.1407 (7) | 1.1070 (9) | 0.3848 (8) | 0.029 (3) | |
H12A | 0.1650 | 1.0758 | 0.4928 | 0.035* | |
H12B | 0.0947 | 1.1754 | 0.3832 | 0.035* | |
C11 | 0.1701 (5) | 1.0596 (6) | 0.2448 (10) | 0.0223 (14) | |
C21 | 0.2927 (5) | 0.5895 (6) | 0.2475 (11) | 0.0200 (13) | |
C3 | −0.0067 (17) | 0.8555 (10) | 0.5030 (10) | 0.054 (3) | |
H3A | 0.0068 | 0.9494 | 0.5094 | 0.065* | |
N | 0.0367 (8) | 0.6648 (7) | 0.4347 (9) | 0.039 (2) | |
H0A | 0.0840 | 0.6066 | 0.3905 | 0.047* | |
C2 | 0.0576 (8) | 0.7814 (10) | 0.4435 (11) | 0.046 (3) | |
H2A | 0.1223 | 0.8145 | 0.4052 | 0.055* | |
C5 | −0.1077 (8) | 0.6987 (10) | 0.5442 (13) | 0.050 (3) | |
H5A | −0.1710 | 0.6646 | 0.5882 | 0.060* | |
C4 | −0.0872 (9) | 0.8179 (10) | 0.5506 (13) | 0.045 (3) | |
H4A | −0.1358 | 0.8808 | 0.5958 | 0.054* | |
C6 | −0.0413 (12) | 0.6216 (12) | 0.4806 (15) | 0.055 (3) | |
H6A | −0.0542 | 0.5281 | 0.4669 | 0.065* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.01158 (12) | 0.01272 (12) | 0.01549 (12) | −0.00139 (18) | 0.0007 (4) | 0.0001 (2) |
S1 | 0.0390 (8) | 0.0404 (8) | 0.0132 (5) | 0.0288 (8) | −0.0004 (11) | 0.0005 (13) |
S2 | 0.0220 (6) | 0.0280 (6) | 0.0138 (5) | −0.0128 (6) | 0.0008 (10) | −0.0019 (11) |
N21 | 0.023 (5) | 0.030 (5) | 0.016 (3) | −0.020 (4) | 0.006 (3) | 0.005 (3) |
N22 | 0.028 (5) | 0.031 (4) | 0.016 (3) | −0.014 (4) | 0.000 (3) | 0.009 (3) |
N11 | 0.040 (6) | 0.032 (5) | 0.006 (3) | 0.021 (4) | −0.008 (3) | −0.002 (3) |
N12 | 0.033 (6) | 0.039 (7) | 0.016 (4) | 0.018 (5) | −0.009 (3) | −0.003 (4) |
C11 | 0.028 (3) | 0.029 (3) | 0.010 (2) | 0.012 (3) | 0.009 (4) | −0.006 (4) |
C21 | 0.018 (3) | 0.027 (3) | 0.015 (2) | −0.009 (2) | −0.013 (4) | 0.000 (4) |
C3 | 0.083 (9) | 0.030 (5) | 0.049 (4) | −0.019 (8) | 0.007 (9) | −0.016 (4) |
N | 0.047 (6) | 0.038 (5) | 0.033 (4) | 0.011 (4) | 0.014 (4) | 0.004 (3) |
C2 | 0.034 (5) | 0.061 (7) | 0.044 (4) | −0.015 (5) | 0.000 (4) | 0.008 (5) |
C5 | 0.041 (6) | 0.048 (6) | 0.061 (6) | −0.013 (5) | 0.019 (5) | −0.018 (5) |
C4 | 0.046 (7) | 0.034 (5) | 0.056 (6) | 0.010 (5) | 0.002 (5) | −0.017 (4) |
C6 | 0.078 (9) | 0.027 (5) | 0.059 (7) | 0.000 (6) | 0.018 (6) | −0.010 (5) |
Geometric parameters (Å, º) top
S1—C11 | 1.701 (7) | C3—C2 | 1.36 (2) |
S2—C21 | 1.728 (7) | C3—C4 | 1.33 (2) |
N21—C21 | 1.316 (11) | N—C6 | 1.313 (16) |
N22—C21 | 1.329 (10) | N—C2 | 1.354 (14) |
N11—C11 | 1.300 (10) | C5—C4 | 1.381 (15) |
N12—C11 | 1.353 (10) | C5—C6 | 1.418 (18) |
| | | |
N11—C11—N12 | 118.6 (7) | C2—C3—C4 | 122.8 (11) |
N11—C11—S1 | 121.9 (6) | C6—N—C2 | 123.2 (11) |
N12—C11—S1 | 119.5 (7) | C3—C2—N | 117.1 (11) |
N21—C21—N22 | 119.8 (6) | C4—C5—C6 | 117.3 (12) |
N21—C21—S2 | 120.6 (6) | C3—C4—C5 | 119.9 (12) |
N22—C21—S2 | 119.6 (7) | N—C6—C5 | 119.6 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0A···S2 | 1.03 | 2.31 | 3.318 (10) | 167 |
C3—H3A···I1i | 1.08 | 3.10 | 3.987 (10) | 140 |
C2—H2A···S1 | 1.08 | 2.69 | 3.723 (11) | 160 |
C6—H6A···I1ii | 1.08 | 2.88 | 3.754 (13) | 138 |
N11—H11A···S2iii | 1.03 | 2.33 | 3.350 (7) | 172 |
N11—H11B···I1iv | 1.03 | 2.70 | 3.661 (9) | 155 |
N12—H12A···S2v | 1.03 | 2.37 | 3.388 (8) | 170 |
N12—H12B···I1iv | 1.03 | 2.68 | 3.638 (10) | 156 |
N21—H21A···S1iii | 1.03 | 2.32 | 3.347 (8) | 172 |
N21—H21B···I1 | 1.03 | 2.74 | 3.649 (9) | 147 |
N22—H22B···I1 | 1.03 | 2.66 | 3.597 (9) | 151 |
N22—H22A···S1v | 1.03 | 2.33 | 3.358 (8) | 175 |
Symmetry codes: (i) x−1/2, −y+2, −z+1; (ii) x−1/2, y−1/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) x−1/2, y+1/2, −z+1/2; (v) x, −y+3/2, z+1/2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C7H14IN5S2 | 2[SC(NH2)2][C5H6N]+[I]− | 2[SC(NH2)2][C5H6N]+[I]− |
Mr | 359.25 | 359.25 | 359.25 |
Crystal system, space group | Orthorhombic, Cmcm | Orthorhombic, C2cm | Orthorhombic, P21cn |
Temperature (K) | 295 | 155 | 110 |
a, b, c (Å) | 15.180 (3), 11.827 (2), 8.375 (2) | 15.022 (3), 11.227 (2), 8.3410 (17) | 14.860 (1), 11.291 (1), 8.307 (2) |
V (Å3) | 1503.6 (5) | 1406.7 (5) | 1393.8 (4) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kαlpha | Mo Kαlpha | Mo Kαlpha |
µ (mm−1) | 2.39 | 2.55 | 2.58 |
Crystal size (mm) | 0.6 × 0.1 × 0.1 | 0.6 × 0.1 × 0.05 | 0.6 × 0.1 × 0.05 |
|
Data collection |
Diffractometer | KUMA KM-4 diffractometer | KUMA KM-4 diffractometer | KUMA KM-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) | ψ scan (North et al.1968) |
Tmin, Tmax | 0.51, 0.56 | 0.55, 0.62 | 0.539, 0.596 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2244, 1158, 965 | 1960, 1010, 920 | 4104, 2116, 1223 |
Rint | 0.024 | 0.027 | 0.036 |
(sin θ/λ)max (Å−1) | 0.703 | 0.705 | 0.706 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.090, 0.74 | 0.022, 0.058, 1.01 | 0.027, 0.075, 0.99 |
No. of reflections | 1158 | 1010 | 2116 |
No. of parameters | 50 | 104 | 137 |
No. of restraints | 0 | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
(Δ/σ)max | 0.135 | 0.148 | 0.001 |
Δρmax, Δρmin (e Å−3) | 0.67, −0.92 | 0.76, −0.69 | 2.14, −1.10 |
Absolute structure | ? | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | ? | 0.35 (10) | 0.46 (7) |
Selected geometric parameters (Å, º) for (I) topS1—C11 | 1.724 (4) | C2—C1 | 1.13 (4) |
C11—N11 | 1.333 (3) | C2—C3ii | 1.42 (4) |
C11—N11i | 1.333 (3) | C3—C1 | 1.58 (4) |
| | | |
N11—C11—N11i | 116.7 (4) | C1—C2—C3ii | 122 (4) |
N11—C11—S1 | 121.7 (2) | C2ii—C3—C1 | 118 (3) |
N11i—C11—S1 | 121.7 (2) | C2iii—C1—C3 | 119 (2) |
Symmetry codes: (i) x, y, −z+1/2; (ii) x, −y+1, −z; (iii) −x+1, y, z. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···S1iv | 1.03 | 2.37 | 3.403 (3) | 176.1 |
N11—H11B···I1v | 1.03 | 2.80 | 3.763 (3) | 156.1 |
Symmetry codes: (iv) −x+1/2, −y+1/2, −z; (v) x+1/2, y−1/2, z. |
Selected geometric parameters (Å, º) for (II) topS1—C11 | 1.708 (10) | C4—C2 | 1.49 (8) |
S2—C21 | 1.705 (11) | C4—C6 | 1.20 (7) |
C11—N11 | 1.319 (7) | C1—C3 | 1.47 (7) |
C11—N11i | 1.319 (7) | C1—C2ii | 1.33 (4) |
C21—N21i | 1.336 (7) | C3—C5 | 1.15 (10) |
C21—N21 | 1.336 (7) | C5—C6ii | 1.49 (7) |
| | | |
N11—C11—N11i | 118.8 (9) | C2—C4—C6 | 124 (5) |
N11—C11—S1 | 120.6 (4) | C3—C1—C2ii | 120 (3) |
N11i—C11—S1 | 120.6 (4) | C1—C3—C5 | 117 (3) |
N21i—C21—N21 | 119.2 (10) | C4—C2—C1ii | 113 (4) |
N21i—C21—S2 | 120.4 (5) | C6ii—C5—C3 | 126 (4) |
N21—C21—S2 | 120.4 (5) | C5ii—C6—C4 | 114 (4) |
Symmetry codes: (i) x, y, −z+1/2; (ii) x, −y, −z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···S2iii | 1.03 | 2.34 | 3.372 (7) | 175.1 |
N11—H11B···I1iv | 1.03 | 2.71 | 3.638 (7) | 150.3 |
N21—H21A···S1iii | 1.03 | 2.33 | 3.358 (7) | 173.9 |
N21—H21B···I1v | 1.03 | 2.71 | 3.664 (8) | 154.5 |
Symmetry codes: (iii) x, −y, z−1/2; (iv) x−1/2, y−1/2, z; (v) x, y−1, z. |
Selected geometric parameters (Å, º) for (III) topS1—C11 | 1.701 (7) | C3—C2 | 1.36 (2) |
S2—C21 | 1.728 (7) | C3—C4 | 1.33 (2) |
N21—C21 | 1.316 (11) | N—C6 | 1.313 (16) |
N22—C21 | 1.329 (10) | N—C2 | 1.354 (14) |
N11—C11 | 1.300 (10) | C5—C4 | 1.381 (15) |
N12—C11 | 1.353 (10) | C5—C6 | 1.418 (18) |
| | | |
N11—C11—N12 | 118.6 (7) | C2—C3—C4 | 122.8 (11) |
N11—C11—S1 | 121.9 (6) | C6—N—C2 | 123.2 (11) |
N12—C11—S1 | 119.5 (7) | C3—C2—N | 117.1 (11) |
N21—C21—N22 | 119.8 (6) | C4—C5—C6 | 117.3 (12) |
N21—C21—S2 | 120.6 (6) | C3—C4—C5 | 119.9 (12) |
N22—C21—S2 | 119.6 (7) | N—C6—C5 | 119.6 (12) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0A···S2 | 1.03 | 2.31 | 3.318 (10) | 167.4 |
C3—H3A···I1i | 1.08 | 3.10 | 3.987 (10) | 140.3 |
C2—H2A···S1 | 1.08 | 2.69 | 3.723 (11) | 159.9 |
C6—H6A···I1ii | 1.08 | 2.88 | 3.754 (13) | 138.3 |
N11—H11A···S2iii | 1.03 | 2.33 | 3.350 (7) | 172.3 |
N11—H11B···I1iv | 1.03 | 2.70 | 3.661 (9) | 154.7 |
N12—H12A···S2v | 1.03 | 2.37 | 3.388 (8) | 169.8 |
N12—H12B···I1iv | 1.03 | 2.68 | 3.638 (10) | 155.6 |
N21—H21A···S1iii | 1.03 | 2.32 | 3.347 (8) | 171.9 |
N21—H21B···I1 | 1.03 | 2.74 | 3.649 (9) | 147.2 |
N22—H22B···I1 | 1.03 | 2.66 | 3.597 (9) | 150.8 |
N22—H22A···S1v | 1.03 | 2.33 | 3.358 (8) | 175.0 |
Symmetry codes: (i) x−1/2, −y+2, −z+1; (ii) x−1/2, y−1/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) x−1/2, y+1/2, −z+1/2; (v) x, −y+3/2, z+1/2. |
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