Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680002047X/cf6017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680002047X/cf6017Isup2.hkl |
CCDC reference: 155894
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (N-C) = 0.005 Å
- R factor = 0.044
- wR factor = 0.109
- Data-to-parameter ratio = 18.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_352 Alert C Short N-H Bond (0.87A) N(41) - H(41) = 0.74 Ang. PLAT_420 Alert C D-H without acceptor N(41) - H(41) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
The four amine H atoms were located on difference syntheses and both displacement and positional parameters were refined, while the CH2 H atoms were included in the refinement at calculated positions as riding models, with C—H set to 0.99 Å. The largest difference map features were close to the I- anions.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
C3H6N3S2+·I− | Dx = 2.267 Mg m−3 |
Mr = 275.13 | Melting point: ? K K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.050 (2) Å | Cell parameters from 5412 reflections |
b = 18.964 (4) Å | θ = 1.0–27.5° |
c = 8.1307 (16) Å | µ = 4.41 mm−1 |
β = 108.87 (3)° | T = 150 K |
V = 1612.2 (6) Å3 | Plate, colourless |
Z = 8 | 0.35 × 0.20 × 0.08 mm |
F(000) = 1040 |
Enraf Nonius KappaCCD area-detector diffractometer | 1818 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 1726 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ϕ and ω scans | h = −14→13 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −24→24 |
Tmin = 0.307, Tmax = 0.719 | l = −10→10 |
7382 measured reflections |
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)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.085P)2 + 0.3966P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1818 reflections | Δρmax = 2.79 e Å−3 |
100 parameters | Δρmin = −2.70 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0043 (5) |
C3H6N3S2+·I− | V = 1612.2 (6) Å3 |
Mr = 275.13 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.050 (2) Å | µ = 4.41 mm−1 |
b = 18.964 (4) Å | T = 150 K |
c = 8.1307 (16) Å | 0.35 × 0.20 × 0.08 mm |
β = 108.87 (3)° |
Enraf Nonius KappaCCD area-detector diffractometer | 1818 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1726 reflections with I > 2σ(I) |
Tmin = 0.307, Tmax = 0.719 | Rint = 0.074 |
7382 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 2.79 e Å−3 |
1818 reflections | Δρmin = −2.70 e Å−3 |
100 parameters |
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.5000 | 0.127771 (16) | 0.2500 | 0.01778 (18) | |
I2 | 0.0000 | 0.10986 (2) | 0.2500 | 0.01743 (18) | |
S1 | 0.17012 (7) | 0.19044 (5) | 0.82791 (10) | 0.0177 (2) | |
C2 | 0.3142 (3) | 0.22011 (17) | 0.7927 (4) | 0.0158 (6) | |
H21 | 0.3122 | 0.2722 | 0.7829 | 0.020* | |
H22 | 0.3885 | 0.2072 | 0.8946 | 0.020* | |
S3 | 0.33490 (7) | 0.18302 (5) | 0.60085 (10) | 0.0157 (2) | |
C4 | 0.3257 (3) | 0.09344 (18) | 0.6500 (4) | 0.0136 (6) | |
N41 | 0.3741 (3) | 0.05065 (16) | 0.5627 (3) | 0.0194 (6) | |
H41 | 0.371 (3) | 0.012 (2) | 0.576 (5) | 0.016 (9)* | |
H42 | 0.415 (4) | 0.066 (3) | 0.488 (5) | 0.041 (12)* | |
N5 | 0.2748 (2) | 0.06531 (14) | 0.7617 (3) | 0.0157 (5) | |
C6 | 0.2010 (3) | 0.09970 (17) | 0.8345 (4) | 0.0149 (6) | |
N61 | 0.1375 (3) | 0.06203 (17) | 0.9149 (4) | 0.0194 (6) | |
H61 | 0.131 (4) | 0.018 (2) | 0.897 (6) | 0.042 (12)* | |
H62 | 0.098 (4) | 0.080 (3) | 0.980 (5) | 0.036 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0276 (3) | 0.0190 (3) | 0.0091 (2) | 0.000 | 0.00924 (17) | 0.000 |
I2 | 0.0201 (2) | 0.0194 (3) | 0.0158 (2) | 0.000 | 0.00999 (15) | 0.000 |
S1 | 0.0187 (4) | 0.0180 (4) | 0.0190 (4) | 0.0000 (3) | 0.0095 (3) | −0.0039 (3) |
C2 | 0.0164 (13) | 0.0184 (14) | 0.0135 (13) | −0.0035 (11) | 0.0062 (10) | −0.0004 (11) |
S3 | 0.0234 (4) | 0.0159 (4) | 0.0092 (4) | −0.0006 (3) | 0.0072 (3) | 0.0014 (3) |
C4 | 0.0129 (13) | 0.0168 (15) | 0.0098 (13) | 0.0021 (11) | 0.0017 (10) | 0.0008 (11) |
N41 | 0.0274 (14) | 0.0195 (15) | 0.0152 (12) | 0.0003 (12) | 0.0123 (10) | 0.0001 (11) |
N5 | 0.0194 (10) | 0.0170 (12) | 0.0127 (11) | −0.0008 (11) | 0.0078 (8) | 0.0016 (10) |
C6 | 0.0151 (13) | 0.0174 (16) | 0.0123 (13) | −0.0007 (11) | 0.0046 (10) | −0.0011 (12) |
N61 | 0.0226 (13) | 0.0211 (14) | 0.0203 (13) | −0.0055 (12) | 0.0150 (11) | −0.0030 (12) |
S1—C6 | 1.752 (3) | C4—N5 | 1.325 (4) |
S1—C2 | 1.797 (3) | N41—H41 | 0.74 (4) |
C2—S3 | 1.792 (3) | N41—H42 | 0.91 (4) |
C2—H21 | 0.99 | N5—C6 | 1.325 (4) |
C2—H22 | 0.99 | C6—N61 | 1.314 (4) |
S3—C4 | 1.756 (4) | N61—H61 | 0.85 (5) |
C4—N41 | 1.302 (4) | N61—H62 | 0.86 (4) |
C6—S1—C2 | 97.97 (15) | C4—N41—H41 | 119 (3) |
S3—C2—S1 | 112.62 (15) | C4—N41—H42 | 123 (3) |
S3—C2—H21 | 109.1 | H41—N41—H42 | 117 (4) |
S1—C2—H21 | 109.1 | C4—N5—C6 | 124.6 (3) |
S3—C2—H22 | 109.1 | N61—C6—N5 | 117.4 (3) |
S1—C2—H22 | 109.1 | N61—C6—S1 | 114.8 (2) |
H21—C2—H22 | 107.8 | N5—C6—S1 | 127.7 (2) |
C4—S3—C2 | 98.54 (15) | C6—N61—H61 | 118 (3) |
N41—C4—N5 | 117.6 (3) | C6—N61—H62 | 123 (3) |
N41—C4—S3 | 114.5 (2) | H61—N61—H62 | 118 (4) |
N5—C4—S3 | 127.9 (3) | ||
C6—S1—C2—S3 | 57.53 (18) | S3—C4—N5—C6 | 12.7 (4) |
S1—C2—S3—C4 | −55.58 (18) | C4—N5—C6—N61 | 166.9 (3) |
C2—S3—C4—N41 | −160.5 (2) | C4—N5—C6—S1 | −9.6 (4) |
C2—S3—C4—N5 | 20.3 (3) | C2—S1—C6—N61 | 158.1 (2) |
N41—C4—N5—C6 | −166.4 (3) | C2—S1—C6—N5 | −25.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N41—H41···I1i | 0.74 (4) | 3.13 (4) | 3.786 (3) | 150 (3) |
N41—H42···I1 | 0.91 (4) | 2.68 (4) | 3.581 (3) | 169 (4) |
N61—H61···I2ii | 0.85 (5) | 2.88 (5) | 3.663 (3) | 155 (4) |
N61—H62···I2iii | 0.86 (4) | 2.80 (4) | 3.638 (3) | 165 (4) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z+1; (iii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C3H6N3S2+·I− |
Mr | 275.13 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 11.050 (2), 18.964 (4), 8.1307 (16) |
β (°) | 108.87 (3) |
V (Å3) | 1612.2 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 4.41 |
Crystal size (mm) | 0.35 × 0.20 × 0.08 |
Data collection | |
Diffractometer | Enraf Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.307, 0.719 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7382, 1818, 1726 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.109, 1.05 |
No. of reflections | 1818 |
No. of parameters | 100 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 2.79, −2.70 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N41—H41···I1i | 0.74 (4) | 3.13 (4) | 3.786 (3) | 150 (3) |
N41—H42···I1 | 0.91 (4) | 2.68 (4) | 3.581 (3) | 169 (4) |
N61—H61···I2ii | 0.85 (5) | 2.88 (5) | 3.663 (3) | 155 (4) |
N61—H62···I2iii | 0.86 (4) | 2.80 (4) | 3.638 (3) | 165 (4) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z+1; (iii) x, y, z+1. |
Compound (I) is marketed as 4,6-diimino-1,3,5-dithiazolidine hydrogen iodide (Fig. 2a) whereas elucidation of the crystal structure reveals a delocalized cation with an I- anion. The two resonant forms, from which the compound has been named, are shown in Fig 2(b). Bond distances for the atoms between the two amines are listed in Table 2.