Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030590/tk2169sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030590/tk2169Isup2.hkl |
CCDC reference: 655048
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- R factor = 0.037
- wR factor = 0.088
- Data-to-parameter ratio = 15.3
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ....... 0.93
Author Response: The structure was solved and refined for a nonmerohedral twin. 250 partially overlapping reflections were removed from the data set and they are the cause of low completness |
Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 26.50 From the CIF: _diffrn_reflns_theta_full 26.50 From the CIF: _reflns_number_total 4006 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 4335 Completeness (_total/calc) 92.41% PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .... 0.92 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 700 Deg. PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C2D PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C3D PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 19 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C5 H4 N3 S3
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For synthesis and other data for the title compound see Saczewski et al. (2003). For related literature, see: Allen (2002); Cooper et al. (2002); Farrugia (1999).
The title compound was prepared according to the known procedure (Saczewski et al., 2003). Crystals for X-ray analysis were obtained by recrystallization from a dimethylformamide solution of (I).
The twin matrix, 1 0 0 0.475 - 1 0 0.003 0 - 1, corresponding to 180° rotation about [100] direct lattice direction has been determined with the program ROTAX (Cooper et al., 2002). For the refinement with the SHELXL97 program (Sheldrick, 1997), the reflection data file was prepared in the HKLF 5 format using the 'Make HKLF5' function of the WinGX program (Farrugia, 1999). The overlapping reflections and those belonging to only one twin domain are used in the refinement (HKLF 5 format of SHELXL). Those which were excluded, 250 reflections, are partial overlaps which could not be integrated properly at the data processing stage.
The H atoms of the N—H groups were freely refined. The H atoms bonded to C atoms were placed at calculated positions, with C—H = 0.95–0.99 Å, and refined as riding on their parent atoms, with Uiso(H) = x Ueq(C), where x = 1.5 for the H atoms from methyl groups and x = 1.2 for the remaining H atoms.
In course of our research on the reactivity of 2-hydroxylamino-4,5-dihydroimidazolium-O-sulfonate, it was reacted with carbon disulfide in aqueous NaOH, forming, unexpectedly, the salt of 2-aminoimidazoline and 7,8-dihydroimidazo [1,2-c][1,3,5]thiadiazine-2,4(6H)-dithione (Saczewski et al., 2003). The crystal structure of (I) has been solved based on diffraction data collected for a twinned specimen. The structure was refined to a R1 factor = 0.20 but twinning was not taken into account, neither at the data processing stage nor during refinement. The structure just served to confirm the connectivity of atoms deduced from spectroscopic methods. When we noticed that this is the first crystal structure of a 2-aminoimdazoline in the Cambridge Structural Databank (Allen, 2002) we decided to refine this structure taking twinning into account. Here, we present the structure of (I) refined as a nonmerohedral twin.
The asymmetric unit is shown in Fig. 1. The cation and anion are linked via two N—H···N hydrogen bonds into an ionic pair and the two solvate molecule are joined via N—H···O interactions to the cation, thus forming discrete hydrogen-bonded assemblies. The five-membered ring of the 2-aminoimidazolinium cation, with the largest endocyclic torsion angle of 15.8 (2)°, forms a slightly puckered half-chair. The three C—N bonds of the guanidinium fragment in the cation range from 1.315 (3) to 1.342 (3) Å, with the shortest bond being to the exocyclic amino group and the longest to the ring N3 atom exhibiting slightly pyramidal sp2 hybridization. Deprotonation has an enormous influence on the geometry of the 7,8-dihydroimidazo[1,2-c][1,3,5]thiadiazine-2,4(6H)dithione molecule. For example, in the neutral form, with the acidic proton bonded to N7A (Saczewski et al., 2003), the endocyclic bond angle at this atom is 113.72(16.)° whereas in the ionic form this angle is much smaller, 108.93 (17)°. Bond lengths are also strongly altered and, for example, the N1A—C6A bond length changes from 1.323 (2) in the neutral acid to 1.373 (3) Å in the anion.
For synthesis and other data for the title compound see Saczewski et al. (2003). For related literature, see: Allen (2002); Cooper et al. (2002); Farrugia (1999).
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation (Siemens, 1989) and Mercury (Version 1.4; Macrae et al., 2006); software used to prepare material for publication: SHELXL97.
C3H8N3+·C5H4N3S3−·2C3H7NO | Z = 2 |
Mr = 434.61 | F(000) = 460 |
Triclinic, P1 | Dx = 1.383 Mg m−3 |
Hall symbol: -P 1 | Melting point: 447 K |
a = 6.8301 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.1321 (14) Å | Cell parameters from 2455 reflections |
c = 12.9487 (10) Å | θ = 4.0–25.0° |
α = 79.232 (7)° | µ = 0.38 mm−1 |
β = 89.907 (7)° | T = 120 K |
γ = 82.125 (7)° | Prism, yellow |
V = 1043.82 (18) Å3 | 0.60 × 0.20 × 0.10 mm |
Kuma KM-4-CCD κ-geometry diffractometer | 3627 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 26.5°, θmin = 4.2° |
ω scans | h = −8→8 |
8801 measured reflections | k = −15→15 |
4006 independent reflections | l = −16→16 |
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)] = 0.037 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0351P)2 + 0.3779P] where P = (Fo2 + 2Fc2)/3 |
4006 reflections | (Δ/σ)max < 0.001 |
261 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C3H8N3+·C5H4N3S3−·2C3H7NO | γ = 82.125 (7)° |
Mr = 434.61 | V = 1043.82 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.8301 (7) Å | Mo Kα radiation |
b = 12.1321 (14) Å | µ = 0.38 mm−1 |
c = 12.9487 (10) Å | T = 120 K |
α = 79.232 (7)° | 0.60 × 0.20 × 0.10 mm |
β = 89.907 (7)° |
Kuma KM-4-CCD κ-geometry diffractometer | 3627 reflections with I > 2σ(I) |
8801 measured reflections | Rint = 0.035 |
4006 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.26 e Å−3 |
4006 reflections | Δρmin = −0.28 e Å−3 |
261 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. |
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. |
x | y | z | Uiso*/Ueq | ||
S1A | 0.74388 (10) | −0.03696 (5) | 0.69870 (4) | 0.02750 (15) | |
S2A | 0.73548 (10) | −0.34589 (5) | 1.09680 (5) | 0.02675 (15) | |
N1A | 0.7458 (3) | 0.01169 (14) | 0.88951 (13) | 0.0205 (4) | |
C2A | 0.7457 (3) | −0.06552 (17) | 0.83134 (16) | 0.0194 (4) | |
S3A | 0.74710 (10) | −0.21218 (4) | 0.88413 (4) | 0.02568 (15) | |
C4A | 0.7430 (3) | −0.22047 (17) | 1.02092 (17) | 0.0199 (5) | |
N5A | 0.7464 (3) | −0.12406 (14) | 1.05684 (13) | 0.0192 (4) | |
C6A | 0.7493 (3) | −0.01300 (17) | 0.99742 (16) | 0.0190 (4) | |
N7A | 0.7534 (3) | 0.06311 (14) | 1.05371 (13) | 0.0224 (4) | |
C8A | 0.7578 (4) | 0.00908 (18) | 1.16541 (16) | 0.0222 (5) | |
H8B | 0.6442 | 0.0435 | 1.2016 | 0.027* | |
H8A | 0.8815 | 0.0187 | 1.2004 | 0.027* | |
C9A | 0.7465 (4) | −0.11769 (17) | 1.16928 (16) | 0.0224 (5) | |
H9B | 0.8624 | −0.1660 | 1.2074 | 0.027* | |
H9A | 0.6240 | −0.1401 | 1.2028 | 0.027* | |
N1B | 0.7728 (3) | 0.28829 (16) | 0.93022 (15) | 0.0236 (4) | |
H1B | 0.765 (4) | 0.227 (2) | 0.965 (2) | 0.027 (7)* | |
C2B | 0.7435 (3) | 0.31567 (17) | 0.82677 (18) | 0.0224 (5) | |
N3B | 0.7231 (3) | 0.42843 (15) | 0.79407 (16) | 0.0263 (5) | |
H3B | 0.750 (4) | 0.456 (2) | 0.735 (2) | 0.020 (6)* | |
C4B | 0.7636 (4) | 0.48437 (18) | 0.88018 (18) | 0.0280 (5) | |
H4BA | 0.6611 | 0.5497 | 0.8833 | 0.034* | |
H4BB | 0.8950 | 0.5105 | 0.8738 | 0.034* | |
C5B | 0.7578 (4) | 0.38891 (18) | 0.97749 (18) | 0.0266 (5) | |
H5BA | 0.8704 | 0.3851 | 1.0267 | 0.032* | |
H5BB | 0.6325 | 0.3996 | 1.0152 | 0.032* | |
N6B | 0.7384 (3) | 0.24212 (17) | 0.76439 (17) | 0.0275 (5) | |
H6BB | 0.742 (4) | 0.177 (2) | 0.794 (2) | 0.032 (7)* | |
H6BA | 0.717 (4) | 0.2707 (19) | 0.700 (2) | 0.020 (6)* | |
O1C | 0.6385 (3) | 0.33821 (18) | 0.55175 (14) | 0.0496 (5) | |
N1C | 0.6926 (3) | 0.29562 (18) | 0.38911 (15) | 0.0336 (5) | |
C1C | 0.6495 (4) | 0.3658 (2) | 0.4563 (2) | 0.0388 (6) | |
H1CA | 0.6252 | 0.4445 | 0.4274 | 0.047* | |
C2C | 0.7292 (5) | 0.1734 (2) | 0.4252 (2) | 0.0477 (7) | |
H2CA | 0.7208 | 0.1559 | 0.5019 | 0.072* | |
H2CB | 0.8614 | 0.1441 | 0.4045 | 0.072* | |
H2CC | 0.6301 | 0.1379 | 0.3934 | 0.072* | |
C3C | 0.7023 (5) | 0.3360 (3) | 0.2762 (2) | 0.0536 (8) | |
H3CA | 0.6770 | 0.4190 | 0.2610 | 0.080* | |
H3CB | 0.6024 | 0.3056 | 0.2397 | 0.080* | |
H3CC | 0.8340 | 0.3106 | 0.2521 | 0.080* | |
O1D | 0.8400 (3) | 0.58284 (15) | 0.62367 (14) | 0.0491 (5) | |
N1D | 0.8126 (3) | 0.72687 (15) | 0.48209 (14) | 0.0252 (4) | |
C1D | 0.8103 (4) | 0.6845 (2) | 0.58456 (18) | 0.0330 (6) | |
H1D | 0.7839 | 0.7366 | 0.6310 | 0.040* | |
C2D | 0.8469 (4) | 0.65334 (19) | 0.40540 (19) | 0.0325 (6) | |
H2DA | 0.8733 | 0.5742 | 0.4419 | 0.049* | |
H2DB | 0.9610 | 0.6726 | 0.3632 | 0.049* | |
H2DC | 0.7296 | 0.6635 | 0.3593 | 0.049* | |
C3D | 0.7716 (5) | 0.84823 (19) | 0.44212 (18) | 0.0374 (7) | |
H3DA | 0.7507 | 0.8883 | 0.5012 | 0.056* | |
H3DB | 0.6526 | 0.8647 | 0.3967 | 0.056* | |
H3DC | 0.8839 | 0.8734 | 0.4016 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0346 (4) | 0.0317 (3) | 0.0166 (3) | −0.0039 (3) | 0.0002 (3) | −0.0062 (2) |
S2A | 0.0287 (3) | 0.0186 (3) | 0.0310 (3) | −0.0042 (2) | 0.0013 (2) | 0.0009 (2) |
N1A | 0.0238 (11) | 0.0208 (8) | 0.0162 (8) | −0.0017 (8) | −0.0001 (8) | −0.0026 (7) |
C2A | 0.0159 (12) | 0.0216 (10) | 0.0201 (10) | −0.0011 (9) | −0.0014 (9) | −0.0030 (8) |
S3A | 0.0347 (4) | 0.0194 (3) | 0.0233 (3) | −0.0025 (2) | −0.0010 (2) | −0.0058 (2) |
C4A | 0.0134 (12) | 0.0206 (10) | 0.0248 (11) | −0.0019 (8) | −0.0021 (9) | −0.0021 (8) |
N5A | 0.0210 (10) | 0.0190 (8) | 0.0159 (8) | 0.0007 (7) | −0.0003 (7) | −0.0016 (6) |
C6A | 0.0191 (11) | 0.0187 (10) | 0.0170 (9) | 0.0005 (8) | 0.0001 (9) | 0.0000 (8) |
N7A | 0.0285 (11) | 0.0222 (9) | 0.0168 (8) | −0.0033 (8) | −0.0006 (8) | −0.0043 (7) |
C8A | 0.0243 (13) | 0.0270 (11) | 0.0163 (10) | −0.0043 (10) | 0.0006 (9) | −0.0059 (8) |
C9A | 0.0233 (13) | 0.0248 (11) | 0.0179 (10) | −0.0011 (9) | −0.0005 (9) | −0.0022 (8) |
N1B | 0.0294 (12) | 0.0172 (9) | 0.0232 (9) | −0.0038 (8) | 0.0002 (8) | −0.0006 (8) |
C2B | 0.0174 (12) | 0.0193 (10) | 0.0290 (11) | −0.0008 (9) | 0.0029 (9) | −0.0022 (9) |
N3B | 0.0334 (13) | 0.0183 (9) | 0.0262 (10) | −0.0053 (8) | 0.0057 (9) | −0.0003 (8) |
C4B | 0.0313 (14) | 0.0182 (10) | 0.0343 (13) | −0.0034 (9) | 0.0017 (11) | −0.0046 (9) |
C5B | 0.0284 (14) | 0.0236 (11) | 0.0286 (12) | −0.0027 (10) | 0.0007 (10) | −0.0075 (9) |
N6B | 0.0377 (13) | 0.0207 (10) | 0.0237 (10) | −0.0047 (9) | 0.0026 (9) | −0.0030 (8) |
O1C | 0.0513 (14) | 0.0707 (14) | 0.0281 (10) | −0.0133 (11) | −0.0030 (9) | −0.0089 (9) |
N1C | 0.0322 (13) | 0.0425 (12) | 0.0232 (10) | −0.0066 (10) | −0.0023 (9) | 0.0024 (9) |
C1C | 0.0346 (17) | 0.0461 (15) | 0.0365 (14) | −0.0132 (13) | −0.0034 (13) | −0.0041 (12) |
C2C | 0.047 (2) | 0.0425 (15) | 0.0499 (17) | −0.0003 (14) | 0.0001 (15) | −0.0027 (13) |
C3C | 0.053 (2) | 0.074 (2) | 0.0271 (13) | −0.0011 (17) | −0.0008 (14) | 0.0007 (13) |
O1D | 0.0645 (15) | 0.0369 (10) | 0.0366 (10) | −0.0008 (10) | 0.0105 (10) | 0.0126 (8) |
N1D | 0.0314 (12) | 0.0224 (9) | 0.0207 (9) | −0.0032 (8) | 0.0014 (9) | −0.0016 (7) |
C1D | 0.0376 (16) | 0.0335 (12) | 0.0251 (12) | −0.0045 (11) | 0.0047 (11) | 0.0013 (10) |
C2D | 0.0391 (16) | 0.0282 (12) | 0.0300 (12) | −0.0010 (11) | 0.0039 (12) | −0.0073 (10) |
C3D | 0.063 (2) | 0.0230 (11) | 0.0244 (12) | −0.0014 (12) | −0.0032 (13) | −0.0034 (9) |
S1A—C2A | 1.687 (2) | C5B—H5BA | 0.9900 |
S2A—C4A | 1.657 (2) | C5B—H5BB | 0.9900 |
N1A—C2A | 1.307 (3) | N6B—H6BB | 0.81 (3) |
N1A—C6A | 1.373 (3) | N6B—H6BA | 0.85 (2) |
C2A—S3A | 1.782 (2) | O1C—C1C | 1.224 (3) |
S3A—C4A | 1.756 (2) | N1C—C1C | 1.333 (3) |
C4A—N5A | 1.340 (3) | N1C—C2C | 1.456 (3) |
N5A—C6A | 1.424 (3) | N1C—C3C | 1.457 (3) |
N5A—C9A | 1.472 (3) | C1C—H1CA | 0.9500 |
C6A—N7A | 1.282 (3) | C2C—H2CA | 0.9800 |
N7A—C8A | 1.471 (2) | C2C—H2CB | 0.9800 |
C8A—C9A | 1.542 (3) | C2C—H2CC | 0.9800 |
C8A—H8B | 0.9900 | C3C—H3CA | 0.9800 |
C8A—H8A | 0.9900 | C3C—H3CB | 0.9800 |
C9A—H9B | 0.9900 | C3C—H3CC | 0.9800 |
C9A—H9A | 0.9900 | O1D—C1D | 1.232 (3) |
N1B—C2B | 1.327 (3) | N1D—C1D | 1.331 (3) |
N1B—C5B | 1.456 (3) | N1D—C2D | 1.452 (3) |
N1B—H1B | 0.81 (3) | N1D—C3D | 1.455 (3) |
C2B—N6B | 1.315 (3) | C1D—H1D | 0.9500 |
C2B—N3B | 1.342 (3) | C2D—H2DA | 0.9800 |
N3B—C4B | 1.455 (3) | C2D—H2DB | 0.9800 |
N3B—H3B | 0.81 (3) | C2D—H2DC | 0.9800 |
C4B—C5B | 1.548 (3) | C3D—H3DA | 0.9800 |
C4B—H4BA | 0.9900 | C3D—H3DB | 0.9800 |
C4B—H4BB | 0.9900 | C3D—H3DC | 0.9800 |
C2A—N1A—C6A | 123.01 (17) | C4B—C5B—H5BA | 111.3 |
N1A—C2A—S1A | 123.67 (16) | N1B—C5B—H5BB | 111.3 |
N1A—C2A—S3A | 123.39 (15) | C4B—C5B—H5BB | 111.3 |
S1A—C2A—S3A | 112.95 (12) | H5BA—C5B—H5BB | 109.2 |
C4A—S3A—C2A | 104.71 (10) | C2B—N6B—H6BB | 115.3 (19) |
N5A—C4A—S2A | 124.40 (16) | C2B—N6B—H6BA | 115.2 (16) |
N5A—C4A—S3A | 117.30 (15) | H6BB—N6B—H6BA | 129 (2) |
S2A—C4A—S3A | 118.30 (12) | C1C—N1C—C2C | 121.3 (2) |
C4A—N5A—C6A | 128.01 (17) | C1C—N1C—C3C | 122.3 (2) |
C4A—N5A—C9A | 123.64 (17) | C2C—N1C—C3C | 116.4 (2) |
C6A—N5A—C9A | 108.35 (16) | O1C—C1C—N1C | 126.0 (3) |
N7A—C6A—N1A | 122.48 (18) | O1C—C1C—H1CA | 117.0 |
N7A—C6A—N5A | 114.00 (18) | N1C—C1C—H1CA | 117.0 |
N1A—C6A—N5A | 123.52 (18) | N1C—C2C—H2CA | 109.5 |
C6A—N7A—C8A | 108.93 (17) | N1C—C2C—H2CB | 109.5 |
N7A—C8A—C9A | 106.84 (16) | H2CA—C2C—H2CB | 109.5 |
N7A—C8A—H8B | 110.4 | N1C—C2C—H2CC | 109.5 |
C9A—C8A—H8B | 110.4 | H2CA—C2C—H2CC | 109.5 |
N7A—C8A—H8A | 110.4 | H2CB—C2C—H2CC | 109.5 |
C9A—C8A—H8A | 110.4 | N1C—C3C—H3CA | 109.5 |
H8B—C8A—H8A | 108.6 | N1C—C3C—H3CB | 109.5 |
N5A—C9A—C8A | 101.81 (15) | H3CA—C3C—H3CB | 109.5 |
N5A—C9A—H9B | 111.4 | N1C—C3C—H3CC | 109.5 |
C8A—C9A—H9B | 111.4 | H3CA—C3C—H3CC | 109.5 |
N5A—C9A—H9A | 111.4 | H3CB—C3C—H3CC | 109.5 |
C8A—C9A—H9A | 111.4 | C1D—N1D—C2D | 121.24 (19) |
H9B—C9A—H9A | 109.3 | C1D—N1D—C3D | 121.4 (2) |
C2B—N1B—C5B | 111.22 (18) | C2D—N1D—C3D | 117.33 (18) |
C2B—N1B—H1B | 124.7 (18) | O1D—C1D—N1D | 124.8 (2) |
C5B—N1B—H1B | 121.5 (18) | O1D—C1D—H1D | 117.6 |
N6B—C2B—N1B | 124.5 (2) | N1D—C1D—H1D | 117.6 |
N6B—C2B—N3B | 124.5 (2) | N1D—C2D—H2DA | 109.5 |
N1B—C2B—N3B | 111.0 (2) | N1D—C2D—H2DB | 109.5 |
C2B—N3B—C4B | 110.62 (19) | H2DA—C2D—H2DB | 109.5 |
C2B—N3B—H3B | 120.9 (17) | N1D—C2D—H2DC | 109.5 |
C4B—N3B—H3B | 119.5 (18) | H2DA—C2D—H2DC | 109.5 |
N3B—C4B—C5B | 102.30 (17) | H2DB—C2D—H2DC | 109.5 |
N3B—C4B—H4BA | 111.3 | N1D—C3D—H3DA | 109.5 |
C5B—C4B—H4BA | 111.3 | N1D—C3D—H3DB | 109.5 |
N3B—C4B—H4BB | 111.3 | H3DA—C3D—H3DB | 109.5 |
C5B—C4B—H4BB | 111.3 | N1D—C3D—H3DC | 109.5 |
H4BA—C4B—H4BB | 109.2 | H3DA—C3D—H3DC | 109.5 |
N1B—C5B—C4B | 102.14 (18) | H3DB—C3D—H3DC | 109.5 |
N1B—C5B—H5BA | 111.3 | ||
C6A—N1A—C2A—S1A | −179.33 (17) | N5A—C6A—N7A—C8A | 1.1 (3) |
C6A—N1A—C2A—S3A | 0.8 (3) | C6A—N7A—C8A—C9A | −2.4 (3) |
N1A—C2A—S3A—C4A | 1.3 (2) | C4A—N5A—C9A—C8A | 178.2 (2) |
S1A—C2A—S3A—C4A | −178.67 (13) | C6A—N5A—C9A—C8A | −2.1 (2) |
C2A—S3A—C4A—N5A | −2.1 (2) | N7A—C8A—C9A—N5A | 2.6 (2) |
C2A—S3A—C4A—S2A | 177.92 (14) | C5B—N1B—C2B—N6B | −176.4 (2) |
S2A—C4A—N5A—C6A | −178.78 (18) | C5B—N1B—C2B—N3B | 4.6 (3) |
S3A—C4A—N5A—C6A | 1.2 (3) | N6B—C2B—N3B—C4B | −172.0 (2) |
S2A—C4A—N5A—C9A | 0.9 (3) | N1B—C2B—N3B—C4B | 7.0 (3) |
S3A—C4A—N5A—C9A | −179.10 (17) | C2B—N3B—C4B—C5B | −14.5 (3) |
C2A—N1A—C6A—N7A | 178.6 (2) | C2B—N1B—C5B—C4B | −13.1 (3) |
C2A—N1A—C6A—N5A | −2.2 (4) | N3B—C4B—C5B—N1B | 15.8 (2) |
C4A—N5A—C6A—N7A | −179.6 (2) | C2C—N1C—C1C—O1C | 1.0 (5) |
C9A—N5A—C6A—N7A | 0.7 (3) | C3C—N1C—C1C—O1C | 179.9 (3) |
C4A—N5A—C6A—N1A | 1.1 (4) | C2D—N1D—C1D—O1D | 1.5 (4) |
C9A—N5A—C6A—N1A | −178.6 (2) | C3D—N1D—C1D—O1D | 178.6 (3) |
N1A—C6A—N7A—C8A | −179.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B···N7A | 0.81 (3) | 2.11 (3) | 2.916 (3) | 178 (3) |
N3B—H3B···O1D | 0.81 (3) | 2.07 (3) | 2.806 (3) | 153 (2) |
N6B—H6BB···N1A | 0.81 (3) | 2.14 (3) | 2.952 (3) | 173 (3) |
N6B—H6BA···O1C | 0.85 (2) | 1.98 (3) | 2.827 (3) | 174 (3) |
Experimental details
Crystal data | |
Chemical formula | C3H8N3+·C5H4N3S3−·2C3H7NO |
Mr | 434.61 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 6.8301 (7), 12.1321 (14), 12.9487 (10) |
α, β, γ (°) | 79.232 (7), 89.907 (7), 82.125 (7) |
V (Å3) | 1043.82 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.60 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Kuma KM-4-CCD κ-geometry |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8801, 4006, 3627 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.088, 1.12 |
No. of reflections | 4006 |
No. of parameters | 261 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.28 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Stereochemical Workstation (Siemens, 1989) and Mercury (Version 1.4; Macrae et al., 2006), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B···N7A | 0.81 (3) | 2.11 (3) | 2.916 (3) | 178 (3) |
N3B—H3B···O1D | 0.81 (3) | 2.07 (3) | 2.806 (3) | 153 (2) |
N6B—H6BB···N1A | 0.81 (3) | 2.14 (3) | 2.952 (3) | 173 (3) |
N6B—H6BA···O1C | 0.85 (2) | 1.98 (3) | 2.827 (3) | 174 (3) |
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In course of our research on the reactivity of 2-hydroxylamino-4,5-dihydroimidazolium-O-sulfonate, it was reacted with carbon disulfide in aqueous NaOH, forming, unexpectedly, the salt of 2-aminoimidazoline and 7,8-dihydroimidazo [1,2-c][1,3,5]thiadiazine-2,4(6H)-dithione (Saczewski et al., 2003). The crystal structure of (I) has been solved based on diffraction data collected for a twinned specimen. The structure was refined to a R1 factor = 0.20 but twinning was not taken into account, neither at the data processing stage nor during refinement. The structure just served to confirm the connectivity of atoms deduced from spectroscopic methods. When we noticed that this is the first crystal structure of a 2-aminoimdazoline in the Cambridge Structural Databank (Allen, 2002) we decided to refine this structure taking twinning into account. Here, we present the structure of (I) refined as a nonmerohedral twin.
The asymmetric unit is shown in Fig. 1. The cation and anion are linked via two N—H···N hydrogen bonds into an ionic pair and the two solvate molecule are joined via N—H···O interactions to the cation, thus forming discrete hydrogen-bonded assemblies. The five-membered ring of the 2-aminoimidazolinium cation, with the largest endocyclic torsion angle of 15.8 (2)°, forms a slightly puckered half-chair. The three C—N bonds of the guanidinium fragment in the cation range from 1.315 (3) to 1.342 (3) Å, with the shortest bond being to the exocyclic amino group and the longest to the ring N3 atom exhibiting slightly pyramidal sp2 hybridization. Deprotonation has an enormous influence on the geometry of the 7,8-dihydroimidazo[1,2-c][1,3,5]thiadiazine-2,4(6H)dithione molecule. For example, in the neutral form, with the acidic proton bonded to N7A (Saczewski et al., 2003), the endocyclic bond angle at this atom is 113.72(16.)° whereas in the ionic form this angle is much smaller, 108.93 (17)°. Bond lengths are also strongly altered and, for example, the N1A—C6A bond length changes from 1.323 (2) in the neutral acid to 1.373 (3) Å in the anion.