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Crystals of 1-(diamino­methyl­ene)thio­uron-1-ium chloride, C2H7N4S+·Cl-, 1-(diamino­methyl­ene)thio­uron-1-ium bromide, C2H7N4S+·Br-, and 1-(diamino­methyl­ene)thio­uron-1-ium iodide, C2H7N4S+·I-, are built up from the nonplanar 1-(di­amino­methyl­ene)thio­uron-1-ium cation and the respective halogenide anion. The conformation of the 1-(diamino­methyl­ene)thio­uron-1-ium cation in each case is twisted. Both arms of the cation are planar and rotated in opposite directions around the C-N bonds involving the central N atom. The dihedral angles describing the twisted conformation are 22.9 (1), 15.2 (1) and 4.2 (1)° in the chloride, bromide and iodide salts, respectively. Ionic and extensive hydrogen-bonding inter­actions join oppositely charged units into a supra­molecular network. The aim of the investigation is to study the influence of the size of the ionic radii of the Cl-, Br- and I- ions on the dimensionality of the hydrogen-bonding network of the 1-(diamino­methyl­ene)thio­uron-1-ium cation. The 1-(diamino­methyl­ene)thio­uron-1-ium system should be of use in crystal engin­eering to form multidimensional networks.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108008688/sk3208sup1.cif
Contains datablocks global, Ia, Ib, Ic

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108008688/sk3208Iasup2.hkl
Contains datablock Ia

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108008688/sk3208Ibsup3.hkl
Contains datablock Ib

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108008688/sk3208Icsup4.hkl
Contains datablock Ic

CCDC references: 690190; 690191; 690192

Comment top

The oresent work continues our investigations of the characterization of the compounds that in solids form multiple hydrogen-bonding systems (Janczak & Perpétuo, 2008a; Perpétuo & Janczak, 2007, 2008; Janczak & Kubiak, 2005a,b). Previously, we have investigated the crystal structure of commercially available 2-imino-4-thiobiuret (Aldrich, CAS No. 2114–02–05) and stated that it exists in the tautomeric form, i.e. 1-(diaminomethylene)thiourea (Janczak & Perpétuo, 2008b). 2-Iminio-4-thiourea and its tautomer have several potential coordinating modes, since they can act as N,N- or N,S-donor ligands and can form several different complexes with metal ions. The coordination of metals by this ligand is possible by either the neutral or a deprotonated (anionic) form. A search of the Cambridge Structural Database (Version 5.29 of November 2007; Allen, 2002) for structures containing this ligand yielded only three structures of Pt complexes in which Pt is coordinated by 2-imino-4-thiobiuret or its deprotonated form (Doxiadi et al., 2003). Besides these known Pt complexes with neutral and deproronated negatively charged ligands, 2-iminio-4-thiobiuret and its tautomer [i.e. 1-(diaminomethylene)thiourea] can form salts, since they contain an N atom with a lone pair of electron, which can accept an H atom forming a positively charged C2H7N4S+ unit. In the present work, we investigate the crystal structures of three salts, namely 1-(diaminomethylene)thiouron-1-ium chloride, (Ia), bromide, (Ib), and iodide, (Ic). In addition the X-ray geometry and the conformation of the protonated C2H7N4S+ cation is compared with that in the gas-phase, as predicted for an isolated cation by density functional theory (Frisch et al., 1998), as well as with the geometry of the neutral C2H6N4S molecule reported previously (Janczak & Perpétuo, 2008b). Ab-initio molecular orbital (MO) calculations were performed at the B3LYP/6–31+G* level and the results are illustrated in Fig. 1.

The asymmetric units of the title salts are illustrated in Fig. 2. The geometry of the 1-(diaminomethylene)thiouron-1-ium cation in these salts is not planar. However, both arms of the cation, containing atoms N1, C2, N3 and N4, and atoms N1, C1, N2 and S1, are planar. The deviations of the non-H atoms from these planes are smaller than 0.029 (2) and 0.014 (2) Å, respectively. The two arms of the cation are oppositely turned around the C—N bonds involving the central N1 atom. Thus the conformation of the 1-(diaminomethylene)thiouron-1-ium cation is twisted. The dihedral angles between the planes are 22.9 (1), 15.2 (1) and 4.2 (1)° in the chloride, bromide and iodide salts, respectively. The rotation angles correlate with the electronegativity of the halogen: 3.16 for Cl, 2.96 for Br and 2.66 for I (Pauling, 1960). A similar twisted conformation is observed in the crystal structure of neutral 1-(diaminomethylene)thiourea [22.2 (1)°; Janczak & Perpétuo, 2008b]. The gas-phase conformation of the 1-(diaminomethylene)thiouron-1-ium cation as shown by ab-initio MO calculations is also twisted, with a dihedral angle of 6.2°. The difference between the conformation of the cation in the crystal and in the gas phase results from the interionic and hydrogen-bonding interactions present in the crystals.

In the present salts, the respective C—N and CS bond lengths are essentially the same. The C—N bond lengths involving the central N1 atom are significantly longer than the other C—N bond lengths linking the amine groups (Tables 1, 3 and 5). The C1S1 bond lengths in these salts are comparable to those in thiourea derivatives (where the average CS distance is 1.663 Å; Allen et al. 1997). However the gas-phase data for thioformaldehyde, CH2S, give for the CS bond distance a value of 1.6109 (8) Å, which represents 100% double-bond character (Johnson et al., 1971), while CS bond lengths of ca 1.74 Å are cited as representing 50% double-bond character, as observed in dithiolate anions (Abrahams, 1956; Allen et al., 1987). The planarity of the amine groups indicates the sp2-hybridization of the orbitals on the amine N atoms, and the lone pair of electrons occupies the p orbital, which is perpendicular to the plane of the NH2 groups. The p orbitals of the C and S atoms, forming the π bonds of the C2N1 and C1S1 double bonds, are also perpendicular to the plane; therefore, partial delocalization, due to the symmetry of the p orbitals, of the π electrons over whole cation is possible, and leads to elongation of the C1S1 and C2N1 double bonds and to shortening of the other single C—N bonds (Table 1, 3 and 5). Thus, the bond order of C1 S1 and C2N1 is smaller than 2, and the bond order of the C—N bonds linking the amine groups is greater than 1. The bond order of the C—N bonds joining the amine groups is greater than the bond order of the C—N bonds involved the central N1 atom. The repulsion between the S atom and the amine group at N4 causes the rotation of both arms of the cation around the C—N1 bonds and is responsible for the twisted conformation of the cation. This interaction decreases the overlapping of the p orbitals of atoms C2 and N1 and of atoms N1 and C1, and leads to the elongation of the C2—N1 and N1—C1 bonds compared with the other C—Namine bonds, in which the overlapping of the p orbitals is more effective. The steric interaction between atom S1 and amine atom N4 is also responsible for the distortion of the N—C—N, C—N1—C and N—C1—S1 angles, as expected for sp2-hybridization. A similar correlation between the bond lengths and angles can be found in the gas-phase structure as obtained by ab-initio MO calculations (Fig. 1). The protonation of the central N1 atom leads to a decrease of the steric effect of the lone pair of electron on atom N1 and makes the C2—N1—C1 angle greater by \sim 6° in relation to that in the neutral diaminomethylenethiourea molecule (Janczak & Perpétuo, 2008b). This is consistent with the valence-shell electron-pair repulsion model (Gillespie, 1963, 1992), according to which the lone pair of electrons on the N atom occupies a wider region than the bonding pair N—H.

In the crystal structures, besides the interionic interactions, the oppositely charged units are linked by hydrogen bonds. In the crystal structure of (Ia), the 1-(diaminomethylene)thiouron-1-ium cations are arranged almost parallel to the (100) crystallographic plane, forming layers with a distance of a/2 (~3.26 Å) between the layers (Fig. 3a). Within the layers, as well as between the layers, the cations are interconnected by N—H···Cl hydrogen bonds (Table 2). In the crystal structures of both (Ib) and (Ic), C2H7N4S+ cations related by an inversion center interact via N—H···S hydrogen bonds, forming a dimeric structure (Figs. 2b and 2c). The S atom contains two lone pairs of electrons that can be involved in hydrogen bonds as acceptors. The non-bonded S···H contact requires that the distance between the S and H atoms should be less than the sum of the van der Waals radii of S and H atoms [rS = 1.80 Å (Bondi, 1964) and rH = 1.10 Å (Rowland & Taylor, 1996)]. S···H contacts shorter than 2.90 Å are observed in both (Ib) and (Ic) (Tables 4 and 6). The dimers of C2H7N4S+ cations in (Ib) are interconnected by N—H···Br hydrogen bonds, forming layers that lie almost parallel to the (102) plane and are separated by a distance of ~3.16 Å. No hydrogen bonds of the Br···H type with a distance shorter than the sum of the van der Waals radii of Br and H (rBr=1.81 and rH=1.10 Å; Rowland & Taylor, 1996; Pauling, 1960) were found between the layers; therefore, they interact only by the van der Waals forces. In the crystal structure of (Ic), the dimers interact via N—H···I hydrogen bonds, forming layers almost parallel to (302). Similarly to the crystal structure of (Ib), there are no I···H contacts with a distance shorter than the sum of the van der Waals radii of I and H (rI = 2.20 Å; Pauling, 1960).

This study underscores the utility of 1-(diaminomethylene)thiourea for developing supramolecular structures with acids. The larger anions, such as Br- and I- , interconnect the 1-(diaminomethylene)thiouron-1-ium dimers into layers. The large anionic radii cause the layers to be separated by a greater distance than the sum of van der Waals radii of I or Br and H atoms, and therefore there are no hydrogen-bonding interactions between the layers in (Ib) and (Ic). However, in the chloride salt, the smaller chloride anions link the 1-(diaminomethylene)thiouron-1-ium cations into layers that are interconnected via Cl···H interactions into a three-dimensional network.

Related literature top

For related literature, see: Abrahams (1956); Allen (2002); Allen et al. (1987, 1997); Bondi (1964); Doxiadi et al. (2003); Frisch et al. (1998); Gillespie (1963, 1992); Janczak & Kubiak (2005a, 2005b); Janczak & Perpétuo (2008a, 2008b); Johnson et al. (1971); Pauling (1960); Perpétuo & Janczak (2007, 2008); Rowland & Taylor (1996).

Experimental top

Suitable crystals of (Ia), (Ib) and (Ic) were obtained from 2-imino-4-thiobiuret (purchased from Aldrich) dissolved in 5% aqueous solutions of HCl, HBr and HI. [Quantities? reaction conditions?]

Refinement top

The H atoms were located from difference Fourier maps and and their positions refined.

Computing details top

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Results of the optimized molecular orbital calculations (B3LYP/6–31+G*) for the 1-(diaminomethylene)thiouronium cation (Å, °).
[Figure 2] Fig. 2. Views of (a) (Ia), (b) (Ib) and (c) (Ic), with the atom-labelling schemes. Displacement ellipsoids are shown at the 50% probability level and H atoms as spheres of arbitrary radii.
[Figure 3] Fig. 3. Views of the crystal packing in (Ia), (Ib) and (Ic), showing the hydrogen-bonded three-dimensional network in (Ia) (a), and the hydrogen-bonded layers in (Ib) (b) and (Ic) (c). Dashed lines represent hydrogen bonds.
(Ia) 1-(diaminomethylene)thiouron-1-ium chloride top
Crystal data top
C2H7N4S+·ClF(000) = 320
Mr = 154.63Dx = 1.567 Mg m3
Dm = 1.56 Mg m3
Dm measured by flotation
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 562 reflections
a = 6.517 (1) Åθ = 2.8–28.4°
b = 6.807 (1) ŵ = 0.80 mm1
c = 14.777 (3) ÅT = 295 K
β = 90.36 (2)°Paralellepiped, colourless
V = 655.51 (19) Å30.37 × 0.22 × 0.17 mm
Z = 4
Data collection top
Kuma KM-4 with area CCD detector
diffractometer
1635 independent reflections
Radiation source: fine-focus sealed tube1164 reflections with σ > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1θmax = 28.4°, θmin = 2.8°
ω–scanh = 88
Absorption correction: analytical
(face-indexed; SHELXTL; Sheldrick, 2008)
k = 98
Tmin = 0.760, Tmax = 0.878l = 1819
6665 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030Only H-atom coordinates refined
wR(F2) = 0.062 w = 1/[σ2(Fo2) + (0.0275P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
1635 reflectionsΔρmax = 0.21 e Å3
95 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.041 (3)
Crystal data top
C2H7N4S+·ClV = 655.51 (19) Å3
Mr = 154.63Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.517 (1) ŵ = 0.80 mm1
b = 6.807 (1) ÅT = 295 K
c = 14.777 (3) Å0.37 × 0.22 × 0.17 mm
β = 90.36 (2)°
Data collection top
Kuma KM-4 with area CCD detector
diffractometer
1635 independent reflections
Absorption correction: analytical
(face-indexed; SHELXTL; Sheldrick, 2008)
1164 reflections with σ > 2σ(I)
Tmin = 0.760, Tmax = 0.878Rint = 0.031
6665 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.062Only H-atom coordinates refined
S = 0.99Δρmax = 0.21 e Å3
1635 reflectionsΔρmin = 0.20 e Å3
95 parameters
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
xyzUiso*/Ueq
Cl10.51493 (6)0.72135 (7)0.41465 (3)0.04362 (16)
S10.89198 (7)0.05688 (7)0.26804 (3)0.03941 (16)
C10.7581 (2)0.2129 (2)0.33105 (10)0.0295 (4)
N10.8064 (2)0.2597 (2)0.42000 (9)0.0339 (4)
H10.719 (3)0.302 (3)0.4489 (12)0.041*
C20.9855 (2)0.2404 (2)0.46644 (10)0.0293 (4)
N20.5888 (2)0.3002 (3)0.30276 (11)0.0444 (4)
H210.532 (3)0.393 (3)0.3335 (12)0.053*
H220.553 (3)0.277 (3)0.2486 (14)0.053*
N30.9824 (3)0.2867 (3)0.55275 (10)0.0402 (4)
H310.869 (3)0.304 (3)0.5781 (13)0.048*
H321.084 (3)0.269 (3)0.5815 (13)0.048*
N41.1546 (2)0.1858 (3)0.42755 (11)0.0436 (4)
H411.150 (3)0.147 (3)0.3760 (13)0.052*
H421.268 (3)0.190 (3)0.4549 (13)0.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0321 (2)0.0687 (4)0.0300 (2)0.0027 (2)0.00419 (17)0.0038 (2)
S10.0482 (3)0.0429 (3)0.0271 (2)0.0086 (2)0.00226 (18)0.00554 (19)
C10.0305 (8)0.0304 (10)0.0277 (8)0.0028 (7)0.0030 (7)0.0011 (7)
N10.0267 (7)0.0491 (10)0.0260 (7)0.0046 (7)0.0007 (6)0.0085 (6)
C20.0292 (8)0.0306 (10)0.0281 (8)0.0040 (7)0.0036 (7)0.0023 (7)
N20.0452 (9)0.0523 (11)0.0354 (8)0.0157 (8)0.0129 (7)0.0094 (8)
N30.0375 (8)0.0553 (11)0.0277 (8)0.0032 (9)0.0053 (6)0.0007 (7)
N40.0278 (8)0.0638 (12)0.0389 (8)0.0025 (8)0.0059 (7)0.0103 (8)
Geometric parameters (Å, º) top
S1—C11.6636 (17)N2—H210.86 (2)
C1—N21.319 (2)N2—H220.85 (2)
C1—N11.3866 (19)N3—H310.84 (2)
N1—C21.3565 (19)N3—H320.79 (2)
N1—H10.773 (17)N4—H410.806 (19)
C2—N41.300 (2)N4—H420.844 (19)
C2—N31.314 (2)
N2—C1—N1112.45 (15)C1—N2—H21121.5 (13)
N2—C1—S1123.43 (12)C1—N2—H22116.1 (13)
N1—C1—S1124.07 (12)H21—N2—H22121.2 (18)
C2—N1—C1130.32 (14)C2—N3—H31119.1 (13)
C2—N1—H1113.2 (14)C2—N3—H32117.8 (14)
C1—N1—H1116.5 (14)H31—N3—H32121.0 (19)
N4—C2—N3121.03 (15)C2—N4—H41118.8 (14)
N4—C2—N1122.20 (15)C2—N4—H42121.5 (13)
N3—C2—N1116.73 (15)H41—N4—H42119.6 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl1i0.773 (17)2.539 (18)3.2305 (16)149.9 (18)
N2—H21···Cl10.86 (2)2.54 (2)3.3458 (18)156.0 (16)
N2—H22···Cl1ii0.85 (2)2.48 (2)3.3225 (18)174.2 (18)
N3—H31···Cl1i0.84 (2)2.51 (2)3.2804 (18)152.9 (17)
N3—H32···Cl1iii0.79 (2)2.62 (2)3.3084 (18)146.9 (18)
N4—H41···S10.806 (19)2.390 (19)3.0339 (17)137.5 (18)
N4—H42···Cl1iii0.844 (19)2.46 (2)3.2268 (17)152.2 (17)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y1/2, z+1/2; (iii) x+2, y+1, z+1.
(Ib) 1-(diaminomethylene)thiouron-1-ium bromide top
Crystal data top
C2H7N4S+·BrZ = 2
Mr = 199.09F(000) = 196
Triclinic, P1Dx = 1.921 Mg m3
Dm = 1.92 Mg m3
Dm measured by flotation
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.9661 (9) ÅCell parameters from 827 reflections
b = 7.4841 (17) Åθ = 3.4–29.4°
c = 9.5739 (19) ŵ = 6.18 mm1
α = 94.220 (14)°T = 295 K
β = 90.091 (11)°Paralellepiped, colourless
γ = 104.012 (15)°0.32 × 0.22 × 0.16 mm
V = 344.23 (12) Å3
Data collection top
Kuma KM-4 with area CCD detector
diffractometer
1737 independent reflections
Radiation source: fine-focus sealed tube1295 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1θmax = 29.4°, θmin = 3.4°
ω–scanh = 56
Absorption correction: analytical
(face-indexed; SHELXTL; Sheldrick, 2008)
k = 99
Tmin = 0.244, Tmax = 0.441l = 1212
4034 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Only H-atom coordinates refined
wR(F2) = 0.085 w = 1/[σ2(Fo2) + (0.0481P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.005
1737 reflectionsΔρmax = 0.76 e Å3
95 parametersΔρmin = 0.51 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.079 (6)
Crystal data top
C2H7N4S+·Brγ = 104.012 (15)°
Mr = 199.09V = 344.23 (12) Å3
Triclinic, P1Z = 2
a = 4.9661 (9) ÅMo Kα radiation
b = 7.4841 (17) ŵ = 6.18 mm1
c = 9.5739 (19) ÅT = 295 K
α = 94.220 (14)°0.32 × 0.22 × 0.16 mm
β = 90.091 (11)°
Data collection top
Kuma KM-4 with area CCD detector
diffractometer
1737 independent reflections
Absorption correction: analytical
(face-indexed; SHELXTL; Sheldrick, 2008)
1295 reflections with I > 2σ(I)
Tmin = 0.244, Tmax = 0.441Rint = 0.017
4034 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.085Only H-atom coordinates refined
S = 0.99Δρmax = 0.76 e Å3
1737 reflectionsΔρmin = 0.51 e Å3
95 parameters
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
xyzUiso*/Ueq
Br10.78860 (7)0.69979 (4)0.10439 (3)0.05125 (18)
S10.1687 (2)0.25428 (13)0.48486 (9)0.0536 (3)
C10.2765 (6)0.3567 (4)0.3381 (3)0.0370 (6)
N10.4595 (6)0.3053 (4)0.2455 (3)0.0464 (6)
H10.545 (8)0.397 (5)0.196 (4)0.056*
N20.1940 (7)0.5028 (4)0.3028 (3)0.0540 (7)
H210.244 (8)0.554 (5)0.230 (4)0.065*
H220.067 (8)0.542 (5)0.366 (4)0.065*
C20.5473 (6)0.1463 (4)0.2300 (3)0.0407 (7)
N30.7246 (8)0.1378 (5)0.1304 (4)0.0591 (8)
H310.782 (8)0.049 (6)0.118 (4)0.071*
H320.777 (8)0.236 (5)0.080 (4)0.071*
N40.4618 (6)0.0105 (4)0.3068 (3)0.0546 (8)
H410.549 (8)0.092 (6)0.289 (4)0.066*
H420.357 (9)0.033 (6)0.368 (4)0.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0621 (3)0.0501 (3)0.0452 (2)0.01754 (17)0.00881 (15)0.01380 (15)
S10.0645 (6)0.0557 (5)0.0500 (5)0.0273 (4)0.0219 (4)0.0213 (4)
C10.0341 (14)0.0353 (15)0.0425 (15)0.0090 (12)0.0044 (12)0.0059 (13)
N10.0595 (17)0.0462 (15)0.0403 (14)0.0219 (13)0.0146 (12)0.0159 (12)
N20.068 (2)0.0515 (17)0.0526 (17)0.0297 (15)0.0117 (15)0.0176 (14)
C20.0427 (16)0.0420 (16)0.0390 (15)0.0141 (13)0.0008 (13)0.0016 (13)
N30.070 (2)0.0545 (19)0.0586 (18)0.0255 (17)0.0214 (15)0.0063 (15)
N40.0586 (19)0.0464 (16)0.064 (2)0.0213 (15)0.0182 (15)0.0113 (15)
Geometric parameters (Å, º) top
S1—C11.676 (3)C2—N41.286 (4)
C1—N21.322 (4)C2—N31.308 (4)
C1—N11.372 (4)N3—H310.79 (4)
N1—C21.362 (4)N3—H320.90 (4)
N1—H10.89 (4)N4—H410.97 (4)
N2—H210.83 (4)N4—H420.82 (4)
N2—H220.96 (4)
N2—C1—N1113.0 (3)N4—C2—N3121.2 (3)
N2—C1—S1121.6 (2)N4—C2—N1123.0 (3)
N1—C1—S1125.4 (2)N3—C2—N1115.9 (3)
C2—N1—C1130.2 (3)C2—N3—H31119 (3)
C2—N1—H1117 (2)C2—N3—H32117 (3)
C1—N1—H1112 (2)H31—N3—H32123 (4)
C1—N2—H21123 (3)C2—N4—H41115 (2)
C1—N2—H22114 (2)C2—N4—H42113 (3)
H21—N2—H22123 (4)H41—N4—H42132 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.89 (4)2.51 (4)3.387 (3)167 (3)
N2—H21···Br10.83 (4)2.95 (4)3.580 (4)134 (3)
N2—H22···S1i0.96 (4)2.50 (4)3.426 (3)161 (3)
N3—H31···Br1ii0.79 (4)2.61 (4)3.361 (3)159 (4)
N3—H32···Br1iii0.90 (4)2.76 (4)3.372 (4)126 (3)
N4—H41···Br1ii0.97 (4)2.73 (4)3.601 (3)149 (3)
N4—H42···S10.82 (4)2.32 (4)3.031 (3)147 (4)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y1, z; (iii) x+2, y+1, z.
(Ic) 1-(diaminomethylene)thiouron-1-ium iodide top
Crystal data top
C2H7N4S+·IF(000) = 464
Mr = 246.08Dx = 2.153 Mg m3
Dm = 2.15 Mg m3
Dm measured by flotation
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 876 reflections
a = 10.929 (3) Åθ = 3.3–29.0°
b = 7.875 (1) ŵ = 4.41 mm1
c = 9.456 (2) ÅT = 295 K
β = 111.10 (1)°Paralellepiped, colourless
V = 759.3 (3) Å30.38 × 0.24 × 0.22 mm
Z = 4
Data collection top
Kuma KM-4 with area CCD detector
diffractometer
2001 independent reflections
Radiation source: fine-focus sealed tube1785 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.013
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1θmax = 29.0°, θmin = 3.3°
ω–scanh = 1414
Absorption correction: analytical
(face-indexed; SHELXTL; Sheldrick, 2008)
k = 1010
Tmin = 0.286, Tmax = 0.445l = 912
10077 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Only H-atom coordinates refined
wR(F2) = 0.055 w = 1/[σ2(Fo2) + (0.0332P)2 + 0.3719P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.004
2001 reflectionsΔρmax = 0.81 e Å3
95 parametersΔρmin = 0.68 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0257 (9)
Crystal data top
C2H7N4S+·IV = 759.3 (3) Å3
Mr = 246.08Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.929 (3) ŵ = 4.41 mm1
b = 7.875 (1) ÅT = 295 K
c = 9.456 (2) Å0.38 × 0.24 × 0.22 mm
β = 111.10 (1)°
Data collection top
Kuma KM-4 with area CCD detector
diffractometer
2001 independent reflections
Absorption correction: analytical
(face-indexed; SHELXTL; Sheldrick, 2008)
1785 reflections with I > 2σ(I)
Tmin = 0.286, Tmax = 0.445Rint = 0.013
10077 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0210 restraints
wR(F2) = 0.055Only H-atom coordinates refined
S = 1.00Δρmax = 0.81 e Å3
2001 reflectionsΔρmin = 0.68 e Å3
95 parameters
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
xyzUiso*/Ueq
I10.373664 (15)0.34350 (2)0.591594 (16)0.04108 (9)
S10.04026 (6)0.76529 (8)0.09361 (7)0.04611 (16)
C10.1532 (2)0.6433 (3)0.2193 (3)0.0327 (4)
N10.2498 (2)0.7006 (3)0.3494 (2)0.0386 (4)
H10.293 (3)0.627 (4)0.411 (4)0.046*
N20.1595 (3)0.4770 (3)0.2012 (3)0.0462 (5)
H210.215 (3)0.414 (5)0.268 (4)0.055*
H220.106 (3)0.428 (4)0.123 (4)0.055*
C20.2737 (2)0.8575 (3)0.4123 (3)0.0343 (4)
N30.3736 (2)0.8725 (4)0.5399 (3)0.0520 (6)
H310.386 (3)0.964 (6)0.586 (4)0.062*
H320.420 (4)0.797 (5)0.575 (4)0.062*
N40.1994 (2)0.9890 (3)0.3521 (3)0.0455 (5)
H410.220 (3)1.083 (5)0.392 (4)0.055*
H420.140 (3)0.978 (4)0.269 (4)0.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.04361 (12)0.03428 (11)0.03844 (12)0.00127 (5)0.00640 (7)0.00020 (5)
S10.0429 (3)0.0382 (3)0.0424 (3)0.0049 (2)0.0025 (3)0.0033 (2)
C10.0342 (10)0.0313 (10)0.0334 (10)0.0004 (8)0.0132 (9)0.0031 (8)
N10.0386 (10)0.0320 (9)0.0365 (10)0.0079 (8)0.0029 (8)0.0025 (8)
N20.0548 (13)0.0310 (9)0.0420 (11)0.0001 (9)0.0045 (10)0.0022 (8)
C20.0343 (10)0.0360 (11)0.0326 (10)0.0022 (8)0.0120 (9)0.0037 (8)
N30.0427 (12)0.0492 (13)0.0489 (13)0.0041 (10)0.0020 (10)0.0180 (11)
N40.0558 (13)0.0286 (9)0.0422 (11)0.0003 (9)0.0056 (10)0.0039 (8)
Geometric parameters (Å, º) top
S1—C11.674 (2)C2—N31.309 (3)
C1—N21.326 (3)C2—N41.312 (3)
C1—N11.377 (3)N3—H310.83 (4)
N1—C21.355 (3)N3—H320.78 (4)
N1—H10.84 (3)N4—H410.82 (4)
N2—H210.86 (4)N4—H420.82 (3)
N2—H220.85 (4)
N2—C1—N1112.3 (2)N3—C2—N4120.6 (2)
N2—C1—S1122.29 (19)N3—C2—N1116.9 (2)
N1—C1—S1125.36 (16)N4—C2—N1122.5 (2)
C2—N1—C1130.9 (2)C2—N3—H31119 (2)
C2—N1—H1111 (2)C2—N3—H32122 (3)
C1—N1—H1117 (2)H31—N3—H32119 (4)
C1—N2—H21122 (2)C2—N4—H41119 (2)
C1—N2—H22121 (2)C2—N4—H42119 (2)
H21—N2—H22117 (3)H41—N4—H42122 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···I10.84 (3)2.75 (3)3.571 (2)165 (3)
N2—H21···I10.86 (4)2.98 (4)3.741 (3)149 (3)
N2—H22···S1i0.85 (4)2.59 (4)3.434 (2)171 (3)
N3—H31···I1ii0.83 (4)2.99 (5)3.741 (3)151 (3)
N4—H41···I1ii0.82 (4)2.88 (4)3.667 (2)160 (3)
N4—H42···S10.82 (3)2.33 (3)3.007 (2)140 (3)
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z.

Experimental details

(Ia)(Ib)(Ic)
Crystal data
Chemical formulaC2H7N4S+·ClC2H7N4S+·BrC2H7N4S+·I
Mr154.63199.09246.08
Crystal system, space groupMonoclinic, P21/cTriclinic, P1Monoclinic, P21/c
Temperature (K)295295295
a, b, c (Å)6.517 (1), 6.807 (1), 14.777 (3)4.9661 (9), 7.4841 (17), 9.5739 (19)10.929 (3), 7.875 (1), 9.456 (2)
α, β, γ (°)90, 90.36 (2), 9094.220 (14), 90.091 (11), 104.012 (15)90, 111.10 (1), 90
V3)655.51 (19)344.23 (12)759.3 (3)
Z424
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.806.184.41
Crystal size (mm)0.37 × 0.22 × 0.170.32 × 0.22 × 0.160.38 × 0.24 × 0.22
Data collection
DiffractometerKuma KM-4 with area CCD detector
diffractometer
Kuma KM-4 with area CCD detector
diffractometer
Kuma KM-4 with area CCD detector
diffractometer
Absorption correctionAnalytical
(face-indexed; SHELXTL; Sheldrick, 2008)
Analytical
(face-indexed; SHELXTL; Sheldrick, 2008)
Analytical
(face-indexed; SHELXTL; Sheldrick, 2008)
Tmin, Tmax0.760, 0.8780.244, 0.4410.286, 0.445
No. of measured, independent and
observed reflections
6665, 1635, 1164 [σ > 2σ(I)]4034, 1737, 1295 [I > 2σ(I)]10077, 2001, 1785 [I > 2σ(I)]
Rint0.0310.0170.013
(sin θ/λ)max1)0.6690.6900.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.062, 0.99 0.036, 0.085, 0.99 0.021, 0.055, 1.00
No. of reflections163517372001
No. of parameters959595
H-atom treatmentOnly H-atom coordinates refinedOnly H-atom coordinates refinedOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.21, 0.200.76, 0.510.81, 0.68

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006).

Selected geometric parameters (Å, º) for (Ia) top
S1—C11.6636 (17)N1—C21.3565 (19)
C1—N21.319 (2)C2—N41.300 (2)
C1—N11.3866 (19)C2—N31.314 (2)
N2—C1—N1112.45 (15)N4—C2—N3121.03 (15)
N2—C1—S1123.43 (12)N4—C2—N1122.20 (15)
N1—C1—S1124.07 (12)N3—C2—N1116.73 (15)
C2—N1—C1130.32 (14)
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl1i0.773 (17)2.539 (18)3.2305 (16)149.9 (18)
N2—H21···Cl10.86 (2)2.54 (2)3.3458 (18)156.0 (16)
N2—H22···Cl1ii0.85 (2)2.48 (2)3.3225 (18)174.2 (18)
N3—H31···Cl1i0.84 (2)2.51 (2)3.2804 (18)152.9 (17)
N3—H32···Cl1iii0.79 (2)2.62 (2)3.3084 (18)146.9 (18)
N4—H41···S10.806 (19)2.390 (19)3.0339 (17)137.5 (18)
N4—H42···Cl1iii0.844 (19)2.46 (2)3.2268 (17)152.2 (17)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y1/2, z+1/2; (iii) x+2, y+1, z+1.
Selected geometric parameters (Å, º) for (Ib) top
S1—C11.676 (3)N1—C21.362 (4)
C1—N21.322 (4)C2—N41.286 (4)
C1—N11.372 (4)C2—N31.308 (4)
N2—C1—N1113.0 (3)N4—C2—N3121.2 (3)
N2—C1—S1121.6 (2)N4—C2—N1123.0 (3)
N1—C1—S1125.4 (2)N3—C2—N1115.9 (3)
C2—N1—C1130.2 (3)
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.89 (4)2.51 (4)3.387 (3)167 (3)
N2—H21···Br10.83 (4)2.95 (4)3.580 (4)134 (3)
N2—H22···S1i0.96 (4)2.50 (4)3.426 (3)161 (3)
N3—H31···Br1ii0.79 (4)2.61 (4)3.361 (3)159 (4)
N3—H32···Br1iii0.90 (4)2.76 (4)3.372 (4)126 (3)
N4—H41···Br1ii0.97 (4)2.73 (4)3.601 (3)149 (3)
N4—H42···S10.82 (4)2.32 (4)3.031 (3)147 (4)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y1, z; (iii) x+2, y+1, z.
Selected geometric parameters (Å, º) for (Ic) top
S1—C11.674 (2)N1—C21.355 (3)
C1—N21.326 (3)C2—N31.309 (3)
C1—N11.377 (3)C2—N41.312 (3)
N2—C1—N1112.3 (2)N3—C2—N4120.6 (2)
N2—C1—S1122.29 (19)N3—C2—N1116.9 (2)
N1—C1—S1125.36 (16)N4—C2—N1122.5 (2)
C2—N1—C1130.9 (2)
Hydrogen-bond geometry (Å, º) for (Ic) top
D—H···AD—HH···AD···AD—H···A
N1—H1···I10.84 (3)2.75 (3)3.571 (2)165 (3)
N2—H21···I10.86 (4)2.98 (4)3.741 (3)149 (3)
N2—H22···S1i0.85 (4)2.59 (4)3.434 (2)171 (3)
N3—H31···I1ii0.83 (4)2.99 (5)3.741 (3)151 (3)
N4—H41···I1ii0.82 (4)2.88 (4)3.667 (2)160 (3)
N4—H42···S10.82 (3)2.33 (3)3.007 (2)140 (3)
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z.
 

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