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The structures of the first two organic carboxyl­ate salts of 1-(diamino­methyl­ene)thio­urea (HATU), namely 1-(diamino­methyl­ene)thio­uron-1-ium formate, C2H7N4S+·HCOO-, (I), and bis­[1-(diamino­methyl­ene)thio­uron-1-ium] oxalate dihydrate, 2C2H7N4S+·C2O42-·2H2O, (II), in which the oxalate lies on a symmetry centre, possess different extended hydrogen-bonding networks with different graph-set motifs. The R22(8) motif present in (I) does not appear in (II), but an R21(6) motif is present in both (I) and (II). Compound (I) has a three-dimensional hydrogen-bonding network, whereas (II) has a layered structure with layers joined by hydrogen-bonding motifs that form R42(8) patterns. This work extends the known supra­molecular structural data for HATU to include these organic carboxyl­ates in addition to the previously characterized salts with inorganic acids.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109026390/fa3194sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109026390/fa3194Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109026390/fa3194IIsup3.hkl
Contains datablock II

CCDC references: 746090; 746091

Comment top

1-(diaminomethylene)thiourea (HATU; Janczak & Perpétuo, 2008a; Hołyńska et al., 2009) and its oxidation products (Hołyńska & Kubiak, 2008) are already considered to be useful building blocks in crystal engineering. To explore the possibility of HATU forming predictable hydrogen-bonding patterns, it would be useful to observe its behaviour towards other known building blocks. Carboxylates and carboxylic acids (Steiner, 2001) are widely used in this context. In particular, aggregation patterns have been studied for carboxylates of amino acids (e.g. Prasad & Vijayan, 1993). Other examples in this line of research include the structures of inclusion compounds based on thiourea and carboxylic acids (Li & Mak, 1997). Supramolecular motifs have been successfully utilized in tuning the nonlinear properties of a series of N-(2-aminoethyl)-4-nitroaniline adducts with carboxylic acids (Jaya Prakash & Radhakrishnan, 2006). Molecular recognition of carboxylates by guanidinium cations has also been investigated in biological systems (Best et al., 2003). The crystal engineering of thioureas is still considered to be less developed than that of ureas (Custelcean, 2001).

The known crystal structures of 1-(diaminomethylene)thiouron-1-ium ([HATUH]+) salts include hydrogen halides (Perpétuo & Janczak, 2008), perchlorate, hydrogen sulfate, dihydrogen phosphate and dihydrogen arsenate (Janczak & Perpétuo, 2008b), as well as hydrogen difluoride and hexafluoridosilicate (Hołyńska & Kubiak, 2009). None of these is a salt of an organic acid. In this paper, the crystal structures of two representative [HATUH]+ carboxylates, the formate, (I), and the oxalate monohydrate, (II), are described and compared, with emphasis on the hydrogen-bonding motifs present.

Compounds (I) and (II) (Figs. 1 and 2) are the first structurally characterized organic [HATUH]+ carboxylates. Compound (I) is the formate, whereas (II) is the oxalate, with the anion sitting astride a symmetry centre. These anions were chosen as being the simplest examples of mono- and dicarboxylate anions, and were expected to participate in different supramolecular motifs in the crystal structures. The results reported herein ratify these expectations. In contrast, however, the acetate salt, homologous with the formate salt, is also isomorphous with the latter (see Experimental section), which underlines the role of the carboxylate group in motif formation in the crystal. Also, (II), in contrast with (I), incorporates water in the crystal structure, which further influences the hydrogen-bonding network.

The [HATUH]+ cation in both (I) and (II) is twisted, as previously observed for other salts of this cation (e.g. Janczak & Perpétuo, 2009a). The dihedral angles between the planes N1/C2/N3/N4 and N1/C1/N2/S1 are 5.5 (2)° for (I) and 4.5 (2)° for (II). These values are close to those calculated for the most stable conformation of [HATUH]+ by ab initio molecular orbital calculations (Table 1). The currently available data on [HATUH]+ salts show that the cation twisting may differ when different anions are used and is dependent on hydrogen bonding (Table 1). For the 1-(diaminomethylene)uron-1-ium cation in its hydrogen sulfate salt (Hołyńska & Kubiak, 2008) the analogous value is 1.8 (2)°.

The geometric parameters of the formate and oxalate anions in (I) and (II), respectively, do not deviate significantly from the reported values (e.g. melaminium formate; Perpétuo et al., 2005). The oxalate anion, as in most of the available structures [e.g. bis(N,N'-diphenylguanidinium) oxalate; Paixão et al., 1999], is flat and centrosymmetric. However, there are also cases of twisted oxalate anions, e.g. in 4-ammonio-1-methylpiperazin-1-ium oxalate dihydrate (Guo, 2004) or in (S,S)-N,N'-bis(2-hydroxy-2-butyl)ethylenediammonium oxalate pentahydrate (Bai et al., 2006).

The hydrogen-bonding patterns involving the carboxylate groups are different in (I) and (II). For (I), an R22(8) motif (Etter et al., 1990) is formed by donation to the formate anion from the amino groups bonded to atom C2 (N3—H32···O2 and N4—H42···O1; Figs. 1 and 3 and Table 2). In (II), these amino groups do not participate in a similar motif; rather, they are donors in an R21(6) pattern [N3—H32···O1Wiii and N4—H42···O1Wiii; symmetry code (iii) as in Table 3]. However, a similar motif to R22(8) in (I) is the R22(9) motif in (II), created via participation of the central atom N1 and the N2 amino group of the cation as donors, and atoms O1 and O2i [symmetry code: (i) 1 - x, 1 - y, 1 - z] from two different carboxyl groups of the centrosymmetric oxalate anion as acceptors (Figs. 2 and 4 and Table 3). It is interesting that the R21(6) motif present in (I) (Figs. 1 and 3), involving two hydrogen bonds with the central atom N1 and the N3 amino group of the cation as donors and a carboxylate O atom of the anion as acceptor, is robust enough to be retained in (II) (Fig. 4). This motif is also present in 1-(diaminomethylene)uron-1-ium hydrogen sulfate (Hołyńska & Kubiak, 2008).

A further structure-building principle is different in (I) and (II). Whereas in (I) subunits consisting of two formate anions and two [HATUH]+ cations, forming extended R44(16) motifs, can be distinguished (Fig. 3), in (II) a layered arrangement is present (Fig. 4). The hydrogen-bonded layers in (II) are connected via O—H···O hydrogen bonds (with a water molecule as donor and an oxalate anion as acceptor), which leads to the formation of R42(8) motifs consisting of two water molecules and two oxalate anions belonging to neighbouring layers. The presence of these specific contacts is possible since the plane of the oxalate anion interacting via the [HATUH]+ cation to form an R22(9) motif is inclined with respect to this cation [dihedral angles to the two cation `arms' are 40.8 (1) and 42.6 (1)° for N1/C2/N3/N4 and N1/C1/N2/S1, respectively]. On the other hand, in (I) the formate anion plane is also somewhat inclined to the planes of the `arms' of the interacting cation to form an R22(8) motif [dihedral angles 13.9 (2) and 9.3 (2)° to N1/C2/N3/N4 and N1/C1/N2/S1, respectively].

Recently, Janczak & Perpétuo (2009) reported a new type of interaction in [HATUH]+ salts, claimed to be a ππ stacking of parallel [HATUH]+ cations separated by about 3.27 Å. These interactions are said to stabilize the charge delocalization over the cation and significantly increase its planarity. In (II), the cations stack in an antiparallel fashion parallel to [100]. The N1/C1/N2/S1 arm of the molecule at (2 - x, -y, -z) eclipses the N1/C2/N3/N4 fragment of the molecule at (x, y, z), with a dihedral angle of 4.5 (2)° and with the distances of the atoms of one fragment from the plane of the other lying within the range 3.18 (1)–3.39 (1) Å. The molecule at (x, y, z) also interacts with the molecule at (1 - x, -y, -z) [the relevant distances as defined above are in the range 3.08 (1)–3.35 (1) Å]. In (I), on the other hand, the cations are arranged in chains rather than stacks, extending along [010]. Although the extent of the postulated cation ππ interactions differs greatly between (I) and (II), the twisting of the cations in these structures is not much affected by this difference.

The presence of S in the [HATUH]+ cation in (I) and (II) raises the question of whether there are hydrogen bonds with S as acceptor, although the importance of such interactions has been questioned (Allen et al., 1997b). Nevertheless, there are authors motivated by the high S content in biological systems, who claim to utilize weak D—H···S (D = donor) interactions in crystal engineering. For example, Valdez-Martinez et al. (2004) claim to have successfully designed a strategy of constructing thiourea derivatives so as to avoid the formation of intramolecular hydrogen bonds. Such intramolecular N—H···S hydrogen bonds seem to be present in the [HATUH]+ cation in (I) and (II) (Tables 2 and 3), as well as in other reported [HATUH]+ salts (e.g. Janczak & Perpétuo, 2009). Their formation is favoured based on considerations put forward by Etter et al. (1990) for six-membered hydrogen-bonded rings; the presence of the CS bond makes it possible for some resonance-assisted stabilization to occur. Also, Allen et al. (1997a) discuss the possibility of resonance-induced hydrogen-bond formation with the S atom of a CS group with N substituents. In (I) and (II), additional weak N—H···S interactions seem to occur. However, in both cases the `hydrogen bonds' involving S seem to be driven by the stronger hydrogen bonds present (Tables 2 and 3).

This study confirms the usefulness of HATU as a building block in crystal engineering and demonstrates its interaction with carboxylate, another common building block. Further insight into this field might be gained through examination of HATU-derivative carboxylate salts. We hope that the data for the simplest carboxylate and dicarboxylate [HATUH]+ salts will be useful in the design and description of new organic materials based on HATU ligand derivatives, which are worth investigating due to their potentially interesting properties and structures. The results of this study imply that the R21(6) graph-set motif (Etter et al., 1990) may be of importance in these investigations, but further conclusions await the analysis of different carboxylates.

Experimental top

For the preparation of (I), HATU (0.05 g) was dissolved in an excess of 5% formic acid. On slow evaporation of the solution, crystals of (I) in the form of colourless plates were obtained. A similar procedure using acetic acid instead of formic acid yields crystals of the isomorphous acetate salt [a = 11.978 (4), b = 6.208 (3), c = 11.753 (4) Å, β = 116.57 (3)°, P21/c].

For the preparation of (II), HATU (0.5 g) was dissolved in water (10 ml). A stoichiometric amount of oxalic acid dihydrate was dissolved in water (15 ml). The two solutions were combined to yield a white crystalline precipitate. The mixture obtained was allowed to stand for a week for slow recrystallization. A single-crystal in the form of a colourless polyhedron was chosen from the precipitate.

Refinement top

All H atoms were found in difference Fourier maps. For (I), the formate H atom was refined as riding on its parent C atom. The remaining H atoms bonded to N atoms were first refined with restraints (DFIX; Sheldrick, 2008), with N—H = 0.870 (2) Å, and subsequently constrained as riding (AFIX 3) [All H atoms in CIF tables for (I) have freely refined Uiso values - please clarify]. The highest final difference Fourier peak of 0.28 e Å-3 is located 0.78 Å from atom C1 and 0.91 Å from atom S1. In the case of (II), H-atom parameters were refined freely. In the final difference Fourier map, the highest peak of 0.44 e Å-3 was located on the oxalate C—C bond (0.79 Å from atom C10).

Computing details top

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (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, 2005) and SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. The structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines. The non-labelled part of the oxalate is generated by the symmetry operation (-x + 1, -y + 1, -z + 1).
[Figure 3] Fig. 3. The three-dimensional hydrogen-bonding network in (I). Hydrogen bonds are shown as dashed lines and the graph-set motifs are marked. [Symmetry codes: (i) x, -y + 3/2, z + 1/2; (ii) -x + 1, y + 1/2, -z + 3/2.]
[Figure 4] Fig. 4. The hydrogen-bonded layers and interlayer contacts in (II). Hydrogen bonds are shown as dashed lines. Cation H atoms not involved in hydrogen bonds have been omitted. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) x, y, z - 1; (iii) x, y - 1, z; (iv) -x + 2, -y + 1, -z + 1.]
(I) 1-(diaminomethylene)thiouron-1-ium formate top
Crystal data top
C2H7N4S+·CHO2F(000) = 344
Mr = 164.19Dx = 1.496 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2935 reflections
a = 12.693 (4) Åθ = 3.5–28.6°
b = 5.509 (3) ŵ = 0.39 mm1
c = 11.576 (4) ÅT = 100 K
β = 115.80 (3)°Plate, colourless
V = 728.8 (5) Å30.19 × 0.14 × 0.04 mm
Z = 4
Data collection top
Kuma KM4 CCD area-detector
diffractometer
1774 independent reflections
Radiation source: fine-focus sealed tube1336 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
ω scansθmax = 28.6°, θmin = 3.5°
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006)
h = 1616
Tmin = 0.955, Tmax = 0.981k = 77
6097 measured reflectionsl = 1314
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: difference Fourier map
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.060P)2]
where P = (Fo2 + 2Fc2)/3
1774 reflections(Δ/σ)max < 0.001
99 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C2H7N4S+·CHO2V = 728.8 (5) Å3
Mr = 164.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.693 (4) ŵ = 0.39 mm1
b = 5.509 (3) ÅT = 100 K
c = 11.576 (4) Å0.19 × 0.14 × 0.04 mm
β = 115.80 (3)°
Data collection top
Kuma KM4 CCD area-detector
diffractometer
1774 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006)
1336 reflections with I > 2σ(I)
Tmin = 0.955, Tmax = 0.981Rint = 0.044
6097 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.28 e Å3
1774 reflectionsΔρmin = 0.20 e Å3
99 parameters
Special details top

Experimental. IR spectrum was collected on a Bruker spectrometer for a sample suspended in Nujol mull (KBr windows). (I): 424.5 (w), 436.0 (w), 490.9 (w), 547.4 (m), 617.1 (m), 669.9 (w), 737.2 (m), 774.5 (m), 821.5 (w), 888.9 (vw), 989.8 (vw), 1097.6 (m), 1180.6 (m), 1332.1 (vs), 1354.3 (s), 1381.0 (s), 1413.8 (m), 1464.6 (s), 1521.7 (s), 1594.8 (vs), 1713.6 (s), 2738.9 (s), 2854.5 (vs), 2924.2 (vs), 3220.8 (vs)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C100.59229 (19)0.2747 (4)0.5572 (2)0.0213 (5)
H100.55500.16450.48810.038 (7)*
O10.68204 (13)0.3827 (3)0.56317 (14)0.0234 (4)
O20.54835 (13)0.2994 (3)0.63342 (14)0.0250 (4)
S10.94571 (5)1.19873 (11)0.84467 (5)0.02242 (18)
C10.85516 (18)1.1867 (4)0.9164 (2)0.0191 (5)
N10.76401 (15)1.0245 (3)0.88731 (17)0.0190 (4)
H10.72371.04050.93140.031 (7)*
N30.63657 (15)0.7091 (4)0.79700 (17)0.0231 (4)
H310.59980.75580.84140.031 (7)*
H320.61300.58360.74650.042 (8)*
C20.72944 (18)0.8301 (4)0.8053 (2)0.0184 (5)
N20.86412 (17)1.3394 (3)1.00847 (17)0.0220 (4)
H210.81931.31871.04700.021 (6)*
H220.91821.45031.03850.027 (7)*
N40.78502 (17)0.7640 (3)0.73713 (18)0.0241 (5)
H410.84790.84830.75360.045 (8)*
H420.75880.63720.68820.033 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C100.0227 (12)0.0202 (12)0.0229 (11)0.0007 (9)0.0119 (10)0.0015 (9)
O10.0221 (8)0.0275 (9)0.0250 (8)0.0039 (7)0.0143 (7)0.0015 (7)
O20.0250 (9)0.0268 (9)0.0299 (9)0.0006 (7)0.0181 (8)0.0016 (7)
S10.0223 (3)0.0285 (3)0.0208 (3)0.0014 (3)0.0134 (2)0.0004 (2)
C10.0188 (11)0.0214 (11)0.0169 (10)0.0043 (9)0.0076 (9)0.0043 (9)
N10.0177 (9)0.0237 (10)0.0191 (9)0.0021 (8)0.0113 (8)0.0001 (7)
N30.0221 (10)0.0265 (10)0.0259 (10)0.0003 (9)0.0154 (9)0.0043 (9)
C20.0187 (11)0.0181 (11)0.0183 (10)0.0035 (9)0.0080 (9)0.0032 (9)
N20.0246 (10)0.0248 (11)0.0230 (10)0.0043 (9)0.0162 (9)0.0046 (8)
N40.0284 (11)0.0235 (11)0.0289 (10)0.0035 (9)0.0205 (9)0.0054 (8)
Geometric parameters (Å, º) top
C10—O21.240 (3)N3—C21.321 (3)
C10—O11.260 (3)N3—H310.8699
C10—H100.9500N3—H320.8700
S1—C11.686 (2)C2—N41.318 (3)
C1—N21.324 (3)N2—H210.8700
C1—N11.383 (3)N2—H220.8702
N1—C21.370 (3)N4—H410.8701
N1—H10.8698N4—H420.8696
O2—C10—O1125.8 (2)H31—N3—H32121.1
O2—C10—H10117.1N4—C2—N3120.7 (2)
O1—C10—H10117.1N4—C2—N1122.5 (2)
N2—C1—N1112.09 (18)N3—C2—N1116.85 (19)
N2—C1—S1122.24 (17)C1—N2—H21118.9
N1—C1—S1125.67 (16)C1—N2—H22123.0
C2—N1—C1130.95 (18)H21—N2—H22117.7
C2—N1—H1113.1C2—N4—H41113.6
C1—N1—H1115.8C2—N4—H42117.4
C2—N3—H31119.9H41—N4—H42128.8
C2—N3—H32119.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.871.872.708 (2)162
N3—H31···O2ii0.872.042.838 (2)152
N3—H32···O20.871.982.844 (3)176
N2—H21···O1i0.872.142.918 (2)148
N4—H42···O10.871.942.808 (3)172
N4—H41···S10.872.293.039 (2)144
N2—H22···S1iii0.872.553.409 (2)168
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x+1, y+1/2, z+3/2; (iii) x+2, y+3, z+2.
(II) bis[1-(diaminomethylene)thiouron-1-ium] oxalate dihydrate top
Crystal data top
2C2H7N4S+·C2O42·2H2OZ = 1
Mr = 362.40F(000) = 190
Triclinic, P1Dx = 1.636 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.006 (3) ÅCell parameters from 3612 reflections
b = 7.221 (3) Åθ = 3.0–36.9°
c = 7.837 (3) ŵ = 0.41 mm1
α = 111.89 (3)°T = 100 K
β = 90.82 (3)°Polyhedron, colourless
γ = 91.02 (3)°0.24 × 0.21 × 0.13 mm
V = 367.7 (3) Å3
Data collection top
Kuma KM4 CCD area-detector
diffractometer
2114 independent reflections
Radiation source: fine-focus sealed tube1827 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.010
ω scansθmax = 36.9°, θmin = 3.0°
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006)
h = 118
Tmin = 0.909, Tmax = 0.952k = 99
4151 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: difference Fourier map
wR(F2) = 0.077All H-atom parameters refined
S = 1.00 w = 1/[σ2(Fo2) + (0.0552P)2 + 0.0457P]
where P = (Fo2 + 2Fc2)/3
2114 reflections(Δ/σ)max = 0.001
136 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
2C2H7N4S+·C2O42·2H2Oγ = 91.02 (3)°
Mr = 362.40V = 367.7 (3) Å3
Triclinic, P1Z = 1
a = 7.006 (3) ÅMo Kα radiation
b = 7.221 (3) ŵ = 0.41 mm1
c = 7.837 (3) ÅT = 100 K
α = 111.89 (3)°0.24 × 0.21 × 0.13 mm
β = 90.82 (3)°
Data collection top
Kuma KM4 CCD area-detector
diffractometer
2114 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006)
1827 reflections with I > 2σ(I)
Tmin = 0.909, Tmax = 0.952Rint = 0.010
4151 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.077All H-atom parameters refined
S = 1.00Δρmax = 0.44 e Å3
2114 reflectionsΔρmin = 0.25 e Å3
136 parameters
Special details top

Experimental. IR spectrum was collected on a Bruker spectrometer for a sample prepared as KBr pellet. (II): 437.4 (w), 612.2 (m), 739.5 (m), 1000.3 (vw), 1113.6 (w), 1151.1 (w), 1290.9 (s), 1349.0 (m), 1506.3 (m), 1609.1 (vs), 1705.2 (vs), 3164.6 (s), 3414.0 (vs)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C100.56225 (13)0.44763 (15)0.55224 (14)0.0102 (2)
O10.71513 (10)0.37060 (11)0.47447 (11)0.01222 (16)
O20.50434 (11)0.44719 (12)0.70129 (11)0.01379 (17)
S10.75312 (4)0.08046 (4)0.26075 (4)0.01355 (9)
N10.72837 (12)0.08000 (14)0.11236 (13)0.01075 (18)
H10.703 (2)0.180 (2)0.205 (2)0.015 (3)*
N20.64192 (13)0.27517 (15)0.04141 (14)0.01331 (19)
H210.616 (2)0.347 (2)0.055 (2)0.013 (3)*
H220.622 (2)0.302 (3)0.145 (3)0.034 (5)*
C10.70619 (13)0.09845 (16)0.05663 (15)0.0108 (2)
C20.78428 (13)0.07949 (15)0.15482 (14)0.0108 (2)
N30.77517 (14)0.05506 (15)0.33008 (13)0.0139 (2)
H310.740 (2)0.057 (3)0.407 (2)0.019 (4)*
H320.817 (2)0.150 (3)0.361 (2)0.033 (5)*
N40.84268 (13)0.24755 (15)0.03189 (14)0.01358 (19)
H410.8466 (19)0.266 (2)0.075 (2)0.011 (3)*
H420.878 (2)0.333 (2)0.073 (2)0.018 (4)*
O1W0.95343 (11)0.57493 (13)0.30177 (12)0.01514 (18)
H1W0.882 (2)0.524 (3)0.348 (2)0.032 (5)*
H2W1.055 (2)0.592 (2)0.362 (2)0.022 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C100.0116 (4)0.0088 (4)0.0100 (5)0.0006 (3)0.0014 (3)0.0034 (4)
O10.0118 (3)0.0124 (4)0.0124 (4)0.0024 (3)0.0007 (3)0.0044 (3)
O20.0175 (3)0.0150 (4)0.0103 (4)0.0033 (3)0.0022 (3)0.0061 (3)
S10.01694 (13)0.01423 (15)0.00827 (15)0.00054 (9)0.00136 (9)0.00274 (11)
N10.0146 (4)0.0095 (4)0.0079 (4)0.0020 (3)0.0015 (3)0.0028 (4)
N20.0177 (4)0.0132 (5)0.0089 (5)0.0029 (3)0.0012 (3)0.0039 (4)
C10.0091 (4)0.0136 (5)0.0101 (5)0.0014 (3)0.0003 (3)0.0050 (4)
C20.0096 (4)0.0114 (5)0.0118 (5)0.0001 (3)0.0003 (3)0.0050 (4)
N30.0197 (4)0.0123 (5)0.0110 (5)0.0042 (3)0.0021 (3)0.0057 (4)
N40.0175 (4)0.0119 (4)0.0114 (5)0.0028 (3)0.0005 (3)0.0042 (4)
O1W0.0138 (3)0.0179 (4)0.0167 (4)0.0007 (3)0.0023 (3)0.0100 (3)
Geometric parameters (Å, º) top
C10—O21.2431 (14)N2—H220.907 (19)
C10—O11.2709 (14)C2—N41.3136 (16)
C10—C10i1.571 (2)C2—N31.3206 (15)
S1—C11.6809 (14)N3—H310.851 (17)
N1—C21.3743 (15)N3—H320.861 (19)
N1—C11.3864 (15)N4—H410.796 (15)
N1—H10.834 (16)N4—H420.835 (17)
N2—C11.3243 (15)O1W—H1W0.782 (19)
N2—H210.769 (16)O1W—H2W0.828 (16)
O2—C10—O1126.00 (10)N1—C1—S1124.96 (9)
O2—C10—C10i118.11 (11)N4—C2—N3120.87 (11)
O1—C10—C10i115.90 (11)N4—C2—N1123.43 (10)
C2—N1—C1130.45 (10)N3—C2—N1115.69 (10)
C2—N1—H1113.2 (10)C2—N3—H31118.9 (11)
C1—N1—H1116.3 (10)C2—N3—H32117.0 (12)
C1—N2—H21117.2 (11)H31—N3—H32123.7 (16)
C1—N2—H22119.2 (12)C2—N4—H41122.4 (10)
H21—N2—H22123.4 (16)C2—N4—H42115.9 (11)
N2—C1—N1112.50 (10)H41—N4—H42121.7 (15)
N2—C1—S1122.55 (9)H1W—O1W—H2W105.8 (16)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.83 (2)2.05 (2)2.835 (2)157 (2)
N2—H21···O2i0.77 (2)2.13 (2)2.888 (2)169 (2)
N2—H22···O2ii0.91 (2)2.05 (2)2.897 (2)155 (2)
N3—H31···O10.85 (2)2.14 (2)2.893 (2)148 (2)
N3—H32···O1Wiii0.86 (2)2.11 (2)2.904 (2)152 (2)
N4—H42···O1Wiii0.84 (2)2.20 (2)2.954 (2)151 (2)
O1W—H1W···O10.78 (2)2.10 (2)2.874 (2)174 (2)
O1W—H2W···O1iv0.83 (2)2.00 (2)2.821 (2)175 (2)
N4—H41···S10.80 (2)2.41 (2)3.026 (2)135 (2)
N3—H32···S1v0.86 (2)2.86 (2)3.285 (2)112 (2)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y, z1; (iii) x, y1, z; (iv) x+2, y+1, z+1; (v) x, y, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC2H7N4S+·CHO22C2H7N4S+·C2O42·2H2O
Mr164.19362.40
Crystal system, space groupMonoclinic, P21/cTriclinic, P1
Temperature (K)100100
a, b, c (Å)12.693 (4), 5.509 (3), 11.576 (4)7.006 (3), 7.221 (3), 7.837 (3)
α, β, γ (°)90, 115.80 (3), 90111.89 (3), 90.82 (3), 91.02 (3)
V3)728.8 (5)367.7 (3)
Z41
Radiation typeMo KαMo Kα
µ (mm1)0.390.41
Crystal size (mm)0.19 × 0.14 × 0.040.24 × 0.21 × 0.13
Data collection
DiffractometerKuma KM4 CCD area-detector
diffractometer
Kuma KM4 CCD area-detector
diffractometer
Absorption correctionAnalytical
(CrysAlis RED; Oxford Diffraction, 2006)
Analytical
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.955, 0.9810.909, 0.952
No. of measured, independent and
observed [I > 2σ(I)] reflections
6097, 1774, 1336 4151, 2114, 1827
Rint0.0440.010
(sin θ/λ)max1)0.6740.844
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.108, 1.00 0.027, 0.077, 1.00
No. of reflections17742114
No. of parameters99136
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.28, 0.200.44, 0.25

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005) and SHELXTL-NT (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.871.872.708 (2)162
N3—H31···O2ii0.872.042.838 (2)152
N3—H32···O20.871.982.844 (3)176
N2—H21···O1i0.872.142.918 (2)148
N4—H42···O10.871.942.808 (3)172
N4—H41···S10.872.293.039 (2)144
N2—H22···S1iii0.872.553.409 (2)168
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x+1, y+1/2, z+3/2; (iii) x+2, y+3, z+2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.83 (2)2.05 (2)2.835 (2)157 (2)
N2—H21···O2i0.77 (2)2.13 (2)2.888 (2)169 (2)
N2—H22···O2ii0.91 (2)2.05 (2)2.897 (2)155 (2)
N3—H31···O10.85 (2)2.14 (2)2.893 (2)148 (2)
N3—H32···O1Wiii0.86 (2)2.11 (2)2.904 (2)152 (2)
N4—H42···O1Wiii0.84 (2)2.20 (2)2.954 (2)151 (2)
O1W—H1W···O10.78 (2)2.10 (2)2.874 (2)174 (2)
O1W—H2W···O1iv0.83 (2)2.00 (2)2.821 (2)175 (2)
N4—H41···S10.80 (2)2.41 (2)3.026 (2)135 (2)
N3—H32···S1v0.86 (2)2.86 (2)3.285 (2)112 (2)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y, z1; (iii) x, y1, z; (iv) x+2, y+1, z+1; (v) x, y, z+1.
Currently available data on HATU and its salts - dihedral angles between the planes N1/C2/N3/N4 and N1/C1/N2/S1 (°) top
CompoundAngleReference
HATU at room temperature22.2 (1)(a)
HATU at 100 K19.4 (2)(b)
HATU, ab initio calculations6.2(c)
[HATUH]+ nitrate7.2 (1)(d)
[HATUH]+ phosphonate monohydrate3.7 (1)(d)
[HATUH]+ chloride22.9 (1)(c)
[HATUH]+ bromide15.2 (1)(c)
[HATUH]+ iodide4.2 (1)(c)
[HATUH]+ chlorate(VII)1.4 (1)(e)
[HATUH]+ hydrogen sulfate9.8 (1)(e)
[HATUH]+ dihydrogen phosphate4.4 (1)(e)
[HATUH]+ dihydrogen arsenate2.1 (1)(e)
References: (a) Janczak & Perpétuo (2008a); (b) Hołyńska et al. (2009); (c) Perpétuo & Janczak (2008); (d) Janczak & Perpétuo (2009); (e) Janczak & Perpétuo (2008b).
 

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