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Crystals of 2,4,6-triamino-1,3,5-triazine-1,3-dium bis­(trifluoro­acetate) trihydrate, C3H8N62+·2CF3COO-·3H2O, and 2,4,6-triamino-1,3,5-triazine-1,3-dium bis­(trichloro­acetate) dihydrate, C3H8N62+·2CCl3COO-·2H2O, both contain doubly protonated melamine rings that lie on crystallographic twofold axes. In the former structure, one water mol­ecule also lies on a twofold axis. While the trifluoro­acetate compound crystallizes in a centrosymmetric space group, the trichloro­acetate is non-centrosymmetric, so it is useful as a material for non-linear optics. The efficiency of second harmonic generation is about three times greater than that of KDP (KH2PO4). A combination of ionic and donor-acceptor hydrogen-bond inter­actions link the melaminium(2+) residues with trifluoro­acetate or trichloro­acetate ions and water mol­ecules to form a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106015873/fa3013sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106015873/fa3013Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106015873/fa3013IIsup3.hkl
Contains datablock c2

CCDC references: 616127; 616128

Comment top

The present study is a continuation of our investigations into the characterization of the hydrogen-bonding system formed by melamine in the solid state (Perpétuo & Janczak, 2005). Melamine and its derivatives and organic and inorganic complexes or salts can develop well defined non-covalent supramolecular architectures via multiple hydrogen bonds since they contain complementary arrays of hydrogen-bonding sites (Desiraju, 1990; MacDonald & Whitesides, 1994; Row, 1999; Krische & Lehn, 2000; Sherrington & Taskinen, 2001). In order to expand the understanding of the solid-state physical-organic chemistry of compounds that form multiple N—H···N, N—H···O and O—H···O hydrogen-bonding systems, we present here the solid-state structure of melaminium bis(trifluoroacetate) trihydrate, (I), and melaminium bis(trichloroacetate) dihydrate, (II).

Both crystals contain melamine protonated at two of the three ring N atoms (Figs. 1 and 2); the ring has a crystallographic twofold axis, and thus half of the melaminium(2+) ring is independent. The melaminium ring (C3H8N62+) in both crystals is almost planar, but shows significant distortion from an ideal hexagonal form. The internal C—N—C angle at the non-protonated N atom is significantly smaller than the C—N—C angles at the protonated N atoms (Tables 1 amd 3). The differences between the internal C—N—C angles within the melaminium ring residue correlate with the steric effect of the lone-pair electrons and are fully consistent with the valence-shell electron-pair repulsion therory (VSEPR; Gillespie, 1963, 1992). As a result of the protonation of the melamine ring at two of three ring N atoms, the internal N—C—N angle involving only protonated N atoms is significantly smaller than the N—C—N angles involving both protonated and non-protonated N atoms. The ab initio gas-phase geometry calculated for the isolated doubly protonated melaminium(2+) cation shows quite similar correlation between the internal C—N—C and N—C—N angles within the ring (Drozd & Marchewka, 2005). Thus the ring distortions of the protonated melaminium residue result mainly from the protonation and, to a lesser degree, from the hydrogen-bonding system and the crystal packing. Protonation of the melamine ring also modifies the C—N bonds within the ring when compared with the neutral melamine crystal structure (Varghese et al., 1977). The C—N bonds involving the protonated N atom are slightly longer than the other C—N bonds within the ring. Thus there is evidence for a partially localized double-bond form, in which, for example, the bond order of N2—C4 is greater than that of the other N—C (N1—C4 and N1—C3) bonds. Additionally, protonation of the triazine ring of melamine leads to shortening of the C—NH2 bond in relation to the melamine molecule in the solid state (Varghese et al., 1977) as well as in the gas phase (Drozd & Marchewka, 2005). A search of Cambridge Structural Database (Version 5.27; Allen, 2002) for crystals containing a protonated melaminium residue yields over 30 structures, but only six of them contain doubly protonated melaminium(2+) residues; all of these show melaminium ring distortions quite similar to those found here.

The geometry of the trifluoroacetate ion, CF3COO, is different from that of the trichloroacetate ion, CCl3COO. The conformation of the anion in the crystals is well described by the O1—C1—C2—X1 torsion angle [X1 = F2 in (I) and X1 = Cl2 in (II)] and by the C1—C2 bond length. In the trifluoroacetate ion, this torsion angle is −160.0 (1)°, while in the trichloroacetate ion it is −179.0 (1)°, so atoms O1, C1, C2 and Cl2 are almost coplanar. Molecular orbital (MO) calculation using density functional theory and the B3LYP/6–31+G** basis sets (Frisch et al., 1998) performed for the isolated CCl3COO ion shows a minimum on the potential energy surface (PES) for the conformation observed in the crystal (O1—C1—C2—Cl2 = −179.9°), whereas MO calculation for the CF3COO ion shows a minimum on the PES for a more rotated conformation (O1—C1—C2—F2 = −175.2°); thus, in the crystal, the rotation of the COO group in relation to CF3 around the C1—C2 bond results from the hydrogen-bonding interactions. The C1—C2 bond length of 1.531 (3) Å in CF3COO is shorter than that in CCl3COO [1.570 (3) Å]. However, this bond in both crystals is longer than that found in typical acetate crystals, for example melaminium acetate (Janczak & Perpétuo, 2001). The differences between the C1—C2 distances, as well as those between the C—F and C—Cl bond lengths, correlate well with the ionic radii of F and Cl (1.31 Å and 1.81 Å, respectively; Shannon, 1976) and their electronegativity (3.98 and 3.16 for F and Cl, respectively; Pauling, 1967). The lengthening of the C1—C2 bond in relation to the typical acetate ion (CH3COO) results from the repulsion between the negatively charged O atoms and the three Cl or F atoms joined in the α-position in relation to the COO group. This effect is more pronounced in the gas-phase structures obtained by MO calculations, where C1—C2 equals to 1.588 Å in CF3CCO and 1.650 Å in CCl3COO (Frisch et al., 1998). The average C—F and C—Cl bond lengths in the crystal are 1.320 and 1.768 Å, respectively. These values correlate well with the values observed for Csp3—F (1.314–1.332 Å) and for Csp3—Cl (1.761–1.776 Å) (Allen et al., 1987). The C—O bond lengths in the carboxylate group are intermediate between single Csp2—O (1.308–1.320 Å) and double Csp2—O bond values (1.214–1.224 Å; Allen et al. 1987) indicating delocalization of the charge on both O atoms of the COO group.

An extensive set of hydrogen bonds (Tables 2 and 4) links the components of (I) and (II) into a continuous framework superstructure (Figs. 3 and 4). All H atoms of the doubly protonated melaminium residues in both structures form N—H···O hydrogen bonds. In (I), the melaminum residue acts a donor in eight hydrogen bonds with four symmetrically equivalent CF3COO ions and two water (O3) molecules forming two-dimensional layers almost parallel to the (101) plane. The two O atoms of the trifluoroacetate ion act as acceptors in two hydrogen bonds; atom O1 interacts with a water molecule and with the H atom of a protonated N atom of the melaminium ring, while atom O2 links two translationally equivalent melaminium residues via the H atoms of amine groups. The two almost parallel N—H···O hydrogen bonding interactions between the melaminium residues and CF3COO ions are the strongest hydrogen bonds in the structure (Table 2). The water molecules are interconnected via O—H···O hydrogen bonds into chains along the [001] direction. In the chain, the water molecule O4 is surrounded by four water molecules O3, which are related in pairs by the twofold axis upon which atom O4 lies. Each O3 atom is hydrogen bonded to O4 and to another O4 atom related by the inversion center. In conclusion, water molecule O4 has a tetrahedral-like geometry. The chains of water molecules join the melaminium–trifluoroacetate ions into a three-dimensional superstructure (Fig. 3). The melaminium ions are arranged parallel to one another and are separated by ~3.33 Å in the [001] direction.

In (II), each melaminium residue acts as donor in eight N—H···O hydrogen bonds – with four CCl3COO anions related by the twofold axis and by a unit translation along the b axis, and with two symmetrically equivalent water molecules – to form separate but interacting two-dimensional layers almost parallel to the (−401) plane. These layers are separated by ~3.50 Å. Both O atoms of trichloroacetate act as acceptors in two almost linear bifurcated hydrogen bonds (Table 4). Atom O1 is involved in hydrogen bonds with two amine groups of two symmetry-equivalent melaminium cations, while atom O2 accepts hydrogen bonds from the protonated ring N atom and from one water molecule. This same water molecule also takes part in two hydrogen bonds in which it acts as acceptor for an amine group of the melaminium ion and as a donor to Cl (O3—H32···Cl2ii). In both (I) and (II), the non-protonated ring N atom with the lone pair does not form any hydrogen bonds.

The second harmonic generation (SHG) experiment was carried out using the Kurtz–Perry powder technique (Kurtz & Perry, 1968). The calibrated samples (melaminium trichloroacetate and KDP) were irradiated at 1064 nm by an Nd:YAG laser and the second harmonic beam power diffused by the sample (at 532 nm) was measured as a function of the fundamental beam power. SHG efficiency for melaminium bis(trichloroacetate) dihydrate is about three times greater than for KDP [deff ~3deff(KDP)].

Experimental top

Melamine was dissolved in 10% aqueous trifluoroacetic or trichloroacetic acid; after several days, colourless single crystals formed, which proved to be suitable for single-crystal X-ray diffraction analysis.

Computing details top

For both compounds, data collection: KM-4 CCD Software (Kuma, 2002); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990b); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (I), showing displacement ellipsoids at the 50% probability level and H atoms as spheres of arbitrary radii. Hydrogen bonds are drawn as dashed lines.
[Figure 2] Fig. 2. A view of (II), showing displacement ellipsoids at the 50% probability level and H atoms as spheres of arbitrary radii. Hydrogen bonds are drawn as dashed lines.
[Figure 3] Fig. 3. A view of the crystal packing in (I), showing the chain of hydrogen-bonded water molecules that join the hydrogen-bonded melaminium–trifluoroacetate units into a three-dimensional-superstructure.
[Figure 4] Fig. 4. A view of the crystal packing in (II), showing the hydrogen-bonding interactions.
(I) 2,4,6-triamino-1,3,5-triazin-1,3-dium bis(trifluoroacetate) trihydrate top
Crystal data top
C3H8N62+·2C2F3O2·3H2OF(000) = 416
Mr = 408.24Dx = 1.707 Mg m3
Dm = 1.70 Mg m3
Dm measured by flotation
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 1101 reflections
a = 12.442 (3) Åθ = 2.9–28.5°
b = 8.3330 (17) ŵ = 0.19 mm1
c = 7.6600 (15) ÅT = 295 K
β = 90.14 (3)°Parallelepiped, colourless
V = 794.2 (3) Å30.32 × 0.18 × 0.14 mm
Z = 2
Data collection top
KUMA KM-4
diffractometer with CCD detector
2076 independent reflections
Radiation source: fine-focus sealed tube1101 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 33.133 pixels mm-1θmax = 29.5°, θmin = 2.9°
ω scanh = 1616
Absorption correction: analytical
face-indexed (SHELXTL; Sheldrick, 1990b)
k = 1111
Tmin = 0.932, Tmax = 0.981l = 910
9531 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)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105 w = 1/[σ2(Fo2) + (0.0462P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2076 reflectionsΔρmax = 0.30 e Å3
136 parametersΔρmin = 0.20 e Å3
3 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.015 (3)
Crystal data top
C3H8N62+·2C2F3O2·3H2OV = 794.2 (3) Å3
Mr = 408.24Z = 2
Monoclinic, P2/cMo Kα radiation
a = 12.442 (3) ŵ = 0.19 mm1
b = 8.3330 (17) ÅT = 295 K
c = 7.6600 (15) Å0.32 × 0.18 × 0.14 mm
β = 90.14 (3)°
Data collection top
KUMA KM-4
diffractometer with CCD detector
2076 independent reflections
Absorption correction: analytical
face-indexed (SHELXTL; Sheldrick, 1990b)
1101 reflections with I > 2σ(I)
Tmin = 0.932, Tmax = 0.981Rint = 0.023
9531 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0453 restraints
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.30 e Å3
2076 reflectionsΔρmin = 0.20 e Å3
136 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
N30.00000.4856 (2)0.25000.0449 (6)
H30.0535 (15)0.540 (2)0.208 (2)0.054*
C30.00000.3276 (3)0.25000.0369 (6)
N10.08039 (12)0.24452 (16)0.1730 (2)0.0380 (4)
H20.1287 (15)0.292 (2)0.117 (2)0.046*
C40.08051 (13)0.07955 (19)0.1805 (2)0.0344 (4)
N20.00000.0030 (2)0.25000.0377 (5)
N40.16400 (11)0.00395 (16)0.11539 (19)0.0429 (4)
H4A0.16650.09920.11770.051*
H4B0.21610.05760.07040.051*
O20.16287 (10)0.65543 (13)0.08532 (18)0.0559 (4)
O10.23821 (10)0.42017 (14)0.03021 (19)0.0619 (4)
C10.23546 (15)0.5683 (2)0.0370 (2)0.0418 (4)
C20.33896 (16)0.6524 (2)0.0202 (3)0.0570 (5)
F10.40184 (11)0.56597 (17)0.1193 (2)0.0859 (5)
F20.31502 (12)0.78282 (17)0.1163 (2)0.0912 (6)
F30.39624 (12)0.6997 (2)0.11303 (19)0.1099 (7)
O30.36372 (11)0.14220 (15)0.00606 (17)0.0495 (4)
H130.4122 (12)0.144 (3)0.078 (2)0.074*
H230.3543 (17)0.2394 (4)0.012 (3)0.074*
O40.50000.0095 (2)0.25000.0470 (5)
H140.5361 (13)0.0905 (13)0.266 (3)0.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N30.0368 (13)0.0256 (11)0.0722 (16)0.0000.0116 (11)0.000
C30.0352 (14)0.0277 (13)0.0477 (15)0.0000.0001 (12)0.000
N10.0303 (8)0.0287 (8)0.0551 (10)0.0011 (6)0.0064 (7)0.0012 (7)
C40.0315 (10)0.0290 (9)0.0426 (10)0.0008 (8)0.0006 (8)0.0048 (8)
N20.0331 (11)0.0267 (10)0.0533 (13)0.0000.0012 (10)0.000
N40.0374 (9)0.0269 (7)0.0645 (10)0.0006 (6)0.0122 (7)0.0028 (7)
O20.0472 (8)0.0318 (7)0.0888 (10)0.0011 (6)0.0256 (7)0.0005 (6)
O10.0517 (9)0.0270 (7)0.1072 (11)0.0019 (6)0.0264 (8)0.0023 (7)
C10.0412 (11)0.0332 (9)0.0510 (11)0.0016 (9)0.0020 (9)0.0012 (9)
C20.0583 (12)0.0427 (10)0.0699 (12)0.0020 (9)0.0156 (10)0.0115 (9)
F10.0737 (9)0.0732 (9)0.1113 (13)0.0011 (8)0.0521 (9)0.0116 (9)
F20.0885 (11)0.0743 (9)0.1111 (13)0.0054 (8)0.0426 (9)0.0552 (9)
F30.1010 (13)0.1393 (17)0.0894 (10)0.0826 (12)0.0037 (9)0.0046 (10)
O30.0490 (9)0.0414 (7)0.0584 (8)0.0053 (7)0.0156 (6)0.0020 (7)
O40.0455 (12)0.0448 (11)0.0506 (11)0.0000.0048 (9)0.000
Geometric parameters (Å, º) top
N3—C31.317 (3)N4—H4B0.8600
N3—H30.868 (18)O2—C11.217 (2)
C3—N11.3530 (18)O1—C11.236 (2)
C3—N1i1.3530 (18)C1—C21.531 (3)
N1—C41.376 (2)C2—F31.304 (2)
N1—H20.838 (19)C2—F11.308 (2)
C4—N41.314 (2)C2—F21.346 (2)
C4—N21.3278 (18)O3—H130.818 (15)
N2—C4i1.3278 (18)O3—H230.820 (5)
N4—H4A0.8600O4—H140.820 (13)
C3—N3—H3121.5 (13)C4—N4—H4B120.0
N3—C3—N1120.78 (10)H4A—N4—H4B120.0
N3—C3—N1i120.78 (10)O2—C1—O1128.97 (17)
N1—C3—N1i118.4 (2)O2—C1—C2116.08 (15)
C3—N1—C4119.59 (16)O1—C1—C2114.93 (16)
C3—N1—H2120.8 (12)F3—C2—F1107.12 (17)
C4—N1—H2119.5 (13)F3—C2—F2107.66 (17)
N4—C4—N2120.10 (15)F1—C2—F2105.01 (16)
N4—C4—N1117.63 (15)F3—C2—C1111.90 (16)
N2—C4—N1122.27 (16)F1—C2—C1114.77 (15)
C4—N2—C4i117.55 (19)F2—C2—C1109.92 (16)
C4—N4—H4A120.0H13—O3—H2393 (2)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O20.868 (18)1.915 (18)2.7772 (17)172.3 (17)
N1—H2···O10.838 (19)1.86 (2)2.684 (2)169.4 (17)
N4—H4A···O2ii0.862.062.9134 (19)171
N4—H4B···O30.862.052.895 (2)165
O3—H13···O4iii0.82 (2)2.14 (1)2.8250 (16)141 (2)
O3—H23···O10.82 (1)2.11 (1)2.8078 (18)143 (2)
O4—H14···O3iv0.82 (1)2.26 (2)2.8157 (17)126 (2)
O4—H14···F2v0.82 (1)2.42 (2)3.0581 (17)135 (2)
Symmetry codes: (ii) x, y1, z; (iii) x+1, y, z; (iv) x+1, y, z+1/2; (v) x+1, y+1, z.
(II) 2,4,6-triamino-1,3,5-triazin-1,3-dium bis(trichloroacetate) dihydrate top
Crystal data top
C3H8N62+·2C2Cl3O2·2H2OF(000) = 492
Mr = 488.93Dx = 1.784 Mg m3
Dm = 1.78 Mg m3
Dm measured by flotation
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 1456 reflections
a = 17.865 (3) Åθ = 3.4–28.5°
b = 8.465 (2) ŵ = 0.98 mm1
c = 6.117 (1) ÅT = 295 K
β = 100.22 (1)°Paralellepiped, colourless
V = 910.4 (3) Å30.32 × 0.27 × 0.21 mm
Z = 2
Data collection top
KUMA KM-4
diffractometer with CCD detector
2229 independent reflections
Radiation source: fine-focus sealed tube2109 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 33.133 pixels mm-1θmax = 28.5°, θmin = 3.4°
ω scanh = 2323
Absorption correction: analytical
face-indexed, SHELXTL (Sheldrick, 1990b)
k = 1111
Tmin = 0.743, Tmax = 0.814l = 87
6412 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.035 w = 1/[σ2(Fo2) + (0.0313P)2 + 1.7329P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.085(Δ/σ)max = 0.010
S = 1.00Δρmax = 0.61 e Å3
2229 reflectionsΔρmin = 0.66 e Å3
125 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
5 restraintsExtinction coefficient: 0.0089 (10)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack, 1983, 997 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.08 (8)
Crystal data top
C3H8N62+·2C2Cl3O2·2H2OV = 910.4 (3) Å3
Mr = 488.93Z = 2
Monoclinic, C2Mo Kα radiation
a = 17.865 (3) ŵ = 0.98 mm1
b = 8.465 (2) ÅT = 295 K
c = 6.117 (1) Å0.32 × 0.27 × 0.21 mm
β = 100.22 (1)°
Data collection top
KUMA KM-4
diffractometer with CCD detector
2229 independent reflections
Absorption correction: analytical
face-indexed, SHELXTL (Sheldrick, 1990b)
2109 reflections with I > 2σ(I)
Tmin = 0.743, Tmax = 0.814Rint = 0.028
6412 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.085Δρmax = 0.61 e Å3
S = 1.00Δρmin = 0.66 e Å3
2229 reflectionsAbsolute structure: Flack, 1983, 997 Friedel pairs
125 parametersAbsolute structure parameter: 0.08 (8)
5 restraints
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
Cl10.11173 (4)0.25144 (9)0.83577 (11)0.04295 (18)
Cl20.21077 (6)0.01624 (11)0.90741 (16)0.0728 (3)
Cl30.23833 (5)0.23057 (13)0.60373 (16)0.0615 (3)
C20.16740 (15)0.1215 (3)0.7056 (4)0.0332 (5)
C10.11440 (15)0.0389 (3)0.5062 (4)0.0292 (5)
O10.08149 (13)0.1281 (2)0.3610 (3)0.0432 (5)
O20.11062 (15)0.1066 (2)0.5134 (4)0.0502 (6)
C30.00000.7984 (3)0.00000.0232 (6)
N10.03729 (11)0.7166 (2)0.1746 (3)0.0262 (4)
H10.06190.76590.28790.031*
N20.00000.4728 (3)0.00000.0262 (5)
N30.00000.9522 (3)0.00000.0321 (7)
H30.0237 (15)1.001 (3)0.115 (3)0.039*
N40.07323 (13)0.4792 (3)0.3465 (3)0.0368 (5)
H410.07400.37760.34900.044*
H420.09670.53190.45820.044*
C40.03612 (14)0.5540 (3)0.1719 (4)0.0254 (5)
O30.12951 (13)0.6302 (2)0.7636 (4)0.0459 (5)
H310.1363 (17)0.7189 (18)0.717 (6)0.069*
H320.1733 (7)0.597 (4)0.781 (7)0.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0596 (4)0.0338 (3)0.0355 (3)0.0021 (3)0.0086 (3)0.0084 (3)
Cl20.0929 (6)0.0337 (4)0.0676 (5)0.0040 (4)0.0516 (5)0.0019 (4)
Cl30.0454 (4)0.0672 (6)0.0734 (5)0.0188 (4)0.0151 (4)0.0133 (5)
C20.0391 (13)0.0234 (11)0.0322 (12)0.0001 (10)0.0068 (10)0.0020 (10)
C10.0356 (12)0.0253 (10)0.0241 (11)0.0006 (9)0.0017 (9)0.0036 (9)
O10.0619 (12)0.0243 (9)0.0346 (9)0.0026 (9)0.0152 (9)0.0004 (8)
O20.0765 (15)0.0221 (9)0.0398 (11)0.0029 (9)0.0228 (11)0.0029 (8)
C30.0271 (14)0.0177 (13)0.0237 (14)0.0000.0018 (12)0.000
N10.0349 (9)0.0175 (9)0.0227 (9)0.0010 (7)0.0040 (7)0.0013 (7)
N20.0362 (14)0.0187 (12)0.0211 (12)0.0000.0016 (10)0.000
N30.0475 (17)0.0153 (13)0.0289 (15)0.0000.0061 (12)0.000
N40.0540 (13)0.0204 (9)0.0297 (10)0.0032 (10)0.0100 (9)0.0035 (9)
C40.0321 (11)0.0182 (10)0.0247 (11)0.0005 (8)0.0016 (9)0.0031 (8)
O30.0509 (12)0.0324 (10)0.0492 (11)0.0049 (9)0.0050 (10)0.0073 (9)
Geometric parameters (Å, º) top
Cl1—C21.765 (3)N1—H10.8600
Cl2—C21.773 (3)N2—C41.324 (3)
Cl3—C21.768 (3)N2—C4i1.324 (3)
C2—C11.570 (3)N3—H30.86 (2)
C1—O11.233 (3)N4—C41.315 (3)
C1—O21.234 (3)N4—H410.8600
C3—N31.302 (4)N4—H420.8600
C3—N1i1.346 (2)O3—H310.82 (2)
C3—N11.346 (2)O3—H320.82 (2)
N1—C41.377 (3)
C1—C2—Cl1108.53 (17)C3—N1—C4120.0 (2)
C1—C2—Cl3109.27 (18)C3—N1—H1120.0
Cl1—C2—Cl3109.26 (14)C4—N1—H1120.0
C1—C2—Cl2112.14 (18)C4—N2—C4i117.5 (3)
Cl1—C2—Cl2107.91 (14)C3—N3—H3119 (2)
Cl3—C2—Cl2109.68 (15)C4—N4—H41120.0
O1—C1—O2127.9 (3)C4—N4—H42120.0
O1—C1—C2115.6 (2)H41—N4—H42120.0
O2—C1—C2116.5 (2)N4—C4—N2120.0 (2)
N3—C3—N1i120.97 (13)N4—C4—N1117.8 (2)
N3—C3—N1120.97 (13)N2—C4—N1122.2 (2)
N1i—C3—N1118.1 (3)H31—O3—H3299 (3)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2ii0.861.842.700 (3)173
N3—H3···O1ii0.86 (2)1.98 (2)2.841 (2)174 (3)
N4—H41···O10.862.122.977 (3)177
N4—H42···O30.862.032.872 (3)164
O3—H31···O2ii0.82 (2)1.93 (2)2.690 (3)153 (4)
O3—H31···Cl2ii0.82 (2)2.76 (3)3.374 (2)133 (3)
O3—H32···Cl2iii0.82 (2)2.73 (2)3.419 (2)143 (4)
Symmetry codes: (ii) x, y+1, z; (iii) x+1/2, y+1/2, z+2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC3H8N62+·2C2F3O2·3H2OC3H8N62+·2C2Cl3O2·2H2O
Mr408.24488.93
Crystal system, space groupMonoclinic, P2/cMonoclinic, C2
Temperature (K)295295
a, b, c (Å)12.442 (3), 8.3330 (17), 7.6600 (15)17.865 (3), 8.465 (2), 6.117 (1)
β (°) 90.14 (3) 100.22 (1)
V3)794.2 (3)910.4 (3)
Z22
Radiation typeMo KαMo Kα
µ (mm1)0.190.98
Crystal size (mm)0.32 × 0.18 × 0.140.32 × 0.27 × 0.21
Data collection
DiffractometerKUMA KM-4
diffractometer with CCD detector
KUMA KM-4
diffractometer with CCD detector
Absorption correctionAnalytical
face-indexed (SHELXTL; Sheldrick, 1990b)
Analytical
face-indexed, SHELXTL (Sheldrick, 1990b)
Tmin, Tmax0.932, 0.9810.743, 0.814
No. of measured, independent and
observed [I > 2σ(I)] reflections
9531, 2076, 1101 6412, 2229, 2109
Rint0.0230.028
(sin θ/λ)max1)0.6930.671
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.105, 1.00 0.035, 0.085, 1.00
No. of reflections20762229
No. of parameters136125
No. of restraints35
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.30, 0.200.61, 0.66
Absolute structure?Flack, 1983, 997 Friedel pairs
Absolute structure parameter?0.08 (8)

Computer programs: KM-4 CCD Software (Kuma, 2002), KM-4 CCD Software, SHELXS97 (Sheldrick, 1990a), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1990b), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
N3—C31.317 (3)O1—C11.236 (2)
C3—N11.3530 (18)C1—C21.531 (3)
N1—C41.376 (2)C2—F31.304 (2)
C4—N41.314 (2)C2—F11.308 (2)
C4—N21.3278 (18)C2—F21.346 (2)
O2—C11.217 (2)
N1—C3—N1i118.4 (2)C4—N2—C4i117.55 (19)
C3—N1—C4119.59 (16)O2—C1—O1128.97 (17)
N2—C4—N1122.27 (16)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O20.868 (18)1.915 (18)2.7772 (17)172.3 (17)
N1—H2···O10.838 (19)1.86 (2)2.684 (2)169.4 (17)
N4—H4A···O2ii0.862.062.9134 (19)171.2
N4—H4B···O30.862.052.895 (2)165.4
O3—H13···O4iii0.818 (15)2.137 (13)2.8250 (16)141 (2)
O3—H23···O10.820 (5)2.112 (14)2.8078 (18)143 (2)
O4—H14···O3iv0.820 (13)2.260 (18)2.8157 (17)125.5 (19)
O4—H14···F2v0.820 (13)2.424 (17)3.0581 (17)135 (2)
Symmetry codes: (ii) x, y1, z; (iii) x+1, y, z; (iv) x+1, y, z+1/2; (v) x+1, y+1, z.
Selected geometric parameters (Å, º) for (II) top
Cl1—C21.765 (3)C3—N31.302 (4)
Cl2—C21.773 (3)C3—N11.346 (2)
Cl3—C21.768 (3)N1—C41.377 (3)
C2—C11.570 (3)N2—C41.324 (3)
C1—O11.233 (3)N4—C41.315 (3)
C1—O21.234 (3)
O1—C1—O2127.9 (3)C4—N2—C4i117.5 (3)
N1i—C3—N1118.1 (3)N4—C4—N2120.0 (2)
C3—N1—C4120.0 (2)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2ii0.861.842.700 (3)173.2
N3—H3···O1ii0.86 (2)1.98 (2)2.841 (2)174 (3)
N4—H41···O10.862.122.977 (3)177.3
N4—H42···O30.862.032.872 (3)164.2
O3—H31···O2ii0.82 (2)1.934 (16)2.690 (3)153 (4)
O3—H31···Cl2ii0.82 (2)2.76 (3)3.374 (2)133 (3)
O3—H32···Cl2iii0.82 (2)2.73 (2)3.419 (2)143 (4)
Symmetry codes: (ii) x, y+1, z; (iii) x+1/2, y+1/2, z+2.
 

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