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In the crystal structures of 2-amino-5-chloro­pyridinium trichloro­acetate, C5H6ClN2+·C2Cl3O2-, (I), and 2-methyl-5-nitro­anilinium trichloro­acetate monohydrate, C7H9N2O2+·C2Cl3O2-·H2O, (II), the protonated planar 2-amino-5-chloro­pyridinium [in (I)] and 2-methyl-5-nitro­anilinium [in (II)] cations inter­act with the oppositely charged trichloro­acetate anions to form hydrogen-bonded one-dimensional chains in (I) and, together with water mol­ecules, a three-dimensional network in (II). The crystals of (I) exhibit nonlinear optical properties. The second harmonic generation efficiency in relation to potassium dihydrogen phosphate is 0.77. This work demonstrates the usefulness of trichloro­acetic acid in crystal engineering for obtaining new materials for nonlinear optics.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109021490/sk3318sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109021490/sk3318Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109021490/sk3318IIsup3.hkl
Contains datablock II

CCDC references: 742249; 742250

Comment top

The hybrid crystals of base–acid interactions are potentially good materials for exhibiting nonlinear optical properties (Chemla & Zyss, 1987; Marchewka et al. 2003). In these materials, the anion is responsible for favourable chemical and mechanical properties as a result of directional and relatively strong hydrogen-bond interactions, while the organic base, owing to its relatively high hyperpolarizability, is mainly responsible for the nonlinear optical properties (Bhattacharya et al. 1994; Blagden & Seddon, 1999; Głowiak et al. 2001). Continuing our studies on characterization of the acid–base hybrid crystals exhibiting nonlinear properties as well as hydrogen-bond interactions and molecular recognition in the solid-state (Janczak & Perpétuo, 2007; Perpétuo & Janczak, 2007), in the present work we investigate the solid-state structures of two crystals, 2-amino-5-chloropyridinium trichloroacetate, (I), and 2-methyl-5-nitroanilinium trichloroacetate monohydrate, (II).

The asymmetric unit of (I) consists of a 2-amino-5-chloropyridinium cation protonated at the ring N atom and a trichloroacetate anion joined together by two almost linear N—H···O hydrogen bonds (Fig. 1). Oppositely charged hydrogen-bonded C5H6ClN2+ and C2Cl3O2- units related by a c-glide plane interact with one another via an additional pair of symmetry-equivalent N—H···O hydrogen bonds (Table 1) between the amine group of the 2-amino-5-chloropyridinium cation and an O atom of the trichloroacetate anion [N2—H21···O1i; symmetry code: (i) x - 1/2, -y + 1/2, z - 1/2] forming a one-dimensional chain in the [101] direction. The hydrogen-bonded chains related by a translation along the a axis form sheets located parallel to the (010) crystallographic plane at b = 1/2 and 3/4 (Fig. 2). No hydrogen bonds are present between the sheets; they interact only through van der Waals forces. The C—O bond lengths of the COO- group of the trichloroacetate anion are slightly different [C1—O1 = 1.236 (2) Å and C1—O2 = 1.220 (2) Å] and correlate well with the number and the strength of the hydrogen bonds in which they are involved as acceptors. The O atom with the longer C—O bond is involved in two hydrogen bonds and that with the shorter C—O bond in only one hydrogen bond.

The asymmetric unit of (II) consists of a 2-methyl-5-nitroanilinium cation, a trichloroacetate anion and a water molecule joined together via N—H···O hydrogen bonds (Fig. 3). All H atoms of the protonated amine group are involved in N—H···O hydrogen bonds, with the neighbouring trichloroacetate anions and with the water molecule as acceptors. The water molecule, besides the N—H···O(water) hydrogen bond in which it acts as an acceptor, acts also as a donor in two O—H···O hydrogen bonds linking two trichloroacetate anions (Table 2). Hydrogen-bonded aggregates related by an inversion center form a stacking structure along the a axis. The aromatic rings of the 2-methyl-5-nitroanilinium cations are slipped and separated by a distance of 3.408 (3) Å, pointing to a ππ interactions between the rings, since the value is comparable to the sum of the van der Waals radii of the C atoms of the interacting ring systems (Pauling, 1960; Janiak, 2000; Hunter et al. 2001). The oppositely charged 2-methyl-5-nitroanilinium and trichloroacetate units are interconnected via N—H···O hydrogen bonds, together with much weaker C4—H41···Cl1iv [symmetry code: (i) -x + 1, -y + 1, -z + 2] hydrogen bonds, form double chains that are interconnected via hydrogen bonds with water molecules into a three-dimensional network (Fig. 4).

This study illustrates the utility of trichloroacetic acid in crystal engineering for developing supramolecular structures in solids. One of the investigated crystals exhibits nonlinear optical properties. The structures illustrate that weak ππ aromatic interactions between slipped rings modulated by stronger hydrogen bonds play a significant role in assembling of the components of the supramolecular systems. In (I), the components interact via an R22(8) hydrogen-bond motif between the COO- group and the 2-amino-5-chloropyridinium cation, whereas in (II), the O atoms of COO- are involved as acceptors with two 2-methyl-5-nitroanilinium cations. Thus the different topology of the hydrogen-bonding interractions between the components reflects in the dimensionality of the formed hydrogen-bonding networks.

Related literature top

For related literature, see: Bhattacharya et al. (1994); Blagden & Seddon (1999); Hunter et al. (2001); Janczak & Perpétuo (2007); Janiak (2000); Kutz & Perry (1968); Marchewka et al. (2003); Pauling (1960); Perpétuo & Janczak (2007).

Experimental top

Suitable crystals of (I) and (II) were obtained by slow evaporation of a solution of 2-amino-5-chloropyridine or 2-methyl-5-nitroaniline in 5% trichloroacetic acid. An SHG (second harmonic generation) experiment was carried out using the Kutz–Perry powder technique (Kutz & Perry, 1968). Samples of 2-amino-5-chloropyridinium trichloroacetate 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. The SHG efficiency in relation to potassium dihydrogen phosphate KDP is equal to 0.77 [deff = 0.77deff(KDP)].

Refinement top

H atoms involved in hydrogen bonding were located in difference Fourier maps and their positions refined. C-bound H atoms were introduced at calculated positions and refined as riding on their carrier atoms. Uiso(H) values were constrained as 1.5 or 1.2 times Ueq of the carrier atoms.

Computing details top

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction Poland, 2008); cell refinement: CrysAlis RED (Oxford Diffraction Poland, 2008); data reduction: CrysAlis RED (Oxford Diffraction Poland, 2008); 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. A view of the molecular structure of (I), with the atom labelling scheme. Displacement ellipsoids are shown at the 50% probability level and H atoms as spheres of arbitrary radii. Dashed lines indicate N—H···O hydrogen bonds.
[Figure 2] Fig. 2. A view of the crystal packing of (I), showing N—H···O hydrogen-bonded chains.
[Figure 3] Fig. 3. A view of the molecular structure of (II) with the atom-labelling scheme. Displacement ellipsoids are shown at the 50% probability level and H atoms as spheres of arbitrary radii. Dashed lines indicate hydrogen-bond interactions.
[Figure 4] Fig. 4. A view of the hydrogen-bonded three-dimensional network of (II).
(I) 2-amino-5-chloropyridinium trichloroacetate top
Crystal data top
C5H6ClN2+·C2Cl3O2F(000) = 584
Mr = 291.94Dx = 1.738 Mg m3
Dm = 1.73 Mg m3
Dm measured by flotation
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 1217 reflections
a = 5.6426 (11) Åθ = 2.9–29.5°
b = 17.512 (3) ŵ = 1.04 mm1
c = 11.323 (2) ÅT = 295 K
β = 94.36 (1)°Paralellepiped, colourless
V = 1115.6 (4) Å30.32 × 0.24 × 0.16 mm
Z = 4
Data collection top
KUMA KM-4
diffractometer with CCD area detector
2699 independent reflections
Radiation source: fine-focus sealed tube1817 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1θmax = 29.5°, θmin = 2.9°
ω–scanh = 77
Absorption correction: numerical
(CrysAlis RED; Oxford Diffraction Poland, 2008)
k = 2323
Tmin = 0.732, Tmax = 0.851l = 1515
7423 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)] = 0.029H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.047 w = 1/[σ2(Fo2) + (0.018P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2699 reflectionsΔρmax = 0.35 e Å3
145 parametersΔρmin = 0.20 e Å3
2 restraintsAbsolute structure: Flack (1983) , 1226 Friedel-pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.10 (5)
Crystal data top
C5H6ClN2+·C2Cl3O2V = 1115.6 (4) Å3
Mr = 291.94Z = 4
Monoclinic, CcMo Kα radiation
a = 5.6426 (11) ŵ = 1.04 mm1
b = 17.512 (3) ÅT = 295 K
c = 11.323 (2) Å0.32 × 0.24 × 0.16 mm
β = 94.36 (1)°
Data collection top
KUMA KM-4
diffractometer with CCD area detector
2699 independent reflections
Absorption correction: numerical
(CrysAlis RED; Oxford Diffraction Poland, 2008)
1817 reflections with I > 2σ(I)
Tmin = 0.732, Tmax = 0.851Rint = 0.023
7423 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.047Δρmax = 0.35 e Å3
S = 1.00Δρmin = 0.20 e Å3
2699 reflectionsAbsolute structure: Flack (1983) , 1226 Friedel-pairs
145 parametersAbsolute structure parameter: 0.10 (5)
2 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
O10.8197 (3)0.20645 (8)0.43104 (13)0.0379 (3)
O20.8956 (3)0.19674 (9)0.24250 (14)0.0538 (4)
C10.9029 (3)0.17544 (12)0.3453 (2)0.0331 (5)
C21.0399 (3)0.09901 (11)0.37160 (19)0.0332 (5)
Cl10.92493 (11)0.04745 (4)0.48701 (6)0.06049 (19)
Cl21.03526 (11)0.03988 (4)0.24724 (6)0.0648 (2)
Cl31.33706 (11)0.12339 (4)0.41361 (7)0.0659 (2)
Cl40.03208 (11)0.40766 (4)0.55293 (6)0.0687 (2)
C30.3297 (4)0.33705 (12)0.46320 (19)0.0407 (6)
H30.38680.32840.54130.049*
N10.4502 (3)0.31029 (10)0.37330 (17)0.0369 (4)
H10.564 (5)0.2805 (14)0.386 (2)0.055*
C40.3780 (4)0.31981 (12)0.25802 (19)0.0376 (5)
C50.1671 (4)0.36193 (14)0.2344 (2)0.0453 (6)
H50.11080.37130.15640.054*
C60.0477 (4)0.38837 (14)0.3227 (2)0.0481 (6)
H60.09210.41570.30560.058*
C70.1287 (4)0.37587 (13)0.4395 (2)0.0414 (6)
N20.5010 (4)0.29059 (13)0.17702 (18)0.0526 (5)
H210.440 (4)0.2925 (15)0.1043 (9)0.063*
H220.620 (3)0.2601 (11)0.193 (2)0.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0441 (8)0.0385 (8)0.0302 (8)0.0071 (7)0.0030 (7)0.0036 (7)
O20.0758 (10)0.0521 (11)0.0332 (10)0.0147 (9)0.0033 (8)0.0078 (8)
C10.0285 (12)0.0388 (13)0.0310 (13)0.0031 (10)0.0041 (10)0.0007 (11)
C20.0298 (12)0.0371 (12)0.0323 (11)0.0037 (9)0.0009 (9)0.0018 (10)
Cl10.0725 (4)0.0495 (4)0.0617 (4)0.0052 (3)0.0196 (3)0.0202 (3)
Cl20.0858 (5)0.0555 (4)0.0517 (4)0.0141 (4)0.0038 (3)0.0169 (3)
Cl30.0343 (3)0.0683 (5)0.0923 (5)0.0045 (3)0.0133 (3)0.0067 (4)
Cl40.0605 (4)0.0788 (5)0.0696 (5)0.0130 (4)0.0221 (4)0.0065 (4)
C30.0520 (15)0.0392 (13)0.0313 (13)0.0043 (12)0.0045 (11)0.0008 (10)
N10.0429 (12)0.0377 (11)0.0292 (9)0.0070 (9)0.0025 (9)0.0031 (9)
C40.0462 (14)0.0342 (13)0.0306 (13)0.0039 (11)0.0076 (11)0.0038 (10)
C50.0440 (14)0.0477 (14)0.0417 (13)0.0012 (11)0.0120 (12)0.0056 (11)
C60.0337 (14)0.0486 (14)0.0608 (17)0.0041 (12)0.0035 (12)0.0092 (13)
C70.0388 (13)0.0384 (13)0.0471 (15)0.0024 (12)0.0042 (11)0.0032 (12)
N20.0636 (15)0.0665 (15)0.0269 (11)0.0182 (12)0.0024 (11)0.0028 (11)
Geometric parameters (Å, º) top
O1—C11.236 (2)N1—C41.348 (3)
O2—C11.220 (2)N1—H10.83 (3)
C1—C21.563 (3)C4—N21.297 (3)
C2—Cl21.746 (2)C4—C51.409 (3)
C2—Cl11.753 (2)C5—C61.330 (3)
C2—Cl31.761 (2)C5—H50.9300
Cl4—C71.720 (2)C6—C71.383 (3)
C3—C71.332 (3)C6—H60.9300
C3—N11.350 (3)N2—H210.87 (2)
C3—H30.9300N2—H220.87 (2)
O2—C1—O1128.9 (2)N2—C4—N1119.8 (2)
O2—C1—C2115.1 (2)N2—C4—C5124.2 (2)
O1—C1—C2116.0 (2)N1—C4—C5115.9 (2)
C1—C2—Cl2112.15 (15)C6—C5—C4120.6 (2)
C1—C2—Cl1112.20 (15)C6—C5—H5119.7
Cl2—C2—Cl1108.18 (11)C4—C5—H5119.7
C1—C2—Cl3106.91 (14)C5—C6—C7120.9 (2)
Cl2—C2—Cl3108.49 (12)C5—C6—H6119.5
Cl1—C2—Cl3108.80 (12)C7—C6—H6119.5
C7—C3—N1119.7 (2)C3—C7—C6119.2 (2)
C7—C3—H3120.2C3—C7—Cl4120.25 (18)
N1—C3—H3120.2C6—C7—Cl4120.54 (18)
C4—N1—C3123.7 (2)C4—N2—H21117.4 (19)
C4—N1—H1114.7 (18)C4—N2—H22122.8 (16)
C3—N1—H1120.9 (18)H21—N2—H22118 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.83 (2)1.98 (2)2.806 (3)174 (2)
N2—H21···O1i0.87 (2)2.03 (1)2.893 (3)176 (3)
N2—H22···O20.87 (2)1.96 (2)2.821 (3)175 (2)
Symmetry code: (i) x1/2, y+1/2, z1/2.
(II) 2-methyl-5-nitroanilinium trichloroacetate monohydrate top
Crystal data top
C7H9N2O2+·C2Cl3O2·H2OZ = 2
Mr = 333.55F(000) = 340
Triclinic, P1Dx = 1.606 Mg m3
Dm = 1.60 Mg m3
Dm measured by flotation
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9810 (14) ÅCell parameters from 2229 reflections
b = 8.3611 (17) Åθ = 3.3–28.0°
c = 12.229 (2) ŵ = 0.68 mm1
α = 103.74 (1)°T = 295 K
β = 92.29 (1)°Paralellepiped, colourless
γ = 94.77 (1)°0.34 × 0.30 × 0.16 mm
V = 689.6 (2) Å3
Data collection top
KUMA KM-4
diffractometer with CCD area detector
3305 independent reflections
Radiation source: fine-focus sealed tube2306 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1θmax = 28.0°, θmin = 3.3°
ω–scanh = 96
Absorption correction: numerical
(CrysAlis RED; Oxford Diffraction Poland, 2008)
k = 1011
Tmin = 0.811, Tmax = 0.908l = 1516
7531 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)] = 0.058H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.131 w = 1/[σ2(Fo2) + (0.036P)2 + 1.180P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
3305 reflectionsΔρmax = 0.42 e Å3
189 parametersΔρmin = 0.46 e Å3
2 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.368 (12)
Crystal data top
C7H9N2O2+·C2Cl3O2·H2Oγ = 94.77 (1)°
Mr = 333.55V = 689.6 (2) Å3
Triclinic, P1Z = 2
a = 6.9810 (14) ÅMo Kα radiation
b = 8.3611 (17) ŵ = 0.68 mm1
c = 12.229 (2) ÅT = 295 K
α = 103.74 (1)°0.34 × 0.30 × 0.16 mm
β = 92.29 (1)°
Data collection top
KUMA KM-4
diffractometer with CCD area detector
3305 independent reflections
Absorption correction: numerical
(CrysAlis RED; Oxford Diffraction Poland, 2008)
2306 reflections with I > 2σ(I)
Tmin = 0.811, Tmax = 0.908Rint = 0.020
7531 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0582 restraints
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.42 e Å3
3305 reflectionsΔρmin = 0.46 e Å3
189 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
Cl10.09763 (12)0.49673 (11)0.72041 (7)0.0545 (3)
Cl20.14642 (12)0.67926 (12)0.61423 (8)0.0597 (3)
Cl30.13394 (16)0.85225 (13)0.79153 (8)0.0725 (3)
C80.0874 (4)0.6815 (4)0.6751 (3)0.0443 (7)
C90.2460 (4)0.6981 (3)0.5892 (2)0.0409 (6)
O10.2077 (3)0.7828 (3)0.52093 (19)0.0516 (6)
O20.3938 (3)0.6314 (3)0.59792 (19)0.0507 (5)
C10.5921 (4)0.3670 (4)0.7533 (2)0.0411 (6)
C20.6526 (5)0.2370 (4)0.7937 (3)0.0496 (7)
C30.7331 (5)0.2737 (5)0.9034 (3)0.0600 (9)
H30.77250.18840.93320.072*
C40.7561 (5)0.4325 (5)0.9692 (3)0.0625 (10)
H40.81140.45541.04230.075*
C50.6957 (5)0.5566 (4)0.9244 (3)0.0523 (8)
C60.6115 (4)0.5270 (4)0.8161 (3)0.0455 (7)
H60.56990.61240.78720.055*
N10.5078 (4)0.3350 (4)0.6382 (2)0.0452 (6)
H110.471 (6)0.428 (5)0.625 (3)0.068*
H120.406 (6)0.260 (5)0.629 (3)0.068*
H130.595 (6)0.296 (5)0.590 (4)0.068*
C70.6315 (6)0.0630 (5)0.7225 (4)0.0721 (11)
H710.49740.02750.70360.108*
H720.68600.00840.76370.108*
H730.69750.05870.65460.108*
N20.7213 (5)0.7267 (5)0.9930 (3)0.0680 (9)
O30.6749 (6)0.8364 (4)0.9505 (3)0.0991 (11)
O40.7880 (5)0.7511 (4)1.0915 (3)0.0983 (11)
O50.1684 (4)0.1276 (3)0.5972 (3)0.0748 (8)
H510.062 (5)0.156 (5)0.562 (4)0.112*
H520.158 (7)0.0142 (13)0.576 (4)0.112*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0525 (5)0.0609 (5)0.0601 (5)0.0046 (4)0.0063 (4)0.0342 (4)
Cl20.0452 (4)0.0767 (6)0.0653 (6)0.0053 (4)0.0033 (4)0.0344 (5)
Cl30.0869 (7)0.0688 (6)0.0479 (5)0.0117 (5)0.0117 (4)0.0080 (4)
C80.0428 (15)0.0491 (16)0.0424 (16)0.0020 (12)0.0025 (12)0.0156 (13)
C90.0473 (16)0.0383 (14)0.0348 (14)0.0072 (12)0.0046 (12)0.0093 (11)
O10.0624 (14)0.0485 (12)0.0517 (13)0.0043 (10)0.0074 (10)0.0272 (10)
O20.0463 (12)0.0578 (13)0.0528 (13)0.0013 (10)0.0032 (10)0.0240 (11)
C10.0376 (14)0.0490 (16)0.0394 (15)0.0009 (12)0.0046 (11)0.0171 (12)
C20.0447 (16)0.0583 (19)0.0511 (18)0.0012 (14)0.0004 (13)0.0254 (15)
C30.058 (2)0.072 (2)0.058 (2)0.0040 (17)0.0054 (16)0.0353 (19)
C40.0459 (18)0.096 (3)0.0493 (19)0.0014 (18)0.0048 (15)0.029 (2)
C50.0452 (17)0.064 (2)0.0449 (17)0.0050 (14)0.0029 (13)0.0108 (15)
C60.0417 (15)0.0523 (17)0.0447 (16)0.0006 (13)0.0068 (12)0.0170 (13)
N10.0500 (15)0.0469 (15)0.0414 (14)0.0005 (12)0.0049 (11)0.0171 (12)
C70.081 (3)0.059 (2)0.083 (3)0.0110 (19)0.002 (2)0.030 (2)
N20.0630 (19)0.073 (2)0.0567 (19)0.0048 (16)0.0093 (15)0.0035 (16)
O30.142 (3)0.0557 (18)0.089 (2)0.0053 (19)0.005 (2)0.0024 (16)
O40.097 (2)0.111 (3)0.0638 (19)0.0080 (19)0.0163 (17)0.0201 (18)
O50.0735 (18)0.0490 (14)0.099 (2)0.0083 (12)0.0243 (16)0.0224 (14)
Geometric parameters (Å, º) top
Cl1—C81.766 (3)C4—H40.9300
Cl2—C81.763 (3)C5—C61.386 (4)
Cl3—C81.759 (3)C5—N21.462 (5)
C8—C91.576 (4)C6—H60.9300
C9—O21.226 (4)N1—H110.86 (4)
C9—O11.251 (3)N1—H120.88 (4)
C1—C61.368 (4)N1—H130.86 (4)
C1—C21.385 (4)C7—H710.9600
C1—N11.458 (4)C7—H720.9600
C2—C31.387 (5)C7—H730.9600
C2—C71.499 (5)N2—O31.216 (5)
C3—C41.372 (6)N2—O41.238 (4)
C3—H30.9300O5—H510.92 (4)
C4—C51.370 (5)O5—H520.92 (4)
C9—C8—Cl3107.0 (2)C4—C5—N2119.0 (3)
C9—C8—Cl2111.6 (2)C6—C5—N2118.6 (3)
Cl3—C8—Cl2110.00 (17)C1—C6—C5117.3 (3)
C9—C8—Cl1111.1 (2)C1—C6—H6121.4
Cl3—C8—Cl1109.49 (16)C5—C6—H6121.4
Cl2—C8—Cl1107.61 (16)C1—N1—H11110 (2)
O2—C9—O1127.2 (3)C1—N1—H12110 (2)
O2—C9—C8117.4 (2)H11—N1—H12110 (4)
O1—C9—C8115.4 (3)C1—N1—H13110 (3)
C6—C1—C2122.8 (3)H11—N1—H13110 (4)
C6—C1—N1117.7 (3)H12—N1—H13109 (4)
C2—C1—N1119.5 (3)C2—C7—H71109.5
C1—C2—C3117.3 (3)C2—C7—H72109.5
C1—C2—C7121.6 (3)H71—C7—H72109.5
C3—C2—C7121.0 (3)C2—C7—H73109.5
C4—C3—C2121.8 (3)H71—C7—H73109.5
C4—C3—H3119.1H72—C7—H73109.5
C2—C3—H3119.1O3—N2—O4123.5 (4)
C5—C4—C3118.4 (3)O3—N2—C5118.3 (3)
C5—C4—H4120.8O4—N2—C5118.2 (4)
C3—C4—H4120.8H51—O5—H52104 (2)
C4—C5—C6122.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H11···O20.86 (4)1.95 (4)2.810 (4)179 (6)
N1—H12···O50.88 (4)1.90 (4)2.772 (4)169 (4)
N1—H13···O1i0.86 (4)2.04 (4)2.903 (4)177 (4)
N1—H13···O2i0.86 (4)2.52 (4)3.066 (3)122 (3)
O5—H51···O1ii0.92 (4)2.26 (4)3.175 (4)178 (4)
O5—H52···O1iii0.92 (4)1.96 (4)2.851 (4)165 (5)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1; (iii) x, y1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC5H6ClN2+·C2Cl3O2C7H9N2O2+·C2Cl3O2·H2O
Mr291.94333.55
Crystal system, space groupMonoclinic, CcTriclinic, P1
Temperature (K)295295
a, b, c (Å)5.6426 (11), 17.512 (3), 11.323 (2)6.9810 (14), 8.3611 (17), 12.229 (2)
α, β, γ (°)90, 94.36 (1), 90103.74 (1), 92.29 (1), 94.77 (1)
V3)1115.6 (4)689.6 (2)
Z42
Radiation typeMo KαMo Kα
µ (mm1)1.040.68
Crystal size (mm)0.32 × 0.24 × 0.160.34 × 0.30 × 0.16
Data collection
DiffractometerKUMA KM-4
diffractometer with CCD area detector
KUMA KM-4
diffractometer with CCD area detector
Absorption correctionNumerical
(CrysAlis RED; Oxford Diffraction Poland, 2008)
Numerical
(CrysAlis RED; Oxford Diffraction Poland, 2008)
Tmin, Tmax0.732, 0.8510.811, 0.908
No. of measured, independent and
observed [I > 2σ(I)] reflections
7423, 2699, 1817 7531, 3305, 2306
Rint0.0230.020
(sin θ/λ)max1)0.6920.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.047, 1.00 0.058, 0.131, 1.01
No. of reflections26993305
No. of parameters145189
No. of restraints22
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)0.35, 0.200.42, 0.46
Absolute structureFlack (1983) , 1226 Friedel-pairs?
Absolute structure parameter0.10 (5)?

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

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.83 (2)1.98 (2)2.806 (3)174 (2)
N2—H21···O1i0.87 (2)2.03 (1)2.893 (3)176 (3)
N2—H22···O20.87 (2)1.96 (2)2.821 (3)175 (2)
Symmetry code: (i) x1/2, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H11···O20.86 (4)1.95 (4)2.810 (4)179 (6)
N1—H12···O50.88 (4)1.90 (4)2.772 (4)169 (4)
N1—H13···O1i0.86 (4)2.04 (4)2.903 (4)177 (4)
N1—H13···O2i0.86 (4)2.52 (4)3.066 (3)122 (3)
O5—H51···O1ii0.92 (4)2.26 (4)3.175 (4)178 (4)
O5—H52···O1iii0.92 (4)1.96 (4)2.851 (4)165 (5)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1; (iii) x, y1, z.
 

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