metal-organic compounds
Bis[(1RS,2RS)-4,4′-(1-azaniumyl-2-hydroxyethane-1,2-diyl)dipyridinium] tris[tetrachloridopalladate(II)]
aFacultad de Ingenieria Mochis, Universidad Autonoma de Sinaloa, Fuente Poseidon y Prol. A. Flores S/N, CP 81223, C.U. Los Mochis, Sinaloa, Mexico, bCentro de Investigaciones Quimicas, Universidad Autonoma del Estado de Morelos, Av. Universidad 1001, CP 62210, Cuernavaca, Morelos, Mexico, and cCentro de Graduados del Instituto Tecnologico de Tijuana, Blvd. Industrial S/N, Col. Otay, CP 22500, Tijuana, B.C., Mexico
*Correspondence e-mail: gaxiolajose@yahoo.com.mx
The 12H16N3O)2[PdCl4]3, consists of a 4,4′-(1-azaniumyl-2-hydroxyethane-1,2-diyl)dipyridinium dication and one and a half tetrachloridopalladate(II) anions; the latter has inversion symmetry. In the cation, the pyridinium rings attached to the central 1-azaniumyl-2-hydroxyethane fragment show an anti conformation, as indicated by the central C—C—C—C torsion angle of −178.1 (4)°, and they are inclined to one another by 25.7 (2)°. In the crystal, the cations and anions are linked through N—H⋯Cl and O—H⋯Cl hydrogen bonds. There are also π–π contacts [centroid–centroid distance = 3.788 (3) Å] and a number of C—H⋯O and C—H⋯Cl interactions are present, consolidating the formation of a three-dimensional structure.
of the title compound, (CRelated literature
For potential applications of organic–inorganic hybrid materials with magnetic, optical and electrical properties, see: Yao et al. (2010); Sanchez et al. (2011); Pardo et al. (2011). For related tetrachloridopalladate(II) compounds, see: Kumar et al. (2006); Adams et al. (2005, 2006); Maris (2008). For the synthesis of the ligand, see: Campos-Gaxiola et al. (2012).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536812050817/su2540sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050817/su2540Isup2.hkl
The organic entities in the title compound are the product of partial hydrolysis starting from 2,4,5-tris(pyridin-4-yl)-4,5-dihydro-1,3-oxazole, which was synthesized according to a previously reported procedure (Campos-Gaxiola et al., 2012). For the preparation of the palladium complex, a solution of 2,4,5-tris(pyridin-4-yl)-4,5-dihydro-1,3-oxazole (0.05 g, 0.16 mmol) in methanol and concentrated HCl (37%, 3 ml) was added dropwise to a stirring solution of potassium tetrachloridopalladate (0.05 g, 0.16 mmol) in water (5 ml). The resulting yellow solution was stirred for 30 min at 333 K, whereupon the solution was left to evaporate slowly at room temperature. After two weeks, red crystals were isolated [Yield: 30%]. Spectroscopic and TGA data for the title compound are available in the archived CIF.
C bound H atoms were positioned geometrically and constrained using the riding-model approximation [aryl C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. The N—H and O—H hydrogen atoms were located in difference Fourier maps and were refined with distance restraints: N-H = 0.86 (1) for NH3+ H atoms and 0.84 (1) Å for O—H and pyN-H+ H atoms, with Uiso(H) = 1.2Ueq(O,N).
Hydrogen bond based organic–inorganic hybrid materials are receiving continuous interest because of their structural, magnetic, optical and electrical properties (Yao et al., 2010; Sanchez et al., 2011; Pardo et al., 2011). An interesting approach for the preparation of such materials consists in the utilization of supramolecular synthons containing charge-assisted N+–H···Cl- hydrogen bonds, through which organic cations and anionic metal complexes are linked to form crystalline organic–inorganic hybrid solids (Kumar et al., 2006; Adams et al., 2005,2006; Maris, 2008). As a further contribution we report herein on the
of the title compound.The
of the title compound consists of one threefold charged organic cation in a general position and two independent [PdCl4]2- dianions, one of which is located on a crystallographic inversion center (Fig. 1). In the cation, the pyridinium rings attached to the central 2-ammoniumethanol fragment show an anti conformation, as indicated by the C8—C1—C2—C3 torsion angle of -178.1 (4)°, and form a dihedral angle of 25.7 (2)°. The Pd atoms have square-planar coordination environments with Pd—Cl distances ranging from 2.2760 (10) to 2.3056 (11) Å.In the crystal, the cations and anions are linked by N+—H···Cl- and O—H···Cl- hydrogen bonds (Table 1 and Fig. 2). There are π—π interactions present involving inversion related pyridinium rings [Cg···Cgi distance = 3.788 (3) Å; Cg centroid of the N3,C3-C7 ring; symmetry code (i) -x, -y+2, -z]. There are also a number of C-H···O and C-H···Cl interactions present, consolidating the formation of a three-dimensional structure (Table 1 and Fig. 2).
For potential applications of organic–inorganic hybrid materials with magnetic, optical and electrical properties, see: Yao et al. (2010); Sanchez et al. (2011); Pardo et al. (2011). For related tetrachloridopalladate(II) compounds, see: Kumar et al. (2006); Adams et al. (2005, 2006); Maris (2008). For the synthesis of the ligand, see: Campos-Gaxiola et al. (2012).
Data collection: SMART (Bruker, 2000); cell
SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of the asymmetric unit of the title compound, with the atom-labelling. Displacement ellipsoids are drawn at the 50% probability level. [symmetry code: (i) -x + 1, -y + 2, -z + 1]. | |
Fig. 2. A view along the a axis of the crystal packing of the title compound, with the hydrogen bonds shown as dashed lines (see Table 1 for details). |
(C12H16N3O)2[PdCl4]3 | Z = 1 |
Mr = 1181.16 | F(000) = 576 |
Triclinic, P1 | Dx = 2.166 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6970 (7) Å | Cell parameters from 3544 reflections |
b = 7.7339 (7) Å | θ = 2.7–28.2° |
c = 15.7254 (13) Å | µ = 2.40 mm−1 |
α = 84.541 (2)° | T = 100 K |
β = 81.314 (2)° | Rectangular prism, red |
γ = 78.717 (1)° | 0.29 × 0.22 × 0.17 mm |
V = 905.40 (14) Å3 |
Bruker SMART CCD area-detector diffractometer | 3143 independent reflections |
Radiation source: fine-focus sealed tube | 2927 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
phi and ω scans | θmax = 25.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→7 |
Tmin = 0.543, Tmax = 0.686 | k = −9→9 |
5043 measured reflections | l = −16→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0322P)2 + 2.1607P] where P = (Fo2 + 2Fc2)/3 |
3143 reflections | (Δ/σ)max < 0.001 |
232 parameters | Δρmax = 1.23 e Å−3 |
6 restraints | Δρmin = −0.48 e Å−3 |
(C12H16N3O)2[PdCl4]3 | γ = 78.717 (1)° |
Mr = 1181.16 | V = 905.40 (14) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.6970 (7) Å | Mo Kα radiation |
b = 7.7339 (7) Å | µ = 2.40 mm−1 |
c = 15.7254 (13) Å | T = 100 K |
α = 84.541 (2)° | 0.29 × 0.22 × 0.17 mm |
β = 81.314 (2)° |
Bruker SMART CCD area-detector diffractometer | 3143 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2927 reflections with I > 2σ(I) |
Tmin = 0.543, Tmax = 0.686 | Rint = 0.019 |
5043 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 6 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 1.23 e Å−3 |
3143 reflections | Δρmin = −0.48 e Å−3 |
232 parameters |
Experimental. Spectroscopic and TGA data for the title compound: IR(KBr, cm-1): 3440, 3211, 3064, 2937, 2888, 1669, 1630, 1509, 1421, 1358, 1294, 999, 832. TGA: Calcd. for HCl: 3.08. Found: 3.26% (303–448 K); Calcd. for PdCl2: 15.49. Found: 15.85% (448–523 K). |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.0806 (4) | 0.6561 (4) | 0.14345 (19) | 0.0254 (10) | |
N1 | −0.3332 (5) | 0.8197 (5) | 0.2757 (2) | 0.0243 (12) | |
N2 | 0.1298 (5) | 0.3847 (5) | 0.4127 (2) | 0.0229 (11) | |
N3 | −0.2750 (5) | 1.2478 (5) | 0.0153 (2) | 0.0209 (11) | |
C1 | −0.1380 (6) | 0.8184 (6) | 0.2689 (3) | 0.0240 (12) | |
C2 | −0.0541 (6) | 0.8136 (6) | 0.1750 (3) | 0.0255 (12) | |
C3 | −0.1379 (6) | 0.9732 (6) | 0.1205 (3) | 0.0221 (12) | |
C4 | −0.2352 (6) | 0.9472 (6) | 0.0571 (3) | 0.0269 (14) | |
C5 | −0.3016 (6) | 1.0887 (6) | 0.0040 (3) | 0.0250 (12) | |
C6 | −0.1864 (6) | 1.2805 (6) | 0.0775 (3) | 0.0239 (12) | |
C7 | −0.1160 (6) | 1.1430 (6) | 0.1307 (3) | 0.0219 (12) | |
C8 | −0.0458 (6) | 0.6609 (6) | 0.3204 (3) | 0.0229 (12) | |
C9 | −0.1047 (6) | 0.5003 (6) | 0.3334 (3) | 0.0259 (12) | |
C10 | −0.0142 (6) | 0.3628 (6) | 0.3807 (3) | 0.0233 (12) | |
C11 | 0.1937 (6) | 0.5346 (6) | 0.4001 (3) | 0.0226 (12) | |
C12 | 0.1067 (6) | 0.6767 (6) | 0.3539 (3) | 0.0234 (12) | |
Pd1 | 0.50000 | 1.00000 | 0.50000 | 0.0165 (1) | |
Cl1 | 0.53138 (14) | 0.71363 (13) | 0.46422 (7) | 0.0220 (3) | |
Cl2 | 0.19678 (14) | 1.02190 (13) | 0.52122 (7) | 0.0250 (3) | |
Pd2 | 0.39126 (4) | 0.32273 (4) | 0.19078 (2) | 0.0158 (1) | |
Cl3 | 0.56147 (14) | 0.25575 (14) | 0.30002 (7) | 0.0247 (3) | |
Cl4 | 0.30607 (16) | 0.05224 (14) | 0.21810 (8) | 0.0300 (3) | |
Cl5 | 0.23446 (15) | 0.37787 (13) | 0.07476 (7) | 0.0241 (3) | |
Cl6 | 0.46316 (15) | 0.60016 (13) | 0.16265 (7) | 0.0261 (3) | |
H1 | −0.12040 | 0.92890 | 0.29190 | 0.0290* | |
H1' | 0.014 (4) | 0.584 (5) | 0.130 (3) | 0.0380* | |
H1A | −0.391 (6) | 0.924 (3) | 0.265 (3) | 0.0360* | |
H1B | −0.361 (7) | 0.742 (5) | 0.247 (3) | 0.0360* | |
H1C | −0.374 (7) | 0.788 (7) | 0.3275 (12) | 0.0360* | |
H2 | 0.07710 | 0.81200 | 0.17130 | 0.0300* | |
H2' | 0.175 (6) | 0.299 (4) | 0.444 (3) | 0.0350* | |
H3' | −0.309 (6) | 1.338 (4) | −0.016 (3) | 0.0310* | |
H4 | −0.25600 | 0.83250 | 0.05030 | 0.0320* | |
H5 | −0.36640 | 1.07190 | −0.04050 | 0.0300* | |
H6 | −0.17290 | 1.39760 | 0.08450 | 0.0290* | |
H7 | −0.05210 | 1.16390 | 0.17470 | 0.0260* | |
H9 | −0.20700 | 0.48570 | 0.30960 | 0.0310* | |
H10 | −0.05410 | 0.25300 | 0.39050 | 0.0280* | |
H11 | 0.29880 | 0.54330 | 0.42300 | 0.0280* | |
H12 | 0.15060 | 0.78450 | 0.34500 | 0.0280* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0310 (18) | 0.0191 (15) | 0.0257 (17) | −0.0019 (13) | −0.0048 (14) | −0.0037 (13) |
N1 | 0.023 (2) | 0.025 (2) | 0.022 (2) | 0.0003 (16) | −0.0014 (16) | 0.0011 (16) |
N2 | 0.022 (2) | 0.0226 (19) | 0.0203 (19) | 0.0029 (15) | −0.0056 (15) | 0.0074 (15) |
N3 | 0.0170 (18) | 0.0227 (19) | 0.0197 (19) | −0.0009 (15) | −0.0016 (15) | 0.0078 (15) |
C1 | 0.022 (2) | 0.026 (2) | 0.025 (2) | −0.0060 (18) | −0.0078 (18) | 0.0033 (19) |
C2 | 0.022 (2) | 0.026 (2) | 0.028 (2) | −0.0038 (18) | −0.0023 (19) | −0.0030 (19) |
C3 | 0.022 (2) | 0.025 (2) | 0.019 (2) | −0.0064 (18) | −0.0026 (18) | 0.0042 (18) |
C4 | 0.036 (3) | 0.021 (2) | 0.025 (2) | −0.009 (2) | −0.005 (2) | 0.0004 (18) |
C5 | 0.026 (2) | 0.032 (2) | 0.020 (2) | −0.011 (2) | −0.0088 (19) | 0.0037 (19) |
C6 | 0.029 (2) | 0.022 (2) | 0.021 (2) | −0.0080 (19) | −0.0011 (19) | 0.0007 (18) |
C7 | 0.022 (2) | 0.029 (2) | 0.018 (2) | −0.0110 (18) | −0.0060 (17) | 0.0006 (18) |
C8 | 0.024 (2) | 0.023 (2) | 0.022 (2) | −0.0039 (18) | −0.0070 (18) | 0.0019 (18) |
C9 | 0.029 (2) | 0.023 (2) | 0.028 (2) | −0.0077 (19) | −0.010 (2) | 0.0029 (19) |
C10 | 0.025 (2) | 0.018 (2) | 0.026 (2) | −0.0040 (18) | −0.0014 (19) | −0.0009 (18) |
C11 | 0.018 (2) | 0.030 (2) | 0.019 (2) | −0.0020 (18) | −0.0055 (18) | 0.0026 (18) |
C12 | 0.022 (2) | 0.026 (2) | 0.023 (2) | −0.0082 (18) | −0.0049 (18) | 0.0052 (18) |
Pd1 | 0.0180 (2) | 0.0144 (2) | 0.0185 (2) | −0.0050 (2) | −0.0073 (2) | 0.0038 (2) |
Cl1 | 0.0290 (6) | 0.0162 (5) | 0.0224 (5) | −0.0075 (4) | −0.0071 (4) | 0.0026 (4) |
Cl2 | 0.0193 (5) | 0.0206 (5) | 0.0357 (6) | −0.0063 (4) | −0.0081 (4) | 0.0079 (4) |
Pd2 | 0.0177 (2) | 0.0147 (2) | 0.0151 (2) | −0.0023 (1) | −0.0044 (1) | 0.0000 (1) |
Cl3 | 0.0261 (6) | 0.0283 (5) | 0.0216 (5) | −0.0071 (4) | −0.0102 (4) | 0.0034 (4) |
Cl4 | 0.0375 (6) | 0.0182 (5) | 0.0389 (7) | −0.0095 (5) | −0.0204 (5) | 0.0085 (5) |
Cl5 | 0.0303 (6) | 0.0203 (5) | 0.0245 (5) | −0.0067 (4) | −0.0132 (4) | 0.0031 (4) |
Cl6 | 0.0338 (6) | 0.0204 (5) | 0.0286 (6) | −0.0114 (4) | −0.0137 (5) | 0.0039 (4) |
Pd1—Cl2 | 2.2821 (11) | C1—C8 | 1.514 (7) |
Pd1—Cl1i | 2.2950 (10) | C2—C3 | 1.526 (7) |
Pd1—Cl1 | 2.2950 (10) | C3—C4 | 1.385 (7) |
Pd1—Cl2i | 2.2821 (11) | C3—C7 | 1.383 (6) |
Pd2—Cl4 | 2.2960 (12) | C4—C5 | 1.376 (7) |
Pd2—Cl5 | 2.2985 (12) | C6—C7 | 1.366 (7) |
Pd2—Cl3 | 2.2760 (12) | C8—C9 | 1.391 (7) |
Pd2—Cl6 | 2.3056 (11) | C8—C12 | 1.388 (7) |
O1—C2 | 1.419 (6) | C9—C10 | 1.373 (7) |
O1—H1' | 0.84 (4) | C11—C12 | 1.375 (7) |
N1—C1 | 1.488 (6) | C1—H1 | 1.0000 |
N2—C10 | 1.330 (6) | C2—H2 | 1.0000 |
N2—C11 | 1.332 (6) | C4—H4 | 0.9500 |
N3—C5 | 1.319 (6) | C5—H5 | 0.9500 |
N3—C6 | 1.342 (6) | C6—H6 | 0.9500 |
N1—H1C | 0.86 (2) | C7—H7 | 0.9500 |
N1—H1A | 0.86 (3) | C9—H9 | 0.9500 |
N1—H1B | 0.86 (4) | C10—H10 | 0.9500 |
N2—H2' | 0.84 (4) | C11—H11 | 0.9500 |
N3—H3' | 0.84 (4) | C12—H12 | 0.9500 |
C1—C2 | 1.521 (7) | ||
Cl1i—Pd1—Cl2i | 89.74 (4) | C3—C4—C5 | 119.5 (4) |
Cl1—Pd1—Cl2i | 90.26 (4) | N3—C5—C4 | 119.6 (4) |
Cl1—Pd1—Cl2 | 89.74 (4) | N3—C6—C7 | 119.1 (4) |
Cl1—Pd1—Cl1i | 180.00 | C3—C7—C6 | 120.0 (4) |
Cl1i—Pd1—Cl2 | 90.26 (4) | C1—C8—C9 | 122.8 (4) |
Cl2—Pd1—Cl2i | 180.00 | C9—C8—C12 | 118.9 (4) |
Cl4—Pd2—Cl5 | 89.59 (4) | C1—C8—C12 | 118.3 (4) |
Cl3—Pd2—Cl6 | 92.45 (4) | C8—C9—C10 | 119.6 (4) |
Cl3—Pd2—Cl4 | 89.51 (4) | N2—C10—C9 | 119.4 (4) |
Cl4—Pd2—Cl6 | 177.33 (4) | N2—C11—C12 | 119.7 (4) |
Cl5—Pd2—Cl6 | 88.58 (4) | C8—C12—C11 | 119.3 (4) |
Cl3—Pd2—Cl5 | 176.06 (4) | C8—C1—H1 | 109.00 |
C2—O1—H1' | 114 (3) | N1—C1—H1 | 109.00 |
C10—N2—C11 | 123.0 (4) | C2—C1—H1 | 109.00 |
C5—N3—C6 | 123.1 (4) | C3—C2—H2 | 109.00 |
C1—N1—H1C | 110 (4) | C1—C2—H2 | 109.00 |
C1—N1—H1A | 111 (3) | O1—C2—H2 | 109.00 |
H1A—N1—H1B | 113 (4) | C3—C4—H4 | 120.00 |
C1—N1—H1B | 115 (4) | C5—C4—H4 | 120.00 |
H1B—N1—H1C | 102 (5) | N3—C5—H5 | 120.00 |
H1A—N1—H1C | 106 (5) | C4—C5—H5 | 120.00 |
C10—N2—H2' | 115 (3) | C7—C6—H6 | 120.00 |
C11—N2—H2' | 122 (3) | N3—C6—H6 | 121.00 |
C6—N3—H3' | 113 (3) | C3—C7—H7 | 120.00 |
C5—N3—H3' | 124 (3) | C6—C7—H7 | 120.00 |
N1—C1—C8 | 111.3 (4) | C8—C9—H9 | 120.00 |
C2—C1—C8 | 109.4 (4) | C10—C9—H9 | 120.00 |
N1—C1—C2 | 110.0 (4) | N2—C10—H10 | 120.00 |
O1—C2—C3 | 109.6 (4) | C9—C10—H10 | 120.00 |
O1—C2—C1 | 107.9 (4) | N2—C11—H11 | 120.00 |
C1—C2—C3 | 111.6 (4) | C12—C11—H11 | 120.00 |
C2—C3—C7 | 122.2 (4) | C11—C12—H12 | 120.00 |
C4—C3—C7 | 118.7 (4) | C8—C12—H12 | 120.00 |
C2—C3—C4 | 119.1 (4) | ||
C11—N2—C10—C9 | −1.0 (7) | C1—C2—C3—C4 | −114.2 (5) |
C10—N2—C11—C12 | 1.7 (7) | C1—C2—C3—C7 | 67.6 (6) |
C6—N3—C5—C4 | −0.7 (7) | C2—C3—C4—C5 | −175.9 (4) |
C5—N3—C6—C7 | 1.7 (7) | C7—C3—C4—C5 | 2.4 (7) |
N1—C1—C2—O1 | −61.0 (5) | C2—C3—C7—C6 | 176.8 (4) |
N1—C1—C2—C3 | 59.5 (5) | C4—C3—C7—C6 | −1.4 (7) |
C8—C1—C2—O1 | 61.5 (5) | C3—C4—C5—N3 | −1.4 (7) |
C8—C1—C2—C3 | −178.1 (4) | N3—C6—C7—C3 | −0.6 (7) |
N1—C1—C8—C9 | 30.7 (6) | C1—C8—C9—C10 | 179.9 (4) |
N1—C1—C8—C12 | −151.1 (4) | C12—C8—C9—C10 | 1.7 (7) |
C2—C1—C8—C9 | −91.0 (5) | C1—C8—C12—C11 | −179.3 (4) |
C2—C1—C8—C12 | 87.2 (5) | C9—C8—C12—C11 | −1.0 (7) |
O1—C2—C3—C4 | 5.3 (6) | C8—C9—C10—N2 | −0.7 (7) |
O1—C2—C3—C7 | −172.9 (4) | N2—C11—C12—C8 | −0.6 (7) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1′···Cl5 | 0.84 (4) | 2.22 (4) | 3.047 (3) | 168 (4) |
N1—H1A···Cl3ii | 0.86 (3) | 2.62 (2) | 3.355 (4) | 145 (4) |
N1—H1A···Cl4ii | 0.86 (3) | 2.54 (4) | 3.203 (4) | 135 (4) |
N1—H1B···Cl6iii | 0.86 (4) | 2.49 (5) | 3.310 (4) | 160 (4) |
N1—H1C···Cl1iii | 0.86 (2) | 2.22 (2) | 3.080 (3) | 177 (6) |
N2—H2′···Cl2iv | 0.84 (4) | 2.35 (4) | 3.137 (4) | 157 (4) |
N3—H3′···Cl5v | 0.84 (4) | 2.44 (4) | 3.150 (4) | 143 (4) |
N3—H3′···Cl6v | 0.84 (4) | 2.71 (5) | 3.353 (4) | 135 (3) |
C4—H4···Cl5vi | 0.95 | 2.64 | 3.406 (5) | 139 |
C6—H6···O1vii | 0.95 | 2.54 | 3.454 (6) | 161 |
C9—H9···Cl3iii | 0.95 | 2.78 | 3.599 (5) | 145 |
C10—H10···Cl2viii | 0.95 | 2.75 | 3.649 (5) | 159 |
C11—H11···Cl1 | 0.95 | 2.61 | 3.486 (5) | 154 |
C11—H11···Cl1ix | 0.95 | 2.80 | 3.422 (5) | 124 |
Symmetry codes: (ii) x−1, y+1, z; (iii) x−1, y, z; (iv) x, y−1, z; (v) −x, −y+2, −z; (vi) −x, −y+1, −z; (vii) x, y+1, z; (viii) −x, −y+1, −z+1; (ix) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C12H16N3O)2[PdCl4]3 |
Mr | 1181.16 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.6970 (7), 7.7339 (7), 15.7254 (13) |
α, β, γ (°) | 84.541 (2), 81.314 (2), 78.717 (1) |
V (Å3) | 905.40 (14) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.40 |
Crystal size (mm) | 0.29 × 0.22 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.543, 0.686 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5043, 3143, 2927 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.077, 1.07 |
No. of reflections | 3143 |
No. of parameters | 232 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.23, −0.48 |
Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1'···Cl5 | 0.84 (4) | 2.22 (4) | 3.047 (3) | 168 (4) |
N1—H1A···Cl3i | 0.86 (3) | 2.62 (2) | 3.355 (4) | 145 (4) |
N1—H1A···Cl4i | 0.86 (3) | 2.54 (4) | 3.203 (4) | 135 (4) |
N1—H1B···Cl6ii | 0.86 (4) | 2.49 (5) | 3.310 (4) | 160 (4) |
N1—H1C···Cl1ii | 0.86 (2) | 2.22 (2) | 3.080 (3) | 177 (6) |
N2—H2'···Cl2iii | 0.84 (4) | 2.35 (4) | 3.137 (4) | 157 (4) |
N3—H3'···Cl5iv | 0.84 (4) | 2.44 (4) | 3.150 (4) | 143 (4) |
N3—H3'···Cl6iv | 0.84 (4) | 2.71 (5) | 3.353 (4) | 135 (3) |
C4—H4···Cl5v | 0.95 | 2.64 | 3.406 (5) | 139 |
C6—H6···O1vi | 0.95 | 2.54 | 3.454 (6) | 161 |
C9—H9···Cl3ii | 0.95 | 2.78 | 3.599 (5) | 145 |
C10—H10···Cl2vii | 0.95 | 2.75 | 3.649 (5) | 159 |
C11—H11···Cl1 | 0.95 | 2.61 | 3.486 (5) | 154 |
C11—H11···Cl1viii | 0.95 | 2.80 | 3.422 (5) | 124 |
Symmetry codes: (i) x−1, y+1, z; (ii) x−1, y, z; (iii) x, y−1, z; (iv) −x, −y+2, −z; (v) −x, −y+1, −z; (vi) x, y+1, z; (vii) −x, −y+1, −z+1; (viii) −x+1, −y+1, −z+1. |
Acknowledgements
This work was financially supported by the Universidad Autónoma de Sinaloa (PROFAPI 2012/032).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Hydrogen bond based organic–inorganic hybrid materials are receiving continuous interest because of their structural, magnetic, optical and electrical properties (Yao et al., 2010; Sanchez et al., 2011; Pardo et al., 2011). An interesting approach for the preparation of such materials consists in the utilization of supramolecular synthons containing charge-assisted N+–H···Cl- hydrogen bonds, through which organic cations and anionic metal complexes are linked to form crystalline organic–inorganic hybrid solids (Kumar et al., 2006; Adams et al., 2005,2006; Maris, 2008). As a further contribution we report herein on the crystal structure of the title compound.
The asymmetric unit of the title compound consists of one threefold charged organic cation in a general position and two independent [PdCl4]2- dianions, one of which is located on a crystallographic inversion center (Fig. 1). In the cation, the pyridinium rings attached to the central 2-ammoniumethanol fragment show an anti conformation, as indicated by the C8—C1—C2—C3 torsion angle of -178.1 (4)°, and form a dihedral angle of 25.7 (2)°. The Pd atoms have square-planar coordination environments with Pd—Cl distances ranging from 2.2760 (10) to 2.3056 (11) Å.
In the crystal, the cations and anions are linked by N+—H···Cl- and O—H···Cl- hydrogen bonds (Table 1 and Fig. 2). There are π—π interactions present involving inversion related pyridinium rings [Cg···Cgi distance = 3.788 (3) Å; Cg centroid of the N3,C3-C7 ring; symmetry code (i) -x, -y+2, -z]. There are also a number of C-H···O and C-H···Cl interactions present, consolidating the formation of a three-dimensional structure (Table 1 and Fig. 2).