Bis[(1RS,2RS)-4,4'-(1-aza-niumyl-2-hy-droxy-ethane-1,2-di-yl)dipyridinium] tris-[tetra-chloridopalladate(II)].

The asymmetric unit of the title compound, (C12H16N3O)2[PdCl4]3, consists of a 4,4'-(1-aza-niumyl-2-hy-droxy-ethane-1,2-di-yl)dipyridinium dication and one and a half tetra-chloridopalladate(II) anions; the latter has inversion symmetry. In the cation, the pyridinium rings attached to the central 1-aza-niumyl-2-hy-droxy-ethane 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 inter-actions are present, consolidating the formation of a three-dimensional structure.

Related 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

(C12H16N3O)2[PdCl4]3

M = 1181.16

Triclinic,

a = 7.6970 (7) Å

b = 7.7339 (7) Å

c = 15.7254 (13) Å

α = 84.541 (2)°

β = 81.314 (2)°

γ = 78.717 (1)°

V = 905.40 (14) Å3

Z = 1

Mo Kα radiation

μ = 2.40 mm−1

T = 100 K

0.29 × 0.22 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.543, T max = 0.686

5043 measured reflections

3143 independent reflections

2927 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.077

S = 1.07

3143 reflections

232 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.23 e Å−3

Δρmin = −0.48 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812050817/su2540sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812050817/su2540Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(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

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)

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

Table 1

Hydrogen-bond geometry (Å, °)

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) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .