2-(4-Pyridinio)benzimidazolium tetra­chloridopalladium(II)

Chen, J.; Wu, S.-F.

doi:10.1107/S1600536808043523

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page m133

doi:10.1107/S1600536808043523

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2-(4-Pyridinio)benzimidazolium tetrachloridopalladium(II)

Jie Chen ^a and Shao-Fan Wu ^b ^*

^aDepartment of Civil Engineering, Fujian University of Technology, Fuzhou, Fujian 350002, People's Republic of China, and ^bFujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China
^*Correspondence e-mail: yq014@163.com

(Received 13 December 2008; accepted 22 December 2008; online 8 January 2009)

The asymmetric unit of the title compound, (C₁₂H₁₁N₃)[PdCl₄], consists of a 2-(4-pyridinio)benzimidazolium cation and two half [PdCl₄]²⁻ anions, which are located on inversion centres. The cations lie in sheets parallel to ( $[\overline{2}]$ 1 $[\overline{2}]$ ). The cations and anions are connected by N—H⋯Cl and C—H⋯Cl contacts.

Related literature

For related structures, see: Alcade et al. (1992 ); Chen et al. (2006 ); Huang et al. (2004 ); Wang et al. (1999 ).

Experimental

Crystal data

(C₁₂H₁₁N₃)[PdCl₄]
M_r = 445.44
Triclinic, $[P \overline 1]$
a = 8.2221 (1) Å
b = 8.3964 (2) Å
c = 12.3768 (5) Å
α = 94.09 (3)°
β = 97.42 (2)°
γ = 116.102 (10)°
V = 752.95 (11) Å³
Z = 2
Mo Kα radiation
μ = 1.93 mm⁻¹
T = 293 (2) K
0.30 × 0.15 × 0.04 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002 ) T_min = 0.713, T_max = 0.916
5851 measured reflections
3406 independent reflections
2816 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.074
S = 1.06
3406 reflections
184 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl4	0.86	2.55	3.207 (3)	134
N2—H2A⋯Cl3ⁱ	0.86	2.32	3.165 (2)	167
N3—H3A⋯Cl1	0.86	2.28	3.138 (3)	172
C5—H5A⋯Cl1ⁱⁱ	0.93	2.64	3.556 (3)	167
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z.

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808043523/bt2834sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043523/bt2834Isup2.hkl

checkCIF report

Comment top

The 2-(4-pyridyl)benzimidazole ligand is often used to act as terminal or bridging ligand in complexes, the noncoordinating N—H and N groups act as hydrogen bond donor or acceptor for the formation of hydrogen bonds, contributing to the crystal packing. Herein we report the synthesis and structure of title complex.

The asymmetry unit of the crystal structure of the title compound comprises one protonated 2-(4-pyridinio)benzimidazolium cation and two independent half [PdCl₄]^2- anion. Each Pd^II atom has a slightly distorted square planar coordination geometry (Fig. 1). The N—H···Cl interactions generate a two-dimensional sheet structure, as show in Fig. 2. The sheets are further connected into a three-dimensional network via C—H···Cl contacts (Fig. 3).

Related literature top

For related literature, see: Alcade et al. (1992); Chen et al. (2006); Huang et al. (2004); Wang et al. (1999). It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···.? etc. Please revise this section as indicated.

Experimental top

An aqueous solution of PdCl₂ 10 ml (0.108 g, 0.61 mmol), 2-(4-pyridyl)benzimidazole (Alcade et al., 1992) (0.12 g, 0.61 mmol) and concentrated HCl (5 ml) was stirred continuously for about 30 min. the solution was allowed to stand at room temperature for several days and produced red crystals of the title compound (yield 85%).

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound with the atomic labels and 30% probability displacement ellipsoids for non-H atoms. Symmetry codes: (i) 2 - x, 2 - y, -z; (ii) -x, -y, 1 - z.
	Fig. 2. Hydrogen bond pattern of (I). The H atoms have been omitted for clarity; hydrogen bonds are shown as dashed lines.
	Fig. 3. The crystal packing of (I), the N—H···Cl interactions are shown as dashed lines.

2-(4-Pyridinio)benzimidazolium tetrachloridopalladium(II) top

Crystal data top

(C₁₂H₁₁N₃)[PdCl₄]	Z = 2
M_r = 445.44	F(000) = 436
Triclinic, P1	D_x = 1.964 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2221 (1) Å	Cell parameters from 1904 reflections
b = 8.3964 (2) Å	θ = 3.3–27.5°
c = 12.3768 (5) Å	µ = 1.93 mm⁻¹
α = 94.09 (3)°	T = 293 K
β = 97.42 (2)°	Prism, red
γ = 116.102 (10)°	0.30 × 0.15 × 0.04 mm
V = 752.95 (11) Å³

Data collection top

Rigaku Mercury CCD diffractometer	3406 independent reflections
Radiation source: fine-focus sealed tube	2816 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	h = −10→10
T_min = 0.713, T_max = 0.916	k = −10→10
5851 measured reflections	l = −16→15

Refinement top

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0306P)² + 0.584P] where P = (F_o² + 2F_c²)/3
3406 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

(C₁₂H₁₁N₃)[PdCl₄]	γ = 116.102 (10)°
M_r = 445.44	V = 752.95 (11) Å³
Triclinic, P1	Z = 2
a = 8.2221 (1) Å	Mo Kα radiation
b = 8.3964 (2) Å	µ = 1.93 mm⁻¹
c = 12.3768 (5) Å	T = 293 K
α = 94.09 (3)°	0.30 × 0.15 × 0.04 mm
β = 97.42 (2)°

Data collection top

Rigaku Mercury CCD diffractometer	3406 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	2816 reflections with I > 2σ(I)
T_min = 0.713, T_max = 0.916	R_int = 0.017
5851 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.06	Δρ_max = 0.81 e Å⁻³
3406 reflections	Δρ_min = −0.61 e Å⁻³
184 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

	x	y	z	U_iso*/U_eq
Pd1	1.0000	1.0000	0.0000	0.02528 (9)
Pd2	0.0000	0.0000	0.5000	0.02595 (9)
C1	0.2054 (5)	0.5925 (5)	0.3660 (3)	0.0415 (8)
H1B	0.1425	0.5664	0.4248	0.050*
C2	0.2983 (5)	0.7664 (4)	0.3483 (3)	0.0367 (7)
H2B	0.2983	0.8586	0.3946	0.044*
C3	0.3925 (4)	0.8040 (4)	0.2610 (2)	0.0281 (6)
C4	0.3862 (5)	0.6625 (4)	0.1924 (3)	0.0389 (8)
H4A	0.4468	0.6845	0.1325	0.047*
C5	0.2904 (5)	0.4902 (4)	0.2129 (3)	0.0390 (8)
H5A	0.2849	0.3947	0.1669	0.047*
C6	0.4975 (4)	0.9893 (4)	0.2438 (2)	0.0269 (6)
C7	0.6195 (4)	1.2852 (4)	0.2627 (3)	0.0318 (7)
C8	0.6740 (5)	1.4663 (4)	0.2955 (3)	0.0428 (8)
H8A	0.6320	1.5050	0.3532	0.051*
C9	0.7928 (5)	1.5835 (5)	0.2379 (4)	0.0519 (10)
H9A	0.8324	1.7056	0.2571	0.062*
C10	0.8567 (5)	1.5272 (5)	0.1519 (4)	0.0523 (10)
H10A	0.9340	1.6124	0.1137	0.063*
C11	0.8097 (5)	1.3500 (5)	0.1212 (3)	0.0428 (8)
H11A	0.8555	1.3130	0.0649	0.051*
C12	0.6896 (4)	1.2291 (4)	0.1793 (3)	0.0326 (7)
N1	0.2050 (4)	0.4609 (4)	0.2996 (2)	0.0376 (6)
H1A	0.1475	0.3527	0.3128	0.045*
N2	0.5007 (3)	1.1324 (3)	0.2995 (2)	0.0299 (6)
H2A	0.4383	1.1300	0.3505	0.036*
N3	0.6107 (4)	1.0441 (3)	0.1709 (2)	0.0305 (6)
H3A	0.6313	0.9751	0.1258	0.037*
Cl1	0.69047 (11)	0.81997 (12)	−0.00991 (7)	0.0429 (2)
Cl2	0.95830 (12)	0.96403 (11)	−0.18905 (6)	0.0393 (2)
Cl3	0.30176 (11)	0.19239 (11)	0.48955 (7)	0.03794 (19)
Cl4	−0.09172 (12)	0.20039 (11)	0.43218 (7)	0.0396 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.02766 (18)	0.02197 (16)	0.02590 (17)	0.01006 (13)	0.00961 (13)	0.00102 (12)
Pd2	0.02897 (18)	0.02667 (17)	0.02514 (17)	0.01380 (14)	0.01011 (13)	0.00409 (13)
C1	0.046 (2)	0.0370 (18)	0.0417 (19)	0.0152 (16)	0.0212 (16)	0.0093 (15)
C2	0.044 (2)	0.0273 (16)	0.0375 (18)	0.0135 (15)	0.0144 (15)	0.0000 (13)
C3	0.0252 (15)	0.0271 (15)	0.0322 (16)	0.0113 (12)	0.0079 (12)	0.0042 (12)
C4	0.041 (2)	0.0327 (17)	0.0446 (19)	0.0152 (15)	0.0205 (16)	0.0054 (15)
C5	0.044 (2)	0.0293 (16)	0.045 (2)	0.0169 (15)	0.0129 (16)	−0.0019 (14)
C6	0.0248 (14)	0.0272 (14)	0.0292 (15)	0.0119 (12)	0.0059 (12)	0.0036 (12)
C7	0.0278 (16)	0.0287 (15)	0.0382 (17)	0.0123 (13)	0.0045 (13)	0.0077 (13)
C8	0.042 (2)	0.0283 (17)	0.059 (2)	0.0178 (15)	0.0087 (17)	0.0022 (16)
C9	0.041 (2)	0.0237 (16)	0.084 (3)	0.0088 (15)	0.008 (2)	0.0118 (18)
C10	0.043 (2)	0.041 (2)	0.071 (3)	0.0129 (18)	0.016 (2)	0.027 (2)
C11	0.0372 (19)	0.045 (2)	0.047 (2)	0.0156 (16)	0.0148 (16)	0.0177 (17)
C12	0.0295 (17)	0.0289 (15)	0.0392 (17)	0.0125 (13)	0.0065 (14)	0.0077 (13)
N1	0.0400 (16)	0.0259 (13)	0.0485 (17)	0.0138 (12)	0.0150 (13)	0.0101 (12)
N2	0.0311 (14)	0.0261 (13)	0.0356 (14)	0.0144 (11)	0.0118 (11)	0.0031 (11)
N3	0.0338 (14)	0.0278 (13)	0.0322 (14)	0.0140 (11)	0.0141 (11)	0.0045 (11)
Cl1	0.0280 (4)	0.0474 (5)	0.0406 (5)	0.0061 (4)	0.0134 (3)	−0.0099 (4)
Cl2	0.0485 (5)	0.0319 (4)	0.0271 (4)	0.0082 (4)	0.0105 (3)	0.0025 (3)
Cl3	0.0306 (4)	0.0347 (4)	0.0446 (5)	0.0098 (3)	0.0157 (4)	−0.0004 (3)
Cl4	0.0478 (5)	0.0428 (4)	0.0433 (5)	0.0293 (4)	0.0193 (4)	0.0180 (4)

Geometric parameters (Å, º) top

Pd1—Cl2	2.2987 (8)	C7—N2	1.380 (4)
Pd1—Cl1	2.2989 (8)	C7—C12	1.394 (4)
Pd2—Cl4	2.2937 (8)	C7—C8	1.395 (4)
Pd2—Cl3	2.3170 (8)	C8—C9	1.366 (5)
C1—N1	1.328 (4)	C8—H8A	0.9300
C1—C2	1.368 (4)	C9—C10	1.387 (6)
C1—H1B	0.9300	C9—H9A	0.9300
C2—C3	1.385 (4)	C10—C11	1.373 (5)
C2—H2B	0.9300	C10—H10A	0.9300
C3—C4	1.388 (4)	C11—C12	1.388 (4)
C3—C6	1.458 (4)	C11—H11A	0.9300
C4—C5	1.371 (5)	C12—N3	1.386 (4)
C4—H4A	0.9300	N1—Cl4	3.207 (3)
C5—N1	1.336 (4)	N1—H1A	0.8600
C5—Cl1ⁱ	3.556 (3)	N2—Cl3ⁱⁱ	3.165 (2)
C5—H5A	0.9300	N2—H2A	0.8600
C6—N2	1.330 (3)	N3—Cl1	3.138 (3)
C6—N3	1.338 (3)	N3—H3A	0.8600

Cl2—Pd1—Cl2ⁱⁱⁱ	180.00 (4)	N2—C6—N3	108.6 (3)
Cl2—Pd1—Cl1	89.78 (4)	N2—C6—C3	125.9 (2)
Cl2ⁱⁱⁱ—Pd1—Cl1	90.22 (4)	N3—C6—C3	125.5 (3)
Cl2—Pd1—Cl1	89.78 (4)	N2—C7—C12	106.6 (3)
Cl2ⁱⁱⁱ—Pd1—Cl1	90.22 (4)	N2—C7—C8	131.9 (3)
Cl1—Pd1—Cl1	0.00 (4)	C12—C7—C8	121.5 (3)
Cl2—Pd1—Cl1ⁱⁱⁱ	90.22 (4)	C9—C8—C7	116.0 (3)
Cl2ⁱⁱⁱ—Pd1—Cl1ⁱⁱⁱ	89.78 (4)	C9—C8—H8A	122.0
Cl1—Pd1—Cl1ⁱⁱⁱ	180.0	C7—C8—H8A	122.0
Cl1—Pd1—Cl1ⁱⁱⁱ	180.0	C8—C9—C10	122.4 (3)
Cl4—Pd2—Cl4	0.00 (7)	C8—C9—H9A	118.8
Cl4—Pd2—Cl4^iv	180.0	C10—C9—H9A	118.8
Cl4—Pd2—Cl4^iv	180.0	C11—C10—C9	122.2 (3)
Cl4—Pd2—Cl3^iv	90.27 (3)	C11—C10—H10A	118.9
Cl4—Pd2—Cl3^iv	90.27 (3)	C9—C10—H10A	118.9
Cl4^iv—Pd2—Cl3^iv	89.73 (3)	C10—C11—C12	116.1 (3)
Cl4—Pd2—Cl3	89.73 (3)	C10—C11—H11A	122.0
Cl4—Pd2—Cl3	89.73 (3)	C12—C11—H11A	122.0
Cl4^iv—Pd2—Cl3	90.27 (3)	N3—C12—C11	132.4 (3)
Cl3^iv—Pd2—Cl3	180.0	N3—C12—C7	105.9 (3)
N1—C1—C2	120.2 (3)	C11—C12—C7	121.7 (3)
N1—C1—H1B	119.9	C1—N1—C5	122.5 (3)
C2—C1—H1B	119.9	C1—N1—Cl4	85.01 (19)
C1—C2—C3	119.5 (3)	C5—N1—Cl4	151.2 (2)
C1—C2—H2B	120.3	C1—N1—H1A	118.7
C3—C2—H2B	120.3	C5—N1—H1A	118.7
C2—C3—C4	118.6 (3)	C6—N2—C7	109.5 (2)
C2—C3—C6	119.9 (3)	C6—N2—Cl3ⁱⁱ	134.59 (18)
C4—C3—C6	121.5 (3)	C7—N2—Cl3ⁱⁱ	115.88 (18)
C5—C4—C3	119.9 (3)	C6—N2—H2A	125.2
C5—C4—H4A	120.0	C7—N2—H2A	125.2
C3—C4—H4A	120.0	C6—N3—C12	109.4 (2)
N1—C5—C4	119.3 (3)	C6—N3—Cl1	130.00 (19)
N1—C5—Cl1ⁱ	129.9 (2)	C12—N3—Cl1	120.44 (18)
C4—C5—Cl1ⁱ	110.8 (2)	C6—N3—H3A	125.3
N1—C5—H5A	120.4	C12—N3—H3A	125.3
C4—C5—H5A	120.4

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+2, −y+2, −z; (iv) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl4	0.86	2.55	3.207 (3)	134
N2—H2A···Cl3ⁱⁱ	0.86	2.32	3.165 (2)	167
N3—H3A···Cl1	0.86	2.28	3.138 (3)	172
C5—H5A···Cl1ⁱ	0.93	2.64	3.556 (3)	167

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₁N₃)[PdCl₄]
M_r	445.44
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.2221 (1), 8.3964 (2), 12.3768 (5)
α, β, γ (°)	94.09 (3), 97.42 (2), 116.102 (10)
V (Å³)	752.95 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.93
Crystal size (mm)	0.30 × 0.15 × 0.04

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2002)
T_min, T_max	0.713, 0.916
No. of measured, independent and observed [I > 2σ(I)] reflections	5851, 3406, 2816
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.074, 1.06
No. of reflections	3406
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.61

Computer programs: CrystalClear (Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006) and SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl4	0.86	2.55	3.207 (3)	134.1
N2—H2A···Cl3ⁱ	0.86	2.32	3.165 (2)	167.2
N3—H3A···Cl1	0.86	2.28	3.138 (3)	172.2
C5—H5A···Cl1ⁱⁱ	0.93	2.64	3.556 (3)	167.1

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z.

Acknowledgements

We gratefully acknowledge financial support by the Key Science and Technology Project of Fujian Province (No. 2005H045)

References

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