Bis(4-chloro­pyridinium) tetra­chlorido­nickelate(II)

Cao, L.; Englert, U.; Li, Q.

doi:10.1107/S1600536808001360

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page m377

doi:10.1107/S1600536808001360

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Bis(4-chloropyridinium) tetrachloridonickelate(II)

Lili Cao,^a Ulli Englert ^b and Qi Li ^a ^*

^aCollege of Chemistry, Beijing Normal University, Xinjiekouwai Street 19, Beijing 100875, People's Republic of China, and ^bInstitut für Anorganische Chemie, RWTH Aachen, Prof.-Pirlet-Strasse 1, 52074 Aachen, Germany
^*Correspondence e-mail: qili@bnu.edu.cn

(Received 7 January 2008; accepted 14 January 2008; online 23 January 2008)

In the title compound, (C₅H₅ClN)₂[NiCl₄], the dianion lies on a twofold rotation axis. Two cations are linked to each anion by classical N—H⋯Cl hydrogen bonds, and short Cl⋯Cl contacts and Cl⋯π stacking interactions [with distances of 3.376 (2) and 3.684 (2) Å, respectively] extend this pattern into a chain. The [NiCl₄]²⁻ anion shows significant deviation from ideal tetrahedral geometry.

Related literature

For related literature, see: Espallargas et al. (2006 ); Luque et al. (2001 ); Willett et al. (2003 ).

Experimental

Crystal data

(C₅H₅ClN)₂[NiCl₄]
M_r = 429.61
Monoclinic, C 2/c
a = 16.513 (2) Å
b = 7.2862 (11) Å
c = 13.948 (2) Å
β = 100.526 (3)°
V = 1650.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 298 (2) K
0.36 × 0.28 × 0.26 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.46, T_max = 0.57
5779 measured reflections
2049 independent reflections
1820 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.123
S = 1.07
2049 reflections
87 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.98 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Cl3	0.93	2.79	3.586 (4)	145
N1—H1⋯Cl2ⁱ	0.86	2.41	3.158 (3)	145
C5—H5A⋯Cl2ⁱⁱ	0.93	2.75	3.633 (4)	159
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001360/at2533sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001360/at2533Isup2.hkl

checkCIF report

Comment top

Short intermolecular X···X (X = F, Cl, Br) interactions in crystals have attracted increasing attention. The title compound is isotypic and probably isomorphous with (4-X'pyH)₂[CoX₄], wherein X' = Cl, X = Cl or X' = Br, X = Cl (Espallargas et al., 2006). Studies by Willett et al. have been devoted to bromopyridinium tetrahalocuprate salts (Willett et al., 2003), and methyl pyridinium derivatives were reported earlier by Luque and his coworkers (Luque et al., 2001). In the structure communicated here, the anionic building block is a [NiCl₄]^2- group with site symmetry 2 and metal–halide distances of 2.2280 (9) and 2.2833 (10) Å and Cl—Ni—Cl bond angles ranging from 98.06 (6) to 115.62 (4)°. The 4-chloropyridinium cation is located in general position and planar within error. A displacement ellipsoid plot of the ionic constituents is given in Fig. 1. Fig. 2 shows the classical hydrogen bonds and the short interhalogen contacts (dashed red lines, Cl···Cl = 3.3762 (16) Å). Shortest interatomic distances between neighbouring cations amount to ca 3.5Å and indicate π interactions. A projection of the unit cell is provided in Fig. 3. The above-mentioned contacts and the classical N—H···Cl bonds result in a chain which extends in [101] direction. Adjacent strands are crosslinked by additional weak non-classical H bonds.

Related literature top

For related literature, see: Espallargas et al. (2006); Luque et al. (2001); Willett et al. (2003).

Experimental top

2.0 mmol NiCl₂.6H₂O (476 mg) were dissolved in ca 10 ml conc hydrochloric acid. 4.0 mmol 4-chloropyridine (600 mg) in 2 ml H₂O were added. The mixture was stirred at room temp for 1 h. After several days of isothermal evaporation, 1.9 mmol, 816 mg of the product were obtained, corresp to yield of 95%.

The product does not melt but decomposes at temperatures above 443 K. At this temperature, pyridine may be sublimed off under vacuum.

Microanalytical data, found: C 27.14, H 2.71, N 6.37%. Calculated for C₁₀H₁₀Cl₆N₂Ni: C 27.96, H2.35, N 6.52%.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Displacement ellipsoid plot (50% probability level) of the cation (left) and anion in the title compound; symmetry code: i = 1 - x, y, 1.5 - z.
	Fig. 2. Closest intermolecular interactions between cations and anions; hydrogen bonds and Cl···Cl contacts are drawn as dashed lines. Symmetry codes: ii = 1 - x, -y, 1 - z; iii = x, -y, z - 1/2; iv = x - 1/2, y + 1/2, z; v = 0.5 - x, 0.5 - y, 1 - z.
	Fig. 3. Packing diagram of the titie compound. Shortest interactions (shown in Fig. 2) extend along [101].

Bis(4-chloropyridinium) tetrachloridonickelate(II) top

Crystal data top

(C₅H₅ClN)₂[NiCl₄]	F(000) = 856
M_r = 429.61	D_x = 1.729 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5779 reflections
a = 16.513 (2) Å	θ = 2.5–28.3°
b = 7.2862 (11) Å	µ = 2.13 mm⁻¹
c = 13.948 (2) Å	T = 298 K
β = 100.526 (3)°	Block, light green
V = 1650.0 (4) Å³	0.36 × 0.28 × 0.26 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2049 independent reflections
Radiation source: fine-focus sealed tube	1820 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 28.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→22
T_min = 0.46, T_max = 0.57	k = −9→9
5779 measured reflections	l = −16→18

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0592P)² + 3.4552P] where P = (F_o² + 2F_c²)/3
2049 reflections	(Δ/σ)_max < 0.001
87 parameters	Δρ_max = 0.80 e Å⁻³
0 restraints	Δρ_min = −0.98 e Å⁻³

Crystal data top

(C₅H₅ClN)₂[NiCl₄]	V = 1650.0 (4) Å³
M_r = 429.61	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.513 (2) Å	µ = 2.13 mm⁻¹
b = 7.2862 (11) Å	T = 298 K
c = 13.948 (2) Å	0.36 × 0.28 × 0.26 mm
β = 100.526 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2049 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1820 reflections with I > 2σ(I)
T_min = 0.46, T_max = 0.57	R_int = 0.026
5779 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.07	Δρ_max = 0.80 e Å⁻³
2049 reflections	Δρ_min = −0.98 e Å⁻³
87 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
Ni1	0.5000	0.04605 (7)	0.7500	0.03657 (17)
Cl1	0.23687 (6)	0.54295 (11)	0.57163 (7)	0.0551 (2)
N1	0.4043 (2)	0.3152 (4)	0.3908 (3)	0.0575 (8)
H1	0.4372	0.2717	0.3553	0.069*
C6	0.3310 (2)	0.3788 (5)	0.3468 (3)	0.0561 (8)
H6A	0.3162	0.3745	0.2792	0.067*
C5	0.2776 (2)	0.4503 (4)	0.4014 (3)	0.0488 (7)
H5A	0.2262	0.4942	0.3719	0.059*
C4	0.30238 (19)	0.4555 (4)	0.5012 (2)	0.0425 (6)
C3	0.3784 (2)	0.3868 (5)	0.5454 (3)	0.0557 (8)
H3A	0.3947	0.3887	0.6129	0.067*
C2	0.4285 (2)	0.3161 (5)	0.4867 (3)	0.0604 (9)
H2A	0.4798	0.2685	0.5141	0.072*
Cl2	0.42552 (5)	−0.15941 (15)	0.64578 (9)	0.0716 (3)
Cl3	0.59081 (7)	0.21312 (15)	0.68764 (8)	0.0692 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0316 (3)	0.0336 (3)	0.0470 (3)	0.000	0.0137 (2)	0.000
Cl1	0.0570 (5)	0.0507 (5)	0.0633 (5)	0.0008 (4)	0.0259 (4)	−0.0050 (3)
N1	0.0537 (17)	0.0489 (15)	0.077 (2)	0.0035 (13)	0.0319 (16)	−0.0008 (14)
C6	0.063 (2)	0.0528 (18)	0.0570 (18)	0.0012 (17)	0.0217 (16)	0.0033 (15)
C5	0.0463 (17)	0.0456 (16)	0.0560 (18)	0.0044 (13)	0.0130 (14)	0.0072 (13)
C4	0.0402 (15)	0.0360 (14)	0.0538 (16)	−0.0028 (11)	0.0146 (13)	−0.0009 (12)
C3	0.0510 (19)	0.0515 (18)	0.062 (2)	0.0024 (15)	0.0026 (16)	0.0000 (16)
C2	0.0416 (17)	0.0540 (19)	0.085 (3)	0.0063 (15)	0.0112 (17)	−0.0002 (18)
Cl2	0.0384 (4)	0.0777 (6)	0.0951 (7)	0.0017 (4)	0.0026 (4)	−0.0373 (6)
Cl3	0.0636 (6)	0.0751 (6)	0.0769 (6)	−0.0151 (5)	0.0337 (5)	0.0112 (5)

Geometric parameters (Å, º) top

Ni1—Cl3	2.2280 (9)	C6—C5	1.368 (5)
Ni1—Cl3ⁱ	2.2280 (9)	C6—H6A	0.9300
Ni1—Cl2	2.2833 (10)	C5—C4	1.379 (5)
Ni1—Cl2ⁱ	2.2833 (10)	C5—H5A	0.9300
Cl1—C4	1.712 (3)	C4—C3	1.387 (5)
N1—C2	1.324 (5)	C3—C2	1.368 (5)
N1—C6	1.336 (5)	C3—H3A	0.9300
N1—H1	0.8600	C2—H2A	0.9300

Cl3—Ni1—Cl3ⁱ	113.76 (6)	C6—C5—C4	118.0 (3)
Cl3—Ni1—Cl2	115.62 (4)	C6—C5—H5A	121.0
Cl3ⁱ—Ni1—Cl2	106.51 (4)	C4—C5—H5A	121.0
Cl3—Ni1—Cl2ⁱ	106.51 (4)	C5—C4—C3	121.1 (3)
Cl3ⁱ—Ni1—Cl2ⁱ	115.62 (4)	C5—C4—Cl1	119.2 (3)
Cl2—Ni1—Cl2ⁱ	98.06 (6)	C3—C4—Cl1	119.6 (3)
C2—N1—C6	122.9 (3)	C2—C3—C4	117.8 (3)
C2—N1—H1	118.5	C2—C3—H3A	121.1
C6—N1—H1	118.5	C4—C3—H3A	121.1
N1—C6—C5	119.9 (3)	N1—C2—C3	120.2 (3)
N1—C6—H6A	120.1	N1—C2—H2A	119.9
C5—C6—H6A	120.1	C3—C2—H2A	119.9

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl3	0.93	2.79	3.586 (4)	145
N1—H1···Cl2ⁱⁱ	0.86	2.41	3.158 (3)	145
C5—H5A···Cl2ⁱⁱⁱ	0.93	2.75	3.633 (4)	159

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

Experimental details

Crystal data
Chemical formula	(C₅H₅ClN)₂[NiCl₄]
M_r	429.61
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	16.513 (2), 7.2862 (11), 13.948 (2)
β (°)	100.526 (3)
V (Å³)	1650.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.13
Crystal size (mm)	0.36 × 0.28 × 0.26

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.46, 0.57
No. of measured, independent and observed [I > 2σ(I)] reflections	5779, 2049, 1820
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.07
No. of reflections	2049
No. of parameters	87
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.98

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 1999), SHELXTL (Sheldrick, 2008), SHELXTL (Bruker, 2000), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl3	0.93	2.786	3.586 (4)	144.8
N1—H1···Cl2ⁱ	0.86	2.413	3.158 (3)	145.2
C5—H5A···Cl2ⁱⁱ	0.93	2.749	3.633 (4)	159.1

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

Acknowledgements

Support from the NSFC (grant No. 20571012) and the NSFBJ (grant No. 2042013) is gratefully acknowledged.

References

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