4,4′-(Propane-1,3-di­yl)dipyridinium tetra­chloridonickelate(II)

Du, Z.-X.; Qu, J.-P.

doi:10.1107/S1600536809048843

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1656

doi:10.1107/S1600536809048843

Open

access

4,4′-(Propane-1,3-diyl)dipyridinium tetrachloridonickelate(II)

Zhong-Xiang Du ^a ^* and Ju-Ping Qu ^b

^aDepartment of Chemistry, Luoyang Normal University, Luoyang, Henan 471022, People's Republic of China, and ^bDepartment of Chemical Engineering and Environmental Engineering, Jiaozuo University, Jiaozuo, Henan 450042, People's Republic of China
^*Correspondence e-mail: dzx6281@126.com

(Received 3 November 2009; accepted 17 November 2009; online 21 November 2009)

The title compound, (C₁₃H₁₆N₂)[NiCl₄] or (H₂bpp)·NiCl₄ [bpp is 1,3-bis(4-pyridyl)propane], is isostructural with its already reported Cu, Zn and Hg analogues. The structure consists of a doubly charged (H₂bpp)²⁺ cation and a tetrahedral [NiCl₄]²⁻ dianion. Both pyridyl N atoms are protonated and form a (H₂bpp)²⁺ cation which adopts an anti–anti conformation with a dihedral angle of 6.287 (7)° between the pyridyl rings. The two pyridyl N atoms are both involved in strong N—H⋯Cl hydrogen bonds, which link both units into a dimer.

Related literature

For the isostructural Cu, Zn and Hg analogues, see: Kao & Chen (2004 ).

Experimental

Crystal data

(C₁₃H₁₆N₂)[NiCl₄]
M_r = 400.79
Monoclinic, P 2₁ /n
a = 7.2358 (7) Å
b = 20.773 (2) Å
c = 11.1246 (11) Å
β = 90.627 (1)°
V = 1672.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.79 mm⁻¹
T = 294 K
0.36 × 0.25 × 0.24 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.565, T_max = 0.673
12584 measured reflections
3107 independent reflections
2556 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.045
S = 1.90
3107 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.86	2.43	3.150 (2)	142
N2—H2A⋯Cl3ⁱⁱ	0.86	2.25	3.114 (2)	178
Symmetry codes: (i) $[x+{\script{3\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048843/bg2307sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048843/bg2307Isup2.hkl

checkCIF report

Comment top

The title complex (I) is isostructural with its analogues (H₂bpp).CuCl₄ and (H₂bpp).MCl₄.H₂O(M = Zn, Hg)(Kao and Chen, 2004), whose structures have been described in detail. The structure consists of a doubly charged (H₂bpp)²⁺ cation and a tetrahedral NiCl₄^2- dianion (Figure 1). Both pyridyl N atoms are protonated and form a (H₂bpp)²⁺ cation, which adopts an anti-anti conformations with a dihedral angle of 6.287° between the two pyridyl rings. The two pyridyl N atoms are both involved in strong N—H···Cl hydrogen bonds (Table 1) and link both units into a dimer (Figure 2).

Related literature top

For the isostructural Cu, Zn and Hg analogues, see: Kao & Chen (2004).

Experimental top

NiCl₂.6H₂O (1.0 mmol, 0.237 g), bpp (1.0 mmol, 0.198 g) and oxydiacetatic acid (1.0 mmol, 0.134 g) were dissolved in 20 ml of methanol-H₂O (v/v, 1:3). Then the mixture was sealed in a 25 mL Teflon reactor and kept under autogeneous pressure at 403 K for 5 days. After cooling to room temperature at a rate of 6°C.h^-1, blue block shaped crystals suitable for X-ray diffraction were grown from the filtrate by slow evaporation. Yield: 200 mg (50% based on Ni). Anal. Calcd for C₁₃H₁₆Cl₄N₂Ni(%): C, 38.92; H, 3.99; N, 6.98. Found: C, 38.85; H, 4.03; N, 6.85. CCDC 752249.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The dimer of (I) formed by N—H···Cl hydrogen bonds showing as dashed lines.

4,4'-(Propane-1,3-diyl)dipyridinium tetrachloridonickelate(II) top

Crystal data top

(C₁₃H₁₆N₂)[NiCl₄]	F(000) = 816
M_r = 400.79	D_x = 1.592 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3858 reflections
a = 7.2358 (7) Å	θ = 2.7–25.6°
b = 20.773 (2) Å	µ = 1.79 mm⁻¹
c = 11.1246 (11) Å	T = 294 K
β = 90.627 (1)°	Block, blue
V = 1672.1 (3) Å³	0.36 × 0.25 × 0.24 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3107 independent reflections
Radiation source: fine-focus sealed tube	2556 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.565, T_max = 0.673	k = −24→25
12584 measured reflections	l = −13→13

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.045	H-atom parameters constrained
S = 1.90	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
3107 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

(C₁₃H₁₆N₂)[NiCl₄]	V = 1672.1 (3) Å³
M_r = 400.79	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2358 (7) Å	µ = 1.79 mm⁻¹
b = 20.773 (2) Å	T = 294 K
c = 11.1246 (11) Å	0.36 × 0.25 × 0.24 mm
β = 90.627 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3107 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2556 reflections with I > 2σ(I)
T_min = 0.565, T_max = 0.673	R_int = 0.026
12584 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.045	H-atom parameters constrained
S = 1.90	Δρ_max = 0.36 e Å⁻³
3107 reflections	Δρ_min = −0.45 e Å⁻³
181 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
C1	0.9569 (3)	0.39288 (13)	0.4993 (2)	0.0604 (7)
H1	0.9940	0.4331	0.5272	0.073*
C2	0.7956 (3)	0.38678 (11)	0.4357 (2)	0.0534 (7)
H2	0.7226	0.4228	0.4204	0.064*
C3	0.7409 (3)	0.32701 (11)	0.3941 (2)	0.0425 (6)
C4	0.8519 (3)	0.27500 (12)	0.4223 (2)	0.0546 (7)
H4	0.8166	0.2340	0.3976	0.066*
C5	1.0119 (4)	0.28295 (13)	0.4855 (2)	0.0611 (7)
H5	1.0862	0.2476	0.5034	0.073*
C6	0.5730 (3)	0.31581 (10)	0.3173 (2)	0.0544 (7)
H6A	0.5005	0.2821	0.3546	0.065*
H6B	0.6135	0.2995	0.2403	0.065*
C7	0.4473 (3)	0.37229 (10)	0.2940 (2)	0.0462 (6)
H7A	0.5157	0.4064	0.2548	0.055*
H7B	0.4019	0.3888	0.3697	0.055*
C8	0.2851 (3)	0.35192 (10)	0.2146 (2)	0.0472 (6)
H8A	0.3340	0.3356	0.1397	0.057*
H8B	0.2227	0.3165	0.2539	0.057*
C9	0.1435 (3)	0.40250 (11)	0.1848 (2)	0.0403 (6)
C10	−0.0087 (3)	0.38588 (11)	0.1149 (2)	0.0497 (7)
H10	−0.0194	0.3442	0.0853	0.060*
C11	−0.1429 (3)	0.42979 (12)	0.0891 (2)	0.0551 (7)
H11	−0.2454	0.4180	0.0429	0.066*
C12	0.0190 (3)	0.50868 (12)	0.1949 (2)	0.0594 (7)
H12	0.0274	0.5511	0.2213	0.071*
C13	0.1564 (3)	0.46566 (11)	0.2227 (2)	0.0519 (7)
H13	0.2589	0.4791	0.2673	0.062*
Cl1	−0.06721 (8)	0.21383 (3)	0.12980 (6)	0.05653 (19)
Cl2	−0.12187 (9)	0.05327 (3)	0.13195 (6)	0.05657 (19)
Cl3	−0.06868 (9)	0.09147 (3)	0.42665 (6)	0.0606 (2)
Cl4	0.29570 (8)	0.16495 (3)	0.30041 (6)	0.0633 (2)
N1	1.0614 (3)	0.34138 (11)	0.52139 (17)	0.0574 (6)
H1A	1.1641	0.3462	0.5601	0.069*
N2	−0.1267 (3)	0.48968 (10)	0.13015 (19)	0.0558 (6)
H2A	−0.2130	0.5170	0.1143	0.067*
Ni1	0.01874 (4)	0.129429 (13)	0.24398 (3)	0.03832 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0602 (19)	0.0548 (17)	0.066 (2)	−0.0016 (15)	−0.0134 (15)	0.0003 (15)
C2	0.0527 (17)	0.0443 (15)	0.0628 (18)	0.0060 (12)	−0.0155 (14)	0.0009 (13)
C3	0.0421 (15)	0.0413 (14)	0.0441 (15)	0.0019 (11)	−0.0031 (12)	0.0036 (12)
C4	0.0569 (17)	0.0454 (15)	0.0613 (18)	0.0086 (13)	−0.0117 (14)	−0.0033 (14)
C5	0.0621 (19)	0.0602 (19)	0.0610 (19)	0.0188 (15)	−0.0051 (15)	0.0026 (16)
C6	0.0508 (17)	0.0451 (15)	0.0669 (19)	0.0019 (12)	−0.0131 (14)	0.0016 (14)
C7	0.0389 (14)	0.0463 (14)	0.0533 (16)	−0.0002 (12)	−0.0049 (12)	0.0005 (13)
C8	0.0482 (16)	0.0417 (14)	0.0515 (16)	0.0019 (12)	−0.0069 (12)	0.0035 (12)
C9	0.0373 (14)	0.0404 (14)	0.0433 (15)	−0.0034 (11)	−0.0009 (11)	0.0003 (12)
C10	0.0482 (16)	0.0410 (15)	0.0597 (18)	−0.0033 (12)	−0.0107 (13)	−0.0013 (13)
C11	0.0455 (16)	0.0567 (17)	0.0627 (19)	−0.0034 (14)	−0.0103 (13)	0.0016 (15)
C12	0.0577 (18)	0.0470 (16)	0.073 (2)	0.0026 (14)	−0.0017 (15)	−0.0097 (15)
C13	0.0435 (15)	0.0476 (15)	0.0643 (18)	−0.0020 (12)	−0.0090 (13)	−0.0059 (14)
Cl1	0.0603 (4)	0.0411 (4)	0.0678 (5)	−0.0059 (3)	−0.0164 (3)	0.0108 (3)
Cl2	0.0692 (5)	0.0397 (4)	0.0607 (4)	−0.0071 (3)	−0.0095 (3)	−0.0059 (3)
Cl3	0.0596 (4)	0.0696 (5)	0.0525 (4)	−0.0197 (3)	−0.0093 (3)	0.0093 (4)
Cl4	0.0462 (4)	0.0542 (4)	0.0892 (5)	−0.0103 (3)	−0.0145 (4)	0.0059 (4)
N1	0.0438 (14)	0.0767 (16)	0.0514 (14)	0.0044 (12)	−0.0110 (11)	0.0038 (13)
N2	0.0462 (14)	0.0540 (14)	0.0671 (16)	0.0139 (11)	0.0006 (11)	0.0067 (12)
Ni1	0.03720 (18)	0.03082 (16)	0.04678 (19)	−0.00285 (13)	−0.00648 (13)	0.00183 (15)

Geometric parameters (Å, º) top

C1—N1	1.332 (3)	C8—H8A	0.9700
C1—C2	1.364 (3)	C8—H8B	0.9700
C1—H1	0.9300	C9—C13	1.381 (3)
C2—C3	1.381 (3)	C9—C10	1.385 (3)
C2—H2	0.9300	C10—C11	1.361 (3)
C3—C4	1.380 (3)	C10—H10	0.9300
C3—C6	1.496 (3)	C11—N2	1.330 (3)
C4—C5	1.358 (3)	C11—H11	0.9300
C4—H4	0.9300	C12—N2	1.330 (3)
C5—N1	1.326 (3)	C12—C13	1.370 (3)
C5—H5	0.9300	C12—H12	0.9300
C6—C7	1.505 (3)	C13—H13	0.9300
C6—H6A	0.9700	Cl1—Ni1	2.2487 (6)
C6—H6B	0.9700	Cl2—Ni1	2.2503 (6)
C7—C8	1.521 (3)	Cl3—Ni1	2.2760 (7)
C7—H7A	0.9700	Cl4—Ni1	2.2198 (7)
C7—H7B	0.9700	N1—H1A	0.8600
C8—C9	1.502 (3)	N2—H2A	0.8600

N1—C1—C2	120.2 (2)	C9—C8—H8B	108.1
N1—C1—H1	119.9	C7—C8—H8B	108.1
C2—C1—H1	119.9	H8A—C8—H8B	107.3
C1—C2—C3	119.8 (2)	C13—C9—C10	117.3 (2)
C1—C2—H2	120.1	C13—C9—C8	123.6 (2)
C3—C2—H2	120.1	C10—C9—C8	119.1 (2)
C4—C3—C2	117.6 (2)	C11—C10—C9	120.9 (2)
C4—C3—C6	118.3 (2)	C11—C10—H10	119.6
C2—C3—C6	124.0 (2)	C9—C10—H10	119.6
C5—C4—C3	120.9 (2)	N2—C11—C10	119.6 (2)
C5—C4—H4	119.6	N2—C11—H11	120.2
C3—C4—H4	119.6	C10—C11—H11	120.2
N1—C5—C4	119.6 (2)	N2—C12—C13	119.8 (2)
N1—C5—H5	120.2	N2—C12—H12	120.1
C4—C5—H5	120.2	C13—C12—H12	120.1
C3—C6—C7	117.56 (19)	C12—C13—C9	120.3 (2)
C3—C6—H6A	107.9	C12—C13—H13	119.9
C7—C6—H6A	107.9	C9—C13—H13	119.9
C3—C6—H6B	107.9	C5—N1—C1	121.9 (2)
C7—C6—H6B	107.9	C5—N1—H1A	119.1
H6A—C6—H6B	107.2	C1—N1—H1A	119.1
C6—C7—C8	110.12 (18)	C12—N2—C11	122.0 (2)
C6—C7—H7A	109.6	C12—N2—H2A	119.0
C8—C7—H7A	109.6	C11—N2—H2A	119.0
C6—C7—H7B	109.6	Cl4—Ni1—Cl1	98.27 (2)
C8—C7—H7B	109.6	Cl4—Ni1—Cl2	142.34 (3)
H7A—C7—H7B	108.2	Cl1—Ni1—Cl2	96.59 (3)
C9—C8—C7	116.96 (19)	Cl4—Ni1—Cl3	96.98 (3)
C9—C8—H8A	108.1	Cl1—Ni1—Cl3	134.16 (3)
C7—C8—H8A	108.1	Cl2—Ni1—Cl3	97.04 (3)

N1—C1—C2—C3	−0.1 (4)	C7—C8—C9—C10	−178.6 (2)
C1—C2—C3—C4	1.8 (4)	C13—C9—C10—C11	−2.5 (4)
C1—C2—C3—C6	−176.1 (2)	C8—C9—C10—C11	178.0 (2)
C2—C3—C4—C5	−2.0 (4)	C9—C10—C11—N2	0.8 (4)
C6—C3—C4—C5	176.0 (2)	N2—C12—C13—C9	−0.7 (4)
C3—C4—C5—N1	0.5 (4)	C10—C9—C13—C12	2.4 (4)
C4—C3—C6—C7	176.3 (2)	C8—C9—C13—C12	−178.1 (2)
C2—C3—C6—C7	−5.9 (4)	C4—C5—N1—C1	1.3 (4)
C3—C6—C7—C8	179.9 (2)	C2—C1—N1—C5	−1.5 (4)
C6—C7—C8—C9	178.7 (2)	C13—C12—N2—C11	−1.1 (4)
C7—C8—C9—C13	1.8 (3)	C10—C11—N2—C12	1.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.86	2.43	3.150 (2)	142
N2—H2A···Cl3ⁱⁱ	0.86	2.25	3.114 (2)	178

Symmetry codes: (i) x+3/2, −y+1/2, z+1/2; (ii) −x−1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	(C₁₃H₁₆N₂)[NiCl₄]
M_r	400.79
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	7.2358 (7), 20.773 (2), 11.1246 (11)
β (°)	90.627 (1)
V (Å³)	1672.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.79
Crystal size (mm)	0.36 × 0.25 × 0.24

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.565, 0.673
No. of measured, independent and observed [I > 2σ(I)] reflections	12584, 3107, 2556
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.045, 1.90
No. of reflections	3107
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.45

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.8600	2.4296	3.150 (2)	141.67
N2—H2A···Cl3ⁱⁱ	0.8600	2.2540	3.114 (2)	177.85

Symmetry codes: (i) x+3/2, −y+1/2, z+1/2; (ii) −x−1/2, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 20471026 and 20331010) and the Natural Science Foundation of Henan province (No. 0311021200).

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kao, Y.-C. & Chen, J.-D. (2004). Struct. Chem. 15, 269–276. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar