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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1656.
Published online 2009 November 21. doi:  10.1107/S1600536809048843
PMCID: PMC2972160

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

Abstract

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 antianti 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 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1656-scheme1.jpg

Experimental

Crystal data

  • (C13H16N2)[NiCl4]
  • M r = 400.79
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1656-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.045
  • S = 1.90
  • 3107 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.45 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

Acknowledgments

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).

supplementary crystallographic information

Comment

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 NiCl42- 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).

Experimental

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.

Refinement

H atoms bonded to C and N atoms were positioned geometrically with C—H distance 0.93–0.97Å and N—H distances of 0.8600 Å, and treated as riding atoms, with Uiso(H)=1.2Ueq(C,N).

Figures

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.

Crystal data

(C13H16N2)[NiCl4]F(000) = 816
Mr = 400.79Dx = 1.592 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3858 reflections
a = 7.2358 (7) Åθ = 2.7–25.6°
b = 20.773 (2) ŵ = 1.79 mm1
c = 11.1246 (11) ÅT = 294 K
β = 90.627 (1)°Block, blue
V = 1672.1 (3) Å30.36 × 0.25 × 0.24 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer3107 independent reflections
Radiation source: fine-focus sealed tube2556 reflections with I > 2σ(I)
graphiteRint = 0.026
[var phi] and ω scansθmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −8→8
Tmin = 0.565, Tmax = 0.673k = −24→25
12584 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.045H-atom parameters constrained
S = 1.90w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3
3107 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = −0.45 e Å3

Special details

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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)

xyzUiso*/Ueq
C10.9569 (3)0.39288 (13)0.4993 (2)0.0604 (7)
H10.99400.43310.52720.073*
C20.7956 (3)0.38678 (11)0.4357 (2)0.0534 (7)
H20.72260.42280.42040.064*
C30.7409 (3)0.32701 (11)0.3941 (2)0.0425 (6)
C40.8519 (3)0.27500 (12)0.4223 (2)0.0546 (7)
H40.81660.23400.39760.066*
C51.0119 (4)0.28295 (13)0.4855 (2)0.0611 (7)
H51.08620.24760.50340.073*
C60.5730 (3)0.31581 (10)0.3173 (2)0.0544 (7)
H6A0.50050.28210.35460.065*
H6B0.61350.29950.24030.065*
C70.4473 (3)0.37229 (10)0.2940 (2)0.0462 (6)
H7A0.51570.40640.25480.055*
H7B0.40190.38880.36970.055*
C80.2851 (3)0.35192 (10)0.2146 (2)0.0472 (6)
H8A0.33400.33560.13970.057*
H8B0.22270.31650.25390.057*
C90.1435 (3)0.40250 (11)0.1848 (2)0.0403 (6)
C10−0.0087 (3)0.38588 (11)0.1149 (2)0.0497 (7)
H10−0.01940.34420.08530.060*
C11−0.1429 (3)0.42979 (12)0.0891 (2)0.0551 (7)
H11−0.24540.41800.04290.066*
C120.0190 (3)0.50868 (12)0.1949 (2)0.0594 (7)
H120.02740.55110.22130.071*
C130.1564 (3)0.46566 (11)0.2227 (2)0.0519 (7)
H130.25890.47910.26730.062*
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)
Cl40.29570 (8)0.16495 (3)0.30041 (6)0.0633 (2)
N11.0614 (3)0.34138 (11)0.52139 (17)0.0574 (6)
H1A1.16410.34620.56010.069*
N2−0.1267 (3)0.48968 (10)0.13015 (19)0.0558 (6)
H2A−0.21300.51700.11430.067*
Ni10.01874 (4)0.129429 (13)0.24398 (3)0.03832 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0602 (19)0.0548 (17)0.066 (2)−0.0016 (15)−0.0134 (15)0.0003 (15)
C20.0527 (17)0.0443 (15)0.0628 (18)0.0060 (12)−0.0155 (14)0.0009 (13)
C30.0421 (15)0.0413 (14)0.0441 (15)0.0019 (11)−0.0031 (12)0.0036 (12)
C40.0569 (17)0.0454 (15)0.0613 (18)0.0086 (13)−0.0117 (14)−0.0033 (14)
C50.0621 (19)0.0602 (19)0.0610 (19)0.0188 (15)−0.0051 (15)0.0026 (16)
C60.0508 (17)0.0451 (15)0.0669 (19)0.0019 (12)−0.0131 (14)0.0016 (14)
C70.0389 (14)0.0463 (14)0.0533 (16)−0.0002 (12)−0.0049 (12)0.0005 (13)
C80.0482 (16)0.0417 (14)0.0515 (16)0.0019 (12)−0.0069 (12)0.0035 (12)
C90.0373 (14)0.0404 (14)0.0433 (15)−0.0034 (11)−0.0009 (11)0.0003 (12)
C100.0482 (16)0.0410 (15)0.0597 (18)−0.0033 (12)−0.0107 (13)−0.0013 (13)
C110.0455 (16)0.0567 (17)0.0627 (19)−0.0034 (14)−0.0103 (13)0.0016 (15)
C120.0577 (18)0.0470 (16)0.073 (2)0.0026 (14)−0.0017 (15)−0.0097 (15)
C130.0435 (15)0.0476 (15)0.0643 (18)−0.0020 (12)−0.0090 (13)−0.0059 (14)
Cl10.0603 (4)0.0411 (4)0.0678 (5)−0.0059 (3)−0.0164 (3)0.0108 (3)
Cl20.0692 (5)0.0397 (4)0.0607 (4)−0.0071 (3)−0.0095 (3)−0.0059 (3)
Cl30.0596 (4)0.0696 (5)0.0525 (4)−0.0197 (3)−0.0093 (3)0.0093 (4)
Cl40.0462 (4)0.0542 (4)0.0892 (5)−0.0103 (3)−0.0145 (4)0.0059 (4)
N10.0438 (14)0.0767 (16)0.0514 (14)0.0044 (12)−0.0110 (11)0.0038 (13)
N20.0462 (14)0.0540 (14)0.0671 (16)0.0139 (11)0.0006 (11)0.0067 (12)
Ni10.03720 (18)0.03082 (16)0.04678 (19)−0.00285 (13)−0.00648 (13)0.00183 (15)

Geometric parameters (Å, °)

C1—N11.332 (3)C8—H8A0.9700
C1—C21.364 (3)C8—H8B0.9700
C1—H10.9300C9—C131.381 (3)
C2—C31.381 (3)C9—C101.385 (3)
C2—H20.9300C10—C111.361 (3)
C3—C41.380 (3)C10—H100.9300
C3—C61.496 (3)C11—N21.330 (3)
C4—C51.358 (3)C11—H110.9300
C4—H40.9300C12—N21.330 (3)
C5—N11.326 (3)C12—C131.370 (3)
C5—H50.9300C12—H120.9300
C6—C71.505 (3)C13—H130.9300
C6—H6A0.9700Cl1—Ni12.2487 (6)
C6—H6B0.9700Cl2—Ni12.2503 (6)
C7—C81.521 (3)Cl3—Ni12.2760 (7)
C7—H7A0.9700Cl4—Ni12.2198 (7)
C7—H7B0.9700N1—H1A0.8600
C8—C91.502 (3)N2—H2A0.8600
N1—C1—C2120.2 (2)C9—C8—H8B108.1
N1—C1—H1119.9C7—C8—H8B108.1
C2—C1—H1119.9H8A—C8—H8B107.3
C1—C2—C3119.8 (2)C13—C9—C10117.3 (2)
C1—C2—H2120.1C13—C9—C8123.6 (2)
C3—C2—H2120.1C10—C9—C8119.1 (2)
C4—C3—C2117.6 (2)C11—C10—C9120.9 (2)
C4—C3—C6118.3 (2)C11—C10—H10119.6
C2—C3—C6124.0 (2)C9—C10—H10119.6
C5—C4—C3120.9 (2)N2—C11—C10119.6 (2)
C5—C4—H4119.6N2—C11—H11120.2
C3—C4—H4119.6C10—C11—H11120.2
N1—C5—C4119.6 (2)N2—C12—C13119.8 (2)
N1—C5—H5120.2N2—C12—H12120.1
C4—C5—H5120.2C13—C12—H12120.1
C3—C6—C7117.56 (19)C12—C13—C9120.3 (2)
C3—C6—H6A107.9C12—C13—H13119.9
C7—C6—H6A107.9C9—C13—H13119.9
C3—C6—H6B107.9C5—N1—C1121.9 (2)
C7—C6—H6B107.9C5—N1—H1A119.1
H6A—C6—H6B107.2C1—N1—H1A119.1
C6—C7—C8110.12 (18)C12—N2—C11122.0 (2)
C6—C7—H7A109.6C12—N2—H2A119.0
C8—C7—H7A109.6C11—N2—H2A119.0
C6—C7—H7B109.6Cl4—Ni1—Cl198.27 (2)
C8—C7—H7B109.6Cl4—Ni1—Cl2142.34 (3)
H7A—C7—H7B108.2Cl1—Ni1—Cl296.59 (3)
C9—C8—C7116.96 (19)Cl4—Ni1—Cl396.98 (3)
C9—C8—H8A108.1Cl1—Ni1—Cl3134.16 (3)
C7—C8—H8A108.1Cl2—Ni1—Cl397.04 (3)
N1—C1—C2—C3−0.1 (4)C7—C8—C9—C10−178.6 (2)
C1—C2—C3—C41.8 (4)C13—C9—C10—C11−2.5 (4)
C1—C2—C3—C6−176.1 (2)C8—C9—C10—C11178.0 (2)
C2—C3—C4—C5−2.0 (4)C9—C10—C11—N20.8 (4)
C6—C3—C4—C5176.0 (2)N2—C12—C13—C9−0.7 (4)
C3—C4—C5—N10.5 (4)C10—C9—C13—C122.4 (4)
C4—C3—C6—C7176.3 (2)C8—C9—C13—C12−178.1 (2)
C2—C3—C6—C7−5.9 (4)C4—C5—N1—C11.3 (4)
C3—C6—C7—C8179.9 (2)C2—C1—N1—C5−1.5 (4)
C6—C7—C8—C9178.7 (2)C13—C12—N2—C11−1.1 (4)
C7—C8—C9—C131.8 (3)C10—C11—N2—C121.0 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.862.433.150 (2)142
N2—H2A···Cl3ii0.862.253.114 (2)178

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BG2307).

References

  • Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kao, Y.-C. & Chen, J.-D. (2004). Struct. Chem. 15, 269–276.
  • Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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