2,2′-(Butane-1,4-di­yl)diisoquinolinium tetra­chloridozincate(II)

Fan, Z.-F.; Xiao, X.; Zhang, Y.-Q.; Xue, S.-F.; Tao, Z.

doi:10.1107/S1600536808038932

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1620

doi:10.1107/S1600536808038932

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2,2′-(Butane-1,4-diyl)diisoquinolinium tetrachloridozincate(II)

Zhi-Fang Fan,^a Xin Xiao,^a Yun-Qian Zhang,^a Sai-Feng Xue ^a ^* and Zhu Tao ^b

^aKey Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, People's Republic of China, and ^bInstitute of Applied Chemistry, Guizhou University, Guiyang 550025, People's Republic of China
^*Correspondence e-mail: gyhxxiaoxin@163.com

(Received 29 October 2008; accepted 20 November 2008; online 26 November 2008)

The crystal of the title compound, (C₂₂H₂₂N₂)[ZnCl₄], consists of 2,2′-(butane-1,4-diyl)diisoquinolinium organic cations and [ZnCl₄]²⁻ complex anions. The cation is located across a twofold axis and the Zn^II atom of the anion is located on the other twofold axis. The centroid–centroid distance between parallel pyridine rings of neighboring molecules is 3.699 (3) Å, but the face-to-face separation of 3.601 (3) Å suggests there is no significant π–π stacking in the crystal structure.

Related literature

For general background, see: Day & Arnold (2000 ); Day et al. (2002 ); Freeman et al. (1981 ); Kim et al. (2000 ). For a related structure, see: Pan & Xu (2004 ).

Experimental

Crystal data

(C₂₂H₂₂N₂)[ZnCl₄]
M_r = 521.61
Monoclinic, C 2/c
a = 10.729 (3) Å
b = 11.040 (3) Å
c = 18.955 (4) Å
β = 99.179 (9)°
V = 2216.4 (10) Å³
Z = 4
Mo Kα radiation
μ = 1.60 mm⁻¹
T = 273 (2) K
0.23 × 0.19 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.680, T_max = 0.760
12088 measured reflections
2172 independent reflections
1855 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.206
S = 1.13
2172 reflections
132 parameters
H-atom parameters constrained
Δρ_max = 1.28 e Å⁻³
Δρ_min = −1.15 e Å⁻³

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038932/xu2462sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038932/xu2462Isup2.hkl

checkCIF report

Comment top

As part of our ongoing investigation on quinoline compounds, we present here the crystal structure of the compound with multiple functional groups, which can develop strong intermolecular interactions with cucurbit[n]urils (CB[n]) (Freeman et al., 1981; Day & Arnold, 2000; Day et al., 2002; Kim et al., 2000).

The crystal structure of the title compound (Fig. 1) consists of organic cations and anionic (ZnCl₄)^2- complexes. The (ZnCl₄)^2- anion assumes a distorted tetrahedron coordination geometry with Zn–Cl bond distances of 2.3043 (14) Å and 2.3158 (12) Å. The centroids distance between parallel pyridine rings of neighboring molecules is 3.699 (3) Å, but the face-to-face separation of 3.601 (3) Å suggests no significant π-π stacking in the crystal structure (Pan & Xu, 2004).

Related literature top

For general background, see: Day & Arnold (2000); Day et al. (2002); Freeman et al. (1981); Kim et al. (2000). For a related structure, see: Pan & Xu (2004).

Experimental top

A solution of 1,4-dibromine-butane (2.16 g, 0.01 mol) was added to a stirred solution of isoquinoline (2.58 g, 0.02 mol) in 1,4-dioxane (50 ml) at 373 K in a period of 5 h. After cooling to room temperature, the mixture was filtered. The residue was added to an aqueous solution (50 ml) of ZnCl₂ (0.01 mol, 1.37 g). After stirring for 2 h, the solution was filtered. Colorless single crystals of the title compound were obtained from the filtrate after 5 weeks.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (a) -x, y, 3/2-z; (b) -x, y, 1/2-z].

2,2'-(Butane-1,4-diyl)diisoquinolinium tetrachloridozincate(II) top

Crystal data top

(C₂₂H₂₂N₂)[ZnCl₄]	F(000) = 1064
M_r = 521.61	D_x = 1.563 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2184 reflections
a = 10.729 (3) Å	θ = 2.2–26.0°
b = 11.040 (3) Å	µ = 1.60 mm⁻¹
c = 18.955 (4) Å	T = 273 K
β = 99.179 (9)°	Prism, colorless
V = 2216.4 (10) Å³	0.23 × 0.19 × 0.17 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2172 independent reflections
Radiation source: fine-focus sealed tube	1855 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→13
T_min = 0.680, T_max = 0.760	k = −13→13
12088 measured reflections	l = −23→21

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.206	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.1169P)² + 12.0521P] where P = (F_o² + 2F_c²)/3
2172 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 1.28 e Å⁻³
0 restraints	Δρ_min = −1.15 e Å⁻³

Crystal data top

(C₂₂H₂₂N₂)[ZnCl₄]	V = 2216.4 (10) Å³
M_r = 521.61	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 10.729 (3) Å	µ = 1.60 mm⁻¹
b = 11.040 (3) Å	T = 273 K
c = 18.955 (4) Å	0.23 × 0.19 × 0.17 mm
β = 99.179 (9)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2172 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1855 reflections with I > 2σ(I)
T_min = 0.680, T_max = 0.760	R_int = 0.032
12088 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.206	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.1169P)² + 12.0521P] where P = (F_o² + 2F_c²)/3
2172 reflections	Δρ_max = 1.28 e Å⁻³
132 parameters	Δρ_min = −1.15 e Å⁻³

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
Zn1	0.0000	0.15361 (8)	0.2500	0.0412 (3)
Cl2	0.12762 (10)	0.03371 (11)	0.19106 (6)	0.0349 (4)
Cl1	0.12438 (13)	0.27560 (13)	0.33123 (8)	0.0483 (4)
N1	0.4868 (4)	0.1136 (4)	0.3832 (2)	0.0416 (10)
C11	0.4355 (5)	0.1981 (5)	0.2617 (3)	0.0449 (13)
H11A	0.4248	0.2744	0.2854	0.054*
H11B	0.3715	0.1945	0.2193	0.054*
C3	0.6202 (6)	0.1461 (5)	0.5206 (3)	0.0439 (13)
C9	0.5975 (6)	0.0584 (5)	0.4013 (3)	0.0442 (13)
H9	0.6286	0.0098	0.3680	0.053*
C10	0.4120 (6)	0.0967 (6)	0.3108 (3)	0.0463 (13)
H10A	0.3228	0.0938	0.3143	0.056*
H10B	0.4347	0.0203	0.2910	0.056*
C1	0.4382 (6)	0.1876 (6)	0.4311 (3)	0.0528 (15)
H1	0.3614	0.2265	0.4171	0.063*
C8	0.6687 (5)	0.0723 (5)	0.4702 (3)	0.0415 (12)
C6	0.8489 (7)	0.0222 (6)	0.5569 (4)	0.0583 (16)
H6	0.9255	−0.0177	0.5700	0.070*
C7	0.7856 (6)	0.0107 (6)	0.4893 (3)	0.0533 (15)
H7	0.8182	−0.0368	0.4560	0.064*
C5	0.7995 (7)	0.0947 (6)	0.6080 (3)	0.0581 (17)
H5	0.8434	0.1003	0.6543	0.070*
C4	0.6894 (7)	0.1560 (6)	0.5902 (3)	0.0524 (15)
H4	0.6594	0.2046	0.6239	0.063*
C2	0.5011 (7)	0.2039 (6)	0.4980 (3)	0.0542 (15)
H2	0.4668	0.2532	0.5297	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0383 (5)	0.0406 (6)	0.0448 (6)	0.000	0.0074 (4)	0.000
Cl2	0.0276 (6)	0.0410 (7)	0.0363 (6)	0.0026 (4)	0.0056 (4)	−0.0100 (5)
Cl1	0.0393 (7)	0.0457 (8)	0.0587 (9)	−0.0063 (6)	0.0043 (6)	−0.0239 (6)
N1	0.038 (2)	0.046 (3)	0.040 (2)	0.000 (2)	0.0034 (18)	0.0025 (19)
C11	0.048 (3)	0.045 (3)	0.039 (3)	0.005 (2)	−0.001 (2)	0.002 (2)
C3	0.047 (3)	0.044 (3)	0.041 (3)	−0.005 (2)	0.008 (2)	0.000 (2)
C9	0.050 (3)	0.044 (3)	0.038 (3)	0.001 (2)	0.006 (2)	−0.001 (2)
C10	0.041 (3)	0.053 (3)	0.043 (3)	−0.006 (3)	0.002 (2)	0.000 (2)
C1	0.045 (3)	0.061 (4)	0.054 (4)	0.006 (3)	0.012 (3)	0.003 (3)
C8	0.043 (3)	0.041 (3)	0.040 (3)	−0.003 (2)	0.005 (2)	0.002 (2)
C6	0.052 (4)	0.058 (4)	0.061 (4)	0.005 (3)	−0.001 (3)	0.006 (3)
C7	0.056 (4)	0.056 (4)	0.045 (3)	0.009 (3)	0.000 (3)	0.001 (3)
C5	0.066 (4)	0.062 (4)	0.042 (3)	−0.014 (3)	−0.005 (3)	0.008 (3)
C4	0.066 (4)	0.053 (4)	0.039 (3)	−0.006 (3)	0.009 (3)	−0.002 (2)
C2	0.060 (4)	0.060 (4)	0.045 (3)	0.009 (3)	0.016 (3)	−0.005 (3)

Geometric parameters (Å, º) top

Zn1—Cl1ⁱ	2.3043 (14)	C9—H9	0.9300
Zn1—Cl1	2.3043 (14)	C10—H10A	0.9700
Zn1—Cl2ⁱ	2.3158 (12)	C10—H10B	0.9700
Zn1—Cl2	2.3158 (12)	C1—C2	1.350 (9)
N1—C9	1.330 (7)	C1—H1	0.9300
N1—C1	1.384 (8)	C8—C7	1.423 (9)
N1—C10	1.488 (7)	C6—C7	1.357 (9)
C11—C10	1.502 (8)	C6—C5	1.423 (10)
C11—C11ⁱⁱ	1.520 (12)	C6—H6	0.9300
C11—H11A	0.9700	C7—H7	0.9300
C11—H11B	0.9700	C5—C4	1.356 (10)
C3—C4	1.412 (9)	C5—H5	0.9300
C3—C8	1.416 (8)	C4—H4	0.9300
C3—C2	1.431 (9)	C2—H2	0.9300
C9—C8	1.411 (8)

Cl1ⁱ—Zn1—Cl1	108.47 (9)	N1—C10—H10B	109.4
Cl1ⁱ—Zn1—Cl2ⁱ	109.41 (5)	C11—C10—H10B	109.4
Cl1—Zn1—Cl2ⁱ	109.62 (5)	H10A—C10—H10B	108.0
Cl1ⁱ—Zn1—Cl2	109.62 (5)	C2—C1—N1	120.7 (6)
Cl1—Zn1—Cl2	109.41 (5)	C2—C1—H1	119.7
Cl2ⁱ—Zn1—Cl2	110.28 (7)	N1—C1—H1	119.7
C9—N1—C1	121.0 (5)	C9—C8—C3	118.9 (5)
C9—N1—C10	120.6 (5)	C9—C8—C7	120.6 (5)
C1—N1—C10	118.4 (5)	C3—C8—C7	120.4 (5)
C10—C11—C11ⁱⁱ	115.5 (4)	C7—C6—C5	120.7 (6)
C10—C11—H11A	108.4	C7—C6—H6	119.7
C11ⁱⁱ—C11—H11A	108.4	C5—C6—H6	119.7
C10—C11—H11B	108.4	C6—C7—C8	119.0 (6)
C11ⁱⁱ—C11—H11B	108.4	C6—C7—H7	120.5
H11A—C11—H11B	107.5	C8—C7—H7	120.5
C4—C3—C8	118.7 (6)	C4—C5—C6	121.1 (6)
C4—C3—C2	123.8 (6)	C4—C5—H5	119.5
C8—C3—C2	117.5 (5)	C6—C5—H5	119.5
N1—C9—C8	121.2 (5)	C5—C4—C3	120.1 (6)
N1—C9—H9	119.4	C5—C4—H4	120.0
C8—C9—H9	119.4	C3—C4—H4	120.0
N1—C10—C11	111.1 (5)	C1—C2—C3	120.7 (6)
N1—C10—H10A	109.4	C1—C2—H2	119.7
C11—C10—H10A	109.4	C3—C2—H2	119.7

C1—N1—C9—C8	0.7 (9)	C2—C3—C8—C7	−179.1 (6)
C10—N1—C9—C8	−179.1 (5)	C5—C6—C7—C8	0.0 (10)
C9—N1—C10—C11	−96.2 (6)	C9—C8—C7—C6	−177.3 (6)
C1—N1—C10—C11	83.9 (6)	C3—C8—C7—C6	1.0 (9)
C11ⁱⁱ—C11—C10—N1	71.4 (7)	C7—C6—C5—C4	−1.3 (10)
C9—N1—C1—C2	−1.2 (9)	C6—C5—C4—C3	1.6 (10)
C10—N1—C1—C2	178.6 (6)	C8—C3—C4—C5	−0.5 (9)
N1—C9—C8—C3	0.3 (8)	C2—C3—C4—C5	177.7 (6)
N1—C9—C8—C7	178.6 (6)	N1—C1—C2—C3	0.7 (10)
C4—C3—C8—C9	177.6 (5)	C4—C3—C2—C1	−178.0 (6)
C2—C3—C8—C9	−0.7 (8)	C8—C3—C2—C1	0.2 (10)
C4—C3—C8—C7	−0.8 (9)

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

Experimental details

Crystal data
Chemical formula	(C₂₂H₂₂N₂)[ZnCl₄]
M_r	521.61
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	273
a, b, c (Å)	10.729 (3), 11.040 (3), 18.955 (4)
β (°)	99.179 (9)
V (Å³)	2216.4 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.60
Crystal size (mm)	0.23 × 0.19 × 0.17

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.680, 0.760
No. of measured, independent and observed [I > 2σ(I)] reflections	12088, 2172, 1855
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.206, 1.13
No. of reflections	2172
No. of parameters	132
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.1169P)² + 12.0521P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.28, −1.15

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

References

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