2,2′-Ethyl­enediisoquinolinium dibromide dihydrate

Li, J.-S.; Li, P.-Y.

doi:10.1107/S1600536809045036

organic compounds

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Volume 65| Part 11| November 2009| Page o2966

https://doi.org/10.1107/S1600536809045036

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2,2′-Ethylenediisoquinolinium dibromide dihydrate

Jiang-Sheng Li ^a ^* and Peng-Yu Li ^a

^aSchool of Chemistry and Biological Engineering, Changsha University of Science & Technology, Changsha 410004, People's Republic of China
^*Correspondence e-mail: js_li@yahoo.com.cn

(Received 27 October 2009; accepted 28 October 2009; online 31 October 2009)

In the title compound, C₂₀H₁₈N₂²⁺·2Br⁻·2H₂O, the complete dication is generated by a crystallographic centre of symmetry. In the crystal, O—H⋯Br, C—H⋯Br and C—H⋯O hydrogen bonds and π–π stacking [shortest centroid–centroid separation = 3.657 (2) Å] help to establish the packing.

Related literature

For background to supramolecular chemistry related to the title compound, see: Loeb & Wisner (1998 ); Li (2007 ). For related structures, see: Li et al. (2008 ); Xu et al. (2007 ); Fan et al. (2007 ).

Experimental

Crystal data

C₂₀H₁₈N₂²⁺·2Br⁻·2H₂O
M_r = 482.22
Triclinic, $[P \overline 1]$
a = 7.5203 (15) Å
b = 8.0749 (16) Å
c = 9.2059 (18) Å
α = 110.34 (3)°
β = 106.96 (3)°
γ = 97.26 (3)°
V = 484.9 (2) Å³
Z = 1
Mo Kα radiation
μ = 4.20 mm⁻¹
T = 113 K
0.18 × 0.16 × 0.14 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.519, T_max = 0.591
3994 measured reflections
2262 independent reflections
1800 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.078
S = 1.07
2262 reflections
126 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Br1ⁱ	0.90 (4)	2.41 (4)	3.308 (3)	176 (3)
O1—H1B⋯Br1ⁱⁱ	0.81 (5)	2.51 (5)	3.313 (3)	178 (5)
C1—H1⋯Br1ⁱⁱⁱ	0.95	2.84	3.593 (3)	137
C9—H9⋯Br1^iv	0.95	2.81	3.691 (3)	154
C10—H10B⋯Br1^iv	0.99	2.87	3.683 (3)	140
C3—H3⋯O1^v	0.95	2.57	3.396 (4)	145
C4—H4⋯O1^vi	0.95	2.54	3.380 (4)	147
C10—H10A⋯O1ⁱⁱⁱ	0.99	2.27	3.214 (4)	158
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z; (iii) x, y+1, z+1; (iv) -x+1, -y+1, -z+1; (v) -x+1, -y+2, -z+1; (vi) x-1, y+1, z.

Data collection: CrystalClear (Rigaku, 2005); 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809045036/hb5199sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809045036/hb5199Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of analogs of 1,2-bis(pyridinium) ethane dications (Li et al., 2008), we synthesized a new dication 1,2-bis(isoquinolinium)ethane. Herein, its crystal structure is reported.

The molecular structure of (I) is shown in Fig. 1. The molecule has a centre of symmetry at the mid-point of the C10—C10A bond. The two isoquinoline rings are parallel to each other. The N⁺···N⁺ distance in the title compound is 3.7609 (8) Å, similar to the value previously reported (ca 3.75 Å) in the 1,2-bis(pyridinium)ethane dication (Loeb & Wisner, 1998). The crystal structure is stabilized by a series of intermolecular hydrogen bonds (Table 1). The hydrate tends to form an extensive network in the crystal by the aid of Br anions and water molecules. Also, the title cation were stacked via π-π interactions between isoquinolinium rings.

Related literature top

For background to supramolecular chemistry related to the title compound, see: Loeb & Wisner (1998); Li (2007). For related structures, see: Li et al. (2008); Xu et al. (2007); Fan et al. (2007).

Experimental top

The title compound was obtained according to the method of Loeb and Wisner (1998). Light yellow blocks of (I) were grown from its aqueous solution.

Structure description top

For background to supramolecular chemistry related to the title compound, see: Loeb & Wisner (1998); Li (2007). For related structures, see: Li et al. (2008); Xu et al. (2007); Fan et al. (2007).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 50% probability displacement displacement ellipsoids. [Symmetry codes: (i) 1 - x, 2 - y, 2 - z.]

2,2'-Ethylenediisoquinolinium dibromide dihydrate top

Crystal data top

C₂₀H₁₈N₂²⁺·2Br⁻·2H₂O	Z = 1
M_r = 482.22	F(000) = 242
Triclinic, P1	D_x = 1.651 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5203 (15) Å	Cell parameters from 1667 reflections
b = 8.0749 (16) Å	θ = 2.5–27.9°
c = 9.2059 (18) Å	µ = 4.20 mm⁻¹
α = 110.34 (3)°	T = 113 K
β = 106.96 (3)°	Block, light yellow
γ = 97.26 (3)°	0.18 × 0.16 × 0.14 mm
V = 484.9 (2) Å³

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2262 independent reflections
Radiation source: rotating anode	1800 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.027
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 2.5°
ω and φ scans	h = −8→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→10
T_min = 0.519, T_max = 0.591	l = −11→12
3994 measured reflections

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) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0391P)²] where P = (F_o² + 2F_c²)/3
2262 reflections	(Δ/σ)_max = 0.001
126 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₂₀H₁₈N₂²⁺·2Br⁻·2H₂O	γ = 97.26 (3)°
M_r = 482.22	V = 484.9 (2) Å³
Triclinic, P1	Z = 1
a = 7.5203 (15) Å	Mo Kα radiation
b = 8.0749 (16) Å	µ = 4.20 mm⁻¹
c = 9.2059 (18) Å	T = 113 K
α = 110.34 (3)°	0.18 × 0.16 × 0.14 mm
β = 106.96 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2262 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1800 reflections with I > 2σ(I)
T_min = 0.519, T_max = 0.591	R_int = 0.027
3994 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.40 e Å⁻³
2262 reflections	Δρ_min = −0.60 e Å⁻³
126 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
Br1	0.30313 (4)	0.40880 (4)	0.11468 (3)	0.02152 (11)
N1	0.4507 (3)	0.9986 (3)	0.7872 (2)	0.0144 (5)
C1	0.3923 (4)	1.1342 (4)	0.7547 (3)	0.0158 (5)
H1	0.4226	1.2506	0.8429	0.019*
C2	0.2857 (4)	1.1081 (4)	0.5912 (3)	0.0148 (5)
C3	0.2230 (4)	1.2538 (4)	0.5580 (3)	0.0211 (6)
H3	0.2509	1.3701	0.6457	0.025*
C4	0.1210 (4)	1.2239 (4)	0.3969 (4)	0.0263 (7)
H4	0.0762	1.3196	0.3727	0.032*
C5	0.0829 (4)	1.0516 (5)	0.2675 (3)	0.0260 (7)
H5	0.0148	1.0340	0.1564	0.031*
C6	0.1411 (4)	0.9094 (4)	0.2972 (3)	0.0226 (6)
H6	0.1120	0.7941	0.2078	0.027*
C7	0.2446 (4)	0.9341 (4)	0.4610 (3)	0.0159 (5)
C8	0.3097 (4)	0.7935 (4)	0.5028 (3)	0.0182 (6)
H8	0.2827	0.6753	0.4180	0.022*
C9	0.4100 (4)	0.8262 (4)	0.6625 (3)	0.0174 (6)
H9	0.4525	0.7310	0.6893	0.021*
C10	0.5660 (4)	1.0297 (4)	0.9599 (3)	0.0173 (6)
H10A	0.6328	1.1608	1.0248	0.021*
H10B	0.6643	0.9589	0.9589	0.021*
O1	0.8807 (4)	0.4163 (3)	0.1546 (3)	0.0267 (5)
H1A	0.994 (5)	0.408 (4)	0.142 (4)	0.022 (9)*
H1B	0.838 (6)	0.458 (6)	0.088 (5)	0.067 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02605 (18)	0.02344 (16)	0.01838 (16)	0.01248 (12)	0.00851 (12)	0.00973 (12)
N1	0.0142 (11)	0.0168 (11)	0.0109 (10)	0.0027 (9)	0.0026 (9)	0.0062 (9)
C1	0.0194 (14)	0.0150 (13)	0.0136 (12)	0.0039 (11)	0.0073 (11)	0.0056 (10)
C2	0.0160 (13)	0.0176 (13)	0.0138 (12)	0.0027 (11)	0.0079 (11)	0.0083 (11)
C3	0.0245 (15)	0.0259 (15)	0.0236 (14)	0.0127 (13)	0.0146 (12)	0.0152 (13)
C4	0.0251 (16)	0.0406 (19)	0.0315 (16)	0.0139 (14)	0.0149 (14)	0.0297 (15)
C5	0.0162 (15)	0.0469 (19)	0.0175 (14)	0.0038 (14)	0.0034 (12)	0.0197 (14)
C6	0.0177 (15)	0.0316 (16)	0.0142 (13)	−0.0020 (13)	0.0041 (12)	0.0085 (12)
C7	0.0128 (13)	0.0211 (14)	0.0148 (12)	0.0016 (11)	0.0073 (11)	0.0074 (11)
C8	0.0210 (15)	0.0142 (13)	0.0145 (12)	0.0013 (11)	0.0060 (11)	0.0014 (11)
C9	0.0183 (14)	0.0150 (13)	0.0188 (13)	0.0052 (11)	0.0057 (11)	0.0073 (11)
C10	0.0177 (14)	0.0186 (14)	0.0109 (12)	0.0006 (11)	0.0004 (11)	0.0059 (11)
O1	0.0271 (13)	0.0288 (12)	0.0299 (11)	0.0089 (10)	0.0099 (10)	0.0182 (10)

Geometric parameters (Å, º) top

N1—C1	1.324 (3)	C5—H5	0.9500
N1—C9	1.387 (3)	C6—C7	1.410 (4)
N1—C10	1.486 (3)	C6—H6	0.9500
C1—C2	1.409 (3)	C7—C8	1.417 (4)
C1—H1	0.9500	C8—C9	1.354 (4)
C2—C3	1.416 (4)	C8—H8	0.9500
C2—C7	1.418 (4)	C9—H9	0.9500
C3—C4	1.374 (4)	C10—C10ⁱ	1.521 (5)
C3—H3	0.9500	C10—H10A	0.9900
C4—C5	1.408 (4)	C10—H10B	0.9900
C4—H4	0.9500	O1—H1A	0.90 (4)
C5—C6	1.364 (4)	O1—H1B	0.81 (5)

C1—N1—C9	121.6 (2)	C5—C6—H6	120.1
C1—N1—C10	120.1 (2)	C7—C6—H6	120.1
C9—N1—C10	118.3 (2)	C6—C7—C8	123.4 (3)
N1—C1—C2	120.9 (2)	C6—C7—C2	118.5 (3)
N1—C1—H1	119.5	C8—C7—C2	118.1 (2)
C2—C1—H1	119.5	C9—C8—C7	120.6 (2)
C1—C2—C3	120.5 (2)	C9—C8—H8	119.7
C1—C2—C7	118.6 (2)	C7—C8—H8	119.7
C3—C2—C7	120.9 (2)	C8—C9—N1	120.1 (3)
C4—C3—C2	118.9 (3)	C8—C9—H9	119.9
C4—C3—H3	120.6	N1—C9—H9	119.9
C2—C3—H3	120.6	N1—C10—C10ⁱ	109.4 (3)
C3—C4—C5	120.1 (3)	N1—C10—H10A	109.8
C3—C4—H4	119.9	C10ⁱ—C10—H10A	109.8
C5—C4—H4	119.9	N1—C10—H10B	109.8
C6—C5—C4	121.8 (3)	C10ⁱ—C10—H10B	109.8
C6—C5—H5	119.1	H10A—C10—H10B	108.2
C4—C5—H5	119.1	H1A—O1—H1B	99 (4)
C5—C6—C7	119.8 (3)

C9—N1—C1—C2	0.0 (4)	C1—C2—C7—C6	−178.8 (2)
C10—N1—C1—C2	178.9 (2)	C3—C2—C7—C6	0.5 (4)
N1—C1—C2—C3	179.6 (3)	C1—C2—C7—C8	1.3 (4)
N1—C1—C2—C7	−1.0 (4)	C3—C2—C7—C8	−179.3 (3)
C1—C2—C3—C4	179.4 (3)	C6—C7—C8—C9	179.4 (3)
C7—C2—C3—C4	0.0 (4)	C2—C7—C8—C9	−0.7 (4)
C2—C3—C4—C5	−1.0 (4)	C7—C8—C9—N1	−0.2 (4)
C3—C4—C5—C6	1.4 (5)	C1—N1—C9—C8	0.6 (4)
C4—C5—C6—C7	−0.9 (4)	C10—N1—C9—C8	−178.2 (3)
C5—C6—C7—C8	179.7 (3)	C1—N1—C10—C10ⁱ	96.5 (3)
C5—C6—C7—C2	−0.1 (4)	C9—N1—C10—C10ⁱ	−84.7 (4)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Br1ⁱⁱ	0.90 (4)	2.41 (4)	3.308 (3)	176 (3)
O1—H1B···Br1ⁱⁱⁱ	0.81 (5)	2.51 (5)	3.313 (3)	178 (5)
C1—H1···Br1^iv	0.95	2.84	3.593 (3)	137
C9—H9···Br1^v	0.95	2.81	3.691 (3)	154
C10—H10B···Br1^v	0.99	2.87	3.683 (3)	140
C3—H3···O1^vi	0.95	2.57	3.396 (4)	145
C4—H4···O1^vii	0.95	2.54	3.380 (4)	147
C10—H10A···O1^iv	0.99	2.27	3.214 (4)	158

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

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₂²⁺·2Br⁻·2H₂O
M_r	482.22
Crystal system, space group	Triclinic, P1
Temperature (K)	113
a, b, c (Å)	7.5203 (15), 8.0749 (16), 9.2059 (18)
α, β, γ (°)	110.34 (3), 106.96 (3), 97.26 (3)
V (Å³)	484.9 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	4.20
Crystal size (mm)	0.18 × 0.16 × 0.14

Data collection
Diffractometer	Rigaku Saturn CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.519, 0.591
No. of measured, independent and observed [I > 2σ(I)] reflections	3994, 2262, 1800
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.078, 1.07
No. of reflections	2262
No. of parameters	126
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.60

Computer programs: CrystalClear (Rigaku, 2005), 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
O1—H1A···Br1ⁱ	0.90 (4)	2.41 (4)	3.308 (3)	176 (3)
O1—H1B···Br1ⁱⁱ	0.81 (5)	2.51 (5)	3.313 (3)	178 (5)
C1—H1···Br1ⁱⁱⁱ	0.95	2.84	3.593 (3)	137
C9—H9···Br1^iv	0.95	2.81	3.691 (3)	154
C10—H10B···Br1^iv	0.99	2.87	3.683 (3)	140
C3—H3···O1^v	0.95	2.57	3.396 (4)	145
C4—H4···O1^vi	0.95	2.54	3.380 (4)	147
C10—H10A···O1ⁱⁱⁱ	0.99	2.27	3.214 (4)	158

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

Acknowledgements

This project was supported by Changsha University of Science and Technology Talent Fund (Project No. 1004214).

References

Fan, X.-P., Li, J.-S., Zhang, Y.-Y. & Zhou, X.-L. (2007). Acta Cryst. E63, o1717–o1718. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, J. S. (2007). PhD dissertation, Tianjin University, People's Republic of China. Google Scholar
Li, J.-S., Liu, W.-D. & Yang, D.-W. (2008). Acta Cryst. E64, o35. Web of Science CSD CrossRef IUCr Journals Google Scholar
Loeb, S. J. & Wisner, J. A. (1998). Angew. Chem. Int. Ed. 37, 2838–2840. CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, Y.-J., Li, J.-S., Qin, L. & Wang, W. (2007). Acta Cryst. E63, o1825–o1826. Web of Science CSD CrossRef IUCr Journals Google Scholar