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Acta Cryst. (2007). E63, o2786    [ doi:10.1107/S1600536807020594 ]

(S)-2-(Pyrrolidinium-2-ylmethyl)isoquinolinium dibromide

B.-T. Wang, S.-P. Luo, H.-D. Yue, L.-P. Wang and D.-Q. Xu

Abstract top

In the crystal structure of the title compound, C14H18N2+·2Br-, molecules are linked by N-H...Br hydrogen bonds.

Comment top

The title compound is a relatively new structural class of organocatalysts that play an important role in asymmetric reactions. For example, L-proline is an efficient organocatalyst and has been defined as a universal catalyst because of its utility in enantioselective aldol (List et al., 2000), Mannich (Notz et al., 2001) and Michael (List et al., 2001) reactions.

The crystallographic asymmetric unit of (I) consists of an isoquinoline cation and a bromide anion (Fig. 1) which are linked by an N—H···Br hydrogen bond. The angle of C11, C10 and N1 is 111.4 (3)° (Table 1). The isoquinoline group lies above the pyrrolidine five-membered ring.

Related literature top

For related literature, see: List & Lerner (2000); List & Pojarliev (2001); Notz & Sakthivel (2001).

Experimental top

(S)-2-(Bromomethyl)pyrrolidine hydrobromide (20 mmol), prepared by reaction of proline with sodium borohydride, was added slowly to isoquinoline (22 mmol) in methanol (50 ml) at 338 K. The mixture was stirred for 12 h and then the solvent was removed to give the title compound. Crystals suitable for X-ray analysis were obtained from diethyl ether by slow evaporation.

Refinement top

All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry with C—H distances of 0.98 Å and Uiso(H) = 1.5Ueq(C), but each group was allowed to rotate freely about its C—C bond. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.93–0.98 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of the asymmetric unit in (1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
(S)-2-(Pyrrolidinium-2-ylmethyl)isoquinolinium dibromide top
Crystal data top
C14H18N2+·2Br−Z = 1
Mr = 374.12F(000) = 186
Triclinic, P1Dx = 1.618 Mg m−3
Hall symbol: P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.1326 (6) ÅCell parameters from 1985 reflections
b = 7.3174 (7) Åθ = 3.1–24.9°
c = 9.8781 (10) ŵ = 5.27 mm−1
α = 93.817 (2)°T = 298 K
β = 104.335 (2)°Blcok, colorless
γ = 114.408 (1)°0.34 × 0.23 × 0.19 mm
V = 383.86 (7) Å3
Data collection top
Bruker APEX area-detector
diffractometer		2423 independent reflections
Radiation source: fine-focus sealed tube2281 reflections with I > 2σ(I)
graphiteRint = 0.014
φ and ω scansθmax = 25.1°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −7→7
Tmin = 0.256, Tmax = 0.375k = −8→8
2761 measured reflectionsl = −11→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.052 w = 1/[σ2(Fo2) + (0.0026P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
2423 reflectionsΔρmax = 0.22 e Å−3
163 parametersΔρmin = −0.29 e Å−3
3 restraintsAbsolute structure: Flack (1983), 1061 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.062 (1)
Crystal data top
C14H18N2+·2Br−γ = 114.408 (1)°
Mr = 374.12V = 383.86 (7) Å3
Triclinic, P1Z = 1
a = 6.1326 (6) ÅMo Kα radiation
b = 7.3174 (7) ŵ = 5.27 mm−1
c = 9.8781 (10) ÅT = 298 K
α = 93.817 (2)°0.34 × 0.23 × 0.19 mm
β = 104.335 (2)°
Data collection top
Bruker APEX area-detector
diffractometer		2423 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		2281 reflections with I > 2σ(I)
Tmin = 0.256, Tmax = 0.375Rint = 0.014
2761 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.052Δρmax = 0.22 e Å−3
S = 0.96Δρmin = −0.29 e Å−3
2423 reflectionsAbsolute structure: Flack (1983), 1061 Friedel pairs
163 parametersFlack parameter: 0.062 (1)
3 restraints
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
xyzUiso*/Ueq
Br10.27632 (5)0.78925 (4)0.83981 (4)0.05390 (15)
Br20.23689 (5)0.26066 (4)1.18024 (4)0.05562 (16)
N10.5178 (8)0.3772 (7)0.8240 (4)0.0441 (11)
N20.5946 (5)0.6520 (4)1.0843 (3)0.0396 (7)
H2A0.50520.69271.01720.048*
H2B0.49160.52881.09670.048*
C10.2876 (7)0.2516 (6)0.8219 (4)0.0431 (9)
H10.26160.19180.90030.052*
C20.0848 (7)0.2085 (5)0.7033 (4)0.0397 (8)
C3−0.1629 (8)0.0811 (6)0.7041 (4)0.0502 (10)
H3−0.18960.02030.78200.060*
C4−0.3627 (8)0.0481 (7)0.5888 (4)0.0590 (11)
H4−0.5258−0.03450.58860.071*
C5−0.3201 (9)0.1394 (7)0.4713 (5)0.0598 (11)
H5−0.45680.11640.39380.072*
C6−0.0830 (8)0.2611 (6)0.4678 (4)0.0537 (11)
H6−0.05970.31890.38840.064*
C70.1259 (7)0.2989 (6)0.5846 (4)0.0434 (9)
C80.3782 (8)0.4274 (6)0.5923 (4)0.0531 (11)
H80.41260.48670.51500.064*
C90.5690 (8)0.4647 (6)0.7107 (4)0.0505 (10)
H90.73390.54920.71490.061*
C100.7300 (9)0.4310 (8)0.9574 (6)0.0465 (14)
H10A0.87260.42840.93300.056*
H10B0.67900.32971.01630.056*
C110.8078 (9)0.6415 (8)1.0411 (5)0.0408 (12)
H110.86520.74470.98310.049*
C121.0133 (10)0.6959 (9)1.1816 (6)0.0498 (14)
H12A1.04320.57841.20000.060*
H12B1.16870.80621.17870.060*
C130.9224 (8)0.7617 (7)1.2967 (4)0.0606 (11)
H13A0.86560.65421.35030.073*
H13B1.05570.88401.36180.073*
C140.7107 (7)0.8025 (6)1.2197 (4)0.0514 (10)
H14A0.59190.78121.27310.062*
H14B0.77150.94131.20240.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0522 (3)0.0563 (3)0.0681 (4)0.0318 (3)0.0261 (3)0.0247 (3)
Br20.0613 (4)0.0498 (3)0.0561 (3)0.0177 (3)0.0282 (3)0.0203 (3)
N10.046 (2)0.046 (2)0.044 (2)0.026 (2)0.011 (2)0.0081 (19)
N20.0307 (16)0.0364 (17)0.0496 (18)0.0126 (13)0.0126 (13)0.0081 (14)
C10.054 (3)0.035 (2)0.041 (2)0.0191 (19)0.0170 (19)0.0072 (17)
C20.046 (2)0.037 (2)0.039 (2)0.0214 (18)0.0132 (17)0.0043 (16)
C30.052 (2)0.047 (2)0.048 (2)0.020 (2)0.013 (2)0.0112 (19)
C40.051 (3)0.058 (3)0.061 (3)0.022 (2)0.012 (2)0.002 (2)
C50.059 (3)0.068 (3)0.050 (2)0.034 (2)0.005 (2)0.001 (2)
C60.068 (3)0.058 (3)0.038 (2)0.033 (2)0.012 (2)0.009 (2)
C70.055 (2)0.040 (2)0.040 (2)0.0252 (19)0.0163 (19)0.0061 (17)
C80.066 (3)0.060 (3)0.043 (2)0.029 (2)0.030 (2)0.017 (2)
C90.050 (2)0.056 (3)0.049 (2)0.022 (2)0.024 (2)0.011 (2)
C100.044 (3)0.049 (3)0.052 (3)0.028 (2)0.010 (2)0.010 (2)
C110.032 (2)0.042 (3)0.048 (3)0.014 (2)0.016 (2)0.009 (2)
C120.042 (3)0.046 (3)0.057 (3)0.021 (3)0.006 (2)0.002 (3)
C130.051 (3)0.066 (3)0.052 (3)0.020 (2)0.007 (2)0.007 (2)
C140.045 (2)0.047 (2)0.061 (2)0.0160 (19)0.023 (2)0.002 (2)
Geometric parameters (Å, °) top
N1—C11.322 (6)C6—H60.9300
N1—C91.366 (5)C7—C81.419 (6)
N1—C101.498 (6)C8—C91.352 (5)
N2—C141.481 (5)C8—H80.9300
N2—C111.501 (6)C9—H90.9300
N2—H2A0.9000C10—C111.521 (5)
N2—H2B0.9000C10—H10A0.9700
C1—C21.387 (5)C10—H10B0.9700
C1—H10.9300C11—C121.523 (7)
C2—C71.410 (5)C11—H110.9800
C2—C31.419 (5)C12—C131.516 (6)
C3—C41.373 (6)C12—H12A0.9700
C3—H30.9300C12—H12B0.9700
C4—C51.404 (6)C13—C141.488 (6)
C4—H40.9300C13—H13A0.9700
C5—C61.366 (6)C13—H13B0.9700
C5—H50.9300C14—H14A0.9700
C6—C71.408 (5)C14—H14B0.9700
C1—N1—C9122.6 (4)C8—C9—N1119.4 (4)
C1—N1—C10118.8 (4)C8—C9—H9120.3
C9—N1—C10118.6 (4)N1—C9—H9120.3
C14—N2—C11106.1 (3)N1—C10—C11111.4 (3)
C14—N2—H2A110.5N1—C10—H10A109.3
C11—N2—H2A110.5C11—C10—H10A109.3
C14—N2—H2B110.5N1—C10—H10B109.3
C11—N2—H2B110.5C11—C10—H10B109.3
H2A—N2—H2B108.7H10A—C10—H10B108.0
N1—C1—C2120.3 (4)N2—C11—C10111.4 (3)
N1—C1—H1119.8N2—C11—C12104.0 (4)
C2—C1—H1119.8C10—C11—C12112.7 (4)
C1—C2—C7119.5 (3)N2—C11—H11109.5
C1—C2—C3120.1 (4)C10—C11—H11109.5
C7—C2—C3120.4 (3)C12—C11—H11109.5
C4—C3—C2119.4 (4)C13—C12—C11106.9 (4)
C4—C3—H3120.3C13—C12—H12A110.3
C2—C3—H3120.3C11—C12—H12A110.3
C3—C4—C5119.8 (4)C13—C12—H12B110.3
C3—C4—H4120.1C11—C12—H12B110.3
C5—C4—H4120.1H12A—C12—H12B108.6
C6—C5—C4121.7 (4)C14—C13—C12105.2 (3)
C6—C5—H5119.2C14—C13—H13A110.7
C4—C5—H5119.2C12—C13—H13A110.7
C5—C6—C7120.0 (4)C14—C13—H13B110.7
C5—C6—H6120.0C12—C13—H13B110.7
C7—C6—H6120.0H13A—C13—H13B108.8
C6—C7—C2118.7 (3)N2—C14—C13103.6 (3)
C6—C7—C8124.0 (4)N2—C14—H14A111.0
C2—C7—C8117.3 (3)C13—C14—H14A111.0
C9—C8—C7120.8 (4)N2—C14—H14B111.0
C9—C8—H8119.6C13—C14—H14B111.0
C7—C8—H8119.6H14A—C14—H14B109.0
C9—N1—C1—C2−2.1 (6)C2—C7—C8—C9−1.7 (6)
C10—N1—C1—C2176.0 (4)C7—C8—C9—N10.1 (6)
N1—C1—C2—C70.3 (5)C1—N1—C9—C81.9 (6)
N1—C1—C2—C3−177.1 (4)C10—N1—C9—C8−176.2 (4)
C1—C2—C3—C4176.7 (4)C1—N1—C10—C11−101.6 (5)
C7—C2—C3—C4−0.7 (6)C9—N1—C10—C1176.6 (5)
C2—C3—C4—C50.4 (6)C14—N2—C11—C10149.9 (3)
C3—C4—C5—C60.2 (7)C14—N2—C11—C1228.2 (5)
C4—C5—C6—C7−0.5 (6)N1—C10—C11—N260.3 (5)
C5—C6—C7—C20.2 (6)N1—C10—C11—C12176.7 (5)
C5—C6—C7—C8−178.2 (4)N2—C11—C12—C13−7.2 (6)
C1—C2—C7—C6−177.1 (3)C10—C11—C12—C13−128.0 (4)
C3—C2—C7—C60.4 (5)C11—C12—C13—C14−16.0 (6)
C1—C2—C7—C81.5 (5)C11—N2—C14—C13−38.6 (4)
C3—C2—C7—C8178.9 (4)C12—C13—C14—N233.2 (5)
C6—C7—C8—C9176.8 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Br10.902.303.203 (3)178
N2—H2B···Br20.902.303.180 (3)166
Table 1
Selected geometric parameters (°) top
N1—C10—C11111.4 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Br10.902.303.203 (3)178
N2—H2B···Br20.902.303.180 (3)166
Acknowledgements top

We acknowledge the Analytic Centre of Wenzhou Uniniversity for access to their diffractometer. We are also grateful for financial support from the Catalytic Hydrogenation Center of Zhejiang University of Technology

references
References top

Bruker (2002). SADABS (Version 2.03), SAINT (Version 6.02), SMART (Version 5.62) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Winsonsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

List, B. & Lerner, R. A. (2000). J. Am. Chem. Soc. 122, 2395–2396.

List, B. & Pojarliev, P. (2001). Org. Lett. 3, 2423–2425.

Notz, W. & Sakthivel, K. (2001). Tetrahedron Lett. 42, 199–201.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.