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

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020594/sg2162sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020594/sg2162Isup2.hkl
Contains datablock I

CCDC reference: 624624

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.023
  • wR factor = 0.052
  • Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 Br
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.06 From the CIF: _reflns_number_total 2423 Count of symmetry unique reflns 1362 Completeness (_total/calc) 177.90% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1061 Fraction of Friedel pairs measured 0.779 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C11 = . S PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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).

Structure description 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.

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

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+·2BrZ = 1
Mr = 374.12F(000) = 186
Triclinic, P1Dx = 1.618 Mg m3
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 mm1
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)
Graphite monochromatorRint = 0.014
φ and ω scansθmax = 25.1°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 77
Tmin = 0.256, Tmax = 0.375k = 88
2761 measured reflectionsl = 1111
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 Å3
163 parametersΔρmin = 0.29 e Å3
3 restraintsAbsolute structure: Flack (1983), 1061 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.062 (1)
Crystal data top
C14H18N2+·2Brγ = 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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.052Δρmax = 0.22 e Å3
S = 0.96Δρmin = 0.29 e Å3
2423 reflectionsAbsolute structure: Flack (1983), 1061 Friedel pairs
163 parametersAbsolute structure 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)
C30.1629 (8)0.0811 (6)0.7041 (4)0.0502 (10)
H30.18960.02030.78200.060*
C40.3627 (8)0.0481 (7)0.5888 (4)0.0590 (11)
H40.52580.03450.58860.071*
C50.3201 (9)0.1394 (7)0.4713 (5)0.0598 (11)
H50.45680.11640.39380.072*
C60.0830 (8)0.2611 (6)0.4678 (4)0.0537 (11)
H60.05970.31890.38840.064*
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, º) 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—C22.1 (6)C2—C7—C8—C91.7 (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—C3177.1 (4)C10—N1—C9—C8176.2 (4)
C1—C2—C3—C4176.7 (4)C1—N1—C10—C11101.6 (5)
C7—C2—C3—C40.7 (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—C70.5 (6)N1—C10—C11—N260.3 (5)
C5—C6—C7—C20.2 (6)N1—C10—C11—C12176.7 (5)
C5—C6—C7—C8178.2 (4)N2—C11—C12—C137.2 (6)
C1—C2—C7—C6177.1 (3)C10—C11—C12—C13128.0 (4)
C3—C2—C7—C60.4 (5)C11—C12—C13—C1416.0 (6)
C1—C2—C7—C81.5 (5)C11—N2—C14—C1338.6 (4)
C3—C2—C7—C8178.9 (4)C12—C13—C14—N233.2 (5)
C6—C7—C8—C9176.8 (4)
Hydrogen-bond geometry (Å, º) 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

Experimental details

Crystal data
Chemical formulaC14H18N2+·2Br
Mr374.12
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)6.1326 (6), 7.3174 (7), 9.8781 (10)
α, β, γ (°)93.817 (2), 104.335 (2), 114.408 (1)
V3)383.86 (7)
Z1
Radiation typeMo Kα
µ (mm1)5.27
Crystal size (mm)0.34 × 0.23 × 0.19
Data collection
DiffractometerBruker APEX area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.256, 0.375
No. of measured, independent and
observed [I > 2σ(I)] reflections
2761, 2423, 2281
Rint0.014
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.052, 0.96
No. of reflections2423
No. of parameters163
No. of restraints3
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.29
Absolute structureFlack (1983), 1061 Friedel pairs
Absolute structure parameter0.062 (1)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.

Selected bond angles (º) top
N1—C10—C11111.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Br10.902.303.203 (3)178.1
N2—H2B···Br20.902.303.180 (3)165.7
 

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