Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020594/sg2162sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020594/sg2162Isup2.hkl |
CCDC reference: 624624
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (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
For related literature, see: List & Lerner (2000); List & Pojarliev (2001); Notz & Sakthivel (2001).
(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.
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).
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).
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.
Fig. 1. View of the asymmetric unit in (1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C14H18N2+·2Br− | Z = 1 |
Mr = 374.12 | F(000) = 186 |
Triclinic, P1 | Dx = 1.618 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1326 (6) Å | Cell parameters from 1985 reflections |
b = 7.3174 (7) Å | θ = 3.1–24.9° |
c = 9.8781 (10) Å | µ = 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 |
Bruker APEX area-detector diffractometer | 2423 independent reflections |
Radiation source: fine-focus sealed tube | 2281 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
φ and ω scans | θmax = 25.1°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −7→7 |
Tmin = 0.256, Tmax = 0.375 | k = −8→8 |
2761 measured reflections | l = −11→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.023 | H-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 reflections | Δρmax = 0.22 e Å−3 |
163 parameters | Δρmin = −0.29 e Å−3 |
3 restraints | Absolute structure: Flack (1983), 1061 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.062 (1) |
C14H18N2+·2Br− | γ = 114.408 (1)° |
Mr = 374.12 | V = 383.86 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.1326 (6) Å | Mo Kα radiation |
b = 7.3174 (7) Å | µ = 5.27 mm−1 |
c = 9.8781 (10) Å | T = 298 K |
α = 93.817 (2)° | 0.34 × 0.23 × 0.19 mm |
β = 104.335 (2)° |
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 = 0.375 | Rint = 0.014 |
2761 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
wR(F2) = 0.052 | Δρmax = 0.22 e Å−3 |
S = 0.96 | Δρmin = −0.29 e Å−3 |
2423 reflections | Absolute structure: Flack (1983), 1061 Friedel pairs |
163 parameters | Absolute structure parameter: 0.062 (1) |
3 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.27632 (5) | 0.78925 (4) | 0.83981 (4) | 0.05390 (15) | |
Br2 | 0.23689 (5) | 0.26066 (4) | 1.18024 (4) | 0.05562 (16) | |
N1 | 0.5178 (8) | 0.3772 (7) | 0.8240 (4) | 0.0441 (11) | |
N2 | 0.5946 (5) | 0.6520 (4) | 1.0843 (3) | 0.0396 (7) | |
H2A | 0.5052 | 0.6927 | 1.0172 | 0.048* | |
H2B | 0.4916 | 0.5288 | 1.0967 | 0.048* | |
C1 | 0.2876 (7) | 0.2516 (6) | 0.8219 (4) | 0.0431 (9) | |
H1 | 0.2616 | 0.1918 | 0.9003 | 0.052* | |
C2 | 0.0848 (7) | 0.2085 (5) | 0.7033 (4) | 0.0397 (8) | |
C3 | −0.1629 (8) | 0.0811 (6) | 0.7041 (4) | 0.0502 (10) | |
H3 | −0.1896 | 0.0203 | 0.7820 | 0.060* | |
C4 | −0.3627 (8) | 0.0481 (7) | 0.5888 (4) | 0.0590 (11) | |
H4 | −0.5258 | −0.0345 | 0.5886 | 0.071* | |
C5 | −0.3201 (9) | 0.1394 (7) | 0.4713 (5) | 0.0598 (11) | |
H5 | −0.4568 | 0.1164 | 0.3938 | 0.072* | |
C6 | −0.0830 (8) | 0.2611 (6) | 0.4678 (4) | 0.0537 (11) | |
H6 | −0.0597 | 0.3189 | 0.3884 | 0.064* | |
C7 | 0.1259 (7) | 0.2989 (6) | 0.5846 (4) | 0.0434 (9) | |
C8 | 0.3782 (8) | 0.4274 (6) | 0.5923 (4) | 0.0531 (11) | |
H8 | 0.4126 | 0.4867 | 0.5150 | 0.064* | |
C9 | 0.5690 (8) | 0.4647 (6) | 0.7107 (4) | 0.0505 (10) | |
H9 | 0.7339 | 0.5492 | 0.7149 | 0.061* | |
C10 | 0.7300 (9) | 0.4310 (8) | 0.9574 (6) | 0.0465 (14) | |
H10A | 0.8726 | 0.4284 | 0.9330 | 0.056* | |
H10B | 0.6790 | 0.3297 | 1.0163 | 0.056* | |
C11 | 0.8078 (9) | 0.6415 (8) | 1.0411 (5) | 0.0408 (12) | |
H11 | 0.8652 | 0.7447 | 0.9831 | 0.049* | |
C12 | 1.0133 (10) | 0.6959 (9) | 1.1816 (6) | 0.0498 (14) | |
H12A | 1.0432 | 0.5784 | 1.2000 | 0.060* | |
H12B | 1.1687 | 0.8062 | 1.1787 | 0.060* | |
C13 | 0.9224 (8) | 0.7617 (7) | 1.2967 (4) | 0.0606 (11) | |
H13A | 0.8656 | 0.6542 | 1.3503 | 0.073* | |
H13B | 1.0557 | 0.8840 | 1.3618 | 0.073* | |
C14 | 0.7107 (7) | 0.8025 (6) | 1.2197 (4) | 0.0514 (10) | |
H14A | 0.5919 | 0.7812 | 1.2731 | 0.062* | |
H14B | 0.7715 | 0.9413 | 1.2024 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0522 (3) | 0.0563 (3) | 0.0681 (4) | 0.0318 (3) | 0.0261 (3) | 0.0247 (3) |
Br2 | 0.0613 (4) | 0.0498 (3) | 0.0561 (3) | 0.0177 (3) | 0.0282 (3) | 0.0203 (3) |
N1 | 0.046 (2) | 0.046 (2) | 0.044 (2) | 0.026 (2) | 0.011 (2) | 0.0081 (19) |
N2 | 0.0307 (16) | 0.0364 (17) | 0.0496 (18) | 0.0126 (13) | 0.0126 (13) | 0.0081 (14) |
C1 | 0.054 (3) | 0.035 (2) | 0.041 (2) | 0.0191 (19) | 0.0170 (19) | 0.0072 (17) |
C2 | 0.046 (2) | 0.037 (2) | 0.039 (2) | 0.0214 (18) | 0.0132 (17) | 0.0043 (16) |
C3 | 0.052 (2) | 0.047 (2) | 0.048 (2) | 0.020 (2) | 0.013 (2) | 0.0112 (19) |
C4 | 0.051 (3) | 0.058 (3) | 0.061 (3) | 0.022 (2) | 0.012 (2) | 0.002 (2) |
C5 | 0.059 (3) | 0.068 (3) | 0.050 (2) | 0.034 (2) | 0.005 (2) | 0.001 (2) |
C6 | 0.068 (3) | 0.058 (3) | 0.038 (2) | 0.033 (2) | 0.012 (2) | 0.009 (2) |
C7 | 0.055 (2) | 0.040 (2) | 0.040 (2) | 0.0252 (19) | 0.0163 (19) | 0.0061 (17) |
C8 | 0.066 (3) | 0.060 (3) | 0.043 (2) | 0.029 (2) | 0.030 (2) | 0.017 (2) |
C9 | 0.050 (2) | 0.056 (3) | 0.049 (2) | 0.022 (2) | 0.024 (2) | 0.011 (2) |
C10 | 0.044 (3) | 0.049 (3) | 0.052 (3) | 0.028 (2) | 0.010 (2) | 0.010 (2) |
C11 | 0.032 (2) | 0.042 (3) | 0.048 (3) | 0.014 (2) | 0.016 (2) | 0.009 (2) |
C12 | 0.042 (3) | 0.046 (3) | 0.057 (3) | 0.021 (3) | 0.006 (2) | 0.002 (3) |
C13 | 0.051 (3) | 0.066 (3) | 0.052 (3) | 0.020 (2) | 0.007 (2) | 0.007 (2) |
C14 | 0.045 (2) | 0.047 (2) | 0.061 (2) | 0.0160 (19) | 0.023 (2) | 0.002 (2) |
N1—C1 | 1.322 (6) | C6—H6 | 0.9300 |
N1—C9 | 1.366 (5) | C7—C8 | 1.419 (6) |
N1—C10 | 1.498 (6) | C8—C9 | 1.352 (5) |
N2—C14 | 1.481 (5) | C8—H8 | 0.9300 |
N2—C11 | 1.501 (6) | C9—H9 | 0.9300 |
N2—H2A | 0.9000 | C10—C11 | 1.521 (5) |
N2—H2B | 0.9000 | C10—H10A | 0.9700 |
C1—C2 | 1.387 (5) | C10—H10B | 0.9700 |
C1—H1 | 0.9300 | C11—C12 | 1.523 (7) |
C2—C7 | 1.410 (5) | C11—H11 | 0.9800 |
C2—C3 | 1.419 (5) | C12—C13 | 1.516 (6) |
C3—C4 | 1.373 (6) | C12—H12A | 0.9700 |
C3—H3 | 0.9300 | C12—H12B | 0.9700 |
C4—C5 | 1.404 (6) | C13—C14 | 1.488 (6) |
C4—H4 | 0.9300 | C13—H13A | 0.9700 |
C5—C6 | 1.366 (6) | C13—H13B | 0.9700 |
C5—H5 | 0.9300 | C14—H14A | 0.9700 |
C6—C7 | 1.408 (5) | C14—H14B | 0.9700 |
C1—N1—C9 | 122.6 (4) | C8—C9—N1 | 119.4 (4) |
C1—N1—C10 | 118.8 (4) | C8—C9—H9 | 120.3 |
C9—N1—C10 | 118.6 (4) | N1—C9—H9 | 120.3 |
C14—N2—C11 | 106.1 (3) | N1—C10—C11 | 111.4 (3) |
C14—N2—H2A | 110.5 | N1—C10—H10A | 109.3 |
C11—N2—H2A | 110.5 | C11—C10—H10A | 109.3 |
C14—N2—H2B | 110.5 | N1—C10—H10B | 109.3 |
C11—N2—H2B | 110.5 | C11—C10—H10B | 109.3 |
H2A—N2—H2B | 108.7 | H10A—C10—H10B | 108.0 |
N1—C1—C2 | 120.3 (4) | N2—C11—C10 | 111.4 (3) |
N1—C1—H1 | 119.8 | N2—C11—C12 | 104.0 (4) |
C2—C1—H1 | 119.8 | C10—C11—C12 | 112.7 (4) |
C1—C2—C7 | 119.5 (3) | N2—C11—H11 | 109.5 |
C1—C2—C3 | 120.1 (4) | C10—C11—H11 | 109.5 |
C7—C2—C3 | 120.4 (3) | C12—C11—H11 | 109.5 |
C4—C3—C2 | 119.4 (4) | C13—C12—C11 | 106.9 (4) |
C4—C3—H3 | 120.3 | C13—C12—H12A | 110.3 |
C2—C3—H3 | 120.3 | C11—C12—H12A | 110.3 |
C3—C4—C5 | 119.8 (4) | C13—C12—H12B | 110.3 |
C3—C4—H4 | 120.1 | C11—C12—H12B | 110.3 |
C5—C4—H4 | 120.1 | H12A—C12—H12B | 108.6 |
C6—C5—C4 | 121.7 (4) | C14—C13—C12 | 105.2 (3) |
C6—C5—H5 | 119.2 | C14—C13—H13A | 110.7 |
C4—C5—H5 | 119.2 | C12—C13—H13A | 110.7 |
C5—C6—C7 | 120.0 (4) | C14—C13—H13B | 110.7 |
C5—C6—H6 | 120.0 | C12—C13—H13B | 110.7 |
C7—C6—H6 | 120.0 | H13A—C13—H13B | 108.8 |
C6—C7—C2 | 118.7 (3) | N2—C14—C13 | 103.6 (3) |
C6—C7—C8 | 124.0 (4) | N2—C14—H14A | 111.0 |
C2—C7—C8 | 117.3 (3) | C13—C14—H14A | 111.0 |
C9—C8—C7 | 120.8 (4) | N2—C14—H14B | 111.0 |
C9—C8—H8 | 119.6 | C13—C14—H14B | 111.0 |
C7—C8—H8 | 119.6 | H14A—C14—H14B | 109.0 |
C9—N1—C1—C2 | −2.1 (6) | C2—C7—C8—C9 | −1.7 (6) |
C10—N1—C1—C2 | 176.0 (4) | C7—C8—C9—N1 | 0.1 (6) |
N1—C1—C2—C7 | 0.3 (5) | C1—N1—C9—C8 | 1.9 (6) |
N1—C1—C2—C3 | −177.1 (4) | C10—N1—C9—C8 | −176.2 (4) |
C1—C2—C3—C4 | 176.7 (4) | C1—N1—C10—C11 | −101.6 (5) |
C7—C2—C3—C4 | −0.7 (6) | C9—N1—C10—C11 | 76.6 (5) |
C2—C3—C4—C5 | 0.4 (6) | C14—N2—C11—C10 | 149.9 (3) |
C3—C4—C5—C6 | 0.2 (7) | C14—N2—C11—C12 | 28.2 (5) |
C4—C5—C6—C7 | −0.5 (6) | N1—C10—C11—N2 | 60.3 (5) |
C5—C6—C7—C2 | 0.2 (6) | N1—C10—C11—C12 | 176.7 (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—C6 | 0.4 (5) | C11—C12—C13—C14 | −16.0 (6) |
C1—C2—C7—C8 | 1.5 (5) | C11—N2—C14—C13 | −38.6 (4) |
C3—C2—C7—C8 | 178.9 (4) | C12—C13—C14—N2 | 33.2 (5) |
C6—C7—C8—C9 | 176.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Br1 | 0.90 | 2.30 | 3.203 (3) | 178 |
N2—H2B···Br2 | 0.90 | 2.30 | 3.180 (3) | 166 |
Experimental details
Crystal data | |
Chemical formula | C14H18N2+·2Br− |
Mr | 374.12 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 383.86 (7) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 5.27 |
Crystal size (mm) | 0.34 × 0.23 × 0.19 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.256, 0.375 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2761, 2423, 2281 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.052, 0.96 |
No. of reflections | 2423 |
No. of parameters | 163 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.29 |
Absolute structure | Flack (1983), 1061 Friedel pairs |
Absolute structure parameter | 0.062 (1) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Br1 | 0.90 | 2.30 | 3.203 (3) | 178.1 |
N2—H2B···Br2 | 0.90 | 2.30 | 3.180 (3) | 165.7 |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
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.