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In the cation of the title compound, C20H26N22+·2Cl-·CH4O, there is an approximate twofold rotation axis. All the four chiral centers are in the S configuration. All three six-membered rings in the central part of the cation adopt a boat conformation. Both chloride anions and the O atom in the solvent mol­ecule form hydrogen bonds with the cation, resulting in a chain along [010].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805022762/wn6368sup1.cif
Contains datablocks I, globa

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805022762/wn6368Isup2.hkl
Contains datablock I

CCDC reference: 195192

Key indicators

  • Single-crystal X-ray study
  • T = 193 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.043
  • wR factor = 0.128
  • Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT726_ALERT_1_B H...A Calc 2.36000, Rep 2.38200 Dev... 0.02 Ang. H1 -CL2 1.555 2.646
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.70 mm PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent ......... 2 PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 6 PLAT480_ALERT_4_C Long H...A H-Bond Reported H14B .. O1 .. 2.68 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H6B .. CL1 .. 2.94 Ang. PLAT725_ALERT_1_C D-H Calc 0.84000, Rep 0.82000 Dev... 0.02 Ang. O1 -H1 1.555 1.555
Alert level G REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 25.48 From the CIF: _reflns_number_total 2874 Count of symmetry unique reflns 2020 Completeness (_total/calc) 142.28% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 854 Fraction of Friedel pairs measured 0.423 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 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 4 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: CrystalClear (Rigaku, 1990); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(1S,2S,4S,5S)-2,5-Dibenzyl-1,4-diazoniabicyclo[2.2.2]octane dichloride methanol solvate top
Crystal data top
C20H26N22+·2Cl·CH4OF(000) = 424
Mr = 397.37Dx = 1.310 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71070 Å
Hall symbol: p 2ybCell parameters from 3734 reflections
a = 11.7262 (13) Åθ = 3.0–25.5°
b = 7.6968 (7) ŵ = 0.34 mm1
c = 11.8788 (13) ÅT = 193 K
β = 109.970 (5)°Prism, colorless
V = 1007.65 (18) Å30.70 × 0.50 × 0.50 mm
Z = 2
Data collection top
Rigaku Mercury
diffractometer
2874 independent reflections
Radiation source: fine-focus sealed tube2855 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
Detector resolution: 14.62 pixels mm-1θmax = 25.5°, θmin = 3.0°
ω scansh = 1414
Absorption correction: multi-scan
(Jacobson, 1998)
k = 98
Tmin = 0.799, Tmax = 0.850l = 1314
6594 measured reflections
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)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.128 w = 1/[σ2(Fo2) + (0.0733P)2 + 0.7886P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
2874 reflectionsΔρmax = 0.60 e Å3
236 parametersΔρmin = 0.49 e Å3
2 restraintsAbsolute structure: Flack (1983), 855 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (9)
Special details top

Experimental. Compound 3: pale yellow oil, yield 29%, [a\]D25 + 104 (c, 0.8, CH3OH). 1H NMR (400 MHz, CDCl3): d\ 2.49–2.57 (m, 2H, PhCH2), 2.65–2.75 (m, 4H, CHH), 2.89–2.96 (m, 6H, 2- and 5-CHH, 3- and 6-CH, PhCH X 2), 3.03–3.0 (m, 2H, 7-and 8-CHH), 7.17–7.29 (m, 10H, PhH); MS: m/z: 292.19 (M+, 73%), 250.16 (8), 201.13 (100), 160.11 (20), 146.16 (25), 117.07 (29), 91.05 (31).

Compound 3 with 2HCl: white crystal, m.p.: 188–190°C. Anal. calcd for (%) C20H26N2Cl2: C 65.75, H 7.17, N 7.67. Found (%): C 65.48, H 7.42, N 7.63. IR ν: 3455, 3070, 2988, 2240, 1499 cm-1.

Compound 4: pale yellow oil, yield 25%, [a\]D25 + 134 (c, 0.8, CH3OH). 1H NMR (400 MHz, CDCl3) d\: 2.69–2.78 (m, 10H), 2.89–3.00 (m, 4H), 7.20–7.33 (m, 10H, PhH). MS m/z (%): 292.19 (71, M+), 250.16 (9), 201.13 (100), 160.11 (21), 146.16 (25), 117.07 (32), 91.05 (35).

Compound 4 with 2HCl: white crystal, m.p.: 136–138°C. IR (KBr) νmax: 3456, 3070, 2986, 2238, 1497 cm-1.

Compound 4 with 2picrate: yellow crystal, m.p.: 158–160°C. Anal. calcd (%) for C32H30N8O14: C 51.20, H 4.03, N 14.93. Found (%): C 50.87, H 4.01, N 14.91.

Scheme 2. Synthesis of the title compound

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
Cl10.40910 (7)0.56743 (12)0.32834 (8)0.0320 (2)
Cl20.09437 (7)0.65047 (12)0.48121 (10)0.0385 (3)
O10.6239 (6)0.1698 (12)0.3596 (6)0.128 (2)*
H10.69780.16470.40140.193*
N10.2888 (2)0.2593 (4)0.3883 (3)0.0254 (6)
N20.1871 (2)0.0101 (4)0.4494 (3)0.0260 (6)
C10.1563 (3)0.2582 (5)0.3125 (3)0.0238 (7)
H1B0.11460.35360.34060.029*
C20.1036 (3)0.0827 (5)0.3340 (3)0.0260 (7)
H2A0.02160.09970.33840.031*
H2B0.09730.00160.26740.031*
C30.2144 (3)0.1487 (5)0.5453 (3)0.0241 (7)
H30.13700.21010.53800.029*
C40.3004 (3)0.2787 (5)0.5180 (3)0.0261 (7)
H4A0.27900.39860.53350.031*
H4B0.38500.25550.57010.031*
C50.3495 (3)0.0946 (5)0.3740 (3)0.0301 (8)
H5A0.43850.10580.41240.036*
H5B0.33130.06940.28790.036*
C60.3024 (3)0.0531 (5)0.4327 (3)0.0302 (8)
H6A0.28560.15760.38100.036*
H6B0.36360.08360.51110.036*
C70.1402 (3)0.2903 (5)0.1815 (3)0.0292 (8)
H7A0.18180.39990.17520.035*
H7B0.17990.19490.15280.035*
C80.0086 (3)0.3021 (5)0.1006 (3)0.0253 (7)
C90.0819 (3)0.3776 (6)0.1361 (4)0.0334 (9)
H90.06250.42080.21540.040*
C100.2006 (3)0.3904 (6)0.0562 (4)0.0381 (9)
H100.26130.44180.08170.046*
C110.2310 (3)0.3292 (6)0.0595 (4)0.0372 (9)
H110.31190.33840.11360.045*
C120.1416 (4)0.2540 (6)0.0956 (3)0.0376 (9)
H120.16130.21160.17510.045*
C130.0236 (3)0.2404 (5)0.0160 (3)0.0308 (8)
H130.03640.18770.04180.037*
C140.2644 (3)0.0669 (6)0.6694 (3)0.0296 (7)
H14A0.20590.02080.67770.035*
H14B0.34130.00620.67770.035*
C150.2872 (3)0.1989 (5)0.7685 (3)0.0279 (8)
C160.4021 (3)0.2126 (7)0.8542 (4)0.0423 (10)
H160.46720.14670.84570.051*
C170.4230 (4)0.3220 (8)0.9525 (4)0.0583 (15)
H170.50250.33171.00960.070*
C180.3295 (4)0.4162 (7)0.9678 (4)0.0504 (12)
H180.34330.48671.03680.060*
C190.2154 (4)0.4068 (6)0.8812 (4)0.0391 (10)
H190.15140.47620.88890.047*
C200.1932 (3)0.2974 (5)0.7832 (3)0.0319 (8)
H200.11370.28930.72590.038*
C210.5785 (10)0.1697 (18)0.2341 (9)0.143 (4)*
H21A0.50690.24490.20590.214*
H21B0.55600.05100.20510.214*
H21C0.64100.21300.20360.214*
H1A0.324 (4)0.357 (6)0.366 (3)0.025 (10)*
H20.158 (4)0.084 (7)0.479 (4)0.034 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0224 (4)0.0371 (5)0.0355 (5)0.0052 (3)0.0086 (3)0.0044 (4)
Cl20.0283 (4)0.0250 (4)0.0649 (6)0.0003 (4)0.0194 (4)0.0047 (5)
N10.0197 (13)0.0292 (18)0.0253 (15)0.0032 (12)0.0053 (11)0.0008 (13)
N20.0236 (13)0.0214 (15)0.0313 (16)0.0023 (11)0.0074 (11)0.0016 (13)
C10.0158 (14)0.0280 (19)0.0260 (17)0.0002 (12)0.0051 (12)0.0036 (14)
C20.0205 (13)0.0317 (19)0.0230 (16)0.0035 (14)0.0037 (12)0.0025 (15)
C30.0223 (13)0.0260 (16)0.0227 (16)0.0026 (14)0.0061 (11)0.0045 (15)
C40.0250 (15)0.0272 (19)0.0215 (17)0.0013 (13)0.0021 (12)0.0056 (15)
C50.0216 (14)0.037 (2)0.0323 (18)0.0022 (14)0.0102 (13)0.0030 (16)
C60.0280 (17)0.027 (2)0.034 (2)0.0069 (14)0.0079 (14)0.0064 (16)
C70.0290 (17)0.033 (2)0.0255 (18)0.0029 (14)0.0098 (14)0.0003 (15)
C80.0294 (16)0.0223 (18)0.0246 (18)0.0050 (13)0.0096 (13)0.0021 (14)
C90.0305 (17)0.039 (2)0.0288 (18)0.0013 (16)0.0072 (14)0.0043 (17)
C100.0304 (18)0.040 (2)0.041 (2)0.0007 (16)0.0086 (16)0.0019 (19)
C110.0307 (17)0.036 (2)0.035 (2)0.0043 (16)0.0022 (14)0.0057 (18)
C120.045 (2)0.038 (2)0.0242 (18)0.0110 (18)0.0058 (15)0.0015 (17)
C130.0361 (18)0.028 (2)0.0274 (19)0.0022 (16)0.0100 (15)0.0005 (16)
C140.0317 (15)0.0302 (18)0.0268 (17)0.0051 (16)0.0100 (13)0.0008 (17)
C150.0264 (15)0.032 (2)0.0246 (17)0.0029 (14)0.0080 (13)0.0012 (15)
C160.0272 (17)0.058 (3)0.042 (2)0.0044 (18)0.0115 (15)0.014 (2)
C170.0295 (19)0.084 (4)0.053 (3)0.002 (2)0.0026 (18)0.035 (3)
C180.040 (2)0.063 (3)0.047 (3)0.003 (2)0.0130 (18)0.029 (2)
C190.0331 (18)0.046 (3)0.040 (2)0.0085 (18)0.0162 (16)0.010 (2)
C200.0256 (16)0.036 (2)0.032 (2)0.0035 (15)0.0074 (14)0.0004 (16)
Geometric parameters (Å, º) top
O1—C211.401 (10)C8—C131.388 (5)
O1—H10.8400C8—C91.396 (5)
N1—C51.492 (5)C9—C101.395 (5)
N1—C11.507 (4)C9—H90.9500
N1—C41.507 (4)C10—C111.379 (6)
N1—H1A0.94 (4)C10—H100.9500
N2—C21.495 (4)C11—C121.387 (6)
N2—C31.512 (5)C11—H110.9500
N2—C61.512 (4)C12—C131.388 (5)
N2—H20.92 (5)C12—H120.9500
C1—C71.522 (5)C13—H130.9500
C1—C21.543 (5)C14—C151.508 (5)
C1—H1B1.0000C14—H14A0.9900
C2—H2A0.9900C14—H14B0.9900
C2—H2B0.9900C15—C161.388 (5)
C3—C141.525 (5)C15—C201.398 (5)
C3—C41.532 (5)C16—C171.392 (6)
C3—H31.0000C16—H160.9500
C4—H4A0.9900C17—C181.377 (6)
C4—H4B0.9900C17—H170.9500
C5—C61.532 (5)C18—C191.384 (6)
C5—H5A0.9900C18—H180.9500
C5—H5B0.9900C19—C201.387 (6)
C6—H6A0.9900C19—H190.9500
C6—H6B0.9900C20—H200.9500
C7—C81.517 (5)C21—H21A0.9800
C7—H7A0.9900C21—H21B0.9800
C7—H7B0.9900C21—H21C0.9800
C21—O1—H1124.7C8—C7—H7B108.8
C5—N1—C1111.2 (3)C1—C7—H7B108.8
C5—N1—C4108.7 (3)H7A—C7—H7B107.7
C1—N1—C4109.0 (3)C13—C8—C9117.9 (3)
C5—N1—H1A112 (2)C13—C8—C7118.9 (3)
C1—N1—H1A107 (2)C9—C8—C7123.2 (3)
C4—N1—H1A109 (2)C10—C9—C8120.5 (4)
C2—N2—C3109.3 (3)C10—C9—H9119.7
C2—N2—C6109.5 (3)C8—C9—H9119.7
C3—N2—C6110.9 (3)C11—C10—C9120.8 (4)
C2—N2—H2116 (3)C11—C10—H10119.6
C3—N2—H2106 (3)C9—C10—H10119.6
C6—N2—H2105 (3)C10—C11—C12119.0 (3)
N1—C1—C7110.6 (3)C10—C11—H11120.5
N1—C1—C2107.2 (3)C12—C11—H11120.5
C7—C1—C2113.2 (3)C11—C12—C13120.2 (4)
N1—C1—H1B108.6C11—C12—H12119.9
C7—C1—H1B108.6C13—C12—H12119.9
C2—C1—H1B108.6C8—C13—C12121.5 (3)
N2—C2—C1107.8 (3)C8—C13—H13119.2
N2—C2—H2A110.1C12—C13—H13119.2
C1—C2—H2A110.1C15—C14—C3112.6 (3)
N2—C2—H2B110.1C15—C14—H14A109.1
C1—C2—H2B110.1C3—C14—H14A109.1
H2A—C2—H2B108.5C15—C14—H14B109.1
N2—C3—C14110.5 (3)C3—C14—H14B109.1
N2—C3—C4106.6 (2)H14A—C14—H14B107.8
C14—C3—C4114.3 (3)C16—C15—C20118.5 (3)
N2—C3—H3108.4C16—C15—C14119.5 (3)
C14—C3—H3108.4C20—C15—C14121.7 (3)
C4—C3—H3108.4C15—C16—C17120.7 (4)
N1—C4—C3108.4 (3)C15—C16—H16119.7
N1—C4—H4A110.0C17—C16—H16119.7
C3—C4—H4A110.0C18—C17—C16120.6 (4)
N1—C4—H4B110.0C18—C17—H17119.7
C3—C4—H4B110.0C16—C17—H17119.7
H4A—C4—H4B108.4C17—C18—C19119.1 (4)
N1—C5—C6108.6 (3)C17—C18—H18120.5
N1—C5—H5A110.0C19—C18—H18120.5
C6—C5—H5A110.0C18—C19—C20120.8 (4)
N1—C5—H5B110.0C18—C19—H19119.6
C6—C5—H5B110.0C20—C19—H19119.6
H5A—C5—H5B108.4C19—C20—C15120.3 (3)
N2—C6—C5107.4 (3)C19—C20—H20119.9
N2—C6—H6A110.2C15—C20—H20119.9
C5—C6—H6A110.2O1—C21—H21A109.5
N2—C6—H6B110.2O1—C21—H21B109.5
C5—C6—H6B110.2H21A—C21—H21B109.5
H6A—C6—H6B108.5O1—C21—H21C109.5
C8—C7—C1113.7 (3)H21A—C21—H21C109.5
C8—C7—H7A108.8H21B—C21—H21C109.5
C1—C7—H7A108.8
C5—N1—C1—C776.2 (4)C1—C7—C8—C13146.2 (3)
C4—N1—C1—C7164.0 (3)C1—C7—C8—C936.1 (5)
C5—N1—C1—C247.7 (3)C13—C8—C9—C100.1 (6)
C4—N1—C1—C272.1 (3)C7—C8—C9—C10177.6 (4)
C3—N2—C2—C149.2 (3)C8—C9—C10—C110.2 (6)
C6—N2—C2—C172.6 (3)C9—C10—C11—C120.2 (6)
N1—C1—C2—N219.9 (3)C10—C11—C12—C130.2 (6)
C7—C1—C2—N2142.2 (3)C9—C8—C13—C120.5 (5)
C2—N2—C3—C14162.0 (3)C7—C8—C13—C12177.4 (3)
C6—N2—C3—C1477.0 (3)C11—C12—C13—C80.5 (6)
C2—N2—C3—C473.3 (3)N2—C3—C14—C15177.2 (2)
C6—N2—C3—C447.7 (4)C4—C3—C14—C1562.6 (4)
C5—N1—C4—C373.3 (3)C3—C14—C15—C16123.7 (4)
C1—N1—C4—C348.1 (4)C3—C14—C15—C2062.5 (4)
N2—C3—C4—N120.5 (3)C20—C15—C16—C170.0 (7)
C14—C3—C4—N1142.8 (3)C14—C15—C16—C17174.1 (5)
C1—N1—C5—C669.7 (4)C15—C16—C17—C181.2 (9)
C4—N1—C5—C650.3 (3)C16—C17—C18—C192.9 (9)
C2—N2—C6—C550.7 (4)C17—C18—C19—C203.3 (8)
C3—N2—C6—C570.1 (4)C18—C19—C20—C152.2 (7)
N1—C5—C6—N216.8 (4)C16—C15—C20—C190.5 (6)
N1—C1—C7—C8176.4 (3)C14—C15—C20—C19174.4 (4)
C2—C1—C7—C863.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl10.94 (4)2.03 (4)2.967 (3)176 (4)
C5—H5A···O10.992.513.331 (7)140
N2—H2···Cl2i0.92 (5)2.18 (5)3.045 (3)157 (4)
C6—H6A···Cl1i0.992.753.563 (4)139
O1—H1···Cl2ii0.822.383.201 (4)180
C6—H6B···O1ii0.992.413.151 (9)131
C14—H14B···O1ii0.992.683.389 (7)129
C6—H6B···Cl1ii0.992.943.715 (4)136
C4—H4A···O1iii0.992.513.329 (8)140
C3—H3···Cl2iv0.992.683.526 (4)142
Symmetry codes: (i) x, y1, z; (ii) x+1, y1/2, z+1; (iii) x+1, y+1/2, z+1; (iv) x, y1/2, z+1.
 

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