Tetra­butyl­ammonium meso-octa­methyl­calix­[4]­pyrrole fluoride di­chloro­methane solvate

Camiolo, S.; Coles, S.J.; Gale, P.A.; Hursthouse, M.B.; Sessler, J.L.

doi:10.1107/S1600536801012880

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Tetrabutylammonium meso-octamethylcalix[4]pyrrole fluoride dichloromethane solvate

S. Camiolo, S. J. Coles, P. A. Gale, M. B. Hursthouse and J. L. Sessler

The title compound, C₁₆H₃₆N⁺·C₂₈H₃₆N₄·F^-·CH₂Cl₂, is a calix[4]pyrrole macrocycle acting as a fluoride receptor by means of hydrogen bonding. Geometric comparisons with the previously published non-isostructural chloride-bound analogue are presented.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801012880/bt6058sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801012880/bt6058Isup2.hkl Contains datablock I

CCDC reference: 172198

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.006 Å
Disorder in main residue
R factor = 0.074
wR factor = 0.216
Data-to-parameter ratio = 9.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_030  Alert B Refined Extinction parameter within range ....       2.30 Sigma


 Alert Level C:



SHFSU_01  Alert C The absolute value of parameter shift to su ratio > 0.05
          Absolute value of the parameter shift to su ratio given   0.054
          Additional refinement cycles may be required.

PLAT_301  Alert C Main Residue Disorder ........................      20.00 Perc.

PLAT_302  Alert C Anion/Solvent Disorder .......................      20.00 Perc.

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C45 H64 Cl2 F1 N5
          Atom count from _chemical_formula_moiety:C45 H74 Cl2 F1 N5

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.47
         From the CIF: _reflns_number_total               2739
         Count of symmetry unique reflns         2756
         Completeness (_total/calc)             99.38%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 3 Alert Level C = Please check

Comment top

The anion complexation properties of the calix[4]pyrrole family of macrocycles (Sessler & Gale, 2000) has been an area of continuing interest since the first paper describing anion complexation in these systems was published in 1996 (Gale et al., 1996). In this paper, we present the crystal structure of the fluoride complex, (I), of meso-octamethylcalix[4]pyrrole, a macrocycle regarded as the `parent' of this class of receptor due to its original synthesis by Baeyer in 1886 from acetone and pyrrole (Baeyer, 1886). This structure is of particular interest as calix[4]pyrroles are selective receptors for fluoride.

The structure of the title compound, (I), is meso-octamethyl-substituted calix[4]pyrrole coordinated to a fluoride anion, the charge of which is balanced by a tetrabutylammonium (TBA) cation, crystallizing with a dichloromethane (DCM) solvent (Fig. 1a shows the disordered TBA in its major component, whilst Fig. 1 b depicts the minor conformation). For clarity, Fig. 2 depicts solely the macrocycle–anion complex. The crystal structure of the TBA chloride complex of (I) was published in 1996 (Gale et al., 1996) (CSD refcode TEQKIJ; Allen & Kennard, 1993), but is not isostructural, as one might expect, to the structure reported herein. The structure of (I) therefore allows a comparison of the effects of chloride and fluoride binding to the parent macrocycle.

The macrocycle adopts a cone conformation in order to allow all four NH protons to hydrogen bond to the fluoride anion (Fig. 2). The average N···F separation is 2.767 (7) Å [3.303 (5) Å] and the average H···F interaction distance is 1.905 (7) Å [2.404 (6) Å], values in square brackets indicate the equivalent value for the chloride complex. The N···N cross-ring separations are N1···N1ⁱ = 4.688 (3) Å [4.723 (4) Å] and N2···N3 = 4.688 (3) Å [4.682 (5) Å] [symmetry code: (i) -x + 1, y, z], whilst the cavity formed by the meso-carbons is an average of 5.043 Å in length [5.07 Å] and 7.132 Å diagonally [7.169 Å]. These geometric parameters demonstrate a slight contraction of the fluoride-bound macrocycle with respect to that of the chloride complex. The meso-C atoms deviate from planarity with an average r.m.s. deviation from the plane of -0.2162 Å [-0.202 Å]. The dihedral angles formed between this plane and the pyrrole rings are 41.57 (5), 44.25 (5) and 40.03 (6)° [45.28 (6), 45.56 (7), 46.18 (5) and 41.05 (6)°] for the N1, N2 and N3 rings, respectively. The average dihedral angle between these planes is smaller for the fluoride versus the chloride complex, reflecting the smaller radius of F^- and hence the need for the pyrrole rings to be less angled with respect to the macrocycle. An average angle of 109.47 (3)° on both unique meso-carbons (C5 and C10) indicates ideal tetrahedral geometry and hence absence of any strain imposed on the macrocycle due to coordination to the anion.

Experimental top

Compound (I) was synthesized according to literature methods (Gale et al., 1996). Crystals of the tetrabutylammonium fluoride complex of (I) were obtained by slow evaporation of a dichloromethane solution of (I) in the presence of excess tetrabutylammonium fluoride.

Computing details top

Cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990) and CAMERON (Watkin et al., 1993).

Figures top

	Fig. 1. View of (I) (50% probability displacement ellipsoids), showing the disordered TBA in (a) the major component and (b) the minor component.
	Fig. 2. The meso-octamethylcalix[4]pyrrole complex with fluoride.

(I) top

Crystal data top

C₁₆H₃₆N⁺·C₂₈H₃₆N₄·F⁻·CH₂Cl₂	D_x = 1.148 Mg m⁻³
M_r = 764.91	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pmn2₁	Cell parameters from 45620 reflections
a = 19.846 (4) Å	θ = 2.9–27.5°
b = 10.653 (2) Å	µ = 0.19 mm⁻¹
c = 10.469 (2) Å	T = 100 K
V = 2213.3 (8) Å³	Block, colourless
Z = 2	0.18 × 0.16 × 0.16 mm
F(000) = 824

Data collection top

Nonius KappaCCD area-detector diffractometer	2396 reflections with I > 2σ(I)
ϕ and ω scans to fill Ewald sphere	R_int = 0.020
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	θ_max = 27.5°, θ_min = 2.9°
T_min = 0.967, T_max = 0.971	h = −25→25
5325 measured reflections	k = −13→0
2739 independent reflections	l = 0→13

Refinement top

Refinement on F²	w = 1/[σ²(F_o²) + (0.1422P)² + 0.5073P] where P = (F_o² + 2F_c²)/3
Least-squares matrix: full	(Δ/σ)_max = 0.054
R[F² > 2σ(F²)] = 0.074	Δρ_max = 0.69 e Å⁻³
wR(F²) = 0.216	Δρ_min = −0.73 e Å⁻³
S = 1.09	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2739 reflections	Extinction coefficient: 0.023 (10)
291 parameters	Absolute structure: Flack (1983)
7 restraints	Absolute structure parameter: 0.0 (3)
H-atom parameters constrained

Crystal data top

C₁₆H₃₆N⁺·C₂₈H₃₆N₄·F⁻·CH₂Cl₂	V = 2213.3 (8) Å³
M_r = 764.91	Z = 2
Orthorhombic, Pmn2₁	Mo Kα radiation
a = 19.846 (4) Å	µ = 0.19 mm⁻¹
b = 10.653 (2) Å	T = 100 K
c = 10.469 (2) Å	0.18 × 0.16 × 0.16 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	2739 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	2396 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.971	R_int = 0.020
5325 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	H-atom parameters constrained
wR(F²) = 0.216	Δρ_max = 0.69 e Å⁻³
S = 1.09	Δρ_min = −0.73 e Å⁻³
2739 reflections	Absolute structure: Flack (1983)
291 parameters	Absolute structure parameter: 0.0 (3)
7 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C23	0.5	0.6387 (14)	0.9583 (10)	0.124 (5)
H23A	0.5	0.7081	0.8954	0.148*
H23B	0.5	0.559	0.9097	0.148*
Cl1	0.4255 (2)	0.6468 (3)	1.0462 (3)	0.1823 (19)
C1	0.35361 (17)	0.0451 (3)	0.6689 (4)	0.0314 (7)
C2	0.30480 (18)	0.0584 (4)	0.5779 (4)	0.0389 (9)
H2	0.2763	−0.0063	0.5465	0.047*
C3	0.3042 (2)	0.1854 (4)	0.5385 (4)	0.0420 (9)
H3	0.2748	0.2214	0.4769	0.05*
C4	0.35389 (19)	0.2475 (3)	0.6053 (4)	0.0337 (8)
C5	0.37307 (18)	−0.0667 (3)	0.7510 (4)	0.0312 (8)
C6	0.3705 (2)	−0.0278 (4)	0.8931 (4)	0.0413 (9)
H6A	0.4041	0.0377	0.9092	0.062*
H6B	0.3803	−0.1009	0.9469	0.062*
H6C	0.3255	0.0044	0.9135	0.062*
C7	0.32212 (19)	−0.1737 (4)	0.7299 (5)	0.0449 (10)
H7A	0.2765	−0.1429	0.7469	0.067*
H7B	0.3324	−0.2432	0.788	0.067*
H7C	0.325	−0.2031	0.6413	0.067*
C8	0.44301 (17)	−0.1155 (3)	0.7193 (3)	0.0260 (7)
C9	0.46408 (16)	−0.2248 (3)	0.6618 (3)	0.0260 (7)
H9	0.4358	−0.2888	0.6281	0.031*
C10	0.3733 (2)	0.3863 (4)	0.6102 (4)	0.0401 (9)
C11	0.3697 (3)	0.4327 (4)	0.7504 (4)	0.0463 (10)
H11A	0.4017	0.385	0.8026	0.069*
H11B	0.324	0.4204	0.7834	0.069*
H11C	0.3812	0.5222	0.7538	0.069*
C12	0.3210 (3)	0.4598 (5)	0.5309 (6)	0.0608 (14)
H12A	0.3289	0.5501	0.5408	0.091*
H12B	0.2756	0.4392	0.5607	0.091*
H12C	0.3254	0.4368	0.4406	0.091*
C13	0.4429 (2)	0.4112 (3)	0.5585 (4)	0.0379 (9)
C14	0.4645 (2)	0.4790 (4)	0.4531 (4)	0.0436 (9)
H14	0.4364	0.5185	0.3917	0.052*
N1	0.38363 (14)	0.1611 (3)	0.6846 (3)	0.0302 (6)
H1	0.4169	0.1772	0.7376	0.036*
N2	0.5	−0.0491 (3)	0.7543 (4)	0.0244 (8)
H2A	0.5	0.0243	0.7929	0.029*
N3	0.5	0.3712 (4)	0.6214 (4)	0.0326 (9)
H3A	0.5	0.3264	0.692	0.039*
F1	0.5	0.2000 (2)	0.8234 (3)	0.0289 (6)
N4	0.5	0.0539 (4)	0.2866 (4)	0.0239 (8)
C15	0.4582 (3)	−0.0020 (6)	0.3947 (6)	0.0139 (12)	0.4
H15A	0.4444	0.012	0.4844	0.017*	0.4
H15B	0.4444	0.0739	0.3468	0.017*	0.4
C16	0.4110 (2)	−0.1152 (4)	0.3420 (7)	0.0603 (16)	0.5
H16A	0.4387	−0.1595	0.2776	0.072*	0.5
H16B	0.4062	−0.174	0.4146	0.072*	0.5
C17	0.3488 (4)	−0.1065 (8)	0.2898 (8)	0.0422 (16)	0.6
H17A	0.3534	−0.0992	0.1959	0.051*	0.6
H17B	0.3269	−0.0289	0.3212	0.051*	0.6
C18	0.3001 (2)	−0.2269 (5)	0.3229 (5)	0.0505 (11)	0.5
H18A	0.3217	−0.3043	0.2933	0.076*	0.5
H18B	0.2567	−0.2166	0.2796	0.076*	0.5
H18C	0.2929	−0.2315	0.4153	0.076*	0.5
C19	0.4566 (3)	0.1044 (6)	0.1796 (6)	0.0148 (12)	0.4
H19A	0.4435	0.091	0.0894	0.018*	0.4
H19B	0.4435	0.0271	0.2257	0.018*	0.4
C20	0.4060 (3)	0.2131 (5)	0.2323 (11)	0.091 (3)	0.5
H20A	0.3742	0.1802	0.297	0.11*	0.5
H20B	0.431	0.2854	0.2681	0.11*	0.5
C21	0.3684 (4)	0.2486 (9)	0.1004 (9)	0.0516 (18)	0.6
H21A	0.402	0.2615	0.0317	0.062*	0.6
H21B	0.3381	0.1794	0.0744	0.062*	0.6
C22	0.3317 (3)	0.3574 (6)	0.1192 (6)	0.0696 (15)	0.5
H22A	0.2961	0.3417	0.1821	0.104*	0.5
H22B	0.3113	0.3838	0.0383	0.104*	0.5
H22C	0.3615	0.4238	0.1507	0.104*	0.5
C15'	0.4551 (4)	−0.0459 (7)	0.2263 (7)	0.0414 (15)	0.6
H15C	0.483	−0.1088	0.181	0.05*	0.6
H15D	0.4242	−0.0068	0.1637	0.05*	0.6
C16'	0.4110 (2)	−0.1152 (4)	0.3420 (7)	0.0603 (16)	0.5
C17'	0.3463 (6)	−0.1661 (13)	0.2460 (12)	0.048 (3)	0.4
H17C	0.3248	−0.0938	0.2027	0.058*	0.4
H17D	0.3637	−0.2242	0.18	0.058*	0.4
C18'	0.3001 (2)	−0.2269 (5)	0.3229 (5)	0.0505 (11)	0.5
C19'	0.4577 (3)	0.1589 (6)	0.3477 (7)	0.0384 (14)	0.6
H19C	0.4872	0.227	0.3795	0.046*	0.6
H19D	0.4311	0.1256	0.4203	0.046*	0.6
C20'	0.4060 (3)	0.2131 (5)	0.2323 (11)	0.091 (3)	0.5
C21'	0.4106 (5)	0.2930 (9)	0.1543 (10)	0.037 (2)	0.4
H21C	0.4306	0.2577	0.0754	0.044*	0.4
H21D	0.441	0.3599	0.186	0.044*	0.4
C22'	0.3317 (3)	0.3574 (6)	0.1192 (6)	0.0696 (15)	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C23	0.220 (16)	0.114 (9)	0.037 (4)	0	0	−0.005 (5)
Cl1	0.292 (5)	0.142 (3)	0.113 (2)	−0.098 (3)	0.046 (3)	0.031 (2)
C1	0.0295 (15)	0.0304 (16)	0.0342 (17)	−0.0004 (12)	0.0054 (15)	−0.0083 (15)
C2	0.0286 (15)	0.043 (2)	0.045 (2)	0.0012 (14)	−0.0004 (16)	−0.0136 (17)
C3	0.0346 (18)	0.054 (2)	0.037 (2)	0.0096 (16)	−0.0023 (16)	−0.0057 (18)
C4	0.0383 (17)	0.0340 (18)	0.0288 (17)	0.0059 (14)	−0.0017 (15)	−0.0005 (14)
C5	0.0306 (15)	0.0274 (15)	0.0355 (19)	−0.0056 (13)	0.0099 (14)	−0.0065 (15)
C6	0.054 (2)	0.0348 (19)	0.0353 (19)	−0.0041 (17)	0.0201 (18)	−0.0035 (16)
C7	0.0359 (19)	0.0333 (18)	0.066 (3)	−0.0086 (15)	0.020 (2)	−0.0056 (19)
C8	0.0324 (16)	0.0214 (14)	0.0243 (15)	−0.0034 (12)	0.0048 (13)	−0.0002 (12)
C9	0.0338 (16)	0.0206 (14)	0.0237 (15)	−0.0053 (12)	0.0011 (13)	−0.0006 (12)
C10	0.052 (2)	0.0322 (18)	0.0363 (19)	0.0130 (16)	−0.0041 (18)	0.0042 (16)
C11	0.066 (3)	0.0252 (16)	0.048 (2)	0.0098 (17)	0.012 (2)	−0.0052 (18)
C12	0.068 (3)	0.050 (3)	0.064 (3)	0.021 (2)	−0.012 (3)	0.012 (2)
C13	0.061 (2)	0.0237 (15)	0.0289 (17)	0.0069 (15)	−0.0047 (17)	0.0011 (14)
C14	0.073 (3)	0.0278 (17)	0.0302 (18)	0.0047 (18)	−0.0076 (19)	0.0036 (15)
N1	0.0308 (13)	0.0302 (14)	0.0297 (13)	0.0022 (11)	−0.0033 (12)	−0.0019 (12)
N2	0.0308 (18)	0.0199 (16)	0.0225 (18)	0	0	−0.0044 (14)
N3	0.049 (2)	0.0243 (18)	0.0241 (19)	0	0	0.0011 (16)
F1	0.0393 (14)	0.0245 (12)	0.0228 (13)	0	0	−0.0022 (11)
N4	0.0248 (16)	0.0276 (18)	0.0192 (18)	0	0	0.0021 (15)
C15	0.015 (3)	0.018 (3)	0.008 (3)	0.000 (2)	0.004 (2)	0.002 (2)
C16	0.036 (2)	0.034 (2)	0.111 (5)	−0.0078 (16)	0.025 (3)	0.000 (3)
C17	0.040 (3)	0.041 (4)	0.045 (4)	−0.004 (3)	−0.005 (3)	0.015 (3)
C18	0.040 (2)	0.065 (3)	0.046 (2)	−0.0112 (19)	−0.0119 (19)	0.007 (2)
C19	0.023 (3)	0.012 (3)	0.009 (3)	−0.001 (2)	−0.003 (3)	0.001 (2)
C20	0.073 (4)	0.038 (2)	0.163 (8)	0.020 (2)	−0.058 (5)	−0.011 (4)
C21	0.043 (4)	0.063 (5)	0.049 (4)	0.002 (3)	−0.005 (4)	−0.004 (4)
C22	0.080 (4)	0.076 (4)	0.053 (3)	0.008 (3)	−0.022 (3)	0.014 (3)
C15'	0.050 (4)	0.039 (3)	0.035 (3)	−0.005 (3)	−0.007 (3)	−0.002 (3)
C16'	0.036 (2)	0.034 (2)	0.111 (5)	−0.0078 (16)	0.025 (3)	0.000 (3)
C17'	0.061 (7)	0.049 (6)	0.035 (6)	−0.038 (6)	−0.008 (5)	0.002 (5)
C18'	0.040 (2)	0.065 (3)	0.046 (2)	−0.0112 (19)	−0.0119 (19)	0.007 (2)
C19'	0.042 (3)	0.038 (3)	0.034 (3)	0.002 (3)	0.004 (3)	−0.002 (3)
C20'	0.073 (4)	0.038 (2)	0.163 (8)	0.020 (2)	−0.058 (5)	−0.011 (4)
C21'	0.042 (5)	0.032 (5)	0.035 (5)	0.005 (4)	−0.001 (4)	0.013 (4)
C22'	0.080 (4)	0.076 (4)	0.053 (3)	0.008 (3)	−0.022 (3)	0.014 (3)

Geometric parameters (Å, º) top

C23—Cl1	1.745 (7)	N2—H2A	0.88
C23—Cl1ⁱ	1.745 (7)	N3—C13ⁱ	1.378 (5)
C23—H23A	0.99	N3—H3A	0.88
C23—H23B	0.99	N4—C15'	1.525 (7)
C1—C2	1.366 (6)	N4—C15'ⁱ	1.525 (7)
C1—N1	1.382 (5)	N4—C19'ⁱ	1.538 (7)
C1—C5	1.518 (5)	N4—C19'	1.538 (7)
C2—C3	1.415 (6)	C15—C16	1.623 (8)
C2—H2	0.95	C15—C15ⁱ	1.660 (12)
C3—C4	1.379 (6)	C15—H15A	0.99
C3—H3	0.95	C15—H15B	0.99
C4—N1	1.373 (5)	C16—C17	1.353 (9)
C4—C10	1.529 (5)	C16—H16A	0.99
C5—C8	1.519 (5)	C16—H16B	0.99
C5—C7	1.539 (5)	C17—C18	1.643 (9)
C5—C6	1.546 (6)	C17—H17A	0.99
C6—H6A	0.98	C17—H17B	0.99
C6—H6B	0.98	C18—H18A	0.98
C6—H6C	0.98	C18—H18B	0.98
C7—H7A	0.98	C18—H18C	0.98
C7—H7B	0.98	C19—C20	1.629 (9)
C7—H7C	0.98	C19—C19ⁱ	1.722 (13)
C8—C9	1.376 (5)	C19—H19A	0.99
C8—N2	1.384 (4)	C19—H19B	0.99
C9—C9ⁱ	1.426 (6)	C20—C21	1.615 (12)
C9—H9	0.95	C20—H20A	0.99
C10—C13	1.508 (6)	C20—H20B	0.99
C10—C12	1.542 (6)	C21—C22	1.384 (10)
C10—C11	1.550 (6)	C21—H21A	0.99
C11—H11A	0.98	C21—H21B	0.99
C11—H11B	0.98	C22—H22A	0.98
C11—H11C	0.98	C22—H22B	0.98
C12—H12A	0.98	C22—H22C	0.98
C12—H12B	0.98	C15'—H15C	0.99
C12—H12C	0.98	C15'—H15D	0.99
C13—N3	1.378 (5)	C17'—H17C	0.99
C13—C14	1.387 (6)	C17'—H17D	0.99
C14—C14ⁱ	1.408 (10)	C19'—H19C	0.99
C14—H14	0.95	C19'—H19D	0.99
N1—H1	0.88	C21'—H21C	0.99
N2—C8ⁱ	1.384 (4)	C21'—H21D	0.99

Cl1—C23—Cl1ⁱ	116.0 (7)	C13—C14—C14ⁱ	108.0 (3)
Cl1—C23—H23A	108.3	C13—C14—H14	126
Cl1ⁱ—C23—H23A	108.3	C14ⁱ—C14—H14	126
Cl1—C23—H23B	108.3	C4—N1—C1	110.1 (3)
Cl1ⁱ—C23—H23B	108.3	C4—N1—H1	125
H23A—C23—H23B	107.4	C1—N1—H1	125
C2—C1—N1	107.2 (3)	C8—N2—C8ⁱ	109.6 (4)
C2—C1—C5	131.0 (3)	C8—N2—H2A	125.2
N1—C1—C5	121.7 (3)	C8ⁱ—N2—H2A	125.2
C1—C2—C3	108.0 (3)	C13—N3—C13ⁱ	110.6 (4)
C1—C2—H2	126	C13—N3—H3A	124.7
C3—C2—H2	126	C13ⁱ—N3—H3A	124.7
C4—C3—C2	107.8 (4)	C15'—N4—C15'ⁱ	71.5 (6)
C4—C3—H3	126.1	C15'—N4—C19'ⁱ	177.2 (4)
C2—C3—H3	126.1	C15'ⁱ—N4—C19'ⁱ	111.1 (4)
N1—C4—C3	107.0 (3)	C15'—N4—C19'	111.1 (4)
N1—C4—C10	121.4 (3)	C15'ⁱ—N4—C19'	177.2 (4)
C3—C4—C10	131.4 (4)	C19'ⁱ—N4—C19'	66.2 (5)
C8—C5—C1	112.2 (3)	C16—C15—C15ⁱ	125.2 (3)
C8—C5—C7	108.4 (3)	C16—C15—H15A	106
C1—C5—C7	109.4 (3)	C15ⁱ—C15—H15A	106
C8—C5—C6	109.4 (3)	C16—C15—H15B	106
C1—C5—C6	109.0 (3)	C15ⁱ—C15—H15B	106
C7—C5—C6	108.4 (3)	H15A—C15—H15B	106.3
C5—C6—H6A	109.5	C17—C16—C15	127.8 (5)
C5—C6—H6B	109.5	C17—C16—H16A	105.4
H6A—C6—H6B	109.5	C15—C16—H16A	105.4
C5—C6—H6C	109.5	C17—C16—H16B	105.4
H6A—C6—H6C	109.5	C15—C16—H16B	105.4
H6B—C6—H6C	109.5	H16A—C16—H16B	106
C5—C7—H7A	109.5	C16—C17—C18	113.5 (5)
C5—C7—H7B	109.5	C16—C17—H17A	108.9
H7A—C7—H7B	109.5	C18—C17—H17A	108.9
C5—C7—H7C	109.5	C16—C17—H17B	108.9
H7A—C7—H7C	109.5	C18—C17—H17B	108.9
H7B—C7—H7C	109.5	H17A—C17—H17B	107.7
C9—C8—N2	107.5 (3)	C20—C19—C19ⁱ	128.0 (3)
C9—C8—C5	131.5 (3)	C20—C19—H19A	105.3
N2—C8—C5	120.9 (3)	C19ⁱ—C19—H19A	105.3
C8—C9—C9ⁱ	107.69 (19)	C20—C19—H19B	105.3
C8—C9—H9	126.2	C19ⁱ—C19—H19B	105.3
C9ⁱ—C9—H9	126.2	H19A—C19—H19B	106
C13—C10—C4	112.8 (3)	C21—C20—C19	99.3 (7)
C13—C10—C12	109.5 (4)	C21—C20—H20A	111.9
C4—C10—C12	107.7 (4)	C19—C20—H20A	111.9
C13—C10—C11	109.0 (4)	C21—C20—H20B	111.9
C4—C10—C11	109.2 (3)	C19—C20—H20B	111.9
C12—C10—C11	108.5 (4)	H20A—C20—H20B	109.6
C10—C11—H11A	109.5	C22—C21—C20	108.5 (7)
C10—C11—H11B	109.5	C22—C21—H21A	110
H11A—C11—H11B	109.5	C20—C21—H21A	110
C10—C11—H11C	109.5	C22—C21—H21B	110
H11A—C11—H11C	109.5	C20—C21—H21B	110
H11B—C11—H11C	109.5	H21A—C21—H21B	108.4
C10—C12—H12A	109.5	N4—C15'—H15C	110
C10—C12—H12B	109.5	N4—C15'—H15D	110
H12A—C12—H12B	109.5	H15C—C15'—H15D	108.4
C10—C12—H12C	109.5	H17C—C17'—H17D	108.5
H12A—C12—H12C	109.5	N4—C19'—H19C	110.4
H12B—C12—H12C	109.5	N4—C19'—H19D	110.4
N3—C13—C14	106.7 (4)	H19C—C19'—H19D	108.6
N3—C13—C10	121.8 (3)	H21C—C21'—H21D	108
C14—C13—C10	131.4 (4)

Symmetry code: (i) −x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₃₆N⁺·C₂₈H₃₆N₄·F⁻·CH₂Cl₂
M_r	764.91
Crystal system, space group	Orthorhombic, Pmn2₁
Temperature (K)	100
a, b, c (Å)	19.846 (4), 10.653 (2), 10.469 (2)
V (Å³)	2213.3 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.18 × 0.16 × 0.16

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.967, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	5325, 2739, 2396
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.216, 1.09
No. of reflections	2739
No. of parameters	291
No. of restraints	7
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.73
Absolute structure	Flack (1983)
Absolute structure parameter	0.0 (3)

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990) and CAMERON (Watkin et al., 1993).

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