N,N-Di­methyl-5-di­methyl­amino-3-(1-pyrrolyl)-2,4-pentadieniminium tetra­fluoro­borate

In the crystal structure of the title salt, C₁₃H₂₀N₃⁺·BF₄^-, the asymmetric unit has two independent cations and anions. The cations have similar markedly non-planar pentamethinecyan­ine moieties with a trans-cis-cis-trans conformation of the pentamethinecyanine NC₅N chain. The pyrrole substituents are rotated 21.14 (9) and 23.43 (19)° from planarity with the adjacent atoms in the pentamethinecyanine chains.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in solvent or counterion
• R factor = 0.061
• wR factor = 0.220
• Data-to-parameter ratio = 10.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               4505
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         5562
         Completeness (_total/calc)             81.00%
          Alert A: < 85% complete (theta max?)

Author response: 1. Data were collected (in 1987) in two shells (2-20 and 20-25 degrees). on a CAD4 diffractometer collecting layers of increasing k-index. The complete 2-20 shell was collected and had index k in the range 0 to 9. It became apparent that there were very few reflections being measured as "observed" in the 20-25 degree shell (which would have had a maximum k-index of 12). When this was noticed, it was decided to stop data collection in the middle of this 20-25 degree shell (at which point the k-index had a value of 7). 2. We fully realise that this data collection does NOT fully meet the current Acta requirements (for at least a full data collection to 25 degrees) but we felt at the time that nothing substantial would be gained by spending time measuring "unobserved" reflections. The data set is 100% complete to a resolution of 0.48 but only 83.7% complete to 0.6 resolution. The reflection/parameter ratio is a satisfactory 10.9/1. 3. We were of the opinion that the data were adequate to establish the conformation of the cations unequivocally - and this was all that was of interest to chemists at that time - and they nested on the data for 14 years.....

 Alert Level C:



PLAT_302  Alert C Anion/Solvent Disorder .......................      50.00 Perc.

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               4505
         From the CIF: _diffrn_reflns_limit_ max hkl   15.    9.   28.
         From the CIF: _diffrn_reflns_limit_ min hkl  -17.    0.    0.
         TEST1: Expected hkl limits for theta max
         Calculated maximum hkl   17.   12.   28.
         Calculated minimum hkl  -17.  -12.  -28.
          ALERT: Expected hkl max differ from CIF values


 1 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The title salt, (1), containing the relatively electron-rich 1-pyrrolyl substituent was prepared in order to determine what effect the 1-pyrrolyl substitution would have on the conformation of the pentamethinecyanine moiety of the cation.

There are two independent cations and anions in the asymmetric unit of (1) with each of the anions disordered over two sites. The pentamethinecyanine moieties in the cations (Fig. 1) have similar, markedly non-planar, trans–cis–cis–trans conformations, with torsion angles Cn1—Cn2—Cn3—Cn4 and Cn2—Cn3—Cn4—Cn5 having values -22.8 (6), -30.7 (6), and -27.2 (6) and -26.4 (6)° for n = 1 and 2, respectively. It is interesting to compare these conformations with those found for the pentamethinecyanine moieties in 5-dimethylamino-N,N-dimethyl-3-(4-pyridyl)-2,4-pentadieniminium tetrafluorobate [(2); all-trans; Ferguson et al., 2001] and in tris(2-dimethylaminoethenyl)methylium perchlorate [(3); trans–trans–cis–trans; Dale, et al. 1988]. In (2), the relatively electron-poor 4-pyridyl substitutent is not conjugated with the pentamethinecyanine, and these two moieties form a dihedral angle of 60.58 (9)°. In (3), which may be regarded as a pentamethinecyanine carrying an electron-rich 2-dimethylaminoethenyl substituent at the central carbon, conjugative interaction results in a change in the conformation of the pentamethincyanine moiety in order to avoid a potentially severe steric interaction between C1—H (or C5—H) and C2—H of the 2-dimethylaminoethenyl substituent. In addition, the cation in (3), which has a threefold symmetry axis, is not planar but adopts a twisted-propeller shape.

In spite of their different conformations, bond lengths within the pentamethinecyanine moiety of (1) do not differ significantly from those reported for the all-trans pentamethinecyanine moieties in the simple parent salt (4) (Honda et al., 1986) and the 3-(4-pyridyl) derivative (2) (Ferguson et al., 2001). The bond lengths within the 1-pyrrolyl substituent of (1) are very similar to those reported (Ferguson & McAlees, 1990) for the 1-pyrrolyl fragment in the pyridinium salt (5), consistent with direct conjugation between the relatively electron-rich 1-pyrrolyl substituent and the electron-poor pentamethinecyanine and pyridinium moieties in (1) and (5) respectively. Such conjugation is also suggested by the relatively short bond between the pyrrole and pentamethinecyanine moieties [C13—N13 1.399 (5) Å and C23—N23 1.409 (5) Å]. With the pentamethinecyanine chain in the all-trans conformation, coplanarity with the pyrrole would result in severe steric interactions between the pyrrole α-H atoms and C1—H and C5—H. These and other interactions are avoided in (1) by adoption of the trans–cis–cis–trans conformation along with out-of-plane twisting as found for (3) (Dale et al., 1988).

S2. Experimental

A solution of dimethylamine (0.98 g, 22 mmol) in ethanol (7 ml) was added to a suspension of N-(2,4-dinitrophenyl)-4-(1-pyrrolyl)pyridinium chloride [(5); 3.47 g, 10.0 mmol; Ferguson & McAlees, 1990] in ethanol (20 ml) and the mixture was stirred at ambient temperature for 16 h. The resulting mixture was filtered, and the collected green–yellow powder (2,4-dinitroaniline) was washed with ethanol (3 × 10 ml). The combined filtrate and washings were evaporated in vacuo to leave a clear orange gum which was taken up in water (50 ml) and filtered to remove yellow insoluble material. The aqueous filtrate was then washed with chloroform (3 × 25 ml) and treated with an aqueous solution (10 ml) of NaBF₄ (1.2 g, 11.0 mmol). The resulting mixture was extracted with dichloromethane (3 × 30 ml), the combined extracts were dried (Na₂SO₄) and the solvent was evaporated to leave an orange–red gum. Crystallization from ethanol gave yellow hexagonal plates of (1) (2.32 g, 76% yield; m.p. 397.5–398.5 K).

S3. Refinement

Compound (1) crystallized in the monoclinic system; space group P2₁/c from the systematic absences. H atoms were treated as riding atoms with C—H 0.93 and 0.96 Å. Difference maps showed that methyl H atoms at C17, C19 and C29 were disordered and they were modelled using six H sites, each with occupancy 1/2, mutually offset by 60°. The H atoms of the other methyl groups were modelled with free rotation about the relevant C—C bond. It was also apparent that the F atoms of the BF₄^- ions were disordered over major and minor occupancy sites with common B atoms. The geometry of these tetrahedral BF₄^- anions was restrained to be near to tetrahedral by use of DFIX commands with an overall restrained B—F distance. The minor occupancy F atoms were allowed for with overall isotropic displacement parameters.

Computing details

Data collection: CAD-4-PC Software (Nonius, 1992); cell refinement: SET4 and CELDIM (Nonius 1992); data reduction: HELENA in PLATON (Spek, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON; software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 1998).

Figures

Fig. 1. Views of the two independent cations of (1) with our numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

N,N-dimethyl-5-dimethylamino-3-(pyrrole)-2,4-pentadieniminium tetrafluoroborate

Crystal data

C13H20N3^+·BF4^−	F(000) = 1280
Mr = 305.13	Dx = 1.287 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.882 (3) Å	Cell parameters from 25 reflections
b = 10.366 (2) Å	θ = 10.4–12.8°
c = 24.064 (3) Å	µ = 0.11 mm^−1
β = 121.987 (11)°	T = 293 K
V = 3148.7 (10) Å^3	Plate, yellow
Z = 8	0.43 × 0.43 × 0.30 mm

Data collection

Nonius CAD-4 diffractometer	Rint = 0.036
Radiation source: fine-focus sealed X-ray tube	θmax = 25.0°, θmin = 2.2°
Graphite monochromator	h = −17→15
θ–2θ scans	k = 0→9
5728 measured reflections	l = 0→28
4505 independent reflections	3 standard reflections every 120 min
2271 reflections with I > 2σ(I)	intensity decay: 1.0%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.061	H-atom parameters constrained
wR(F^2) = 0.220	w = 1/[σ^2(Fo^2) + (0.1129P)^2 + 0.6033P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
4505 reflections	Δρmax = 0.45 e Å^−3
414 parameters	Δρmin = −0.25 e Å^−3
40 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0060 (12)

Special details

Geometry. Mean-plane data from the final SHELXL97 refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

14.5859 (0.0061) x - 2.0099 (0.0203) y - 11.6285 (0.0323) z = 6.4419 (0.0217)

* -0.0338 (0.0020) C13 * 0.0352 (0.0029) N13 * 0.0181 (0.0028) C110 * -0.0200 (0.0030) C111 * -0.0161 (0.0030) C112 * 0.0165 (0.0029) C113 - 0.5126 (0.0059) C12 0.3706 (0.0060) C14

Rms deviation of fitted atoms = 0.0246

14.4318 (0.0082) x + 1.4102 (0.0212) y - 8.2248 (0.0458) z = 8.8197 (0.0186)

Angle to previous plane (with approximate e.s.d.) = 21.14 (0.09)

* -0.0015 (0.0011) C12 * 0.0043 (0.0032) C13 * -0.0015 (0.0011) C14 * -0.0013 (0.0010) N13

Rms deviation of fitted atoms = 0.0025

############################################################################

12.4475 (0.0180) x - 3.4360 (0.0209) y - 1.7526 (0.0400) z = 3.6544 (0.0156)

* -0.0157 (0.0021) C23 * 0.0146 (0.0029) N23 * 0.0058 (0.0029) C210 * -0.0030 (0.0031) C211 * -0.0148 (0.0032) C212 * 0.0132 (0.0030) C213 - 0.5310 (0.0059) C22 0.4506 (0.0059) C24

Rms deviation of fitted atoms = 0.0122

14.3297 (0.0088) x + 0.1696 (0.0211) y - 6.7756 (0.0480) z = 1.9557 (0.0201)

Angle to previous plane (with approximate e.s.d.) = 23.43 (0.19)

* -0.0020 (0.0011) C22 * 0.0057 (0.0031) C23 * -0.0020 (0.0011) C24 * -0.0018 (0.0009) N23

Rms deviation of fitted atoms = 0.0033

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N11	0.8488 (2)	0.5848 (4)	0.47096 (16)	0.0631 (10)
N12	0.7392 (3)	0.1643 (3)	0.33407 (16)	0.0642 (10)
N13	0.9173 (2)	0.1632 (4)	0.56541 (16)	0.0603 (9)
C11	0.8654 (3)	0.4606 (5)	0.47170 (19)	0.0594 (11)
H11	0.8763	0.4292	0.4395	0.071*
C12	0.8686 (3)	0.3708 (4)	0.51547 (19)	0.0602 (11)
H12	0.8640	0.4000	0.5504	0.072*
C13	0.8782 (3)	0.2392 (4)	0.50916 (19)	0.0552 (10)
C14	0.8509 (3)	0.1759 (4)	0.45105 (19)	0.0607 (11)
H14	0.8884	0.1024	0.4533	0.073*
C15	0.7707 (3)	0.2180 (4)	0.39070 (19)	0.0573 (11)
H15	0.7352	0.2924	0.3901	0.069*
C16	0.8466 (4)	0.6665 (5)	0.4216 (2)	0.0846 (14)
H16A	0.8698	0.6181	0.3974	0.127*
H16B	0.8930	0.7388	0.4423	0.127*
H16C	0.7757	0.6969	0.3922	0.127*
C17	0.8247 (4)	0.6455 (5)	0.5156 (2)	0.0932 (16)
H17A	0.8153	0.7365	0.5070	0.140*	0.50
H17B	0.8820	0.6312	0.5599	0.140*	0.50
H17C	0.7608	0.6092	0.5096	0.140*	0.50
H17D	0.8234	0.5814	0.5440	0.140*	0.50
H17E	0.7568	0.6868	0.4911	0.140*	0.50
H17F	0.8780	0.7087	0.5414	0.140*	0.50
C18	0.6483 (3)	0.2133 (5)	0.2737 (2)	0.0855 (15)
H18A	0.6178	0.2845	0.2836	0.128*
H18B	0.5965	0.1461	0.2529	0.128*
H18C	0.6706	0.2416	0.2449	0.128*
C19	0.7948 (4)	0.0557 (5)	0.3275 (2)	0.0938 (16)
H19A	0.7596	0.0304	0.2824	0.141*	0.50
H19B	0.7951	−0.0153	0.3532	0.141*	0.50
H19C	0.8664	0.0803	0.3427	0.141*	0.50
H19D	0.8545	0.0332	0.3698	0.141*	0.50
H19E	0.8189	0.0789	0.2990	0.141*	0.50
H19F	0.7477	−0.0167	0.3095	0.141*	0.50
C110	0.9735 (3)	0.2048 (5)	0.6302 (2)	0.0675 (12)
H110	0.9972	0.2884	0.6443	0.081*
C111	0.9878 (4)	0.1033 (6)	0.6689 (2)	0.0796 (14)
H111	1.0226	0.1047	0.7144	0.096*
C112	0.9406 (4)	−0.0059 (5)	0.6282 (3)	0.0818 (14)
H112	0.9390	−0.0891	0.6421	0.098*
C113	0.8988 (3)	0.0320 (5)	0.5665 (2)	0.0699 (12)
H113	0.8629	−0.0209	0.5298	0.084*
N21	0.3126 (3)	0.1161 (4)	0.31442 (18)	0.0724 (10)
N22	0.2958 (3)	−0.3225 (4)	0.40602 (17)	0.0643 (10)
N23	0.3872 (2)	0.0634 (3)	0.53204 (17)	0.0609 (9)
C21	0.3462 (3)	0.0524 (4)	0.3690 (2)	0.0603 (11)
H21	0.3822	−0.0242	0.3738	0.072*
C22	0.3340 (3)	0.0865 (4)	0.4201 (2)	0.0606 (11)
H22	0.3070	0.1677	0.4195	0.073*
C23	0.3601 (3)	0.0047 (4)	0.4723 (2)	0.0548 (11)
C24	0.3605 (3)	−0.1290 (4)	0.4707 (2)	0.0594 (11)
H24	0.4047	−0.1743	0.5092	0.071*
C25	0.2964 (3)	−0.1966 (4)	0.4133 (2)	0.0564 (11)
H25	0.2495	−0.1487	0.3765	0.068*
C26	0.3412 (4)	0.0793 (5)	0.2675 (2)	0.0950 (16)
H26A	0.3897	0.0080	0.2846	0.143*
H26B	0.3742	0.1510	0.2600	0.143*
H26C	0.2787	0.0544	0.2270	0.143*
C27	0.2450 (4)	0.2278 (5)	0.2980 (3)	0.1067 (18)
H27A	0.2866	0.3004	0.3233	0.160*
H27B	0.1912	0.2105	0.3075	0.160*
H27C	0.2124	0.2466	0.2522	0.160*
C28	0.2199 (4)	−0.3841 (5)	0.3437 (2)	0.0820 (14)
H28A	0.2575	−0.4317	0.3280	0.123*
H28B	0.1769	−0.3193	0.3122	0.123*
H28C	0.1755	−0.4419	0.3499	0.123*
C29	0.3691 (4)	−0.4083 (4)	0.4590 (2)	0.0796 (14)
H29A	0.3555	−0.4959	0.4438	0.119*	0.50
H29B	0.3593	−0.3996	0.4952	0.119*	0.50
H29C	0.4406	−0.3858	0.4729	0.119*	0.50
H29D	0.4148	−0.3582	0.4975	0.119*	0.50
H29E	0.4109	−0.4546	0.4461	0.119*	0.50
H29F	0.3297	−0.4684	0.4684	0.119*	0.50
C210	0.4237 (3)	0.1886 (5)	0.5507 (2)	0.0731 (13)
H210	0.4365	0.2475	0.5265	0.088*
C211	0.4372 (4)	0.2102 (6)	0.6097 (3)	0.0878 (16)
H211	0.4617	0.2863	0.6337	0.105*
C212	0.4079 (4)	0.0977 (6)	0.6288 (2)	0.0884 (16)
H212	0.4083	0.0863	0.6673	0.106*
C213	0.3788 (3)	0.0085 (5)	0.5808 (2)	0.0737 (13)
H213	0.3569	−0.0754	0.5810	0.088*
B1	0.9333 (3)	0.1009 (4)	0.80918 (15)	0.0781 (16)	0.779 (8)
F11	0.8449 (3)	0.1397 (5)	0.75446 (18)	0.138 (2)	0.779 (8)
F12	1.0163 (4)	0.1713 (6)	0.8198 (2)	0.146 (3)	0.779 (8)
F13	0.9211 (4)	0.1121 (7)	0.8600 (2)	0.198 (4)	0.779 (8)
F14	0.9517 (5)	−0.0213 (4)	0.8017 (3)	0.203 (4)	0.779 (8)
B2	0.5105 (3)	0.4095 (3)	0.34963 (18)	0.0850 (18)	0.903 (8)
F21	0.5381 (3)	0.2949 (3)	0.37923 (18)	0.1270 (18)	0.903 (8)
F22	0.4450 (3)	0.3908 (5)	0.28493 (16)	0.150 (2)	0.903 (8)
F23	0.4596 (3)	0.4834 (4)	0.3697 (2)	0.158 (2)	0.903 (8)
F24	0.5972 (3)	0.4702 (4)	0.3596 (3)	0.172 (3)	0.903 (8)
B3	0.9333 (3)	0.1009 (4)	0.80918 (15)	0.0781 (16)	0.221 (8)
F31	0.9290 (12)	0.2270 (5)	0.8182 (7)	0.124 (5)*	0.221 (8)
F32	1.0302 (6)	0.0696 (16)	0.8232 (7)	0.124 (5)*	0.221 (8)
F33	0.9136 (12)	0.0352 (13)	0.8494 (6)	0.124 (5)*	0.221 (8)
F34	0.8625 (9)	0.0686 (14)	0.7474 (3)	0.124 (5)*	0.221 (8)
B4	0.5105 (3)	0.4095 (3)	0.34963 (18)	0.0850 (18)	0.097 (8)
F41	0.6021 (18)	0.469 (4)	0.3895 (16)	0.195 (17)*	0.097 (8)
F42	0.473 (3)	0.362 (4)	0.3851 (17)	0.195 (17)*	0.097 (8)
F43	0.440 (3)	0.493 (3)	0.3059 (19)	0.195 (17)*	0.097 (8)
F44	0.526 (3)	0.313 (3)	0.319 (2)	0.195 (17)*	0.097 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.062 (2)	0.061 (3)	0.063 (2)	0.0031 (18)	0.0307 (18)	0.0050 (19)
N12	0.061 (2)	0.070 (2)	0.058 (2)	0.0012 (19)	0.0291 (18)	−0.0100 (19)
N13	0.0518 (18)	0.065 (3)	0.063 (2)	0.0034 (18)	0.0296 (17)	0.0033 (19)
C11	0.047 (2)	0.073 (4)	0.055 (2)	−0.004 (2)	0.0247 (19)	−0.004 (2)
C12	0.059 (2)	0.067 (3)	0.057 (3)	0.004 (2)	0.033 (2)	−0.002 (2)
C13	0.046 (2)	0.062 (3)	0.058 (3)	0.002 (2)	0.0273 (19)	0.001 (2)
C14	0.056 (2)	0.061 (3)	0.061 (3)	0.002 (2)	0.029 (2)	−0.005 (2)
C15	0.054 (2)	0.059 (3)	0.062 (3)	−0.006 (2)	0.032 (2)	−0.008 (2)
C16	0.081 (3)	0.081 (3)	0.094 (3)	0.002 (3)	0.048 (3)	0.020 (3)
C17	0.118 (4)	0.079 (3)	0.090 (3)	0.020 (3)	0.060 (3)	−0.001 (3)
C18	0.082 (3)	0.090 (4)	0.060 (3)	0.005 (3)	0.021 (2)	0.000 (3)
C19	0.096 (4)	0.109 (4)	0.072 (3)	0.015 (3)	0.042 (3)	−0.018 (3)
C110	0.062 (3)	0.085 (3)	0.054 (3)	0.002 (2)	0.030 (2)	0.001 (3)
C111	0.064 (3)	0.107 (4)	0.067 (3)	0.011 (3)	0.034 (2)	0.021 (3)
C112	0.061 (3)	0.082 (4)	0.092 (4)	0.008 (3)	0.034 (3)	0.026 (3)
C113	0.058 (3)	0.066 (4)	0.076 (3)	0.003 (2)	0.029 (2)	0.006 (3)
N21	0.068 (2)	0.071 (3)	0.065 (2)	0.000 (2)	0.0264 (19)	0.014 (2)
N22	0.070 (2)	0.054 (3)	0.074 (2)	0.0013 (19)	0.041 (2)	0.001 (2)
N23	0.0516 (19)	0.062 (3)	0.068 (2)	−0.0054 (17)	0.0311 (17)	−0.004 (2)
C21	0.049 (2)	0.055 (3)	0.065 (3)	−0.003 (2)	0.022 (2)	0.007 (2)
C22	0.055 (2)	0.054 (3)	0.069 (3)	0.004 (2)	0.030 (2)	0.006 (2)
C23	0.043 (2)	0.053 (3)	0.064 (3)	−0.0012 (19)	0.0255 (19)	0.001 (2)
C24	0.049 (2)	0.059 (3)	0.064 (3)	0.002 (2)	0.025 (2)	0.006 (2)
C25	0.054 (2)	0.055 (3)	0.065 (3)	0.006 (2)	0.035 (2)	0.008 (2)
C26	0.104 (4)	0.107 (4)	0.068 (3)	−0.004 (3)	0.042 (3)	0.007 (3)
C27	0.103 (4)	0.091 (4)	0.107 (4)	0.023 (3)	0.042 (3)	0.039 (3)
C28	0.097 (3)	0.073 (3)	0.079 (3)	−0.008 (3)	0.049 (3)	−0.014 (3)
C29	0.087 (3)	0.059 (3)	0.091 (3)	0.013 (3)	0.046 (3)	0.017 (3)
C210	0.058 (3)	0.065 (3)	0.085 (3)	−0.001 (2)	0.030 (2)	−0.007 (3)
C211	0.067 (3)	0.091 (4)	0.080 (4)	0.010 (3)	0.022 (3)	−0.020 (3)
C212	0.072 (3)	0.114 (5)	0.070 (3)	0.005 (3)	0.032 (3)	−0.009 (3)
C213	0.067 (3)	0.088 (4)	0.065 (3)	−0.014 (3)	0.035 (2)	−0.006 (3)
B1	0.082 (4)	0.083 (4)	0.075 (4)	0.010 (3)	0.045 (3)	0.012 (3)
F11	0.114 (3)	0.162 (5)	0.111 (3)	0.043 (3)	0.042 (3)	0.060 (3)
F12	0.170 (5)	0.167 (5)	0.124 (3)	−0.096 (4)	0.094 (3)	−0.047 (3)
F13	0.183 (5)	0.348 (10)	0.118 (4)	0.045 (6)	0.117 (4)	0.034 (5)
F14	0.219 (7)	0.070 (3)	0.310 (9)	0.043 (4)	0.132 (6)	0.028 (4)
B2	0.091 (4)	0.074 (4)	0.095 (5)	0.016 (4)	0.053 (4)	0.010 (4)
F21	0.151 (3)	0.092 (3)	0.119 (3)	0.033 (2)	0.059 (3)	0.046 (2)
F22	0.163 (4)	0.157 (4)	0.092 (3)	0.027 (3)	0.041 (3)	0.026 (3)
F23	0.196 (5)	0.131 (4)	0.224 (5)	0.045 (3)	0.164 (4)	0.005 (3)
F24	0.125 (4)	0.102 (3)	0.308 (7)	−0.015 (3)	0.127 (4)	−0.037 (4)
B3	0.082 (4)	0.083 (4)	0.075 (4)	0.010 (3)	0.045 (3)	0.012 (3)
B4	0.091 (4)	0.074 (4)	0.095 (5)	0.016 (4)	0.053 (4)	0.010 (4)

Geometric parameters (Å, º)

N11—C11	1.310 (5)	N23—C210	1.387 (5)
N11—C16	1.447 (5)	N23—C213	1.368 (5)
N11—C17	1.444 (6)	C21—C22	1.381 (5)
N12—C15	1.308 (5)	C21—H21	0.93
N12—C18	1.455 (5)	C22—C23	1.389 (5)
N12—C19	1.454 (6)	C22—H22	0.93
N13—C13	1.399 (5)	C23—C24	1.387 (6)
N13—C110	1.390 (5)	C24—C25	1.383 (5)
N13—C113	1.390 (5)	C24—H24	0.93
C11—C12	1.387 (6)	C25—H25	0.93
C11—H11	0.93	C26—H26A	0.96
C12—C13	1.389 (6)	C26—H26B	0.96
C12—H12	0.93	C26—H26C	0.96
C13—C14	1.396 (5)	C27—H27A	0.96
C14—C15	1.374 (5)	C27—H27B	0.96
C14—H14	0.93	C27—H27C	0.96
C15—H15	0.93	C28—H28A	0.96
C16—H16A	0.96	C28—H28B	0.96
C16—H16B	0.96	C28—H28C	0.96
C16—H16C	0.96	C29—H29A	0.96
C17—H17A	0.96	C29—H29B	0.96
C17—H17B	0.96	C29—H29C	0.96
C17—H17C	0.96	C29—H29D	0.96
C17—H17D	0.96	C29—H29E	0.96
C17—H17E	0.96	C29—H29F	0.96
C17—H17F	0.96	C210—C211	1.343 (6)
C18—H18A	0.96	C210—H210	0.93
C18—H18B	0.96	C211—C212	1.406 (7)
C18—H18C	0.96	C211—H211	0.93
C19—H19A	0.96	C212—C213	1.359 (6)
C19—H19B	0.96	C212—H212	0.93
C19—H19C	0.96	C213—H213	0.93
C19—H19D	0.96	B1—F11	1.338 (3)
C19—H19E	0.96	B1—F12	1.338 (3)
C19—H19F	0.96	B1—F13	1.332 (3)
C110—C111	1.345 (6)	B1—F14	1.329 (3)
C110—H110	0.93	B1—F31	1.332 (3)
C111—C112	1.417 (7)	B1—F32	1.335 (3)
C111—H111	0.93	B1—F33	1.336 (3)
C112—C113	1.330 (6)	B1—F34	1.332 (3)
C112—H112	0.93	B2—F21	1.333 (3)
C113—H113	0.93	B2—F22	1.343 (3)
N21—C21	1.310 (5)	B2—F23	1.334 (3)
N21—C26	1.452 (6)	B2—F24	1.338 (3)
N21—C27	1.444 (6)	B2—F41	1.334 (3)
N22—C25	1.316 (5)	B2—F42	1.339 (3)
N22—C28	1.462 (5)	B2—F43	1.334 (3)
N22—C29	1.461 (5)	B2—F44	1.334 (3)
N23—C23	1.409 (5)
C11—N11—C17	122.6 (4)	C29—N22—C28	116.4 (4)
C11—N11—C16	120.6 (4)	C213—N23—C210	108.0 (4)
C17—N11—C16	116.7 (4)	C213—N23—C23	126.1 (4)
C15—N12—C19	122.2 (4)	C210—N23—C23	125.8 (4)
C15—N12—C18	121.5 (4)	N21—C21—C22	127.1 (4)
C19—N12—C18	116.4 (3)	N21—C21—H21	116.4
C113—N13—C110	106.8 (4)	C22—C21—H21	116.4
C113—N13—C13	125.7 (4)	C21—C22—C23	122.9 (4)
C110—N13—C13	127.2 (4)	C21—C22—H22	118.6
N11—C11—C12	126.8 (4)	C23—C22—H22	118.6
N11—C11—H11	116.6	C24—C23—C22	126.1 (4)
C12—C11—H11	116.6	C24—C23—N23	117.1 (4)
C11—C12—C13	122.6 (4)	C22—C23—N23	116.8 (4)
C11—C12—H12	118.7	C25—C24—C23	121.5 (4)
C13—C12—H12	118.7	C25—C24—H24	119.2
C12—C13—C14	125.4 (4)	C23—C24—H24	119.2
C12—C13—N13	117.5 (4)	N22—C25—C24	126.0 (4)
C14—C13—N13	117.1 (4)	N22—C25—H25	117.0
C15—C14—C13	122.6 (4)	C24—C25—H25	117.0
C15—C14—H14	118.7	N21—C26—H26A	109.5
C13—C14—H14	118.7	N21—C26—H26B	109.5
N12—C15—C14	126.7 (4)	H26A—C26—H26B	109.5
N12—C15—H15	116.7	N21—C26—H26C	109.5
C14—C15—H15	116.7	H26A—C26—H26C	109.5
N11—C16—H16A	109.5	H26B—C26—H26C	109.5
N11—C16—H16B	109.5	N21—C27—H27A	109.5
H16A—C16—H16B	109.5	N21—C27—H27B	109.5
N11—C16—H16C	109.5	H27A—C27—H27B	109.5
H16A—C16—H16C	109.5	N21—C27—H27C	109.5
H16B—C16—H16C	109.5	H27A—C27—H27C	109.5
N11—C17—H17A	109.5	H27B—C27—H27C	109.5
N11—C17—H17B	109.5	N22—C28—H28A	109.5
H17A—C17—H17B	109.5	N22—C28—H28B	109.5
N11—C17—H17C	109.5	H28A—C28—H28B	109.5
H17A—C17—H17C	109.5	N22—C28—H28C	109.5
H17B—C17—H17C	109.5	H28A—C28—H28C	109.5
N11—C17—H17D	109.5	H28B—C28—H28C	109.5
H17A—C17—H17D	141.1	N22—C29—H29A	109.5
H17B—C17—H17D	56.3	N22—C29—H29B	109.5
H17C—C17—H17D	56.3	H29A—C29—H29B	109.5
N11—C17—H17E	109.5	N22—C29—H29C	109.5
H17A—C17—H17E	56.3	H29A—C29—H29C	109.5
H17B—C17—H17E	141.1	H29B—C29—H29C	109.5
H17C—C17—H17E	56.3	N22—C29—H29D	109.5
H17D—C17—H17E	109.5	H29A—C29—H29D	141.1
N11—C17—H17F	109.5	H29B—C29—H29D	56.3
H17A—C17—H17F	56.3	H29C—C29—H29D	56.3
H17B—C17—H17F	56.3	N22—C29—H29E	109.5
H17C—C17—H17F	141.1	H29A—C29—H29E	56.3
H17D—C17—H17F	109.5	H29B—C29—H29E	141.1
H17E—C17—H17F	109.5	H29C—C29—H29E	56.3
N12—C18—H18A	109.5	H29D—C29—H29E	109.5
N12—C18—H18B	109.5	N22—C29—H29F	109.5
H18A—C18—H18B	109.5	H29A—C29—H29F	56.3
N12—C18—H18C	109.5	H29B—C29—H29F	56.3
H18A—C18—H18C	109.5	H29C—C29—H29F	141.1
H18B—C18—H18C	109.5	H29D—C29—H29F	109.5
N12—C19—H19A	109.5	H29E—C29—H29F	109.5
N12—C19—H19B	109.5	C211—C210—N23	108.2 (5)
H19A—C19—H19B	109.5	C211—C210—H210	125.9
N12—C19—H19C	109.5	N23—C210—H210	125.9
H19A—C19—H19C	109.5	C210—C211—C212	108.0 (5)
H19B—C19—H19C	109.5	C210—C211—H211	126.0
N12—C19—H19D	109.5	C212—C211—H211	126.0
H19A—C19—H19D	141.1	C213—C212—C211	107.5 (5)
H19B—C19—H19D	56.3	C213—C212—H212	126.3
H19C—C19—H19D	56.3	C211—C212—H212	126.3
N12—C19—H19E	109.5	C212—C213—N23	108.3 (5)
H19A—C19—H19E	56.3	C212—C213—H213	125.9
H19B—C19—H19E	141.1	N23—C213—H213	125.9
H19C—C19—H19E	56.3	F14—B1—F13	110.2 (4)
H19D—C19—H19E	109.5	F31—B1—F34	110.5 (4)
N12—C19—H19F	109.5	F31—B1—F32	109.7 (5)
H19A—C19—H19F	56.3	F34—B1—F32	109.3 (4)
H19B—C19—H19F	56.3	F31—B1—F33	109.6 (4)
H19C—C19—H19F	141.1	F34—B1—F33	109.5 (5)
H19D—C19—H19F	109.5	F32—B1—F33	108.3 (4)
H19E—C19—H19F	109.5	F14—B1—F12	108.0 (3)
C111—C110—N13	108.4 (4)	F13—B1—F12	109.7 (3)
C111—C110—H110	125.8	F14—B1—F11	108.6 (3)
N13—C110—H110	125.8	F13—B1—F11	109.7 (3)
C110—C111—C112	107.9 (4)	F12—B1—F11	110.6 (3)
C110—C111—H111	126.1	F21—B2—F23	113.1 (3)
C112—C111—H111	126.1	F43—B2—F44	109.9 (5)
C113—C112—C111	107.7 (5)	F43—B2—F41	109.8 (5)
C113—C112—H112	126.2	F44—B2—F41	109.9 (5)
C111—C112—H112	126.2	F21—B2—F24	109.1 (3)
C112—C113—N13	109.3 (4)	F23—B2—F24	110.1 (3)
C112—C113—H113	125.4	F43—B2—F42	109.1 (5)
N13—C113—H113	125.4	F44—B2—F42	109.0 (5)
C21—N21—C27	121.3 (4)	F41—B2—F42	109.1 (5)
C21—N21—C26	122.2 (4)	F21—B2—F22	108.6 (3)
C27—N21—C26	116.5 (4)	F23—B2—F22	107.5 (3)
C25—N22—C29	122.5 (4)	F24—B2—F22	108.3 (3)
C25—N22—C28	121.1 (4)
C17—N11—C11—C12	−3.6 (6)	C27—N21—C21—C22	−7.6 (6)
C16—N11—C11—C12	−179.3 (4)	C26—N21—C21—C22	172.3 (4)
N11—C11—C12—C13	174.6 (4)	N21—C21—C22—C23	171.4 (4)
C11—C12—C13—C14	−22.8 (6)	C21—C22—C23—C24	−27.2 (6)
C11—C12—C13—N13	158.0 (3)	C21—C22—C23—N23	153.9 (4)
C113—N13—C13—C12	155.7 (4)	C213—N23—C23—C24	−23.8 (6)
C110—N13—C13—C12	−18.3 (6)	C210—N23—C23—C24	158.5 (4)
C113—N13—C13—C14	−23.5 (5)	C213—N23—C23—C22	155.1 (4)
C110—N13—C13—C14	162.5 (4)	C210—N23—C23—C22	−22.6 (5)
C12—C13—C14—C15	−30.7 (6)	C22—C23—C24—C25	−26.4 (6)
N13—C13—C14—C15	148.5 (4)	N23—C23—C24—C25	152.5 (3)
C19—N12—C15—C14	−6.4 (7)	C29—N22—C25—C24	−3.2 (6)
C18—N12—C15—C14	175.7 (4)	C28—N22—C25—C24	176.3 (4)
C13—C14—C15—N12	−179.3 (4)	C23—C24—C25—N22	175.6 (4)
C113—N13—C110—C111	−0.5 (4)	C213—N23—C210—C211	−0.1 (5)
C13—N13—C110—C111	174.4 (4)	C23—N23—C210—C211	177.9 (4)
N13—C110—C111—C112	0.5 (5)	N23—C210—C211—C212	−0.6 (5)
C110—C111—C112—C113	−0.3 (5)	C210—C211—C212—C213	1.1 (6)
C111—C112—C113—N13	0.0 (5)	C211—C212—C213—N23	−1.2 (5)
C110—N13—C113—C112	0.2 (5)	C210—N23—C213—C212	0.8 (5)
C13—N13—C113—C112	−174.7 (4)	C23—N23—C213—C212	−177.2 (4)