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Bis­[μ-2-(phenyl­amido)­pyridine]­bis­{[2-(phenyl­amino)­pyridine]­lithium(I)}

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aSchool of Natural Sciences (Chemistry), University of Newcastle upon Tyne, Newcastle upon Tyne NE1 7RU, England
*Correspondence e-mail: w.clegg@ncl.ac.uk

(Received 29 September 2004; accepted 1 October 2004; online 9 October 2004)

The title complex, [Li(PhN-2-C5H4N)(PhNH-2-C5H4N)]2 or [Li2(C11H9N2)2(C11H10N2)2], is centrosymmetric with a central Li2N2 ring formed by two amide ligands bridging the two Li+ centres. Each amide ligand also coordinates through its pyridine N atom to one of the Li+ cations, giving LiNCN chelate four-membered rings. Each neutral amine ligand coordinates terminally to one Li+ cation and forms an intramolecular N—H⋯N hydrogen bond by donation from its amine group to the bridging amido N atom of one of the amide ligands. The coordination of Li is distorted tetrahedral by two bridging amido and two pyridyl N atoms. The complex is the product of partial deprotonation of 2-phenyl­amino­pyridine by alkyl­lithium reagents, the remaining amine NH groups being sterically inaccessible even to strong bases.

Comment

The anion L of 2-phenyl­amino­pyridine (HL) has been extensively used as a ligand in transition metal chemistry. Its two N atoms can be used to bridge pairs of metal ions or to chelate a single metal ion. The Cambridge Structural Database (CSD, Version 5.25, with updates to April 2004; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) contains over 30 examples of the former type of complex and ten of the latter. Its use in complexes of main-group metals has been more restricted. The 20 structures in the CSD include three with aluminium, nine with alkali metals, and the others contain two metals (Li and Zn, or Li and Al). In these complexes, the ligand displays a variety of chelating and bridging modes, with attachment to as many as four metal centres. Some of the lithium complexes are fascinating clusters encapsulating hydride anions (Armstrong et al., 1999[Armstrong, D. R., Clegg, W., Davies, R. P., Liddle, S. T., Linton, D. J., Raithby, P. R., Snaith, R. & Wheatley, A. E. H. (1999). Angew. Chem. Int. Ed. Engl. 38, 3367-3370.]). We have recently reported some structures in which the anion remains uncoordinated to alkali metal cations, which are sandwiched by crown ethers to generate separated ion-pair complexes (Liddle et al., 2004[Liddle, S. T., Clegg, W. & Morrison, C. A. (2004). Dalton Trans. pp. 2514-2525.]).[link]

[Scheme 1]

In our previous work with this ligand, we found that it was surprisingly difficult to deprotonate it fully by treatment with alkyl­lithium reagents. In many reactions, the product contained equal amounts of the desired anion and the parent amine, often linked together by an N—H⋯N hydrogen bond. Various attempts to overcome this reluctance of the amine to full stoichiometric deprotonation included metathesis reactions in which a complex of the fully deprotonated ligand with a different alkali metal was treated with a compound of lithium. In order to generate the complex [(15-crown-5)2Li]+·L, the corresponding potassium salt was treated with lithium iodide in THF solution. The title complex was the unexpected solid product, in low yield (ca 20%), indicating that other unidentified products remained in solution.

After determining its crystal structure, we discovered that the same complex had been prepared previously by Polamo & Leskelä (1996[Polamo, M. & Leskelä, M. (1996). J. Chem. Soc. Dalton Trans. pp. 4345-4349.]), who also determined its structure. It is of interest that their synthesis was also unintentional (in an attempt to produce a zirconium complex), and that it represents another half-deprotonation of HL by butyl­lithium. We report the results of our work here because the structure is of significantly higher precision and in order to compare the structure with those of related compounds, some of which have only recently been published.

The title complex, (I[link]), is dimeric and centrosymmetric (Fig. 1[link]). Two L ligands act as bridges between two Li+ cations, through their amido N atoms, to give a central four-membered Li2N2 ring, a common feature in structural lithium amide chemistry. The pyridine N atom of each bridging ligand coordinates to one lithium centre, generating a four-membered LiNCN chelate ring. Distorted tetrahedral coord­ination of each Li+ is completed by terminal attachment of the pyridine N atoms of a neutral LH mol­ecule, the NH group of which is hydrogen bonded to one of the bridging amido N atoms (Tables 1 and 2).

The combined chelating and bridging functions of the anionic ligand L and the combination of coordination and hydrogen bonding for the neutral ligand HL bring both of these ligands into a syn arrangement of the two N atoms, in contrast to the preferred anti arrangement for the uncomplexed anion (Liddle et al., 2004[Liddle, S. T., Clegg, W. & Morrison, C. A. (2004). Dalton Trans. pp. 2514-2525.]). The syn arrangement, unlike the anti arrangement, does not permit coplanarity of the two rings, because of unfavourable steric interaction of H atoms, so the phenyl ring is twisted around the N—C bond, well out of the mean plane of the rest of the ligand [dihedral angles are 51.39 (3) and 53.45 (4)° for L and HL, respectively, in the title complex]. A similar effect has been seen for other chelate complexes of L (Liddle et al., 2004[Liddle, S. T., Clegg, W. & Morrison, C. A. (2004). Dalton Trans. pp. 2514-2525.]) and for uncomplexed HL (Polamo et al., 1997[Polamo, M., Repo, T. & Leskelä, M. (1997). Acta Chem. Scand. 51, 325-329.]), which forms a hydrogen-bonded dimer.

A relatively strong hydrogen bond between HL and L occurs also in the complexes [(12-crown-4)2M]+[L·HL], with M = Li, Na, K (Liddle & Clegg, 2003[Liddle, S. T. & Clegg, W. (2003). Polyhedron, 22, 3507-3513.]). The lithium complex in this series was also obtained as an unexpected product of partial li­thia­tion of HL and has the hydrogen-bonded [L·HL] unit as an uncoordinated anion; the sodium and potassium complexes were generated from it by metathesis reactions. The same behaviour was observed 20 years ago by Barr et al. (1984a[Barr, D., Clegg, W., Mulvey, R. E. & Snaith, R. (1984a). J. Chem. Soc. Chem. Commun. pp. 469-470.]), also in a lithium complex, [{(Me2N)3PO}Li(L)(HL)], which was first obtained as a minor product in the synthesis of [{(Me2N)3PO}Li(L)]2 (Barr et al., 1984b[Barr, D., Clegg, W., Mulvey, R. E. & Snaith, R. (1984b). J. Chem. Soc. Chem. Commun. pp. 700-701.]) and subsequently in a targeted synthesis with reagents in the appropriate stoichiometry. As in the title complex, the hydrogen-bonded combination of coordinated L and HL ligands here necessarily involves a short Li⋯H contact, but this should probably not be regarded as a direct interaction, of the agostic kind or otherwise. The apparent tendency of HL and L to associate by hydrogen bonding does, however, seem to be linked to the failure of organolithium reagents to deprotonate HL completely in these reactions, and may be the cause rather than a result of this, the N—H⋯N proton being thereby shielded from attack by the base. The inaccessibility of this site is demonstrated by the space-filling representation in Fig. 2[link], where the amine H atom is barely visible; this is true in all directions of view.

[Figure 1]
Figure 1
The molecular structure of (I[link]) with atom labels and 50% probability ellipsoids. H atoms, except for those involved in hydrogen bonding, have been omitted. Hydro­gen bonds are shown as dashed lines. Unlabelled atoms are related to the labelled atoms by the symmetry code (1 − x, 1 − y, 1z − z.
[Figure 2]
Figure 2
Space-filling representation of (I[link]), including H atoms. The amine H atom is barely visible, next to its N atom and an Li atom.

Experimental

A solution of [(15-crown-5)2K]L (Liddle et al., 2004[Liddle, S. T., Clegg, W. & Morrison, C. A. (2004). Dalton Trans. pp. 2514-2525.]) (0.89 g, 1.38 mmol) in THF (50 ml) was added to solid LiI (0.18 g, 1.38 mmol), giving a turbid yellow solution, which was stirred for one day. The solution was filtered and volatile materials removed in vacuo, to give a dark orange oil. Recrystallization from toluene yielded crystals of the title compound (0.05 g, 21%).

Crystal data
  • [Li2(C11H9N2)2(C11H10N2)2]

  • Mr = 692.70

  • Triclinic, [P\overline 1]

  • a = 8.7031 (8) Å

  • b = 10.3718 (10) Å

  • c = 11.5289 (11) Å

  • α = 116.715 (2)°

  • β = 92.739 (2)°

  • γ = 91.216 (2)°

  • V = 927.46 (15) Å3

  • Z = 1

  • Dx = 1.240 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3543 reflections

  • θ = 2.2–28.5°

  • μ = 0.08 mm−1

  • T = 160 (2) K

  • Plate, yellow

  • 0.70 × 0.52 × 0.08 mm

Data collection
  • Bruker SMART 1 K CCD diffractometer

  • Thin-slice ω scans

  • Absorption correction: none

  • 5683 measured reflections

  • 4165 independent reflections

  • 2868 reflections with I > 2σ(I)

  • Rint = 0.014

  • θmax = 28.6°

  • h = −11 → 11

  • k = −13 → 11

  • l = −14 → 14

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.102

  • S = 0.92

  • 4165 reflections

  • 321 parameters

  • All H-atom parameters refined

  • w = 1/[σ2(Fo2) + (0.0563P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.20 e Å−3

  • Extinction correction: SHELXTL

  • Extinction coefficient: 0.011 (3)

Table 1
Selected geometric parameters (Å, °)

Li—N1 2.036 (3)
Li—N2 2.187 (3)
Li—N2i 2.022 (3)
Li—N3 2.002 (3)
N1—Li—N2 65.19 (8)
N1—Li—N2i 118.30 (13)
N1—Li—N3 112.43 (13)
N2—Li—N2i 110.67 (12)
N2—Li—N3 120.85 (13)
N2i—Li—N3 118.54 (12)
Symmetry code: (i) 1-x,1-y,1-z.

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N4—H4N⋯N2i 0.900 (16) 2.288 (17) 3.1763 (16) 169.1 (13)
Symmetry code: (i) 1-x,1-y,1-z.

All H atoms were located in a difference Fourier synthesis and refined with individual isotropic displacement parameters. C—H distances are in the range 0.916 (17)–0.992 (17) Å, and the unique N—H distance is 0.900 (16) Å.

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001[Sheldrick, G. M. (2001). SHELXTL. Version 5. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information


Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Bis[µ-2-(phenylamido)pyridine]bis{[2-(phenylamino)pyridine]lithium(I)} top
Crystal data top
[Li2(C11H9N2)2(C11H10N2)2]Z = 1
Mr = 692.70F(000) = 364
Triclinic, P1Dx = 1.240 Mg m3
a = 8.7031 (8) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.3718 (10) ÅCell parameters from 3543 reflections
c = 11.5289 (11) Åθ = 2.2–28.5°
α = 116.715 (2)°µ = 0.08 mm1
β = 92.739 (2)°T = 160 K
γ = 91.216 (2)°Plate, yellow
V = 927.46 (15) Å30.70 × 0.52 × 0.08 mm
Data collection top
Bruker SMART 1K CCD
diffractometer
2868 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.014
Graphite monochromatorθmax = 28.6°, θmin = 2.0°
Detector resolution: 8.192 pixels mm-1h = 1111
thin–slice ω scansk = 1311
5683 measured reflectionsl = 1414
4165 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040All H-atom parameters refined
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0563P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.92(Δ/σ)max < 0.001
4165 reflectionsΔρmax = 0.23 e Å3
321 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.011 (3)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Li0.3855 (3)0.5671 (3)0.5221 (2)0.0406 (6)
N10.27806 (13)0.42171 (12)0.56848 (11)0.0317 (3)
N20.52228 (12)0.50692 (11)0.65280 (10)0.0264 (2)
C10.14004 (17)0.36108 (15)0.56935 (15)0.0357 (3)
H10.0743 (18)0.3379 (16)0.4933 (15)0.044 (4)*
C20.09729 (17)0.33301 (16)0.66845 (15)0.0372 (3)
H20.0035 (19)0.2903 (16)0.6635 (15)0.045 (4)*
C30.20271 (18)0.36851 (16)0.77320 (15)0.0395 (4)
H30.1773 (19)0.3497 (17)0.8474 (16)0.056 (5)*
C40.34521 (17)0.42868 (15)0.77534 (14)0.0338 (3)
H40.4166 (18)0.4513 (16)0.8458 (14)0.040 (4)*
C50.38331 (15)0.45526 (13)0.67015 (12)0.0253 (3)
C60.62527 (15)0.58820 (13)0.76016 (12)0.0251 (3)
C70.58101 (17)0.68904 (15)0.88262 (13)0.0327 (3)
H70.4730 (19)0.7012 (16)0.8940 (14)0.043 (4)*
C80.68913 (18)0.76838 (16)0.98206 (14)0.0386 (4)
H80.6545 (18)0.8382 (17)1.0639 (15)0.048 (4)*
C90.84486 (18)0.75217 (16)0.96387 (14)0.0381 (4)
H90.9204 (17)0.8091 (15)1.0341 (14)0.038 (4)*
C100.89026 (17)0.65500 (15)0.84356 (14)0.0355 (3)
H101.0009 (19)0.6393 (16)0.8305 (15)0.047 (4)*
C110.78262 (16)0.57577 (14)0.74348 (13)0.0293 (3)
H110.8158 (19)0.5099 (17)0.6655 (16)0.051 (5)*
N30.28231 (13)0.75574 (11)0.59060 (11)0.0314 (3)
N40.33760 (14)0.79794 (13)0.41807 (11)0.0323 (3)
H4N0.3784 (19)0.7106 (17)0.3870 (15)0.046 (4)*
C120.20863 (18)0.78881 (16)0.69984 (14)0.0370 (3)
H120.2276 (17)0.7254 (16)0.7419 (14)0.042 (4)*
C130.11184 (19)0.90076 (15)0.75203 (14)0.0385 (4)
H130.065 (2)0.9179 (17)0.8293 (16)0.051 (5)*
C140.09143 (18)0.98592 (15)0.68881 (14)0.0370 (3)
H140.0199 (19)1.0660 (17)0.7219 (15)0.047 (4)*
C150.16715 (16)0.95821 (14)0.57888 (14)0.0333 (3)
H150.1526 (17)1.0182 (16)0.5340 (14)0.041 (4)*
C160.26182 (15)0.84025 (13)0.53066 (12)0.0278 (3)
C170.31804 (15)0.85230 (14)0.32528 (13)0.0306 (3)
C180.34383 (18)0.99792 (17)0.35960 (17)0.0407 (4)
H180.3774 (18)1.0631 (17)0.4482 (15)0.044 (4)*
C190.3265 (2)1.0454 (2)0.2653 (2)0.0527 (5)
H190.347 (2)1.144 (2)0.2929 (18)0.074 (6)*
C200.2847 (2)0.9495 (2)0.13783 (19)0.0540 (5)
H200.271 (2)0.9811 (19)0.0716 (18)0.066 (5)*
C210.26074 (18)0.8049 (2)0.10362 (17)0.0455 (4)
H210.229 (2)0.7353 (18)0.0125 (17)0.056 (5)*
C220.27653 (16)0.75598 (17)0.19709 (14)0.0354 (3)
H220.2593 (18)0.6514 (17)0.1689 (15)0.047 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Li0.0473 (15)0.0401 (13)0.0407 (14)0.0186 (11)0.0176 (11)0.0217 (11)
N10.0314 (6)0.0335 (6)0.0311 (6)0.0035 (5)0.0012 (5)0.0154 (5)
N20.0263 (6)0.0302 (6)0.0232 (5)0.0040 (5)0.0053 (4)0.0119 (4)
C10.0318 (8)0.0343 (8)0.0403 (8)0.0017 (6)0.0029 (7)0.0168 (7)
C20.0301 (8)0.0339 (8)0.0502 (9)0.0019 (6)0.0064 (7)0.0209 (7)
C30.0409 (9)0.0439 (9)0.0432 (9)0.0010 (7)0.0089 (7)0.0275 (7)
C40.0344 (8)0.0402 (8)0.0330 (8)0.0019 (6)0.0020 (6)0.0220 (6)
C50.0279 (7)0.0228 (6)0.0253 (6)0.0082 (5)0.0052 (5)0.0104 (5)
C60.0288 (7)0.0243 (6)0.0255 (6)0.0047 (5)0.0039 (5)0.0138 (5)
C70.0317 (8)0.0351 (8)0.0293 (7)0.0073 (6)0.0065 (6)0.0121 (6)
C80.0449 (9)0.0379 (8)0.0267 (7)0.0059 (7)0.0057 (7)0.0086 (6)
C90.0405 (9)0.0359 (8)0.0326 (8)0.0028 (7)0.0047 (7)0.0118 (6)
C100.0300 (8)0.0348 (8)0.0415 (8)0.0013 (6)0.0041 (6)0.0168 (7)
C110.0315 (7)0.0278 (7)0.0274 (7)0.0044 (6)0.0078 (6)0.0107 (6)
N30.0362 (7)0.0288 (6)0.0312 (6)0.0097 (5)0.0056 (5)0.0146 (5)
N40.0381 (7)0.0291 (6)0.0334 (6)0.0125 (5)0.0082 (5)0.0164 (5)
C120.0473 (9)0.0337 (7)0.0330 (8)0.0100 (7)0.0082 (7)0.0168 (6)
C130.0487 (9)0.0341 (8)0.0308 (8)0.0105 (7)0.0117 (7)0.0116 (6)
C140.0403 (9)0.0297 (7)0.0358 (8)0.0114 (6)0.0057 (7)0.0095 (6)
C150.0374 (8)0.0276 (7)0.0341 (8)0.0081 (6)0.0025 (6)0.0129 (6)
C160.0288 (7)0.0252 (6)0.0272 (7)0.0023 (5)0.0003 (5)0.0100 (5)
C170.0239 (7)0.0359 (7)0.0390 (8)0.0061 (6)0.0061 (6)0.0224 (6)
C180.0387 (9)0.0379 (8)0.0502 (10)0.0014 (7)0.0030 (7)0.0240 (8)
C190.0492 (10)0.0510 (10)0.0795 (14)0.0085 (8)0.0151 (9)0.0473 (10)
C200.0481 (10)0.0799 (13)0.0637 (12)0.0216 (9)0.0189 (9)0.0564 (11)
C210.0372 (9)0.0666 (11)0.0411 (9)0.0151 (8)0.0113 (7)0.0304 (9)
C220.0308 (8)0.0410 (8)0.0386 (8)0.0096 (6)0.0097 (6)0.0207 (7)
Geometric parameters (Å, º) top
Li—N12.036 (3)C10—C111.3768 (19)
Li—N22.187 (3)C11—H110.916 (17)
Li—N2i2.022 (3)N3—C121.3465 (18)
Li—N32.002 (3)N3—C161.3481 (16)
N1—C11.3466 (18)N4—H4N0.900 (16)
N1—C51.3606 (16)N4—C161.3764 (17)
N2—Lii2.022 (3)N4—C171.4213 (16)
N2—C51.3718 (17)C12—H120.989 (14)
N2—C61.4035 (15)C12—C131.372 (2)
C1—H10.954 (15)C13—H130.942 (17)
C1—C21.365 (2)C13—C141.384 (2)
C2—H20.962 (16)C14—H140.991 (17)
C2—C31.384 (2)C14—C151.372 (2)
C3—H30.992 (17)C15—H150.978 (14)
C3—C41.371 (2)C15—C161.3999 (18)
C4—H40.936 (15)C17—C181.3885 (19)
C4—C51.4113 (18)C17—C221.385 (2)
C6—C71.4061 (18)C18—H180.963 (15)
C6—C111.3926 (18)C18—C191.384 (2)
C7—H70.959 (17)C19—H190.934 (19)
C7—C81.376 (2)C19—C201.379 (3)
C8—H80.963 (17)C20—H200.961 (18)
C8—C91.384 (2)C20—C211.378 (2)
C9—H90.969 (14)C21—H210.992 (17)
C9—C101.381 (2)C21—C221.385 (2)
C10—H100.988 (17)C22—H220.988 (16)
N1—Li—N265.19 (8)H10—C10—C11119.8 (9)
N1—Li—N2i118.30 (13)C6—C11—C10121.60 (13)
N1—Li—N3112.43 (13)C6—C11—H11119.4 (10)
N2—Li—N2i110.67 (12)C10—C11—H11118.9 (10)
N2—Li—N3120.85 (13)Li—N3—C12114.62 (11)
N2i—Li—N3118.54 (12)Li—N3—C16127.06 (11)
Li—N1—C1143.87 (12)C12—N3—C16117.65 (12)
Li—N1—C590.45 (11)H4N—N4—C16116.2 (10)
C1—N1—C5119.05 (12)H4N—N4—C17114.3 (10)
Li—N2—Lii69.33 (12)C16—N4—C17126.39 (12)
Li—N2—C584.03 (10)N3—C12—H12115.4 (9)
Lii—N2—C5123.09 (12)N3—C12—C13124.16 (13)
Li—N2—C6131.59 (11)H12—C12—C13120.4 (9)
Lii—N2—C6114.85 (11)C12—C13—H13119.4 (10)
C5—N2—C6120.29 (10)C12—C13—C14117.42 (14)
N1—C1—H1113.8 (9)H13—C13—C14123.2 (10)
N1—C1—C2123.67 (14)C13—C14—H14119.8 (9)
H1—C1—C2122.5 (9)C13—C14—C15120.38 (14)
C1—C2—H2119.6 (9)H14—C14—C15119.8 (9)
C1—C2—C3117.76 (14)C14—C15—H15120.4 (9)
H2—C2—C3122.7 (9)C14—C15—C16118.60 (13)
C2—C3—H3120.8 (9)H15—C15—C16120.9 (9)
C2—C3—C4120.40 (14)N3—C16—N4114.41 (12)
H3—C3—C4118.8 (10)N3—C16—C15121.77 (12)
C3—C4—H4120.1 (9)N4—C16—C15123.79 (12)
C3—C4—C5119.42 (13)N4—C17—C18121.58 (13)
H4—C4—C5120.5 (9)N4—C17—C22118.64 (12)
N1—C5—N2113.04 (11)C18—C17—C22119.76 (13)
N1—C5—C4119.68 (12)C17—C18—H18119.0 (9)
N2—C5—C4127.20 (12)C17—C18—C19119.53 (16)
N2—C6—C7124.44 (12)H18—C18—C19121.4 (9)
N2—C6—C11118.43 (11)C18—C19—H19116.3 (11)
C7—C6—C11117.00 (12)C18—C19—C20120.70 (16)
C6—C7—H7117.7 (9)H19—C19—C20123.0 (11)
C6—C7—C8121.09 (14)C19—C20—H20121.6 (11)
H7—C7—C8121.2 (9)C19—C20—C21119.73 (15)
C7—C8—H8118.7 (10)H20—C20—C21118.6 (11)
C7—C8—C9120.83 (14)C20—C21—H21120.4 (10)
H8—C8—C9120.4 (10)C20—C21—C22120.21 (16)
C8—C9—H9120.4 (9)H21—C21—C22119.3 (10)
C8—C9—C10118.78 (14)C17—C22—C21120.07 (15)
H9—C9—C10120.8 (9)C17—C22—H22122.0 (9)
C9—C10—H10119.5 (9)C21—C22—H22118.0 (9)
C9—C10—C11120.66 (14)
N2—Li—N1—C1162.8 (2)N2—C6—C7—C8177.74 (12)
N2i—Li—N1—C196.1 (2)C11—C6—C7—C81.82 (19)
N2—Li—N1—C516.23 (8)C6—C7—C8—C90.7 (2)
N2i—Li—N1—C5117.34 (14)C7—C8—C9—C100.2 (2)
N3—Li—N1—C147.9 (3)C8—C9—C10—C110.1 (2)
N3—Li—N1—C598.63 (14)C9—C10—C11—C61.3 (2)
N1—Li—N2—Lii112.58 (14)N2—C6—C11—C10178.31 (11)
N1—Li—N2—C516.18 (8)C7—C6—C11—C102.13 (19)
N1—Li—N2—C6142.01 (12)N1—Li—N3—C1228.69 (19)
N2i—Li—N2—Lii0.0N1—Li—N3—C16141.62 (13)
N2i—Li—N2—C5128.76 (14)N2—Li—N3—C1244.9 (2)
N2i—Li—N2—C6105.42 (15)N2i—Li—N3—C12172.62 (14)
N3—Li—N2—Lii145.1 (2)N2—Li—N3—C16144.76 (13)
N3—Li—N2—C586.15 (15)N2i—Li—N3—C162.3 (2)
N3—Li—N2—C639.7 (2)Li—N3—C12—C13169.80 (15)
Li—N1—C1—C2139.68 (19)C16—N3—C12—C131.5 (2)
C5—N1—C1—C21.2 (2)N3—C12—C13—C141.1 (2)
N1—C1—C2—C30.3 (2)C12—C13—C14—C150.5 (2)
C1—C2—C3—C40.5 (2)C13—C14—C15—C161.6 (2)
C2—C3—C4—C50.5 (2)Li—N3—C16—N48.5 (2)
Li—N1—C5—N226.08 (12)Li—N3—C16—C15169.81 (14)
Li—N1—C5—C4156.96 (13)C12—N3—C16—N4178.51 (12)
C1—N1—C5—N2175.75 (12)C12—N3—C16—C150.25 (19)
C1—N1—C5—C41.21 (19)C17—N4—C16—N3169.57 (12)
Li—N2—C5—N124.30 (12)C17—N4—C16—C158.6 (2)
Lii—N2—C5—N136.25 (17)C14—C15—C16—N31.3 (2)
Li—N2—C5—C4159.01 (15)C14—C15—C16—N4176.84 (13)
Lii—N2—C5—C4140.44 (14)C16—N4—C17—C1858.73 (19)
C6—N2—C5—N1159.69 (10)C16—N4—C17—C22123.15 (15)
C6—N2—C5—C423.63 (19)N4—C17—C18—C19178.61 (14)
C3—C4—C5—N10.4 (2)C22—C17—C18—C190.5 (2)
C3—C4—C5—N2176.10 (14)C17—C18—C19—C200.3 (2)
Li—N2—C6—C773.60 (18)C18—C19—C20—C210.4 (3)
Lii—N2—C6—C7157.34 (13)C19—C20—C21—C220.8 (2)
Li—N2—C6—C11102.27 (15)C20—C21—C22—C170.6 (2)
Lii—N2—C6—C1118.53 (15)N4—C17—C22—C21178.20 (13)
C5—N2—C6—C737.35 (18)C18—C17—C22—C210.0 (2)
C5—N2—C6—C11146.78 (12)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4N···N2i0.900 (16)2.288 (17)3.1763 (16)169.1 (13)
Symmetry code: (i) x+1, y+1, z+1.
 

Footnotes

Current address: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, England

Acknowledgements

We thank the EPSRC for financial support.

References

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