The crystal structure of the title compound, bis(
N,N,
N′-trimethylethylenediamine)lithium indenide, [Li(C
5H
14N
2)
2](C
9H
7), forms discrete layers of cations and anions, with N—H
C hydrogen-bond interactions between these layers. Both the cation and anion exhibit a crystallographic centre of inversion. This leads to a twofold disorder of the anion.
Supporting information
CCDC reference: 177179
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- Disorder in solvent or counterion
- R factor = 0.040
- wR factor = 0.114
- Data-to-parameter ratio = 9.7
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550
Calculated sin(theta_max)/wavelength = 0.5310
Alert Level C:
REFNR_01 Alert C Ratio of reflections to parameters is < 10 for a
centrosymmetric structure
sine(theta)/lambda 0.5310
Proportion of unique data used 1.0000
Ratio reflections to parameters 9.6569
PLAT_302 Alert C Anion/Solvent Disorder ....................... 50.00 Perc.
PLAT_420 Alert C D-H Without Acceptor N(1) - H(1) ?
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1996); software used to prepare material for publication: SHELXTL.
Crystal data top
[Li(C5H14N2)2](C9H7) | F(000) = 720 |
Mr = 326.45 | Dx = 1.034 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54178 Å |
a = 17.669 (8) Å | Cell parameters from 25 reflections |
b = 7.921 (2) Å | θ = 39.8–46.9° |
c = 15.598 (4) Å | µ = 0.46 mm−1 |
β = 106.10 (1)° | T = 173 K |
V = 2097.4 (12) Å3 | Prism, colourless |
Z = 4 | 0.40 × 0.25 × 0.20 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.058 |
Radiation source: fine-focus sealed tube | θmax = 55.0°, θmin = 5.2° |
Graphite monochromator | h = −18→18 |
ω scans | k = −8→8 |
2624 measured reflections | l = 0→16 |
1323 independent reflections | 3 standard reflections every 60 min |
1111 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom, NH located |
R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.8262P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1323 reflections | Δρmax = 0.11 e Å−3 |
137 parameters | Δρmin = −0.14 e Å−3 |
23 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0016 (2) |
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. |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.7307 (4) | 0.2323 (9) | 0.1137 (3) | 0.0622 (19) | 0.50 |
H1A | 0.7146 | 0.1637 | 0.1554 | 0.075* | 0.50 |
C2 | 0.7550 (4) | 0.4011 (9) | 0.1237 (4) | 0.075 (2) | 0.50 |
H2A | 0.7572 | 0.4663 | 0.1754 | 0.090* | 0.50 |
C3 | 0.7755 (4) | 0.4626 (7) | 0.0508 (4) | 0.0716 (19) | 0.50 |
H3A | 0.7939 | 0.5731 | 0.0439 | 0.086* | 0.50 |
C4 | 0.7771 (3) | 0.3127 (6) | −0.0952 (3) | 0.0616 (19) | 0.50 |
H4A | 0.7982 | 0.4045 | −0.1204 | 0.074* | 0.50 |
C5 | 0.7598 (2) | 0.1621 (6) | −0.1421 (3) | 0.064 (2) | 0.50 |
H5A | 0.7673 | 0.1537 | −0.1999 | 0.076* | 0.50 |
C6 | 0.7313 (2) | 0.0223 (6) | −0.1054 (3) | 0.0631 (19) | 0.50 |
H6A | 0.7199 | −0.0802 | −0.1381 | 0.076* | 0.50 |
C7 | 0.7201 (3) | 0.0346 (6) | −0.0213 (3) | 0.0537 (16) | 0.50 |
H7A | 0.7017 | −0.0605 | 0.0043 | 0.064* | 0.50 |
C8 | 0.7357 (3) | 0.1859 (6) | 0.0263 (3) | 0.0444 (16) | 0.50 |
C9 | 0.7637 (3) | 0.3305 (6) | −0.0115 (3) | 0.0516 (18) | 0.50 |
Li1 | 1.0000 | 0.1746 (5) | 0.2500 | 0.0400 (9) | |
N1 | 0.91235 (8) | 0.0589 (2) | 0.15426 (8) | 0.0453 (4) | |
H1 | 0.8703 (10) | 0.125 (2) | 0.1486 (11) | 0.056 (5)* | |
N2 | 1.03682 (7) | 0.29299 (19) | 0.14997 (8) | 0.0445 (4) | |
C10 | 0.93977 (10) | 0.0799 (3) | 0.07387 (10) | 0.0557 (6) | |
H10A | 0.8956 | 0.0592 | 0.0199 | 0.067* | |
H10B | 0.9817 | −0.0035 | 0.0746 | 0.067* | |
C11 | 0.97093 (9) | 0.2544 (3) | 0.07065 (10) | 0.0559 (6) | |
H11A | 0.9891 | 0.2666 | 0.0164 | 0.067* | |
H11B | 0.9280 | 0.3368 | 0.0667 | 0.067* | |
C12 | 0.88743 (12) | −0.1136 (3) | 0.16408 (15) | 0.0730 (7) | |
H12A | 0.8659 | −0.1202 | 0.2155 | 0.110* | |
H12B | 0.9328 | −0.1896 | 0.1734 | 0.110* | |
H12C | 0.8469 | −0.1471 | 0.1100 | 0.110* | |
C13 | 1.10932 (9) | 0.2109 (3) | 0.14345 (11) | 0.0598 (6) | |
H13A | 1.1013 | 0.0885 | 0.1388 | 0.090* | |
H13B | 1.1523 | 0.2370 | 0.1968 | 0.090* | |
H13C | 1.1229 | 0.2524 | 0.0904 | 0.090* | |
C14 | 1.04974 (13) | 0.4753 (3) | 0.15885 (14) | 0.0717 (7) | |
H14A | 1.0004 | 0.5314 | 0.1593 | 0.108* | |
H14B | 1.0673 | 0.5170 | 0.1084 | 0.108* | |
H14C | 1.0901 | 0.4994 | 0.2147 | 0.108* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.047 (3) | 0.095 (5) | 0.037 (2) | 0.010 (3) | −0.001 (2) | −0.012 (3) |
C2 | 0.043 (3) | 0.098 (5) | 0.066 (3) | 0.019 (4) | −0.014 (3) | −0.042 (4) |
C3 | 0.041 (3) | 0.060 (4) | 0.098 (5) | −0.002 (3) | −0.007 (3) | −0.025 (3) |
C4 | 0.030 (3) | 0.080 (4) | 0.072 (4) | 0.004 (3) | 0.010 (3) | 0.016 (3) |
C5 | 0.038 (3) | 0.102 (6) | 0.049 (3) | 0.011 (3) | 0.010 (2) | 0.001 (3) |
C6 | 0.042 (3) | 0.077 (4) | 0.066 (4) | 0.002 (3) | 0.006 (2) | −0.016 (3) |
C7 | 0.036 (3) | 0.060 (4) | 0.061 (3) | 0.004 (3) | 0.008 (2) | −0.001 (2) |
C8 | 0.027 (3) | 0.057 (4) | 0.047 (3) | 0.003 (3) | 0.007 (2) | −0.007 (3) |
C9 | 0.033 (4) | 0.057 (4) | 0.057 (3) | 0.005 (3) | 0.000 (2) | 0.000 (3) |
Li1 | 0.0449 (19) | 0.046 (3) | 0.0264 (18) | 0.000 | 0.0050 (14) | 0.000 |
N1 | 0.0411 (8) | 0.0494 (11) | 0.0417 (8) | 0.0040 (7) | 0.0053 (6) | −0.0087 (7) |
N2 | 0.0424 (8) | 0.0554 (11) | 0.0347 (7) | 0.0071 (7) | 0.0090 (6) | 0.0078 (6) |
C10 | 0.0436 (9) | 0.0852 (16) | 0.0331 (9) | 0.0108 (10) | 0.0022 (7) | −0.0161 (9) |
C11 | 0.0476 (10) | 0.0866 (17) | 0.0308 (9) | 0.0146 (11) | 0.0061 (7) | 0.0116 (9) |
C12 | 0.0740 (13) | 0.0565 (15) | 0.0782 (14) | −0.0095 (11) | 0.0039 (11) | −0.0140 (11) |
C13 | 0.0423 (9) | 0.0958 (18) | 0.0420 (10) | 0.0101 (10) | 0.0128 (7) | 0.0051 (10) |
C14 | 0.0803 (14) | 0.0611 (16) | 0.0743 (14) | −0.0020 (12) | 0.0224 (11) | 0.0209 (11) |
Geometric parameters (Å, º) top
C1—C2 | 1.400 | Li1—C11 | 2.7736 (19) |
C1—C8 | 1.437 | Li1—C11i | 2.7736 (19) |
C1—H1A | 0.950 | N1—C12 | 1.457 (3) |
C2—C3 | 1.373 | N1—C10 | 1.474 (2) |
C2—H2A | 0.950 | N1—H1 | 0.892 (19) |
C3—C9 | 1.404 | N2—C14 | 1.462 (3) |
C3—H3A | 0.950 | N2—C13 | 1.465 (2) |
C4—C5 | 1.388 | N2—C11 | 1.477 (2) |
C4—C9 | 1.398 | C10—C11 | 1.494 (3) |
C4—H4A | 0.950 | C10—H10A | 0.990 |
C5—C6 | 1.402 | C10—H10B | 0.990 |
C5—H5A | 0.950 | C11—H11A | 0.990 |
C6—C7 | 1.385 | C11—H11B | 0.990 |
C6—H6A | 0.950 | C12—H12A | 0.980 |
C7—C8 | 1.396 | C12—H12B | 0.980 |
C7—H7A | 0.950 | C12—H12C | 0.980 |
C8—C9 | 1.438 | C13—H13A | 0.980 |
Li1—N1 | 2.046 (2) | C13—H13B | 0.980 |
Li1—N1i | 2.046 (2) | C13—H13C | 0.980 |
Li1—N2 | 2.074 (2) | C14—H14A | 0.980 |
Li1—N2i | 2.074 (2) | C14—H14B | 0.980 |
Li1—C10i | 2.761 (2) | C14—H14C | 0.980 |
Li1—C10 | 2.761 (2) | | |
| | | |
C2—C1—C8 | 104.6 | Li1—N1—H1 | 104.5 (11) |
C3—C2—C1 | 112.9 | C14—N2—C13 | 109.16 (16) |
C2—C3—C9 | 106.6 | C14—N2—C11 | 110.47 (14) |
C5—C4—C9 | 120.6 | C13—N2—C11 | 110.58 (14) |
C4—C5—C6 | 121.1 | C14—N2—Li1 | 116.64 (15) |
C7—C6—C5 | 119.5 | C13—N2—Li1 | 108.32 (12) |
C6—C7—C8 | 120.4 | C11—N2—Li1 | 101.42 (11) |
C7—C8—C1 | 132.0 | N1—C10—C11 | 110.14 (14) |
C7—C8—C9 | 120.3 | N1—C10—Li1 | 46.44 (8) |
C1—C8—C9 | 107.7 | C11—C10—Li1 | 74.81 (11) |
C4—C9—C3 | 133.7 | N1—C10—H10A | 109.6 |
C4—C9—C8 | 118.0 | C11—C10—H10A | 109.6 |
C3—C9—C8 | 108.1 | Li1—C10—H10A | 152.4 |
N1—Li1—N1i | 126.8 (2) | N1—C10—H10B | 109.6 |
N1—Li1—N2 | 89.15 (6) | C11—C10—H10B | 109.6 |
N1i—Li1—N2 | 114.83 (6) | Li1—C10—H10B | 95.1 |
N1—Li1—N2i | 114.83 (6) | H10A—C10—H10B | 108.1 |
N1i—Li1—N2i | 89.16 (6) | N2—C11—C10 | 112.06 (14) |
N2—Li1—N2i | 126.2 (2) | N2—C11—Li1 | 47.13 (8) |
N1—Li1—C10i | 127.56 (15) | C10—C11—Li1 | 73.86 (11) |
N1i—Li1—C10i | 31.47 (6) | N2—C11—H11A | 109.2 |
N2—Li1—C10i | 139.19 (7) | C10—C11—H11A | 109.2 |
N2i—Li1—C10i | 59.26 (6) | Li1—C11—H11A | 150.6 |
N1—Li1—C10 | 31.46 (6) | N2—C11—H11B | 109.2 |
N1i—Li1—C10 | 127.55 (15) | C10—C11—H11B | 109.2 |
N2—Li1—C10 | 59.26 (6) | Li1—C11—H11B | 97.9 |
N2i—Li1—C10 | 139.19 (7) | H11A—C11—H11B | 107.9 |
C10i—Li1—C10 | 148.47 (18) | N1—C12—H12A | 109.5 |
N1—Li1—C11 | 58.33 (6) | N1—C12—H12B | 109.5 |
N1i—Li1—C11 | 136.83 (7) | H12A—C12—H12B | 109.5 |
N2—Li1—C11 | 31.46 (5) | N1—C12—H12C | 109.5 |
N2i—Li1—C11 | 130.31 (15) | H12A—C12—H12C | 109.5 |
C10i—Li1—C11 | 168.00 (6) | H12B—C12—H12C | 109.5 |
C10—Li1—C11 | 31.32 (6) | N2—C13—H13A | 109.5 |
N1—Li1—C11i | 136.83 (7) | N2—C13—H13B | 109.5 |
N1i—Li1—C11i | 58.33 (6) | H13A—C13—H13B | 109.5 |
N2—Li1—C11i | 130.31 (15) | N2—C13—H13C | 109.5 |
N2i—Li1—C11i | 31.46 (5) | H13A—C13—H13C | 109.5 |
C10i—Li1—C11i | 31.32 (6) | H13B—C13—H13C | 109.5 |
C10—Li1—C11i | 168.00 (6) | N2—C14—H14A | 109.5 |
C11—Li1—C11i | 153.65 (19) | N2—C14—H14B | 109.5 |
C12—N1—C10 | 112.07 (16) | H14A—C14—H14B | 109.5 |
C12—N1—Li1 | 122.21 (15) | N2—C14—H14C | 109.5 |
C10—N1—Li1 | 102.10 (11) | H14A—C14—H14C | 109.5 |
C12—N1—H1 | 107.0 (12) | H14B—C14—H14C | 109.5 |
C10—N1—H1 | 108.2 (11) | | |
| | | |
C8—C1—C2—C3 | −0.7 | C11i—Li1—N2—C13 | 93.71 (19) |
C1—C2—C3—C9 | 0.6 | N1—Li1—N2—C11 | 10.83 (15) |
C9—C4—C5—C6 | −2.4 | N1i—Li1—N2—C11 | 141.59 (17) |
C4—C5—C6—C7 | 0.2 | N2i—Li1—N2—C11 | −109.82 (11) |
C5—C6—C7—C8 | 1.1 | C10i—Li1—N2—C11 | 167.1 (2) |
C6—C7—C8—C1 | −178.7 | C10—Li1—N2—C11 | 21.18 (11) |
C6—C7—C8—C9 | −0.2 | C11i—Li1—N2—C11 | −149.89 (16) |
C2—C1—C8—C7 | 179.2 | C12—N1—C10—C11 | −175.27 (14) |
C2—C1—C8—C9 | 0.6 | Li1—N1—C10—C11 | −42.81 (18) |
C5—C4—C9—C3 | 179.4 | C12—N1—C10—Li1 | −132.46 (19) |
C5—C4—C9—C8 | 3.2 | N1i—Li1—C10—N1 | 101.0 (2) |
C2—C3—C9—C4 | −176.7 | N2—Li1—C10—N1 | −159.88 (19) |
C2—C3—C9—C8 | −0.2 | N2i—Li1—C10—N1 | −48.6 (2) |
C7—C8—C9—C4 | −2.0 | C10i—Li1—C10—N1 | 64.51 (14) |
C1—C8—C9—C4 | 176.9 | C11—Li1—C10—N1 | −138.62 (19) |
C7—C8—C9—C3 | −179.1 | C11i—Li1—C10—N1 | −14.6 (8) |
C1—C8—C9—C3 | −0.2 | N1—Li1—C10—C11 | 138.62 (19) |
N1i—Li1—N1—C12 | 22.42 (14) | N1i—Li1—C10—C11 | −120.41 (15) |
N2—Li1—N1—C12 | 143.29 (16) | N2—Li1—C10—C11 | −21.26 (10) |
N2i—Li1—N1—C12 | −86.6 (2) | N2i—Li1—C10—C11 | 90.0 (3) |
C10i—Li1—N1—C12 | −17.4 (2) | C10i—Li1—C10—C11 | −156.87 (10) |
C10—Li1—N1—C12 | 126.1 (2) | C11i—Li1—C10—C11 | 124.0 (8) |
C11—Li1—N1—C12 | 149.91 (17) | C14—N2—C11—C10 | −162.56 (15) |
C11i—Li1—N1—C12 | −58.3 (3) | C13—N2—C11—C10 | 76.49 (18) |
N1i—Li1—N1—C10 | −103.68 (13) | Li1—N2—C11—C10 | −38.25 (18) |
N2—Li1—N1—C10 | 17.20 (16) | C14—N2—C11—Li1 | −124.32 (18) |
N2i—Li1—N1—C10 | 147.32 (17) | C13—N2—C11—Li1 | 114.73 (18) |
C10i—Li1—N1—C10 | −143.45 (16) | N1—C10—C11—N2 | 58.86 (18) |
C11—Li1—N1—C10 | 23.81 (12) | Li1—C10—C11—N2 | 28.18 (12) |
C11i—Li1—N1—C10 | 175.6 (2) | N1—C10—C11—Li1 | 30.68 (11) |
N1—Li1—N2—C14 | 130.87 (15) | N1—Li1—C11—N2 | −167.24 (18) |
N1i—Li1—N2—C14 | −98.4 (2) | N1i—Li1—C11—N2 | −55.5 (2) |
N2i—Li1—N2—C14 | 10.22 (11) | N2i—Li1—C11—N2 | 95.7 (2) |
C10i—Li1—N2—C14 | −72.8 (3) | C10i—Li1—C11—N2 | −44.4 (8) |
C10—Li1—N2—C14 | 141.21 (14) | C10—Li1—C11—N2 | −143.33 (17) |
C11—Li1—N2—C14 | 120.04 (17) | C11i—Li1—C11—N2 | 59.51 (12) |
C11i—Li1—N2—C14 | −29.85 (19) | N1—Li1—C11—C10 | −23.92 (11) |
N1—Li1—N2—C13 | −105.57 (14) | N1i—Li1—C11—C10 | 87.8 (3) |
N1i—Li1—N2—C13 | 25.2 (2) | N2—Li1—C11—C10 | 143.33 (17) |
N2i—Li1—N2—C13 | 133.78 (12) | N2i—Li1—C11—C10 | −121.02 (15) |
C10i—Li1—N2—C13 | 50.7 (3) | C10i—Li1—C11—C10 | 98.9 (8) |
C10—Li1—N2—C13 | −95.22 (13) | C11i—Li1—C11—C10 | −157.16 (9) |
C11—Li1—N2—C13 | −116.40 (18) | | |
Symmetry code: (i) −x+2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···C1 | 0.892 (19) | 2.522 (19) | 3.386 (7) | 163.0 (15) |
N1—H1···C4ii | 0.892 (19) | 2.553 (19) | 3.373 (6) | 153.0 (14) |
N1—H1···C5ii | 0.892 (19) | 2.830 (18) | 3.721 (9) | 176.5 (14) |
N1—H1···C8 | 0.892 (19) | 2.648 (18) | 3.359 (5) | 137.3 (13) |
N1—H1···C9ii | 0.892 (19) | 2.738 (18) | 3.400 (5) | 131.9 (13) |
Symmetry code: (ii) −x+3/2, −y+1/2, −z. |