[Indenyl­lithium·2(N,N,N′-tri­methyl­ethyl­ene­diamine)]_∞: N–H hydrogen bridges to the indenyl anion

The crystal structure of the title compound, bis(N,N,N′-tri­methyl­ethyl­enedi­amine)­lithium indenide, [Li(C₅H₁₄N₂)₂](C₉H₇), 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.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](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

---

Computing details

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.

(I)

Crystal data

[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) Å^3	Prism, colourless
Z = 4	0.40 × 0.25 × 0.20 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom, NH located
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0452P)^2 + 0.8262P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0016 (2)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

C1—C2	1.400	Li1—C11	2.7736 (19)
C1—C8	1.437	Li1—C11^i	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—N1^i	2.046 (2)	C13—H13C	0.980
Li1—N2	2.074 (2)	C14—H14A	0.980
Li1—N2^i	2.074 (2)	C14—H14B	0.980
Li1—C10^i	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—N1^i	126.8 (2)	N1—C10—H10B	109.6
N1—Li1—N2	89.15 (6)	C11—C10—H10B	109.6
N1^i—Li1—N2	114.83 (6)	Li1—C10—H10B	95.1
N1—Li1—N2^i	114.83 (6)	H10A—C10—H10B	108.1
N1^i—Li1—N2^i	89.16 (6)	N2—C11—C10	112.06 (14)
N2—Li1—N2^i	126.2 (2)	N2—C11—Li1	47.13 (8)
N1—Li1—C10^i	127.56 (15)	C10—C11—Li1	73.86 (11)
N1^i—Li1—C10^i	31.47 (6)	N2—C11—H11A	109.2
N2—Li1—C10^i	139.19 (7)	C10—C11—H11A	109.2
N2^i—Li1—C10^i	59.26 (6)	Li1—C11—H11A	150.6
N1—Li1—C10	31.46 (6)	N2—C11—H11B	109.2
N1^i—Li1—C10	127.55 (15)	C10—C11—H11B	109.2
N2—Li1—C10	59.26 (6)	Li1—C11—H11B	97.9
N2^i—Li1—C10	139.19 (7)	H11A—C11—H11B	107.9
C10^i—Li1—C10	148.47 (18)	N1—C12—H12A	109.5
N1—Li1—C11	58.33 (6)	N1—C12—H12B	109.5
N1^i—Li1—C11	136.83 (7)	H12A—C12—H12B	109.5
N2—Li1—C11	31.46 (5)	N1—C12—H12C	109.5
N2^i—Li1—C11	130.31 (15)	H12A—C12—H12C	109.5
C10^i—Li1—C11	168.00 (6)	H12B—C12—H12C	109.5
C10—Li1—C11	31.32 (6)	N2—C13—H13A	109.5
N1—Li1—C11^i	136.83 (7)	N2—C13—H13B	109.5
N1^i—Li1—C11^i	58.33 (6)	H13A—C13—H13B	109.5
N2—Li1—C11^i	130.31 (15)	N2—C13—H13C	109.5
N2^i—Li1—C11^i	31.46 (5)	H13A—C13—H13C	109.5
C10^i—Li1—C11^i	31.32 (6)	H13B—C13—H13C	109.5
C10—Li1—C11^i	168.00 (6)	N2—C14—H14A	109.5
C11—Li1—C11^i	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	C11^i—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	N1^i—Li1—N2—C11	141.59 (17)
C4—C5—C6—C7	0.2	N2^i—Li1—N2—C11	−109.82 (11)
C5—C6—C7—C8	1.1	C10^i—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	C11^i—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	N1^i—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	N2^i—Li1—C10—N1	−48.6 (2)
C7—C8—C9—C4	−2.0	C10^i—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	C11^i—Li1—C10—N1	−14.6 (8)
C1—C8—C9—C3	−0.2	N1—Li1—C10—C11	138.62 (19)
N1^i—Li1—N1—C12	22.42 (14)	N1^i—Li1—C10—C11	−120.41 (15)
N2—Li1—N1—C12	143.29 (16)	N2—Li1—C10—C11	−21.26 (10)
N2^i—Li1—N1—C12	−86.6 (2)	N2^i—Li1—C10—C11	90.0 (3)
C10^i—Li1—N1—C12	−17.4 (2)	C10^i—Li1—C10—C11	−156.87 (10)
C10—Li1—N1—C12	126.1 (2)	C11^i—Li1—C10—C11	124.0 (8)
C11—Li1—N1—C12	149.91 (17)	C14—N2—C11—C10	−162.56 (15)
C11^i—Li1—N1—C12	−58.3 (3)	C13—N2—C11—C10	76.49 (18)
N1^i—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)
N2^i—Li1—N1—C10	147.32 (17)	C13—N2—C11—Li1	114.73 (18)
C10^i—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)
C11^i—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)
N1^i—Li1—N2—C14	−98.4 (2)	N1^i—Li1—C11—N2	−55.5 (2)
N2^i—Li1—N2—C14	10.22 (11)	N2^i—Li1—C11—N2	95.7 (2)
C10^i—Li1—N2—C14	−72.8 (3)	C10^i—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)	C11^i—Li1—C11—N2	59.51 (12)
C11^i—Li1—N2—C14	−29.85 (19)	N1—Li1—C11—C10	−23.92 (11)
N1—Li1—N2—C13	−105.57 (14)	N1^i—Li1—C11—C10	87.8 (3)
N1^i—Li1—N2—C13	25.2 (2)	N2—Li1—C11—C10	143.33 (17)
N2^i—Li1—N2—C13	133.78 (12)	N2^i—Li1—C11—C10	−121.02 (15)
C10^i—Li1—N2—C13	50.7 (3)	C10^i—Li1—C11—C10	98.9 (8)
C10—Li1—N2—C13	−95.22 (13)	C11^i—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)

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···C4^ii	0.892 (19)	2.553 (19)	3.373 (6)	153.0 (14)
N1—H1···C5^ii	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···C9^ii	0.892 (19)	2.738 (18)	3.400 (5)	131.9 (13)

Symmetry code: (ii) −x+3/2, −y+1/2, −z.