[4-(2-Amino­ethyl)-1,4,7,10-tetra­azadeca­ne]lithium chloride: a bilayered structure displaying the rare TRENEN ligand

The penta­dentate ligand TRENEN [4-(2-aminoet­yl)-1,4,7,10-tetra­azadeca­ne] is not readily available in the pure state, but is present as a major impurity in commercial tetra­ethyl­ene penta­mine. Therefore, only four structures containing TRENEN have been reported previously. We report here the crystal structure of the title compound, [Li(trenen)]Cl or [Li(C₈H₂₃N₅)]Cl. The Li atom has a distorted trigonal–bipyramidal coordination geometry. The [Li(trenen)]⁺ cation is chiral since one of the N atoms is a chirogenic centre. A second type of chirality arises as a consequence of the chelate-ring conformations. In the racemic crystal structure, mol­ecules assemble into bilayers via N—H...Cl inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 303 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.077
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H10    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H12    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N5     -   H15    ...          ?
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              Cl

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

[4-(2-Aminoethyl)-1,4,7,10-tetraazadecane]lithium chloride

Crystal data

[Li(C8H23N5)]Cl	F(000) = 504
Mr = 231.70	Dx = 1.191 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8324 reflections
a = 12.079 (9) Å	θ = 3.0–25.5°
b = 7.914 (5) Å	µ = 0.27 mm^−1
c = 13.559 (10) Å	T = 303 K
β = 94.48 (3)°	Prism, colourless
V = 1292.2 (16) Å^3	0.15 × 0.10 × 0.10 mm
Z = 4

Data collection

Rigaku R-AXIS IIc image-plate system diffractometer	2170 reflections with I > 2σ(I)
Radiation source: rotating-anode X-ray tube, Rigaku RU-H3R	Rint = 0.034
Graphite monochromator	θmax = 25.5°, θmin = 3.0°
Detector resolution: 105 pixels mm^-1	h = −13→14
φ scans	k = −9→9
8324 measured reflections	l = −16→16
2386 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0234P)^2 + 0.8724P] where P = (Fo^2 + 2Fc^2)/3
2386 reflections	(Δ/σ)max = 0.001
164 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

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
C1	0.00724 (13)	0.2750 (2)	0.59569 (12)	0.0182 (3)
H1A	−0.0222	0.3530	0.5450	0.022*
H1B	−0.0476	0.1873	0.6030	0.022*
C2	0.11396 (13)	0.1968 (2)	0.56514 (12)	0.0167 (3)
H2B	0.1412	0.1147	0.6143	0.020*
H2A	0.0997	0.1387	0.5025	0.020*
C3	0.31350 (12)	0.27008 (19)	0.56960 (11)	0.0141 (3)
H3A	0.3301	0.1958	0.5158	0.017*
H3B	0.3251	0.2078	0.6312	0.017*
C4	0.38905 (12)	0.42409 (19)	0.57200 (11)	0.0145 (3)
H4B	0.4659	0.3882	0.5817	0.017*
H4A	0.3792	0.4831	0.5092	0.017*
C5	0.42644 (13)	0.4980 (2)	0.74639 (11)	0.0160 (3)
H5A	0.4981	0.5537	0.7489	0.019*
H5B	0.4392	0.3771	0.7499	0.019*
C6	0.36486 (13)	0.5533 (2)	0.83450 (11)	0.0179 (3)
H6B	0.4055	0.5178	0.8955	0.021*
H6A	0.3585	0.6755	0.8353	0.021*
C8	0.26365 (13)	0.77565 (19)	0.56771 (11)	0.0156 (3)
H8B	0.2695	0.8937	0.5495	0.019*
H8A	0.2510	0.7097	0.5076	0.019*
C7	0.37017 (13)	0.71836 (19)	0.62518 (11)	0.0150 (3)
H7A	0.4323	0.7351	0.5851	0.018*
H7B	0.3829	0.7862	0.6846	0.018*
N1	0.02939 (12)	0.3655 (2)	0.69003 (10)	0.0192 (3)
N2	0.19777 (10)	0.32792 (16)	0.55556 (10)	0.0127 (3)
N3	0.36348 (10)	0.53899 (16)	0.65252 (9)	0.0120 (3)
N4	0.25387 (12)	0.4767 (2)	0.82674 (10)	0.0180 (3)
N5	0.17037 (11)	0.75233 (17)	0.63072 (10)	0.0154 (3)
Li1	0.1824 (2)	0.5004 (3)	0.67806 (19)	0.0154 (5)
Cl1	−0.22911 (3)	0.54135 (5)	0.68048 (3)	0.01946 (12)
H12	0.2132 (17)	0.514 (3)	0.8737 (16)	0.032 (6)*
H13	0.2613 (18)	0.366 (3)	0.8348 (16)	0.037 (6)*
H15	0.1059 (17)	0.785 (3)	0.5967 (15)	0.025 (5)*
H14	0.1802 (17)	0.824 (3)	0.6801 (16)	0.028 (5)*
H11	0.1889 (16)	0.373 (3)	0.4945 (15)	0.026 (5)*
H10	0.0475 (17)	0.290 (3)	0.7367 (17)	0.032 (6)*
H9	−0.0333 (19)	0.415 (3)	0.7045 (15)	0.031 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0150 (8)	0.0184 (8)	0.0208 (8)	−0.0060 (6)	−0.0013 (6)	0.0001 (7)
C2	0.0203 (8)	0.0125 (7)	0.0172 (8)	−0.0039 (6)	−0.0008 (6)	−0.0021 (6)
C3	0.0168 (8)	0.0122 (7)	0.0135 (7)	0.0019 (6)	0.0022 (6)	−0.0019 (6)
C4	0.0134 (7)	0.0155 (8)	0.0152 (7)	0.0012 (6)	0.0043 (6)	−0.0008 (6)
C5	0.0137 (7)	0.0161 (8)	0.0173 (8)	−0.0002 (6)	−0.0036 (6)	0.0015 (6)
C6	0.0220 (8)	0.0178 (8)	0.0129 (7)	−0.0020 (7)	−0.0045 (6)	0.0005 (6)
C8	0.0226 (8)	0.0107 (7)	0.0132 (7)	−0.0002 (6)	0.0002 (6)	0.0012 (6)
C7	0.0165 (8)	0.0123 (7)	0.0161 (8)	−0.0047 (6)	0.0013 (6)	0.0005 (6)
N1	0.0163 (7)	0.0229 (7)	0.0188 (7)	−0.0011 (6)	0.0036 (5)	−0.0004 (6)
N2	0.0138 (7)	0.0121 (6)	0.0121 (6)	−0.0017 (5)	0.0007 (5)	0.0011 (5)
N3	0.0141 (6)	0.0108 (6)	0.0108 (6)	−0.0002 (5)	−0.0005 (5)	−0.0006 (5)
N4	0.0208 (7)	0.0202 (8)	0.0134 (7)	−0.0012 (6)	0.0036 (5)	0.0002 (6)
N5	0.0158 (7)	0.0142 (7)	0.0156 (7)	0.0017 (5)	−0.0017 (5)	−0.0022 (6)
Li1	0.0154 (12)	0.0159 (13)	0.0149 (12)	−0.0004 (10)	0.0007 (10)	0.0002 (10)
Cl1	0.0267 (2)	0.0190 (2)	0.01255 (19)	0.00515 (16)	0.00072 (14)	0.00212 (15)

Geometric parameters (Å, º)

C1—N1	1.472 (2)	C6—H6A	0.9700
C1—C2	1.517 (2)	C8—N5	1.478 (2)
C1—H1A	0.9700	C8—C7	1.520 (2)
C1—H1B	0.9700	C8—H8B	0.9700
C2—N2	1.462 (2)	C8—H8A	0.9700
C2—H2B	0.9700	C7—N3	1.471 (2)
C2—H2A	0.9700	C7—H7A	0.9700
C3—N2	1.469 (2)	C7—H7B	0.9700
C3—C4	1.521 (2)	N1—Li1	2.151 (3)
C3—H3A	0.9700	N1—H10	0.88 (2)
C3—H3B	0.9700	N1—H9	0.89 (2)
C4—N3	1.472 (2)	N2—Li1	2.169 (3)
C4—H4B	0.9700	N2—H11	0.90 (2)
C4—H4A	0.9700	N3—Li1	2.262 (3)
C5—N3	1.467 (2)	N4—Li1	2.139 (3)
C5—C6	1.520 (2)	N4—H12	0.89 (2)
C5—H5A	0.9700	N4—H13	0.89 (2)
C5—H5B	0.9700	N5—Li1	2.096 (3)
C6—N4	1.468 (2)	N5—H15	0.91 (2)
C6—H6B	0.9700	N5—H14	0.88 (2)
N1—C1—C2	109.58 (13)	C8—C7—H7A	109.5
N1—C1—H1A	109.8	N3—C7—H7B	109.5
C2—C1—H1A	109.8	C8—C7—H7B	109.5
N1—C1—H1B	109.8	H7A—C7—H7B	108.1
C2—C1—H1B	109.8	C1—N1—Li1	105.95 (12)
H1A—C1—H1B	108.2	C1—N1—H10	108.2 (14)
N2—C2—C1	110.11 (14)	Li1—N1—H10	102.9 (14)
N2—C2—H2B	109.6	C1—N1—H9	107.8 (13)
C1—C2—H2B	109.6	Li1—N1—H9	123.4 (14)
N2—C2—H2A	109.6	H10—N1—H9	107.9 (18)
C1—C2—H2A	109.6	C2—N2—C3	115.20 (13)
H2B—C2—H2A	108.2	C2—N2—Li1	106.08 (12)
N2—C3—C4	108.44 (13)	C3—N2—Li1	103.57 (11)
N2—C3—H3A	110.0	C2—N2—H11	109.1 (13)
C4—C3—H3A	110.0	C3—N2—H11	106.6 (12)
N2—C3—H3B	110.0	Li1—N2—H11	116.5 (13)
C4—C3—H3B	110.0	C5—N3—C7	113.40 (12)
H3A—C3—H3B	108.4	C5—N3—C4	112.47 (13)
N3—C4—C3	110.52 (12)	C7—N3—C4	112.98 (12)
N3—C4—H4B	109.5	C5—N3—Li1	106.22 (12)
C3—C4—H4B	109.5	C7—N3—Li1	103.99 (11)
N3—C4—H4A	109.5	C4—N3—Li1	106.95 (11)
C3—C4—H4A	109.5	C6—N4—Li1	109.32 (12)
H4B—C4—H4A	108.1	C6—N4—H12	111.4 (14)
N3—C5—C6	111.45 (13)	Li1—N4—H12	116.3 (13)
N3—C5—H5A	109.3	C6—N4—H13	108.4 (14)
C6—C5—H5A	109.3	Li1—N4—H13	103.4 (14)
N3—C5—H5B	109.3	H12—N4—H13	107 (2)
C6—C5—H5B	109.3	C8—N5—Li1	104.97 (12)
H5A—C5—H5B	108.0	C8—N5—H15	109.5 (12)
N4—C6—C5	108.95 (13)	Li1—N5—H15	117.3 (13)
N4—C6—H6B	109.9	C8—N5—H14	107.3 (13)
C5—C6—H6B	109.9	Li1—N5—H14	112.2 (13)
N4—C6—H6A	109.9	H15—N5—H14	105.3 (18)
C5—C6—H6A	109.9	N5—Li1—N4	112.66 (13)
H6B—C6—H6A	108.3	N5—Li1—N1	117.13 (14)
N5—C8—C7	108.63 (13)	N4—Li1—N1	99.87 (12)
N5—C8—H8B	110.0	N5—Li1—N2	111.84 (13)
C7—C8—H8B	110.0	N4—Li1—N2	127.89 (14)
N5—C8—H8A	110.0	N1—Li1—N2	82.59 (11)
C7—C8—H8A	110.0	N5—Li1—N3	82.48 (10)
H8B—C8—H8A	108.3	N4—Li1—N3	80.32 (11)
N3—C7—C8	110.85 (12)	N1—Li1—N3	157.70 (14)
N3—C7—H7A	109.5	N2—Li1—N3	79.97 (10)