1,3,5-Triaza­adamantan-7-amine

Abstract

The title compound, C₇H₁₄N₄, represents the first structurally characterized, isolated triaza­adamantane. In the crystal structure, weak inter­molecular N—H⋯N hydrogen bonds link the mol­ecules into columns about the crystallographic fourfold axis.

Related literature

For general background to applications of the title compound and its preparation, see: Hodge (1972 ▶); Karelina et al. (1987 ▶); Kuznetsov et al. (2001 ▶); Nielsen (1975 ▶, 1977 ▶); Safar et al. (1975 ▶). For related structures, see: de Namor et al. (2008 ▶).

Experimental

Crystal data

• C₇H₁₄N₄

• M _r = 154.22

• Tetragonal,

• a = 15.5402 (8) Å

• c = 6.5074 (7) Å

• V = 1571.5 (2) ų

• Z = 8

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 150 K

• 0.32 × 0.24 × 0.15 mm

Data collection

• Bruker APEXII diffractometer

• Absorption correction: numerical (SADABS; Sheldrick, 2008a ▶) T _min = 0.973, T _max = 0.987

• 15555 measured reflections

• 1960 independent reflections

• 1662 reflections with I > 2σ(I)

• R _int = 0.032

Refinement

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.122

• S = 1.52

• 1960 reflections

• 106 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.28 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: XP (Sheldrick, 2008b ▶) and POV-RAY (Cason, 2003 ▶); software used to prepare material for publication: XCIF (Sheldrick, 2008b ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11A⋯N3i	0.898 (12)	2.335 (13)	3.2316 (13)	176.0 (12)
N11—H11B⋯N11ii	0.895 (14)	2.253 (14)	3.1465 (14)	175.2 (11)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The title compound, 7-amino-1,3,5-triazaadamantane, 1, is a member of the class of adamantane compounds. To the best of our knowledge there are only two structurally characterized compounds containing the 1,3,5-triazaadamantane moiety (de Namor et al., 2008). However, both of the previously characterized species incorporate 7-nitro-1,3,5-triazaadamantane and are complexed with mercury.

7-Amino-1,3,5-triazaadamantane has been used as a curing agent in a number of processes from providing an alternative fuel source (Nielsen, 1977) to rubber manufacture (Karelina et al., 1987). Further it has been used as a precursor to other adamantane compounds (notably phosphaazaadamantanes, see for example Kuznetsov et al., 2001). The reactivity of the amino functionality has been investigated widely.

In the solid state the compound forms one-dimensional H-bonded (Table 1) chains that run through the lattice parallel to the crystallographic c-axis about the 4₂ screw-axis (Figure 2). The hydrogen-bonding is only exhibited through contacts from the amino group to neighbouring amino groups. The three N atoms in the azaadamantane portion of the molecule are not involved in any intermolecular contacts.

Experimental

7-Amino-1,3,5-triazaadamantane was prepared (Safar et al., 1975) by Pd/C/H₂ reduction of 7-nitro-1,3,5-triazaadamantane (Hodge, 1972) in ethanol. NMR data was consistent with literature values (Nielsen, 1975). Single crystals suitable for X-ray crystallography were obtained from cooling a saturated ethanol solution of 7-amino-1,3,5-triazaadamantane to 4°C for one week.

Refinement

C-bound H atoms were placed in geometrically idealized positions (C—H = 0.99 Å), and refined as riding with U_iso(H) = 1.2U_eq(C) . Amino H-atoms were located on a difference map, and refined with bond restraint N—H = 0.90 (1) Å, and constraint U_iso(H) = 1.2U_eq(N).

Figures

Fig. 1.

View of 1 showing 50% probability displacement ellipsoids.

Fig. 2.

Hydrogen-bonding and packing of 1 viewed along the c-axis. Dotted lines represent hydrogen bonding.

Crystal data

C7H14N4	Dx = 1.304 Mg m−3
Mr = 154.22	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/n	Cell parameters from 4624 reflections
Hall symbol: -P 4bc	θ = 2.6–28.2°
a = 15.5402 (8) Å	µ = 0.09 mm−1
c = 6.5074 (7) Å	T = 150 K
V = 1571.5 (2) Å3	Columnar, colourless
Z = 8	0.32 × 0.24 × 0.15 mm
F(000) = 672

Data collection

Bruker APEXII diffractometer	1960 independent reflections
Radiation source: fine-focus sealed tube	1662 reflections with I > 2σ(I)
graphite	Rint = 0.032
Detector resolution: 83.33 pixels mm-1	θmax = 28.3°, θmin = 1.9°
ω/2θ–scans	h = −20→20
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	k = −19→20
Tmin = 0.973, Tmax = 0.987	l = −8→8
15555 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.52	w = 1/[σ2(Fo2) + (0.056P)2] where P = (Fo2 + 2Fc2)/3
1960 reflections	(Δ/σ)max = 0.035
106 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.17 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.The amino H atoms were located from a difference Fourier map and included with refined coordinates and thermal parameters tied to that of N11. All other H atoms were included in geometrically calculated positions with thermal parameters tied to that of the carbon to which they are bonded.

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

	x	y	z	Uiso*/Ueq
N1	0.62365 (6)	0.43256 (6)	0.53674 (13)	0.0254 (2)
C2	0.62425 (7)	0.48052 (7)	0.73108 (16)	0.0269 (3)
H2A	0.6191	0.4393	0.8464	0.032*
H2B	0.5734	0.5189	0.7352	0.032*
N3	0.70245 (6)	0.53264 (6)	0.76040 (12)	0.0251 (2)
C4	0.77644 (8)	0.47390 (7)	0.75022 (15)	0.0304 (3)
H4A	0.7729	0.4328	0.8661	0.037*
H4B	0.8300	0.5077	0.7673	0.037*
N5	0.78167 (6)	0.42511 (6)	0.55650 (14)	0.0283 (2)
C6	0.78851 (7)	0.48753 (7)	0.38591 (16)	0.0251 (2)
H6A	0.7917	0.4560	0.2539	0.030*
H6B	0.8422	0.5212	0.4014	0.030*
C7	0.71110 (6)	0.54920 (6)	0.38172 (14)	0.0199 (2)
C8	0.62901 (7)	0.49473 (7)	0.36610 (16)	0.0243 (2)
H8A	0.5781	0.5329	0.3692	0.029*
H8B	0.6287	0.4634	0.2337	0.029*
C9	0.70056 (7)	0.37757 (7)	0.53292 (17)	0.0297 (3)
H9A	0.6961	0.3346	0.6448	0.036*
H9B	0.7020	0.3458	0.4010	0.036*
C10	0.70855 (7)	0.59524 (6)	0.59025 (14)	0.0222 (2)
H10A	0.7613	0.6303	0.6070	0.027*
H10B	0.6584	0.6344	0.5947	0.027*
N11	0.71492 (6)	0.61249 (6)	0.21797 (14)	0.0255 (2)
H11A	0.7093 (8)	0.5886 (8)	0.0929 (19)	0.031*
H11B	0.7652 (9)	0.6402 (9)	0.2292 (18)	0.031*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0272 (5)	0.0259 (5)	0.0232 (4)	−0.0056 (3)	0.0002 (3)	−0.0014 (3)
C2	0.0300 (6)	0.0293 (6)	0.0213 (5)	−0.0041 (4)	0.0042 (4)	0.0000 (4)
N3	0.0312 (5)	0.0259 (5)	0.0181 (4)	−0.0026 (4)	−0.0029 (3)	0.0000 (3)
C4	0.0318 (6)	0.0313 (6)	0.0282 (6)	0.0007 (5)	−0.0092 (4)	0.0038 (4)
N5	0.0273 (5)	0.0244 (5)	0.0332 (5)	0.0036 (3)	−0.0004 (4)	0.0017 (4)
C6	0.0224 (5)	0.0244 (5)	0.0285 (5)	0.0022 (4)	0.0039 (4)	−0.0012 (4)
C7	0.0200 (5)	0.0217 (5)	0.0179 (5)	0.0001 (4)	0.0004 (3)	−0.0009 (3)
C8	0.0238 (5)	0.0294 (6)	0.0198 (5)	−0.0038 (4)	−0.0027 (4)	−0.0024 (4)
C9	0.0364 (7)	0.0216 (6)	0.0312 (6)	−0.0017 (4)	0.0015 (4)	−0.0014 (4)
C10	0.0249 (5)	0.0216 (5)	0.0202 (5)	−0.0003 (4)	−0.0017 (4)	−0.0019 (4)
N11	0.0300 (5)	0.0274 (5)	0.0191 (4)	−0.0016 (4)	0.0006 (3)	0.0009 (3)

Geometric parameters (Å, °)

N1—C2	1.4679 (13)	C6—H6A	0.9900
N1—C9	1.4695 (15)	C6—H6B	0.9900
N1—C8	1.4742 (13)	C7—N11	1.4514 (12)
C2—N3	1.4729 (14)	C7—C10	1.5346 (13)
C2—H2A	0.9900	C7—C8	1.5343 (14)
C2—H2B	0.9900	C8—H8A	0.9900
N3—C4	1.4696 (14)	C8—H8B	0.9900
N3—C10	1.4769 (12)	C9—H9A	0.9900
C4—N5	1.4733 (13)	C9—H9B	0.9900
C4—H4A	0.9900	C10—H10A	0.9900
C4—H4B	0.9900	C10—H10B	0.9900
N5—C9	1.4691 (14)	N11—H11A	0.898 (12)
N5—C6	1.4780 (13)	N11—H11B	0.895 (14)
C6—C7	1.5383 (14)
C2—N1—C9	107.74 (8)	N11—C7—C10	109.53 (8)
C2—N1—C8	108.41 (8)	N11—C7—C8	111.06 (8)
C9—N1—C8	108.81 (8)	C10—C7—C8	107.12 (8)
N1—C2—N3	113.33 (8)	N11—C7—C6	113.78 (8)
N1—C2—H2A	108.9	C10—C7—C6	107.16 (8)
N3—C2—H2A	108.9	C8—C7—C6	107.92 (8)
N1—C2—H2B	108.9	N1—C8—C7	111.01 (8)
N3—C2—H2B	108.9	N1—C8—H8A	109.4
H2A—C2—H2B	107.7	C7—C8—H8A	109.4
C4—N3—C2	107.35 (8)	N1—C8—H8B	109.4
C4—N3—C10	108.97 (8)	C7—C8—H8B	109.4
C2—N3—C10	108.54 (8)	H8A—C8—H8B	108.0
N3—C4—N5	113.67 (8)	N5—C9—N1	113.80 (9)
N3—C4—H4A	108.8	N5—C9—H9A	108.8
N5—C4—H4A	108.8	N1—C9—H9A	108.8
N3—C4—H4B	108.8	N5—C9—H9B	108.8
N5—C4—H4B	108.8	N1—C9—H9B	108.8
H4A—C4—H4B	107.7	H9A—C9—H9B	107.7
C9—N5—C4	107.51 (9)	N3—C10—C7	110.95 (8)
C9—N5—C6	108.26 (8)	N3—C10—H10A	109.4
C4—N5—C6	107.99 (8)	C7—C10—H10A	109.5
N5—C6—C7	111.46 (8)	N3—C10—H10B	109.4
N5—C6—H6A	109.3	C7—C10—H10B	109.5
C7—C6—H6A	109.3	H10A—C10—H10B	108.0
N5—C6—H6B	109.3	C7—N11—H11A	112.4 (8)
C7—C6—H6B	109.3	C7—N11—H11B	107.6 (8)
H6A—C6—H6B	108.0	H11A—N11—H11B	110.9 (11)
C9—N1—C2—N3	57.51 (11)	C9—N1—C8—C7	−57.88 (10)
C8—N1—C2—N3	−60.09 (11)	N11—C7—C8—N1	−177.96 (8)
N1—C2—N3—C4	−57.78 (11)	C10—C7—C8—N1	−58.39 (10)
N1—C2—N3—C10	59.87 (11)	C6—C7—C8—N1	56.69 (10)
C2—N3—C4—N5	57.63 (11)	C4—N5—C9—N1	56.62 (11)
C10—N3—C4—N5	−59.73 (11)	C6—N5—C9—N1	−59.81 (11)
N3—C4—N5—C9	−57.06 (12)	C2—N1—C9—N5	−57.07 (11)
N3—C4—N5—C6	59.55 (12)	C8—N1—C9—N5	60.27 (11)
C9—N5—C6—C7	57.55 (11)	C4—N3—C10—C7	58.16 (11)
C4—N5—C6—C7	−58.57 (11)	C2—N3—C10—C7	−58.45 (11)
N5—C6—C7—N11	179.47 (8)	N11—C7—C10—N3	178.59 (8)
N5—C6—C7—C10	58.25 (10)	C8—C7—C10—N3	58.05 (10)
N5—C6—C7—C8	−56.81 (10)	C6—C7—C10—N3	−57.55 (10)
C2—N1—C8—C7	59.04 (11)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···N3i	0.898 (12)	2.335 (13)	3.2316 (13)	176.0 (12)
N11—H11B···N11ii	0.895 (14)	2.253 (14)	3.1465 (14)	175.2 (11)

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