1,3,5-Triaza­adamantan-7-amine

Thomson, J.; Chisholm, D.M.; Oliver, A.G.; McIndoe, J.S.

doi:10.1107/S1600536810037657

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2637

doi:10.1107/S1600536810037657

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1,3,5-Triazaadamantan-7-amine

Jaclyn Thomson,^a Danielle M. Chisholm,^a Allen G. Oliver ^b ^* and J. Scott McIndoe ^a ^*

^aDepartment of Chemistry, University of Victoria, PO Box 3065, Victoria, BC V8W 3V6, Canada, and ^bUniversity of Notre Dame, Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, Notre Dame, IN 46556-5670, USA
^*Correspondence e-mail: aoliver2@nd.edu, mcindoe@uvic.ca

(Received 16 September 2010; accepted 20 September 2010; online 25 September 2010)

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, P 4₂ /n
a = 15.5402 (8) Å
c = 6.5074 (7) Å
V = 1571.5 (2) Å³
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[F² > 2σ(F²)] = 0.039
wR(F²) = 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

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) x, y, z-1; (ii) $[-y+{\script{3\over 2}}, x, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037657/cv2767sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037657/cv2767Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).

Figures top

	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.

1,3,5-Triazaadamantan-7-amine top

Crystal data top

C₇H₁₄N₄	D_x = 1.304 Mg m⁻³
M_r = 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 top

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

Refinement top

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(F_o²) + (0.056P)²] where P = (F_o² + 2F_c²)/3
1960 reflections	(Δ/σ)_max = 0.035
106 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₇H₁₄N₄	Z = 8
M_r = 154.22	Mo Kα radiation
Tetragonal, P4₂/n	µ = 0.09 mm⁻¹
a = 15.5402 (8) Å	T = 150 K
c = 6.5074 (7) Å	0.32 × 0.24 × 0.15 mm
V = 1571.5 (2) Å³

Data collection top

Bruker APEXII diffractometer	1960 independent reflections
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	1662 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.987	R_int = 0.032
15555 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.52	Δρ_max = 0.28 e Å⁻³
1960 reflections	Δρ_min = −0.17 e Å⁻³
106 parameters

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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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.

Experimental details

Crystal data
Chemical formula	C₇H₁₄N₄
M_r	154.22
Crystal system, space group	Tetragonal, P4₂/n
Temperature (K)	150
a, c (Å)	15.5402 (8), 6.5074 (7)
V (Å³)	1571.5 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.32 × 0.24 × 0.15

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Numerical (SADABS; Sheldrick, 2008a)
T_min, T_max	0.973, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	15555, 1960, 1662
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.122, 1.52
No. of reflections	1960
No. of parameters	106
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.17

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), XP (Sheldrick, 2008b) and POV-RAY (Cason, 2003), XCIF (Sheldrick, 2008b) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

Data were recorded on an instrument supported by the National Science Foundation, Major Research Instrumentation (MRI) Program under grant No. CHE-0521569.

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