5,7,7,12,14,14-Hexamethyl-4,11-di­aza-1,8-di­azonia­cyclo­tetra­deca-4,11-diene bis­(methane­sulfonate)

Spendel, K.; Nazarenko, A.Y.

doi:10.1107/S2414314616010336

organic compounds

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ISSN: 2414-3146

Volume 1| Part 6| June 2016| x161033

doi:10.1107/S2414314616010336

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5,7,7,12,14,14-Hexamethyl-4,11-diaza-1,8-diazoniacyclotetradeca-4,11-diene bis(methanesulfonate)

Katherine Spendel ^a and Alexander Y. Nazarenko ^a ^*

^aChemistry Department, SUNY Buffalo State, 1300 Elmwood Ave, Buffalo, NY 14222, USA
^*Correspondence e-mail: nazareay@buffalostate.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 June 2016; accepted 25 June 2016; online 30 June 2016)

In the title molecular salt, C₁₆H₃₄N₄²⁺·2CH₃SO₃⁻, the centrosymmetric macrocyclic molecule has all four N atoms oriented towards the inside of the cavity, similar to its conformation in metal complexes. The conformation of the ethylenediamine fragment is trans–gauche–trans and the conformation of the propylenediamine group is trans–cis–gauche–gauche. In the crystal, each protonated N atom makes a strong hydrogen bond with a sulfonate O atom and another intramolecular hydrogen bond connects two N atoms of the same macrocyclic ring to generate ensembles of one dication and two anions.

Keywords: crystal structure; macrocyclic tetraamine; methanesulfonate.

CCDC reference: 1487686

Structure description

The title salt belongs to a class of widely studied azamacrocycles discovered by Curtis (1960 ). The reaction between ethylenediamine and acetone after addition of perchloric acid (Curtis, 1968 ) is, perhaps, the simplest known macrocyclic synthesis. However, the potentially hazardous nature of perchloric acid prevents its use in an undergraduate laboratory. Several alternatives to HClO₄ were suggested (Curtis, 1968; Tait & Busch, 1978 ), requiring more complicated preparations. We report here the synthesis of the Curtis macrocycle in the presence of methanesulfonic acid. Its availability in an anhydrous liquid form favors a condensation reaction.

In the crystal structure of the title salt, the centrosymmetric macrocyclic molecule has all four N atoms oriented towards the inside of the cavity, similar to its conformation in metal complexes (Fig. 1). The conformations of the ethylenediamine fragments are trans–gauche–trans and the conformations of the propylenediamine fragments are trans–cis–gauche–gauche (see Table 1). The diprotonated tetramine macrocycle forms a neutral salt with two methanesulfonate ions. Each protonated N atom makes a strong hydrogen bond with one of the O atoms of the sulfonate group (Table 2, Fig. 2). Another hydrogen bond connects two N atoms of the same macrocyclic ring (Fig. 3).

Table 1
Selected torsion angles (°)

C6—N1—C5—C4	179.58 (8)	C6ⁱ—C2—C3—N2	18.86 (14)
N2—C4—C5—N1	64.44 (11)	N1—C6—C2ⁱ—C3ⁱ	54.12 (11)
C3—N2—C4—C5	−153.05 (9)	C5—N1—C6—C2ⁱ	67.30 (11)
C4—N2—C3—C2	−177.43 (9)
Symmetry code: (i) -x+1, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.908 (16)	1.993 (16)	2.7572 (13)	140.9 (13)
N1—H1B⋯O1	0.880 (15)	1.875 (15)	2.7453 (12)	169.5 (14)
Symmetry code: (i) -x+1, -y, -z+1.

Figure 1
The molecular structure of the title compound, showing the atom-labeling scheme and 50% probability displacement ellipsoids.

Figure 2
Packing diagram (view along the c axis).

Figure 3
Packing diagram (view along the a axis).

Synthesis and crystallization

The title compound was prepared in a manner similar to a known procedure with perchloric acid (Tait & Busch, 1978) by slow addition of 0.96 g (0.01 mol) methanesulfonic acid to a solution of ethylenediamine (0.6 g, 0.01 mol) in 20 ml of acetone. (Caution! Potentially violent neutralization reaction.) Colorless crystals were collected after several hours. Some of these crystals appeared to be suitable for X-ray crystallography analysis. The bulk product reacts with Cu^II ions yielding a solution of the well-known red macrocyclic complex.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₆H₃₄N₄²⁺·2CH₃O₃S⁻
M_r	472.66
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	9.7931 (12), 8.6816 (11), 14.1098 (17)
β (°)	94.003 (4)
V (Å³)	1196.7 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.26
Crystal size (mm)	0.59 × 0.42 × 0.22

Data collection
Diffractometer	Bruker PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.893, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	62436, 5245, 3974
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.806

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.110, 1.05
No. of reflections	5245
No. of parameters	206
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.38
Computer programs: APEX2 and SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1487686

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616010336/hb4059sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616010336/hb4059Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616010336/hb4059Isup3.cdx

Supporting information file. DOI: 10.1107/S2414314616010336/hb4059Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

5,7,7,12,14,14-Hexamethyl-4,11-diaza-1,8-diazoniacyclotetradeca-4,11-diene bis(methanesulfonate) top

Crystal data top

C₁₆H₃₄N₄²⁺·2CH₃O₃S⁻	F(000) = 512
M_r = 472.66	D_x = 1.312 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.7931 (12) Å	Cell parameters from 9910 reflections
b = 8.6816 (11) Å	θ = 3.1–33.8°
c = 14.1098 (17) Å	µ = 0.26 mm⁻¹
β = 94.003 (4)°	T = 173 K
V = 1196.7 (3) Å³	Block, colourless
Z = 2	0.59 × 0.42 × 0.22 mm

Data collection top

Bruker PHOTON 100 CMOS diffractometer	3974 reflections with I > 2σ(I)
Radiation source: sealedtube	R_int = 0.052
φ and ω scans	θ_max = 35.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −15→15
T_min = 0.893, T_max = 0.952	k = −14→14
62436 measured reflections	l = −22→22
5245 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0567P)² + 0.2818P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
5245 reflections	Δρ_max = 0.51 e Å⁻³
206 parameters	Δρ_min = −0.38 e Å⁻³

Special details top

Experimental. SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0555 before and 0.0536 after correction. The Ratio of minimum to maximum transmission is 0.9378. The λ/2 correction factor is 0.00150.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.59253 (8)	0.19791 (10)	0.43144 (6)	0.01580 (14)
H1A	0.5572 (15)	0.1012 (18)	0.4307 (10)	0.026 (4)*
H1B	0.5421 (14)	0.2614 (18)	0.3951 (11)	0.024 (3)*
N2	0.38388 (9)	0.11848 (10)	0.56274 (6)	0.01794 (15)
C1	0.15447 (12)	0.23278 (13)	0.52301 (10)	0.0294 (2)
H1C	0.0816 (8)	0.2253 (7)	0.5587 (6)	0.035*
H1D	0.1260 (8)	0.2250 (6)	0.4608 (6)	0.035*
H1E	0.1961 (5)	0.3248 (9)	0.5338 (6)	0.035*
C2	0.18794 (10)	−0.05125 (11)	0.55689 (7)	0.01856 (17)
H2A	0.1594 (15)	−0.0847 (17)	0.4937 (11)	0.024 (3)*
H2B	0.1079 (17)	−0.0392 (18)	0.5879 (11)	0.032 (4)*
C3	0.25378 (10)	0.10527 (11)	0.54911 (7)	0.01759 (17)
C4	0.44688 (11)	0.27092 (12)	0.55915 (8)	0.02115 (19)
H4A	0.3995 (15)	0.3410 (18)	0.5181 (11)	0.028 (4)*
H4B	0.4501 (16)	0.3166 (19)	0.6210 (12)	0.033 (4)*
C5	0.59251 (10)	0.25877 (12)	0.53033 (7)	0.01873 (17)
H5A	0.6330 (15)	0.3588 (18)	0.5318 (10)	0.026 (4)*
H5B	0.6485 (15)	0.1925 (17)	0.5700 (10)	0.024 (3)*
C6	0.73047 (10)	0.17883 (12)	0.38985 (7)	0.01878 (17)
C7	0.80936 (12)	0.33048 (14)	0.39918 (10)	0.0276 (2)
H7A	0.8375 (15)	0.3512 (17)	0.4650 (11)	0.025 (4)*
H7B	0.8870 (17)	0.324 (2)	0.3631 (12)	0.038 (4)*
H7C	0.7508 (16)	0.4143 (19)	0.3701 (11)	0.033 (4)*
C8	0.69890 (13)	0.13881 (16)	0.28543 (8)	0.0286 (2)
H8A	0.6461 (17)	0.218 (2)	0.2539 (12)	0.041 (4)*
H8B	0.7831 (17)	0.125 (2)	0.2553 (12)	0.040 (4)*
H8C	0.6453 (17)	0.0418 (18)	0.2775 (11)	0.031 (4)*
S1	0.37838 (3)	0.46573 (3)	0.24372 (2)	0.01973 (7)
O1	0.42782 (10)	0.41405 (11)	0.33881 (6)	0.03133 (19)
O2	0.43476 (10)	0.61414 (11)	0.22043 (7)	0.0351 (2)
O3	0.39480 (10)	0.34887 (11)	0.17162 (6)	0.0320 (2)
C9	0.20072 (13)	0.49311 (18)	0.24961 (11)	0.0343 (3)
H9A	0.1624 (19)	0.399 (2)	0.2635 (12)	0.045 (5)*
H9B	0.1858 (18)	0.566 (2)	0.2955 (13)	0.042 (5)*
H9C	0.1639 (19)	0.533 (2)	0.1860 (14)	0.043 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0155 (3)	0.0160 (3)	0.0158 (3)	0.0005 (3)	0.0003 (3)	0.0006 (3)
N2	0.0177 (4)	0.0166 (3)	0.0197 (4)	−0.0006 (3)	0.0025 (3)	−0.0016 (3)
C1	0.0221 (5)	0.0214 (5)	0.0437 (7)	0.0030 (4)	−0.0044 (4)	0.0033 (5)
C2	0.0148 (4)	0.0184 (4)	0.0224 (4)	−0.0002 (3)	0.0008 (3)	0.0001 (3)
C3	0.0187 (4)	0.0170 (4)	0.0169 (4)	0.0009 (3)	0.0001 (3)	−0.0018 (3)
C4	0.0211 (4)	0.0172 (4)	0.0259 (5)	−0.0018 (3)	0.0061 (4)	−0.0046 (4)
C5	0.0187 (4)	0.0198 (4)	0.0177 (4)	−0.0028 (3)	0.0011 (3)	−0.0031 (3)
C6	0.0178 (4)	0.0204 (4)	0.0185 (4)	0.0004 (3)	0.0042 (3)	0.0025 (3)
C7	0.0239 (5)	0.0221 (5)	0.0376 (6)	−0.0033 (4)	0.0078 (4)	0.0066 (4)
C8	0.0309 (6)	0.0383 (6)	0.0168 (4)	0.0053 (5)	0.0042 (4)	0.0015 (4)
S1	0.02069 (12)	0.01985 (12)	0.01816 (11)	0.00210 (8)	−0.00218 (8)	0.00111 (8)
O1	0.0413 (5)	0.0299 (4)	0.0213 (4)	0.0110 (4)	−0.0083 (3)	0.0019 (3)
O2	0.0368 (5)	0.0267 (4)	0.0421 (5)	−0.0053 (4)	0.0046 (4)	0.0071 (4)
O3	0.0383 (5)	0.0340 (5)	0.0239 (4)	0.0045 (4)	0.0023 (3)	−0.0075 (3)
C9	0.0221 (5)	0.0346 (6)	0.0456 (7)	0.0035 (5)	−0.0018 (5)	−0.0082 (6)

Geometric parameters (Å, º) top

N1—H1A	0.908 (16)	C5—H5B	0.950 (15)
N1—H1B	0.880 (15)	C6—C2ⁱ	1.5316 (14)
N1—C5	1.4921 (12)	C6—C7	1.5275 (15)
N1—C6	1.5190 (13)	C6—C8	1.5242 (15)
N2—C3	1.2803 (13)	C7—H7A	0.966 (15)
N2—C4	1.4625 (13)	C7—H7B	0.946 (17)
C1—H1C	0.905 (9)	C7—H7C	0.997 (17)
C1—H1D	0.905 (9)	C8—H8A	0.952 (18)
C1—H1E	0.905 (9)	C8—H8B	0.962 (17)
C1—C3	1.5023 (15)	C8—H8C	0.994 (16)
C2—H2A	0.960 (15)	S1—O1	1.4647 (9)
C2—H2B	0.930 (16)	S1—O2	1.4485 (9)
C2—C3	1.5113 (14)	S1—O3	1.4536 (9)
C2—C6ⁱ	1.5317 (14)	S1—C9	1.7637 (13)
C4—H4A	0.940 (16)	C9—H9A	0.92 (2)
C4—H4B	0.956 (17)	C9—H9B	0.925 (18)
C4—C5	1.5137 (14)	C9—H9C	1.006 (19)
C5—H5A	0.954 (15)

H1A—N1—H1B	112.0 (13)	C4—C5—H5B	113.6 (8)
C5—N1—H1A	108.3 (9)	H5A—C5—H5B	108.5 (12)
C5—N1—H1B	106.6 (10)	N1—C6—C2ⁱ	109.68 (8)
C5—N1—C6	117.26 (8)	N1—C6—C7	109.32 (8)
C6—N1—H1A	104.1 (9)	N1—C6—C8	105.81 (8)
C6—N1—H1B	108.8 (9)	C7—C6—C2ⁱ	109.73 (9)
C3—N2—C4	119.58 (9)	C8—C6—C2ⁱ	111.91 (9)
H1C—C1—H1D	109.5	C8—C6—C7	110.30 (9)
H1C—C1—H1E	109.5	C6—C7—H7A	110.6 (9)
H1D—C1—H1E	109.5	C6—C7—H7B	108.8 (11)
C3—C1—H1C	109.5	C6—C7—H7C	108.7 (9)
C3—C1—H1D	109.5	H7A—C7—H7B	110.0 (14)
C3—C1—H1E	109.5	H7A—C7—H7C	112.1 (13)
H2A—C2—H2B	105.7 (13)	H7B—C7—H7C	106.5 (13)
C3—C2—H2A	107.6 (9)	C6—C8—H8A	110.7 (10)
C3—C2—H2B	108.1 (10)	C6—C8—H8B	109.5 (10)
C3—C2—C6ⁱ	118.37 (8)	C6—C8—H8C	111.8 (9)
C6ⁱ—C2—H2A	110.2 (9)	H8A—C8—H8B	109.8 (14)
C6ⁱ—C2—H2B	106.2 (10)	H8A—C8—H8C	107.1 (14)
N2—C3—C1	126.24 (9)	H8B—C8—H8C	107.8 (14)
N2—C3—C2	119.65 (9)	O1—S1—C9	105.20 (7)
C1—C3—C2	114.09 (8)	O2—S1—O1	111.93 (6)
N2—C4—H4A	114.6 (9)	O2—S1—O3	113.55 (6)
N2—C4—H4B	109.3 (10)	O2—S1—C9	106.48 (7)
N2—C4—C5	110.73 (8)	O3—S1—O1	112.43 (5)
H4A—C4—H4B	106.1 (13)	O3—S1—C9	106.54 (6)
C5—C4—H4A	108.2 (9)	S1—C9—H9A	107.9 (12)
C5—C4—H4B	107.6 (9)	S1—C9—H9B	109.3 (11)
N1—C5—C4	109.73 (8)	S1—C9—H9C	107.3 (10)
N1—C5—H5A	108.4 (9)	H9A—C9—H9B	111.6 (15)
N1—C5—H5B	107.4 (9)	H9A—C9—H9C	111.6 (16)
C4—C5—H5A	109.2 (9)	H9B—C9—H9C	108.9 (15)

C6—N1—C5—C4	179.58 (8)	C5—N1—C6—C8	−171.83 (9)
N2—C4—C5—N1	64.44 (11)	C6ⁱ—C2—C3—N2	18.86 (14)
C3—N2—C4—C5	−153.05 (9)	C6ⁱ—C2—C3—C1	−162.42 (9)
C4—N2—C3—C1	4.03 (16)	N1—C6—C2ⁱ—C3ⁱ	54.12 (11)
C4—N2—C3—C2	−177.43 (9)	C5—N1—C6—C2ⁱ	67.30 (11)
C5—N1—C6—C7	−53.05 (11)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.908 (16)	1.993 (16)	2.7572 (13)	140.9 (13)
N1—H1B···O1	0.880 (15)	1.875 (15)	2.7453 (12)	169.5 (14)

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

Financial support from the State University of New York for the acquisition and maintenance of the X-ray diffractometer is gratefully acknowledged.

References

Bruker (2013). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2014). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Curtis, N. F. (1960). J. Chem. Soc. pp. 4409–4416. CrossRef Google Scholar
Curtis, N. F. (1968). Coord. Chem. Rev. 3, 3–47. CrossRef CAS Web of Science Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Tait, A. M. & Busch, D. H. (1978). Inorg. Synth. 18, 2–9. CAS Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

5,7,7,12,14,14-Hexa­methyl-4,11-di­aza-1,8-di­azonia­cyclo­tetra­deca-4,11-diene bis­­(methane­sulfonate)

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

5,7,7,12,14,14-Hexamethyl-4,11-diaza-1,8-diazoniacyclotetradeca-4,11-diene bis(methanesulfonate)