1,4,8,11-Tetra-azonia-cyclo-tetra-decane tetra-kis-(hydrogensulfate).

In the title salt, C10H28N4 (4+)·4HSO4 (-), the cation lies about an inversion center. In the crystal, O-H⋯O and N-H⋯O hydrogen bonds connect the anions and cations, forming a three-dimensional network.

Related literature

For the chemistry and applications of macrocyclic polyamine ligands, see: Wainwright (2001 ▶); Lukes et al. (2001 ▶); Zhang et al. (2003 ▶); Liu (2004 ▶). For related structures, see: Melson (1979 ▶); Subramanian & Zaworotko (1995 ▶); Ferchichi et al. (2010 ▶); Pojarová et al. (2010 ▶).

Experimental

Crystal data

C10H28N4 4+·4HSO4 −

M = 592.68

Monoclinic,

a = 7.8177 (2) Å

b = 16.6464 (3) Å

c = 8.7222 (2) Å

β = 97.165 (1)°

V = 1126.21 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.51 mm−1

T = 293 K

0.03 × 0.02 × 0.01 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: analytical (face-indexed; de Meulenaer & Tompa, 1965 ▶) T min = 0.988, T max = 0.995

18757 measured reflections

4952 independent reflections

4074 reflections with I > 2σ(I)

R int = 0.060

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.123

S = 1.05

4952 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.65 e Å−3

Δρmin = −0.54 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813018953/lh5619sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018953/lh5619Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813018953/lh5619Isup3.cml

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

C10H28N44+·4HSO4−	F(000) = 624.0
Mr = 592.68	Dx = 1.748 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15635 reflections
a = 7.8177 (2) Å	θ = 2.9–35.0°
b = 16.6464 (3) Å	µ = 0.51 mm−1
c = 8.7222 (2) Å	T = 293 K
β = 97.165 (1)°	Prism, colourless
V = 1126.21 (4) Å3	0.03 × 0.02 × 0.01 mm
Z = 2

Nonius KappaCCD diffractometer	4952 independent reflections
Radiation source: fine-focus sealed tube	4074 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
CCD rotation images, thick slices scans	θmax = 35.0°, θmin = 3.4°
Absorption correction: analytical (a face-indexed absorption correction was applied using the Tompa method; de Meulenaer & Tompa, 1965)	h = −12→10
Tmin = 0.988, Tmax = 0.995	k = −26→26
18757 measured reflections	l = −13→14

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042	H-atom parameters constrained
wR(F2) = 0.123	w = 1/[σ2(Fo2) + (0.0623P)2 + 0.4049P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
4952 reflections	Δρmax = 0.65 e Å−3
163 parameters	Δρmin = −0.54 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.019 (6)

Experimental. Data were corrected for Lorentz-polarization effects and an analytical absorption correction (de Meulenaer & Tompa, 1965) was applied. The structure was solved in the P 1 21/c 1 space group by the direct methods (S and O) and subsequent difference Fourier syntheses (all other atoms), with an exception for H atoms bonded to C and N atoms which are positioned geometrically.

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.

	x	y	z	Uiso*/Ueq
S1	0.34278 (4)	0.656923 (16)	0.06576 (3)	0.02143 (8)
S2	0.23332 (4)	0.351066 (18)	0.25289 (4)	0.02525 (9)
O1	0.49495 (13)	0.67391 (6)	0.17729 (12)	0.0309 (2)
O2	0.37660 (15)	0.69761 (7)	−0.08875 (11)	0.0345 (2)
O3	0.18911 (13)	0.69666 (7)	0.10348 (12)	0.0326 (2)
O4	0.3244 (2)	0.57165 (7)	0.04142 (15)	0.0463 (3)
O6	0.38228 (16)	0.32441 (7)	0.38175 (14)	0.0396 (3)
O5	0.21214 (17)	0.43447 (6)	0.28810 (17)	0.0425 (3)
O7	0.08566 (15)	0.30213 (7)	0.27346 (18)	0.0456 (3)
O8	0.29980 (19)	0.33486 (11)	0.10785 (15)	0.0550 (4)
N1	0.28066 (13)	0.46125 (6)	−0.20331 (12)	0.02426 (19)
H1A	0.3615	0.4232	−0.1801	0.029*
H1B	0.2844	0.4940	−0.1209	0.029*
C1	0.10770 (16)	0.42072 (7)	−0.22403 (13)	0.0239 (2)
H1C	0.0170	0.4609	−0.2348	0.029*
H1D	0.0945	0.3882	−0.1340	0.029*
N2	−0.08305 (14)	0.33181 (6)	−0.40184 (12)	0.02342 (19)
H2A	−0.1098	0.3079	−0.3154	0.028*
H2B	−0.0790	0.2932	−0.4735	0.028*
C2	0.09283 (15)	0.36783 (7)	−0.36757 (13)	0.0224 (2)
H2C	0.1175	0.3997	−0.4553	0.027*
H2D	0.1777	0.3252	−0.3524	0.027*
C4	−0.22592 (16)	0.38901 (7)	−0.45835 (14)	0.0239 (2)
H4A	−0.2325	0.4310	−0.3821	0.029*
H4B	−0.3349	0.3604	−0.4708	0.029*
C5	0.33057 (15)	0.50958 (7)	−0.33674 (15)	0.0253 (2)
H5A	0.3433	0.4739	−0.4226	0.030*
H5B	0.4409	0.5353	−0.3062	0.030*
C3	−0.19624 (18)	0.42678 (8)	−0.61163 (15)	0.0283 (2)
H3A	−0.0825	0.4510	−0.6014	0.034*
H3B	−0.2000	0.3852	−0.6899	0.034*
H2	0.4133	0.2736	0.3570	0.103 (11)*
H1	0.4645	0.6890	−0.1022	0.085 (10)*

	U11	U22	U33	U12	U13	U23
S1	0.02404 (14)	0.02050 (13)	0.01984 (13)	0.00254 (8)	0.00312 (9)	0.00086 (8)
S2	0.02107 (15)	0.02753 (15)	0.02768 (15)	0.00164 (9)	0.00516 (10)	−0.00477 (10)
O1	0.0275 (5)	0.0362 (5)	0.0274 (4)	0.0037 (4)	−0.0028 (3)	−0.0011 (4)
O2	0.0327 (5)	0.0474 (6)	0.0247 (4)	0.0048 (4)	0.0084 (4)	0.0110 (4)
O3	0.0251 (4)	0.0431 (5)	0.0307 (5)	0.0095 (4)	0.0082 (3)	0.0078 (4)
O4	0.0715 (9)	0.0225 (4)	0.0434 (6)	−0.0033 (5)	0.0013 (6)	−0.0054 (4)
O6	0.0375 (6)	0.0399 (6)	0.0382 (6)	0.0056 (4)	−0.0078 (4)	−0.0025 (5)
O5	0.0433 (6)	0.0233 (4)	0.0630 (8)	0.0016 (4)	0.0149 (5)	0.0004 (5)
O7	0.0285 (5)	0.0374 (6)	0.0720 (9)	−0.0091 (4)	0.0108 (5)	−0.0178 (6)
O8	0.0425 (7)	0.0928 (11)	0.0314 (6)	0.0243 (7)	0.0119 (5)	−0.0037 (6)
N1	0.0230 (4)	0.0228 (4)	0.0249 (4)	0.0006 (3)	−0.0051 (3)	−0.0002 (3)
C1	0.0255 (5)	0.0250 (5)	0.0204 (4)	−0.0032 (4)	0.0001 (4)	−0.0003 (4)
N2	0.0273 (5)	0.0176 (4)	0.0246 (4)	−0.0037 (3)	0.0001 (3)	0.0006 (3)
C2	0.0225 (5)	0.0211 (4)	0.0230 (5)	0.0002 (3)	0.0009 (4)	0.0000 (4)
C4	0.0219 (5)	0.0232 (5)	0.0263 (5)	−0.0024 (4)	0.0019 (4)	0.0014 (4)
C5	0.0187 (5)	0.0236 (5)	0.0328 (6)	−0.0003 (3)	0.0007 (4)	0.0014 (4)
C3	0.0297 (6)	0.0284 (5)	0.0270 (5)	0.0079 (4)	0.0046 (4)	0.0049 (4)

S1—O4	1.4399 (11)	C1—H1D	0.9700
S1—O3	1.4449 (10)	N2—C2	1.4957 (15)
S1—O1	1.4672 (10)	N2—C4	1.5033 (16)
S1—O2	1.5601 (10)	N2—H2A	0.9000
S2—O5	1.4360 (11)	N2—H2B	0.9000
S2—O7	1.4423 (12)	C2—H2C	0.9700
S2—O8	1.4516 (13)	C2—H2D	0.9700
S2—O6	1.5779 (11)	C4—C3	1.5211 (17)
O2—H1	0.7258	C4—H4A	0.9700
O6—H2	0.9134	C4—H4B	0.9700
N1—C1	1.5017 (16)	C5—C3i	1.5199 (17)
N1—C5	1.5058 (17)	C5—H5A	0.9700
N1—H1A	0.9000	C5—H5B	0.9700
N1—H1B	0.9000	C3—C5i	1.5199 (17)
C1—C2	1.5232 (16)	C3—H3A	0.9700
C1—H1C	0.9700	C3—H3B	0.9700
O4—S1—O3	114.47 (8)	C4—N2—H2A	108.3
O4—S1—O1	110.22 (7)	C2—N2—H2B	108.3
O3—S1—O1	112.91 (6)	C4—N2—H2B	108.3
O4—S1—O2	108.98 (7)	H2A—N2—H2B	107.4
O3—S1—O2	103.49 (6)	N2—C2—C1	111.72 (10)
O1—S1—O2	106.16 (6)	N2—C2—H2C	109.3
O5—S2—O7	113.84 (7)	C1—C2—H2C	109.3
O5—S2—O8	115.43 (9)	N2—C2—H2D	109.3
O7—S2—O8	112.49 (9)	C1—C2—H2D	109.3
O5—S2—O6	102.36 (8)	H2C—C2—H2D	107.9
O7—S2—O6	106.48 (8)	N2—C4—C3	111.19 (10)
O8—S2—O6	104.82 (7)	N2—C4—H4A	109.4
S1—O2—H1	108.7	C3—C4—H4A	109.4
S2—O6—H2	106.6	N2—C4—H4B	109.4
C1—N1—C5	117.60 (9)	C3—C4—H4B	109.4
C1—N1—H1A	107.9	H4A—C4—H4B	108.0
C5—N1—H1A	107.9	N1—C5—C3i	111.43 (10)
C1—N1—H1B	107.9	N1—C5—H5A	109.3
C5—N1—H1B	107.9	C3i—C5—H5A	109.3
H1A—N1—H1B	107.2	N1—C5—H5B	109.3
N1—C1—C2	109.50 (10)	C3i—C5—H5B	109.3
N1—C1—H1C	109.8	H5A—C5—H5B	108.0
C2—C1—H1C	109.8	C5i—C3—C4	111.90 (11)
N1—C1—H1D	109.8	C5i—C3—H3A	109.2
C2—C1—H1D	109.8	C4—C3—H3A	109.2
H1C—C1—H1D	108.2	C5i—C3—H3B	109.2
C2—N2—C4	116.01 (9)	C4—C3—H3B	109.2
C2—N2—H2A	108.3	H3A—C3—H3B	107.9

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ii	0.90	2.60	3.2773 (18)	133
N1—H1A···O1ii	0.90	1.97	2.8445 (14)	165
N1—H1B···O4	0.90	1.91	2.8051 (16)	171
N2—H2A···O3iii	0.90	2.02	2.8675 (15)	156
N2—H2B···O3iv	0.90	2.09	2.9117 (14)	151
N2—H2A···O7v	0.90	2.45	2.9232 (15)	113
O2—H1···O8ii	0.73	1.89	2.6125 (18)	172
O6—H2···O1vi	0.91	1.85	2.7544 (17)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4i	0.90	2.60	3.2773 (18)	133
N1—H1A⋯O1i	0.90	1.97	2.8445 (14)	165
N1—H1B⋯O4	0.90	1.91	2.8051 (16)	171
N2—H2A⋯O3ii	0.90	2.02	2.8675 (15)	156
N2—H2B⋯O3iii	0.90	2.09	2.9117 (14)	151
N2—H2A⋯O7iv	0.90	2.45	2.9232 (15)	113
O2—H1⋯O8i	0.73	1.89	2.6125 (18)	172
O6—H2⋯O1v	0.91	1.85	2.7544 (17)	172

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .