2,13-Dibenzyl-5,16-diethyl-2,6,13,17-tetra­aza­tricyclo­[16.4.0.07,12]docosan-2-ium nitrate

Choi, J.-H.; Subhan, M.A.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811029692

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages o2173-o2174

doi:10.1107/S1600536811029692

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2,13-Dibenzyl-5,16-diethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosan-2-ium nitrate

Jong-Ha Choi,^a ‡ Md Abdus Subhan,^a Seik Weng Ng ^b,^c and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, Andong National University, Andong 760-749, Republic of Korea, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 21 July 2011; accepted 22 July 2011; online 30 July 2011)

One of the tertiary amine atoms has been protonated in the title salt, C₃₆H₅₇N₄⁺·NO₃⁻. The four N atoms of the macrocycle are almost coplanar (r.m.s. deviation = 0.0053 Å), a result correlated with the formation of intramolecular N—H⋯N and N—H⋯(N,N) hydrogen bonds. With respect to this plane, the benzyl groups lie to either side; a similar arrangement pertains for the cyclohexyl rings (each with a chair conformation). Helical supramolecular chains are evident in the crystal, whereby alternating cations and anions are linked by C—H⋯O interactions. The chains are consolidated into supramolecular arrays in the ab plane via C—H⋯π contacts involving both benzene rings.

Related literature

For the synthesis of the precursor macrocycle, see: Lim et al. (2006 ); For related structures, see: Choi et al. (2006 , 2010a ,b ).

Experimental

Crystal data

C₃₆H₅₇N₄⁺·NO₃⁻
M_r = 607.87
Monoclinic, P 2₁ /n
a = 10.7882 (1) Å
b = 16.2785 (1) Å
c = 19.0962 (1) Å
β = 98.2461 (6)°
V = 3318.92 (4) Å³
Z = 4
Cu Kα radiation
μ = 0.61 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.839, T_max = 0.942
24730 measured reflections
6689 independent reflections
6289 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.120
S = 1.06
6689 reflections
409 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C2–C7 and C20–C25 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2	0.90 (1)	2.32 (1)	2.7400 (11)	108 (1)
N1—H1⋯N4	0.90 (1)	2.12 (1)	2.8156 (11)	134 (1)
N2—H2⋯N3	0.88 (1)	2.19 (1)	2.9293 (11)	142 (1)
N4—H4⋯N3	0.88 (1)	2.33 (1)	2.7992 (11)	113 (1)
C1—H1a⋯O1	0.99	2.36	3.2096 (13)	143
C9—H9a⋯O3ⁱ	0.99	2.40	3.3620 (12)	165
C34—H34a⋯O3ⁱ	0.99	2.50	3.3876 (13)	150
C8—H8a⋯Cg3ⁱⁱ	0.99	2.53	3.4008 (11)	146
C26—H26b⋯Cg1ⁱⁱⁱ	0.99	2.71	3.5899 (11)	149
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811029692/hb6328sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811029692/hb6328Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811029692/hb6328Isup3.cml

checkCIF report

Comment top

The title salt, (I), was isolated unexpectedly during the course of studies of partially N-substituted tetraazamacrocycles of interest owing to their various applications (Choi et al., 2006; Choi et al., 2010a; Choi, et al., 2010b). As seen in Fig. 1, one of the tertiary amine-N atoms, i.e. N1, has been protonated with the charge balance provided by the nitrate anion. The four nitrogen atoms lie in a plane with a r.m.s. deviation = 0.0053 Å; the maximum deviation from the least-squares plane is 0.0055 (4) Å for atom N1. This observation is readily explained in terms of the intramolecular N—H···N hydrogen bonds with the N1—H1 atom being bifurcated, Table 1 and Fig. 2. With reference to this plane, the benzyl groups lie to either side and are twisted with respect to the N₄ plane as seen in the values of the dihedral angles of 63.62 (3) and 66.25 (3) ° formed with rings (C2—C7) and (C20—C25), respectively. Similarly, the cyclohexyl rings, each with a chair conformation, lie to either side of the N₄ plane.

The anion is associated with the cation via C—H···O contacts, Table 1, so that the nitrate-O1 forms a contact with a benzyl-methylene-H, and the nitrate-O3 atom bridges a methylene-H derived from a cyclohexyl ring and a methylene-H from the macrocyclic framework. The result is the formation of a helical supramolecular chain along the b-axis, Fig. 2. Chains are consolidated into layers in the ab-plane via C—H···π interactions involving benzene rings, Table 1 and Fig. 3.

Related literature top

For the synthesis of the precursor macrocycle, see: Lim et al. (2006); For related structures, see: Choi et al. (2006, 2010a,b).

Experimental top

The macrocycle, 5,16-diethyl-2,6,13,17-tetraazatricyclo[14.4.0^1,18.0^7,12]docosane, was prepared according to a published procedure (Lim et al., 2006). To a solution of this macrocycle (0.61 g, 2.0 mmol) in methanol (10 ml) was added benzyl bromide (0.68 g, 4.0 mmol) and a solution containing sodium carbonate (0.42 g, 4.0 mmol) in water (5 ml). The mixture was refluxed for 24 h. The solution was cooled, the white solid collected and washed with water. The title di-benzyl substituted macrocyclic nitrate was the unexpected colourless by-product that was obtained when copper nitrate trihydrate (0.06 g, 0.25 mmol) and the dibenzyl-substituted macrocycle (0.16 g, 0.29 mmol) was reacted in THF (10 ml). The compound was recrystallized from acetonitrile-water (1:1) in the form of colourless prisms.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structures of the ions in (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Helical supramolecular chain aligned along the b-axis in (I) mediated by C—H···O interactions shown as orange dashed lines. Intramolecular N—H···N hydrogen bonds are shown as blue dashed lines.
	Fig. 3. A view of the crystal packing of (I) in projection down the a-axis. The C—H···O and C—H···π interactions shown as orange and purple dashed lines, respectively.

2,13-Dibenzyl-5,16-diethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosan-2- ium nitrate top

Crystal data top

C₃₆H₅₇N₄⁺·NO₃⁻	F(000) = 1328
M_r = 607.87	D_x = 1.217 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 15422 reflections
a = 10.7882 (1) Å	θ = 2.7–74.2°
b = 16.2785 (1) Å	µ = 0.61 mm⁻¹
c = 19.0962 (1) Å	T = 100 K
β = 98.2461 (6)°	Prism, colorless
V = 3318.92 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	6689 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	6289 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.040
Detector resolution: 10.4041 pixels mm^-1	θ_max = 74.4°, θ_min = 3.6°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −20→20
T_min = 0.839, T_max = 0.942	l = −23→23
24730 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) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0639P)² + 0.9655P] where P = (F_o² + 2F_c²)/3
6689 reflections	(Δ/σ)_max = 0.001
409 parameters	Δρ_max = 0.31 e Å⁻³
3 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₃₆H₅₇N₄⁺·NO₃⁻	V = 3318.92 (4) Å³
M_r = 607.87	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 10.7882 (1) Å	µ = 0.61 mm⁻¹
b = 16.2785 (1) Å	T = 100 K
c = 19.0962 (1) Å	0.30 × 0.20 × 0.10 mm
β = 98.2461 (6)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	6689 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	6289 reflections with I > 2σ(I)
T_min = 0.839, T_max = 0.942	R_int = 0.040
24730 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	3 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.31 e Å⁻³
6689 reflections	Δρ_min = −0.25 e Å⁻³
409 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.

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

	x	y	z	U_iso*/U_eq
O1	0.50228 (8)	0.10547 (5)	0.24392 (5)	0.0332 (2)
O2	0.56328 (8)	−0.01583 (6)	0.28070 (5)	0.0327 (2)
O3	0.39115 (8)	−0.00135 (5)	0.20754 (4)	0.02779 (19)
N1	0.43505 (7)	0.37105 (5)	0.22433 (4)	0.01185 (17)
N2	0.57885 (7)	0.45766 (5)	0.32911 (4)	0.01289 (18)
N3	0.56192 (7)	0.62777 (5)	0.27861 (4)	0.01193 (17)
N4	0.41868 (7)	0.53381 (5)	0.17396 (4)	0.01209 (17)
N5	0.48585 (8)	0.02911 (6)	0.24405 (5)	0.0209 (2)
C1	0.52521 (9)	0.30042 (6)	0.22417 (5)	0.0158 (2)
H1A	0.4785	0.2479	0.2221	0.019*
H1B	0.5853	0.3011	0.2685	0.019*
C2	0.59572 (9)	0.30616 (6)	0.16165 (5)	0.0148 (2)
C3	0.69049 (9)	0.36427 (6)	0.16127 (5)	0.0176 (2)
H3A	0.7107	0.4000	0.2006	0.021*
C4	0.75561 (10)	0.37032 (7)	0.10379 (6)	0.0207 (2)
H4A	0.8200	0.4101	0.1037	0.025*
C5	0.72593 (10)	0.31770 (7)	0.04624 (5)	0.0212 (2)
H5	0.7700	0.3218	0.0067	0.025*
C6	0.63240 (10)	0.25951 (7)	0.04648 (5)	0.0205 (2)
H6	0.6127	0.2236	0.0072	0.025*
C7	0.56721 (9)	0.25352 (7)	0.10399 (5)	0.0175 (2)
H7	0.5031	0.2135	0.1040	0.021*
C8	0.33318 (9)	0.36493 (6)	0.16142 (5)	0.0138 (2)
H8A	0.2848	0.3140	0.1659	0.017*
H8B	0.3729	0.3601	0.1180	0.017*
C9	0.24291 (9)	0.43716 (6)	0.15289 (5)	0.0135 (2)
H9A	0.2132	0.4475	0.1988	0.016*
H9B	0.1691	0.4220	0.1183	0.016*
C10	0.29874 (9)	0.51689 (6)	0.12824 (5)	0.0129 (2)
H10	0.3172	0.5080	0.0790	0.015*
C11	0.20492 (9)	0.58771 (6)	0.12639 (5)	0.0171 (2)
H11A	0.1853	0.5968	0.1749	0.020*
H11B	0.2448	0.6383	0.1116	0.020*
C12	0.08247 (10)	0.57368 (8)	0.07684 (6)	0.0254 (3)
H12A	0.0277	0.6215	0.0785	0.038*
H12B	0.0407	0.5246	0.0919	0.038*
H12C	0.1004	0.5660	0.0284	0.038*
C13	0.49956 (9)	0.59796 (6)	0.14997 (5)	0.0125 (2)
H13	0.4500	0.6496	0.1400	0.015*
C14	0.55226 (9)	0.57130 (6)	0.08313 (5)	0.0162 (2)
H14A	0.4824	0.5636	0.0440	0.019*
H14B	0.5959	0.5180	0.0919	0.019*
C15	0.64389 (10)	0.63526 (7)	0.06136 (5)	0.0192 (2)
H15A	0.6804	0.6146	0.0201	0.023*
H15B	0.5979	0.6866	0.0471	0.023*
C16	0.74889 (9)	0.65372 (7)	0.12163 (5)	0.0184 (2)
H16A	0.8027	0.6979	0.1070	0.022*
H16B	0.8013	0.6041	0.1322	0.022*
C17	0.69583 (9)	0.68032 (6)	0.18819 (5)	0.0163 (2)
H17A	0.6492	0.7325	0.1789	0.020*
H17B	0.7653	0.6898	0.2272	0.020*
C18	0.60803 (9)	0.61374 (6)	0.21000 (5)	0.0120 (2)
H18	0.6581	0.5619	0.2156	0.014*
C19	0.48660 (9)	0.70312 (6)	0.27985 (5)	0.0147 (2)
H19A	0.4286	0.7079	0.2349	0.018*
H19B	0.5426	0.7516	0.2841	0.018*
C20	0.41211 (9)	0.70173 (6)	0.34134 (5)	0.0145 (2)
C21	0.44026 (9)	0.75553 (6)	0.39824 (5)	0.0171 (2)
H21	0.5065	0.7940	0.3984	0.020*
C22	0.37204 (10)	0.75333 (7)	0.45488 (5)	0.0196 (2)
H22	0.3917	0.7904	0.4933	0.023*
C23	0.27563 (10)	0.69726 (7)	0.45545 (5)	0.0196 (2)
H23	0.2296	0.6956	0.4943	0.024*
C24	0.24625 (10)	0.64323 (7)	0.39889 (6)	0.0197 (2)
H24	0.1801	0.6047	0.3990	0.024*
C25	0.31418 (9)	0.64595 (7)	0.34239 (5)	0.0172 (2)
H25	0.2936	0.6092	0.3038	0.021*
C26	0.66397 (9)	0.63019 (6)	0.33960 (5)	0.0141 (2)
H26A	0.6256	0.6364	0.3834	0.017*
H26B	0.7152	0.6798	0.3350	0.017*
C27	0.75144 (9)	0.55589 (6)	0.34862 (5)	0.0141 (2)
H27A	0.8269	0.5709	0.3820	0.017*
H27B	0.7789	0.5439	0.3024	0.017*
C28	0.69645 (9)	0.47719 (6)	0.37546 (5)	0.0137 (2)
H28	0.6780	0.4864	0.4247	0.016*
C29	0.78903 (9)	0.40598 (7)	0.37584 (5)	0.0182 (2)
H29A	0.7483	0.3551	0.3895	0.022*
H29B	0.8088	0.3982	0.3272	0.022*
C30	0.91137 (10)	0.41840 (8)	0.42597 (6)	0.0260 (3)
H30A	0.9657	0.3706	0.4235	0.039*
H30B	0.8931	0.4248	0.4745	0.039*
H30C	0.9537	0.4678	0.4121	0.039*
C31	0.49519 (9)	0.39720 (6)	0.35440 (5)	0.0128 (2)
H31	0.5424	0.3446	0.3638	0.015*
C32	0.43876 (9)	0.42032 (7)	0.42130 (5)	0.0171 (2)
H32A	0.5070	0.4289	0.4611	0.021*
H32B	0.3916	0.4724	0.4131	0.021*
C33	0.35099 (10)	0.35262 (7)	0.44074 (5)	0.0196 (2)
H33A	0.4000	0.3021	0.4536	0.023*
H33B	0.3128	0.3701	0.4825	0.023*
C34	0.24755 (9)	0.33400 (7)	0.37957 (5)	0.0179 (2)
H34A	0.1921	0.3824	0.3707	0.021*
H34B	0.1965	0.2874	0.3927	0.021*
C35	0.30172 (9)	0.31249 (6)	0.31183 (5)	0.0169 (2)
H35A	0.3502	0.2608	0.3187	0.020*
H35B	0.2329	0.3045	0.2722	0.020*
C36	0.38655 (9)	0.38224 (6)	0.29457 (5)	0.0123 (2)
H36	0.3345	0.4333	0.2903	0.015*
H1	0.4755 (12)	0.4183 (6)	0.2191 (7)	0.030 (4)*
H2	0.5374 (12)	0.5033 (6)	0.3183 (7)	0.029 (4)*
H4	0.4029 (12)	0.5486 (8)	0.2162 (5)	0.023 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0302 (4)	0.0194 (4)	0.0498 (5)	−0.0036 (3)	0.0049 (4)	0.0009 (4)
O2	0.0298 (5)	0.0338 (5)	0.0338 (5)	0.0102 (4)	0.0020 (4)	0.0097 (4)
O3	0.0268 (4)	0.0291 (4)	0.0266 (4)	−0.0065 (3)	0.0007 (3)	−0.0020 (3)
N1	0.0122 (4)	0.0118 (4)	0.0116 (4)	0.0002 (3)	0.0018 (3)	−0.0005 (3)
N2	0.0117 (4)	0.0136 (4)	0.0129 (4)	−0.0015 (3)	0.0001 (3)	0.0025 (3)
N3	0.0116 (4)	0.0130 (4)	0.0110 (4)	0.0007 (3)	0.0010 (3)	−0.0007 (3)
N4	0.0119 (4)	0.0143 (4)	0.0099 (4)	−0.0016 (3)	0.0010 (3)	0.0004 (3)
N5	0.0194 (4)	0.0223 (5)	0.0225 (4)	0.0007 (3)	0.0078 (3)	0.0010 (3)
C1	0.0175 (5)	0.0145 (5)	0.0156 (5)	0.0049 (4)	0.0037 (4)	0.0013 (4)
C2	0.0135 (4)	0.0169 (5)	0.0140 (4)	0.0048 (4)	0.0014 (3)	0.0009 (4)
C3	0.0174 (5)	0.0174 (5)	0.0176 (5)	0.0029 (4)	0.0013 (4)	−0.0021 (4)
C4	0.0170 (5)	0.0209 (5)	0.0249 (5)	0.0017 (4)	0.0054 (4)	0.0034 (4)
C5	0.0194 (5)	0.0294 (6)	0.0158 (5)	0.0079 (4)	0.0059 (4)	0.0038 (4)
C6	0.0179 (5)	0.0285 (6)	0.0142 (5)	0.0060 (4)	−0.0006 (4)	−0.0040 (4)
C7	0.0132 (4)	0.0206 (5)	0.0180 (5)	0.0031 (4)	0.0005 (4)	−0.0026 (4)
C8	0.0137 (4)	0.0142 (5)	0.0127 (4)	−0.0004 (4)	−0.0004 (3)	−0.0015 (3)
C9	0.0118 (4)	0.0142 (5)	0.0142 (4)	−0.0002 (3)	0.0003 (3)	0.0001 (3)
C10	0.0122 (4)	0.0149 (5)	0.0109 (4)	−0.0008 (4)	−0.0003 (3)	0.0004 (3)
C11	0.0149 (5)	0.0163 (5)	0.0193 (5)	0.0017 (4)	0.0005 (4)	0.0029 (4)
C12	0.0156 (5)	0.0270 (6)	0.0316 (6)	0.0006 (4)	−0.0037 (4)	0.0086 (5)
C13	0.0125 (4)	0.0125 (5)	0.0124 (4)	−0.0008 (3)	0.0017 (3)	0.0013 (3)
C14	0.0171 (5)	0.0196 (5)	0.0122 (4)	−0.0008 (4)	0.0034 (4)	−0.0003 (4)
C15	0.0193 (5)	0.0249 (6)	0.0145 (5)	−0.0019 (4)	0.0059 (4)	0.0031 (4)
C16	0.0154 (5)	0.0223 (5)	0.0186 (5)	−0.0024 (4)	0.0064 (4)	0.0015 (4)
C17	0.0149 (5)	0.0173 (5)	0.0172 (5)	−0.0039 (4)	0.0044 (4)	−0.0002 (4)
C18	0.0113 (4)	0.0133 (5)	0.0116 (4)	−0.0002 (3)	0.0024 (3)	0.0002 (3)
C19	0.0156 (4)	0.0136 (5)	0.0150 (5)	0.0020 (4)	0.0030 (4)	0.0006 (3)
C20	0.0138 (4)	0.0158 (5)	0.0138 (4)	0.0041 (4)	0.0012 (3)	0.0006 (4)
C21	0.0133 (4)	0.0195 (5)	0.0178 (5)	0.0018 (4)	0.0001 (4)	−0.0022 (4)
C22	0.0189 (5)	0.0253 (6)	0.0134 (5)	0.0056 (4)	−0.0014 (4)	−0.0043 (4)
C23	0.0194 (5)	0.0258 (6)	0.0145 (5)	0.0067 (4)	0.0052 (4)	0.0035 (4)
C24	0.0181 (5)	0.0194 (5)	0.0223 (5)	0.0015 (4)	0.0057 (4)	0.0021 (4)
C25	0.0171 (5)	0.0176 (5)	0.0172 (5)	0.0014 (4)	0.0028 (4)	−0.0020 (4)
C26	0.0134 (4)	0.0147 (5)	0.0135 (4)	−0.0012 (4)	−0.0004 (4)	−0.0011 (3)
C27	0.0115 (4)	0.0159 (5)	0.0145 (4)	−0.0012 (4)	−0.0001 (3)	0.0009 (4)
C28	0.0125 (4)	0.0167 (5)	0.0111 (4)	−0.0004 (4)	−0.0004 (3)	0.0006 (3)
C29	0.0163 (5)	0.0186 (5)	0.0191 (5)	0.0024 (4)	0.0004 (4)	0.0033 (4)
C30	0.0157 (5)	0.0284 (6)	0.0322 (6)	0.0014 (4)	−0.0028 (4)	0.0095 (5)
C31	0.0130 (4)	0.0134 (5)	0.0120 (4)	−0.0008 (3)	0.0018 (3)	0.0009 (3)
C32	0.0187 (5)	0.0204 (5)	0.0125 (4)	−0.0027 (4)	0.0036 (4)	−0.0008 (4)
C33	0.0206 (5)	0.0249 (5)	0.0141 (5)	−0.0022 (4)	0.0056 (4)	0.0031 (4)
C34	0.0165 (5)	0.0203 (5)	0.0182 (5)	−0.0025 (4)	0.0069 (4)	0.0022 (4)
C35	0.0171 (5)	0.0173 (5)	0.0168 (5)	−0.0052 (4)	0.0046 (4)	−0.0011 (4)
C36	0.0124 (4)	0.0138 (5)	0.0112 (4)	−0.0004 (3)	0.0030 (3)	0.0001 (3)

Geometric parameters (Å, º) top

O1—N5	1.2557 (13)	C15—H15B	0.9900
O2—N5	1.2470 (13)	C16—C17	1.5297 (13)
O3—N5	1.2536 (12)	C16—H16A	0.9900
N1—C1	1.5063 (12)	C16—H16B	0.9900
N1—C8	1.5107 (12)	C17—C18	1.5357 (13)
N1—C36	1.5189 (11)	C17—H17A	0.9900
N1—H1	0.896 (9)	C17—H17B	0.9900
N2—C31	1.4634 (12)	C18—H18	1.0000
N2—C28	1.4737 (12)	C19—C20	1.5152 (13)
N2—H2	0.877 (9)	C19—H19A	0.9900
N3—C19	1.4734 (12)	C19—H19B	0.9900
N3—C26	1.4840 (12)	C20—C21	1.3947 (14)
N3—C18	1.4842 (11)	C20—C25	1.3954 (14)
N4—C13	1.4753 (12)	C21—C22	1.3933 (14)
N4—C10	1.4793 (11)	C21—H21	0.9500
N4—H4	0.881 (8)	C22—C23	1.3850 (16)
C1—C2	1.5077 (13)	C22—H22	0.9500
C1—H1A	0.9900	C23—C24	1.3937 (15)
C1—H1B	0.9900	C23—H23	0.9500
C2—C3	1.3935 (14)	C24—C25	1.3892 (14)
C2—C7	1.3943 (14)	C24—H24	0.9500
C3—C4	1.3890 (14)	C25—H25	0.9500
C3—H3A	0.9500	C26—C27	1.5286 (13)
C4—C5	1.3940 (16)	C26—H26A	0.9900
C4—H4A	0.9500	C26—H26B	0.9900
C5—C6	1.3844 (16)	C27—C28	1.5308 (13)
C5—H5	0.9500	C27—H27A	0.9900
C6—C7	1.3898 (14)	C27—H27B	0.9900
C6—H6	0.9500	C28—C29	1.5295 (14)
C7—H7	0.9500	C28—H28	1.0000
C8—C9	1.5204 (13)	C29—C30	1.5287 (14)
C8—H8A	0.9900	C29—H29A	0.9900
C8—H8B	0.9900	C29—H29B	0.9900
C9—C10	1.5331 (13)	C30—H30A	0.9800
C9—H9A	0.9900	C30—H30B	0.9800
C9—H9B	0.9900	C30—H30C	0.9800
C10—C11	1.5312 (13)	C31—C36	1.5344 (12)
C10—H10	1.0000	C31—C32	1.5387 (13)
C11—C12	1.5277 (14)	C31—H31	1.0000
C11—H11A	0.9900	C32—C33	1.5328 (14)
C11—H11B	0.9900	C32—H32A	0.9900
C12—H12A	0.9800	C32—H32B	0.9900
C12—H12B	0.9800	C33—C34	1.5256 (14)
C12—H12C	0.9800	C33—H33A	0.9900
C13—C14	1.5326 (13)	C33—H33B	0.9900
C13—C18	1.5378 (12)	C34—C35	1.5344 (13)
C13—H13	1.0000	C34—H34A	0.9900
C14—C15	1.5336 (14)	C34—H34B	0.9900
C14—H14A	0.9900	C35—C36	1.5238 (13)
C14—H14B	0.9900	C35—H35A	0.9900
C15—C16	1.5245 (14)	C35—H35B	0.9900
C15—H15A	0.9900	C36—H36	1.0000

C1—N1—C8	110.14 (7)	C16—C17—H17B	109.6
C1—N1—C36	113.44 (7)	C18—C17—H17B	109.6
C8—N1—C36	114.00 (7)	H17A—C17—H17B	108.1
C1—N1—H1	109.2 (9)	N3—C18—C17	115.38 (8)
C8—N1—H1	106.1 (9)	N3—C18—C13	111.61 (7)
C36—N1—H1	103.4 (9)	C17—C18—C13	110.41 (8)
C31—N2—C28	117.74 (7)	N3—C18—H18	106.3
C31—N2—H2	109.3 (9)	C17—C18—H18	106.3
C28—N2—H2	108.9 (9)	C13—C18—H18	106.3
C19—N3—C26	108.30 (7)	N3—C19—C20	110.80 (8)
C19—N3—C18	113.43 (7)	N3—C19—H19A	109.5
C26—N3—C18	113.09 (7)	C20—C19—H19A	109.5
C13—N4—C10	117.05 (7)	N3—C19—H19B	109.5
C13—N4—H4	106.9 (9)	C20—C19—H19B	109.5
C10—N4—H4	108.9 (9)	H19A—C19—H19B	108.1
O2—N5—O3	120.46 (10)	C21—C20—C25	118.57 (9)
O2—N5—O1	119.90 (9)	C21—C20—C19	120.93 (9)
O3—N5—O1	119.64 (9)	C25—C20—C19	120.51 (9)
N1—C1—C2	110.71 (8)	C22—C21—C20	120.56 (10)
N1—C1—H1A	109.5	C22—C21—H21	119.7
C2—C1—H1A	109.5	C20—C21—H21	119.7
N1—C1—H1B	109.5	C23—C22—C21	120.26 (9)
C2—C1—H1B	109.5	C23—C22—H22	119.9
H1A—C1—H1B	108.1	C21—C22—H22	119.9
C3—C2—C7	119.47 (9)	C22—C23—C24	119.83 (9)
C3—C2—C1	120.00 (9)	C22—C23—H23	120.1
C7—C2—C1	120.53 (9)	C24—C23—H23	120.1
C4—C3—C2	120.45 (9)	C25—C24—C23	119.68 (10)
C4—C3—H3A	119.8	C25—C24—H24	120.2
C2—C3—H3A	119.8	C23—C24—H24	120.2
C3—C4—C5	119.63 (10)	C24—C25—C20	121.11 (9)
C3—C4—H4A	120.2	C24—C25—H25	119.4
C5—C4—H4A	120.2	C20—C25—H25	119.4
C6—C5—C4	120.20 (9)	N3—C26—C27	116.35 (8)
C6—C5—H5	119.9	N3—C26—H26A	108.2
C4—C5—H5	119.9	C27—C26—H26A	108.2
C5—C6—C7	120.15 (10)	N3—C26—H26B	108.2
C5—C6—H6	119.9	C27—C26—H26B	108.2
C7—C6—H6	119.9	H26A—C26—H26B	107.4
C6—C7—C2	120.10 (10)	C26—C27—C28	115.93 (8)
C6—C7—H7	120.0	C26—C27—H27A	108.3
C2—C7—H7	120.0	C28—C27—H27A	108.3
N1—C8—C9	114.58 (8)	C26—C27—H27B	108.3
N1—C8—H8A	108.6	C28—C27—H27B	108.3
C9—C8—H8A	108.6	H27A—C27—H27B	107.4
N1—C8—H8B	108.6	N2—C28—C29	110.17 (8)
C9—C8—H8B	108.6	N2—C28—C27	108.73 (7)
H8A—C8—H8B	107.6	C29—C28—C27	110.59 (8)
C8—C9—C10	114.44 (8)	N2—C28—H28	109.1
C8—C9—H9A	108.7	C29—C28—H28	109.1
C10—C9—H9A	108.7	C27—C28—H28	109.1
C8—C9—H9B	108.7	C30—C29—C28	114.03 (9)
C10—C9—H9B	108.7	C30—C29—H29A	108.7
H9A—C9—H9B	107.6	C28—C29—H29A	108.7
N4—C10—C11	113.13 (8)	C30—C29—H29B	108.7
N4—C10—C9	108.99 (7)	C28—C29—H29B	108.7
C11—C10—C9	110.91 (8)	H29A—C29—H29B	107.6
N4—C10—H10	107.9	C29—C30—H30A	109.5
C11—C10—H10	107.9	C29—C30—H30B	109.5
C9—C10—H10	107.9	H30A—C30—H30B	109.5
C12—C11—C10	114.31 (9)	C29—C30—H30C	109.5
C12—C11—H11A	108.7	H30A—C30—H30C	109.5
C10—C11—H11A	108.7	H30B—C30—H30C	109.5
C12—C11—H11B	108.7	N2—C31—C36	107.60 (7)
C10—C11—H11B	108.7	N2—C31—C32	116.47 (8)
H11A—C11—H11B	107.6	C36—C31—C32	107.83 (8)
C11—C12—H12A	109.5	N2—C31—H31	108.2
C11—C12—H12B	109.5	C36—C31—H31	108.2
H12A—C12—H12B	109.5	C32—C31—H31	108.2
C11—C12—H12C	109.5	C33—C32—C31	110.91 (8)
H12A—C12—H12C	109.5	C33—C32—H32A	109.5
H12B—C12—H12C	109.5	C31—C32—H32A	109.5
N4—C13—C14	111.39 (8)	C33—C32—H32B	109.5
N4—C13—C18	107.91 (7)	C31—C32—H32B	109.5
C14—C13—C18	109.56 (8)	H32A—C32—H32B	108.0
N4—C13—H13	109.3	C34—C33—C32	111.53 (8)
C14—C13—H13	109.3	C34—C33—H33A	109.3
C18—C13—H13	109.3	C32—C33—H33A	109.3
C13—C14—C15	111.35 (8)	C34—C33—H33B	109.3
C13—C14—H14A	109.4	C32—C33—H33B	109.3
C15—C14—H14A	109.4	H33A—C33—H33B	108.0
C13—C14—H14B	109.4	C33—C34—C35	111.45 (8)
C15—C14—H14B	109.4	C33—C34—H34A	109.3
H14A—C14—H14B	108.0	C35—C34—H34A	109.3
C16—C15—C14	111.55 (8)	C33—C34—H34B	109.3
C16—C15—H15A	109.3	C35—C34—H34B	109.3
C14—C15—H15A	109.3	H34A—C34—H34B	108.0
C16—C15—H15B	109.3	C36—C35—C34	109.00 (8)
C14—C15—H15B	109.3	C36—C35—H35A	109.9
H15A—C15—H15B	108.0	C34—C35—H35A	109.9
C15—C16—C17	110.92 (8)	C36—C35—H35B	109.9
C15—C16—H16A	109.5	C34—C35—H35B	109.9
C17—C16—H16A	109.5	H35A—C35—H35B	108.3
C15—C16—H16B	109.5	N1—C36—C35	113.28 (8)
C17—C16—H16B	109.5	N1—C36—C31	110.70 (7)
H16A—C16—H16B	108.0	C35—C36—C31	112.06 (8)
C16—C17—C18	110.15 (8)	N1—C36—H36	106.8
C16—C17—H17A	109.6	C35—C36—H36	106.8
C18—C17—H17A	109.6	C31—C36—H36	106.8

C8—N1—C1—C2	66.13 (10)	C26—N3—C19—C20	−70.03 (9)
C36—N1—C1—C2	−164.73 (8)	C18—N3—C19—C20	163.57 (8)
N1—C1—C2—C3	74.22 (11)	N3—C19—C20—C21	111.49 (10)
N1—C1—C2—C7	−105.98 (10)	N3—C19—C20—C25	−68.03 (11)
C7—C2—C3—C4	0.50 (15)	C25—C20—C21—C22	0.13 (15)
C1—C2—C3—C4	−179.69 (9)	C19—C20—C21—C22	−179.40 (9)
C2—C3—C4—C5	−0.15 (15)	C20—C21—C22—C23	0.30 (15)
C3—C4—C5—C6	−0.24 (16)	C21—C22—C23—C24	−0.43 (15)
C4—C5—C6—C7	0.29 (16)	C22—C23—C24—C25	0.12 (15)
C5—C6—C7—C2	0.05 (15)	C23—C24—C25—C20	0.32 (15)
C3—C2—C7—C6	−0.45 (15)	C21—C20—C25—C24	−0.44 (15)
C1—C2—C7—C6	179.74 (9)	C19—C20—C25—C24	179.09 (9)
C1—N1—C8—C9	−175.10 (8)	C19—N3—C26—C27	178.66 (8)
C36—N1—C8—C9	56.07 (10)	C18—N3—C26—C27	−54.73 (11)
N1—C8—C9—C10	71.93 (10)	N3—C26—C27—C28	−73.19 (10)
C13—N4—C10—C11	−68.49 (10)	C31—N2—C28—C29	73.32 (10)
C13—N4—C10—C9	167.63 (8)	C31—N2—C28—C27	−165.34 (8)
C8—C9—C10—N4	−50.59 (10)	C26—C27—C28—N2	53.90 (10)
C8—C9—C10—C11	−175.77 (8)	C26—C27—C28—C29	174.98 (8)
N4—C10—C11—C12	177.23 (8)	N2—C28—C29—C30	−176.58 (8)
C9—C10—C11—C12	−59.95 (11)	C27—C28—C29—C30	63.19 (11)
C10—N4—C13—C14	−67.86 (10)	C28—N2—C31—C36	−175.09 (8)
C10—N4—C13—C18	171.85 (7)	C28—N2—C31—C32	63.80 (11)
N4—C13—C14—C15	−175.82 (8)	N2—C31—C32—C33	178.67 (8)
C18—C13—C14—C15	−56.50 (10)	C36—C31—C32—C33	57.68 (10)
C13—C14—C15—C16	55.23 (11)	C31—C32—C33—C34	−56.30 (11)
C14—C15—C16—C17	−55.12 (12)	C32—C33—C34—C35	54.94 (12)
C15—C16—C17—C18	56.98 (11)	C33—C34—C35—C36	−55.57 (11)
C19—N3—C18—C17	61.89 (10)	C1—N1—C36—C35	−67.88 (10)
C26—N3—C18—C17	−61.94 (10)	C8—N1—C36—C35	59.27 (10)
C19—N3—C18—C13	−65.20 (10)	C1—N1—C36—C31	58.97 (10)
C26—N3—C18—C13	170.97 (8)	C8—N1—C36—C31	−173.89 (8)
C16—C17—C18—N3	173.18 (8)	C34—C35—C36—N1	−174.29 (8)
C16—C17—C18—C13	−59.12 (10)	C34—C35—C36—C31	59.58 (10)
N4—C13—C18—N3	−50.19 (10)	N2—C31—C36—N1	45.54 (10)
C14—C13—C18—N3	−171.62 (8)	C32—C31—C36—N1	171.92 (8)
N4—C13—C18—C17	−179.93 (7)	N2—C31—C36—C35	173.06 (7)
C14—C13—C18—C17	58.63 (10)	C32—C31—C36—C35	−60.55 (10)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C7 and C20–C25 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2	0.90 (1)	2.32 (1)	2.7400 (11)	108 (1)
N1—H1···N4	0.90 (1)	2.12 (1)	2.8156 (11)	134 (1)
N2—H2···N3	0.88 (1)	2.19 (1)	2.9293 (11)	142 (1)
N4—H4···N3	0.88 (1)	2.33 (1)	2.7992 (11)	113 (1)
C1—H1a···O1	0.99	2.36	3.2096 (13)	143
C9—H9a···O3ⁱ	0.99	2.40	3.3620 (12)	165
C34—H34a···O3ⁱ	0.99	2.50	3.3876 (13)	150
C8—H8a···Cg3ⁱⁱ	0.99	2.53	3.4008 (11)	146
C26—H26b···Cg1ⁱⁱⁱ	0.99	2.71	3.5899 (11)	149

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

Experimental details

Crystal data
Chemical formula	C₃₆H₅₇N₄⁺·NO₃⁻
M_r	607.87
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.7882 (1), 16.2785 (1), 19.0962 (1)
β (°)	98.2461 (6)
V (Å³)	3318.92 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.839, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	24730, 6689, 6289
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.120, 1.06
No. of reflections	6689
No. of parameters	409
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.25

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C7 and C20–C25 benzene rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2	0.897 (11)	2.323 (13)	2.7400 (11)	108.3 (10)
N1—H1···N4	0.897 (11)	2.122 (11)	2.8156 (11)	133.5 (11)
N2—H2···N3	0.876 (11)	2.193 (10)	2.9293 (11)	141.5 (11)
N4—H4···N3	0.882 (10)	2.332 (12)	2.7992 (11)	113.2 (10)
C1—H1a···O1	0.99	2.36	3.2096 (13)	143
C9—H9a···O3ⁱ	0.99	2.40	3.3620 (12)	165
C34—H34a···O3ⁱ	0.99	2.50	3.3876 (13)	150
C8—H8a···Cg3ⁱⁱ	0.99	2.53	3.4008 (11)	146
C26—H26b···Cg1ⁱⁱⁱ	0.99	2.71	3.5899 (11)	149

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

Footnotes

‡Additional correspondence author, e-mail: jhchoi@andong.ac.kr.

Acknowledgements

We thank Andong National University and the University of Malaya for supporting this study. MAS thanks the National Research Foundation of Korea for a postdoctoral fellowship grant.

References

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Volume 67| Part 8| August 2011| Pages o2173-o2174

doi:10.1107/S1600536811029692

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

2,13-Di­benzyl-5,16-di­ethyl-2,6,13,17-tetra­aza­tri­cyclo­[16.4.0.07,12]docosan-2-ium nitrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

2,13-Dibenzyl-5,16-diethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosan-2-ium nitrate