2,2′,2′′,2′′′-[N,N,N′,N′-(3,6-Dioxaoctane-1,8-diyldinitrilo)tetra­methyl­ene]tetra­kis(benzimidazolium) tetra­nitrate

Zhou, C.-S.; Hu, S.; Meng, X.-G.

doi:10.1107/S1600536807020764

2,2′,2′′,2′′′-[N,N,N′,N′-(3,6-Dioxaoctane-1,8-diyldinitrilo)tetramethylene]tetrakis(benzimidazolium) tetranitrate

The cation of the title compound, C₃₈H₄₄N₁₀O₂⁴⁺·4NO₃⁻, is centrosymmetric. In the crystal structure, cations and anions are linked into a three-dimensional framework by a combination of N—H

O and C—H

O hydrogen bonds and aromatic π–π stacking interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020764/lh2376sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020764/lh2376Isup2.hkl Contains datablock I

CCDC reference: 651377

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.004 Å
R factor = 0.065
wR factor = 0.169
Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N6
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N7
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              N O3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

As part of our continuing studies on the ligands or metal complexes containing multi-benzimidazole groups (Zhang et al., 2005; Li et al., 2005; Qiu et al., 2005), we report here the crystal structure of a related compound, (I), which was obtained unexpectedly by reacting µ₂-N,N, N', N'-tetrakis(Benzimidazol-2-ylmethyl)- 3,6- dioxaoctane-1,8-diamine (EGTB) with Fe(NO₃).6H₂O in H₂O solution.

In the aymmetric unit of (I) (Fig. 1), the cation lies across an inversion center in space group of P2₁/c. The two terminal benzimidazoles rings on one side of the cation are effectively planar with the dihedral angle of only 0.75 (1)°.

All imine N atoms in the benzimidazole groups of are protonated foming a tetracation. Two nitrate anions lie to the inner side of the two end-on benzimidazole groups, forming the four nearly symmetric intra-molecular hydrogen bonds (Table 1). However, the other two anions lie at the outside of the two benzimidazole groups, linking the adjacent cations into a two-dimensional network running parallel the (100) direction. These networks are further joined by the C7–H···O7ⁱ (symmetry code as in Table 1) hydrogen bonds, forming a three-dimensional framework (Fig.2). In addition, the supramolecular aggregation is augmented by π-π stacking interactions between the aromatic rings C5—C10 and C13—C18, respectively. The two phenyl rings which lie in the molecules at (x,y,z) and (-x,1 - y,-z), respectively, are almost parallel with the dihedral angle of only 1.36 (1)°, the ring centroid separation of 3.682 (2) Å and the interpalanar spacing of ca 3.404 Å.

Related literature top

We have already published some crystal structures tha are related to the title compound (Zhang et al., 2005; Li et al., 2005; Qiu et al., 2005).

For related literature, see: Hendriks et al. (1982).

Experimental top

All reagents and solvents were used as obtained without further purification. EGTB [EGTB = (µ₂-N,N,N',N'- tetrakis(Benzimidazol-2-ylmethyl)-3,6-dioxaoctane-1,8-diamine] was prepared according to literature procedure (Hendriks et al., 1982). The title organic salt was obtained unexpectedly by reacting EGTB with Fe(NO₃).6H₂O (molar ratio: 1/2). The mixture was stirred for half an hour at 70° and then filtered. The resulting pale-yellow solution was kept in air for one week. Crystals of (I) suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of the solution at the bottom of the vessel.

Structure description top

We have already published some crystal structures tha are related to the title compound (Zhang et al., 2005; Li et al., 2005; Qiu et al., 2005).

For related literature, see: Hendriks et al. (1982).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. Atoms marked with suffix 'a' are related by the symmetry operator (1 - x, 1 - y, 1 - z).
	Fig. 2. Part of the crystal structure of (I), showing the formation of the three-dimensional network. Hydrogen bonding are shown as dashed lines. For the sake of clarity, H atoms not involved in the motif have been omitted.

2,2',2'',2'''-[N,N,N',N'-(3,6-Dioxaoctane-1,8- diyldinitrilo)tetramethylene]tetrakis(benzimidazolium) tetranitrate top

Crystal data top

C₃₈H₄₄N₁₀O₂⁴⁺·4(NO₃⁻)	F(000) = 964
M_r = 920.87	D_x = 1.439 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2223 reflections
a = 8.4296 (6) Å	θ = 2.4–19.9°
b = 17.6744 (12) Å	µ = 0.11 mm⁻¹
c = 14.279 (1) Å	T = 294 K
β = 92.421 (1)°	Block, colourless
V = 2125.5 (3) Å³	0.20 × 0.12 × 0.10 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4642 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2655 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
0.3° wide ω exposures scans	θ_max = 27.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
T_min = 0.975, T_max = 0.989	k = −19→22
23482 measured reflections	l = −18→18

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0744P)² + 0.3238P] where P = (F_o² + 2F_c²)/3
4642 reflections	(Δ/σ)_max < 0.001
310 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₃₈H₄₄N₁₀O₂⁴⁺·4(NO₃⁻)	V = 2125.5 (3) Å³
M_r = 920.87	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4296 (6) Å	µ = 0.11 mm⁻¹
b = 17.6744 (12) Å	T = 294 K
c = 14.279 (1) Å	0.20 × 0.12 × 0.10 mm
β = 92.421 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4642 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2655 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.989	R_int = 0.067
23482 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.29 e Å⁻³
4642 reflections	Δρ_min = −0.19 e Å⁻³
310 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.

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

	x	y	z	U_iso*/U_eq
C1	0.2091 (3)	0.53564 (19)	0.38291 (19)	0.0604 (8)
H1A	0.2269	0.5895	0.3759	0.072*
H1B	0.1398	0.5284	0.4347	0.072*
C2	0.1299 (3)	0.50482 (16)	0.29426 (18)	0.0481 (7)
H2A	0.1247	0.4502	0.3006	0.058*
H2B	0.0214	0.5233	0.2911	0.058*
C3	0.2078 (3)	0.60132 (15)	0.1804 (2)	0.0516 (7)
H3A	0.2777	0.6079	0.1287	0.062*
H3B	0.2532	0.6287	0.2339	0.062*
C4	0.0490 (3)	0.63386 (16)	0.15382 (17)	0.0439 (6)
C5	−0.2006 (3)	0.64709 (15)	0.10256 (16)	0.0402 (6)
C6	−0.3564 (3)	0.63661 (16)	0.06912 (18)	0.0482 (7)
H6	−0.3976	0.5887	0.0562	0.058*
C7	−0.4458 (3)	0.70087 (19)	0.05621 (18)	0.0538 (8)
H7	−0.5505	0.6964	0.0337	0.065*
C8	−0.3840 (3)	0.77308 (17)	0.07599 (19)	0.0550 (8)
H8	−0.4491	0.8152	0.0670	0.066*
C9	−0.2306 (3)	0.78310 (16)	0.10818 (18)	0.0510 (7)
H9	−0.1892	0.8310	0.1205	0.061*
C10	−0.1396 (3)	0.71858 (15)	0.12152 (17)	0.0420 (6)
C11	0.3475 (3)	0.48165 (16)	0.1873 (2)	0.0505 (7)
H11A	0.4223	0.4907	0.2395	0.061*
H11B	0.3932	0.5013	0.1310	0.061*
C12	0.3205 (3)	0.39871 (16)	0.17669 (17)	0.0453 (7)
C13	0.2109 (3)	0.28778 (17)	0.14316 (17)	0.0481 (7)
C14	0.1108 (4)	0.22818 (18)	0.11782 (19)	0.0564 (8)
H14	0.0065	0.2361	0.0964	0.068*
C15	0.1746 (4)	0.15673 (19)	0.1262 (2)	0.0666 (9)
H15	0.1120	0.1153	0.1088	0.080*
C16	0.3291 (5)	0.1445 (2)	0.1598 (2)	0.0759 (10)
H16	0.3664	0.0951	0.1657	0.091*
C17	0.4284 (4)	0.2034 (2)	0.1844 (2)	0.0676 (9)
H17	0.5324	0.1952	0.2063	0.081*
C18	0.3663 (3)	0.27573 (17)	0.17529 (18)	0.0508 (7)
C19	0.4248 (3)	0.52156 (19)	0.49117 (19)	0.0605 (8)
H19A	0.3520	0.5113	0.5404	0.073*
H19B	0.4468	0.5754	0.4907	0.073*
N1	0.1992 (2)	0.52134 (12)	0.20352 (14)	0.0427 (5)
N2	−0.0788 (2)	0.59601 (14)	0.12376 (15)	0.0450 (6)
H2	−0.084 (3)	0.5449 (17)	0.1178 (18)	0.054*
N3	0.0169 (3)	0.70765 (14)	0.15369 (15)	0.0465 (6)
H3	0.085 (3)	0.7437 (16)	0.1678 (18)	0.056*
N4	0.4296 (3)	0.34628 (16)	0.19490 (16)	0.0548 (7)
H4	0.516 (4)	0.3587 (17)	0.218 (2)	0.066*
N5	0.1875 (3)	0.36534 (14)	0.14572 (15)	0.0456 (6)
H5	0.106 (3)	0.3912 (16)	0.1281 (19)	0.055*
N6	0.7793 (3)	0.37255 (17)	0.32131 (19)	0.0621 (7)
O1	0.3557 (2)	0.49900 (11)	0.40309 (12)	0.0566 (5)
O2	0.6974 (3)	0.42656 (14)	0.29412 (17)	0.0876 (8)
O3	0.8884 (3)	0.37929 (14)	0.38036 (19)	0.0902 (8)
O4	0.7453 (3)	0.30882 (15)	0.28733 (18)	0.0908 (8)
N7	−0.2022 (3)	0.41060 (15)	0.06511 (16)	0.0546 (6)
O5	−0.3230 (2)	0.44713 (13)	0.04530 (17)	0.0787 (7)
O6	−0.0836 (2)	0.44321 (12)	0.10178 (17)	0.0766 (7)
O7	−0.1903 (3)	0.34285 (14)	0.0487 (2)	0.0942 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0578 (18)	0.075 (2)	0.0474 (17)	0.0142 (16)	−0.0083 (13)	−0.0031 (15)
C2	0.0402 (14)	0.0546 (18)	0.0488 (16)	0.0041 (13)	−0.0059 (12)	0.0025 (13)
C3	0.0405 (14)	0.0479 (18)	0.0652 (18)	−0.0094 (12)	−0.0127 (13)	0.0071 (14)
C4	0.0427 (14)	0.0443 (18)	0.0442 (15)	−0.0071 (12)	−0.0053 (11)	0.0033 (12)
C5	0.0433 (14)	0.0412 (16)	0.0360 (13)	0.0016 (12)	0.0003 (11)	0.0054 (11)
C6	0.0455 (14)	0.0530 (18)	0.0455 (15)	−0.0055 (13)	−0.0057 (12)	0.0012 (13)
C7	0.0441 (15)	0.070 (2)	0.0469 (16)	0.0052 (15)	−0.0040 (12)	0.0087 (14)
C8	0.0589 (18)	0.055 (2)	0.0504 (17)	0.0157 (15)	−0.0009 (14)	0.0098 (14)
C9	0.0621 (18)	0.0461 (18)	0.0447 (16)	0.0003 (14)	0.0032 (13)	−0.0003 (13)
C10	0.0459 (14)	0.0434 (17)	0.0364 (14)	0.0002 (12)	−0.0033 (11)	0.0027 (11)
C11	0.0367 (14)	0.062 (2)	0.0527 (17)	−0.0006 (13)	−0.0044 (12)	0.0033 (14)
C12	0.0409 (14)	0.0554 (19)	0.0395 (14)	0.0031 (13)	−0.0007 (11)	0.0018 (13)
C13	0.0538 (16)	0.055 (2)	0.0356 (14)	0.0063 (14)	0.0035 (12)	0.0021 (13)
C14	0.0645 (18)	0.058 (2)	0.0470 (16)	−0.0045 (16)	0.0040 (14)	−0.0006 (14)
C15	0.092 (2)	0.052 (2)	0.0566 (19)	−0.0009 (18)	0.0123 (17)	0.0033 (15)
C16	0.111 (3)	0.059 (2)	0.058 (2)	0.021 (2)	0.005 (2)	0.0032 (17)
C17	0.075 (2)	0.072 (2)	0.0546 (19)	0.0264 (19)	−0.0056 (16)	0.0036 (17)
C18	0.0571 (17)	0.056 (2)	0.0393 (15)	0.0119 (15)	0.0001 (12)	−0.0011 (13)
C19	0.0645 (19)	0.070 (2)	0.0456 (17)	0.0011 (15)	−0.0152 (14)	−0.0014 (14)
N1	0.0360 (11)	0.0454 (14)	0.0460 (13)	−0.0016 (10)	−0.0062 (9)	0.0050 (10)
N2	0.0433 (12)	0.0399 (13)	0.0507 (13)	−0.0031 (11)	−0.0087 (10)	0.0027 (11)
N3	0.0482 (13)	0.0407 (15)	0.0499 (13)	−0.0080 (10)	−0.0078 (10)	−0.0014 (11)
N4	0.0441 (13)	0.0697 (18)	0.0498 (14)	0.0114 (13)	−0.0078 (11)	0.0008 (12)
N5	0.0409 (12)	0.0483 (16)	0.0469 (13)	0.0074 (11)	−0.0052 (10)	−0.0007 (11)
N6	0.0457 (14)	0.066 (2)	0.0738 (18)	0.0063 (14)	−0.0011 (13)	0.0094 (15)
O1	0.0544 (11)	0.0675 (14)	0.0464 (11)	0.0091 (10)	−0.0150 (9)	−0.0071 (9)
O2	0.0809 (16)	0.0818 (18)	0.0986 (18)	0.0335 (14)	−0.0129 (14)	0.0038 (14)
O3	0.0605 (14)	0.0913 (19)	0.116 (2)	−0.0012 (13)	−0.0352 (14)	0.0062 (15)
O4	0.0764 (16)	0.0726 (18)	0.121 (2)	0.0040 (14)	−0.0302 (15)	−0.0099 (15)
N7	0.0473 (14)	0.0551 (17)	0.0602 (15)	−0.0020 (12)	−0.0134 (11)	−0.0018 (12)
O5	0.0533 (12)	0.0746 (16)	0.1052 (18)	0.0111 (11)	−0.0310 (12)	−0.0085 (13)
O6	0.0480 (12)	0.0495 (13)	0.129 (2)	−0.0029 (10)	−0.0305 (12)	−0.0134 (12)
O7	0.0891 (17)	0.0481 (15)	0.141 (2)	0.0016 (13)	−0.0459 (16)	−0.0181 (15)

Geometric parameters (Å, º) top

C1—O1	1.414 (3)	C12—N4	1.323 (3)
C1—C2	1.508 (4)	C12—N5	1.326 (3)
C1—H1A	0.9700	C13—N5	1.386 (4)
C1—H1B	0.9700	C13—C18	1.386 (4)
C2—N1	1.473 (3)	C13—C14	1.388 (4)
C2—H2A	0.9700	C14—C15	1.376 (4)
C2—H2B	0.9700	C14—H14	0.9300
C3—N1	1.454 (3)	C15—C16	1.385 (5)
C3—C4	1.491 (3)	C15—H15	0.9300
C3—H3A	0.9700	C16—C17	1.374 (5)
C3—H3B	0.9700	C16—H16	0.9300
C4—N2	1.324 (3)	C17—C18	1.385 (4)
C4—N3	1.332 (3)	C17—H17	0.9300
C5—C10	1.387 (4)	C18—N4	1.380 (4)
C5—C6	1.391 (3)	C19—O1	1.421 (3)
C5—N2	1.391 (3)	C19—C19ⁱ	1.491 (6)
C6—C7	1.371 (4)	C19—H19A	0.9700
C6—H6	0.9300	C19—H19B	0.9700
C7—C8	1.403 (4)	N2—H2	0.91 (3)
C7—H7	0.9300	N3—H3	0.87 (3)
C8—C9	1.366 (4)	N4—H4	0.82 (3)
C8—H8	0.9300	N5—H5	0.86 (3)
C9—C10	1.383 (4)	N6—O3	1.227 (3)
C9—H9	0.9300	N6—O2	1.231 (3)
C10—N3	1.392 (3)	N6—O4	1.255 (3)
C11—N1	1.460 (3)	N7—O7	1.225 (3)
C11—C12	1.490 (4)	N7—O5	1.228 (3)
C11—H11A	0.9700	N7—O6	1.249 (3)
C11—H11B	0.9700

O1—C1—C2	111.0 (2)	C18—C13—C14	121.7 (3)
O1—C1—H1A	109.4	C15—C14—C13	116.3 (3)
C2—C1—H1A	109.4	C15—C14—H14	121.9
O1—C1—H1B	109.4	C13—C14—H14	121.9
C2—C1—H1B	109.4	C14—C15—C16	122.1 (3)
H1A—C1—H1B	108.0	C14—C15—H15	118.9
N1—C2—C1	119.3 (2)	C16—C15—H15	118.9
N1—C2—H2A	107.5	C17—C16—C15	121.6 (3)
C1—C2—H2A	107.5	C17—C16—H16	119.2
N1—C2—H2B	107.5	C15—C16—H16	119.2
C1—C2—H2B	107.5	C16—C17—C18	116.9 (3)
H2A—C2—H2B	107.0	C16—C17—H17	121.6
N1—C3—C4	112.3 (2)	C18—C17—H17	121.6
N1—C3—H3A	109.1	N4—C18—C17	132.3 (3)
C4—C3—H3A	109.1	N4—C18—C13	106.3 (2)
N1—C3—H3B	109.1	C17—C18—C13	121.4 (3)
C4—C3—H3B	109.1	O1—C19—C19ⁱ	108.7 (3)
H3A—C3—H3B	107.9	O1—C19—H19A	110.0
N2—C4—N3	109.4 (2)	C19ⁱ—C19—H19A	110.0
N2—C4—C3	126.6 (3)	O1—C19—H19B	110.0
N3—C4—C3	124.0 (2)	C19ⁱ—C19—H19B	110.0
C10—C5—C6	121.7 (2)	H19A—C19—H19B	108.3
C10—C5—N2	106.5 (2)	C3—N1—C11	112.3 (2)
C6—C5—N2	131.8 (2)	C3—N1—C2	114.7 (2)
C7—C6—C5	116.2 (3)	C11—N1—C2	114.7 (2)
C7—C6—H6	121.9	C4—N2—C5	109.0 (2)
C5—C6—H6	121.9	C4—N2—H2	124.5 (17)
C6—C7—C8	121.9 (3)	C5—N2—H2	126.5 (17)
C6—C7—H7	119.0	C4—N3—C10	109.0 (2)
C8—C7—H7	119.0	C4—N3—H3	125.6 (18)
C9—C8—C7	121.6 (3)	C10—N3—H3	125.2 (18)
C9—C8—H8	119.2	C12—N4—C18	109.5 (2)
C7—C8—H8	119.2	C12—N4—H4	119 (2)
C8—C9—C10	116.8 (3)	C18—N4—H4	131 (2)
C8—C9—H9	121.6	C12—N5—C13	109.3 (2)
C10—C9—H9	121.6	C12—N5—H5	121.4 (19)
C9—C10—C5	121.7 (2)	C13—N5—H5	129.3 (19)
C9—C10—N3	132.2 (3)	O3—N6—O2	122.4 (3)
C5—C10—N3	106.1 (2)	O3—N6—O4	120.3 (3)
N1—C11—C12	111.2 (2)	O2—N6—O4	117.3 (3)
N1—C11—H11A	109.4	C1—O1—C19	112.0 (2)
C12—C11—H11A	109.4	N6—O2—H4	95.9 (8)
N1—C11—H11B	109.4	N6—O4—H4	89.8 (8)
C12—C11—H11B	109.4	O7—N7—O5	122.9 (2)
H11A—C11—H11B	108.0	O7—N7—O6	117.4 (2)
N4—C12—N5	108.9 (3)	O5—N7—O6	119.6 (3)
N4—C12—C11	124.6 (2)	N7—O6—H2	120.4 (9)
N5—C12—C11	126.5 (2)	N7—O6—H5	121.3 (8)
N5—C13—C18	106.1 (2)	H2—O6—H5	117.9 (12)
N5—C13—C14	132.2 (3)

O1—C1—C2—N1	−69.8 (3)	C12—C11—N1—C2	67.7 (3)
N1—C3—C4—N2	−21.2 (4)	C1—C2—N1—C3	−60.6 (3)
N1—C3—C4—N3	161.5 (2)	C1—C2—N1—C11	71.7 (3)
C10—C5—C6—C7	−0.1 (4)	N3—C4—N2—C5	0.2 (3)
N2—C5—C6—C7	179.7 (3)	C3—C4—N2—C5	−177.4 (3)
C5—C6—C7—C8	−0.3 (4)	C10—C5—N2—C4	0.0 (3)
C6—C7—C8—C9	0.8 (4)	C6—C5—N2—C4	−179.9 (3)
C7—C8—C9—C10	−0.8 (4)	N2—C4—N3—C10	−0.3 (3)
C8—C9—C10—C5	0.4 (4)	C3—C4—N3—C10	177.4 (2)
C8—C9—C10—N3	−179.2 (3)	C9—C10—N3—C4	179.9 (3)
C6—C5—C10—C9	0.0 (4)	C5—C10—N3—C4	0.3 (3)
N2—C5—C10—C9	−179.9 (2)	N5—C12—N4—C18	0.0 (3)
C6—C5—C10—N3	179.7 (2)	C11—C12—N4—C18	−178.4 (2)
N2—C5—C10—N3	−0.1 (3)	C17—C18—N4—C12	−178.0 (3)
N1—C11—C12—N4	−154.4 (2)	C13—C18—N4—C12	0.3 (3)
N1—C11—C12—N5	27.5 (4)	N4—C12—N5—C13	−0.3 (3)
N5—C13—C14—C15	−178.5 (3)	C11—C12—N5—C13	178.1 (2)
C18—C13—C14—C15	−0.1 (4)	C18—C13—N5—C12	0.5 (3)
C13—C14—C15—C16	1.2 (4)	C14—C13—N5—C12	179.0 (3)
C14—C15—C16—C17	−1.6 (5)	C2—C1—O1—C19	−174.0 (2)
C15—C16—C17—C18	0.8 (5)	C19ⁱ—C19—O1—C1	177.9 (3)
C16—C17—C18—N4	178.5 (3)	O3—N6—O2—H4	−169.1 (8)
C16—C17—C18—C13	0.3 (4)	O4—N6—O2—H4	9.7 (8)
N5—C13—C18—N4	−0.5 (3)	O3—N6—O4—H4	169.7 (8)
C14—C13—C18—N4	−179.2 (2)	O2—N6—O4—H4	−9.1 (8)
N5—C13—C18—C17	178.1 (2)	O7—N7—O6—H2	173.8 (10)
C14—C13—C18—C17	−0.7 (4)	O5—N7—O6—H2	−4.6 (10)
C4—C3—N1—C11	153.5 (2)	O7—N7—O6—H5	1.3 (10)
C4—C3—N1—C2	−73.1 (3)	O5—N7—O6—H5	−177.1 (10)
C12—C11—N1—C3	−158.9 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O7	0.93	2.58	3.364 (4)	142
C11—H11A···O1	0.97	2.43	3.094 (3)	125
C6—H6···O5	0.93	2.59	3.379 (4)	143
N4—H4···O4	0.82 (3)	2.31 (3)	2.995 (3)	142 (3)
N4—H4···O2	0.82 (3)	2.20 (3)	2.975 (4)	160 (3)
N5—H5···O6	0.86 (3)	1.87 (3)	2.719 (3)	174 (3)
N2—H2···O6	0.91 (3)	1.81 (3)	2.719 (3)	177 (3)
C7—H7···O7ⁱⁱ	0.93	2.53	3.443 (4)	166
N3—H3···O4ⁱⁱⁱ	0.87 (3)	1.93 (3)	2.789 (3)	169 (3)
N3—H3···O3ⁱⁱⁱ	0.87 (3)	2.51 (3)	3.180 (3)	134 (2)

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

Experimental details

Crystal data
Chemical formula	C₃₈H₄₄N₁₀O₂⁴⁺·4(NO₃⁻)
M_r	920.87
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	8.4296 (6), 17.6744 (12), 14.279 (1)
β (°)	92.421 (1)
V (Å³)	2125.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.975, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	23482, 4642, 2655
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.169, 1.03
No. of reflections	4642
No. of parameters	310
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.19

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.