Crystal structure of octane-1,8-diaminium 4,4′-(diazene-1,2-di­yl)dibenzoate monohydrate

Elkin, I.; Maris, T.; Christopherson, J.-C.; Borchers, T.H.; Barrett, C.J.

doi:10.1107/S2056989018006187

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ISSN: 2056-9890

Volume 74| Part 5| May 2018| Pages 724-727

https://doi.org/10.1107/S2056989018006187

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Crystal structure of octane-1,8-diaminium 4,4′-(diazene-1,2-diyl)dibenzoate monohydrate

Igor Elkin,^a Thierry Maris,^b Jan-Constantin Christopherson,^a Tristan H. Borchers ^a and Christopher J. Barrett ^a ^*

^aChemistry Department, McGill University, Montreal, Quebec, H3A 0B8, Canada, and ^bDepartment of Chemistry, Université de Montréal, Montreal, Quebec, H3C 3J7, Canada
^*Correspondence e-mail: chris.barrett@mcgill.ca

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 17 April 2018; accepted 23 April 2018; online 27 April 2018)

The title salt, C₈H₂₂N₂²⁺·C₁₄H₈N₂O₄²⁻·H₂O, represents a pseudo-polymer ionic material, resulting from the self-organizing behavior of 4,4′-azinodibenzoate dianions and doubly protonated, 1,8-diaminium-octane cations in aqueous solution. The asymmetric unit consists of two halves of octane 1,8-diaminium cations (the complete cations are both generated by crystallographic inversion symmetry), a 4,4′-azinodibenzoate anion [dihedral angle between the aromatic rings = 10.22 (4)°] and a water molecule of crystallization. One of the cations is in a fully extended linear conformation while the second one has a terminal C—C—C—N gauche conformation. In the crystal, the cations, anions and water molecules are linked into a three-dimensional network via a complex pattern of charge-assisted N—H⋯O and O—H⋯O hydrogen bonds.

Keywords: octane-1,8-diaminium 4,4′-azinodibenzoate; crystal structure; ionic pseudo-polymer; 4,4′-azinodibenzoic acid.

CCDC reference: 1839024

1. Chemical context

Ionic pseudo-polymers auto-assembled from oppositely charged organic molecules are of emerging interest for many potential application fields (Webber et al., 2016 ; Mann, 2009 ). It is reasonable to expect that the presence of azobenzene moieties in such materials creates the necessary precondition for achieving their reversible photosensitivity (Bushuyev et al., 2016 , 2018 ). In this context, we report the synthesis and structure of octane-1,8-diaminium 4,4′-(diazene-1,2-diyl)dibenzoate monohydrate, (I), formed by the crystallization of bianionic 4,4′-azinodibenzoic acid and bicationic 1,8-diaminooctane in aqueous solution.

2. Structural commentary

The asymmetric unit (Fig. 1) consists of two halves of octane 1,8-diaminium dications, one 4,4′-azinodibenzoic dianion and one water molecule. Bond lengths and angles of the dication and dianion are in the expected ranges. One of the octane 1,8-diaminium dications shows a fully extended all-trans conformation with torsion angles close to 180° (Table 1). The second cation has its two terminal torsion angles N6—C7—C8—C9 synclinal with a value of −76.89 (12)°. The fully extended conformation corresponds to the most stable one, compared to the arrangement with synclinal torsion angles, as shown from DFT calculations and a database survey performed on α,ω-alkyldiaminium cations (Brozdowska & Chojnacki, 2017 ). The less energetically favorable gauche conformation is presumably stabilized by the charge-assisted hydrogen-bonded network.

Table 1
Selected torsion angles (°)

C2—C3—C4—C5	−177.97 (9)	C7—C8—C9—C10	−179.03 (9)
C3—C4—C5—C5ⁱ	178.25 (10)	C8—C9—C10—C10ⁱⁱ	178.30 (11)
N1—C2—C3—C4	177.78 (9)	N6—C7—C8—C9	−76.89 (12)
Symmetry codes: (i) -x+1, -y, -z+2; (ii) -x, -y+1, -z.

Figure 1
Molecular structure and atom-labelling scheme of (I)

. Displacement ellipsoids are drawn at the 50% probability level and hydrogen bonds are shown as dotted lines. [Symmetry codes: (i) 1 − x, −y, 2 − z; (ii) −x, 1 − y, −z.]

The geometry of the 4,4′-azinodibenzoic dianion is characterized by the presence of two benzoic acid residues linked via a trans-configurated azo group is consistent with known data (Fernández et al., 2015 ; Sahoo et al., 2012 ). The angle between the phenyl rings of 10.22 (4)° is consistent with a small deviation from planarity of the azobenzene moiety. The carboxylate groups are inclined to the molecular mean plane at angles of 38.40 (3)° (O11/C12/O13) and 16.53 (5)° (O29/C28/O30).

3. Supramolecular features

In addition to the electrostatic interactions, the anions and cations are connected by charge-assisted N—H⋯O hydrogen bonds (Table 2). The complex pattern of hydrogen bonds also includes the water molecules. Therefore, the 4,4′-azinodibenzoic dianion is linked through hydrogen bonds with three cations on one side and with two cations and two water molecules on the other side. Anions and cation stack in two-dimensional arrays in the ab plane separated by a zone with the hydrogen-bonded network involving the ionized amino and carboxylic groups and the water molecules (Fig. 2). This network contains two 12-membered rings comprising either two cations and two anions or two cations, two anions and two water molecules (Fig. 3), according to the graph set descriptor R₄⁴(12) (Etter et al., 1990 ).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O30ⁱⁱⁱ	0.895 (17)	1.897 (17)	2.7796 (13)	168.3 (14)
N1—H1B⋯O13	0.916 (16)	1.881 (17)	2.7942 (12)	175.0 (14)
N1—H1C⋯O29^iv	0.918 (16)	1.970 (16)	2.8579 (12)	162.5 (13)
N6—H6A⋯O31^v	0.921 (16)	1.912 (16)	2.8296 (13)	174.0 (13)
N6—H6B⋯O11	0.921 (16)	1.879 (16)	2.7735 (12)	163.2 (13)
N6—H6C⋯O29^vi	0.947 (16)	1.849 (17)	2.7847 (12)	169.0 (14)
N6—H6C⋯O30^vi	0.947 (16)	2.590 (16)	3.0880 (12)	113.2 (11)
O31—H31A⋯O13^vii	0.89 (2)	1.88 (2)	2.7418 (11)	165.2 (17)
O31—H31B⋯O11	0.88 (2)	1.97 (2)	2.8184 (11)	162.2 (16)
Symmetry codes: (iii) -x+1, -y+1, -z; (iv) x+1, y-1, z+1; (v) -x, -y+1, -z+1; (vi) x, y-1, z+1; (vii) -x+1, -y+1, -z+1.

Figure 2
Projection along the b-axis direction showing the packing in layers consolidated by the hydrogen-bond network (dotted lines). Hydrogen atoms not involved in hydrogen bonds and hanging hydrogen bonds are omitted for clarity.

Figure 3
Partial packing view along the b-axis direction showing the R₄⁴(12) graph-set motifs. Hydrogen atoms not involved in hydrogen bonds and hanging hydrogen bonds have been omitted for clarity.

4. Database survey

A search in the Cambridge Structural Database (Version 5.39 with one update; Groom et al., 2016 ) returned 48 entries for octane-1,8-diaminium compounds. These include simple halide salts (Brisson & Brisse, 1984 ; van Blerk & Kruger, 2007 ; van Megen & Reiss, 2013 ); metal halide salts (Kessentini et al., 2011 ) comprising lead halide complexes (Lemmerer & Billing, 2012 ; Smith et al., 2017 ), and more complex systems where the diaminium cations are encapsulated in a macrocycle (Kim et al., 2009 ; Yu et al., 2014 ). A similar search for 4,4′-azinodibenzoic acid and its salts returned 43 entries, including the structure of the simple acid (Yu & Liu, 2009 ). The dianion has been also used as linker to prepare MOF or coordination frameworks (see, for example, Hou et al., 2013 , Zhang et al., 2016 , Guo et al., 2013 and Deng et al., 2015 ), and co-crystallized to give gelator salts (Sahoo & Dastidar, 2012 ; Sahoo et al., 2012) or supramolecular assemblies (Beatty et al., 2002 ; Yu et al., 2011 ).

5. Synthesis and crystallization

Crystals of the title compound were obtained by the dropwise addition with intensive stirring of 5 ml of 0.10 M aqueous 1,8-octamethylenediamine into 25 ml of 0.02 M aqueous 4,4′-dicarboxyazobenzene disodium salt at room temperature. The final solution (pH 12.5) was allowed to partly evaporate at room temperature and atmospheric pressure. The resulting orange oblong crystals in the form of thin narrow leaves up to 1 cm long were gently removed from the liquid phase and air-dried on filter paper.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms bound to nitrogen or oxygen atoms were located from difference syntheses and refined without any restraints. Hydrogen atoms linked to carbon atoms were included using an appropriate riding model (AFIX 43 and AFIX 23 for aromatic and methylene hydrogen atoms respectively) with C—H = 0.95–0.99 Å and U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₈H₂₂N₂²⁺·C₁₄H₈N₂O₄²⁻·H₂O
M_r	432.51
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.3604 (1), 11.4100 (2), 12.4661 (2)
α, β, γ (°)	83.001 (1), 83.364 (1), 73.973 (1)
V (Å³)	1130.24 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	0.75
Crystal size (mm)	0.4 × 0.4 × 0.1

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.525, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	28413, 4048, 3920
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.096, 1.05
No. of reflections	4048
No. of parameters	313
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.30
Computer programs: APEX2 and SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1839024

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018006187/hb7747sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018006187/hb7747Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018006187/hb7747Isup3.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: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Octane-1,8-diaminium 4,4'-(diazene-1,2-diyl)dibenzoate monohydrate top

Crystal data top

C₈H₂₂N₂²⁺·C₁₄H₈N₂O₄²⁻·H₂O	Z = 2
M_r = 432.51	F(000) = 464
Triclinic, P1	D_x = 1.271 Mg m⁻³
a = 8.3604 (1) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.4100 (2) Å	Cell parameters from 3920 reflections
c = 12.4661 (2) Å	θ = 4.1–68.1°
α = 83.001 (1)°	µ = 0.75 mm⁻¹
β = 83.364 (1)°	T = 100 K
γ = 73.973 (1)°	Block, orange
V = 1130.24 (3) Å³	0.4 × 0.4 × 0.1 mm

Data collection top

Bruker APEXII CCD diffractometer	4048 independent reflections
Radiation source: fine-focus sealed tube	3920 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
φ and ω scans	θ_max = 68.1°, θ_min = 4.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −10→10
T_min = 0.525, T_max = 0.753	k = −13→13
28413 measured reflections	l = −14→14

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0541P)² + 0.3252P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.096	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.20 e Å⁻³
4048 reflections	Δρ_min = −0.30 e Å⁻³
313 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0427 (17)
Primary atom site location: structure-invariant direct methods

Special details top

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
C12	0.44977 (13)	0.39551 (9)	0.39040 (8)	0.0164 (2)
C14	0.39242 (13)	0.48992 (10)	0.29711 (9)	0.0163 (2)
C15	0.50609 (13)	0.50353 (10)	0.20773 (9)	0.0180 (2)
H15	0.618450	0.454880	0.207597	0.022*
C16	0.45684 (14)	0.58671 (10)	0.11990 (9)	0.0187 (2)
H16	0.534114	0.593956	0.058933	0.022*
C17	0.29240 (14)	0.66026 (10)	0.12125 (9)	0.0175 (2)
C18	0.17852 (14)	0.64902 (10)	0.21041 (9)	0.0193 (2)
H18	0.067342	0.699946	0.211663	0.023*
C19	0.22842 (14)	0.56296 (10)	0.29746 (9)	0.0185 (2)
H19	0.150301	0.553905	0.357480	0.022*
C22	0.27923 (14)	0.83834 (10)	−0.13411 (9)	0.0169 (2)
C23	0.12601 (14)	0.92810 (10)	−0.13255 (9)	0.0182 (2)
H23	0.049801	0.933790	−0.069462	0.022*
C24	0.08731 (13)	1.00833 (10)	−0.22421 (9)	0.0174 (2)
H24	−0.015163	1.070596	−0.222999	0.021*
C25	0.19653 (13)	0.99937 (9)	−0.31875 (9)	0.0162 (2)
C26	0.35000 (14)	0.91128 (10)	−0.31874 (9)	0.0173 (2)
H26	0.426383	0.905667	−0.381738	0.021*
C27	0.39101 (13)	0.83176 (10)	−0.22644 (9)	0.0178 (2)
H27	0.496160	0.772422	−0.226335	0.021*
C28	0.14659 (13)	1.08221 (10)	−0.42094 (9)	0.0168 (2)
N20	0.23031 (12)	0.75035 (8)	0.03481 (8)	0.0199 (2)
N21	0.33560 (12)	0.75025 (8)	−0.04586 (7)	0.0194 (2)
O11	0.34625 (9)	0.34229 (7)	0.44062 (6)	0.0200 (2)
O13	0.59935 (9)	0.37427 (7)	0.41176 (6)	0.0209 (2)
O29	0.01715 (9)	1.17097 (7)	−0.41274 (6)	0.0204 (2)
O30	0.23647 (10)	1.05688 (7)	−0.50725 (6)	0.0234 (2)
C2	0.54646 (13)	0.18776 (10)	0.66601 (9)	0.0181 (2)
H2A	0.442430	0.177349	0.642576	0.022*
H2B	0.521051	0.269756	0.692620	0.022*
C3	0.60840 (13)	0.08987 (10)	0.75674 (9)	0.0183 (2)
H3A	0.715478	0.098563	0.776743	0.022*
H3B	0.630505	0.008358	0.729672	0.022*
C4	0.48635 (13)	0.09539 (10)	0.85797 (8)	0.0176 (2)
H4A	0.380562	0.083043	0.839346	0.021*
H4B	0.461117	0.177451	0.884428	0.021*
C5	0.55783 (13)	−0.00224 (10)	0.94788 (8)	0.0178 (2)
H5A	0.580205	−0.084114	0.921493	0.021*
H5B	0.665684	0.008692	0.964131	0.021*
N1	0.67578 (12)	0.17874 (9)	0.57222 (8)	0.0177 (2)
H1A	0.6930 (19)	0.1068 (16)	0.5450 (12)	0.033 (4)*
H1B	0.6457 (19)	0.2412 (15)	0.5188 (12)	0.031 (4)*
H1C	0.777 (2)	0.1830 (13)	0.5905 (12)	0.028 (4)*
C7	0.04089 (14)	0.23686 (10)	0.30051 (9)	0.0206 (3)
H7A	−0.076237	0.235667	0.296577	0.025*
H7B	0.107206	0.151394	0.317135	0.025*
C8	0.10729 (14)	0.28667 (10)	0.19086 (9)	0.0222 (3)
H8A	0.134670	0.221260	0.141092	0.027*
H8B	0.212435	0.306963	0.199818	0.027*
C9	−0.01161 (13)	0.39982 (10)	0.13799 (9)	0.0194 (2)
H9A	−0.117543	0.380517	0.129346	0.023*
H9B	−0.037363	0.466406	0.186456	0.023*
C10	0.06004 (14)	0.44447 (10)	0.02760 (9)	0.0210 (3)
H10A	0.089089	0.376931	−0.020020	0.025*
H10B	0.164268	0.465977	0.036703	0.025*
N6	0.04744 (12)	0.31029 (9)	0.39017 (7)	0.0178 (2)
H6A	−0.0289 (18)	0.3860 (14)	0.3860 (11)	0.026 (3)*
H6B	0.153 (2)	0.3200 (13)	0.3926 (12)	0.029 (4)*
H6C	0.0223 (19)	0.2670 (14)	0.4569 (13)	0.033 (4)*
O31	0.20434 (10)	0.46567 (8)	0.62560 (7)	0.0235 (2)
H31A	0.281 (2)	0.5069 (17)	0.6193 (14)	0.049 (5)*
H31B	0.241 (2)	0.4140 (17)	0.5755 (15)	0.048 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C12	0.0197 (6)	0.0127 (5)	0.0160 (5)	−0.0030 (4)	0.0010 (4)	−0.0038 (4)
C14	0.0187 (5)	0.0134 (5)	0.0176 (5)	−0.0050 (4)	−0.0011 (4)	−0.0029 (4)
C15	0.0165 (5)	0.0163 (5)	0.0192 (5)	−0.0014 (4)	−0.0007 (4)	−0.0022 (4)
C16	0.0201 (6)	0.0182 (5)	0.0170 (5)	−0.0046 (4)	0.0020 (4)	−0.0024 (4)
C17	0.0209 (6)	0.0135 (5)	0.0184 (5)	−0.0048 (4)	−0.0030 (4)	−0.0012 (4)
C18	0.0160 (5)	0.0161 (5)	0.0234 (6)	−0.0009 (4)	−0.0009 (4)	−0.0015 (4)
C19	0.0188 (5)	0.0161 (5)	0.0197 (5)	−0.0048 (4)	0.0029 (4)	−0.0017 (4)
C22	0.0203 (5)	0.0137 (5)	0.0174 (5)	−0.0041 (4)	−0.0041 (4)	−0.0023 (4)
C23	0.0193 (5)	0.0183 (5)	0.0168 (5)	−0.0053 (4)	0.0003 (4)	−0.0027 (4)
C24	0.0156 (5)	0.0147 (5)	0.0210 (5)	−0.0017 (4)	−0.0020 (4)	−0.0026 (4)
C25	0.0177 (5)	0.0136 (5)	0.0183 (5)	−0.0051 (4)	−0.0028 (4)	−0.0021 (4)
C26	0.0186 (5)	0.0171 (5)	0.0164 (5)	−0.0044 (4)	−0.0005 (4)	−0.0034 (4)
C27	0.0170 (5)	0.0155 (5)	0.0198 (5)	−0.0006 (4)	−0.0036 (4)	−0.0036 (4)
C28	0.0180 (5)	0.0147 (5)	0.0186 (5)	−0.0057 (4)	−0.0017 (4)	−0.0014 (4)
N20	0.0213 (5)	0.0176 (5)	0.0197 (5)	−0.0042 (4)	−0.0027 (4)	0.0006 (4)
N21	0.0234 (5)	0.0167 (5)	0.0170 (5)	−0.0031 (4)	−0.0027 (4)	−0.0015 (4)
O11	0.0222 (4)	0.0189 (4)	0.0190 (4)	−0.0074 (3)	−0.0003 (3)	0.0013 (3)
O13	0.0196 (4)	0.0197 (4)	0.0220 (4)	−0.0042 (3)	−0.0038 (3)	0.0033 (3)
O29	0.0190 (4)	0.0174 (4)	0.0211 (4)	−0.0002 (3)	−0.0014 (3)	0.0014 (3)
O30	0.0284 (4)	0.0192 (4)	0.0169 (4)	0.0010 (3)	0.0015 (3)	0.0007 (3)
C2	0.0176 (5)	0.0178 (5)	0.0170 (5)	−0.0032 (4)	0.0020 (4)	−0.0009 (4)
C3	0.0162 (5)	0.0195 (5)	0.0176 (5)	−0.0035 (4)	0.0001 (4)	−0.0003 (4)
C4	0.0174 (5)	0.0183 (5)	0.0168 (5)	−0.0049 (4)	0.0007 (4)	−0.0018 (4)
C5	0.0178 (5)	0.0186 (6)	0.0165 (6)	−0.0044 (4)	0.0001 (5)	−0.0020 (4)
N1	0.0176 (5)	0.0169 (5)	0.0163 (5)	−0.0023 (4)	0.0001 (4)	0.0008 (4)
C7	0.0246 (6)	0.0164 (5)	0.0200 (6)	−0.0033 (4)	−0.0032 (4)	−0.0017 (4)
C8	0.0199 (6)	0.0231 (6)	0.0200 (6)	0.0002 (4)	−0.0004 (4)	−0.0035 (4)
C9	0.0178 (5)	0.0213 (6)	0.0170 (5)	−0.0026 (4)	0.0007 (4)	−0.0023 (4)
C10	0.0193 (5)	0.0241 (6)	0.0177 (6)	−0.0037 (5)	0.0023 (4)	−0.0025 (5)
N6	0.0184 (5)	0.0160 (5)	0.0179 (5)	−0.0040 (4)	−0.0016 (4)	0.0008 (4)
O31	0.0213 (4)	0.0217 (4)	0.0262 (4)	−0.0041 (3)	0.0024 (3)	−0.0056 (3)

Geometric parameters (Å, º) top

C12—C14	1.5103 (14)	C2—N1	1.4907 (13)
C12—O11	1.2578 (13)	C3—H3A	0.9900
C12—O13	1.2599 (14)	C3—H3B	0.9900
C14—C15	1.4011 (15)	C3—C4	1.5244 (14)
C14—C19	1.3939 (15)	C4—H4A	0.9900
C15—H15	0.9500	C4—H4B	0.9900
C15—C16	1.3800 (15)	C4—C5	1.5289 (15)
C16—H16	0.9500	C5—C5ⁱ	1.525 (2)
C16—C17	1.3984 (16)	C5—H5A	0.9900
C17—C18	1.3951 (15)	C5—H5B	0.9900
C17—N20	1.4325 (14)	N1—H1A	0.895 (17)
C18—H18	0.9500	N1—H1B	0.916 (16)
C18—C19	1.3909 (16)	N1—H1C	0.918 (16)
C19—H19	0.9500	C7—H7A	0.9900
C22—C23	1.4018 (16)	C7—H7B	0.9900
C22—C27	1.3920 (15)	C7—C8	1.5196 (16)
C22—N21	1.4253 (14)	C7—N6	1.4905 (14)
C23—H23	0.9500	C8—H8A	0.9900
C23—C24	1.3839 (16)	C8—H8B	0.9900
C24—H24	0.9500	C8—C9	1.5247 (15)
C24—C25	1.4008 (15)	C9—H9A	0.9900
C25—C26	1.3944 (16)	C9—H9B	0.9900
C25—C28	1.5172 (15)	C9—C10	1.5228 (15)
C26—H26	0.9500	C10—C10ⁱⁱ	1.527 (2)
C26—C27	1.3891 (15)	C10—H10A	0.9900
C27—H27	0.9500	C10—H10B	0.9900
C28—O29	1.2656 (13)	N6—H6A	0.921 (16)
C28—O30	1.2549 (13)	N6—H6B	0.921 (16)
N20—N21	1.2575 (14)	N6—H6C	0.947 (16)
C2—H2A	0.9900	O31—H31A	0.89 (2)
C2—H2B	0.9900	O31—H31B	0.88 (2)
C2—C3	1.5176 (15)

O11—C12—C14	118.09 (9)	H3A—C3—H3B	107.7
O11—C12—O13	124.36 (10)	C4—C3—H3A	108.8
O13—C12—C14	117.54 (9)	C4—C3—H3B	108.8
C15—C14—C12	119.29 (9)	C3—C4—H4A	109.3
C19—C14—C12	121.45 (9)	C3—C4—H4B	109.3
C19—C14—C15	119.26 (10)	C3—C4—C5	111.41 (9)
C14—C15—H15	119.6	H4A—C4—H4B	108.0
C16—C15—C14	120.82 (10)	C5—C4—H4A	109.3
C16—C15—H15	119.6	C5—C4—H4B	109.3
C15—C16—H16	120.2	C4—C5—H5A	108.9
C15—C16—C17	119.54 (10)	C4—C5—H5B	108.9
C17—C16—H16	120.2	C5ⁱ—C5—C4	113.31 (11)
C16—C17—N20	123.64 (10)	C5ⁱ—C5—H5A	108.9
C18—C17—C16	120.26 (10)	C5ⁱ—C5—H5B	108.9
C18—C17—N20	116.10 (9)	H5A—C5—H5B	107.7
C17—C18—H18	120.1	C2—N1—H1A	109.6 (10)
C19—C18—C17	119.74 (10)	C2—N1—H1B	112.0 (9)
C19—C18—H18	120.1	C2—N1—H1C	113.2 (9)
C14—C19—H19	119.8	H1A—N1—H1B	109.5 (13)
C18—C19—C14	120.36 (10)	H1A—N1—H1C	107.0 (13)
C18—C19—H19	119.8	H1B—N1—H1C	105.4 (13)
C23—C22—N21	125.14 (10)	H7A—C7—H7B	107.8
C27—C22—C23	120.04 (10)	C8—C7—H7A	109.0
C27—C22—N21	114.81 (9)	C8—C7—H7B	109.0
C22—C23—H23	120.5	N6—C7—H7A	109.0
C24—C23—C22	119.07 (10)	N6—C7—H7B	109.0
C24—C23—H23	120.5	N6—C7—C8	112.95 (9)
C23—C24—H24	119.4	C7—C8—H8A	108.5
C23—C24—C25	121.19 (10)	C7—C8—H8B	108.5
C25—C24—H24	119.4	C7—C8—C9	114.99 (9)
C24—C25—C28	120.42 (9)	H8A—C8—H8B	107.5
C26—C25—C24	119.24 (10)	C9—C8—H8A	108.5
C26—C25—C28	120.32 (10)	C9—C8—H8B	108.5
C25—C26—H26	120.1	C8—C9—H9A	109.0
C27—C26—C25	119.89 (10)	C8—C9—H9B	109.0
C27—C26—H26	120.1	H9A—C9—H9B	107.8
C22—C27—H27	119.7	C10—C9—C8	112.75 (9)
C26—C27—C22	120.51 (10)	C10—C9—H9A	109.0
C26—C27—H27	119.7	C10—C9—H9B	109.0
O29—C28—C25	117.57 (9)	C9—C10—C10ⁱⁱ	113.21 (11)
O30—C28—C25	117.37 (9)	C9—C10—H10A	108.9
O30—C28—O29	125.06 (10)	C9—C10—H10B	108.9
N21—N20—C17	112.88 (9)	C10ⁱⁱ—C10—H10A	108.9
N20—N21—C22	114.90 (9)	C10ⁱⁱ—C10—H10B	108.9
H2A—C2—H2B	108.1	H10A—C10—H10B	107.7
C3—C2—H2A	109.6	C7—N6—H6A	112.5 (9)
C3—C2—H2B	109.6	C7—N6—H6B	111.9 (9)
N1—C2—H2A	109.6	C7—N6—H6C	108.3 (9)
N1—C2—H2B	109.6	H6A—N6—H6B	109.4 (13)
N1—C2—C3	110.15 (9)	H6A—N6—H6C	107.9 (12)
C2—C3—H3A	108.8	H6B—N6—H6C	106.5 (13)
C2—C3—H3B	108.8	H31A—O31—H31B	102.9 (16)
C2—C3—C4	113.74 (9)

C12—C14—C15—C16	178.35 (9)	C25—C26—C27—C22	0.71 (16)
C12—C14—C19—C18	−179.80 (9)	C26—C25—C28—O29	−170.63 (9)
C14—C15—C16—C17	1.46 (16)	C26—C25—C28—O30	9.78 (15)
C15—C14—C19—C18	−0.49 (16)	C27—C22—C23—C24	0.85 (16)
C15—C16—C17—C18	−0.48 (16)	C27—C22—N21—N20	−175.22 (9)
C15—C16—C17—N20	179.03 (9)	C28—C25—C26—C27	−176.74 (9)
C16—C17—C18—C19	−0.97 (16)	N20—C17—C18—C19	179.48 (9)
C16—C17—N20—N21	4.90 (15)	N21—C22—C23—C24	179.78 (9)
C17—C18—C19—C14	1.45 (16)	N21—C22—C27—C26	178.99 (9)
C17—N20—N21—C22	179.88 (8)	O11—C12—C14—C15	−146.46 (10)
C18—C17—N20—N21	−175.57 (9)	O11—C12—C14—C19	32.86 (14)
C19—C14—C15—C16	−0.99 (16)	O13—C12—C14—C15	32.65 (14)
C22—C23—C24—C25	1.52 (16)	O13—C12—C14—C19	−148.03 (10)
C23—C22—C27—C26	−1.97 (16)	C2—C3—C4—C5	−177.97 (9)
C23—C22—N21—N20	5.80 (15)	C3—C4—C5—C5ⁱ	178.25 (10)
C23—C24—C25—C26	−2.76 (16)	N1—C2—C3—C4	177.78 (9)
C23—C24—C25—C28	175.60 (9)	C7—C8—C9—C10	−179.03 (9)
C24—C25—C26—C27	1.62 (15)	C8—C9—C10—C10ⁱⁱ	178.30 (11)
C24—C25—C28—O29	11.03 (14)	N6—C7—C8—C9	−76.89 (12)
C24—C25—C28—O30	−168.56 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O30ⁱⁱⁱ	0.895 (17)	1.897 (17)	2.7796 (13)	168.3 (14)
N1—H1B···O13	0.916 (16)	1.881 (17)	2.7942 (12)	175.0 (14)
N1—H1C···O29^iv	0.918 (16)	1.970 (16)	2.8579 (12)	162.5 (13)
N6—H6A···O31^v	0.921 (16)	1.912 (16)	2.8296 (13)	174.0 (13)
N6—H6B···O11	0.921 (16)	1.879 (16)	2.7735 (12)	163.2 (13)
N6—H6C···O29^vi	0.947 (16)	1.849 (17)	2.7847 (12)	169.0 (14)
N6—H6C···O30^vi	0.947 (16)	2.590 (16)	3.0880 (12)	113.2 (11)
O31—H31A···O13^vii	0.89 (2)	1.88 (2)	2.7418 (11)	165.2 (17)
O31—H31B···O11	0.88 (2)	1.97 (2)	2.8184 (11)	162.2 (16)

Symmetry codes: (iii) −x+1, −y+1, −z; (iv) x+1, y−1, z+1; (v) −x, −y+1, −z+1; (vi) x, y−1, z+1; (vii) −x+1, −y+1, −z+1.

Acknowledgements

Prof. Tomislav Friščić and Dr Hatem M. Titi are gratefully acknowledged for their help and valuable advice related to this project. The Fonds de Recherche du Québec – Nature et Technologies is gratefully acknowledged for a postdoctoral fellowship to IE.

References

Beatty, A. M., Schneider, C. M., Simpson, A. E. & Zaher, J. L. (2002). CrystEngComm, 4, 282–287. Web of Science CSD CrossRef CAS Google Scholar
Blerk, C. van & Kruger, G. J. (2007). Acta Cryst. E63, o4289. CrossRef IUCr Journals Google Scholar
Brisson, J. & Brisse, F. (1984). Acta Cryst. C40, 1405–1407. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Brozdowska, A. & Chojnacki, J. (2017). Acta Cryst. B73, 507–518. CrossRef IUCr Journals Google Scholar
Bruker (2013). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bushuyev, O. S., Aizawa, M., Shishido, A. & Barrett, C. J. (2018). Macromol. Rapid Commun. 39, 1700253. CrossRef Google Scholar
Bushuyev, O. S., Friščić, T. & Barrett, C. J. (2016). CrystEngComm, 18, 7204–7211. CrossRef CAS Google Scholar
Deng, M., Tai, S., Zhang, W., Wang, Y., Zhu, J., Zhang, J., Ling, Y. & Zhou, Y. (2015). CrystEngComm, 17, 6023–6029. CrossRef CAS 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
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Fernández, B., Seco, J. M., Cepeda, J., Calahorro, A. J. & Rodríguez-Diéguez, A. (2015). CrystEngComm, 17, 7636–7645. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Guo, J. S., Xu, G., Guo, G.-C. & Huang, J.-S. (2013). Cryst. Growth Des. 13, 2642–2649. CrossRef CAS Google Scholar
Hou, Y.-F., Yu, Y., Yue, K.-F., Wei, Q., Liu, Y., Zhou, C.-S. & Wang, Y.-Y. (2013). CrystEngComm, 15, 7161–7165. CrossRef CAS Google Scholar
Kessentini, A., Belhouchet, M. & Mhiri, T. (2011). X-ray Struct. Anal. Online, 27, 31–32. CrossRef CAS Google Scholar
Kim, Y., Kim, H., Ko, Y. H., Selvapalam, N., Rekharsky, M. V., Inoue, Y. & Kim, K. (2009). Chem. Eur. J. 15, 6143–6151. CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Lemmerer, A. & Billing, D. G. (2012). CrystEngComm, 14, 1954–1966. Web of Science CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mann, S. (2009). Nat. Mater. 8, 781–792. CrossRef CAS Google Scholar
Megen, M. van & Reiss, G. J. (2013). Inorganic 1, 3–13. Google Scholar
Sahoo, P., Chakraborty, I. & Dastidar, P. (2012). Soft Matter, 8, 2595–2598. CrossRef CAS Google Scholar
Sahoo, P. & Dastidar, P. (2012). Cryst. Growth Des. 12, 5917–5924. Web of Science CSD CrossRef CAS 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
Smith, M. D., Jaffe, A., Dohner, E. R., Lindenberg, A. M. & Karunadasa, H. I. (2017). Chem. Sci. 8, 4497–4504. CrossRef CAS Google Scholar
Webber, M. J., Appel, E. A., Meijer, E. W. & Langer, R. (2016). Nat. Mater. 15, 13–26. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, G., Hua, B. & Han, C. (2014). Org. Lett. 16, 2486–2489. CrossRef CAS Google Scholar
Yu, Q.-D. & Liu, Y.-Y. (2009). Acta Cryst. E65, o2326. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yu, Z. B., Sun, J., Huang, Z. T. & Zheng, Q. Y. (2011). CrystEngComm, 13, 1287–1290. CrossRef CAS Google Scholar
Zhang, L., Feng, X. F., Meng, P. P., Gong, L. L. & Luo, F. (2016). CrystEngComm, 18, 1693–1698. CrossRef CAS Google Scholar

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