Crystal structure of 2-(aza­niumylmeth­yl)pyridinium bis(hydrogen squarate)

Salamzadeh, N.; Demircioglu, Z.; Korkmaz, U.; Büyükgüngör, O.

doi:10.1107/S2056989017004376

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Volume 73| Part 4| April 2017| Pages 586-589

https://doi.org/10.1107/S2056989017004376

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Crystal structure of 2-(azaniumylmethyl)pyridinium bis(hydrogen squarate)

Nina Salamzadeh,^a Zeynep Demircioglu,^a ^* Ufuk Korkmaz ^a and Orhan Büyükgüngör ^a

^aDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, Kurupelit, Samsun 55139, Turkey
^*Correspondence e-mail: zeynep.kelesoglu@omu.edu.tr

Edited by J. Simpson, University of Otago, New Zealand (Received 10 March 2017; accepted 20 March 2017; online 24 March 2017)

The asymmetric unit of the title compound, C₆H₁₀N₂²⁺·2C₄HO₄⁻, comprises two hydrogen squarate (Hsq⁻; systematic name: 2-hydroxy-3,4-dioxocyclobutanolate) anions and a 2-(azaniumylmethyl)pyridinium dication. The squaric acid molecules each donate an H atom to the N atoms of the pyridine ring and the aminomethyl units of a 2-(aminomethyl)pyridine molecule, forming the 1:2 salt. The Hsq⁻ anions are linked by strong O—H⋯O hydrogen bonds and an N—H⋯O hydrogen bond links the 2-(azaniumylmethyl)pyridinium cation to one of the squaric acid anions. The crystal structure features additional N—H⋯O and O—H⋯O hydrogen bonds, π–π stacking and unusual weak C—O⋯π(ring) interactions.

Keywords: crystal structure; 2-(azaniumylmethyl)pyridinium; squaric acid; hydrogen bonding.

CCDC reference: 1538918

1. Chemical context

Hydrogen bonding is the most common way of generating supramolecular organic systems in crystal engineering and molecular recognition. Hydrogen-bonded systems generated from organic cations and anions are of special interest as they would be expected to form stronger hydrogen bonds than those in neutral molecules (Reetz et al.,1994 ; Bertolasi et al., 2001 ). Squaric acid (H₂C₄O₄, H₂sq), has been of interest because of its cyclic structure and potential aromaticity and is used as a building block in crystal engineering due to the simplicity of the cyclic units. It can be found in three forms: uncharged H₂sq, the Hsq⁻ monoanion and the sq²⁻ dianion. The mono- and dianions are often produced following deprotonation by amines (Lam & Mak, 2000 ; Mathew et al., 2002 ). The squarate derivatives are almost flat because of the π-conjugation of their C—C and C—O bonds, and therefore their four oxygen atoms behave as planar (sp²) electron donors of one or two lone pairs of electrons. Recently, we reported the synthesis and characterization of the same organoammonium squarate as the title compound but as a hydrate in the triclinic space group P $[\overline{1}]$ (Korkmaz & Bulut, 2013 ). We report here the unsolvated form of this salt, which crystallizes in the monoclinic space group P2₁/c.

2. Structural commentary

2-(Aminomethyl) pyridine forms a salt with two squaric acid molecules and each molecule of the acid loses one proton. One of these is transferred to the N atom of the pyridine ring, generating the 4-(aminomethyl)morpholinium mono-cation. The other from the second acid molecule is engaged in the formation of a homo-conjugated hydrogen squarate anion via a short, symmetric O5—H5A⋯O3 [2.4583 (14) Å] hydrogen bond (Fig. 1). The electron density associated with this H atom is shared by the O5 and O3 atoms, indicating a large degree of ionic character (Gilli & Gilli, 2000 ). Considering the range (2.38–2.50 Å) of Gilli's classification for such an interaction, this hydrogen bonding can be referred to as negative charge-assisted hydrogen bonding [(−) CAHB] (Gilli & Gilli, 2009 ; Gilli et al., 2001 ; Becke, 1993 , Lee et al., 1988 ) and can be represented as [-O⋯H⋯O-]⁻.

Figure 1
A view of the asymmetric unit of (I)

, showing the atom-numbering scheme and 30% probability displacement ellipsoids. Dashed lines indicate hydrogen bonds.

N1/C1–C5, C7–C10 and C11–C14 are defined as rings 1, 2 and 3, respectively, with centroids Cg1, Cg2 and Cg3. The dihedral angles between the mean plane of ring 1 and those of rings 2 and 3 are 18.818 (8) and 31.564 (6)°, respectively. The dihedral angle between the two squarate anions is 29.19 (1)°. The angles between the C—C bonds in the Hsq⁻ anions are close to 90°, with the oxygen atoms directed almost along the diagonals.

The C—C distances in the planar squarate ring systems reflect partial double-bond character for C9—C10, C7—C10, C11—C12 and C11—C14 with distances of 1.4291 (17), 1.4357 (16), 1.4139 (17) and 1.4465 (18) Å, respectively. In contrast C7—C8, C8—C9, C12—C13 and C13—C14 display more single-bond character with distances of 1.4886 (17), 1.4929 (17), 1.4802 (18) and 1.5141 (17) Å, respectively. The Hsq⁻ ion has one C—O bond (C11—O5) at 1.3023 (17) Å, which is significantly longer than a normal single C—O bond. This most likely reflects the involvement in the negative charge-assisted hydrogen bonding mentioned earlier. At 1.3000 (15) Å, the C10—O4 bond is similarly extended. The remaining C—O bonds in both rings display a similar pattern with one obvious C=O double bond in each ring [C8=O2, 1.2268 (15) Å and C13=O7, 1.2141 (17) Å] and the others of intermediate length in the range 1.2356 (16) to 1.2658 (15) Å, indicating some delocalization occurring in both rings.

3. Supramolecular features

The two hydrogen squarate anions are linked in the asymmetric unit by a short hydrogen-bonding interaction O5—H5A⋯O3 [2.4583 (14) Å] related to the proton-sharing interaction discussed earlier. This pair of anions is further linked to the 2-(azaniumylmethyl)pyridinium dication by an N1—H1A⋯O1 hydrogen bond, Fig. 1, Table 1. O5—H5A⋯O3, N2—H2B⋯O2ⁱ and N2—H2B⋯O5ⁱ hydrogen bonds form rings with an R₃²(7) graph-set motif while N2—H2C⋯O6ⁱ and N2—H2B⋯O5ⁱ hydrogen bonds combine to form R₂²(7) rings. In addition, heteronuclear N2—H2C⋯O6ⁱ, and N2—H2A⋯O8ⁱⁱ and homonuclear O4—H4A⋯O6ⁱⁱⁱ and O5—H5A⋯O3 hydrogen bonds generate a larger R₃⁴(14) ring motif (Fig. 2, Table 1). The crystal packing also features unusual weak C7—O1⋯Cg2ⁱⁱ, C7—O1⋯Cg3^iv and C13—O7⋯Cg2^v interactions reinforced by π–π stacking interactions. These latter contacts [Cg1· · ·Cg3 = 2.5382 (9) Å, Cg2· ··Cg2ⁱⁱ = 3.5997 (9) Å, Cg2· · ·Cg3^iv = 3.6406 (10) Å and Cg3·· ·Cg2^v = 3.6406 (10) Å; symmetry codes: (ii) 1 − x, 1 − y, 1 − z; (iv) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (v) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z] also contribute to the stabilization of the crystal packing (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the C7–C10 and C11–C14 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.93 (2)	1.74 (2)	2.6598 (15)	166.7 (19)
N2—H2B⋯O2ⁱ	0.89	2.05	2.8565 (16)	150
N2—H2B⋯O5ⁱ	0.89	2.56	3.1613 (17)	126
N2—H2C⋯O6ⁱ	0.89	2.02	2.8765 (16)	161
N2—H2A⋯O8ⁱⁱ	0.89	1.90	2.7580 (15)	162
O4—H4A⋯O6ⁱⁱⁱ	0.99 (2)	1.51 (2)	2.4993 (14)	175 (2)
O5—H5A⋯O3	1.00 (2)	1.46 (2)	2.4583 (14)	175 (2)
C7—O1⋯Cg2ⁱⁱ	1.25 (1)	3.38 (1)	3.3226 (14)	77 (1)
C7—O1⋯Cg3^iv	1.25 (1)	3.39 (1)	3.3297 (14)	76 (1)
C13—O7⋯Cg2^v	1.21 (1)	3.52 (1)	3.4188 (15)	75 (1)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
A view of the N—H⋯O and O—H⋯O interactions in the crystal of the title compound (hydrogen bonds are shown as dashed lines; see Table 1

for numerical details).

Figure 3
A packing diagram showing the C—O⋯π and π–π stacking interactions. [Symmetry codes: (ii) −x + 1, −y + 1, −z + 1; (iv) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (v) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ .] H atoms not involved in the interactions have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (Version 5.38, update February 2017; Groom et al., 2016 ) revealed the structures of various organoammonium squarates (Georgopoulos et al., 2005 ; Wang & Stucky, 1974 ; Kanters et al., 1991 ; Kolev et al., 2000 ; Karle et al., 1996 ; Angelova et al.,1996 ). In the squarate anion form, the anions are generally linked to amines by N—H⋯O hydrogen bonds (Gilli et al., 2001; Korkmaz et al., 2011 ; Dega-Szafran et al., 2012 ). Structures of 2-(amoniomethyl) pyridinium, dihydrogen squarate and squaric acid derivatives are also known (Korkmaz et al., 2011; Korkmaz & Bulut, 2013, 2014 ). Often, the supramolecular architectures of similar structures have been investigated together with their spectroscopic properties, including their potential non-linear optical (NLO) behaviour (Bosshard et al., 1995 ; Kolev et al., 2008 ). The literature also reveals that squarenes show photo-chemical, photo-conductive and NLO properties and that they can be used as electron acceptors in photo-sensitive devices (Korkmaz et al., 2016 ).

5. Synthesis and crystallization

All chemical reagents were analytical grade commercial products. The solvent was purified by conventional methods. Squaric acid (H₂Sq; 0,46 g, 4 mmol) and 2-(aminomethyl)pyridine (0,24 g; 2 mmol) were dissolved in water (25 cm³) to obtain a mixture in the molar ratio 2:1 and the solution was heated to 323 K in a temperature-controlled bath and stirred for one h. The reaction mixture was then slowly cooled to room temperature. The crystals formed were filtered and washed with 10 cm³ of methanol, and dried in air.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All C-bound hydrogen atoms were included in calculated positions with C—H = 0.93 Å (aromatic) and 0.97 Å (methylene) and allowed to ride, with U_iso(H) = 1.2U_eq(C). The NH₃ group (N—H = 0.89 Å) was also allowed to ride in the refinement with U_iso(H) = 1.5U_eq(N). The O-bound H atoms and N1-bound H atom were located in a difference-Fourier map and refined with U_iso(H) = 1.2U_eq(O) and U_iso(H) = 1.5U_eq(N).

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₁₀N₂²⁺·2C₄HO₄⁻
M_r	336.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.4653 (7), 15.4548 (14), 12.2095 (12)
β (°)	90.073 (4)
V (Å³)	1408.7 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.13
Crystal size (mm)	0.17 × 0.13 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.672, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	70681, 3496, 3090
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.118, 1.11
No. of reflections	3496
No. of parameters	227
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.28
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXT2014 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1538918

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017004376/sj5524sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017004376/sj5524Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017004376/sj5524Isup3.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: SHELXT2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

2-(Azaniumylmethyl)pyridinium bis(2-hydroxy-3,4-dioxocyclobutanolate) top

Crystal data top

C₆H₁₀N₂²⁺·2C₄HO₄⁻	F(000) = 696
M_r = 336.26	D_x = 1.586 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.4653 (7) Å	Cell parameters from 9896 reflections
b = 15.4548 (14) Å	θ = 3.0–28.3°
c = 12.2095 (12) Å	µ = 0.13 mm⁻¹
β = 90.073 (4)°	T = 296 K
V = 1408.7 (2) Å³	Block, bronze
Z = 4	0.17 × 0.13 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	3090 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.042
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θ_max = 28.3°, θ_min = 3.0°
T_min = 0.672, T_max = 0.746	h = −9→9
70681 measured reflections	k = −20→20
3496 independent reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042	H-atom parameters not refined
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0556P)² + 0.5691P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
3496 reflections	Δρ_max = 0.26 e Å⁻³
227 parameters	Δρ_min = −0.28 e Å⁻³

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
C1	0.3472 (2)	0.59963 (10)	0.10814 (12)	0.0377 (3)
H1	0.376471	0.541181	0.111071	0.045*
C2	0.2856 (2)	0.63543 (13)	0.01196 (13)	0.0479 (4)
H2	0.270245	0.601292	−0.050069	0.058*
C3	0.2473 (2)	0.72223 (14)	0.00899 (14)	0.0507 (4)
H3	0.210063	0.747750	−0.056155	0.061*
C4	0.2640 (2)	0.77205 (11)	0.10321 (14)	0.0442 (4)
H4	0.236500	0.830733	0.101700	0.053*
C5	0.32152 (18)	0.73381 (8)	0.19877 (12)	0.0305 (3)
C6	0.3378 (2)	0.78078 (10)	0.30627 (14)	0.0419 (4)
H6A	0.424710	0.751293	0.352098	0.050*
H6B	0.381247	0.839005	0.293104	0.050*
C7	0.61186 (16)	0.53092 (8)	0.38741 (10)	0.0245 (2)
C8	0.59463 (17)	0.44771 (8)	0.32689 (10)	0.0273 (3)
C9	0.71303 (18)	0.40741 (8)	0.41129 (10)	0.0278 (3)
C10	0.72538 (16)	0.48889 (8)	0.46610 (10)	0.0247 (2)
C11	0.64141 (18)	0.16148 (8)	0.29601 (10)	0.0289 (3)
C12	0.54027 (17)	0.10155 (8)	0.23404 (10)	0.0271 (3)
C13	0.57553 (18)	0.03307 (9)	0.31604 (10)	0.0293 (3)
C14	0.67917 (17)	0.09946 (8)	0.38172 (10)	0.0272 (3)
N1	0.36494 (15)	0.64919 (7)	0.19743 (9)	0.0288 (2)
N2	0.16375 (17)	0.78523 (8)	0.36470 (10)	0.0346 (3)
H2A	0.177821	0.813962	0.427290	0.052*
H2C	0.125260	0.731888	0.378838	0.052*
H2B	0.083844	0.812501	0.322984	0.052*
O1	0.54865 (14)	0.60498 (6)	0.37564 (8)	0.0328 (2)
O2	0.51318 (15)	0.42458 (7)	0.24462 (8)	0.0387 (3)
O3	0.77376 (16)	0.33276 (6)	0.42957 (9)	0.0409 (3)
O4	0.80146 (14)	0.51691 (6)	0.55513 (8)	0.0331 (2)
O5	0.68219 (19)	0.24159 (7)	0.27431 (9)	0.0457 (3)
O6	0.45452 (15)	0.10825 (7)	0.14494 (8)	0.0380 (3)
O7	0.54053 (18)	−0.04333 (7)	0.32469 (10)	0.0514 (3)
O8	0.76167 (16)	0.09899 (7)	0.46951 (8)	0.0400 (3)
H1A	0.419 (3)	0.6260 (13)	0.2598 (17)	0.048*
H5A	0.725 (3)	0.2770 (14)	0.3380 (18)	0.060*
H4A	0.868 (3)	0.4687 (15)	0.5894 (17)	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0412 (7)	0.0344 (7)	0.0375 (8)	0.0016 (6)	0.0005 (6)	−0.0072 (6)
C2	0.0440 (8)	0.0679 (11)	0.0320 (7)	−0.0028 (8)	−0.0042 (6)	−0.0111 (7)
C3	0.0442 (9)	0.0732 (12)	0.0346 (8)	0.0039 (8)	−0.0084 (6)	0.0176 (8)
C4	0.0458 (8)	0.0362 (8)	0.0505 (9)	0.0057 (6)	−0.0058 (7)	0.0159 (7)
C5	0.0293 (6)	0.0253 (6)	0.0370 (7)	−0.0015 (5)	−0.0047 (5)	0.0011 (5)
C6	0.0383 (7)	0.0333 (7)	0.0540 (9)	−0.0031 (6)	−0.0126 (7)	−0.0137 (6)
C7	0.0285 (6)	0.0245 (6)	0.0207 (5)	−0.0021 (4)	−0.0029 (4)	0.0028 (4)
C8	0.0327 (6)	0.0254 (6)	0.0237 (6)	−0.0010 (5)	−0.0045 (5)	0.0012 (5)
C9	0.0344 (6)	0.0230 (6)	0.0259 (6)	−0.0008 (5)	−0.0073 (5)	−0.0009 (4)
C10	0.0297 (6)	0.0222 (5)	0.0223 (5)	−0.0007 (4)	−0.0045 (4)	0.0009 (4)
C11	0.0364 (6)	0.0242 (6)	0.0261 (6)	0.0020 (5)	−0.0054 (5)	−0.0052 (5)
C12	0.0307 (6)	0.0257 (6)	0.0248 (6)	0.0040 (5)	−0.0059 (5)	−0.0052 (5)
C13	0.0322 (6)	0.0280 (6)	0.0276 (6)	−0.0013 (5)	−0.0061 (5)	−0.0020 (5)
C14	0.0297 (6)	0.0287 (6)	0.0234 (6)	0.0000 (5)	−0.0039 (5)	−0.0035 (5)
N1	0.0310 (5)	0.0265 (5)	0.0287 (5)	0.0017 (4)	−0.0043 (4)	0.0019 (4)
N2	0.0473 (7)	0.0276 (6)	0.0288 (6)	0.0021 (5)	−0.0120 (5)	−0.0032 (4)
O1	0.0431 (5)	0.0240 (4)	0.0312 (5)	0.0049 (4)	−0.0081 (4)	0.0028 (4)
O2	0.0505 (6)	0.0340 (5)	0.0315 (5)	−0.0006 (4)	−0.0189 (4)	−0.0030 (4)
O3	0.0594 (7)	0.0227 (5)	0.0405 (6)	0.0071 (4)	−0.0227 (5)	−0.0051 (4)
O4	0.0452 (5)	0.0257 (5)	0.0282 (5)	0.0014 (4)	−0.0150 (4)	−0.0028 (4)
O5	0.0797 (9)	0.0227 (5)	0.0346 (5)	−0.0061 (5)	−0.0174 (5)	−0.0021 (4)
O6	0.0520 (6)	0.0309 (5)	0.0310 (5)	0.0043 (4)	−0.0204 (4)	−0.0050 (4)
O7	0.0700 (8)	0.0309 (6)	0.0532 (7)	−0.0154 (5)	−0.0214 (6)	0.0067 (5)
O8	0.0525 (6)	0.0386 (6)	0.0290 (5)	−0.0023 (5)	−0.0171 (4)	−0.0034 (4)

Geometric parameters (Å, º) top

C1—N1	1.3388 (18)	C9—O3	1.2593 (16)
C1—C2	1.377 (2)	C9—C10	1.4291 (17)
C1—H1	0.9300	C10—O4	1.3000 (15)
C2—C3	1.372 (3)	C11—O5	1.3023 (17)
C2—H2	0.9300	C11—C12	1.4139 (17)
C3—C4	1.390 (3)	C11—C14	1.4465 (18)
C3—H3	0.9300	C12—O6	1.2658 (15)
C4—C5	1.376 (2)	C12—C13	1.4802 (18)
C4—H4	0.9300	C13—O7	1.2141 (17)
C5—N1	1.3475 (17)	C13—C14	1.5141 (17)
C5—C6	1.505 (2)	C14—O8	1.2356 (16)
C6—N2	1.485 (2)	N1—H1A	0.93 (2)
C6—H6A	0.9700	N2—H2A	0.8900
C6—H6B	0.9700	N2—H2C	0.8900
C7—O1	1.2462 (15)	N2—H2B	0.8900
C7—C10	1.4357 (16)	O3—H5A	1.46 (2)
C7—C8	1.4886 (17)	O4—H4A	0.99 (2)
C8—O2	1.2268 (15)	O5—H5A	1.00 (2)
C8—C9	1.4929 (17)

N1—C1—C2	119.82 (15)	C10—C9—C8	89.62 (10)
N1—C1—H1	120.1	O4—C10—C9	135.48 (12)
C2—C1—H1	120.1	O4—C10—C7	131.74 (12)
C3—C2—C1	119.01 (15)	C9—C10—C7	92.73 (10)
C3—C2—H2	120.5	O5—C11—C12	129.70 (12)
C1—C2—H2	120.5	O5—C11—C14	137.03 (12)
C2—C3—C4	120.09 (15)	C12—C11—C14	93.24 (11)
C2—C3—H3	120.0	O6—C12—C11	132.49 (13)
C4—C3—H3	120.0	O6—C12—C13	136.82 (12)
C5—C4—C3	119.43 (15)	C11—C12—C13	90.68 (10)
C5—C4—H4	120.3	O7—C13—C12	135.73 (12)
C3—C4—H4	120.3	O7—C13—C14	136.29 (13)
N1—C5—C4	118.78 (14)	C12—C13—C14	87.94 (10)
N1—C5—C6	117.37 (12)	O8—C14—C11	136.71 (12)
C4—C5—C6	123.85 (14)	O8—C14—C13	135.18 (12)
N2—C6—C5	111.82 (11)	C11—C14—C13	88.10 (10)
N2—C6—H6A	109.3	C1—N1—C5	122.79 (12)
C5—C6—H6A	109.3	C1—N1—H1A	119.1 (12)
N2—C6—H6B	109.3	C5—N1—H1A	117.8 (12)
C5—C6—H6B	109.3	C6—N2—H2A	109.5
H6A—C6—H6B	107.9	C6—N2—H2C	109.5
O1—C7—C10	135.70 (12)	H2A—N2—H2C	109.5
O1—C7—C8	134.73 (11)	C6—N2—H2B	109.5
C10—C7—C8	89.54 (10)	H2A—N2—H2B	109.5
O2—C8—C7	134.48 (12)	H2C—N2—H2B	109.5
O2—C8—C9	137.39 (12)	C9—O3—H5A	108.5 (9)
C7—C8—C9	88.12 (9)	C10—O4—H4A	108.8 (12)
O3—C9—C10	134.53 (12)	C11—O5—H5A	115.9 (12)
O3—C9—C8	135.83 (12)

N1—C1—C2—C3	1.5 (2)	O1—C7—C10—C9	177.87 (16)
C1—C2—C3—C4	−2.5 (3)	C8—C7—C10—C9	−0.11 (10)
C2—C3—C4—C5	0.9 (3)	O5—C11—C12—O6	−4.0 (3)
C3—C4—C5—N1	1.8 (2)	C14—C11—C12—O6	177.80 (15)
C3—C4—C5—C6	−177.64 (15)	O5—C11—C12—C13	176.91 (15)
N1—C5—C6—N2	−96.31 (15)	C14—C11—C12—C13	−1.33 (11)
C4—C5—C6—N2	83.15 (19)	O6—C12—C13—O7	4.0 (3)
O1—C7—C8—O2	0.6 (3)	C11—C12—C13—O7	−176.90 (19)
C10—C7—C8—O2	178.65 (16)	O6—C12—C13—C14	−177.79 (17)
O1—C7—C8—C9	−177.91 (15)	C11—C12—C13—C14	1.27 (10)
C10—C7—C8—C9	0.10 (10)	O5—C11—C14—O8	2.2 (3)
O2—C8—C9—O3	−0.3 (3)	C12—C11—C14—O8	−179.74 (17)
C7—C8—C9—O3	178.15 (17)	O5—C11—C14—C13	−176.71 (18)
O2—C8—C9—C10	−178.57 (17)	C12—C11—C14—C13	1.30 (10)
C7—C8—C9—C10	−0.11 (10)	O7—C13—C14—O8	−2.1 (3)
O3—C9—C10—O4	−0.8 (3)	C12—C13—C14—O8	179.77 (16)
C8—C9—C10—O4	177.53 (16)	O7—C13—C14—C11	176.91 (19)
O3—C9—C10—C7	−178.19 (17)	C12—C13—C14—C11	−1.24 (10)
C8—C9—C10—C7	0.11 (10)	C2—C1—N1—C5	1.3 (2)
O1—C7—C10—O4	0.3 (3)	C4—C5—N1—C1	−3.0 (2)
C8—C7—C10—O4	−177.69 (15)	C6—C5—N1—C1	176.53 (13)

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg3 are the centroids of the C7–C10 and C11–C14 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.93 (2)	1.74 (2)	2.6598 (15)	166.7 (19)
N2—H2B···O2ⁱ	0.89	2.05	2.8565 (16)	150
N2—H2B···O5ⁱ	0.89	2.56	3.1613 (17)	126
N2—H2C···O6ⁱ	0.89	2.02	2.8765 (16)	161
N2—H2A···O8ⁱⁱ	0.89	1.90	2.7580 (15)	162
O4—H4A···O6ⁱⁱⁱ	0.99 (2)	1.51 (2)	2.4993 (14)	175 (2)
O5—H5A···O3	1.00 (2)	1.46 (2)	2.4583 (14)	175 (2)
C7—O1···Cg2ⁱⁱ	1.25 (1)	3.38 (1)	3.3226 (14)	77 (1)
C7—O1···Cg3^iv	1.25 (1)	3.39 (1)	3.3297 (14)	76 (1)
C13—O7···Cg2^v	1.21 (1)	3.52 (1)	3.4188 (15)	75 (1)

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

Acknowledgements

The authors are grateful to the Scientific and Technological Research Application and Research Center, Sinop University, Turkey, for the use of the diffractometer.

Funding information

Funding for this research was provided by: Ondokuz Mayıs University, Turkey (award No. PYO.FEN.1904.15.012).

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