Structure of 2,3,5-tri­phenyl­tetra­zol-3-ium chloride hemi­penta­hydrate

Uppu, R.M.; Chikkula, K.; Saneei, S.; Babu, S.; Fronczek, F.R.

doi:10.1107/S205698902400940X

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ISSN: 2056-9890

Volume 80| Part 10| October 2024| Pages 1097-1100

https://doi.org/10.1107/S205698902400940X

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Structure of 2,3,5-triphenyltetrazol-3-ium chloride hemipentahydrate

Rao M Uppu,^a ^* Krishnaveni Chikkula,^a Soheil Saneei,^a Sainath Babu ^a and Frank R. Fronczek ^b

^aDepartment of Environmental Toxicology, Southern University and A&M College, Baton Rouge, LA 70813, USA, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: rao_uppu@subr.edu

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 18 September 2024; accepted 24 September 2024; online 30 September 2024)

The title hydrated molecular salt, C₁₉H₁₅N₄⁺·Cl⁻·2.5H₂O, has two triphenyltetrazolium cations, two chloride anions and five water molecules in the asymmetric unit. The cations differ in the conformations of the phenyl rings with respect to the heterocyclic core, most notably for the C-bonded phenyl ring, for which the N—C—C—C torsion angles differ by 36.4 (3)°. This is likely a result of one cation accepting an O—H⋯N hydrogen bond from a water molecule [O⋯N = 3.1605 (15) Å], while the other cation accepts no hydrogen bonds. In the extended structure, the water molecules are involved in centrosymmetric (H₂O)₂Cl₂ rings as well as (H₂O)₄ chains. An unusual O—H⋯π interaction and weak C—H⋯O and C—H⋯Cl hydrogen bonds are also observed.

Keywords: crystal structure; redox indicator; cellular respiration; tetrazolium reduction assays.

CCDC reference: 2314756

1. Chemical context

2,3,5-Triphenyltetrazolium chloride, commonly known as tetrazolium red or TTC, is a versatile redox indicator extensively used in biochemical experiments, especially for evaluating cellular viability (Rich et al., 2001 ) and seed quality control in various crops (França-Neto & Krzyzanowski, 2019 ). Beyond these applications, TTC demonstrates inducible antagonistic activity in the Bacillales effective against a host of microbes including R. solanacearum, E. coli, and Staphylococcus sp (Sierra-Zapata et al., 2020 ). Furthermore, the utility of TTC extends to infarct (localized dead tissue) measurement of the brain and heart in experimental animal studies (Sanchez-Bezanilla et al., 2021 ), validation of automated colony counting systems (Frost et al., 2016 ), and studying heat tolerance in cotton (Jaconis et al., 2021 ), as well as assessing fine-root vitality in coniferous forest stands (Clemensson-Lindell, 1994 ). Despite its widespread use, the crystallographic aspects of TTC have been relatively unexplored, and we now describe the crystal structure of the title hydrated molecular salt, C₁₉H₁₅N₄⁺ Cl⁻·2.5H₂O (I),

This is important, because the nuances in the conformations of the pendant tetrazolium rings may influence the transport mechanisms of TTC across biological membranes and its reduction by mitochondrial NADH: ubiquinone oxidoreductase (Complex 1) or other cellular sites (Ling et al., 1957 ; Rich et al., 2001). Exploring these structural intricacies is expected to deepen our comprehension of the various applications of TTC, ranging from assessing cell viability to seed testing, measuring infarcts, and exploring its antimicrobial quorum-sensing properties.

2. Structural commentary

The asymmetric unit of (I) is shown in Fig. 1. The central N—N distance in the heterocycle is 1.3341 (14) Å in the N1 molecule and 1.3324 (14) Å in the N5 molecule, while the other heterocyclic N—N distances are in the range 1.3066 (15) to 1.3137 (15) Å. The heterocyclic C—N distances are in the range 1.3442 (16) to 1.3500 (16) Å over the two cations. The two independent tetrazolium cations differ somewhat in their phenyl group conformations, one having N—N—C—C torsion angles about the N—C(phenyl) bond of 48.25 (18)° for N3—N2—C8—C13 and 50.30 (18)° for N2—N3—C14—C15 and the other having corresponding torsion angles of 57.24 (17)° for N7—N6—C27—C28 and 61.37 (17)° for N6—N7—C33—C34. The C-bound phenyl group also differs in conformation, having an N1—C1—C2—C3 torsion angle of 12.26 (19)° in one cation and N5—C20—C21—C22 = −24.14 (19)° in the other. These conformational differences are apparent in the overlay plot, Fig. 2 (Macrae et al., 2020 ). They may result from the fact that the N1 cation accepts a hydrogen bond from a water molecule with an O⋯N distance of 3.1605 (15) Å (Table 1), while the other does not.

Table 1
Hydrogen-bond geometry (Å, °)

Cg6 is the centroid of the C21–C26 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯Cl2ⁱ	0.85 (1)	2.30 (1)	3.1483 (12)	178 (2)
O1—H2W⋯N4	0.85 (1)	2.34 (2)	3.1605 (15)	160 (2)
O2—H3W⋯Cl2	0.84 (1)	2.30 (1)	3.1302 (12)	176 (2)
O2—H4W⋯Cl2ⁱⁱ	0.84 (1)	2.34 (1)	3.1740 (12)	175 (2)
O3—H5W⋯O2	0.85 (1)	1.98 (1)	2.8246 (16)	175 (2)
O3—H6W⋯O5	0.85 (1)	2.16 (2)	3.0040 (17)	171 (2)
O4—H7W⋯Cl1ⁱⁱⁱ	0.85 (1)	2.32 (2)	3.1687 (14)	179 (3)
O4—H8W⋯Cl1	0.85 (1)	2.35 (2)	3.2008 (14)	178 (2)
O5—H9W⋯O4ⁱⁱ	0.86 (1)	1.90 (1)	2.7503 (17)	175 (2)
O5—H10W⋯Cg6	0.85 (1)	2.76 (2)	3.4646 (14)	141 (2)
C4—H4⋯O2^iv	0.95	2.55	3.461 (2)	160
C11—H11⋯O5^v	0.95	2.59	3.429 (2)	147
C15—H15⋯Cl1	0.95	2.82	3.6219 (14)	143
C16—H16⋯O5ⁱⁱ	0.95	2.48	3.4084 (19)	165
C17—H17⋯O2ⁱⁱ	0.95	2.42	3.359 (2)	168
C26—H26⋯O5^vi	0.95	2.50	3.4440 (19)	173
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Figure 1
The asymmetric unit of (I)

showing 50% displacement ellipsoids. Hydrogen bonds are indicated by dashed lines and the orange circle represents the centroid of the C21–C26 ring.

Figure 2
Superimposed structures of the N1 and N5 triphenyltetrazolium cations in (I)

3. Supramolecular features

The hydrogen bonding is illustrated in Fig. 3 and the unit-cell packing is shown in Fig. 4. As mentioned in the Structural commentary, one of the two independent cations accepts no hydrogen bonds, while the other accepts an O—H⋯N hydrogen bond from a water molecule. The remaining water molecules and chloride ions form arrays with chains propagating in the [011] direction, consisting of four hydrogen-bonded water molecules, linked by two independent centrosymmetric (H₂O)₂Cl₂ rings having graph-set notation (Etter et al., 1990 ) R₄²(8). The O4⋯Cl1 distances in one ring are 3.1687 (14) and 3.12008 (14) Å and the O2⋯Cl2 distances in the other ring are 3.1302 (12) and 3.1740 (12) Å. The O⋯O distances in the four-water molecule chain are in the range 2.7503 (17) to 3.0040 (17) Å. The water molecule (O1) that donates a hydrogen bond to a tetrazolium N atom also donates one to an (H₂O)₂Cl₂ ring, with an O1⋯Cl2 distance of 3.1483 (12) Å. Atom O5 forms an unusual O—H⋯π bond to the C21–C26 benzene ring and various weak C—H⋯O and C—H⋯Cl hydrogen bonds are also observed (Table 1). The O—H⋯π contact (Allen et al., 1996 ; Di Mino et al., 2023 ) involves the only water hydrogen atom (H10W) that does not donate a conventional hydrogen bond. The H⋯Cg distance is 2.76 (2) Å, the O⋯Cg distance is 3.4646 (14) Å, and the angle about H is 140.8 (18)°.

Figure 3
Hydrogen bonding (dashed blue lines) in (I)

Figure 4
View of the unit-cell packing of (I)

4. Database survey

We deposited the structure of (I) to the Cambridge Structural Database (CSD, version 5.45, Update 1, March 2024, Groom et al., 2016 ) recently as refcode ROJSUI (Chikkula et al., 2023 ). A search of the CSD for other salts of the same cation revealed that the structures of 2,3,5-triphenyltetrazolium chloride as the acetonitrile solvate (LAWXUD), ethanol solvate (LAWYEO) and monohydrate (LAWYAK) have been reported by Golovanov et al. (2005 ). In addition, the bromide salt ethanol solvate (LEGNUI; Fun et al., 2012a ) and iodide salt (QECKEQ; Fun et al., 2012b ) have been described. These structures have a wide range of N—N—C—C torsion angle magnitudes to the N-bound phenyl groups (41.3–86.5°), but a much smaller range of N—C—C—C torsion angle magnitudes to the C-bound phenyl group (2.2–12.6°).

5. Synthesis and crystallization

TTC was obtained from Sigma-Aldrich (CAS 298-96-4; purity >98% by HPLC) and was used without purification. Single crystals were prepared by slow cooling of a nearly saturated solution of TTC in boiling distilled water (resistance: 18.2 MΩ cm⁻¹).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were located in difference maps, and those on C were treated as riding in geometrically idealized positions having C—H = 0.95 Å and U_iso(H) = 1.2U_eq of the parent C atom. Coordinates of water H atoms were refined with all O—H distances restrained to be approximately equal. Their U_iso values were set to 1.5U_eq times their attached O atom.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₅N₄⁺·Cl⁻·2.5H₂O
M_r	379.84
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.5599 (4), 11.8056 (5), 17.5322 (7)
α, β, γ (°)	94.808 (2), 104.562 (2), 95.408 (2)
V (Å³)	1894.70 (14)
Z	4
Radiation type	Ag Kα, λ = 0.56086 Å
μ (mm⁻¹)	0.12
Crystal size (mm)	0.32 × 0.28 × 0.25

Data collection
Diffractometer	Bruker D8 Venture DUO with Photon III C14
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.944, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	125520, 15816, 13259
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.794

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.141, 1.16
No. of reflections	15816
No. of parameters	508
No. of restraints	45
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.67
Computer programs: APEX4 and SAINT (Bruker, 2022 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2019/1 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2314756

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S205698902400940X/hb8107sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S205698902400940X/hb8107Isup3.cml

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902400940X/hb8107Isup3.hkl

checkCIF report

Computing details top

2,3,5-Triphenyltetrazol-3-ium chloride hemipentahydrate top

Crystal data top

C₁₉H₁₅N₄⁺·Cl⁻·2.5H₂O	Z = 4
M_r = 379.84	F(000) = 796
Triclinic, P1	D_x = 1.332 Mg m⁻³
a = 9.5599 (4) Å	Ag Kα radiation, λ = 0.56086 Å
b = 11.8056 (5) Å	Cell parameters from 9994 reflections
c = 17.5322 (7) Å	θ = 2.6–26.3°
α = 94.808 (2)°	µ = 0.12 mm⁻¹
β = 104.562 (2)°	T = 100 K
γ = 95.408 (2)°	Fragment, colourless
V = 1894.70 (14) Å³	0.32 × 0.28 × 0.25 mm

Data collection top

Bruker D8 Venture DUO with Photon III C14 diffractometer	13259 reflections with I > 2σ(I)
Radiation source: IµS 3.0 microfocus	R_int = 0.084
φ and ω scans	θ_max = 26.4°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −15→15
T_min = 0.944, T_max = 0.970	k = −18→18
125520 measured reflections	l = −27→27
15816 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.141	w = 1/[σ²(F_o²) + (0.0502P)² + 1.073P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max = 0.001
15816 reflections	Δρ_max = 0.63 e Å⁻³
508 parameters	Δρ_min = −0.67 e Å⁻³
45 restraints

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
Cl1	0.70828 (4)	0.44966 (3)	0.10654 (2)	0.02287 (8)
Cl2	0.36722 (5)	0.81273 (4)	0.47669 (2)	0.03148 (10)
N1	1.06087 (12)	0.41493 (9)	0.30022 (7)	0.01281 (18)
N2	1.01796 (12)	0.51703 (9)	0.29532 (6)	0.01148 (18)
N3	0.91361 (12)	0.52776 (9)	0.33271 (6)	0.01127 (18)
N4	0.88812 (12)	0.43342 (9)	0.36428 (7)	0.01265 (18)
C1	0.98037 (13)	0.36431 (10)	0.34357 (7)	0.0119 (2)
C2	0.99419 (14)	0.24860 (10)	0.36518 (7)	0.0127 (2)
C3	1.11278 (15)	0.19497 (12)	0.35379 (8)	0.0168 (2)
H3	1.184221	0.234181	0.333244	0.020*
C4	1.12526 (17)	0.08350 (12)	0.37282 (9)	0.0207 (3)
H4	1.206066	0.046687	0.365849	0.025*
C5	1.01958 (19)	0.02616 (12)	0.40200 (9)	0.0226 (3)
H5	1.027171	−0.050537	0.413628	0.027*
C6	0.90284 (18)	0.08019 (12)	0.41429 (8)	0.0204 (3)
H6	0.831886	0.040812	0.435081	0.025*
C7	0.88968 (15)	0.19187 (11)	0.39619 (8)	0.0154 (2)
H7	0.810327	0.229196	0.404859	0.019*
C8	1.08402 (13)	0.60275 (10)	0.25710 (7)	0.0118 (2)
C9	1.10553 (15)	0.56581 (12)	0.18416 (8)	0.0153 (2)
H9	1.070334	0.490211	0.159463	0.018*
C10	1.18016 (16)	0.64285 (13)	0.14837 (8)	0.0186 (2)
H10	1.197734	0.619924	0.098701	0.022*
C11	1.22917 (15)	0.75340 (13)	0.18512 (9)	0.0195 (3)
H11	1.279070	0.806102	0.160079	0.023*
C12	1.20566 (15)	0.78746 (12)	0.25834 (9)	0.0177 (2)
H12	1.239657	0.863305	0.282850	0.021*
C13	1.13283 (14)	0.71156 (11)	0.29605 (8)	0.0145 (2)
H13	1.117314	0.733548	0.346380	0.017*
C14	0.83772 (14)	0.62624 (10)	0.33853 (7)	0.0122 (2)
C15	0.77717 (15)	0.67406 (12)	0.27005 (8)	0.0160 (2)
H15	0.786806	0.643983	0.219891	0.019*
C16	0.70196 (16)	0.76752 (13)	0.27755 (9)	0.0210 (3)
H16	0.661365	0.803899	0.232134	0.025*
C17	0.68564 (17)	0.80833 (13)	0.35140 (10)	0.0233 (3)
H17	0.632602	0.871611	0.355801	0.028*
C18	0.74620 (18)	0.75730 (13)	0.41848 (9)	0.0228 (3)
H18	0.733652	0.785380	0.468421	0.027*
C19	0.82497 (16)	0.66550 (12)	0.41304 (8)	0.0176 (2)
H19	0.868633	0.630747	0.458692	0.021*
N5	0.34121 (12)	0.77429 (9)	0.78463 (6)	0.01196 (18)
N6	0.45974 (12)	0.72436 (9)	0.79383 (6)	0.01103 (17)
N7	0.54655 (11)	0.75476 (9)	0.86647 (6)	0.01081 (17)
N8	0.48642 (12)	0.82506 (9)	0.90686 (6)	0.01171 (18)
C20	0.35971 (13)	0.83685 (10)	0.85526 (7)	0.01125 (19)
C21	0.25809 (14)	0.91367 (11)	0.87263 (7)	0.0126 (2)
C22	0.16689 (15)	0.95904 (12)	0.81057 (8)	0.0167 (2)
H22	0.168326	0.937903	0.757308	0.020*
C23	0.07367 (18)	1.03559 (13)	0.82727 (10)	0.0233 (3)
H23	0.011239	1.067061	0.785300	0.028*
C24	0.07175 (18)	1.06608 (14)	0.90525 (10)	0.0257 (3)
H24	0.007532	1.117997	0.916441	0.031*
C25	0.16344 (17)	1.02088 (13)	0.96690 (9)	0.0214 (3)
H25	0.161744	1.042165	1.020099	0.026*
C26	0.25762 (15)	0.94473 (12)	0.95119 (8)	0.0164 (2)
H26	0.320861	0.914190	0.993332	0.020*
C27	0.49263 (13)	0.64728 (11)	0.73433 (7)	0.0121 (2)
C28	0.52080 (14)	0.53771 (11)	0.75180 (8)	0.0153 (2)
H28	0.517685	0.512997	0.801599	0.018*
C29	0.55378 (15)	0.46552 (13)	0.69343 (9)	0.0200 (3)
H29	0.573212	0.389835	0.703092	0.024*
C30	0.55841 (16)	0.50361 (15)	0.62116 (9)	0.0237 (3)
H30	0.582347	0.454021	0.582032	0.028*
C31	0.52840 (17)	0.61350 (15)	0.60550 (8)	0.0224 (3)
H31	0.530920	0.638198	0.555610	0.027*
C32	0.49462 (15)	0.68766 (13)	0.66259 (8)	0.0169 (2)
H32	0.473763	0.762990	0.652720	0.020*
C33	0.69328 (13)	0.72747 (11)	0.89345 (7)	0.01130 (19)
C34	0.79458 (14)	0.76919 (12)	0.85529 (8)	0.0147 (2)
H34	0.767638	0.812168	0.811542	0.018*
C35	0.93677 (14)	0.74586 (13)	0.88334 (8)	0.0176 (2)
H35	1.008994	0.772656	0.858364	0.021*
C36	0.97440 (15)	0.68333 (13)	0.94797 (8)	0.0184 (2)
H36	1.072249	0.668184	0.966914	0.022*
C37	0.86978 (15)	0.64294 (13)	0.98493 (8)	0.0181 (2)
H37	0.896309	0.600303	1.028887	0.022*
C38	0.72645 (14)	0.66494 (12)	0.95758 (8)	0.0149 (2)
H38	0.653676	0.637922	0.982119	0.018*
O1	0.83271 (13)	0.41876 (10)	0.53365 (6)	0.0209 (2)
H1W	0.780 (2)	0.3554 (14)	0.5308 (14)	0.031*
H2W	0.828 (3)	0.430 (2)	0.4856 (9)	0.031*
O2	0.53149 (13)	0.99355 (10)	0.61966 (6)	0.0212 (2)
H3W	0.484 (2)	0.9458 (17)	0.5819 (11)	0.032*
H4W	0.558 (3)	1.0481 (16)	0.5968 (13)	0.032*
O3	0.57974 (15)	0.96751 (10)	0.78259 (7)	0.0254 (2)
H5W	0.564 (3)	0.980 (2)	0.7343 (9)	0.038*
H6W	0.556 (3)	1.0222 (17)	0.8094 (13)	0.038*
O4	0.46846 (15)	0.62378 (11)	0.07228 (8)	0.0277 (2)
H7W	0.420 (3)	0.605 (2)	0.0242 (9)	0.041*
H8W	0.533 (2)	0.5782 (19)	0.0806 (15)	0.041*
O5	0.49505 (13)	1.14221 (10)	0.89204 (7)	0.0219 (2)
H9W	0.502 (3)	1.2147 (12)	0.9044 (14)	0.033*
H10W	0.435 (2)	1.1154 (19)	0.9169 (13)	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02495 (17)	0.01712 (15)	0.02952 (18)	−0.00068 (12)	0.01420 (14)	0.00123 (12)
Cl2	0.0403 (2)	0.0297 (2)	0.01840 (16)	−0.01646 (17)	0.00415 (15)	0.00281 (13)
N1	0.0144 (5)	0.0092 (4)	0.0156 (5)	0.0019 (3)	0.0053 (4)	0.0011 (3)
N2	0.0119 (4)	0.0099 (4)	0.0132 (4)	0.0011 (3)	0.0047 (3)	0.0006 (3)
N3	0.0112 (4)	0.0095 (4)	0.0137 (4)	0.0012 (3)	0.0044 (3)	0.0010 (3)
N4	0.0132 (5)	0.0093 (4)	0.0157 (5)	0.0009 (3)	0.0041 (4)	0.0019 (3)
C1	0.0115 (5)	0.0101 (5)	0.0136 (5)	0.0010 (4)	0.0031 (4)	0.0003 (4)
C2	0.0143 (5)	0.0089 (5)	0.0141 (5)	0.0014 (4)	0.0024 (4)	0.0008 (4)
C3	0.0162 (6)	0.0147 (5)	0.0191 (6)	0.0041 (4)	0.0034 (4)	0.0001 (4)
C4	0.0234 (7)	0.0164 (6)	0.0212 (6)	0.0087 (5)	0.0017 (5)	0.0005 (5)
C5	0.0344 (8)	0.0123 (6)	0.0197 (6)	0.0065 (5)	0.0023 (6)	0.0040 (5)
C6	0.0301 (7)	0.0132 (5)	0.0172 (6)	−0.0009 (5)	0.0055 (5)	0.0033 (4)
C7	0.0182 (6)	0.0128 (5)	0.0148 (5)	0.0005 (4)	0.0039 (4)	0.0014 (4)
C8	0.0110 (5)	0.0104 (5)	0.0141 (5)	−0.0001 (4)	0.0035 (4)	0.0027 (4)
C9	0.0155 (6)	0.0155 (5)	0.0151 (5)	0.0002 (4)	0.0051 (4)	0.0013 (4)
C10	0.0174 (6)	0.0224 (6)	0.0176 (6)	0.0010 (5)	0.0071 (5)	0.0057 (5)
C11	0.0141 (6)	0.0202 (6)	0.0249 (6)	−0.0008 (5)	0.0053 (5)	0.0094 (5)
C12	0.0153 (6)	0.0126 (5)	0.0240 (6)	−0.0014 (4)	0.0036 (5)	0.0031 (5)
C13	0.0131 (5)	0.0121 (5)	0.0171 (5)	0.0004 (4)	0.0025 (4)	0.0008 (4)
C14	0.0113 (5)	0.0095 (5)	0.0155 (5)	0.0017 (4)	0.0028 (4)	0.0001 (4)
C15	0.0141 (5)	0.0162 (5)	0.0168 (5)	0.0031 (4)	0.0017 (4)	0.0026 (4)
C16	0.0168 (6)	0.0173 (6)	0.0272 (7)	0.0054 (5)	0.0001 (5)	0.0053 (5)
C17	0.0188 (6)	0.0154 (6)	0.0339 (8)	0.0072 (5)	0.0036 (6)	−0.0023 (5)
C18	0.0247 (7)	0.0195 (6)	0.0238 (7)	0.0064 (5)	0.0067 (5)	−0.0054 (5)
C19	0.0198 (6)	0.0168 (6)	0.0162 (5)	0.0057 (5)	0.0041 (5)	−0.0012 (4)
N5	0.0105 (4)	0.0126 (4)	0.0125 (4)	0.0020 (3)	0.0026 (3)	0.0003 (3)
N6	0.0102 (4)	0.0119 (4)	0.0098 (4)	0.0003 (3)	0.0012 (3)	−0.0002 (3)
N7	0.0093 (4)	0.0126 (4)	0.0097 (4)	−0.0001 (3)	0.0022 (3)	−0.0008 (3)
N8	0.0100 (4)	0.0132 (4)	0.0118 (4)	0.0004 (3)	0.0037 (3)	−0.0005 (3)
C20	0.0104 (5)	0.0112 (5)	0.0121 (5)	−0.0004 (4)	0.0037 (4)	0.0006 (4)
C21	0.0112 (5)	0.0115 (5)	0.0146 (5)	0.0005 (4)	0.0036 (4)	−0.0014 (4)
C22	0.0182 (6)	0.0145 (5)	0.0170 (5)	0.0042 (4)	0.0037 (5)	0.0005 (4)
C23	0.0243 (7)	0.0189 (6)	0.0261 (7)	0.0102 (5)	0.0037 (6)	0.0000 (5)
C24	0.0239 (7)	0.0206 (7)	0.0320 (8)	0.0076 (5)	0.0079 (6)	−0.0086 (6)
C25	0.0191 (6)	0.0226 (7)	0.0216 (6)	0.0007 (5)	0.0078 (5)	−0.0085 (5)
C26	0.0138 (5)	0.0192 (6)	0.0147 (5)	−0.0001 (4)	0.0034 (4)	−0.0031 (4)
C27	0.0099 (5)	0.0141 (5)	0.0115 (5)	0.0005 (4)	0.0028 (4)	−0.0028 (4)
C28	0.0120 (5)	0.0148 (5)	0.0178 (5)	0.0012 (4)	0.0026 (4)	−0.0010 (4)
C29	0.0137 (6)	0.0188 (6)	0.0245 (6)	0.0038 (5)	0.0020 (5)	−0.0070 (5)
C30	0.0152 (6)	0.0338 (8)	0.0194 (6)	0.0061 (5)	0.0030 (5)	−0.0111 (6)
C31	0.0188 (6)	0.0358 (8)	0.0124 (5)	0.0046 (6)	0.0048 (5)	−0.0026 (5)
C32	0.0150 (6)	0.0224 (6)	0.0124 (5)	0.0022 (5)	0.0029 (4)	0.0004 (4)
C33	0.0086 (5)	0.0132 (5)	0.0114 (5)	0.0003 (4)	0.0022 (4)	−0.0005 (4)
C34	0.0129 (5)	0.0172 (5)	0.0133 (5)	−0.0023 (4)	0.0041 (4)	0.0002 (4)
C35	0.0106 (5)	0.0225 (6)	0.0188 (6)	−0.0032 (4)	0.0057 (4)	−0.0029 (5)
C36	0.0105 (5)	0.0223 (6)	0.0201 (6)	0.0021 (5)	0.0019 (4)	−0.0032 (5)
C37	0.0146 (6)	0.0211 (6)	0.0169 (6)	0.0031 (5)	0.0003 (4)	0.0034 (5)
C38	0.0124 (5)	0.0176 (6)	0.0148 (5)	0.0010 (4)	0.0037 (4)	0.0033 (4)
O1	0.0232 (5)	0.0212 (5)	0.0167 (4)	−0.0017 (4)	0.0049 (4)	0.0001 (4)
O2	0.0286 (6)	0.0174 (5)	0.0175 (5)	0.0028 (4)	0.0063 (4)	0.0006 (4)
O3	0.0351 (6)	0.0179 (5)	0.0252 (5)	0.0014 (4)	0.0106 (5)	0.0064 (4)
O4	0.0305 (6)	0.0227 (5)	0.0326 (6)	0.0015 (5)	0.0165 (5)	−0.0037 (5)
O5	0.0256 (5)	0.0187 (5)	0.0214 (5)	−0.0009 (4)	0.0070 (4)	0.0037 (4)

Geometric parameters (Å, º) top

N1—N2	1.3120 (15)	N7—C33	1.4395 (16)
N1—C1	1.3455 (16)	N8—C20	1.3442 (16)
N2—N3	1.3341 (14)	C20—C21	1.4586 (17)
N2—C8	1.4415 (16)	C21—C22	1.3927 (19)
N3—N4	1.3137 (15)	C21—C26	1.3965 (18)
N3—C14	1.4370 (16)	C22—C23	1.391 (2)
N4—C1	1.3500 (16)	C22—H22	0.9500
C1—C2	1.4569 (17)	C23—C24	1.389 (2)
C2—C7	1.3966 (18)	C23—H23	0.9500
C2—C3	1.3979 (18)	C24—C25	1.389 (2)
C3—C4	1.393 (2)	C24—H24	0.9500
C3—H3	0.9500	C25—C26	1.389 (2)
C4—C5	1.389 (2)	C25—H25	0.9500
C4—H4	0.9500	C26—H26	0.9500
C5—C6	1.390 (2)	C27—C32	1.3858 (18)
C5—H5	0.9500	C27—C28	1.3893 (19)
C6—C7	1.3914 (19)	C28—C29	1.3927 (19)
C6—H6	0.9500	C28—H28	0.9500
C7—H7	0.9500	C29—C30	1.389 (2)
C8—C13	1.3835 (17)	C29—H29	0.9500
C8—C9	1.3870 (18)	C30—C31	1.390 (2)
C9—C10	1.3886 (19)	C30—H30	0.9500
C9—H9	0.9500	C31—C32	1.3934 (19)
C10—C11	1.389 (2)	C31—H31	0.9500
C10—H10	0.9500	C32—H32	0.9500
C11—C12	1.391 (2)	C33—C38	1.3834 (18)
C11—H11	0.9500	C33—C34	1.3854 (17)
C12—C13	1.3922 (19)	C34—C35	1.3866 (19)
C12—H12	0.9500	C34—H34	0.9500
C13—H13	0.9500	C35—C36	1.394 (2)
C14—C15	1.3859 (18)	C35—H35	0.9500
C14—C19	1.3877 (18)	C36—C37	1.391 (2)
C15—C16	1.387 (2)	C36—H36	0.9500
C15—H15	0.9500	C37—C38	1.3902 (19)
C16—C17	1.394 (2)	C37—H37	0.9500
C16—H16	0.9500	C38—H38	0.9500
C17—C18	1.387 (2)	O1—H1W	0.851 (14)
C17—H17	0.9500	O1—H2W	0.853 (14)
C18—C19	1.387 (2)	O2—H3W	0.836 (14)
C18—H18	0.9500	O2—H4W	0.838 (14)
C19—H19	0.9500	O3—H5W	0.849 (14)
N5—N6	1.3066 (15)	O3—H6W	0.849 (14)
N5—C20	1.3498 (16)	O4—H7W	0.852 (14)
N6—N7	1.3324 (14)	O4—H8W	0.849 (14)
N6—C27	1.4404 (16)	O5—H9W	0.857 (14)
N7—N8	1.3103 (14)	O5—H10W	0.854 (14)

N2—N1—C1	103.93 (10)	N7—N6—C27	124.54 (10)
N1—N2—N3	110.20 (10)	N8—N7—N6	110.23 (10)
N1—N2—C8	122.11 (10)	N8—N7—C33	124.23 (10)
N3—N2—C8	127.63 (10)	N6—N7—C33	125.03 (10)
N4—N3—N2	109.93 (10)	N7—N8—C20	103.56 (10)
N4—N3—C14	123.73 (10)	N8—C20—N5	112.38 (11)
N2—N3—C14	126.34 (10)	N8—C20—C21	123.45 (11)
N3—N4—C1	103.88 (10)	N5—C20—C21	124.09 (11)
N1—C1—N4	112.03 (11)	C22—C21—C26	120.79 (12)
N1—C1—C2	122.91 (11)	C22—C21—C20	119.33 (11)
N4—C1—C2	125.05 (11)	C26—C21—C20	119.83 (12)
C7—C2—C3	120.57 (12)	C23—C22—C21	119.41 (13)
C7—C2—C1	120.39 (11)	C23—C22—H22	120.3
C3—C2—C1	119.04 (12)	C21—C22—H22	120.3
C4—C3—C2	119.40 (13)	C24—C23—C22	120.09 (15)
C4—C3—H3	120.3	C24—C23—H23	120.0
C2—C3—H3	120.3	C22—C23—H23	120.0
C5—C4—C3	120.02 (13)	C25—C24—C23	120.21 (14)
C5—C4—H4	120.0	C25—C24—H24	119.9
C3—C4—H4	120.0	C23—C24—H24	119.9
C4—C5—C6	120.46 (13)	C24—C25—C26	120.37 (13)
C4—C5—H5	119.8	C24—C25—H25	119.8
C6—C5—H5	119.8	C26—C25—H25	119.8
C5—C6—C7	120.12 (14)	C25—C26—C21	119.12 (13)
C5—C6—H6	119.9	C25—C26—H26	120.4
C7—C6—H6	119.9	C21—C26—H26	120.4
C6—C7—C2	119.40 (13)	C32—C27—C28	123.81 (12)
C6—C7—H7	120.3	C32—C27—N6	117.50 (12)
C2—C7—H7	120.3	C28—C27—N6	118.68 (11)
C13—C8—C9	123.75 (12)	C27—C28—C29	117.38 (13)
C13—C8—N2	120.11 (11)	C27—C28—H28	121.3
C9—C8—N2	115.91 (11)	C29—C28—H28	121.3
C8—C9—C10	117.88 (12)	C30—C29—C28	120.35 (14)
C8—C9—H9	121.1	C30—C29—H29	119.8
C10—C9—H9	121.1	C28—C29—H29	119.8
C9—C10—C11	120.09 (13)	C29—C30—C31	120.68 (13)
C9—C10—H10	120.0	C29—C30—H30	119.7
C11—C10—H10	120.0	C31—C30—H30	119.7
C10—C11—C12	120.44 (13)	C30—C31—C32	120.33 (14)
C10—C11—H11	119.8	C30—C31—H31	119.8
C12—C11—H11	119.8	C32—C31—H31	119.8
C11—C12—C13	120.70 (13)	C27—C32—C31	117.43 (14)
C11—C12—H12	119.7	C27—C32—H32	121.3
C13—C12—H12	119.7	C31—C32—H32	121.3
C8—C13—C12	117.14 (12)	C38—C33—C34	123.74 (12)
C8—C13—H13	121.4	C38—C33—N7	118.40 (11)
C12—C13—H13	121.4	C34—C33—N7	117.82 (11)
C15—C14—C19	123.67 (12)	C33—C34—C35	117.50 (12)
C15—C14—N3	118.95 (11)	C33—C34—H34	121.3
C19—C14—N3	117.34 (11)	C35—C34—H34	121.3
C14—C15—C16	117.46 (13)	C34—C35—C36	120.40 (12)
C14—C15—H15	121.3	C34—C35—H35	119.8
C16—C15—H15	121.3	C36—C35—H35	119.8
C15—C16—C17	120.35 (14)	C37—C36—C35	120.51 (13)
C15—C16—H16	119.8	C37—C36—H36	119.7
C17—C16—H16	119.8	C35—C36—H36	119.7
C18—C17—C16	120.54 (13)	C38—C37—C36	120.04 (13)
C18—C17—H17	119.7	C38—C37—H37	120.0
C16—C17—H17	119.7	C36—C37—H37	120.0
C19—C18—C17	120.35 (14)	C33—C38—C37	117.80 (12)
C19—C18—H18	119.8	C33—C38—H38	121.1
C17—C18—H18	119.8	C37—C38—H38	121.1
C18—C19—C14	117.61 (13)	H1W—O1—H2W	105 (2)
C18—C19—H19	121.2	H3W—O2—H4W	103 (2)
C14—C19—H19	121.2	H5W—O3—H6W	110 (2)
N6—N5—C20	103.54 (10)	H7W—O4—H8W	105 (2)
N5—N6—N7	110.29 (10)	H9W—O5—H10W	103 (2)
N5—N6—C27	125.17 (10)

C1—N1—N2—N3	−1.18 (13)	C20—N5—N6—N7	0.02 (13)
C1—N1—N2—C8	176.26 (11)	C20—N5—N6—C27	179.94 (11)
N1—N2—N3—N4	1.26 (14)	N5—N6—N7—N8	0.34 (14)
C8—N2—N3—N4	−175.99 (11)	C27—N6—N7—N8	−179.58 (11)
N1—N2—N3—C14	−178.51 (11)	N5—N6—N7—C33	−171.74 (11)
C8—N2—N3—C14	4.2 (2)	C27—N6—N7—C33	8.34 (18)
N2—N3—N4—C1	−0.74 (13)	N6—N7—N8—C20	−0.53 (13)
C14—N3—N4—C1	179.04 (11)	C33—N7—N8—C20	171.62 (11)
N2—N1—C1—N4	0.73 (14)	N7—N8—C20—N5	0.56 (14)
N2—N1—C1—C2	−178.88 (11)	N7—N8—C20—C21	−176.25 (11)
N3—N4—C1—N1	0.00 (14)	N6—N5—C20—N8	−0.37 (14)
N3—N4—C1—C2	179.60 (12)	N6—N5—C20—C21	176.42 (11)
N1—C1—C2—C7	−167.19 (12)	N8—C20—C21—C22	152.30 (13)
N4—C1—C2—C7	13.25 (19)	N5—C20—C21—C22	−24.14 (19)
N1—C1—C2—C3	12.26 (19)	N8—C20—C21—C26	−24.95 (19)
N4—C1—C2—C3	−167.30 (13)	N5—C20—C21—C26	158.61 (12)
C7—C2—C3—C4	0.7 (2)	C26—C21—C22—C23	−0.4 (2)
C1—C2—C3—C4	−178.73 (12)	C20—C21—C22—C23	−177.66 (13)
C2—C3—C4—C5	0.7 (2)	C21—C22—C23—C24	−0.1 (2)
C3—C4—C5—C6	−1.6 (2)	C22—C23—C24—C25	0.4 (3)
C4—C5—C6—C7	1.0 (2)	C23—C24—C25—C26	−0.1 (2)
C5—C6—C7—C2	0.4 (2)	C24—C25—C26—C21	−0.4 (2)
C3—C2—C7—C6	−1.3 (2)	C22—C21—C26—C25	0.7 (2)
C1—C2—C7—C6	178.16 (12)	C20—C21—C26—C25	177.93 (12)
N1—N2—C8—C13	−128.71 (13)	N5—N6—C27—C32	57.53 (17)
N3—N2—C8—C13	48.25 (18)	N7—N6—C27—C32	−122.57 (13)
N1—N2—C8—C9	45.93 (17)	N5—N6—C27—C28	−122.66 (14)
N3—N2—C8—C9	−137.11 (13)	N7—N6—C27—C28	57.24 (17)
C13—C8—C9—C10	−0.1 (2)	C32—C27—C28—C29	0.5 (2)
N2—C8—C9—C10	−174.54 (12)	N6—C27—C28—C29	−179.33 (12)
C8—C9—C10—C11	−0.8 (2)	C27—C28—C29—C30	0.3 (2)
C9—C10—C11—C12	0.8 (2)	C28—C29—C30—C31	−0.9 (2)
C10—C11—C12—C13	0.0 (2)	C29—C30—C31—C32	0.7 (2)
C9—C8—C13—C12	0.9 (2)	C28—C27—C32—C31	−0.6 (2)
N2—C8—C13—C12	175.12 (12)	N6—C27—C32—C31	179.15 (12)
C11—C12—C13—C8	−0.9 (2)	C30—C31—C32—C27	0.1 (2)
N4—N3—C14—C15	−129.44 (13)	N8—N7—C33—C38	68.04 (16)
N2—N3—C14—C15	50.30 (18)	N6—N7—C33—C38	−120.96 (13)
N4—N3—C14—C19	48.26 (17)	N8—N7—C33—C34	−109.63 (14)
N2—N3—C14—C19	−132.00 (13)	N6—N7—C33—C34	61.37 (17)
C19—C14—C15—C16	1.1 (2)	C38—C33—C34—C35	0.3 (2)
N3—C14—C15—C16	178.63 (12)	N7—C33—C34—C35	177.85 (11)
C14—C15—C16—C17	−1.8 (2)	C33—C34—C35—C36	−0.5 (2)
C15—C16—C17—C18	1.0 (2)	C34—C35—C36—C37	0.4 (2)
C16—C17—C18—C19	0.6 (2)	C35—C36—C37—C38	−0.1 (2)
C17—C18—C19—C14	−1.3 (2)	C34—C33—C38—C37	−0.1 (2)
C15—C14—C19—C18	0.4 (2)	N7—C33—C38—C37	−177.58 (12)
N3—C14—C19—C18	−177.15 (13)	C36—C37—C38—C33	−0.1 (2)

Hydrogen-bond geometry (Å, º) top

Cg6 is the centroid of the C21–C26 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···Cl2ⁱ	0.85 (1)	2.30 (1)	3.1483 (12)	178 (2)
O1—H2W···N4	0.85 (1)	2.34 (2)	3.1605 (15)	160 (2)
O2—H3W···Cl2	0.84 (1)	2.30 (1)	3.1302 (12)	176 (2)
O2—H4W···Cl2ⁱⁱ	0.84 (1)	2.34 (1)	3.1740 (12)	175 (2)
O3—H5W···O2	0.85 (1)	1.98 (1)	2.8246 (16)	175 (2)
O3—H6W···O5	0.85 (1)	2.16 (2)	3.0040 (17)	171 (2)
O4—H7W···Cl1ⁱⁱⁱ	0.85 (1)	2.32 (2)	3.1687 (14)	179 (3)
O4—H8W···Cl1	0.85 (1)	2.35 (2)	3.2008 (14)	178 (2)
O5—H9W···O4ⁱⁱ	0.86 (1)	1.90 (1)	2.7503 (17)	175 (2)
O5—H10W···Cg6	0.85 (1)	2.76 (2)	3.4646 (14)	141 (2)
C4—H4···O2^iv	0.95	2.55	3.461 (2)	160
C11—H11···O5^v	0.95	2.59	3.429 (2)	147
C15—H15···Cl1	0.95	2.82	3.6219 (14)	143
C16—H16···O5ⁱⁱ	0.95	2.48	3.4084 (19)	165
C17—H17···O2ⁱⁱ	0.95	2.42	3.359 (2)	168
C26—H26···O5^vi	0.95	2.50	3.4440 (19)	173

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

Funding information

Research reported in this publication was supported by the National Science Foundation (NSF) under grant No. 1736136, CREST Center for Next Generation Multifunctional Composites (NextGen Composites Phase II). Purchase of the diffractometer was funded by NSF MRI award CHE-2215262. The contents of this article are solely the responsibility of authors and do not represent the official views of the NSF.

References

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