Hexa­aqua­zinc(II) dinitrate bis­[5-(pyridinium-3-yl)tetra­zol-1-ide]

Chi-Duran, I.; Enriquez, J.; Vega, A.; Herrera, F.; Pratap Singh, D.

doi:10.1107/S205698901801112X

research communications

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ISSN: 2056-9890

Volume 74| Part 9| September 2018| Pages 1231-1234

https://doi.org/10.1107/S205698901801112X

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Hexaaquazinc(II) dinitrate bis[5-(pyridinium-3-yl)tetrazol-1-ide]

Ignacio Chi-Duran,^a Javier Enriquez,^a Andres Vega,^b Felipe Herrera ^a,^c and Dinesh Pratap Singh ^a,^c ^*

^aDepartment of Physics, University of Santiago, Av. Ecuador 3493, Estación Central, Santiago, Chile, ^bDepartamento de Ciencias Quimicas, Universidad Nacional Andres Bello, Av Republica 275 3er Piso, Santiago, Region Metropolitana, Chile, and ^cMillennium Institute for Research in Optics (MIRO), Chile
^*Correspondence e-mail: singh.dinesh@usach.cl

Edited by A. M. Chippindale, University of Reading, England (Received 29 May 2018; accepted 3 August 2018; online 14 August 2018)

Hexaaquazinc(II) dinitrate 5-(pyridinium-3-yl)tetrazol-1-ide, [Zn(H₂O)₆](NO₃)₂·2C₆H₅N₅, crystallizes in the space group P $[\overline{1}]$ . The asymmetric unit contains one zwitterionic 5-(pyridinium-3-yl)tetrazol-1-ide molecule, one NO₃⁻ anion and one half of a [Zn(H₂O)₆]²⁺ cation ( $[\overline{1}]$ symmetry). The pyridinium and tetrazolide rings in the zwitterion are nearly coplanar, with a dihedral angle of 5.4 (2)°. Several O—H⋯N and N—H⋯O hydrogen-bonding interactions exist between the [Zn(H₂O)₆]²⁺ cation and the N atoms of the tetrazolide ring, and between the nitrate anions and the N—H groups of the pyridinium ring, respectively, giving rise to a three-dimensional network. The 5-(pyridinium-3-yl)tetrazol-1-ide molecules show parallel-displaced π–π stacking interactions; the centroid–centroid distance between adjacent tetrazolide rings is 3.6298 (6) Å and that between the pyridinium and tetrazolide rings is 3.6120 (5) Å.

Keywords: crystal stryucture; pyridin-3-yltetrazole; hexaaquazinc(II) complex; π–π stacking; hydrogen-bonding.

CCDC reference: 1860162

1. Chemical context

Tetrazole functional groups have attracted increased attention in recent years due to their use in drug design and their employment as isosteric subtitutents of carboxylic acids (Herr, 2002 ), as well as their ability to produce a large variety of metal–organic frameworks (MOFs) (Zhao et al., 2008 ; Chi-Duran et al., 2018 ). Push–pull tetrazole complexes with both electron-donor and electron-acceptor substituents have shown efficient second-order nonlinear optical activity in powdered samples (Masahiko et al., 1994 ), ferroelectric behaviour (Liu et al., 2015 ) and strong photoluminescence (Zhang et al., 2014 ). The in-situ synthesis of tetrazole compounds can be realized by the Demko–Sharpless method, in which zinc salts catalyze the cycloaddition reaction between sodium azide and nitrile compounds to form the tetrazole ring (Demko & Sharpless, 2001 ). In this work, pyridyltetrazole, synthesized at low pH using the Demko–Sharpless method, is cocrystallized in the presence of [Zn(H₂O)₆]²⁺ and NO₃⁻ ions, to obtain the title compound (Fig. 1).

Figure 1
The molecular structure of the asymmetric unit (plus the three water molecules of the hexaaquazinc cation generated by symmetry), showing the atom labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x, 2 − y, 2 − z.]

2. Structural commentary

The asymmetric unit of the title compound is composed of one 5-(pyridinium-3-yl)tetrazol-1-ide zwitterion, one NO₃⁻ anion and one half of a [Zn(H₂O)₆]²⁺ cation. The hexaaquazinc(II) complex exhibits regular octahedral geometry (Table 1), and the tetrazolide and pyridinium rings of the zwitterion are close to being coplanar, with a dihedral angle of 5.4 (2)° (Fig. 2). The geometric parameters of the tetrazolide ring are comparable to those in other reported tetrazole compounds (Mu et al., 2010 ; Dai & Chen, 2011a ,b ). The H atom attached to the N atom of the pyridine ring could not be located in the Fourier density map. Therefore, the H atom was placed in accordance with similar reported structures containing [Mg(H₂O)₆]X₂ (X = Cl⁻, Br⁻) cocrystallized with 5-(pyridinium-3-yl)tetrazol-1-ide (Dai & Chen, 2011a,b).

Table 1
Selected geometric parameters (Å, °)

Zn1—O3	2.0353 (11)	Zn1—O2ⁱ	2.1011 (12)
Zn1—O3ⁱ	2.0354 (11)	Zn1—O1ⁱ	2.1841 (11)
Zn1—O2	2.1011 (12)	Zn1—O1	2.1841 (11)

O3—Zn1—O2	90.01 (5)	O2—Zn1—O1ⁱ	92.10 (5)
O3—Zn1—O2ⁱ	89.99 (5)	O3—Zn1—O1	89.47 (4)
O3—Zn1—O1ⁱ	90.53 (4)	O2—Zn1—O1	87.90 (5)
Symmetry code: (i) -x, -y+2, -z+2.

Figure 2
Partial crystal packing of the title compound, showing the hydrogen-bonding interactions between [Zn(H₂O)₆]²⁺ and the tetrazolide ring. [Symmetry codes: (ii) −x + 1, −y + 1, −z + 1; (iii) −x + 1, −y + 2, −z + 1; (x) x, y − 1, z − 1; (xi) x + 1, y, z − 1.]

3. Supramolecular features

A three-dimensional network of hydrogen bonds involving the pyridinium–tetrazolide zwitterions, hexaaquazinc(II) complex cations and nitrate ions serves to hold the structure together (Table 2 and Fig. 3). The N atoms of the tetrazole ring interact with the octahedral complex, [Zn(H₂O)₆]²⁺, through O—H⋯N hydrogen bonds, exhibiting D⋯A distances in the range 2.7446 (17)–2.8589 (17) Å. Additionally, the pyridinium ring is involved in N—H⋯O hydrogen bonding to nitrate atom O4, with an N⋯O distance of 2.7384 (18) Å. These interactions are shown in the crystal packing diagram (Fig. 3). The structure also shows parallel-displaced π–π stacking interactions, which arise from partial overlap between the tetrazolide and pyridinium rings in adjacent zwitterions, and extend along the a axis parallel to the (010) plane. These parallel-displaced π–π interactions lead to interplanar distances of 3.21 (1) and 3.10 (3) Å, and two centroid–centroid distances (Table 3). The centroid–centroid distance between the tetrazolide groups is 3.6298 (6) Å and between the pyridinium and tetrazolide rings is 3.6120 (5) Å (Table 3 and Fig. 4).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯O5ⁱⁱ	0.85	1.96	2.8067 (17)	172
O1—H2W⋯N1ⁱⁱⁱ	0.85	1.96	2.8029 (17)	173
O2—H3W⋯N4^iv	0.85	2.02	2.8589 (17)	170
O2—H4W⋯O1^v	0.85	2.08	2.9228 (17)	171
O3—H5W⋯N3ⁱⁱ	0.85	1.91	2.7446 (17)	168
O3—H6W⋯N1^vi	0.85	2.72	3.4294 (17)	142
O3—H6W⋯N2^vi	0.85	1.97	2.8076 (17)	169
N5—H5N⋯N6^vii	0.82	2.61	3.344 (2)	149
N5—H5N⋯O4^vii	0.82	1.92	2.7384 (18)	173
N5—H5N⋯O5^vii	0.82	2.62	3.1347 (19)	123
C4—H4⋯O5^viii	0.93	2.65	3.452 (2)	145
C5—H5⋯O4^ix	0.93	2.52	3.292 (2)	141
C5—H5⋯O6^ix	0.93	2.52	3.422 (3)	165
C6—H6⋯O5^vii	0.93	2.41	3.047 (2)	126
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y+2, -z+1; (iv) x, y+1, z+1; (v) -x+1, -y+2, -z+2; (vi) x-1, y, z+1; (vii) x-1, y, z; (viii) x-1, y+1, z; (ix) -x, -y+1, -z+1.

Table 3
π–π stacking interaction lengths (Å)

Cg1 and Cg2 are the centroids of the C1/N1/N2/N3/N4 and C2–C6/N5 rings, respectively.

Centroid–centroid	Distance	Tetrazolide interplane distance
Cg1–Cg1ⁱⁱ	3.6298 (6)	3.23 (1)
Cg1–Cg2^vii	3.6120 (5)	3.10 (3)
Symmetry codes: (ii) −x + 1, −y + 1, −1 + z; (vii) x − 1, y, z.

Figure 3
The crystal packing of the title compound, viewed along the [100] direction, showing O—H⋯N and N—H⋯O interactions (cyan lines).

Figure 4
Partial crystal packing, showing π–π interactions between tetrazole and pyridinium rings, with d₁ = 3.6298 (6) Å and d₂ = 3.6120 (5) Å. [Symmetry codes: (ii) −x + 1, −y + 1, −1 + z; (vii) x − 1, y, z.]

4. Database survey

We found two previously reported structures that are closely related to the title compound. They both involve a hexaaquamagnesium(II) cation with a halide counter-ion [chloride (Dai & Chen, 2011b) or bromide (Dai & Chen, 2011a)] cocrystallized in the presence of 5-(pyridinium-3-yl)tetrazol-1-ide zwitterions (Dai & Chen, 2011a,b). There are more hydrogen-bonding interactions in our compound than in the [Mg(H₂O)₆]X₂·2C₆H₅N₅ structures, as more hexaaquazinc(II) complexes can interact with the N atoms of the tetrazole units. Parallel-displaced π–π stacking interactions occur in the title compound and in [Mg(H₂O)₆]X₂·2C₆H₅N₅. In [Mg(H₂O)₆]Cl₂·2C₆H₅N₅, the pyridinium–tetrazolide zwitterions have alternating orientations in the supramolecular arrangement, whereas in the title compound, the zwitterions are oriented in the same direction, allowing a possible coupling transition between dipole moments similar to J-aggregates (Spano, 2010 ).

5. Synthesis and crystallization

All the reactants and chemicals were purchased from Sigma Aldrich and utilized without further purification. A mixture of 3-cyanopyridine (4 mmol), NaN₃ (6 mmol) and ZnCl₂ (2 mmol) were dissolved in 6 ml of distilled water. This mixture was transferred to a glass bottle and then heated at 378 K for 24 h. The pH was adjusted using a HNO₃ (66%) solution immediately after mixing the reactants, and was monitored with a pH meter (pH2700 Oakton) until reaching a pH of 2.0. The reaction mixture was then cooled to 318 K and kept at this temperature for 16 h. The colourless block-shaped crystals obtained were washed with ethanol to give 353 mg (yield 30%) of the title compound.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All H atoms bonded to C atoms were positioned geometrically and treated as riding atoms, using C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). Moreover, all H atoms in the hexaaquazinc(II) complex were refined with a distance restraint of O—H = 0.85 Å and with U_iso(H) = 1.5U_eq(O).

Table 4
Experimental details

Crystal data
Chemical formula	[Zn(H₂O)₆](NO₃)₂·2C₆H₅N₅
M_r	591.81
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	5.6582 (11), 8.4632 (16), 12.046 (2)
α, β, γ (°)	97.209 (2), 91.123 (2), 93.949 (2)
V (Å³)	570.67 (19)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	1.16
Crystal size (mm)	0.49 × 0.21 × 0.09

Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Numerical (SADABS; Bruker, 2008 )
T_min, T_max	0.742, 0.903
No. of measured, independent and observed [I > 2σ(I)] reflections	4429, 2217, 2132
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.054, 1.08
No. of reflections	2217
No. of parameters	198
No. of restraints	13
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.35
Computer programs: SMART and SAINT (Bruker, 2008), SHELXTL (Sheldrick, 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Supporting information

CCDC reference: 1860162

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698901801112X/cq2025sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901801112X/cq2025Isup3.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Hexaaquazinc(II) dinitrate bis[5-(pyridinium-3-yl)tetrazol-1-ide] top

Crystal data top

[Zn(H₂O)₆](NO₃)₂·2C₆H₅N₅	Z = 1
M_r = 591.81	F(000) = 304
Triclinic, P1	D_x = 1.722 Mg m⁻³
a = 5.6582 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.4632 (16) Å	Cell parameters from 7831 reflections
c = 12.046 (2) Å	θ = 2.8–29.5°
α = 97.209 (2)°	µ = 1.16 mm⁻¹
β = 91.123 (2)°	T = 293 K
γ = 93.949 (2)°	Block, colorless
V = 570.67 (19) Å³	0.49 × 0.21 × 0.09 mm

Data collection top

Bruker SMART CCD area detector diffractometer	2132 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.013
phi and ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: numerical (SADABS; Bruker, 2008)	h = −6→6
T_min = 0.742, T_max = 0.903	k = −10→10
4429 measured reflections	l = −14→14
2217 independent reflections

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)] = 0.022	w = 1/[σ²(F_o²) + (0.0254P)² + 0.1986P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.054	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.37 e Å⁻³
2217 reflections	Δρ_min = −0.35 e Å⁻³
198 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
13 restraints	Extinction coefficient: 0.009 (2)

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
Zn1	0.0000	1.0000	1.0000	0.02186 (9)
O1	0.25606 (19)	1.00502 (12)	0.86692 (9)	0.0269 (2)
H1W	0.226 (4)	0.9463 (19)	0.8050 (8)	0.044 (6)*
H2W	0.303 (3)	1.0972 (10)	0.8515 (16)	0.041 (5)*
O2	0.2699 (2)	1.10732 (13)	1.11255 (11)	0.0345 (3)
H3W	0.307 (4)	1.2067 (5)	1.1282 (17)	0.048 (6)*
H4W	0.401 (2)	1.065 (3)	1.116 (2)	0.065 (7)*
O3	0.0981 (2)	0.78032 (12)	1.02590 (10)	0.0293 (2)
H5W	0.187 (3)	0.725 (2)	0.9825 (14)	0.051 (6)*
H6W	−0.008 (3)	0.7116 (19)	1.0423 (19)	0.059 (7)*
N1	0.5987 (2)	0.68143 (14)	0.16630 (10)	0.0246 (3)
N2	0.7365 (2)	0.58336 (15)	0.10516 (11)	0.0270 (3)
N3	0.6508 (2)	0.43523 (15)	0.10431 (11)	0.0296 (3)
N4	0.4544 (2)	0.43180 (14)	0.16488 (11)	0.0269 (3)
N5	−0.0918 (2)	0.58146 (17)	0.38266 (11)	0.0315 (3)
H5N	−0.180 (3)	0.5136 (17)	0.4067 (15)	0.042 (5)*
C1	0.4273 (2)	0.58463 (16)	0.20195 (12)	0.0212 (3)
C2	0.2376 (2)	0.64009 (17)	0.27458 (11)	0.0218 (3)
C3	0.2065 (3)	0.80168 (18)	0.30257 (13)	0.0284 (3)
H3A	0.3075	0.8778	0.2748	0.034*
C4	0.0250 (3)	0.8491 (2)	0.37189 (14)	0.0334 (4)
H4	0.0048	0.9570	0.3914	0.040*
C5	−0.1243 (3)	0.7363 (2)	0.41142 (14)	0.0345 (4)
H5	−0.2470	0.7668	0.4578	0.041*
C6	0.0827 (3)	0.53073 (19)	0.31686 (13)	0.0279 (3)
H6	0.0997	0.4219	0.2996	0.033*
N6	0.6295 (3)	0.22071 (16)	0.38657 (12)	0.0353 (3)
O4	0.5953 (2)	0.34960 (14)	0.44531 (11)	0.0442 (3)
O5	0.8117 (2)	0.21012 (15)	0.33009 (11)	0.0431 (3)
O6	0.4892 (4)	0.1062 (2)	0.38679 (19)	0.1001 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02070 (14)	0.01556 (13)	0.02905 (15)	0.00093 (8)	0.00394 (9)	0.00145 (9)
O1	0.0295 (6)	0.0203 (5)	0.0304 (6)	−0.0002 (4)	0.0092 (4)	0.0015 (4)
O2	0.0292 (6)	0.0230 (6)	0.0485 (7)	−0.0009 (5)	−0.0073 (5)	−0.0031 (5)
O3	0.0283 (6)	0.0193 (5)	0.0419 (6)	0.0056 (4)	0.0149 (5)	0.0063 (5)
N1	0.0232 (6)	0.0217 (6)	0.0282 (6)	−0.0018 (5)	0.0064 (5)	0.0013 (5)
N2	0.0232 (6)	0.0257 (7)	0.0315 (7)	0.0011 (5)	0.0082 (5)	0.0013 (5)
N3	0.0282 (7)	0.0241 (6)	0.0360 (7)	0.0024 (5)	0.0095 (6)	0.0006 (5)
N4	0.0268 (7)	0.0199 (6)	0.0333 (7)	−0.0005 (5)	0.0086 (5)	0.0006 (5)
N5	0.0275 (7)	0.0374 (8)	0.0295 (7)	−0.0062 (6)	0.0086 (6)	0.0067 (6)
C1	0.0217 (7)	0.0197 (7)	0.0214 (7)	−0.0017 (5)	0.0015 (5)	0.0014 (5)
C2	0.0218 (7)	0.0228 (7)	0.0199 (7)	−0.0015 (5)	0.0018 (5)	0.0002 (5)
C3	0.0311 (8)	0.0239 (7)	0.0285 (8)	−0.0041 (6)	0.0076 (6)	−0.0004 (6)
C4	0.0373 (9)	0.0279 (8)	0.0332 (8)	0.0044 (7)	0.0079 (7)	−0.0049 (6)
C5	0.0283 (8)	0.0457 (10)	0.0284 (8)	0.0044 (7)	0.0092 (6)	−0.0015 (7)
C6	0.0279 (8)	0.0255 (8)	0.0297 (8)	−0.0030 (6)	0.0055 (6)	0.0033 (6)
N6	0.0398 (8)	0.0279 (7)	0.0346 (8)	−0.0094 (6)	0.0107 (6)	−0.0048 (6)
O4	0.0508 (8)	0.0301 (6)	0.0480 (7)	−0.0067 (5)	0.0237 (6)	−0.0080 (5)
O5	0.0428 (7)	0.0333 (6)	0.0502 (8)	−0.0024 (5)	0.0194 (6)	−0.0063 (6)
O6	0.0959 (14)	0.0607 (11)	0.1238 (16)	−0.0531 (10)	0.0672 (13)	−0.0446 (11)

Geometric parameters (Å, º) top

Zn1—O3	2.0353 (11)	N4—C1	1.3345 (19)
Zn1—O3ⁱ	2.0354 (11)	N5—C6	1.339 (2)
Zn1—O2	2.1011 (12)	N5—C5	1.339 (2)
Zn1—O2ⁱ	2.1011 (12)	N5—H5N	0.8201 (11)
Zn1—O1ⁱ	2.1841 (11)	C1—C2	1.463 (2)
Zn1—O1	2.1841 (11)	C2—C6	1.381 (2)
O1—H1W	0.8500	C2—C3	1.391 (2)
O1—H2W	0.8499	C3—C4	1.385 (2)
O2—H3W	0.8499	C3—H3A	0.9300
O2—H4W	0.8499	C4—C5	1.367 (2)
O3—H5W	0.8499	C4—H4	0.9300
O3—H6W	0.8501	C5—H5	0.9300
N1—C1	1.3384 (18)	C6—H6	0.9300
N1—N2	1.3405 (18)	N6—O6	1.210 (2)
N2—N3	1.3113 (18)	N6—O5	1.2485 (18)
N3—N4	1.3421 (18)	N6—O4	1.2525 (18)

O3—Zn1—O3ⁱ	180.0	N2—N3—N4	109.65 (12)
O3—Zn1—O2	90.01 (5)	C1—N4—N3	104.64 (12)
O3ⁱ—Zn1—O2	89.99 (5)	C6—N5—C5	122.90 (14)
O3—Zn1—O2ⁱ	89.99 (5)	C6—N5—H5N	117.6 (14)
O3ⁱ—Zn1—O2ⁱ	90.01 (5)	C5—N5—H5N	119.5 (14)
O2—Zn1—O2ⁱ	180.0	N4—C1—N1	111.53 (13)
O3—Zn1—O1ⁱ	90.53 (4)	N4—C1—C2	124.52 (13)
O3ⁱ—Zn1—O1ⁱ	89.47 (4)	N1—C1—C2	123.93 (13)
O2—Zn1—O1ⁱ	92.10 (5)	C6—C2—C3	118.26 (14)
O2ⁱ—Zn1—O1ⁱ	87.90 (5)	C6—C2—C1	119.94 (13)
O3—Zn1—O1	89.47 (4)	C3—C2—C1	121.80 (13)
O3ⁱ—Zn1—O1	90.53 (4)	C4—C3—C2	119.93 (14)
O2—Zn1—O1	87.90 (5)	C4—C3—H3A	120.0
O2ⁱ—Zn1—O1	92.10 (5)	C2—C3—H3A	120.0
O1ⁱ—Zn1—O1	180.0	C5—C4—C3	119.67 (15)
Zn1—O1—H1W	118.9 (14)	C5—C4—H4	120.2
Zn1—O1—H2W	115.7 (13)	C3—C4—H4	120.2
H1W—O1—H2W	107.0 (18)	N5—C5—C4	119.30 (15)
Zn1—O2—H3W	126.7 (15)	N5—C5—H5	120.3
Zn1—O2—H4W	120.1 (17)	C4—C5—H5	120.3
H3W—O2—H4W	104 (2)	N5—C6—C2	119.93 (15)
Zn1—O3—H5W	123.7 (14)	N5—C6—H6	120.0
Zn1—O3—H6W	118.5 (15)	C2—C6—H6	120.0
H5W—O3—H6W	103 (2)	O6—N6—O5	120.33 (15)
C1—N1—N2	104.70 (12)	O6—N6—O4	120.02 (15)
N3—N2—N1	109.48 (11)	O5—N6—O4	119.63 (13)

C1—N1—N2—N3	0.11 (16)	N1—C1—C2—C3	7.1 (2)
N1—N2—N3—N4	−0.01 (17)	C6—C2—C3—C4	0.5 (2)
N2—N3—N4—C1	−0.09 (17)	C1—C2—C3—C4	−179.80 (14)
N3—N4—C1—N1	0.17 (17)	C2—C3—C4—C5	−0.7 (3)
N3—N4—C1—C2	−178.53 (13)	C6—N5—C5—C4	0.5 (3)
N2—N1—C1—N4	−0.18 (16)	C3—C4—C5—N5	0.2 (3)
N2—N1—C1—C2	178.53 (13)	C5—N5—C6—C2	−0.7 (2)
N4—C1—C2—C6	5.4 (2)	C3—C2—C6—N5	0.2 (2)
N1—C1—C2—C6	−173.17 (14)	C1—C2—C6—N5	−179.53 (13)
N4—C1—C2—C3	−174.32 (15)

Symmetry code: (i) −x, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O5ⁱⁱ	0.85	1.96	2.8067 (17)	172
O1—H2W···N1ⁱⁱⁱ	0.85	1.96	2.8029 (17)	173
O2—H3W···N4^iv	0.85	2.02	2.8589 (17)	170
O2—H4W···O1^v	0.85	2.08	2.9228 (17)	171
O3—H5W···N3ⁱⁱ	0.85	1.91	2.7446 (17)	168
O3—H6W···N1^vi	0.85	2.72	3.4294 (17)	142
O3—H6W···N2^vi	0.85	1.97	2.8076 (17)	169
N5—H5N···N6^vii	0.82	2.61	3.344 (2)	149
N5—H5N···O4^vii	0.82	1.92	2.7384 (18)	173
N5—H5N···O5^vii	0.82	2.62	3.1347 (19)	123
C4—H4···O5^viii	0.93	2.65	3.452 (2)	145
C5—H5···O4^ix	0.93	2.52	3.292 (2)	141
C5—H5···O6^ix	0.93	2.52	3.422 (3)	165
C6—H6···O5^vii	0.93	2.41	3.047 (2)	126

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

π–π stacking interaction lengths (Å) top

Centroid–centroid	Distance	Tetrazolide interplane distance
Cg1–Cg1ⁱⁱ	3.6298 (6)	3.23 (1)
Cg1–Cg2^vii	3.6120 (5)	3.10 (3)

Symmetry codes: (ii) -x+1, -y+1, -1+z; (vii) x-1, y, z.

Funding information

Funding for this research was provided by: Fondecyt Regular (award No. 1151527); Proyecto REDES ETAPA INICIAL, Convocatoria 2017 (award No. REDI170423); Millennium Institute for Research in Optics (MIRO); Basal USA (award No. 1799).

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