Pyridin-4-ylmethanaminium perchlorate mono­hydrate

Seidel, R.W.; Kolev, T.M.

doi:10.1107/S2414314623004595

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 5| May 2023| x230459

https://doi.org/10.1107/S2414314623004595

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Pyridin-4-ylmethanaminium perchlorate monohydrate

Rüdiger W. Seidel ^a ^* and Tsonko M. Kolev ^b

^aInstitut für Pharmazie, Martin-Luther-Universität Halle-Wittenberg, Wolfgang-Langenbeck-Str. 4, 06120 Halle (Saale), Germany, and ^bInstitute of Molecular Biology "Roumen Tsanev", Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Bl. 21, Sofia 1113, Bulgaria
^*Correspondence e-mail: ruediger.seidel@pharmazie.uni-halle.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 19 May 2023; accepted 24 May 2023; online 26 May 2023)

Pyridin-4-ylmethanaminium perchlorate monohydrate (synonym: 4-picolylammonium perchlorate monohydrate), C₆H₉N₂⁺·ClO₄⁻·H₂O, crystallizes in the monoclinic system (space group P2₁/n) with the asymmetric unit comprising two formula units (Z′ = 2). All molecular entities are located on general positions. The two crystallographically distinct 4-picolylammonium cations exhibit different conformations. The two unique perchlorate anions are non-disordered, showing an r.m.s. deviation of 0.011 Å from molecular T_d symmetry. The supramolecular structure in the solid state features an intricate tri-periodic network of N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds.

Keywords: crystal structure; 4-picolylamine; perchlorate; conformation; heterocycle; hydrogen bonding.

CCDC reference: 2265167

Structure description

The number of structurally characterized 1:1 salts of the feedstock chemical 4-picolylamine is limited. A search of the Cambridge Structural Database (CSD, version 5.43 with November 2022 updates; Groom et al., 2016 ) revealed nine crystal structures: the hydrogen chloride (CSD refcode: QANWOS; de Vries et al., 2005 ) and hydrogen bromide (TENDUP; Zuffa et al., 2023 ), substituted benzoic acid salts (TOHYEV, TOHYIZ; Lemmerer et al., 2008 and WEBXAE; Ding et al., 2012 ), group 10 tetracyanidometallates (OFEWUT, OFEXII and OFEXUU; Karaağaç et al., 2013 ) and a decavanadate (HEBJOR; Msaadi et al., 2022 ). We herein report the crystal structure of the monohydrate of the perchlorate salt of 4-picolylamine, (1).

As shown in Fig. 1, the asymmetric unit of (1) comprises two formula units C₆H₉N₂⁺ClO₄⁻·H₂O (Z′ = 2). The amino group of 4-picolylamine, which is the more basic site (pK_a = 8.30; Milletti et al., 2010 ) compared to the pyridine nitrogen atom, is in a protonated state. The two crystallographically distinct 4-picolylammonium cations differ in their conformations. The C3—C4—C7—N2 torsion angle is 67.4 (3)° in molecule 1 and 13.2 (3)° in molecule 2. The difference is ascribable to intermolecular interactions and packing effects in the solid state. In the nine crystal structures containing 4-picolylammonium ions deposited with the CSD, the torsion angles range from 6.4° in HEBJOR to 88.5° in WEBXAE, indicating great conformational flexibility. The molecular structure of cation 2 in (1) exhibits an r.m.s. deviation from C_S point group symmetry of 0.082 Å, as calculated with MOLSYM in PLATON (Spek, 2020 ). The two crystallographically distinct perchlorate anions are non-disordered, both showing an r.m.s. deviation of 0.011 Å from molecular T_d point group symmetry.

Figure 1
Asymmetric unit of (1). Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are represented by small spheres of arbitrary radius. The number after the underscore indicates unique molecules 1 and 2 in each case. Dashed lines represent O—H⋯O and O—H⋯N hydrogen bonds.

Apart from Coulombic interactions, the supramolecular structure in (1) is dominated by classical N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds. Fig. 2 depicts a part of the crystal structure, illustrating the crystallographically unique hydrogen bonds. As hydrogen-bond donors, the water molecules join the 4-picolylammonium and perchlorate ions through O—H⋯N_pyridine and O—H⋯O hydrogen bonds, respectively. Towards the protonated amino groups, the water molecules act as hydrogen-bond acceptors for N—H⋯O hydrogen bonds, resulting in hydrogen-bonded chains propagating parallel to the c-axis direction. The remaining hydrogen-bond donor sites of the 4-picolylammonium ions form donating bifurcated N—H⋯O hydrogen bonds to perchlorate oxygen atoms, resulting in an intricate tri-periodic network. Table 1 lists numerical details of the relevant hydrogen bonds in (1), which are characteristic of strong hydrogen bonds (Thakuria et al., 2017 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2_1—H2A_1⋯O5_1ⁱ	0.90 (2)	1.96 (2)	2.862 (3)	176 (2)
N2_1—H2B_1⋯O1_1ⁱⁱ	0.90 (2)	2.20 (2)	2.916 (2)	136 (2)
N2_1—H2B_1⋯O4_2ⁱⁱⁱ	0.90 (2)	2.32 (2)	2.924 (2)	125 (2)
N2_1—H2C_1⋯O5_2^iv	0.90 (2)	1.95 (2)	2.838 (3)	168 (2)
O5_1—H5A_1⋯N1_2	0.84 (2)	1.91 (2)	2.751 (2)	176 (3)
O5_1—H5B_1⋯O1_2	0.83 (2)	2.21 (2)	2.986 (2)	156 (3)
N2_2—H2A_2⋯O5_1^iv	0.92 (2)	1.92 (2)	2.839 (3)	173 (2)
N2_2—H2B_2⋯O4_1ⁱⁱⁱ	0.91 (2)	2.42 (2)	3.079 (3)	130 (2)
N2_2—H2B_2⋯O1_2ⁱⁱⁱ	0.91 (2)	2.19 (2)	2.979 (2)	144 (2)
N2_2—H2C_2⋯O5_2^iv	0.90 (2)	1.98 (2)	2.872 (3)	177 (2)
O5_2—H5A_2⋯N1_1	0.83 (2)	1.93 (2)	2.761 (2)	175 (3)
O5_2—H5B_2⋯O1_1	0.83 (2)	2.09 (2)	2.874 (2)	160 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Part of the crystal structure of (1) viewed approximately along the a-axis direction towards the origin, showing N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds (dashed lines). The number after the underscore indicates unique molecules 1 and 2 in each case. Carbon-bound hydrogen atoms are omitted for clarity. Symmetry codes refer to Table 1

Synthesis and crystallization

Compound (1) was synthesized by adding a solution of 4-picolylamine (216 mg, 2 mmol) in 40 ml of ethanol to 40 ml of 0.1 M perchloric acid. The reaction mixture was stirred for 4 h at room temperature and then left at ambient conditions. After one week, the precipitate was collected by filtration and air-dried. Colourless crystals of (1) suitable for X-ray diffraction were grown from a methanol/water solution at room temperature over a period of three weeks, while the solvents were allowed to evaporate slowly. Caution: organic perchlorate salts are potentially explosive and should be handled with care!

Refinement

Crystal data, data collection and structure refinement details are listed in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·ClO₄⁻·H₂O
M_r	226.62
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	110
a, b, c (Å)	9.1239 (2), 22.1397 (6), 9.5463 (3)
β (°)	101.799 (3)
V (Å³)	1887.62 (9)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.41
Crystal size (mm)	0.28 × 0.20 × 0.10

Data collection
Diffractometer	Xcalibur2, Oxford Diffraction
Absorption correction	Multi-scan (ABSPACK in CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.894, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16791, 4422, 3163
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.679

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.101, 1.04
No. of reflections	4422
No. of parameters	299
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.42
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2018 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2265167

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314623004595/wm4189sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623004595/wm4189Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314623004595/wm4189Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314623004595/wm4189Isup4.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2022); cell refinement: CrysAlis PRO (Rigaku OD, 2022); data reduction: CrysAlis PRO (Rigaku OD, 2022); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2018); software used to prepare material for publication: publCIF (Westrip, 2010).

Pyridin-4-ylmethanaminium perchlorate monohydrate top

Crystal data top

C₆H₉N₂⁺·ClO₄⁻·H₂O	F(000) = 944
M_r = 226.62	D_x = 1.595 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.1239 (2) Å	Cell parameters from 4316 reflections
b = 22.1397 (6) Å	θ = 3.6–28.4°
c = 9.5463 (3) Å	µ = 0.41 mm⁻¹
β = 101.799 (3)°	T = 110 K
V = 1887.62 (9) Å³	Prism, colourless
Z = 8	0.28 × 0.20 × 0.10 mm

Data collection top

Xcalibur2, Oxford Diffraction diffractometer	4422 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3163 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 8.4171 pixels mm^-1	θ_max = 28.9°, θ_min = 2.8°
ω scans	h = −12→11
Absorption correction: multi-scan (ABSPACK in CrysAlisPro; Rigaku OD, 2022)	k = −29→27
T_min = 0.894, T_max = 1.000	l = −11→12
16791 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: mixed
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0371P)² + 1.2652P] where P = (F_o² + 2F_c²)/3
4422 reflections	(Δ/σ)_max < 0.001
299 parameters	Δρ_max = 0.44 e Å⁻³
10 restraints	Δρ_min = −0.42 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.

Refinement. Nitrogen-bound and water hydrogen atoms were located from difference-Fourier maps and were refined with N—H and O—H distances restrained to target values of 0.91 (2) and 0.84 (2) Å, respectively. The respective U_iso(H) values were refined freely.

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

	x	y	z	U_iso*/U_eq
C2_1	0.5915 (3)	0.25285 (10)	0.3275 (3)	0.0236 (5)
H2_1	0.613952	0.219921	0.392116	0.028*
C3_1	0.6384 (3)	0.30978 (10)	0.3757 (3)	0.0211 (5)
H3_1	0.691704	0.315629	0.471201	0.025*
C4_1	0.6065 (2)	0.35838 (9)	0.2826 (2)	0.0173 (5)
C5_1	0.5272 (3)	0.34736 (10)	0.1463 (3)	0.0235 (5)
H5_1	0.501877	0.379550	0.080013	0.028*
C6_1	0.4846 (3)	0.28865 (11)	0.1070 (3)	0.0260 (6)
H6_1	0.429816	0.281688	0.012509	0.031*
C7_1	0.6564 (3)	0.42157 (10)	0.3275 (3)	0.0206 (5)
H7A_1	0.610755	0.450463	0.251989	0.025*
H7B_1	0.622219	0.432207	0.416360	0.025*
N1_1	0.5162 (2)	0.24152 (8)	0.1945 (2)	0.0214 (4)
N2_1	0.8230 (2)	0.42629 (9)	0.3526 (2)	0.0171 (4)
H2A_1	0.854 (3)	0.4114 (11)	0.276 (2)	0.027 (7)*
H2B_1	0.853 (3)	0.4645 (8)	0.371 (3)	0.020 (6)*
H2C_1	0.861 (3)	0.4058 (11)	0.434 (2)	0.034 (8)*
Cl1_1	0.71953 (6)	0.05644 (2)	0.38455 (5)	0.01373 (13)
O1_1	0.70326 (17)	0.05322 (6)	0.23033 (16)	0.0180 (3)
O2_1	0.7178 (2)	0.11825 (7)	0.42615 (17)	0.0287 (4)
O3_1	0.85768 (17)	0.02837 (7)	0.45115 (18)	0.0251 (4)
O4_1	0.59712 (18)	0.02479 (8)	0.42438 (18)	0.0268 (4)
O5_1	0.43372 (18)	0.11734 (7)	0.61174 (17)	0.0181 (3)
H5A_1	0.453 (3)	0.1534 (9)	0.638 (3)	0.041 (9)*
H5B_1	0.513 (2)	0.0983 (12)	0.620 (3)	0.042 (9)*
C2_2	0.6473 (3)	0.24806 (10)	0.7655 (3)	0.0221 (5)
H2_2	0.716822	0.216114	0.792595	0.027 (7)*
C3_2	0.6939 (3)	0.30644 (10)	0.8024 (2)	0.0195 (5)
H3_2	0.792866	0.313941	0.853765	0.026 (7)*
C4_2	0.5946 (2)	0.35391 (9)	0.7636 (2)	0.0160 (5)
C5_2	0.4506 (3)	0.33949 (10)	0.6910 (2)	0.0202 (5)
H5_2	0.378075	0.370385	0.663996	0.020 (6)*
C6_2	0.4143 (3)	0.28017 (10)	0.6587 (2)	0.0218 (5)
H6_2	0.315601	0.271289	0.608434	0.025 (7)*
C7_2	0.6330 (2)	0.41931 (10)	0.7943 (3)	0.0193 (5)
H7A_2	0.594521	0.443333	0.707070	0.018 (6)*
H7B_2	0.581862	0.433608	0.870188	0.022 (6)*
N1_2	0.5099 (2)	0.23416 (8)	0.6940 (2)	0.0218 (4)
N2_2	0.7960 (2)	0.43016 (9)	0.8405 (2)	0.0175 (4)
H2A_2	0.833 (3)	0.4138 (10)	0.9295 (19)	0.022 (6)*
H2B_2	0.818 (3)	0.4699 (8)	0.854 (3)	0.028 (7)*
H2C_2	0.841 (3)	0.4149 (11)	0.773 (2)	0.033 (8)*
Cl1_2	0.72640 (6)	0.05939 (2)	0.88521 (5)	0.01431 (13)
O1_2	0.72928 (19)	0.06090 (7)	0.73443 (17)	0.0231 (4)
O2_2	0.67297 (19)	0.11607 (7)	0.92682 (17)	0.0224 (4)
O3_2	0.87356 (17)	0.04688 (7)	0.96603 (18)	0.0249 (4)
O4_2	0.62605 (18)	0.01185 (7)	0.90900 (17)	0.0234 (4)
O5_2	0.43738 (18)	0.12300 (7)	0.12765 (17)	0.0181 (3)
H5A_2	0.458 (3)	0.1593 (8)	0.142 (3)	0.044 (9)*
H5B_2	0.518 (2)	0.1049 (12)	0.137 (3)	0.049 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2_1	0.0233 (12)	0.0177 (11)	0.0287 (14)	0.0016 (10)	0.0028 (10)	0.0043 (10)
C3_1	0.0231 (13)	0.0192 (11)	0.0199 (12)	0.0000 (10)	0.0016 (10)	0.0005 (9)
C4_1	0.0121 (10)	0.0149 (11)	0.0257 (13)	0.0010 (9)	0.0056 (9)	0.0017 (9)
C5_1	0.0205 (12)	0.0223 (12)	0.0253 (13)	−0.0012 (10)	−0.0009 (10)	0.0089 (10)
C6_1	0.0226 (13)	0.0297 (13)	0.0227 (13)	−0.0063 (11)	−0.0024 (10)	0.0006 (10)
C7_1	0.0164 (11)	0.0143 (11)	0.0321 (14)	0.0005 (9)	0.0070 (10)	−0.0004 (9)
N1_1	0.0172 (10)	0.0190 (10)	0.0279 (12)	−0.0034 (8)	0.0042 (9)	−0.0031 (8)
N2_1	0.0198 (10)	0.0133 (10)	0.0180 (11)	−0.0027 (8)	0.0036 (8)	−0.0018 (8)
Cl1_1	0.0121 (2)	0.0130 (2)	0.0158 (3)	0.0005 (2)	0.00203 (19)	0.0011 (2)
O1_1	0.0223 (8)	0.0173 (8)	0.0146 (8)	0.0006 (7)	0.0041 (7)	0.0003 (6)
O2_1	0.0453 (11)	0.0146 (8)	0.0230 (9)	0.0030 (8)	−0.0003 (8)	−0.0031 (7)
O3_1	0.0149 (8)	0.0331 (10)	0.0259 (9)	0.0092 (7)	0.0004 (7)	0.0041 (7)
O4_1	0.0186 (9)	0.0366 (10)	0.0254 (10)	−0.0081 (8)	0.0048 (7)	0.0079 (8)
O5_1	0.0170 (8)	0.0149 (8)	0.0217 (9)	0.0018 (7)	0.0021 (7)	−0.0022 (7)
C2_2	0.0209 (12)	0.0160 (11)	0.0289 (14)	0.0022 (10)	0.0042 (10)	0.0025 (10)
C3_2	0.0158 (11)	0.0180 (11)	0.0238 (13)	0.0006 (9)	0.0017 (10)	0.0022 (9)
C4_2	0.0185 (11)	0.0142 (10)	0.0163 (11)	0.0000 (9)	0.0058 (9)	0.0001 (8)
C5_2	0.0169 (11)	0.0227 (12)	0.0202 (12)	0.0060 (10)	0.0017 (9)	0.0001 (9)
C6_2	0.0164 (12)	0.0274 (12)	0.0207 (13)	−0.0020 (10)	0.0018 (10)	−0.0019 (10)
C7_2	0.0161 (11)	0.0153 (11)	0.0262 (13)	0.0016 (9)	0.0041 (10)	0.0000 (9)
N1_2	0.0210 (10)	0.0193 (10)	0.0255 (11)	−0.0026 (8)	0.0054 (9)	−0.0006 (8)
N2_2	0.0223 (11)	0.0145 (10)	0.0157 (10)	−0.0026 (8)	0.0038 (8)	0.0000 (8)
Cl1_2	0.0141 (3)	0.0136 (2)	0.0150 (3)	0.0009 (2)	0.00248 (19)	0.0008 (2)
O1_2	0.0318 (10)	0.0214 (8)	0.0173 (9)	0.0018 (7)	0.0078 (7)	0.0028 (7)
O2_2	0.0278 (9)	0.0155 (8)	0.0231 (9)	0.0072 (7)	0.0034 (7)	−0.0020 (7)
O3_2	0.0139 (8)	0.0318 (9)	0.0269 (9)	0.0061 (7)	−0.0010 (7)	0.0015 (7)
O4_2	0.0250 (9)	0.0202 (8)	0.0245 (9)	−0.0084 (7)	0.0040 (7)	0.0029 (7)
O5_2	0.0176 (9)	0.0147 (8)	0.0214 (9)	0.0007 (7)	0.0022 (7)	−0.0013 (7)

Geometric parameters (Å, º) top

C2_1—N1_1	1.338 (3)	C2_2—N1_2	1.335 (3)
C2_1—C3_1	1.380 (3)	C2_2—C3_2	1.384 (3)
C2_1—H2_1	0.9500	C2_2—H2_2	0.9500
C3_1—C4_1	1.388 (3)	C3_2—C4_2	1.387 (3)
C3_1—H3_1	0.9500	C3_2—H3_2	0.9500
C4_1—C5_1	1.375 (3)	C4_2—C5_2	1.391 (3)
C4_1—C7_1	1.506 (3)	C4_2—C7_2	1.504 (3)
C5_1—C6_1	1.386 (3)	C5_2—C6_2	1.374 (3)
C5_1—H5_1	0.9500	C5_2—H5_2	0.9500
C6_1—N1_1	1.331 (3)	C6_2—N1_2	1.339 (3)
C6_1—H6_1	0.9500	C6_2—H6_2	0.9500
C7_1—N2_1	1.493 (3)	C7_2—N2_2	1.482 (3)
C7_1—H7A_1	0.9900	C7_2—H7A_2	0.9900
C7_1—H7B_1	0.9900	C7_2—H7B_2	0.9900
N2_1—H2A_1	0.900 (16)	N2_2—H2A_2	0.921 (16)
N2_1—H2B_1	0.895 (16)	N2_2—H2B_2	0.907 (16)
N2_1—H2C_1	0.903 (17)	N2_2—H2C_2	0.897 (17)
Cl1_1—O2_1	1.4260 (16)	Cl1_2—O2_2	1.4316 (15)
Cl1_1—O3_1	1.4323 (16)	Cl1_2—O3_2	1.4322 (16)
Cl1_1—O4_1	1.4341 (16)	Cl1_2—O4_2	1.4431 (16)
Cl1_1—O1_1	1.4508 (15)	Cl1_2—O1_2	1.4454 (16)
O5_1—H5A_1	0.843 (17)	O5_2—H5A_2	0.831 (17)
O5_1—H5B_1	0.827 (17)	O5_2—H5B_2	0.825 (17)

N1_1—C2_1—C3_1	123.5 (2)	N1_2—C2_2—C3_2	123.6 (2)
N1_1—C2_1—H2_1	118.2	N1_2—C2_2—H2_2	118.2
C3_1—C2_1—H2_1	118.2	C3_2—C2_2—H2_2	118.2
C2_1—C3_1—C4_1	119.0 (2)	C2_2—C3_2—C4_2	119.3 (2)
C2_1—C3_1—H3_1	120.5	C2_2—C3_2—H3_2	120.3
C4_1—C3_1—H3_1	120.5	C4_2—C3_2—H3_2	120.3
C5_1—C4_1—C3_1	118.0 (2)	C3_2—C4_2—C5_2	117.2 (2)
C5_1—C4_1—C7_1	120.3 (2)	C3_2—C4_2—C7_2	124.3 (2)
C3_1—C4_1—C7_1	121.7 (2)	C5_2—C4_2—C7_2	118.44 (19)
C4_1—C5_1—C6_1	119.1 (2)	C6_2—C5_2—C4_2	119.4 (2)
C4_1—C5_1—H5_1	120.4	C6_2—C5_2—H5_2	120.3
C6_1—C5_1—H5_1	120.4	C4_2—C5_2—H5_2	120.3
N1_1—C6_1—C5_1	123.5 (2)	N1_2—C6_2—C5_2	123.7 (2)
N1_1—C6_1—H6_1	118.2	N1_2—C6_2—H6_2	118.1
C5_1—C6_1—H6_1	118.2	C5_2—C6_2—H6_2	118.1
N2_1—C7_1—C4_1	110.46 (18)	N2_2—C7_2—C4_2	113.15 (18)
N2_1—C7_1—H7A_1	109.6	N2_2—C7_2—H7A_2	108.9
C4_1—C7_1—H7A_1	109.6	C4_2—C7_2—H7A_2	108.9
N2_1—C7_1—H7B_1	109.6	N2_2—C7_2—H7B_2	108.9
C4_1—C7_1—H7B_1	109.6	C4_2—C7_2—H7B_2	108.9
H7A_1—C7_1—H7B_1	108.1	H7A_2—C7_2—H7B_2	107.8
C6_1—N1_1—C2_1	116.9 (2)	C2_2—N1_2—C6_2	116.7 (2)
C7_1—N2_1—H2A_1	109.1 (17)	C7_2—N2_2—H2A_2	111.7 (16)
C7_1—N2_1—H2B_1	111.0 (16)	C7_2—N2_2—H2B_2	112.4 (17)
H2A_1—N2_1—H2B_1	112 (2)	H2A_2—N2_2—H2B_2	102 (2)
C7_1—N2_1—H2C_1	107.8 (18)	C7_2—N2_2—H2C_2	108.0 (18)
H2A_1—N2_1—H2C_1	112 (2)	H2A_2—N2_2—H2C_2	112 (2)
H2B_1—N2_1—H2C_1	105 (2)	H2B_2—N2_2—H2C_2	110 (2)
O2_1—Cl1_1—O3_1	110.58 (10)	O2_2—Cl1_2—O3_2	110.79 (10)
O2_1—Cl1_1—O4_1	109.98 (11)	O2_2—Cl1_2—O4_2	109.43 (10)
O3_1—Cl1_1—O4_1	109.43 (10)	O3_2—Cl1_2—O4_2	109.22 (10)
O2_1—Cl1_1—O1_1	108.97 (9)	O2_2—Cl1_2—O1_2	109.43 (9)
O3_1—Cl1_1—O1_1	109.10 (9)	O3_2—Cl1_2—O1_2	109.58 (10)
O4_1—Cl1_1—O1_1	108.75 (10)	O4_2—Cl1_2—O1_2	108.36 (10)
H5A_1—O5_1—H5B_1	109 (3)	H5A_2—O5_2—H5B_2	107 (3)

C3_1—C4_1—C7_1—N2_1	67.4 (3)	C3_2—C4_2—C7_2—N2_2	13.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2_1—H2A_1···O5_1ⁱ	0.90 (2)	1.96 (2)	2.862 (3)	176 (2)
N2_1—H2B_1···O1_1ⁱⁱ	0.90 (2)	2.20 (2)	2.916 (2)	136 (2)
N2_1—H2B_1···O4_2ⁱⁱⁱ	0.90 (2)	2.32 (2)	2.924 (2)	125 (2)
N2_1—H2B_1···O4_2ⁱ	0.90 (2)	2.50 (2)	3.034 (3)	119 (2)
N2_1—H2C_1···O5_2^iv	0.90 (2)	1.95 (2)	2.838 (3)	168 (2)
O5_1—H5A_1···N1_2	0.84 (2)	1.91 (2)	2.751 (2)	176 (3)
O5_1—H5B_1···O1_2	0.83 (2)	2.21 (2)	2.986 (2)	156 (3)
N2_2—H2A_2···O5_1^iv	0.92 (2)	1.92 (2)	2.839 (3)	173 (2)
N2_2—H2B_2···O4_1ⁱⁱⁱ	0.91 (2)	2.42 (2)	3.079 (3)	130 (2)
N2_2—H2B_2···O1_2ⁱⁱⁱ	0.91 (2)	2.19 (2)	2.979 (2)	144 (2)
N2_2—H2C_2···O5_2^iv	0.90 (2)	1.98 (2)	2.872 (3)	177 (2)
O5_2—H5A_2···N1_1	0.83 (2)	1.93 (2)	2.761 (2)	175 (3)
O5_2—H5B_2···O1_1	0.83 (2)	2.09 (2)	2.874 (2)	160 (3)

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

Acknowledgements

We are grateful to the late Professor William S. Sheldrick for his support of this research.

Funding information

Funding for this research was provided by: Open Access Publishing by the DFG .

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