Synthesis and crystal structure of bis­(2-phthal­imido­eth­yl)ammonium chloride dihydrate

Young, B.S.; Lee, J.L.; Gembicky, M.; Bailey, J.; Smith, G.L.N.

doi:10.1107/S2056989023004565

research communications

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ISSN: 2056-9890

Volume 79| Part 6| June 2023| Pages 575-577

https://doi.org/10.1107/S2056989023004565

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Synthesis and crystal structure of bis(2-phthalimidoethyl)ammonium chloride dihydrate

Barry S. Young,^a ‡ Jamie L. Lee,^a ‡ Milan Gembicky,^b Jake Bailey ^b and Gary L. N. Smith ^a ^*

^aDepartment of Chemistry, San Diego Miramar College, San Diego, CA 92126, USA, and ^bDepartment of Chemistry, University of California-San Diego, La Jolla, CA 92093, USA
^*Correspondence e-mail: glsmith@sdccd.edu

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 31 March 2023; accepted 23 May 2023; online 26 May 2023)

The title compound {systematic name: bis[2-(1,3-dioxoisoindol-2-yl)ethyl]azanium chloride dihydrate}, C₂₀H₁₈N₃O₄⁺·Cl⁻·2H₂O, is a phthalimide-protected polyamine that was synthesized by a previous method. It was characterized by ESI–MS, ¹H NMR, and FT–IR. Crystals were grown from a solution of H₂O and 0.1 M HCl. The central nitrogen atom is protonated and forms hydrogen bonds with the chloride ion and a water molecule. The two phthalimide units make a dihedral angle of 22.07 (3)°. The crystal packing features a hydrogen-bond network, two-coordinated chloride, and off-set π–π stacking.

Keywords: crystal structure; phthalimides; π–π interactions; tripodal ligand.

CCDC reference: 2264952

1. Chemical context

The title compound was synthesized by Frederick Mann in 1934 (Mann, 1934 ). It has been a key component for the synthesis of tripodal amines (Lundin et al., 2004 ; Blackman, 2005 ), Schiff base macrocycles (Keypour et al., 2008 ), MRI contrast agents of gadolinium(III) (Cheng et al., 2000 ), and as a tricyclic host for anions (Kang et al., 2010 ). Recently, it has also been used to functionalize graphene oxide (Ramesh & Jebasingh, 2019 ), build a nano-polymer dendrimer to uptake salicylic acid (Arshadi et al., 2019 ), and construct a fluorescent ligand (Saga et al., 2020 ). The compound itself has formed a complex with manganese as a superoxide dismutase mimetic (Piacham et al., 2014 ). A variety of phthalimide compounds have been of interest because of the variety of supramolecular interactions that can exist (Howell et al., 2003 ).

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The compound is a protonated polyamine with two phthalimide groups protecting the terminal nitrogens. It crystallizes in the monoclinic space group P2₁/c. The planes of the two phthalimide units (N1/C1–C8 and N3/C13–C20) make a dihedral angle of 22.07 (3)°. These units point in opposite directions to each other from the perspective of the central nitrogen atom. The central tetrahedral nitrogen atom (NH₂) forms hydrogen bonds with a water molecule and the chloride ion.

Figure 1
The molecular structure of the title compound, showing 50% probability ellipsoids.

3. Supramolecular features

The crystal structure features off-set π–π stacking between phthalimide groups running along the b-axis direction (Fig. 2). The Cg (N1/C1–C8)⋯Cg (N3/C13–C20) centroid–centroid distance is 4.0143 (7) Å. A hydrogen-bond network (Table 1) exists between the protonated amine (N2—H2A), a water molecule (O1W), and a second water molecule (O2W). Both water molecules (O1W—H1WB, O2W—H2WA) also form hydrogen bonds with phthalimide oxygen atoms (O4, O2). The chloride ions form two hydrogen bonds with the protonated amine and a water molecule.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1W	0.930 (17)	1.848 (17)	2.7729 (16)	172.7 (14)
O1W—H1WA⋯O2W	0.87	1.88	2.7462 (15)	171
O1W—H1WB⋯O4ⁱ	0.87	2.05	2.9054 (14)	168
O2W—H2WA⋯O2ⁱⁱ	0.87	2.03	2.8929 (15)	172
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) .

Figure 2
Molecular packing of the title compound showing π–π interactions, hydrogen bonding, and chloride coordination.

4. Database survey

A search of the Cambridge Structural Database (version 5.41, update of July 2022; Groom et al., 2016 ) for related compounds with a phthalimide unit gave 2881 hits. A search for the skeletal structure of N(CH₂CH₂NH₂)₂ resulted in 1707 hits, while the structure with protonated amines ⁺HN(CH₂CH₂NH₃⁺)₂ resulted in 182 hits. One of these structures is the triprotonated diethylenetriamine trichloride (ETACLA01; Ilioudis et al., 2000 ). This structure includes one chloride ion that is two-coordinate and two chlorides that are three-coordinate. A search for an amine with two phthalimide groups had 24 hits. The structure of a diphthalimidodiethylammonium and hydrogen phthalate complex showed stabilization by offset π–π stacking, carbonyl–carbonyl, and hydrogen-bonding interactions (REVZAT; Barrett et al., 1995 ). Hydrogen bonding occurs within the complex unit and connects adjacent units. The offset π–π stacking between phthalimide units is characterized by C⋯C distances ranging from 3.297–3.592 Å. We have previously reported a phthalimide-protected polyamine that exhibits offset π–π stacking (Holmberg et al., 2021 ).

5. Synthesis and crystallization

Following a previous protocol (Utz et al., 2008 ), 5.0 mL (48 mmol) of diethylenetriamine were dissolved in 50 mL of methanol. To this, 15.0 g (101 mmol) of phthalic anhydride were slowly added, which turned the solution clear and yellow. The solution was kept at 333 K with minimal fluctuations and stirred for approximately 45 min. The solution became cloudy. It was removed from heat and stirred at room temperature for 7 days. A Büchner funnel and filter paper were saturated with MeOH, and the round-bottom flask was rinsed with MeOH prior to vacuum filtration. The precipitate was a pale-yellow solid. It was rinsed four times with 25 mL of MeOH and 4 × 25 mL of acetone to give 9.609 g of the product (55% yield). Characterization results align with previous work. ESI–MS: m/z = 364.1 (M + H⁺), 386.1 (M + Na⁺). ¹H NMR (90 MHz, CDCl₃) δ ppm 7.75 (m, 8H, aromatics), 3.75 (t, 4H, CH₂—N), 3.0 (t, 4H, CH₂—N), 1.60 (s, 1H, N—H). FTIR (cm⁻¹) = 3326 ν(N—H), 1698 ν(C=O). Crystals suitable for X-ray crystallography were grown by evaporation, with the compound dissolved in a solution of H₂O and 0.1 M HCl.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. N-bound H atoms were refined with U_iso(H) = 1.2U_eq(N). C-bound and water H atoms were positioned geometrically (C—H = 0.96–0.99 Å, O—H = 0.87 Å) and refined as riding with U_iso(H) = 1.2–1.5U_eq(C, O).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₃O₄⁺·Cl⁻·2H₂O
M_r	435.85
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.0401 (6), 15.4829 (7), 11.2543 (6)
β (°)	105.7191 (17)
V (Å³)	2019.52 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.23
Crystal size (mm)	0.18 × 0.18 × 0.05

Data collection
Diffractometer	Bruker SMART APEXII area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.666, 0.744
No. of measured, independent and observed [I > 2σ(I)] reflections	59713, 4126, 3430
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.077, 1.03
No. of reflections	4126
No. of parameters	284
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.23
Computer programs: APEX4 (Bruker, 2022 ), SAINT (Bruker, 2019 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2264952

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004565/ex2070sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004565/ex2070Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989023004565/ex2070Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2056989023004565/ex2070Isup4.cml

checkCIF report

Computing details top

Data collection: APEX4 v2022.1-1 (Bruker, 2022); cell refinement: SAINT v8.40B (Bruker, 2019); data reduction: SAINT v8.40B (Bruker, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

Bis[2-(1,3-dioxoisoindol-2-yl)ethyl]azanium chloride dihydrate top

Crystal data top

C₂₀H₁₈N₃O₄⁺·Cl⁻·2H₂O	F(000) = 912
M_r = 435.85	D_x = 1.434 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.0401 (6) Å	Cell parameters from 8573 reflections
b = 15.4829 (7) Å	θ = 2.6–26.6°
c = 11.2543 (6) Å	µ = 0.23 mm⁻¹
β = 105.7191 (17)°	T = 100 K
V = 2019.52 (17) Å³	Plate, colourless
Z = 4	0.18 × 0.18 × 0.05 mm

Data collection top

Bruker SMART APEXII area detector diffractometer	4126 independent reflections
Radiation source: Micro Focus Rotating Anode, Bruker TXS	3430 reflections with I > 2σ(I)
Double Bounce Multilayer Mirrors monochromator	R_int = 0.082
Detector resolution: 7.407 pixels mm^-1	θ_max = 26.4°, θ_min = 2.6°
ω and φ scans	h = −15→15
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −19→19
T_min = 0.666, T_max = 0.744	l = −14→14
59713 measured 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)] = 0.031	w = 1/[σ²(F_o²) + (0.0289P)² + 1.0135P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.077	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.33 e Å⁻³
4126 reflections	Δρ_min = −0.22 e Å⁻³
284 parameters	Extinction correction: SHELXL-2019/1 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0027 (5)
Primary atom site location: dual

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	0.30610 (3)	0.21490 (2)	0.23479 (3)	0.01891 (10)
O1	0.45753 (9)	0.41672 (7)	0.37854 (9)	0.0222 (2)
O2	0.18461 (8)	0.47720 (6)	0.01946 (9)	0.0188 (2)
O3	0.66232 (8)	0.16482 (7)	0.41798 (9)	0.0192 (2)
O4	0.77243 (9)	0.14778 (7)	0.06066 (9)	0.0203 (2)
N1	0.34112 (10)	0.44489 (7)	0.18374 (11)	0.0145 (3)
N2	0.49938 (11)	0.29689 (7)	0.14298 (11)	0.0132 (2)
H2A	0.5674 (14)	0.3152 (10)	0.1984 (15)	0.016*
H2B	0.4486 (14)	0.2814 (10)	0.1872 (15)	0.016*
N3	0.68861 (10)	0.15627 (7)	0.22242 (11)	0.0144 (3)
C1	0.36218 (13)	0.42849 (9)	0.31025 (13)	0.0168 (3)
C2	0.24799 (13)	0.43156 (9)	0.33647 (13)	0.0172 (3)
C3	0.21870 (14)	0.41977 (10)	0.44585 (14)	0.0232 (3)
H3	0.275327	0.407303	0.520828	0.028*
C4	0.10228 (15)	0.42703 (10)	0.44106 (15)	0.0264 (4)
H4	0.078868	0.418693	0.514353	0.032*
C5	0.01953 (14)	0.44615 (10)	0.33171 (16)	0.0254 (4)
H5	−0.059106	0.450841	0.331866	0.030*
C6	0.04974 (13)	0.45861 (9)	0.22169 (15)	0.0208 (3)
H6	−0.006455	0.471957	0.146751	0.025*
C7	0.16529 (13)	0.45060 (9)	0.22689 (13)	0.0165 (3)
C8	0.22447 (12)	0.45952 (9)	0.12767 (13)	0.0146 (3)
C9	0.43146 (12)	0.45125 (9)	0.12044 (13)	0.0163 (3)
H9A	0.504935	0.466733	0.181225	0.020*
H9B	0.411828	0.498362	0.058814	0.020*
C10	0.44862 (12)	0.36834 (9)	0.05565 (13)	0.0160 (3)
H10A	0.373203	0.349242	0.001902	0.019*
H10B	0.500022	0.380153	0.002199	0.019*
C11	0.51826 (12)	0.21954 (9)	0.07135 (13)	0.0147 (3)
H11A	0.571103	0.235377	0.021083	0.018*
H11B	0.443688	0.202189	0.014086	0.018*
C12	0.56858 (12)	0.14316 (9)	0.15283 (13)	0.0159 (3)
H12A	0.521779	0.132557	0.211393	0.019*
H12B	0.563460	0.091081	0.100582	0.019*
C13	0.72536 (12)	0.16741 (9)	0.35046 (13)	0.0144 (3)
C14	0.85216 (12)	0.18028 (9)	0.38127 (13)	0.0146 (3)
C15	0.93036 (12)	0.19494 (9)	0.49353 (13)	0.0173 (3)
H15	0.907043	0.196796	0.567657	0.021*
C16	1.04548 (13)	0.20700 (9)	0.49417 (14)	0.0196 (3)
H16	1.101625	0.218356	0.569922	0.024*
C17	1.07905 (12)	0.20260 (9)	0.38529 (14)	0.0192 (3)
H17	1.157746	0.211544	0.387946	0.023*
C18	0.99976 (12)	0.18540 (9)	0.27284 (14)	0.0176 (3)
H18	1.023044	0.180774	0.198902	0.021*
C19	0.88563 (12)	0.17528 (9)	0.27268 (13)	0.0152 (3)
C20	0.78104 (12)	0.15836 (9)	0.16934 (13)	0.0154 (3)
O1W	0.70481 (9)	0.36110 (7)	0.29278 (9)	0.0200 (2)
H1WA	0.715322	0.413414	0.269788	0.030*
H1WB	0.717563	0.364549	0.372498	0.030*
O2W	0.72498 (11)	0.52060 (7)	0.19391 (11)	0.0287 (3)
H2WA	0.758477	0.523958	0.134596	0.043*
H2WB	0.720782	0.573778	0.217062	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01688 (18)	0.02079 (19)	0.02101 (19)	−0.00147 (14)	0.00846 (14)	0.00137 (14)
O1	0.0220 (6)	0.0210 (6)	0.0211 (6)	0.0023 (4)	0.0014 (5)	0.0030 (4)
O2	0.0189 (5)	0.0207 (5)	0.0168 (5)	0.0013 (4)	0.0049 (4)	0.0020 (4)
O3	0.0178 (5)	0.0221 (6)	0.0205 (5)	0.0004 (4)	0.0099 (4)	−0.0007 (4)
O4	0.0240 (6)	0.0228 (6)	0.0151 (5)	0.0011 (4)	0.0071 (4)	−0.0004 (4)
N1	0.0146 (6)	0.0143 (6)	0.0160 (6)	0.0023 (5)	0.0062 (5)	0.0014 (5)
N2	0.0133 (6)	0.0129 (6)	0.0139 (6)	0.0002 (5)	0.0048 (5)	0.0006 (5)
N3	0.0139 (6)	0.0141 (6)	0.0157 (6)	0.0007 (4)	0.0050 (5)	−0.0005 (5)
C1	0.0221 (8)	0.0103 (7)	0.0180 (7)	0.0016 (6)	0.0053 (6)	0.0001 (5)
C2	0.0220 (7)	0.0110 (7)	0.0197 (7)	0.0016 (6)	0.0079 (6)	−0.0008 (5)
C3	0.0337 (9)	0.0183 (8)	0.0201 (8)	0.0053 (6)	0.0116 (7)	0.0020 (6)
C4	0.0382 (10)	0.0219 (8)	0.0270 (9)	0.0029 (7)	0.0222 (8)	0.0011 (7)
C5	0.0251 (8)	0.0205 (8)	0.0372 (9)	0.0003 (6)	0.0198 (7)	−0.0021 (7)
C6	0.0194 (8)	0.0180 (8)	0.0266 (8)	0.0017 (6)	0.0092 (6)	−0.0016 (6)
C7	0.0202 (7)	0.0115 (7)	0.0198 (7)	0.0007 (5)	0.0087 (6)	−0.0006 (6)
C8	0.0169 (7)	0.0102 (6)	0.0170 (7)	0.0006 (5)	0.0052 (6)	−0.0016 (5)
C9	0.0147 (7)	0.0146 (7)	0.0218 (8)	0.0007 (5)	0.0085 (6)	0.0024 (6)
C10	0.0179 (7)	0.0151 (7)	0.0160 (7)	0.0033 (6)	0.0063 (6)	0.0043 (6)
C11	0.0154 (7)	0.0136 (7)	0.0154 (7)	0.0012 (5)	0.0046 (6)	−0.0014 (5)
C12	0.0141 (7)	0.0141 (7)	0.0190 (7)	−0.0003 (5)	0.0036 (6)	−0.0003 (6)
C13	0.0179 (7)	0.0095 (7)	0.0168 (7)	0.0021 (5)	0.0063 (6)	0.0004 (5)
C14	0.0154 (7)	0.0108 (7)	0.0187 (7)	0.0024 (5)	0.0062 (6)	0.0009 (5)
C15	0.0196 (7)	0.0162 (7)	0.0169 (7)	0.0031 (6)	0.0063 (6)	0.0001 (6)
C16	0.0177 (7)	0.0179 (8)	0.0216 (8)	0.0026 (6)	0.0023 (6)	−0.0003 (6)
C17	0.0136 (7)	0.0177 (7)	0.0270 (8)	0.0022 (6)	0.0067 (6)	0.0027 (6)
C18	0.0185 (7)	0.0171 (7)	0.0199 (7)	0.0030 (6)	0.0100 (6)	0.0031 (6)
C19	0.0180 (7)	0.0115 (7)	0.0167 (7)	0.0021 (5)	0.0058 (6)	0.0018 (5)
C20	0.0193 (7)	0.0102 (7)	0.0185 (8)	0.0021 (5)	0.0080 (6)	0.0017 (5)
O1W	0.0225 (6)	0.0178 (5)	0.0183 (5)	−0.0029 (4)	0.0029 (4)	0.0011 (4)
O2W	0.0453 (7)	0.0196 (6)	0.0285 (6)	0.0027 (5)	0.0225 (6)	0.0041 (5)

Geometric parameters (Å, º) top

O1—C1	1.2099 (17)	C9—H9A	0.9900
O2—C8	1.2131 (17)	C9—H9B	0.9900
O3—C13	1.2115 (17)	C9—C10	1.5179 (19)
O4—C20	1.2103 (17)	C10—H10A	0.9900
N1—C1	1.4001 (18)	C10—H10B	0.9900
N1—C8	1.3936 (18)	C11—H11A	0.9900
N1—C9	1.4561 (18)	C11—H11B	0.9900
N2—H2A	0.930 (17)	C11—C12	1.5184 (19)
N2—H2B	0.919 (17)	C12—H12A	0.9900
N2—C10	1.4959 (17)	C12—H12B	0.9900
N2—C11	1.4950 (17)	C13—C14	1.4845 (19)
N3—C12	1.4594 (18)	C14—C15	1.375 (2)
N3—C13	1.3988 (18)	C14—C19	1.389 (2)
N3—C20	1.3988 (18)	C15—H15	0.9500
C1—C2	1.483 (2)	C15—C16	1.397 (2)
C2—C3	1.381 (2)	C16—H16	0.9500
C2—C7	1.391 (2)	C16—C17	1.392 (2)
C3—H3	0.9500	C17—H17	0.9500
C3—C4	1.393 (2)	C17—C18	1.389 (2)
C4—H4	0.9500	C18—H18	0.9500
C4—C5	1.389 (2)	C18—C19	1.382 (2)
C5—H5	0.9500	C19—C20	1.488 (2)
C5—C6	1.395 (2)	O1W—H1WA	0.8699
C6—H6	0.9500	O1W—H1WB	0.8699
C6—C7	1.382 (2)	O2W—H2WA	0.8700
C7—C8	1.485 (2)	O2W—H2WB	0.8692

C1—N1—C9	123.81 (12)	N2—C10—H10A	108.9
C8—N1—C1	111.88 (11)	N2—C10—H10B	108.9
C8—N1—C9	124.21 (12)	C9—C10—H10A	108.9
H2A—N2—H2B	108.2 (13)	C9—C10—H10B	108.9
C10—N2—H2A	110.1 (10)	H10A—C10—H10B	107.7
C10—N2—H2B	109.6 (10)	N2—C11—H11A	109.0
C11—N2—H2A	111.8 (10)	N2—C11—H11B	109.0
C11—N2—H2B	107.7 (10)	N2—C11—C12	113.10 (11)
C11—N2—C10	109.44 (11)	H11A—C11—H11B	107.8
C13—N3—C12	124.12 (11)	C12—C11—H11A	109.0
C13—N3—C20	111.77 (11)	C12—C11—H11B	109.0
C20—N3—C12	124.11 (12)	N3—C12—C11	113.01 (11)
O1—C1—N1	123.53 (13)	N3—C12—H12A	109.0
O1—C1—C2	130.53 (14)	N3—C12—H12B	109.0
N1—C1—C2	105.92 (12)	C11—C12—H12A	109.0
C3—C2—C1	130.34 (14)	C11—C12—H12B	109.0
C3—C2—C7	121.60 (14)	H12A—C12—H12B	107.8
C7—C2—C1	108.06 (12)	O3—C13—N3	124.40 (13)
C2—C3—H3	121.6	O3—C13—C14	129.59 (13)
C2—C3—C4	116.88 (15)	N3—C13—C14	105.99 (11)
C4—C3—H3	121.6	C15—C14—C13	129.93 (13)
C3—C4—H4	119.2	C15—C14—C19	121.88 (13)
C5—C4—C3	121.61 (14)	C19—C14—C13	108.19 (12)
C5—C4—H4	119.2	C14—C15—H15	121.4
C4—C5—H5	119.4	C14—C15—C16	117.29 (13)
C4—C5—C6	121.25 (15)	C16—C15—H15	121.4
C6—C5—H5	119.4	C15—C16—H16	119.6
C5—C6—H6	121.6	C17—C16—C15	120.89 (14)
C7—C6—C5	116.84 (15)	C17—C16—H16	119.6
C7—C6—H6	121.6	C16—C17—H17	119.3
C2—C7—C8	108.21 (12)	C18—C17—C16	121.30 (13)
C6—C7—C2	121.82 (14)	C18—C17—H17	119.3
C6—C7—C8	129.97 (14)	C17—C18—H18	121.3
O2—C8—N1	124.57 (13)	C19—C18—C17	117.42 (13)
O2—C8—C7	129.49 (13)	C19—C18—H18	121.3
N1—C8—C7	105.93 (12)	C14—C19—C20	108.16 (12)
N1—C9—H9A	108.9	C18—C19—C14	121.18 (13)
N1—C9—H9B	108.9	C18—C19—C20	130.65 (13)
N1—C9—C10	113.25 (11)	O4—C20—N3	124.62 (13)
H9A—C9—H9B	107.7	O4—C20—C19	129.53 (13)
C10—C9—H9A	108.9	N3—C20—C19	105.85 (11)
C10—C9—H9B	108.9	H1WA—O1W—H1WB	104.5
N2—C10—C9	113.22 (11)	H2WA—O2W—H2WB	104.5

O1—C1—C2—C3	−1.7 (3)	C9—N1—C1—O1	−1.2 (2)
O1—C1—C2—C7	177.56 (15)	C9—N1—C1—C2	177.37 (12)
O3—C13—C14—C15	−2.0 (2)	C9—N1—C8—O2	1.8 (2)
O3—C13—C14—C19	177.98 (14)	C9—N1—C8—C7	−177.10 (12)
N1—C1—C2—C3	179.83 (14)	C10—N2—C11—C12	−179.36 (11)
N1—C1—C2—C7	−0.86 (15)	C11—N2—C10—C9	−177.34 (11)
N1—C9—C10—N2	−69.13 (15)	C12—N3—C13—O3	2.3 (2)
N2—C11—C12—N3	−70.61 (15)	C12—N3—C13—C14	−178.85 (12)
N3—C13—C14—C15	179.24 (14)	C12—N3—C20—O4	−1.6 (2)
N3—C13—C14—C19	−0.76 (15)	C12—N3—C20—C19	178.60 (12)
C1—N1—C8—O2	178.13 (13)	C13—N3—C12—C11	110.75 (14)
C1—N1—C8—C7	−0.76 (15)	C13—N3—C20—O4	177.76 (13)
C1—N1—C9—C10	97.89 (15)	C13—N3—C20—C19	−1.99 (15)
C1—C2—C3—C4	179.82 (14)	C13—C14—C15—C16	−178.35 (13)
C1—C2—C7—C6	−179.45 (13)	C13—C14—C19—C18	179.61 (13)
C1—C2—C7—C8	0.42 (15)	C13—C14—C19—C20	−0.42 (15)
C2—C3—C4—C5	−0.7 (2)	C14—C15—C16—C17	−1.2 (2)
C2—C7—C8—O2	−178.64 (14)	C14—C19—C20—O4	−178.29 (14)
C2—C7—C8—N1	0.18 (15)	C14—C19—C20—N3	1.45 (15)
C3—C2—C7—C6	−0.1 (2)	C15—C14—C19—C18	−0.4 (2)
C3—C2—C7—C8	179.80 (13)	C15—C14—C19—C20	179.58 (13)
C3—C4—C5—C6	0.2 (2)	C15—C16—C17—C18	−0.6 (2)
C4—C5—C6—C7	0.3 (2)	C16—C17—C18—C19	1.8 (2)
C5—C6—C7—C2	−0.4 (2)	C17—C18—C19—C14	−1.4 (2)
C5—C6—C7—C8	179.78 (14)	C17—C18—C19—C20	178.68 (14)
C6—C7—C8—O2	1.2 (3)	C18—C19—C20—O4	1.7 (3)
C6—C7—C8—N1	−179.96 (14)	C18—C19—C20—N3	−178.59 (14)
C7—C2—C3—C4	0.6 (2)	C19—C14—C15—C16	1.6 (2)
C8—N1—C1—O1	−177.56 (13)	C20—N3—C12—C11	−69.92 (16)
C8—N1—C1—C2	1.01 (15)	C20—N3—C13—O3	−177.07 (13)
C8—N1—C9—C10	−86.20 (16)	C20—N3—C13—C14	1.75 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1W	0.930 (17)	1.848 (17)	2.7729 (16)	172.7 (14)
O1W—H1WA···O2W	0.87	1.88	2.7462 (15)	171
O1W—H1WB···O4ⁱ	0.87	2.05	2.9054 (14)	168
O2W—H2WA···O2ⁱⁱ	0.87	2.03	2.8929 (15)	172

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

Footnotes

‡Both authors contributed equally.

Acknowledgements

The authors acknowledge Dr Christal Sohl (San Diego State University) for support and Dr Greg Elliott (San Diego State University) for mass spectrometry.

Funding information

Funding for this research was provided by: San Diego Miramar College Department of Chemistry.

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