In situ deca­rbonylation of N,N-di­methyl­formamide to form di­methyl­ammonium cations in the hybrid framework compound {[(CH3)2NH2]2[Zn{O3PC6H2(OH)2PO3}]}n

Soriano, J.S.; Galeas, B.E.; Garrett, P.; Flores, R.A.; Pinedo, J.L.; Kohlgruber, T.A.; Felton, D.; Adelani, P.O.

doi:10.1107/S2056989019012969

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ISSN: 2056-9890

Volume 75| Part 10| October 2019| Pages 1540-1543

https://doi.org/10.1107/S2056989019012969

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In situ decarbonylation of N,N-dimethylformamide to form dimethylammonium cations in the hybrid framework compound {[(CH₃)₂NH₂]₂[Zn{O₃PC₆H₂(OH)₂PO₃}]}_n

Josemaria S. Soriano,^a Bryan E. Galeas,^a Paul Garrett,^a Ryan A. Flores,^a Juan L. Pinedo,^a Tsuyoshi A. Kohlgruber,^b Daniel Felton ^c and Pius O. Adelani ^a ^*

^aDepartment of Chemistry and Biochemistry, St. Mary's University, San Antonio, Texas 78228, USA, ^bDepartment of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, Indiana 46556, USA, and ^cDepartment of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA
^*Correspondence e-mail: padelani@stmarytx.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 5 August 2019; accepted 19 September 2019; online 27 September 2019)

The title phosphonate-based organic–inorganic hybrid framework, poly[bis(dimethylammonium) [(μ₄-2,5-dihydroxybenzene-1,4-diphosphonato)zinc(II)]], {(C₂H₈N)₂[Zn(C₆H₄O₈P₂)]}_n, was formed unexpectedly when dimethylammonium cations were formed from the in situ decarbonylation of the N,N-dimethylformamide solvent. The framework is built up from ZnO₄ tetrahedra and bridging diphosphonate tetra-anions to generate a three-dimensional network comprising [100] channels occupied by the (CH₃)₂NH₂⁺ cations. Within the channels, an array of N—H⋯O hydrogen bonds help to establish the structure. In addition, intramolecular O—H⋯O hydrogen bonds between the appended –OH groups of the phenyl ring and adjacent PO₃²⁻ groups are observed.

Keywords: crystal structure; decarbonylation; phosphonic acid; inorganic–organic hybrid framework; hydrogen bonding.

CCDC reference: 1954737

1. Chemical context

Studies on the structural chemistry of metal phosphonates developed as a result of the versatility of the phosphonate ligands (Zubieta et al., 2011 ; Mao, 2007 ; Clearfield, 1996 , 1998 , 2002 ). A slight modification of the organic residues of the phosphonic acids (R-PO₃H₂, where R = organic residue) can lead to rich structural diversity. In general, phosphonates tend to assume various coordination modes as a result of the three coordinating oxygen atoms of the central phosphorus units. As a consequence, most metal phosphonates form a low-dimensional and dense layered structure (Deria et al., 2015 ; Gagnon et al., 2012 ). Nevertheless, a large number of isolated metal phosphonates have shown various potential applications in ion-exchange, ionic conductivity, gas storage, catalysis, and as small molecule sensors and magnetic interactions (Adelani & Albrecht-Schmitt, 2010 ; Ramaswamy et al., 2015 ; Deria et al., 2015; Kirumakki et al., 2008 ; Brousseau et al., 1997 ; Zheng et al., 2011 ).

The majority of metal–organic frameworks (MOFs) are designed with carboxylate- and nitrogen-containing heterocyclic ligands, while phosphonate-based MOFs are less well studied. One possible explanation may have to do with the predisposition of phosphonates to precipitate rapidly into less ordered insoluble phases. However, carboxylate-based MOFs are less stable in air and water, and this poses a significant problem if they are to be used in industrial applications. Metal carboxylate MOFs are subject to hydrolysis and are quite soluble in acidic solutions. On the contrary, phosphonates manifest stronger interactions with oxophilic metal ions than carboxylates and are not subject to hydrolysis (Deria et al., 2015; Gagnon et al., 2012).

About a decade ago, a crystalline and porous zinc diphosphonate MOF, {[Zn(DHBP)](DMF)₂} (DMF = N,N-dimethylformamide) was reported (Liang & Shimizu, 2007 ). These researchers utilized a modified phosphonate ligand, 1,4-dihydroxy-2,5-benzenediphosphonate (DHBP), to cross-link one-dimensional Zn(RPO₃) columns into an ordered three-dimensional network. Herein, we report the synthesis and structure of the title inorganic–organic hybrid framework, (I), using 1,4-dihydroxy-2,5-benzenediphosphonate via the in situ formation of the guest cation.

2. Structural commentary

The structure of (I) crystallizes in the monoclinic space group P2₁/n. The asymmetric unit contains one Zn²⁺ cation, a C₆H₄P₂O₈⁴⁻ hydroxyphosphonate tetra-anion and two (CH₃)₂NH₂⁺ cations (Fig. 1). The extended structure is constructed from tetrahedral ZnO₄ units with the O atoms arising from four rigid phenyl spacers into a three-dimensional framework (Fig. 2). Two of the oxygen atoms of each PO₃²⁻ moiety are involved in coordination to the Zn²⁺ ion and the others (O2 and O6) are not. The Zn—O bond distances range from 1.9055 (11) to 1.9671 (11) Å and the hydroxyphosphonate ligand is present in (I) with P—O bonds that range from 1.5129 (11) to 1.5337 (11) Å in length. The latter bond lengths are within the expected range for deprotonated P—O bonds (Liang & Shimizu, 2007).

Figure 1
The asymmetric unit of (I)

in position 1 − x, 1 − y, 1 − z showing 50% displacement ellipsoids.

Figure 2
View down [100] of the three-dimensional framework structure of (I)

with the ZnO₄ and PO₃C moieties shown as polyhedra. Color key: ZnO₄ groups = cyan, PO₃C groups = magenta, oxygen = red, carbon = black, hydrogen = white. The (CH₃)₂NH₂⁺ cations are omitted for clarity.

The structure of (I) is similar to that of {[Zn(DHBP)](DMF)₂} (Liang & Shimizu, 2007; CCDC refcode JIVFUQ) in that the zinc–phosphonate framework comprises one-dimensional channels occupied by guest species, but with the significant difference that the guest species in JIVFUQ are neutral DMF molecules and the phosphonate groups are singly, rather than doubly deprotonated to form C₆H₆P₂O₈²⁻ dianions.

The channels reported here are smaller than those in JIVFUQ and measure approximately 12.9 × 7.1 Å between phenyl groups and 9.9 Å between Zn centers. The (CH₃)₂NH₂⁺ cations in (I) have been formed by the in situ decarbonylation of the DMF solvent. It is known that N,N-dimethylformamide can undergo loss of CO to form dimethylamine in the presence of a metal catalyst or through slow decomposition at elevated temperature around 427 K (Hulushe et al., 2016 ; Siddiqui et al., 2012 ; Chen et al., 2007 ; Karpova et al., 2004 ). In the previous reports, the nitrate salts of Mg²⁺/Pb²⁺/Ho³⁺ and chloride salts of Nd³⁺/Zr⁴⁺ were suggested to act as a metal catalyst in the decarbonylation of the DMF solvent.

3. Supramolecular features

The C6—O8H and C3—O7H groups appended on the phenyl ring of the ligand form intramolecular O—H⋯O hydrogen bonds with the adjacent RPO₃²⁻ moieties (Figs. 1 and 3). Within the channels, the (CH₃)₂NH₂⁺ cations are linked by N—H⋯O hydrogen bonds to the RPO₃²⁻ groups of the framework (Table 1). Some short C—H⋯O contacts (Table 1) may help to consolidate the structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O5	0.79 (2)	1.91 (2)	2.6510 (17)	156 (3)
O8—H8A⋯O2	0.87 (3)	1.73 (3)	2.5846 (18)	168 (3)
N1—H1A⋯O2	0.89 (2)	1.88 (2)	2.7168 (19)	155.2 (18)
N1—H1B⋯O6ⁱ	0.89 (2)	2.02 (2)	2.8125 (19)	148.3 (18)
N2—H2B⋯O3ⁱⁱ	0.83 (3)	2.07 (3)	2.8558 (19)	158 (2)
N2—H2C⋯O6	1.03 (2)	1.63 (2)	2.6518 (18)	173 (2)
C7—H7C⋯O4ⁱⁱⁱ	0.91 (2)	2.54 (2)	3.443 (3)	174 (2)
C9—H9B⋯O8^iv	1.03 (3)	2.57 (2)	3.445 (3)	142.6 (19)
C10—H10A⋯O8^iv	0.92 (3)	2.42 (3)	3.236 (3)	148 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 3
Ball-and-stick representation of the structure of (I)

viewed along the [001] axis. The hydrogen bonds involving the –OH groups are drawn as blue dashed lines. Color key as in Fig. 2

4. Synthesis and crystallization

The title compound was synthesized by placing Zn(NO₃)₂·6H₂O (29.7 mg, 0.1 mmol) and 2,5-dihydroxy-1,4-benzenediphosphonic acid (27.0 mg, 0.1 mmol) into a 125 ml PTFE-lined Parr reaction vessel along with DMF/H₂O/ethanol (2.0/0.5/0.5 ml, respectively). The vessel was heated in a programmable furnace at 353 K for 3 d, and then the autoclave was cooled to 296 K at an average rate of 274 K h⁻¹. The mother liquor was decanted from the products and then placed in a petri dish. The solid products were washed with distilled water, dispersed with ethanol and allowed to dry in air. Colorless tablets of the title compound were isolated and studied for single-crystal X-ray diffraction.

5. Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	(C₂H₈N)₂[Zn(C₆H₄O₈P₂)]
M_r	423.59
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	220
a, b, c (Å)	8.8455 (5), 16.4492 (9), 11.2721 (6)
β (°)	97.338 (1)
V (Å³)	1626.67 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.75
Crystal size (mm)	0.09 × 0.03 × 0.03

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.706, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	19692, 4040, 3582
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.681

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.060, 1.05
No. of reflections	4040
No. of parameters	288
No. of restraints	1
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.31
Computer programs: APEX3 and SAINT (Bruker, 2015 ), SHELXT2014/2 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), XP in SHELXTL (Sheldrick, 2008a ) and CIFTAB (Sheldrick, 2008b ).

Supporting information

CCDC reference: 1954737

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019012969/hb7847sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019012969/hb7847Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008a); software used to prepare material for publication: CIFTAB (Sheldrick, 2008b).

Poly[bis(dimethylammonium) [(µ₄-2,5-dihydroxybenzene-1,4-diphosphonato)zinc(II)]] top

Crystal data top

(C₂H₈N)₂[Zn(C₆H₄O₈P₂)]	F(000) = 872
M_r = 423.59	D_x = 1.730 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.8455 (5) Å	Cell parameters from 8723 reflections
b = 16.4492 (9) Å	θ = 2.2–28.8°
c = 11.2721 (6) Å	µ = 1.75 mm⁻¹
β = 97.338 (1)°	T = 220 K
V = 1626.67 (15) Å³	Block, colorless
Z = 4	0.09 × 0.03 × 0.03 mm

Data collection top

Bruker APEXII diffractometer	4040 independent reflections
Radiation source: Incoatec micro-focus	3582 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	R_int = 0.027
combination of ω and φ–scans	θ_max = 29.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→11
T_min = 0.706, T_max = 0.746	k = −22→21
19692 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022	Hydrogen site location: difference Fourier map
wR(F²) = 0.060	All H-atom parameters refined
S = 1.05	w = 1/[σ²(F_o²) + (0.0327P)² + 0.4955P] where P = (F_o² + 2F_c²)/3
4040 reflections	(Δ/σ)_max = 0.002
288 parameters	Δρ_max = 0.42 e Å⁻³
1 restraint	Δρ_min = −0.31 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
Zn1	0.73693 (2)	0.50748 (2)	−0.00920 (2)	0.01208 (6)
P1	0.53496 (4)	0.52463 (2)	0.21300 (3)	0.01348 (9)
P2	0.52017 (4)	0.86078 (2)	0.50529 (3)	0.01240 (8)
O1	0.61568 (13)	0.54669 (7)	0.10670 (10)	0.0251 (3)
O2	0.61879 (14)	0.46378 (7)	0.29864 (11)	0.0241 (3)
O3	0.37005 (12)	0.49818 (6)	0.17307 (10)	0.0173 (2)
O4	0.66080 (13)	0.90494 (6)	0.47282 (10)	0.0217 (2)
O5	0.37382 (13)	0.90513 (7)	0.45507 (10)	0.0220 (2)
O6	0.53036 (13)	0.84096 (7)	0.63713 (9)	0.0216 (2)
O7	0.31114 (15)	0.80860 (7)	0.26689 (12)	0.0287 (3)
O8	0.71416 (17)	0.57148 (8)	0.45775 (13)	0.0382 (4)
C1	0.52417 (16)	0.61778 (9)	0.29782 (13)	0.0137 (3)
C2	0.42525 (17)	0.67996 (9)	0.25376 (13)	0.0161 (3)
C3	0.41615 (17)	0.75253 (9)	0.31601 (13)	0.0155 (3)
C4	0.51147 (16)	0.76540 (8)	0.42426 (13)	0.0128 (3)
C5	0.60872 (17)	0.70290 (9)	0.46917 (14)	0.0176 (3)
C6	0.61546 (17)	0.62969 (9)	0.40804 (14)	0.0186 (3)
C7	0.5494 (3)	0.29794 (13)	0.13241 (19)	0.0387 (5)
N1	0.57872 (18)	0.30131 (9)	0.26452 (15)	0.0277 (3)
C8	0.7362 (3)	0.27776 (15)	0.3120 (2)	0.0443 (5)
C9	0.5188 (3)	1.01513 (14)	0.8070 (2)	0.0356 (4)
N2	0.63088 (18)	0.94927 (9)	0.80290 (13)	0.0246 (3)
C10	0.6615 (3)	0.90359 (13)	0.91563 (18)	0.0371 (5)
H1A	0.568 (2)	0.3527 (14)	0.287 (2)	0.038 (6)*
H1B	0.515 (2)	0.2695 (14)	0.2980 (19)	0.037 (6)*
H2A	0.360 (2)	0.6731 (12)	0.1787 (17)	0.026 (5)*
H2B	0.709 (3)	0.9705 (14)	0.783 (2)	0.041 (6)*
H2C	0.588 (3)	0.9111 (15)	0.735 (2)	0.054 (7)*
H5A	0.676 (2)	0.7101 (11)	0.5433 (17)	0.024 (5)*
H7A	0.306 (3)	0.8427 (16)	0.316 (2)	0.050 (7)*
H7B	0.450 (3)	0.3113 (17)	0.109 (2)	0.071 (9)*
H7C	0.620 (2)	0.3284 (16)	0.101 (2)	0.055 (7)*
H7D	0.566 (3)	0.2430 (15)	0.109 (2)	0.044 (6)*
H8A	0.691 (3)	0.5308 (18)	0.410 (3)	0.064 (8)*
H8B	0.806 (3)	0.3177 (15)	0.281 (2)	0.052 (7)*
H8C	0.750 (3)	0.2805 (15)	0.402 (2)	0.053 (7)*
H8D	0.748 (3)	0.2232 (16)	0.278 (2)	0.056 (7)*
H9A	0.501 (2)	1.0337 (13)	0.729 (2)	0.036 (6)*
H9B	0.569 (3)	1.0562 (16)	0.869 (2)	0.054 (7)*
H9C	0.431 (3)	0.9924 (13)	0.828 (2)	0.042 (7)*
H10A	0.719 (4)	0.936 (2)	0.970 (3)	0.088 (11)*
H10B	0.564 (4)	0.8940 (17)	0.947 (3)	0.077 (9)*
H10C	0.716 (3)	0.8557 (17)	0.902 (2)	0.062 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01243 (9)	0.01005 (9)	0.01414 (9)	−0.00104 (6)	0.00319 (6)	−0.00073 (6)
P1	0.01327 (18)	0.01165 (17)	0.01539 (18)	0.00072 (13)	0.00134 (14)	−0.00453 (14)
P2	0.01391 (18)	0.00907 (17)	0.01421 (18)	0.00096 (13)	0.00174 (14)	−0.00254 (13)
O1	0.0271 (6)	0.0243 (6)	0.0268 (6)	−0.0033 (5)	0.0146 (5)	−0.0084 (5)
O2	0.0287 (6)	0.0141 (5)	0.0268 (6)	0.0053 (5)	−0.0070 (5)	−0.0053 (5)
O3	0.0153 (5)	0.0196 (5)	0.0167 (5)	−0.0027 (4)	0.0006 (4)	−0.0046 (4)
O4	0.0219 (6)	0.0142 (5)	0.0302 (6)	−0.0051 (4)	0.0085 (5)	−0.0057 (4)
O5	0.0210 (6)	0.0185 (5)	0.0253 (6)	0.0094 (4)	−0.0018 (5)	−0.0068 (5)
O6	0.0331 (6)	0.0162 (5)	0.0152 (5)	−0.0024 (5)	0.0023 (5)	−0.0024 (4)
O7	0.0350 (7)	0.0169 (6)	0.0293 (7)	0.0113 (5)	−0.0149 (5)	−0.0073 (5)
O8	0.0463 (8)	0.0237 (7)	0.0367 (8)	0.0212 (6)	−0.0249 (6)	−0.0140 (6)
C1	0.0132 (7)	0.0125 (7)	0.0156 (7)	0.0004 (5)	0.0019 (5)	−0.0032 (5)
C2	0.0177 (7)	0.0144 (7)	0.0152 (7)	−0.0005 (6)	−0.0020 (6)	−0.0025 (6)
C3	0.0158 (7)	0.0123 (6)	0.0176 (7)	0.0023 (5)	−0.0005 (6)	0.0002 (5)
C4	0.0142 (7)	0.0105 (6)	0.0141 (7)	−0.0008 (5)	0.0029 (5)	−0.0016 (5)
C5	0.0184 (7)	0.0160 (7)	0.0168 (7)	0.0018 (6)	−0.0032 (6)	−0.0032 (6)
C6	0.0192 (7)	0.0147 (7)	0.0207 (8)	0.0062 (6)	−0.0028 (6)	−0.0032 (6)
C7	0.0482 (13)	0.0331 (11)	0.0375 (11)	−0.0098 (10)	0.0162 (10)	−0.0045 (9)
N1	0.0312 (8)	0.0175 (7)	0.0373 (9)	−0.0035 (6)	0.0154 (7)	−0.0030 (6)
C8	0.0363 (11)	0.0374 (12)	0.0601 (16)	0.0052 (9)	0.0091 (11)	−0.0063 (11)
C9	0.0353 (11)	0.0405 (11)	0.0326 (11)	0.0034 (9)	0.0096 (9)	0.0022 (9)
N2	0.0254 (8)	0.0297 (8)	0.0202 (7)	−0.0096 (6)	0.0087 (6)	−0.0050 (6)
C10	0.0577 (14)	0.0300 (10)	0.0236 (9)	0.0000 (10)	0.0052 (9)	−0.0045 (8)

Geometric parameters (Å, º) top

Zn1—O1	1.9055 (11)	C5—C6	1.392 (2)
Zn1—O3ⁱ	1.9671 (11)	C5—H5A	0.971 (19)
Zn1—O4ⁱⁱ	1.9330 (11)	C7—N1	1.480 (3)
Zn1—O5ⁱⁱⁱ	1.9543 (10)	C7—H7B	0.92 (2)
P1—O1	1.5151 (12)	C7—H7C	0.91 (2)
P1—O2	1.5169 (12)	C7—H7D	0.96 (2)
P1—O3	1.5337 (11)	N1—C8	1.479 (3)
P1—C1	1.8150 (14)	N1—H1A	0.89 (2)
P2—O6	1.5129 (11)	N1—H1B	0.89 (2)
P2—O4	1.5249 (11)	C8—H8B	1.00 (3)
P2—O5	1.5301 (11)	C8—H8C	1.01 (3)
P2—C4	1.8121 (14)	C8—H8D	0.98 (3)
O7—C3	1.3743 (18)	C9—N2	1.473 (3)
O7—H7A	0.79 (3)	C9—H9A	0.92 (2)
O8—C6	1.3668 (19)	C9—H9B	1.03 (3)
O8—H8A	0.86 (3)	C9—H9C	0.92 (3)
C1—C2	1.395 (2)	N2—C10	1.471 (2)
C1—C6	1.406 (2)	N2—H2B	0.83 (2)
C2—C3	1.392 (2)	N2—H2C	1.02 (3)
C2—H2A	0.968 (19)	C10—H10A	0.92 (4)
C3—C4	1.408 (2)	C10—H10B	0.98 (3)
C4—C5	1.394 (2)	C10—H10C	0.95 (3)

O1—Zn1—O4ⁱⁱ	116.04 (5)	O8—C6—C5	117.94 (14)
O1—Zn1—O5ⁱⁱⁱ	108.06 (5)	O8—C6—C1	121.95 (13)
O4ⁱⁱ—Zn1—O5ⁱⁱⁱ	113.58 (5)	C5—C6—C1	120.11 (13)
O1—Zn1—O3ⁱ	114.48 (5)	N1—C7—H7B	108.8 (17)
O4ⁱⁱ—Zn1—O3ⁱ	108.30 (5)	N1—C7—H7C	109.5 (15)
O5ⁱⁱⁱ—Zn1—O3ⁱ	94.45 (4)	H7B—C7—H7C	116 (2)
O1—P1—O2	114.83 (7)	N1—C7—H7D	107.5 (14)
O1—P1—O3	111.25 (7)	H7B—C7—H7D	109 (2)
O2—P1—O3	111.65 (7)	H7C—C7—H7D	106 (2)
O1—P1—C1	106.03 (7)	C8—N1—C7	112.97 (17)
O2—P1—C1	106.03 (7)	C8—N1—H1A	106.0 (14)
O3—P1—C1	106.38 (6)	C7—N1—H1A	107.9 (14)
O6—P2—O4	112.98 (7)	C8—N1—H1B	108.3 (14)
O6—P2—O5	114.05 (7)	C7—N1—H1B	111.4 (14)
O4—P2—O5	111.20 (7)	H1A—N1—H1B	110 (2)
O6—P2—C4	107.57 (6)	N1—C8—H8B	107.3 (14)
O4—P2—C4	105.95 (6)	N1—C8—H8C	110.0 (14)
O5—P2—C4	104.29 (6)	H8B—C8—H8C	109 (2)
P1—O1—Zn1	145.53 (8)	N1—C8—H8D	104.0 (15)
P1—O3—Zn1ⁱ	127.91 (7)	H8B—C8—H8D	111 (2)
P2—O4—Zn1^iv	137.62 (7)	H8C—C8—H8D	115 (2)
P2—O5—Zn1^v	142.34 (7)	N2—C9—H9A	104.4 (14)
C3—O7—H7A	107.0 (18)	N2—C9—H9B	105.8 (14)
C6—O8—H8A	101.6 (19)	H9A—C9—H9B	116 (2)
C2—C1—C6	118.38 (13)	N2—C9—H9C	107.6 (14)
C2—C1—P1	120.27 (11)	H9A—C9—H9C	109 (2)
C6—C1—P1	121.34 (11)	H9B—C9—H9C	113 (2)
C3—C2—C1	121.54 (14)	C10—N2—C9	113.51 (16)
C3—C2—H2A	118.3 (11)	C10—N2—H2B	112.3 (17)
C1—C2—H2A	120.1 (11)	C9—N2—H2B	106.7 (16)
O7—C3—C2	116.88 (13)	C10—N2—H2C	110.0 (14)
O7—C3—C4	123.19 (13)	C9—N2—H2C	106.8 (14)
C2—C3—C4	119.93 (13)	H2B—N2—H2C	107 (2)
C5—C4—C3	118.52 (13)	N2—C10—H10A	108 (2)
C5—C4—P2	118.11 (11)	N2—C10—H10B	108.4 (17)
C3—C4—P2	123.32 (11)	H10A—C10—H10B	107 (2)
C6—C5—C4	121.45 (14)	N2—C10—H10C	109.3 (16)
C6—C5—H5A	118.1 (11)	H10A—C10—H10C	110 (3)
C4—C5—H5A	120.4 (11)	H10B—C10—H10C	114 (2)

O2—P1—O1—Zn1	37.88 (16)	C1—C2—C3—O7	−177.72 (14)
O3—P1—O1—Zn1	−90.15 (14)	C1—C2—C3—C4	2.0 (2)
C1—P1—O1—Zn1	154.59 (13)	O7—C3—C4—C5	176.85 (14)
O1—P1—O3—Zn1ⁱ	−0.87 (10)	C2—C3—C4—C5	−2.8 (2)
O2—P1—O3—Zn1ⁱ	−130.59 (8)	O7—C3—C4—P2	−5.8 (2)
C1—P1—O3—Zn1ⁱ	114.17 (8)	C2—C3—C4—P2	174.51 (11)
O6—P2—O4—Zn1^iv	−63.56 (12)	O6—P2—C4—C5	−43.03 (13)
O5—P2—O4—Zn1^iv	66.18 (12)	O4—P2—C4—C5	78.06 (13)
C4—P2—O4—Zn1^iv	178.91 (10)	O5—P2—C4—C5	−164.49 (12)
O6—P2—O5—Zn1^v	43.33 (14)	O6—P2—C4—C3	139.65 (13)
O4—P2—O5—Zn1^v	−85.85 (13)	O4—P2—C4—C3	−99.26 (13)
C4—P2—O5—Zn1^v	160.39 (11)	O5—P2—C4—C3	18.19 (14)
O1—P1—C1—C2	71.83 (13)	C3—C4—C5—C6	1.5 (2)
O2—P1—C1—C2	−165.68 (12)	P2—C4—C5—C6	−175.95 (12)
O3—P1—C1—C2	−46.70 (14)	C4—C5—C6—O8	179.76 (15)
O1—P1—C1—C6	−107.45 (13)	C4—C5—C6—C1	0.7 (2)
O2—P1—C1—C6	15.04 (15)	C2—C1—C6—O8	179.40 (15)
O3—P1—C1—C6	134.02 (13)	P1—C1—C6—O8	−1.3 (2)
C6—C1—C2—C3	0.2 (2)	C2—C1—C6—C5	−1.6 (2)
P1—C1—C2—C3	−179.06 (12)	P1—C1—C6—C5	177.73 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O5	0.79 (2)	1.91 (2)	2.6510 (17)	156 (3)
O8—H8A···O2	0.87 (3)	1.73 (3)	2.5846 (18)	168 (3)
N1—H1A···O2	0.89 (2)	1.88 (2)	2.7168 (19)	155.2 (18)
N1—H1B···O6^vi	0.89 (2)	2.02 (2)	2.8125 (19)	148.3 (18)
N2—H2B···O3^vii	0.83 (3)	2.07 (3)	2.8558 (19)	158 (2)
N2—H2C···O6	1.03 (2)	1.63 (2)	2.6518 (18)	173 (2)
C7—H7C···O4ⁱⁱ	0.91 (2)	2.54 (2)	3.443 (3)	174 (2)
C9—H9B···O8^viii	1.03 (3)	2.57 (2)	3.445 (3)	142.6 (19)
C10—H10A···O8^viii	0.92 (3)	2.42 (3)	3.236 (3)	148 (3)

Symmetry codes: (ii) −x+3/2, y−1/2, −z+1/2; (vi) −x+1, −y+1, −z+1; (vii) x+1/2, −y+3/2, z+1/2; (viii) −x+3/2, y+1/2, −z+3/2.

Acknowledgements

We thank St. Mary's University, the School of Science, Engineering and Technology, and the Department of Chemistry and Biochemistry for supporting undergraduate research. Single-crystal X-ray analyses were conducted at the Materials Characterization Facility of the Center of Sustainable Energy at the University of Notre Dame.

Funding information

Funding for this research was provided by: Welch Foundation Departmental Research Grant Program (grant No. U-0047); St. Mary's University Internal Faculty Research Grant Award.

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