In the title hybrid organic–inorganic compound, the (CH3)2NH2 + cations interact with the zinc–phosphonate framework via N—H⋯O hydrogen bonds. The (CH3)2NH2 + cations were formed by the in situ decarbonylation of the N,N-dimethylformamide (DMF) solvent.
Keywords: crystal structure, decarbonylation, phosphonic acid, inorganic–organic hybrid framework, hydrogen bonding
Abstract
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 PO3 2− groups are observed.
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.
Structural commentary
The structure of (I) crystallizes in the monoclinic space group P21/n. The asymmetric unit contains one Zn2+ cation, a C6H4P2O8 4− 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 PO3 2− 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 C6H6P2O8 2− 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.
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 RPO3 2− moieties (Figs. 1 ▸ and 3 ▸). Within the channels, the (CH3)2NH2 + cations are linked by N—H⋯O hydrogen bonds to the RPO3 2− groups of the framework (Table 1 ▸). Some short C—H⋯O contacts (Table 1 ▸) may help to consolidate the structure.
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 ▸.
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⋯O8iv | 1.03 (3) | 2.57 (2) | 3.445 (3) | 142.6 (19) |
| C10—H10A⋯O8iv | 0.92 (3) | 2.42 (3) | 3.236 (3) | 148 (3) |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
.
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.
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[F 2 > 2σ(F 2)], wR(F 2), 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 |
| Δρmax, Δρmin (e Å−3) | 0.42, −0.31 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019012969/hb7847sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019012969/hb7847Isup2.hkl
CCDC reference: 1954737
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
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.
supplementary crystallographic information
Crystal data
| (C2H8N)2[Zn(C6H4O8P2)] | F(000) = 872 |
| Mr = 423.59 | Dx = 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
| Bruker APEXII diffractometer | 4040 independent reflections |
| Radiation source: Incoatec micro-focus | 3582 reflections with I > 2σ(I) |
| Detector resolution: 8.33 pixels mm-1 | Rint = 0.027 |
| combination of ω and φ–scans | θmax = 29.0°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
| Tmin = 0.706, Tmax = 0.746 | k = −22→21 |
| 19692 measured reflections | l = −14→14 |
Refinement
| 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(Fo2) + (0.0327P)2 + 0.4955P] where P = (Fo2 + 2Fc2)/3 |
| 4040 reflections | (Δ/σ)max = 0.002 |
| 288 parameters | Δρmax = 0.42 e Å−3 |
| 1 restraint | Δρmin = −0.31 e Å−3 |
Special details
| 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)
| x | y | z | Uiso*/Ueq | ||
| 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)
| 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)
| 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—Zn1iv | 137.62 (7) | H8C—C8—H8D | 115 (2) |
| P2—O5—Zn1v | 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—Zn1iv | −63.56 (12) | O6—P2—C4—C5 | −43.03 (13) |
| O5—P2—O4—Zn1iv | 66.18 (12) | O4—P2—C4—C5 | 78.06 (13) |
| C4—P2—O4—Zn1iv | 178.91 (10) | O5—P2—C4—C5 | −164.49 (12) |
| O6—P2—O5—Zn1v | 43.33 (14) | O6—P2—C4—C3 | 139.65 (13) |
| O4—P2—O5—Zn1v | −85.85 (13) | O4—P2—C4—C3 | −99.26 (13) |
| C4—P2—O5—Zn1v | 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)
| 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···O6vi | 0.89 (2) | 2.02 (2) | 2.8125 (19) | 148.3 (18) |
| N2—H2B···O3vii | 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···O8viii | 1.03 (3) | 2.57 (2) | 3.445 (3) | 142.6 (19) |
| C10—H10A···O8viii | 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.
Funding Statement
This work was funded by Welch Foundation Departmental Research Grant Program grant U-0047. St. Mary’s University Internal Faculty Research Grant Award grant .
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019012969/hb7847sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019012969/hb7847Isup2.hkl
CCDC reference: 1954737
Additional supporting information: crystallographic information; 3D view; checkCIF report