1. Chemical context
Since the first report (Harrison et al., 2001) of zincophosphite (ZnPO) networks built up from vertex-sharing ZnO4 or ZnO3N and HPO3 building units templated or ligated by organic species, this family has grown to include well over 200 structures in the Cambridge Structural Database (CSD; Groom et al., 2016). Recent papers have described a ZnPO templated by a chiral amino acid, which displays non-linear optical behaviour (Mao et al., 2021) and a mixed-ligand ZnPO with promising gas sorption properties (Chen et al., 2022). As well as their potential applications, ZnPOs are of ongoing academic interest in terms of the challenge of designing rational and reproducible syntheses and the elucidation of the systematics of their crystal chemistry, for example, the effect of the Zn:P ratio, different polyhedral connectivities, hydrogen bonding and the `dual role' (bonded ligand or protonated guest) of the organic template on the structure (Holmes et al., 2018).
In a continuation of our ongoing studies of these systems (Katinaitė & Harrison, 2017; Holmes et al., 2018), we now describe the hydrothermal syntheses and crystal structures of four organo–zinc phosphites featuring isomeric ligands, viz.: poly[[(2-amino-3-methylpyridine)-μ3-phosphonato-zinc] hemihydrate], {[Zn(HPO3)(C6H8N2)]·0.5H2O}n, (I), poly[(2-amino-4-methylpyridine)-μ3-phosphonato-zinc], [Zn(HPO3)(C6H8N2)]n, (II), poly[(2-amino-5-methylpyridine)-μ3-phosphonato-zinc], [Zn(HPO3)(C6H8N2)]n, (III), and poly[bis(2-amino-4-methylpyridinium) [tetra-μ3-phosphonato-trizinc] monohydrate], {(C6H9N2)2[Zn3(HPO3)4]·H2O}n, (IV). The simple molecular salt bis(2-amino-3-methylpyridinium) tetrachlorozincate monohydrate, (C6H8N2)2·ZnCl4·H2O (V), is also described.
2. Structural commentary
The asymmetric unit of (I) (Fig. 1), which crystallizes in the monoclinic space group C2/c, consists of a Zn2+ ion, a [HPO3]2– hydrogen phosphite anion, a C6H7N2 2-amino-3-methylpyridine molecule and a water molecule, the O atom of the last species lying on a crystallographic twofold axis. The zinc coordination polyhedron is a ZnO3N tetrahedron, i.e., the organic species is acting as a ligand bonding to the metal ion from its pyridine nitrogen atom and the Zn—O bonds (mean = 1.940 Å) are notably shorter than the Zn1—N1 [2.0262 (14) Å] link, as previously observed for related compounds (Holmes et al., 2018). The spread of bond angles about the metal ion [minimum = 104.23 (5) for O2—Zn1—N1, maximum = 113.89 (6)° for O1—Zn1—N1] indicates a slight degree of distortion with τ4′ = 0.974 (Okuniewski et al., 2015). The [HPO3]2– group adopts its usual tetrahedral (including the H atom) or pseudo-pyramidal (excluding H) geometry and the mean P—O separation is 1.522 Å with the O—P—O bond angles tightly clustered in the range 111.98 (7)–113.57 (7)°; the P atom is displaced by 0.4227 (8) Å from the plane of its attached O atoms. Each O atom is bonded to one Zn and one P atom [mean Zn—O—P = 130.2°], thus there are no `dangling' (Holmes et al., 2018) Zn—OH2, P=O or P—OH bonds in this structure. The extended structure of (I) is discussed below.
| Figure 1 The asymmetric unit of (I) expanded to show the complete zinc-atom coordination sphere showing 50% displacement ellipsoids. Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, y + 1, z. |
The asymmetric unit of (II) (Fig. 2), which also crystallizes in C2/c, consists of two Zn2+ ions, two [HPO3]2– hydrogen phosphite anions, and two C6H7N2 2-amino-4-methylpyridine molecules acting as ligands, i.e., Z′ = 2. Unlike (I), (II) does not contain any water molecules of crystallization. The building units – vertex sharing ZnO3N tetrahedra and [HPO3]2– dianions – and the major structural features of (II) are broadly similar to those of (I): mean Zn1—O = 1.942 Å; spread of O—Zn1—O/O—Zn1—N bond angles = 104.06 (5)–114.29 (5)°, τ4′ = 0.97; comparable data for Zn2 = 1.940 Å, 100.10 (5)–121.28 (5)° and 0.91, respectively; mean P1—O = 1.525 Å; spread of O—P1—O bond angles = 110.64 (6)–113.78 (6)°; P1 displacement from its attached O atoms = 0.4278 (7) Å; comparable data for P2 = 1.520 Å, 111.44 (6)–113.14 (7)° and −0.4269 (8) Å, respectively. All six O atoms are bridging between Zn and P atoms with a mean bond angle of 131.3° [range = 123.26 (6)–144.09 (8)°]. The extended structure of (II) is discussed below.
| Figure 2 The asymmetric unit of (II) expanded to show the complete zinc-atom coordination spheres showing 50% displacement ellipsoids. Symmetry codes: (i) − x, − y, 1 − z; (ii) 1 − x, y, − z. |
Compound (III) crystallizes in the orthorhombic space group P212121 with a well-defined absolute structure and its asymmetric unit (Fig. 3) consists of a Zn2+ ion, a [HPO3]2– hydrogen phosphite anion and a C6H7N2 2-amino-5-methylpyridine molecule bonded to the metal ion from its pyridine N atom. Once again, the constituent polyhedra are ZnO3N tetrahedra [mean Zn—O = 1.941 Å, minimum and maximum bond angles = 105.19 (9) and 115.09 (8)°, respectively, τ4′ = 0.96] and [HPO3]2– units [mean P—O = 1.522 Å, minimum and maximum O—P—O = 110.43 (11) and 113.86 (12)°, respectively, deviation of P1 from O1/O2/O3 = 0.4237 (14) Å]. The three O atoms bridge adjacent zinc and phosphorus atoms with a mean Zn—O—P bond angle of 126.7°. For the extended structure of (III), see below.
| Figure 3 The asymmetric unit of (III) expanded to show the complete zinc-atom coordination sphere showing 50% displacement ellipsoids. Symmetry codes: (i) + x, − y, −z; (ii) 1 + x, y, z. |
In (IV), which crystallizes in the triclinic space group P, the expanded asymmetric unit (Fig. 4) reveals different constituent polyhedra of three distinct ZnO4 tetrahedra and four [HPO32–] pseudo pyramids as well as two protonated 2-amino-4-methylpyridinium cations, which therefore act as templates rather than ligands; a water molecule of crystallization (O13) completes the structure. Geometrical data for the zinc polyhedra are as follows: mean Zn1—O = 1.941 Å, spread of bond angles = 100.42 (8)–122.18 (9)°, τ4' = 0.90; equivalent data for Zn2: 1.936 Å, 98.33 (8)–115.30 (9)° and 0.98, respectively; equivalent data for Zn3: 1.945 Å, 99.70 (8)–117.10 (8)° and 0.96, respectively. The four [HPO3]2– anions adopt their normal geometries: mean P1—O = 1.519 Å, minimum and maximum O—P1—O = 111.00 (11) and 112.70 (11)°, respectively, deviation of P1 from its attached O atoms = 0.4498 (13) Å; equivalent data for P2: 1.522 Å, 110.08 (10)°, 115.33 (11)° and −0.4122 (12) Å, respectively; equivalent data for P3: 1.516 Å, 110.19 (11)°, 114.49 (12)° and −0.4123 (13) Å, respectively; equivalent data for P4: 1.516 Å, 112.68 (12)°, 114.13 (12)° and 0.3903 (13) Å, respectively. The twelve unique O atoms all bridge Zn and P atoms (mean bond angle = 134.9, minimum = 125.40 (11), maximum = 146.90 (13), spread = 21.5°). For the extended structure of (IV), see below.
| Figure 4 The asymmetric unit of (IV) expanded to show the complete zinc-atom coordination sphere showing 50% displacement ellipsoids. Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) x − 1, y, z; (iii) −x, 1 − y, −z; (iv) 1 − x, 1 − y, −z. |
Compound (V) is a simple molecular salt (Fig. 5), which crystallizes in the triclinic space group P: its asymmetric unit consists of two 2-amino-3-methylpyridinium C6H8N2+ cations protonated at their pyridine N atoms, a [ZnCl4]2– anion and a water molecule of crystallisation. The tetrachlorozincate ion has a mean Zn—Cl separation of 2.2704 Å [range = 2.2536 (13)–2.2867 (13) Å] and smallest and largest Cl—Zn—Cl bond angles of 104.48 (5) and 113.75 (5)°, respectively. The synthetic intent here was to lower the pH with HCl and establish if a dihydrogen phosphite (H2PO3−) anion containing a terminal P—OH moiety could be incorporated into the structure (Lin et al., 2003) but the presence of excess chloride ions has led to a completely different and unwanted molecular salt containing the tetrachlorozincate complex ion, which has been reported many times before, with over 1000 matches in the CSD.
| Figure 5 The asymmetric unit of (V) showing 50% displacement ellipsoids. Hydrogen bonds are indicated by double-dashed lines. |
3. Supramolecular features
In the extended structure of (I), the constituent ZnO3N and HPO3 polyhedra are linked by Zn—O—P bonds into [010] polyhedral 4-ring (two Zn and two P nodes) `ladder' chains in which the zinc and phosphorus nodes strictly alternate (Fig. 6): the chains are built up by inversion symmetry at the centres of every 4-ring, as well as, of course, translation symmetry in the b-axis direction. Given that the Zn atom forms three bonds (via O atoms) to adjacent P atoms (and a fourth bond to the organic species) and that the P atom forms three links to zinc atoms (and a fourth P—H vertex), the 1:1 Zn:P stoichiometry is to be expected and hence no charge compensating, protonated template is needed. In (II), ladder chains similar to those seen in (I) arise in the extended structure (Fig. 6) although they are more contorted: because Z′ = 2, every other 4-ring is generated by inversion symmetry and translation in the [101] direction leads to the extended array. In (III), the 4-ring ladder motif is again apparent (Fig. 6), although in this case, the combination of a 21 screw-axis parallel to the chain and a-translation symmetry generates the infinite [100] chains. In each structure, the organic molecules are pendant to the chains (Fig. 6).
| Figure 6 Comparison of the zincophosphite 4-ring ladder chains in the extended structures of (I) (left), (II) (centre) and (III) (right). |
The extended structure of (IV) (Fig. 7) is quite different to those of (I)–(III) and features (010) sheets of ZnO4 and HPO3 polyhedra sharing corners. One way to visualize this rather complex arrangement (although this does not necessarily imply that the synthesis proceeds in such a step-by-step fashion) is in terms of contorted chains of 4-rings featuring atoms Zn1, Zn2, Zn3, P2, P3 and P4 as the nodes propagating in the [001] direction. One out of every three 4-rings in a chain is generated by inversion symmetry. These chains are cross-linked in the a-axis direction by the P1-centred hydrogen phosphite groups to form the (010) layers, which encapsulate 8-ring voids built up from four Zn and four P nodes although there is no suggestion of `zeolitic' porosity. So far as stoichiometry is concerned, in this case the zinc nodes forming four bonds (via all their O atoms) to nearby phosphorus atoms and the P nodes forming three bonds to Zn atoms leads to the 3:4 ratio of zinc and phosphorus, which is the proportion most commonly seen in this family of phases (e.g., Phillips et al., 2002; Lin et al., 2009). In this case, the inorganic component bears a charge of −2 per [Zn3(HPO3)4] unit, hence the two protonated template molecules. The template cations and water molecules of crystallisation occupy the inter-layer regions.
| Figure 7 Part of an infinite (010) layer of vertex sharing ZnO4 and HPO3 moieties in the extended structure of (IV) viewed down [010]. |
Various classical (N—H⋯O, N—H⋯Cl and O—H⋯O) and non-classical (C—H⋯O and C—H⋯Cl) hydrogen bonds occur in these structures. As is normal, the hydrogen phosphite P—H unit does not participate in hydrogen bonding (Katinaitė & Harrison, 2017). In (I), the water molecule of crystallization, which lies on a crystallographic twofold axis, appears to play an important role in consolidating the extended structure by accepting two N—H⋯O hydrogen bonds (Table 1) and donating two O—H⋯O hydrogen bonds to cross-link the [001] chains into (100) layers (Fig. 8). The other hydrogen bond arising from the amine group is an intra-chain N—H⋯O link. There are no aromatic π–π stacking interactions in (I), the shortest centroid–centroid separation being some 5.04 Å.
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N2—H1N⋯O4i | 0.78 (2) | 2.19 (2) | 2.919 (2) | 157 (2) | N2—H2N⋯O2ii | 0.84 (2) | 2.54 (2) | 3.098 (2) | 124.8 (18) | O4—H1O⋯O2 | 0.79 (2) | 2.199 (19) | 2.9165 (15) | 152 (2) | Symmetry codes: (i) ; (ii) . | |
| Figure 8 The unit-cell packing in (I) viewed down [001]. Hydrogen bonds are shown as dashed lines. |
In (II), the N—H⋯O hydrogen bonds arising from the amine groups are a mix of intra- (via H2N and H4N) and inter-chain (via H1N and H3N) links, with the latter serving to cross-link the [101] chains into a three-dimensional network (Table 2; Fig. 9). The aromatic rings are interdigitated and this is reflected in the shortest centroid–centroid separation of 3.8234 (17) Å. In the extended structure of (III) (Fig. 10), the single N1—H2B⋯O2 bond (Table 3) cross-links the [100] chains into (001) sheets. The other hydrogen atom (H2A) of the amine grouping does not participate in a hydrogen bond, the closest acceptor O atom being some 2.77 Å distant. There are no significant π–π stacking interactions in (III) [shortest centroid–centroid separation = 5.149 (2) Å].
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N2—H1N⋯O3i | 0.79 (2) | 2.35 (2) | 2.9056 (19) | 128 (2) | N2—H2N⋯O6ii | 0.82 (2) | 2.13 (2) | 2.900 (2) | 155 (2) | N4—H3N⋯O1iii | 0.88 (2) | 2.18 (2) | 3.0310 (18) | 163.7 (18) | N4—H4N⋯O5iv | 0.83 (2) | 2.39 (2) | 3.1555 (19) | 154.3 (18) | C5—H5⋯O2 | 0.95 | 2.57 | 3.315 (2) | 136 | C8—H8⋯O1iii | 0.95 | 2.65 | 3.405 (2) | 137 | C11—H11⋯O4 | 0.95 | 2.51 | 3.105 (2) | 120 | Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . | |
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N2—H2B⋯O2i | 0.79 (4) | 2.35 (4) | 3.111 (3) | 162 (3) | C2—H2⋯O1ii | 0.95 | 2.55 | 3.212 (3) | 127 | Symmetry codes: (i) ; (ii) . | |
| Figure 9 The unit-cell packing in (II) viewed down [101]. Hydrogen bonds are shown as dashed lines. |
| Figure 10 The unit-cell packing in (III) viewed down [100]. Hydrogen bonds are shown as dashed lines. |
In (IV), numerous hydrogen bonds are observed (Table 4, Fig. 11). The water molecule cross-links adjacent (010) layers via two O—H⋯O hydrogen bonds. The N—H⋯O hydrogen bonds originating from the protonated pyridine N atoms and the –NH2 groups of the organic species all link to the same sheet for each template cation, i.e., there are no inter-sheet hydrogen bonds associated with the templates. Significant aromatic π–π stacking interactions occur between centrosymmetric pairs of each template cation, as indicated by the centroid–centroid separation of 3.6167 (15) Å (slippage = 1.196 Å) for the C1 species and 3.4695 (17) Å (0.146 Å) for the C7 cation.
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N1—H1A⋯O5i | 0.88 | 1.97 | 2.833 (3) | 166 | N2—H2N⋯O3 | 0.85 (4) | 2.05 (4) | 2.853 (3) | 157 (3) | N2—H3N⋯O10 | 0.85 (4) | 2.16 (4) | 2.961 (3) | 156 (3) | N3—H4N⋯O1 | 0.83 (4) | 2.07 (4) | 2.873 (3) | 163 (4) | N4—H5N⋯O13ii | 0.93 (4) | 1.95 (4) | 2.871 (4) | 177 (4) | N4—H6N⋯O2 | 0.88 (4) | 2.05 (4) | 2.918 (3) | 167 (4) | O13—H1O⋯O12iii | 0.98 | 2.05 | 3.028 (3) | 175 | O13—H2O⋯O4iv | 0.96 | 2.05 | 2.952 (3) | 157 | C5—H5⋯O4i | 0.95 | 2.64 | 3.370 (3) | 134 | C8—H8⋯O8v | 0.95 | 2.48 | 3.350 (4) | 152 | C11—H11⋯O7 | 0.95 | 2.47 | 3.199 (4) | 133 | C11—H11⋯O13iv | 0.95 | 2.59 | 3.281 (4) | 130 | Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) . | |
| Figure 11 The unit-cell packing in (IV) viewed down [100]. Hydrogen bonds are shown as dashed lines. |
In the extended structure of (V), the hydrogen-bond scheme is completely different (Table 5) and the component cations, anions and water molecules are linked by N—H⋯Cl, N—H⋯Ow (w = water) and O—H⋯Cl interactions to generate [001] chains; within these chains, centrosymmetric assemblages of two C6H8N2+ cations, two [ZnCl4]2– anions and two water molecules are apparent (Fig. 12).
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N1—H1⋯Cl4 | 0.88 | 2.35 | 3.134 (5) | 148 | N2—H2A⋯Cl1 | 0.88 | 2.54 | 3.375 (4) | 158 | N2—H2B⋯O1 | 0.88 | 2.03 | 2.838 (5) | 152 | N3—H3A⋯Cl4 | 0.88 | 2.66 | 3.306 (4) | 132 | N4—H4A⋯Cl3 | 0.88 | 2.40 | 3.268 (4) | 170 | N4—H4B⋯Cl2i | 0.88 | 2.51 | 3.333 (5) | 155 | O1—H1O⋯Cl3ii | 0.88 | 2.95 | 3.669 (4) | 141 | O1—H1O⋯Cl4ii | 0.88 | 2.98 | 3.675 (4) | 138 | O1—H2O⋯Cl1iii | 0.88 | 2.45 | 3.302 (4) | 162 | C10—H10⋯Cl3iv | 0.95 | 2.92 | 3.696 (5) | 140 | Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . | |
| Figure 12 The unit-cell packing in (V) viewed approximately down [10]. Hydrogen bonds are shown as dashed lines. |
4. Database survey
A survey of the Cambridge Structural Database (Groom et al., 2016; updated to February 2023) revealed 213 crystal structures containing zinc cations and hydrogenphosphite anions (Zn—O—P—H fragment) of which 53 contain a ligated organic molecule (Zn—N bond). The only phase that bears a close chemical similarity to the structures described here is [C5H6N2·Zn(HPO3)]n, catena-[(μ3-hydrogenphosphito)(2-aminopyridine)zinc] (CSD refcode LUZYOU) (Liang et al., 2003), in which the ZnO3N and HPO3 polyhedra assemble into (100) layers of 4- and 8-rings.
The fact that the N-bonded zinc ions and HPO3 units in (I), (II) and (III) self assemble to form the same 4-ring ladder chain with different isomeric pyridine-based ligands suggests that it is a reasonably robust structural feature. However, it is not a particularly common motif in the wider ZnPO phase space: two other examples with very different ligating molecules to those in (I)–(III) are [C4H8N2O3·Zn(HPO3)]n (C4H8N2O3 = L-asparagine) (Gordon & Harrison, 2004) and [C3H7NO2·Zn(HPO3)]n (C3H7NO2 = racemic DL-alanine) (Mao et al., 2021); it is notable that these amino acids both bond to the zinc atom via one of their carboxylate O atoms rather than the pyridine N atoms in (I)–(III).
Compound (II), in which the C6H8N2 organic molecule acts as a ligand (a Zn—N bond and a 1:1 Zn:P ratio) and (IV), in which the same organic species acts as a protonated C6H9N2+ template (N—H⋯O hydrogen bonds and a 3:4 Zn:P ratio) arose from similar syntheses, with the only difference being the source of zinc ions (zinc oxide and zinc acetate, respectively). Assuming that hydrothermal synthesis is not just an impenetrable `black box' (Ursu et al., 2022), we may speculate that the acetate synthesis occurred at a lower pH, perhaps with some buffering action between acetic acid formed in situ and acetate ions, to allow for the protonation of the template.
5. Synthesis and crystallization
Compound (I) was prepared by mixing 0.77 g of ZnO, 0.76 g of H3PO3 and 1.14 g of 2-amino-3-methylpyridine (Zn:P:template ratio ≃ 1:1:1), which were placed in a 50 ml polypropylene bottle with 20 ml of water and shaken well to result in a white slurry. The bottle was placed in an 353 K oven for 24 h and then removed and allowed to cool to room temperature. The solids were recovered by vacuum filtration to result in a mass of needle-like transparent crystals. IR: 2383 cm−1 (P—H stretch). Increasing the heating time to one week led to the same product, with a slight improvement in crystallinity, as indicated by sharper peaks in its IR spectrum and X-ray powder diffraction pattern.
Compound (II) was prepared from 0.75 g of ZnO, 0.81 g of H3PO3 and 1.10 g of 2-amino-4-methylpyridine (Zn:P:template ratio ≃ 1:1:1); otherwise following the same procedure as for (I). A mass of blocky transparent crystals was recovered. IR: 2394, 2382 cm−1 (P—H stretch). Two peaks may arise because of the two different P—H groups in the asymmetric unit (Ma et al., 2007).
To prepare compound (III), 2.20 g of Zn(OAc)2, 0.86 g of H3PO3 and 1.09 g of 2-amino-5-methylpyridine (Zn:P:template ratio ≃ 1:1:1) and 20 ml of water were placed in a 50 ml polypropylene bottle and heated to 353 K for three days. Upon cooling, the product consisted of a mass of colourless blocks. IR: 2406 cm−1 (P—H stretch).
Compound (IV) started from a mixture of 2.02 g Zn(OAc)2, 0.77 g of H3PO3 and 1.03 g of 2-amino-4-methylpyridine (Zn:P:template ratio ≃ 1:1:1) and 20 ml of water. These components were placed in a 50-ml polypropylene bottle and heated to 353 K for 24 h. Upon cooling, the product consisted of a mass of colourless blocks. IR: 3000–3600 (broad) (O—H stretch), 2391, 2381 cm−1 (P—H stretch). The same product arises if the mixture is heated for one week.
Compound (V) was prepared from the same reagents as (I) and the same synthesis procedure but with the addition of 10 ml of 1 M HCl.
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 6. Most of the O- and N-bound H atoms were located in difference maps and their positions were freely refined with Uiso(H) = 1.2Ueq(N or O). The phosphite H atoms were geometrically placed (P—H = 1.32 Å) and refined as riding atoms with Uiso(H) = 1.2Ueq(P). All the C-bound H atoms were located geometrically (C—H = 0.95–0.98 Å) and refined as riding atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density. Two peaks greater than 1 e Å−3 were found in the final difference map for (IV) in the vicinity of the C7 cation but they did not correspond to a plausible chemical feature. The data quality for (V) was notably poorer than for the other four crystals.
| (I) | (II) | (III) | (IV) | (V) | Crystal data | Chemical formula | [Zn(HPO3)(C6H8N2)]·0.5H2O | [Zn(HPO3)(C6H8N2)] | [Zn(HPO3)(C6H8N2)] | (C6H9N2)2[Zn3(HPO3)4]·H2O | (C6H8N2)2[ZnCl4]·H2O | Mr | 525.00 | 253.49 | 253.49 | 752.34 | 443.49 | Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c | Orthorhombic, P212121 | Triclinic, P | Triclinic, P | Temperature (K) | 93 | 93 | 93 | 93 | 173 | a, b, c (Å) | 23.282 (6), 5.1926 (1), 17.738 (5) | 22.873 (6), 12.307 (3), 16.633 (4) | 5.1487 (9), 8.5316 (19), 20.371 (5) | 9.03805 (13), 9.36837 (13), 15.0207 (2) | 6.9541 (8), 8.7092 (9), 16.293 (3) | α, β, γ (°) | 90, 117.974 (4), 90 | 90, 128.954 (5), 90 | 90, 90, 90 | 81.0313 (1), 88.0646 (1), 80.0782 (1) | 83.239 (11), 80.167 (10), 72.049 (9) | V (Å3) | 1893.9 (7) | 3641.1 (16) | 894.8 (3) | 1237.46 (3) | 922.7 (2) | Z | 4 | 16 | 4 | 2 | 2 | Radiation type | Mo Kα | Mo Kα | Mo Kα | Cu Kα | Mo Kα | μ (mm−1) | 2.75 | 2.85 | 2.90 | 6.49 | 1.92 | Crystal size (mm) | 0.20 × 0.02 × 0.02 | 0.10 × 0.03 × 0.03 | 0.15 × 0.05 × 0.03 | 0.10 × 0.10 × 0.10 | 0.15 × 0.05 × 0.05 | | Data collection | Diffractometer | Rigaku Pilatus 200K CCD | Rigaku Pilatus 200K CCD | Rigaku Pilatus 200K CCD | Rigaku Pilatus 200K CCD | AFC10: Fixed Chi 2 circle CCD | Absorption correction | Multi-scan CrystalClear (Rigaku, 2015) | Multi-scan CrystalClear (Rigaku, 2015) | Multi-scan CrystalClear (Rigaku, 2015) | Multi-scan CrystalClear (Rigaku, 2015) | Multi-scan | Tmin, Tmax | 0.535, 1.000 | 0.783, 1.000 | 0.505, 1.000 | 0.744, 1.000 | 0.851, 1.000 | No. of measured, independent and observed [I > 2σ(I)] reflections | 22221, 1729, 1644 | 50824, 3308, 3177 | 13254, 1630, 1599 | 11869, 4842, 4831 | 28291, 3383, 3172 | Rint | 0.045 | 0.033 | 0.067 | 0.012 | 0.039 | (sin θ/λ)max (Å−1) | 0.602 | 0.602 | 0.602 | 0.628 | 0.603 | | Refinement | R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.048, 1.04 | 0.017, 0.049, 1.05 | 0.021, 0.051, 1.01 | 0.031, 0.085, 1.10 | 0.047, 0.111, 1.08 | No. of reflections | 1729 | 3308 | 1630 | 4842 | 3383 | No. of parameters | 133 | 249 | 125 | 343 | 203 | H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | Δρmax, Δρmin (e Å−3) | 0.27, −0.31 | 0.30, −0.40 | 0.59, −0.42 | 1.25, −0.67 | 1.10, −1.02 | Absolute structure | – | – | Parsons et al., 2013 | – | – | Absolute structure parameter | – | – | 0.011 (6) | – | – | Computer programs: CrystalClear (Rigaku, 2015), SHELXS97 (Sheldrick, 2008), SHELXL2018/3 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and publCIF (Westrip, 2010). | |
Supporting information
For all structures, data collection: CrystalClear (Rigaku, 2015); cell refinement: CrystalClear (Rigaku, 2015); data reduction: CrystalClear (Rigaku, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015) for (I), (II), (III), (IV); SHELXL-2018/3 (Sheldrick, 2015) for (V). For all structures, molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).
Poly[[(2-amino-3-methylpyridine)-µ
3-phosphonato-zinc] hemihydrate] (I)
top Crystal data top [Zn(HPO3)(C6H8N2)]·0.5H2O | F(000) = 1064 |
Mr = 525.00 | Dx = 1.841 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 23.282 (6) Å | Cell parameters from 2870 reflections |
b = 5.1926 (1) Å | θ = 2.6–27.4° |
c = 17.738 (5) Å | µ = 2.75 mm−1 |
β = 117.974 (4)° | T = 93 K |
V = 1893.9 (7) Å3 | Plate, colourless |
Z = 4 | 0.20 × 0.02 × 0.02 mm |
Data collection top Rigaku Pilatus 200K CCD diffractometer | 1644 reflections with I > 2σ(I) |
ω scans | Rint = 0.045 |
Absorption correction: multi-scan CrystalClear (Rigaku, 2015) | θmax = 25.3°, θmin = 2.0° |
Tmin = 0.535, Tmax = 1.000 | h = −28→28 |
22221 measured reflections | k = −6→6 |
1729 independent reflections | l = −21→21 |
Refinement top Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.017 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.048 | w = 1/[σ2(Fo2) + (0.023P)2 + 2.3217P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
1729 reflections | Δρmax = 0.27 e Å−3 |
133 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | |
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 | Uiso*/Ueq | |
Zn1 | 0.57140 (2) | 0.80209 (4) | 0.58868 (2) | 0.01314 (8) | |
P1 | 0.57761 (2) | 0.29299 (8) | 0.49128 (3) | 0.01281 (11) | |
H1 | 0.623752 | 0.252550 | 0.469333 | 0.015* | |
O1 | 0.57635 (6) | 0.5813 (2) | 0.50423 (8) | 0.0230 (3) | |
O2 | 0.51441 (6) | 0.1968 (2) | 0.41659 (7) | 0.0201 (3) | |
O3 | 0.59745 (6) | 0.1434 (2) | 0.57337 (7) | 0.0202 (3) | |
C1 | 0.62119 (8) | 0.5143 (3) | 0.75510 (10) | 0.0155 (3) | |
C2 | 0.66659 (8) | 0.4595 (3) | 0.84181 (10) | 0.0178 (4) | |
C3 | 0.72325 (8) | 0.6005 (4) | 0.87796 (10) | 0.0210 (4) | |
H3 | 0.754671 | 0.567006 | 0.935325 | 0.025* | |
C4 | 0.73559 (8) | 0.7932 (4) | 0.83177 (11) | 0.0198 (4) | |
H4 | 0.774780 | 0.890002 | 0.856994 | 0.024* | |
C5 | 0.68950 (8) | 0.8368 (3) | 0.74957 (11) | 0.0167 (3) | |
H5 | 0.697186 | 0.967793 | 0.717992 | 0.020* | |
C6 | 0.65085 (10) | 0.2538 (4) | 0.88920 (12) | 0.0232 (4) | |
H6A | 0.609698 | 0.295572 | 0.888912 | 0.035* | |
H6B | 0.685707 | 0.245000 | 0.948255 | 0.035* | |
H6C | 0.646912 | 0.087146 | 0.861266 | 0.035* | |
N1 | 0.63290 (7) | 0.7007 (3) | 0.71073 (9) | 0.0146 (3) | |
N2 | 0.56459 (7) | 0.3842 (3) | 0.71611 (10) | 0.0198 (3) | |
H1N | 0.5571 (10) | 0.268 (4) | 0.7377 (14) | 0.024* | |
H2N | 0.5404 (10) | 0.394 (4) | 0.6633 (13) | 0.024* | |
O4 | 0.500000 | 0.0486 (4) | 0.250000 | 0.0216 (4) | |
H1O | 0.5071 (11) | 0.136 (4) | 0.2897 (12) | 0.026* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.01503 (12) | 0.01152 (13) | 0.01196 (12) | 0.00098 (7) | 0.00558 (9) | 0.00153 (7) |
P1 | 0.0145 (2) | 0.0111 (2) | 0.0136 (2) | 0.00076 (16) | 0.00731 (18) | 0.00110 (15) |
O1 | 0.0414 (8) | 0.0122 (7) | 0.0254 (6) | 0.0024 (6) | 0.0239 (6) | 0.0024 (5) |
O2 | 0.0155 (6) | 0.0297 (8) | 0.0135 (6) | 0.0022 (5) | 0.0056 (5) | −0.0024 (5) |
O3 | 0.0264 (7) | 0.0123 (6) | 0.0157 (6) | −0.0028 (5) | 0.0047 (5) | 0.0016 (5) |
C1 | 0.0194 (8) | 0.0134 (8) | 0.0171 (8) | 0.0051 (7) | 0.0112 (7) | 0.0015 (7) |
C2 | 0.0227 (8) | 0.0166 (9) | 0.0168 (8) | 0.0083 (7) | 0.0116 (7) | 0.0041 (7) |
C3 | 0.0200 (9) | 0.0248 (10) | 0.0147 (8) | 0.0086 (8) | 0.0053 (7) | 0.0037 (7) |
C4 | 0.0149 (8) | 0.0211 (10) | 0.0216 (9) | 0.0014 (7) | 0.0072 (7) | −0.0008 (7) |
C5 | 0.0162 (8) | 0.0160 (9) | 0.0196 (8) | 0.0016 (7) | 0.0100 (7) | 0.0018 (7) |
C6 | 0.0305 (10) | 0.0227 (10) | 0.0192 (9) | 0.0071 (8) | 0.0141 (8) | 0.0073 (7) |
N1 | 0.0149 (7) | 0.0145 (8) | 0.0142 (7) | 0.0019 (5) | 0.0067 (6) | 0.0023 (5) |
N2 | 0.0213 (8) | 0.0189 (8) | 0.0189 (7) | −0.0026 (7) | 0.0093 (6) | 0.0067 (7) |
O4 | 0.0314 (10) | 0.0168 (10) | 0.0210 (9) | 0.000 | 0.0161 (8) | 0.000 |
Geometric parameters (Å, º) top Zn1—O1 | 1.9324 (12) | C3—C4 | 1.405 (3) |
Zn1—O3i | 1.9333 (13) | C3—H3 | 0.9500 |
Zn1—O2ii | 1.9557 (13) | C4—C5 | 1.364 (2) |
Zn1—N1 | 2.0262 (14) | C4—H4 | 0.9500 |
P1—O1 | 1.5167 (13) | C5—N1 | 1.363 (2) |
P1—O3 | 1.5183 (12) | C5—H5 | 0.9500 |
P1—O2 | 1.5301 (13) | C6—H6A | 0.9800 |
P1—H1 | 1.3200 | C6—H6B | 0.9800 |
C1—N2 | 1.348 (2) | C6—H6C | 0.9800 |
C1—N1 | 1.353 (2) | N2—H1N | 0.78 (2) |
C1—C2 | 1.428 (2) | N2—H2N | 0.84 (2) |
C2—C3 | 1.376 (3) | O4—H1O | 0.79 (2) |
C2—C6 | 1.507 (2) | O4—H1Oiii | 0.79 (2) |
| | | |
O1—Zn1—O3i | 107.36 (5) | C2—C3—H3 | 119.3 |
O1—Zn1—O2ii | 113.32 (5) | C4—C3—H3 | 119.3 |
O3i—Zn1—O2ii | 111.79 (5) | C5—C4—C3 | 117.90 (16) |
O1—Zn1—N1 | 113.89 (6) | C5—C4—H4 | 121.1 |
O3i—Zn1—N1 | 106.10 (5) | C3—C4—H4 | 121.1 |
O2ii—Zn1—N1 | 104.23 (5) | N1—C5—C4 | 122.92 (16) |
O1—P1—O3 | 112.24 (7) | N1—C5—H5 | 118.5 |
O1—P1—O2 | 111.98 (7) | C4—C5—H5 | 118.5 |
O3—P1—O2 | 113.57 (7) | C2—C6—H6A | 109.5 |
O1—P1—H1 | 106.1 | C2—C6—H6B | 109.5 |
O3—P1—H1 | 106.1 | H6A—C6—H6B | 109.5 |
O2—P1—H1 | 106.1 | C2—C6—H6C | 109.5 |
P1—O1—Zn1 | 135.67 (7) | H6A—C6—H6C | 109.5 |
P1—O2—Zn1ii | 125.89 (7) | H6B—C6—H6C | 109.5 |
P1—O3—Zn1iv | 129.00 (7) | C1—N1—C5 | 119.16 (14) |
N2—C1—N1 | 118.38 (15) | C1—N1—Zn1 | 124.96 (11) |
N2—C1—C2 | 120.29 (15) | C5—N1—Zn1 | 115.87 (11) |
N1—C1—C2 | 121.32 (15) | C1—N2—H1N | 121.9 (16) |
C3—C2—C1 | 117.33 (15) | C1—N2—H2N | 121.7 (14) |
C3—C2—C6 | 123.23 (15) | H1N—N2—H2N | 114 (2) |
C1—C2—C6 | 119.44 (16) | H1O—O4—H1Oiii | 109 (3) |
C2—C3—C4 | 121.36 (15) | | |
| | | |
O3—P1—O1—Zn1 | −19.79 (15) | C1—C2—C3—C4 | 0.8 (3) |
O2—P1—O1—Zn1 | 109.32 (12) | C6—C2—C3—C4 | −179.11 (16) |
O1—P1—O2—Zn1ii | −65.88 (11) | C2—C3—C4—C5 | 0.0 (3) |
O3—P1—O2—Zn1ii | 62.53 (11) | C3—C4—C5—N1 | −0.6 (3) |
O1—P1—O3—Zn1iv | 148.87 (9) | N2—C1—N1—C5 | 179.08 (15) |
O2—P1—O3—Zn1iv | 20.58 (12) | C2—C1—N1—C5 | 0.6 (2) |
N2—C1—C2—C3 | −179.58 (16) | N2—C1—N1—Zn1 | 0.1 (2) |
N1—C1—C2—C3 | −1.1 (2) | C2—C1—N1—Zn1 | −178.42 (11) |
N2—C1—C2—C6 | 0.3 (2) | C4—C5—N1—C1 | 0.3 (2) |
N1—C1—C2—C6 | 178.77 (15) | C4—C5—N1—Zn1 | 179.41 (13) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y, −z+1/2; (iv) x, y−1, z. |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O4v | 0.78 (2) | 2.19 (2) | 2.919 (2) | 157 (2) |
N2—H2N···O2ii | 0.84 (2) | 2.54 (2) | 3.098 (2) | 124.8 (18) |
O4—H1O···O2 | 0.79 (2) | 2.199 (19) | 2.9165 (15) | 152 (2) |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1. |
Poly[(2-amino-4-methylpyridine)-µ
3-phosphonato-zinc] (II)
top Crystal data top [Zn(HPO3)(C6H8N2)] | F(000) = 2048 |
Mr = 253.49 | Dx = 1.850 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.873 (6) Å | Cell parameters from 5932 reflections |
b = 12.307 (3) Å | θ = 2.0–27.4° |
c = 16.633 (4) Å | µ = 2.85 mm−1 |
β = 128.954 (5)° | T = 93 K |
V = 3641.1 (16) Å3 | Rod, colourless |
Z = 16 | 0.10 × 0.03 × 0.03 mm |
Data collection top Rigaku Pilatus 200K CCD diffractometer | 3177 reflections with I > 2σ(I) |
ω scans | Rint = 0.033 |
Absorption correction: multi-scan CrystalClear (Rigaku, 2015) | θmax = 25.3°, θmin = 2.0° |
Tmin = 0.783, Tmax = 1.000 | h = −27→27 |
50824 measured reflections | k = −14→14 |
3308 independent reflections | l = −19→19 |
Refinement top Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.017 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.049 | w = 1/[σ2(Fo2) + (0.0301P)2 + 3.9697P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
3308 reflections | Δρmax = 0.30 e Å−3 |
249 parameters | Δρmin = −0.40 e Å−3 |
0 restraints | |
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 | Uiso*/Ueq | |
Zn1 | 0.13481 (2) | 0.28075 (2) | 0.46631 (2) | 0.01035 (6) | |
Zn2 | 0.38505 (2) | 0.50195 (2) | 0.68663 (2) | 0.01038 (7) | |
P1 | 0.30317 (2) | 0.28259 (3) | 0.65170 (3) | 0.01005 (9) | |
H1 | 0.342771 | 0.281106 | 0.753047 | 0.012* | |
P2 | 0.46680 (2) | 0.44040 (3) | 0.59502 (3) | 0.01048 (9) | |
H2 | 0.443210 | 0.462953 | 0.501255 | 0.013* | |
O1 | 0.22394 (6) | 0.24425 (9) | 0.60565 (8) | 0.0126 (2) | |
O2 | 0.30176 (6) | 0.40043 (9) | 0.62249 (8) | 0.0142 (2) | |
O3 | 0.34276 (6) | 0.20612 (9) | 0.62797 (8) | 0.0133 (2) | |
O4 | 0.42559 (6) | 0.51766 (9) | 0.61527 (9) | 0.0151 (2) | |
O5 | 0.55137 (6) | 0.45868 (9) | 0.66790 (8) | 0.0141 (2) | |
O6 | 0.44751 (6) | 0.32169 (9) | 0.59323 (9) | 0.0192 (3) | |
C1 | 0.02104 (9) | 0.45553 (13) | 0.39669 (12) | 0.0139 (3) | |
C2 | −0.00238 (9) | 0.56244 (13) | 0.39473 (12) | 0.0159 (3) | |
H2A | −0.051858 | 0.585125 | 0.338516 | 0.019* | |
C3 | 0.04591 (9) | 0.63392 (13) | 0.47361 (12) | 0.0145 (3) | |
C4 | 0.11895 (9) | 0.59656 (13) | 0.55592 (12) | 0.0144 (3) | |
H4 | 0.153296 | 0.642415 | 0.613212 | 0.017* | |
C5 | 0.13951 (9) | 0.49351 (12) | 0.55196 (12) | 0.0127 (3) | |
H5 | 0.189116 | 0.470022 | 0.606940 | 0.015* | |
C6 | 0.02238 (10) | 0.74823 (14) | 0.47273 (14) | 0.0213 (4) | |
H6A | 0.063327 | 0.785428 | 0.536348 | 0.032* | |
H6B | −0.022360 | 0.746660 | 0.468422 | 0.032* | |
H6C | 0.010814 | 0.787141 | 0.412832 | 0.032* | |
N1 | 0.09243 (7) | 0.42276 (10) | 0.47310 (10) | 0.0120 (3) | |
N2 | −0.02674 (9) | 0.38312 (13) | 0.32253 (12) | 0.0209 (3) | |
H1N | −0.0668 (13) | 0.4006 (18) | 0.2726 (17) | 0.025* | |
H2N | −0.0154 (12) | 0.318 (2) | 0.3279 (16) | 0.025* | |
C7 | 0.32300 (8) | 0.68978 (13) | 0.72502 (11) | 0.0113 (3) | |
C8 | 0.29315 (9) | 0.79476 (12) | 0.70867 (12) | 0.0127 (3) | |
H8 | 0.272479 | 0.816001 | 0.741065 | 0.015* | |
C9 | 0.29372 (8) | 0.86715 (13) | 0.64575 (12) | 0.0133 (3) | |
C10 | 0.32631 (9) | 0.83349 (13) | 0.60142 (13) | 0.0168 (3) | |
H10 | 0.329589 | 0.881946 | 0.559930 | 0.020* | |
C11 | 0.35344 (10) | 0.72937 (13) | 0.61886 (13) | 0.0160 (3) | |
H11 | 0.374707 | 0.706960 | 0.587550 | 0.019* | |
C12 | 0.26058 (10) | 0.97887 (14) | 0.62570 (14) | 0.0187 (3) | |
H12A | 0.274259 | 1.022946 | 0.590688 | 0.028* | |
H12B | 0.280148 | 1.013133 | 0.691512 | 0.028* | |
H12C | 0.205714 | 0.973379 | 0.581816 | 0.028* | |
N3 | 0.35144 (7) | 0.65672 (10) | 0.67863 (10) | 0.0118 (3) | |
N4 | 0.32235 (8) | 0.61703 (11) | 0.78641 (11) | 0.0151 (3) | |
H3N | 0.3081 (11) | 0.6407 (16) | 0.8213 (15) | 0.018* | |
H4N | 0.3543 (12) | 0.5680 (17) | 0.8129 (15) | 0.018* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.01047 (10) | 0.00892 (10) | 0.01329 (11) | −0.00061 (6) | 0.00826 (9) | −0.00141 (6) |
Zn2 | 0.01062 (11) | 0.00830 (11) | 0.01323 (11) | 0.00089 (6) | 0.00799 (9) | 0.00035 (6) |
P1 | 0.01020 (19) | 0.0102 (2) | 0.01011 (19) | 0.00065 (14) | 0.00655 (16) | 0.00054 (14) |
P2 | 0.01040 (19) | 0.01063 (19) | 0.01165 (19) | −0.00079 (14) | 0.00753 (16) | −0.00177 (14) |
O1 | 0.0124 (5) | 0.0130 (5) | 0.0136 (5) | 0.0002 (4) | 0.0087 (5) | 0.0015 (4) |
O2 | 0.0123 (5) | 0.0115 (5) | 0.0169 (5) | −0.0004 (4) | 0.0082 (5) | 0.0003 (4) |
O3 | 0.0137 (5) | 0.0138 (5) | 0.0145 (5) | 0.0029 (4) | 0.0099 (5) | 0.0022 (4) |
O4 | 0.0182 (6) | 0.0132 (5) | 0.0200 (6) | 0.0030 (5) | 0.0150 (5) | 0.0016 (4) |
O5 | 0.0129 (5) | 0.0150 (6) | 0.0149 (5) | −0.0029 (4) | 0.0089 (5) | −0.0027 (4) |
O6 | 0.0164 (6) | 0.0125 (6) | 0.0312 (7) | −0.0044 (5) | 0.0163 (5) | −0.0061 (5) |
C1 | 0.0135 (7) | 0.0160 (8) | 0.0144 (7) | 0.0000 (6) | 0.0098 (7) | −0.0005 (6) |
C2 | 0.0134 (8) | 0.0175 (8) | 0.0161 (8) | 0.0046 (6) | 0.0090 (7) | 0.0034 (6) |
C3 | 0.0186 (8) | 0.0139 (8) | 0.0184 (8) | 0.0023 (6) | 0.0152 (7) | 0.0018 (6) |
C4 | 0.0161 (8) | 0.0139 (8) | 0.0151 (8) | −0.0029 (6) | 0.0107 (7) | −0.0036 (6) |
C5 | 0.0099 (7) | 0.0149 (8) | 0.0126 (8) | −0.0004 (6) | 0.0067 (7) | −0.0004 (6) |
C6 | 0.0254 (9) | 0.0146 (8) | 0.0282 (10) | 0.0050 (7) | 0.0189 (8) | 0.0013 (7) |
N1 | 0.0117 (6) | 0.0112 (6) | 0.0142 (6) | −0.0001 (5) | 0.0087 (6) | −0.0011 (5) |
N2 | 0.0125 (7) | 0.0188 (8) | 0.0192 (8) | 0.0004 (6) | 0.0042 (6) | −0.0051 (6) |
C7 | 0.0090 (7) | 0.0122 (7) | 0.0106 (7) | −0.0013 (6) | 0.0052 (6) | −0.0011 (6) |
C8 | 0.0128 (7) | 0.0120 (7) | 0.0146 (8) | 0.0004 (6) | 0.0093 (7) | −0.0015 (6) |
C9 | 0.0125 (7) | 0.0106 (7) | 0.0145 (8) | −0.0010 (6) | 0.0074 (6) | −0.0012 (6) |
C10 | 0.0232 (8) | 0.0124 (8) | 0.0208 (8) | 0.0018 (7) | 0.0167 (7) | 0.0037 (6) |
C11 | 0.0213 (8) | 0.0144 (8) | 0.0200 (8) | 0.0016 (6) | 0.0167 (7) | 0.0016 (6) |
C12 | 0.0234 (9) | 0.0121 (8) | 0.0235 (9) | 0.0043 (7) | 0.0161 (8) | 0.0023 (7) |
N3 | 0.0130 (6) | 0.0098 (6) | 0.0139 (6) | 0.0008 (5) | 0.0092 (5) | 0.0004 (5) |
N4 | 0.0216 (7) | 0.0120 (7) | 0.0185 (7) | 0.0043 (6) | 0.0159 (6) | 0.0037 (6) |
Geometric parameters (Å, º) top Zn1—O3i | 1.9391 (12) | C4—H4 | 0.9500 |
Zn1—O6i | 1.9419 (12) | C5—N1 | 1.365 (2) |
Zn1—O1 | 1.9463 (11) | C5—H5 | 0.9500 |
Zn1—N1 | 2.0358 (13) | C6—H6A | 0.9800 |
Zn2—O4 | 1.9210 (12) | C6—H6B | 0.9800 |
Zn2—O2 | 1.9423 (11) | C6—H6C | 0.9800 |
Zn2—O5ii | 1.9567 (12) | N2—H1N | 0.79 (2) |
Zn2—N3 | 2.0269 (14) | N2—H2N | 0.82 (2) |
P1—O3 | 1.5202 (11) | C7—N3 | 1.347 (2) |
P1—O2 | 1.5234 (12) | C7—N4 | 1.365 (2) |
P1—O1 | 1.5324 (12) | C7—C8 | 1.406 (2) |
P1—H1 | 1.3200 | C8—C9 | 1.381 (2) |
P2—O4 | 1.5182 (12) | C8—H8 | 0.9500 |
P2—O6 | 1.5209 (12) | C9—C10 | 1.401 (2) |
P2—O5 | 1.5211 (12) | C9—C12 | 1.503 (2) |
P2—H2 | 1.3200 | C10—C11 | 1.373 (2) |
C1—N2 | 1.347 (2) | C10—H10 | 0.9500 |
C1—N1 | 1.355 (2) | C11—N3 | 1.359 (2) |
C1—C2 | 1.413 (2) | C11—H11 | 0.9500 |
C2—C3 | 1.376 (2) | C12—H12A | 0.9800 |
C2—H2A | 0.9500 | C12—H12B | 0.9800 |
C3—C4 | 1.415 (2) | C12—H12C | 0.9800 |
C3—C6 | 1.503 (2) | N4—H3N | 0.88 (2) |
C4—C5 | 1.368 (2) | N4—H4N | 0.83 (2) |
| | | |
O3i—Zn1—O6i | 107.84 (5) | N1—C5—C4 | 123.38 (15) |
O3i—Zn1—O1 | 111.75 (5) | N1—C5—H5 | 118.3 |
O6i—Zn1—O1 | 114.29 (5) | C4—C5—H5 | 118.3 |
O3i—Zn1—N1 | 110.52 (5) | C3—C6—H6A | 109.5 |
O6i—Zn1—N1 | 104.06 (5) | C3—C6—H6B | 109.5 |
O1—Zn1—N1 | 108.11 (5) | H6A—C6—H6B | 109.5 |
O4—Zn2—O2 | 114.40 (5) | C3—C6—H6C | 109.5 |
O4—Zn2—O5ii | 121.28 (5) | H6A—C6—H6C | 109.5 |
O2—Zn2—O5ii | 102.36 (5) | H6B—C6—H6C | 109.5 |
O4—Zn2—N3 | 100.10 (5) | C1—N1—C5 | 117.98 (13) |
O2—Zn2—N3 | 111.58 (5) | C1—N1—Zn1 | 122.59 (11) |
O5ii—Zn2—N3 | 107.05 (5) | C5—N1—Zn1 | 119.05 (10) |
O3—P1—O2 | 113.78 (6) | C1—N2—H1N | 121.4 (16) |
O3—P1—O1 | 112.94 (7) | C1—N2—H2N | 121.4 (15) |
O2—P1—O1 | 110.64 (6) | H1N—N2—H2N | 117 (2) |
O3—P1—H1 | 106.3 | N3—C7—N4 | 117.81 (14) |
O2—P1—H1 | 106.3 | N3—C7—C8 | 121.16 (14) |
O1—P1—H1 | 106.3 | N4—C7—C8 | 121.02 (14) |
O4—P2—O6 | 113.14 (7) | C9—C8—C7 | 120.32 (14) |
O4—P2—O5 | 112.73 (7) | C9—C8—H8 | 119.8 |
O6—P2—O5 | 111.44 (6) | C7—C8—H8 | 119.8 |
O4—P2—H2 | 106.3 | C8—C9—C10 | 118.03 (14) |
O6—P2—H2 | 106.3 | C8—C9—C12 | 120.98 (14) |
O5—P2—H2 | 106.3 | C10—C9—C12 | 120.99 (14) |
P1—O1—Zn1 | 123.26 (6) | C11—C10—C9 | 118.96 (15) |
P1—O2—Zn2 | 128.34 (7) | C11—C10—H10 | 120.5 |
P1—O3—Zn1i | 131.45 (7) | C9—C10—H10 | 120.5 |
P2—O4—Zn2 | 133.02 (7) | N3—C11—C10 | 123.37 (15) |
P2—O5—Zn2ii | 127.58 (7) | N3—C11—H11 | 118.3 |
P2—O6—Zn1i | 144.09 (8) | C10—C11—H11 | 118.3 |
N2—C1—N1 | 117.88 (15) | C9—C12—H12A | 109.5 |
N2—C1—C2 | 121.14 (15) | C9—C12—H12B | 109.5 |
N1—C1—C2 | 120.97 (14) | H12A—C12—H12B | 109.5 |
C3—C2—C1 | 120.52 (15) | C9—C12—H12C | 109.5 |
C3—C2—H2A | 119.7 | H12A—C12—H12C | 109.5 |
C1—C2—H2A | 119.7 | H12B—C12—H12C | 109.5 |
C2—C3—C4 | 117.82 (15) | C7—N3—C11 | 118.08 (14) |
C2—C3—C6 | 121.41 (15) | C7—N3—Zn2 | 123.09 (10) |
C4—C3—C6 | 120.77 (15) | C11—N3—Zn2 | 118.72 (11) |
C5—C4—C3 | 119.16 (14) | C7—N4—H3N | 117.5 (13) |
C5—C4—H4 | 120.4 | C7—N4—H4N | 117.1 (14) |
C3—C4—H4 | 120.4 | H3N—N4—H4N | 117.4 (19) |
| | | |
O3—P1—O1—Zn1 | −87.69 (9) | N2—C1—N1—C5 | −175.71 (14) |
O2—P1—O1—Zn1 | 41.16 (9) | C2—C1—N1—C5 | 4.6 (2) |
O3—P1—O2—Zn2 | −69.80 (10) | N2—C1—N1—Zn1 | 11.4 (2) |
O1—P1—O2—Zn2 | 161.80 (7) | C2—C1—N1—Zn1 | −168.38 (11) |
O2—P1—O3—Zn1i | −20.85 (11) | C4—C5—N1—C1 | −2.1 (2) |
O1—P1—O3—Zn1i | 106.36 (9) | C4—C5—N1—Zn1 | 171.05 (12) |
O6—P2—O4—Zn2 | 26.92 (12) | N3—C7—C8—C9 | −1.2 (2) |
O5—P2—O4—Zn2 | −100.68 (10) | N4—C7—C8—C9 | −179.53 (15) |
O4—P2—O5—Zn2ii | 35.10 (11) | C7—C8—C9—C10 | −1.5 (2) |
O6—P2—O5—Zn2ii | −93.38 (9) | C7—C8—C9—C12 | 178.71 (14) |
O4—P2—O6—Zn1i | 51.37 (15) | C8—C9—C10—C11 | 2.5 (2) |
O5—P2—O6—Zn1i | 179.64 (11) | C12—C9—C10—C11 | −177.66 (15) |
N2—C1—C2—C3 | 176.82 (15) | C9—C10—C11—N3 | −1.0 (3) |
N1—C1—C2—C3 | −3.5 (2) | N4—C7—N3—C11 | −178.87 (14) |
C1—C2—C3—C4 | −0.2 (2) | C8—C7—N3—C11 | 2.8 (2) |
C1—C2—C3—C6 | 179.55 (15) | N4—C7—N3—Zn2 | 5.08 (19) |
C2—C3—C4—C5 | 2.6 (2) | C8—C7—N3—Zn2 | −173.28 (11) |
C6—C3—C4—C5 | −177.19 (15) | C10—C11—N3—C7 | −1.7 (2) |
C3—C4—C5—N1 | −1.5 (2) | C10—C11—N3—Zn2 | 174.54 (13) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O3iii | 0.79 (2) | 2.35 (2) | 2.9056 (19) | 128 (2) |
N2—H2N···O6i | 0.82 (2) | 2.13 (2) | 2.900 (2) | 155 (2) |
N4—H3N···O1iv | 0.88 (2) | 2.18 (2) | 3.0310 (18) | 163.7 (18) |
N4—H4N···O5ii | 0.83 (2) | 2.39 (2) | 3.1555 (19) | 154.3 (18) |
C5—H5···O2 | 0.95 | 2.57 | 3.315 (2) | 136 |
C8—H8···O1iv | 0.95 | 2.65 | 3.405 (2) | 137 |
C11—H11···O4 | 0.95 | 2.51 | 3.105 (2) | 120 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, y, −z+3/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, −z+3/2. |
Poly[(2-amino-5-methylpyridine)-µ
3-phosphonato-zinc] (III)
top Crystal data top [Zn(HPO3)(C6H8N2)] | Dx = 1.882 Mg m−3 |
Mr = 253.49 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 3214 reflections |
a = 5.1487 (9) Å | θ = 2.6–27.5° |
b = 8.5316 (19) Å | µ = 2.90 mm−1 |
c = 20.371 (5) Å | T = 93 K |
V = 894.8 (3) Å3 | Prism, colourless |
Z = 4 | 0.15 × 0.05 × 0.03 mm |
F(000) = 512 | |
Data collection top Rigaku Pilatus 200K CCD diffractometer | 1599 reflections with I > 2σ(I) |
ω scans | Rint = 0.067 |
Absorption correction: multi-scan CrystalClear (Rigaku, 2015) | θmax = 25.3°, θmin = 2.6° |
Tmin = 0.505, Tmax = 1.000 | h = −6→6 |
13254 measured reflections | k = −10→10 |
1630 independent reflections | l = −23→24 |
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)] = 0.021 | w = 1/[σ2(Fo2) + (0.0239P)2 + 0.0724P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.051 | (Δ/σ)max = 0.001 |
S = 1.01 | Δρmax = 0.59 e Å−3 |
1630 reflections | Δρmin = −0.41 e Å−3 |
125 parameters | Absolute structure: Parsons et al., 2013 |
0 restraints | Absolute structure parameter: 0.011 (6) |
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 | Uiso*/Ueq | |
Zn1 | 0.72989 (7) | 0.60753 (3) | 0.06019 (2) | 0.01077 (13) | |
P1 | 0.23596 (17) | 0.80347 (7) | 0.08606 (3) | 0.01135 (19) | |
H1 | 0.143314 | 0.860290 | 0.141598 | 0.014* | |
O1 | 0.5244 (4) | 0.7749 (2) | 0.09764 (10) | 0.0133 (5) | |
O2 | 0.1793 (4) | 0.9268 (2) | 0.03353 (10) | 0.0133 (4) | |
O3 | 0.0960 (4) | 0.6496 (2) | 0.07460 (10) | 0.0163 (5) | |
C1 | 0.7698 (7) | 0.2687 (3) | 0.09670 (13) | 0.0125 (6) | |
C2 | 0.6882 (6) | 0.1306 (3) | 0.12868 (15) | 0.0159 (7) | |
H2 | 0.762594 | 0.032284 | 0.117423 | 0.019* | |
C3 | 0.5011 (7) | 0.1398 (3) | 0.17599 (15) | 0.0152 (6) | |
H3 | 0.447008 | 0.046999 | 0.197875 | 0.018* | |
C4 | 0.3865 (6) | 0.2842 (3) | 0.19301 (14) | 0.0141 (6) | |
C5 | 0.4702 (6) | 0.4120 (3) | 0.15785 (14) | 0.0136 (6) | |
H5 | 0.393376 | 0.510660 | 0.167355 | 0.016* | |
C6 | 0.1796 (6) | 0.2972 (3) | 0.24478 (15) | 0.0181 (7) | |
H6A | 0.040112 | 0.222380 | 0.235356 | 0.027* | |
H6B | 0.108871 | 0.403897 | 0.244860 | 0.027* | |
H6C | 0.254815 | 0.274000 | 0.287887 | 0.027* | |
N1 | 0.6561 (5) | 0.4067 (3) | 0.11026 (11) | 0.0116 (5) | |
N2 | 0.9566 (5) | 0.2636 (3) | 0.04934 (13) | 0.0168 (6) | |
H2A | 1.056 (7) | 0.350 (4) | 0.0429 (17) | 0.020* | |
H2B | 1.045 (7) | 0.189 (5) | 0.0452 (17) | 0.020* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.01207 (19) | 0.0079 (2) | 0.0123 (2) | −0.00022 (13) | −0.00027 (14) | 0.00120 (10) |
P1 | 0.0124 (4) | 0.0098 (3) | 0.0119 (4) | 0.0014 (3) | −0.0003 (3) | 0.0005 (3) |
O1 | 0.0133 (11) | 0.0114 (9) | 0.0152 (11) | −0.0001 (9) | −0.0013 (9) | −0.0003 (8) |
O2 | 0.0180 (11) | 0.0108 (9) | 0.0111 (10) | 0.0021 (8) | −0.0004 (9) | 0.0009 (8) |
O3 | 0.0123 (11) | 0.0137 (10) | 0.0228 (11) | −0.0010 (8) | −0.0035 (10) | 0.0024 (8) |
C1 | 0.0160 (16) | 0.0131 (12) | 0.0085 (14) | −0.0009 (13) | −0.0046 (14) | −0.0004 (10) |
C2 | 0.0206 (17) | 0.0096 (13) | 0.0175 (16) | 0.0003 (12) | −0.0030 (14) | −0.0005 (11) |
C3 | 0.0218 (15) | 0.0101 (13) | 0.0139 (15) | −0.0035 (12) | −0.0042 (13) | 0.0033 (11) |
C4 | 0.0159 (15) | 0.0137 (14) | 0.0128 (16) | −0.0024 (12) | −0.0036 (14) | 0.0018 (11) |
C5 | 0.0149 (15) | 0.0108 (13) | 0.0152 (16) | 0.0008 (13) | −0.0022 (12) | −0.0020 (12) |
C6 | 0.0184 (16) | 0.0204 (15) | 0.0156 (17) | −0.0026 (13) | 0.0016 (13) | 0.0014 (12) |
N1 | 0.0151 (13) | 0.0097 (10) | 0.0101 (12) | 0.0003 (10) | −0.0004 (10) | 0.0006 (9) |
N2 | 0.0190 (15) | 0.0110 (13) | 0.0205 (15) | 0.0040 (11) | 0.0026 (12) | −0.0010 (11) |
Geometric parameters (Å, º) top Zn1—O1 | 1.9343 (19) | C2—H2 | 0.9500 |
Zn1—O3i | 1.941 (2) | C3—C4 | 1.409 (4) |
Zn1—O2ii | 1.949 (2) | C3—H3 | 0.9500 |
Zn1—N1 | 2.030 (2) | C4—C5 | 1.374 (4) |
P1—O3 | 1.515 (2) | C4—C6 | 1.503 (4) |
P1—O1 | 1.523 (2) | C5—N1 | 1.363 (4) |
P1—O2 | 1.529 (2) | C5—H5 | 0.9500 |
P1—H1 | 1.3200 | C6—H6A | 0.9800 |
C1—N1 | 1.344 (3) | C6—H6B | 0.9800 |
C1—N2 | 1.363 (4) | C6—H6C | 0.9800 |
C1—C2 | 1.411 (4) | N2—H2A | 0.90 (4) |
C2—C3 | 1.365 (5) | N2—H2B | 0.79 (4) |
| | | |
O1—Zn1—O3i | 109.56 (9) | C2—C3—C4 | 121.3 (3) |
O1—Zn1—O2ii | 115.09 (8) | C2—C3—H3 | 119.4 |
O3i—Zn1—O2ii | 107.80 (9) | C4—C3—H3 | 119.4 |
O1—Zn1—N1 | 108.82 (9) | C5—C4—C3 | 115.8 (3) |
O3i—Zn1—N1 | 105.19 (9) | C5—C4—C6 | 121.9 (3) |
O2ii—Zn1—N1 | 109.90 (8) | C3—C4—C6 | 122.3 (3) |
O3—P1—O1 | 110.43 (11) | N1—C5—C4 | 124.4 (3) |
O3—P1—O2 | 113.41 (12) | N1—C5—H5 | 117.8 |
O1—P1—O2 | 113.86 (12) | C4—C5—H5 | 117.8 |
O3—P1—H1 | 106.2 | C4—C6—H6A | 109.5 |
O1—P1—H1 | 106.2 | C4—C6—H6B | 109.5 |
O2—P1—H1 | 106.2 | H6A—C6—H6B | 109.5 |
P1—O1—Zn1 | 126.17 (12) | C4—C6—H6C | 109.5 |
P1—O2—Zn1iii | 123.84 (11) | H6A—C6—H6C | 109.5 |
P1—O3—Zn1iv | 130.19 (13) | H6B—C6—H6C | 109.5 |
N1—C1—N2 | 118.8 (2) | C1—N1—C5 | 118.8 (2) |
N1—C1—C2 | 120.5 (3) | C1—N1—Zn1 | 123.69 (19) |
N2—C1—C2 | 120.7 (2) | C5—N1—Zn1 | 117.45 (18) |
C3—C2—C1 | 119.2 (3) | C1—N2—H2A | 118 (2) |
C3—C2—H2 | 120.4 | C1—N2—H2B | 121 (3) |
C1—C2—H2 | 120.4 | H2A—N2—H2B | 108 (3) |
| | | |
O3—P1—O1—Zn1 | 31.32 (19) | C2—C3—C4—C6 | 179.8 (3) |
O2—P1—O1—Zn1 | −97.61 (15) | C3—C4—C5—N1 | −1.6 (4) |
O3—P1—O2—Zn1iii | −54.86 (18) | C6—C4—C5—N1 | −179.7 (3) |
O1—P1—O2—Zn1iii | 72.54 (16) | N2—C1—N1—C5 | −179.7 (3) |
O1—P1—O3—Zn1iv | 177.67 (14) | C2—C1—N1—C5 | 3.4 (4) |
O2—P1—O3—Zn1iv | −53.2 (2) | N2—C1—N1—Zn1 | 4.0 (4) |
N1—C1—C2—C3 | −3.3 (5) | C2—C1—N1—Zn1 | −172.9 (2) |
N2—C1—C2—C3 | 179.9 (3) | C4—C5—N1—C1 | −0.9 (4) |
C1—C2—C3—C4 | 0.6 (5) | C4—C5—N1—Zn1 | 175.6 (2) |
C2—C3—C4—C5 | 1.7 (5) | | |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, −z; (iii) x−1/2, −y+3/2, −z; (iv) x−1, y, z. |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O2v | 0.79 (4) | 2.35 (4) | 3.111 (3) | 162 (3) |
C2—H2···O1vi | 0.95 | 2.55 | 3.212 (3) | 127 |
Symmetry codes: (v) x+1, y−1, z; (vi) x, y−1, z. |
Poly[bis(2-amino-4-methylpyridinium) [tetra-µ
3-phosphonato-trizinc] monohydrate] (IV)
top Crystal data top (C6H9N2)2[Zn3(HPO3)4]·H2O | Z = 2 |
Mr = 752.34 | F(000) = 756 |
Triclinic, P1 | Dx = 2.019 Mg m−3 |
a = 9.03805 (13) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 9.36837 (13) Å | Cell parameters from 10623 reflections |
c = 15.0207 (2) Å | θ = 5.7–75.3° |
α = 81.0313 (1)° | µ = 6.49 mm−1 |
β = 88.0646 (1)° | T = 93 K |
γ = 80.0782 (1)° | Prism, colourless |
V = 1237.46 (3) Å3 | 0.10 × 0.10 × 0.10 mm |
Data collection top Rigaku Pilatus 200K CCD diffractometer | 4842 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 4831 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ω scans | θmax = 75.4°, θmin = 3.0° |
Absorption correction: multi-scan CrystalClear (Rigaku, 2015) | h = −11→11 |
Tmin = 0.744, Tmax = 1.000 | k = −11→11 |
11869 measured reflections | l = −18→18 |
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(Fo2) + (0.0455P)2 + 2.3807P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.085 | (Δ/σ)max = 0.001 |
S = 1.10 | Δρmax = 1.25 e Å−3 |
4842 reflections | Δρmin = −0.67 e Å−3 |
343 parameters | Extinction correction: SHELXL-2018/3 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0053 (3) |
Primary atom site location: structure-invariant direct methods | |
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 | Uiso*/Ueq | |
Zn1 | 0.24743 (4) | 0.40103 (4) | 0.26283 (2) | 0.01319 (11) | |
Zn2 | −0.39686 (4) | 0.53650 (4) | 0.37317 (2) | 0.01450 (11) | |
Zn3 | 0.36057 (4) | 0.44962 (4) | −0.08606 (2) | 0.01489 (11) | |
P1 | −0.11180 (7) | 0.49421 (7) | 0.23815 (4) | 0.01223 (14) | |
H1 | −0.085208 | 0.618572 | 0.259906 | 0.015* | |
O1 | 0.0349 (2) | 0.3858 (2) | 0.24886 (13) | 0.0181 (4) | |
O2 | −0.2305 (2) | 0.4425 (2) | 0.30286 (13) | 0.0194 (4) | |
O3 | −0.1634 (2) | 0.5258 (2) | 0.14074 (12) | 0.0198 (4) | |
P2 | 0.43840 (7) | 0.28650 (7) | 0.10450 (4) | 0.01276 (14) | |
H2 | 0.489858 | 0.157007 | 0.080888 | 0.015* | |
O4 | 0.3711 (2) | 0.2551 (2) | 0.19875 (12) | 0.0175 (4) | |
O5 | 0.3142 (2) | 0.3593 (2) | 0.03697 (12) | 0.0172 (4) | |
O6 | 0.5709 (2) | 0.3653 (2) | 0.09860 (13) | 0.0196 (4) | |
P3 | 0.39182 (7) | 0.30396 (7) | 0.46061 (4) | 0.01410 (15) | |
H3 | 0.431225 | 0.160024 | 0.476842 | 0.017* | |
O7 | 0.2721 (2) | 0.3341 (2) | 0.38856 (12) | 0.0223 (4) | |
O8 | 0.3247 (2) | 0.3488 (2) | 0.54810 (12) | 0.0219 (4) | |
O9 | 0.5344 (2) | 0.3632 (2) | 0.43166 (14) | 0.0248 (4) | |
P4 | 0.38437 (7) | 0.69938 (7) | 0.20856 (4) | 0.01361 (15) | |
H4 | 0.303842 | 0.832430 | 0.198557 | 0.016* | |
O10 | 0.2702 (2) | 0.5969 (2) | 0.20914 (14) | 0.0220 (4) | |
O11 | 0.4872 (2) | 0.6985 (2) | 0.12705 (13) | 0.0237 (4) | |
O12 | 0.4649 (2) | 0.6836 (2) | 0.29693 (13) | 0.0240 (4) | |
C1 | 0.0589 (3) | 0.7635 (3) | −0.01704 (17) | 0.0150 (5) | |
C2 | 0.1635 (3) | 0.8612 (3) | −0.03501 (17) | 0.0162 (5) | |
H2A | 0.251603 | 0.845508 | 0.000413 | 0.019* | |
C3 | 0.1385 (3) | 0.9781 (3) | −0.10321 (18) | 0.0171 (5) | |
C4 | 0.0059 (3) | 0.9998 (3) | −0.15470 (18) | 0.0205 (5) | |
H4A | −0.014596 | 1.081128 | −0.201535 | 0.025* | |
C5 | −0.0916 (3) | 0.9041 (3) | −0.13684 (18) | 0.0199 (5) | |
H5 | −0.179518 | 0.917499 | −0.172217 | 0.024* | |
C6 | 0.2478 (3) | 1.0834 (3) | −0.1230 (2) | 0.0228 (6) | |
H6A | 0.193054 | 1.184235 | −0.129661 | 0.034* | |
H6B | 0.302513 | 1.067140 | −0.178991 | 0.034* | |
H6C | 0.319166 | 1.067367 | −0.073283 | 0.034* | |
N1 | −0.0650 (2) | 0.7888 (2) | −0.06862 (15) | 0.0170 (4) | |
H1A | −0.130665 | 0.728796 | −0.057878 | 0.020* | |
N2 | 0.0770 (3) | 0.6485 (3) | 0.04803 (16) | 0.0198 (5) | |
H2N | 0.008 (4) | 0.598 (4) | 0.063 (2) | 0.024* | |
H3N | 0.152 (4) | 0.637 (4) | 0.083 (3) | 0.024* | |
C7 | −0.1126 (4) | 0.0499 (3) | 0.3638 (2) | 0.0293 (6) | |
C8 | −0.0951 (4) | −0.1046 (3) | 0.3921 (2) | 0.0298 (7) | |
H8 | −0.178225 | −0.153971 | 0.391019 | 0.036* | |
C9 | 0.0422 (4) | −0.1811 (3) | 0.4206 (2) | 0.0269 (6) | |
C10 | 0.1682 (4) | −0.1098 (4) | 0.4158 (2) | 0.0312 (7) | |
H10 | 0.264069 | −0.162712 | 0.434784 | 0.037* | |
C11 | 0.1501 (4) | 0.0345 (4) | 0.3839 (2) | 0.0357 (7) | |
H11 | 0.235379 | 0.082043 | 0.376766 | 0.043* | |
C12 | 0.0592 (4) | −0.3416 (3) | 0.4520 (2) | 0.0320 (7) | |
H12A | 0.094069 | −0.363281 | 0.514548 | 0.048* | |
H12B | 0.132633 | −0.393645 | 0.413711 | 0.048* | |
H12C | −0.037868 | −0.373520 | 0.448605 | 0.048* | |
N3 | 0.0130 (3) | 0.1129 (3) | 0.3619 (2) | 0.0287 (6) | |
H4N | 0.011 (5) | 0.199 (5) | 0.338 (3) | 0.034* | |
N4 | −0.2409 (3) | 0.1292 (3) | 0.3372 (2) | 0.0290 (6) | |
H5N | −0.321 (5) | 0.081 (5) | 0.333 (3) | 0.035* | |
H6N | −0.249 (5) | 0.225 (5) | 0.321 (3) | 0.035* | |
O13 | 0.4957 (3) | 0.0103 (2) | −0.32132 (16) | 0.0327 (5) | |
H1O | 0.511797 | 0.109711 | −0.317211 | 0.039* | |
H2O | 0.552497 | −0.056389 | −0.275011 | 0.039* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.01172 (17) | 0.01579 (18) | 0.01205 (17) | −0.00462 (13) | −0.00061 (12) | 0.00056 (12) |
Zn2 | 0.01256 (18) | 0.01957 (19) | 0.01204 (17) | −0.00494 (13) | 0.00048 (12) | −0.00209 (13) |
Zn3 | 0.01393 (18) | 0.01878 (19) | 0.01254 (17) | −0.00717 (13) | −0.00082 (12) | 0.00086 (13) |
P1 | 0.0117 (3) | 0.0135 (3) | 0.0114 (3) | −0.0041 (2) | −0.0004 (2) | 0.0008 (2) |
O1 | 0.0112 (8) | 0.0185 (9) | 0.0246 (9) | −0.0046 (7) | −0.0014 (7) | −0.0009 (7) |
O2 | 0.0194 (9) | 0.0190 (9) | 0.0189 (9) | −0.0047 (7) | 0.0076 (7) | −0.0003 (7) |
O3 | 0.0169 (9) | 0.0286 (10) | 0.0140 (9) | −0.0101 (8) | −0.0033 (7) | 0.0039 (7) |
P2 | 0.0117 (3) | 0.0135 (3) | 0.0128 (3) | −0.0031 (2) | 0.0008 (2) | −0.0003 (2) |
O4 | 0.0191 (9) | 0.0186 (9) | 0.0130 (8) | −0.0021 (7) | 0.0018 (7) | 0.0016 (7) |
O5 | 0.0139 (8) | 0.0230 (9) | 0.0137 (8) | −0.0048 (7) | −0.0006 (7) | 0.0018 (7) |
O6 | 0.0141 (9) | 0.0189 (9) | 0.0264 (10) | −0.0062 (7) | −0.0004 (7) | −0.0012 (7) |
P3 | 0.0157 (3) | 0.0147 (3) | 0.0121 (3) | −0.0053 (2) | 0.0006 (2) | 0.0002 (2) |
O7 | 0.0250 (10) | 0.0290 (10) | 0.0132 (9) | −0.0081 (8) | −0.0028 (7) | 0.0005 (7) |
O8 | 0.0223 (10) | 0.0330 (11) | 0.0144 (9) | −0.0137 (8) | 0.0026 (7) | −0.0065 (8) |
O9 | 0.0196 (10) | 0.0237 (10) | 0.0314 (11) | −0.0089 (8) | 0.0077 (8) | −0.0005 (8) |
P4 | 0.0127 (3) | 0.0129 (3) | 0.0149 (3) | −0.0027 (2) | −0.0015 (2) | −0.0002 (2) |
O10 | 0.0180 (9) | 0.0197 (10) | 0.0285 (10) | −0.0089 (8) | −0.0042 (8) | 0.0031 (8) |
O11 | 0.0281 (10) | 0.0206 (10) | 0.0220 (10) | −0.0060 (8) | 0.0082 (8) | −0.0013 (8) |
O12 | 0.0259 (10) | 0.0257 (10) | 0.0202 (10) | 0.0003 (8) | −0.0084 (8) | −0.0062 (8) |
C1 | 0.0140 (11) | 0.0154 (12) | 0.0148 (11) | −0.0006 (9) | 0.0019 (9) | −0.0026 (9) |
C2 | 0.0130 (11) | 0.0180 (12) | 0.0177 (12) | −0.0025 (10) | 0.0006 (9) | −0.0031 (10) |
C3 | 0.0159 (12) | 0.0154 (12) | 0.0200 (12) | −0.0032 (10) | 0.0049 (10) | −0.0034 (10) |
C4 | 0.0234 (14) | 0.0173 (13) | 0.0189 (12) | −0.0024 (11) | −0.0004 (10) | 0.0021 (10) |
C5 | 0.0186 (13) | 0.0200 (13) | 0.0201 (13) | −0.0027 (10) | −0.0053 (10) | 0.0002 (10) |
C6 | 0.0184 (13) | 0.0176 (13) | 0.0320 (15) | −0.0065 (11) | 0.0049 (11) | 0.0002 (11) |
N1 | 0.0153 (10) | 0.0165 (11) | 0.0196 (11) | −0.0053 (8) | −0.0007 (8) | −0.0007 (8) |
N2 | 0.0174 (11) | 0.0223 (12) | 0.0190 (11) | −0.0069 (9) | −0.0011 (9) | 0.0038 (9) |
C7 | 0.0239 (15) | 0.0257 (15) | 0.0362 (17) | −0.0043 (12) | 0.0044 (12) | 0.0008 (12) |
C8 | 0.0315 (16) | 0.0264 (15) | 0.0319 (16) | −0.0093 (13) | 0.0069 (13) | −0.0021 (12) |
C9 | 0.0274 (15) | 0.0214 (14) | 0.0311 (15) | −0.0061 (12) | 0.0042 (12) | −0.0005 (11) |
C10 | 0.0245 (15) | 0.0275 (16) | 0.0416 (18) | −0.0047 (12) | −0.0027 (13) | −0.0046 (13) |
C11 | 0.0346 (18) | 0.0373 (18) | 0.0385 (18) | −0.0144 (15) | 0.0015 (14) | −0.0074 (14) |
C12 | 0.0360 (17) | 0.0199 (15) | 0.0385 (17) | −0.0029 (13) | −0.0012 (14) | −0.0008 (12) |
N3 | 0.0274 (13) | 0.0162 (12) | 0.0421 (15) | −0.0099 (10) | 0.0027 (11) | 0.0031 (11) |
N4 | 0.0247 (13) | 0.0191 (13) | 0.0415 (15) | −0.0042 (10) | 0.0023 (11) | 0.0010 (11) |
O13 | 0.0342 (12) | 0.0281 (11) | 0.0355 (12) | −0.0088 (10) | −0.0085 (10) | 0.0016 (9) |
Geometric parameters (Å, º) top Zn1—O7 | 1.9028 (19) | C2—H2A | 0.9500 |
Zn1—O10 | 1.9283 (19) | C3—C4 | 1.416 (4) |
Zn1—O4 | 1.9637 (19) | C3—C6 | 1.504 (4) |
Zn1—O1 | 1.9710 (18) | C4—C5 | 1.354 (4) |
Zn2—O9i | 1.913 (2) | C4—H4A | 0.9500 |
Zn2—O8ii | 1.9154 (19) | C5—N1 | 1.363 (3) |
Zn2—O12i | 1.945 (2) | C5—H5 | 0.9500 |
Zn2—O2 | 1.9690 (19) | C6—H6A | 0.9800 |
Zn3—O6iii | 1.9202 (19) | C6—H6B | 0.9800 |
Zn3—O11iii | 1.936 (2) | C6—H6C | 0.9800 |
Zn3—O3iv | 1.9499 (18) | N1—H1A | 0.8800 |
Zn3—O5 | 1.9720 (18) | N2—H2N | 0.85 (4) |
P1—O2 | 1.5142 (18) | N2—H3N | 0.85 (4) |
P1—O3 | 1.5196 (18) | C7—N4 | 1.304 (4) |
P1—O1 | 1.5217 (19) | C7—N3 | 1.364 (4) |
P1—H1 | 1.3200 | C7—C8 | 1.426 (4) |
P2—O6 | 1.5043 (19) | C8—C9 | 1.368 (5) |
P2—O4 | 1.5279 (18) | C8—H8 | 0.9500 |
P2—O5 | 1.5333 (18) | C9—C10 | 1.411 (4) |
P2—H2 | 1.3200 | C9—C12 | 1.486 (4) |
P3—O9 | 1.514 (2) | C10—C11 | 1.346 (5) |
P3—O7 | 1.517 (2) | C10—H10 | 0.9500 |
P3—O8 | 1.5172 (19) | C11—N3 | 1.350 (4) |
P3—H3 | 1.3200 | C11—H11 | 0.9500 |
P4—O12 | 1.5103 (19) | C12—H12A | 0.9800 |
P4—O11 | 1.512 (2) | C12—H12B | 0.9800 |
P4—O10 | 1.5247 (19) | C12—H12C | 0.9800 |
P4—H4 | 1.3200 | N3—H4N | 0.83 (4) |
C1—N2 | 1.329 (3) | N4—H5N | 0.93 (4) |
C1—N1 | 1.349 (3) | N4—H6N | 0.88 (4) |
C1—C2 | 1.417 (4) | O13—H1O | 0.9780 |
C2—C3 | 1.372 (4) | O13—H2O | 0.9570 |
| | | |
O7—Zn1—O10 | 122.18 (9) | N2—C1—C2 | 123.2 (2) |
O7—Zn1—O4 | 107.57 (8) | N1—C1—C2 | 118.3 (2) |
O10—Zn1—O4 | 110.71 (8) | C3—C2—C1 | 120.4 (2) |
O7—Zn1—O1 | 100.42 (8) | C3—C2—H2A | 119.8 |
O10—Zn1—O1 | 106.69 (8) | C1—C2—H2A | 119.8 |
O4—Zn1—O1 | 108.12 (8) | C2—C3—C4 | 118.8 (2) |
O9i—Zn2—O8ii | 115.30 (9) | C2—C3—C6 | 121.2 (2) |
O9i—Zn2—O12i | 118.93 (9) | C4—C3—C6 | 120.0 (2) |
O8ii—Zn2—O12i | 102.04 (9) | C5—C4—C3 | 119.7 (2) |
O9i—Zn2—O2 | 98.33 (8) | C5—C4—H4A | 120.2 |
O8ii—Zn2—O2 | 110.78 (8) | C3—C4—H4A | 120.2 |
O12i—Zn2—O2 | 111.74 (8) | C4—C5—N1 | 120.7 (2) |
O6iii—Zn3—O11iii | 110.85 (8) | C4—C5—H5 | 119.7 |
O6iii—Zn3—O3iv | 110.21 (8) | N1—C5—H5 | 119.7 |
O11iii—Zn3—O3iv | 115.57 (9) | C3—C6—H6A | 109.5 |
O6iii—Zn3—O5 | 117.10 (8) | C3—C6—H6B | 109.5 |
O11iii—Zn3—O5 | 103.07 (8) | H6A—C6—H6B | 109.5 |
O3iv—Zn3—O5 | 99.70 (8) | C3—C6—H6C | 109.5 |
O2—P1—O3 | 112.70 (11) | H6A—C6—H6C | 109.5 |
O2—P1—O1 | 111.00 (11) | H6B—C6—H6C | 109.5 |
O3—P1—O1 | 111.15 (11) | C1—N1—C5 | 122.1 (2) |
O2—P1—H1 | 107.2 | C1—N1—H1A | 118.9 |
O3—P1—H1 | 107.2 | C5—N1—H1A | 118.9 |
O1—P1—H1 | 107.2 | C1—N2—H2N | 122 (2) |
P1—O1—Zn1 | 135.03 (12) | C1—N2—H3N | 118 (2) |
P1—O2—Zn2 | 135.93 (12) | H2N—N2—H3N | 119 (3) |
P1—O3—Zn3iv | 132.51 (12) | N4—C7—N3 | 120.2 (3) |
O6—P2—O4 | 115.33 (11) | N4—C7—C8 | 122.4 (3) |
O6—P2—O5 | 113.41 (11) | N3—C7—C8 | 117.3 (3) |
O4—P2—O5 | 110.08 (10) | C9—C8—C7 | 119.6 (3) |
O6—P2—H2 | 105.7 | C9—C8—H8 | 120.2 |
O4—P2—H2 | 105.7 | C7—C8—H8 | 120.2 |
O5—P2—H2 | 105.7 | C8—C9—C10 | 120.2 (3) |
P2—O4—Zn1 | 125.40 (11) | C8—C9—C12 | 119.5 (3) |
P2—O5—Zn3 | 121.78 (11) | C10—C9—C12 | 120.2 (3) |
P2—O6—Zn3iii | 146.90 (13) | C11—C10—C9 | 118.8 (3) |
O9—P3—O7 | 114.49 (12) | C11—C10—H10 | 120.6 |
O9—P3—O8 | 113.97 (12) | C9—C10—H10 | 120.6 |
O7—P3—O8 | 110.19 (11) | C10—C11—N3 | 121.3 (3) |
O9—P3—H3 | 105.8 | C10—C11—H11 | 119.4 |
O7—P3—H3 | 105.8 | N3—C11—H11 | 119.4 |
O8—P3—H3 | 105.8 | C9—C12—H12A | 109.5 |
P3—O7—Zn1 | 140.37 (13) | C9—C12—H12B | 109.5 |
P3—O8—Zn2ii | 129.47 (12) | H12A—C12—H12B | 109.5 |
P3—O9—Zn2v | 141.65 (14) | C9—C12—H12C | 109.5 |
O12—P4—O11 | 114.13 (12) | H12A—C12—H12C | 109.5 |
O12—P4—O10 | 114.03 (12) | H12B—C12—H12C | 109.5 |
O11—P4—O10 | 112.68 (12) | C11—N3—C7 | 122.5 (3) |
O12—P4—H4 | 104.9 | C11—N3—H4N | 116 (3) |
O11—P4—H4 | 104.9 | C7—N3—H4N | 121 (3) |
O10—P4—H4 | 104.9 | C7—N4—H5N | 118 (3) |
P4—O10—Zn1 | 138.13 (12) | C7—N4—H6N | 121 (3) |
P4—O11—Zn3iii | 133.31 (12) | H5N—N4—H6N | 122 (4) |
P4—O12—Zn2v | 138.52 (13) | H1O—O13—H2O | 108.6 |
N2—C1—N1 | 118.5 (2) | | |
| | | |
O2—P1—O1—Zn1 | −131.13 (16) | O11—P4—O12—Zn2v | −67.0 (2) |
O3—P1—O1—Zn1 | 102.59 (17) | O10—P4—O12—Zn2v | 64.4 (2) |
O3—P1—O2—Zn2 | −89.87 (19) | N2—C1—C2—C3 | 180.0 (2) |
O1—P1—O2—Zn2 | 144.71 (16) | N1—C1—C2—C3 | 0.1 (4) |
O2—P1—O3—Zn3iv | 14.2 (2) | C1—C2—C3—C4 | 0.4 (4) |
O1—P1—O3—Zn3iv | 139.51 (15) | C1—C2—C3—C6 | 179.7 (2) |
O6—P2—O4—Zn1 | 74.23 (16) | C2—C3—C4—C5 | −1.1 (4) |
O5—P2—O4—Zn1 | −55.63 (16) | C6—C3—C4—C5 | 179.6 (3) |
O6—P2—O5—Zn3 | 37.41 (16) | C3—C4—C5—N1 | 1.3 (4) |
O4—P2—O5—Zn3 | 168.29 (11) | N2—C1—N1—C5 | −179.8 (2) |
O4—P2—O6—Zn3iii | −85.7 (2) | C2—C1—N1—C5 | 0.1 (4) |
O5—P2—O6—Zn3iii | 42.5 (3) | C4—C5—N1—C1 | −0.8 (4) |
O9—P3—O7—Zn1 | 12.1 (3) | N4—C7—C8—C9 | −179.0 (3) |
O8—P3—O7—Zn1 | 142.09 (19) | N3—C7—C8—C9 | 3.7 (5) |
O9—P3—O8—Zn2ii | −1.7 (2) | C7—C8—C9—C10 | −4.7 (5) |
O7—P3—O8—Zn2ii | −132.07 (16) | C7—C8—C9—C12 | 178.6 (3) |
O7—P3—O9—Zn2v | 47.6 (3) | C8—C9—C10—C11 | 0.9 (5) |
O8—P3—O9—Zn2v | −80.5 (2) | C12—C9—C10—C11 | 177.5 (3) |
O12—P4—O10—Zn1 | −34.6 (2) | C9—C10—C11—N3 | 4.1 (5) |
O11—P4—O10—Zn1 | 97.6 (2) | C10—C11—N3—C7 | −5.2 (5) |
O12—P4—O11—Zn3iii | 66.5 (2) | N4—C7—N3—C11 | −176.2 (3) |
O10—P4—O11—Zn3iii | −65.6 (2) | C8—C7—N3—C11 | 1.2 (5) |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) −x, −y+1, −z; (v) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O5iv | 0.88 | 1.97 | 2.833 (3) | 166 |
N2—H2N···O3 | 0.85 (4) | 2.05 (4) | 2.853 (3) | 157 (3) |
N2—H3N···O10 | 0.85 (4) | 2.16 (4) | 2.961 (3) | 156 (3) |
N3—H4N···O1 | 0.83 (4) | 2.07 (4) | 2.873 (3) | 163 (4) |
N4—H5N···O13vi | 0.93 (4) | 1.95 (4) | 2.871 (4) | 177 (4) |
N4—H6N···O2 | 0.88 (4) | 2.05 (4) | 2.918 (3) | 167 (4) |
O13—H1O···O12iii | 0.98 | 2.05 | 3.028 (3) | 175 |
O13—H2O···O4vii | 0.96 | 2.05 | 2.952 (3) | 157 |
C5—H5···O4iv | 0.95 | 2.64 | 3.370 (3) | 134 |
C8—H8···O8viii | 0.95 | 2.48 | 3.350 (4) | 152 |
C11—H11···O7 | 0.95 | 2.47 | 3.199 (4) | 133 |
C11—H11···O13vii | 0.95 | 2.59 | 3.281 (4) | 130 |
Symmetry codes: (iii) −x+1, −y+1, −z; (iv) −x, −y+1, −z; (vi) −x, −y, −z; (vii) −x+1, −y, −z; (viii) −x, −y, −z+1. |
Crystal data top (C6H9N2)2[ZnCl4]·H2O | Z = 2 |
Mr = 443.49 | F(000) = 452 |
Triclinic, P1 | Dx = 1.596 Mg m−3 |
a = 6.9541 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.7092 (9) Å | Cell parameters from 3331 reflections |
c = 16.293 (3) Å | θ = 2.5–27.4° |
α = 83.239 (11)° | µ = 1.92 mm−1 |
β = 80.167 (10)° | T = 173 K |
γ = 72.049 (9)° | Prism, colourless |
V = 922.7 (2) Å3 | 0.15 × 0.05 × 0.05 mm |
Data collection top AFC10: Fixed Chi 2 circle CCD diffractometer | 3383 independent reflections |
Radiation source: Rotating Anode | 3172 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.039 |
ω scans | θmax = 25.4°, θmin = 2.5° |
Absorption correction: multi-scan | h = −8→8 |
Tmin = 0.851, Tmax = 1.000 | k = −10→10 |
28291 measured reflections | l = −19→19 |
Refinement top Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0281P)2 + 3.4309P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
3383 reflections | Δρmax = 1.10 e Å−3 |
203 parameters | Δρmin = −1.01 e Å−3 |
0 restraints | |
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 | Uiso*/Ueq | |
C1 | 0.1889 (9) | 0.1476 (6) | 0.5224 (3) | 0.0600 (15) | |
C2 | 0.1527 (15) | 0.0459 (7) | 0.5969 (4) | 0.104 (3) | |
C3 | 0.2121 (8) | −0.1169 (6) | 0.5878 (3) | 0.0520 (12) | |
H3 | 0.211403 | −0.188177 | 0.636650 | 0.062* | |
C4 | 0.2731 (8) | −0.1829 (6) | 0.5112 (3) | 0.0531 (12) | |
H4 | 0.310133 | −0.296598 | 0.507457 | 0.064* | |
C5 | 0.2788 (17) | −0.0840 (8) | 0.4429 (4) | 0.126 (4) | |
H5 | 0.303249 | −0.124879 | 0.389331 | 0.151* | |
C6 | 0.0868 (10) | 0.1186 (7) | 0.6779 (3) | 0.0651 (16) | |
H6A | −0.036542 | 0.210386 | 0.674726 | 0.098* | |
H6B | 0.195698 | 0.156258 | 0.691792 | 0.098* | |
H6C | 0.057412 | 0.037620 | 0.721293 | 0.098* | |
N1 | 0.2493 (9) | 0.0780 (6) | 0.4499 (3) | 0.0705 (15) | |
H1 | 0.271393 | 0.138646 | 0.404236 | 0.085* | |
N2 | 0.1632 (6) | 0.3024 (5) | 0.5236 (2) | 0.0475 (10) | |
H2A | 0.185700 | 0.360039 | 0.476852 | 0.057* | |
H2B | 0.123470 | 0.349100 | 0.571202 | 0.057* | |
C7 | 0.2567 (8) | 0.2446 (6) | −0.0094 (3) | 0.0501 (12) | |
C8 | 0.3081 (8) | 0.1491 (6) | −0.0793 (3) | 0.0496 (12) | |
C9 | 0.2983 (7) | −0.0075 (6) | −0.0664 (3) | 0.0461 (11) | |
H9 | 0.329701 | −0.071870 | −0.112816 | 0.055* | |
C10 | 0.2439 (8) | −0.0740 (7) | 0.0125 (4) | 0.0584 (14) | |
H10 | 0.242538 | −0.183511 | 0.020582 | 0.070* | |
C11 | 0.1918 (9) | 0.0225 (9) | 0.0790 (4) | 0.0737 (19) | |
H11 | 0.148649 | −0.018341 | 0.133404 | 0.088* | |
C12 | 0.3736 (8) | 0.2208 (6) | −0.1633 (3) | 0.0449 (11) | |
H12A | 0.483628 | 0.266937 | −0.159640 | 0.067* | |
H12B | 0.257460 | 0.306089 | −0.182129 | 0.067* | |
H12C | 0.422840 | 0.136364 | −0.203087 | 0.067* | |
N3 | 0.2029 (7) | 0.1758 (6) | 0.0657 (3) | 0.0631 (12) | |
H3A | 0.172986 | 0.234488 | 0.109125 | 0.076* | |
N4 | 0.2588 (7) | 0.3949 (5) | −0.0157 (3) | 0.0602 (12) | |
H4A | 0.225239 | 0.450402 | 0.029029 | 0.072* | |
H4B | 0.293896 | 0.440766 | −0.064693 | 0.072* | |
Zn1 | 0.40814 (8) | 0.39971 (6) | 0.23744 (3) | 0.03752 (16) | |
Cl1 | 0.37981 (18) | 0.50225 (14) | 0.36231 (7) | 0.0428 (3) | |
Cl2 | 0.73745 (17) | 0.33366 (14) | 0.17781 (8) | 0.0471 (3) | |
Cl3 | 0.19082 (18) | 0.57548 (14) | 0.15631 (7) | 0.0460 (3) | |
Cl4 | 0.2998 (2) | 0.17366 (15) | 0.25763 (7) | 0.0508 (3) | |
O1 | 0.1386 (6) | 0.5035 (5) | 0.6524 (2) | 0.0587 (9) | |
H1O | 0.053464 | 0.539417 | 0.697263 | 0.07 (2)* | |
H2O | 0.256463 | 0.514917 | 0.659163 | 0.10 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.084 (4) | 0.041 (3) | 0.049 (3) | −0.024 (3) | 0.024 (3) | −0.010 (2) |
C2 | 0.198 (9) | 0.042 (3) | 0.049 (3) | −0.031 (4) | 0.044 (4) | −0.006 (3) |
C3 | 0.055 (3) | 0.039 (3) | 0.060 (3) | −0.015 (2) | −0.002 (2) | 0.001 (2) |
C4 | 0.054 (3) | 0.040 (3) | 0.062 (3) | −0.012 (2) | 0.001 (2) | −0.014 (2) |
C5 | 0.244 (12) | 0.059 (4) | 0.060 (4) | −0.060 (6) | 0.062 (6) | −0.029 (3) |
C6 | 0.095 (4) | 0.045 (3) | 0.044 (3) | −0.018 (3) | 0.014 (3) | −0.002 (2) |
N1 | 0.113 (4) | 0.052 (3) | 0.043 (2) | −0.038 (3) | 0.028 (3) | −0.013 (2) |
N2 | 0.063 (3) | 0.040 (2) | 0.037 (2) | −0.0188 (19) | 0.0038 (18) | −0.0008 (16) |
C7 | 0.056 (3) | 0.058 (3) | 0.035 (2) | −0.014 (2) | −0.005 (2) | −0.008 (2) |
C8 | 0.059 (3) | 0.053 (3) | 0.039 (3) | −0.019 (2) | −0.007 (2) | −0.003 (2) |
C9 | 0.038 (2) | 0.048 (3) | 0.054 (3) | −0.011 (2) | −0.014 (2) | −0.002 (2) |
C10 | 0.051 (3) | 0.063 (3) | 0.067 (4) | −0.027 (3) | −0.018 (3) | 0.016 (3) |
C11 | 0.051 (3) | 0.112 (6) | 0.056 (4) | −0.031 (3) | −0.008 (3) | 0.022 (4) |
C12 | 0.055 (3) | 0.043 (3) | 0.035 (2) | −0.011 (2) | −0.005 (2) | −0.0054 (19) |
N3 | 0.070 (3) | 0.086 (4) | 0.033 (2) | −0.024 (3) | −0.001 (2) | −0.005 (2) |
N4 | 0.075 (3) | 0.056 (3) | 0.046 (2) | −0.010 (2) | −0.008 (2) | −0.018 (2) |
Zn1 | 0.0406 (3) | 0.0372 (3) | 0.0340 (3) | −0.0110 (2) | −0.0026 (2) | −0.0052 (2) |
Cl1 | 0.0489 (6) | 0.0443 (6) | 0.0345 (5) | −0.0129 (5) | −0.0017 (4) | −0.0090 (4) |
Cl2 | 0.0406 (6) | 0.0446 (6) | 0.0526 (7) | −0.0090 (5) | 0.0021 (5) | −0.0114 (5) |
Cl3 | 0.0487 (6) | 0.0458 (6) | 0.0403 (6) | −0.0067 (5) | −0.0105 (5) | −0.0042 (5) |
Cl4 | 0.0696 (8) | 0.0456 (6) | 0.0439 (6) | −0.0282 (6) | −0.0045 (5) | −0.0039 (5) |
O1 | 0.061 (2) | 0.070 (2) | 0.053 (2) | −0.030 (2) | −0.0003 (18) | −0.0173 (18) |
Geometric parameters (Å, º) top C1—N2 | 1.306 (6) | C8—C9 | 1.376 (7) |
C1—N1 | 1.335 (7) | C8—C12 | 1.494 (6) |
C1—C2 | 1.450 (7) | C9—C10 | 1.387 (7) |
C2—C3 | 1.368 (7) | C9—H9 | 0.9500 |
C2—C6 | 1.472 (8) | C10—C11 | 1.380 (9) |
C3—C4 | 1.380 (7) | C10—H10 | 0.9500 |
C3—H3 | 0.9500 | C11—N3 | 1.351 (8) |
C4—C5 | 1.328 (9) | C11—H11 | 0.9500 |
C4—H4 | 0.9500 | C12—H12A | 0.9800 |
C5—N1 | 1.377 (8) | C12—H12B | 0.9800 |
C5—H5 | 0.9500 | C12—H12C | 0.9800 |
C6—H6A | 0.9800 | N3—H3A | 0.8800 |
C6—H6B | 0.9800 | N4—H4A | 0.8800 |
C6—H6C | 0.9800 | N4—H4B | 0.8800 |
N1—H1 | 0.8800 | Zn1—Cl2 | 2.2536 (13) |
N2—H2A | 0.8800 | Zn1—Cl3 | 2.2704 (13) |
N2—H2B | 0.8800 | Zn1—Cl1 | 2.2710 (12) |
C7—N4 | 1.305 (7) | Zn1—Cl4 | 2.2867 (13) |
C7—N3 | 1.344 (6) | O1—H1O | 0.8802 |
C7—C8 | 1.420 (7) | O1—H2O | 0.8817 |
| | | |
N2—C1—N1 | 119.5 (5) | C9—C8—C12 | 122.6 (4) |
N2—C1—C2 | 122.9 (5) | C7—C8—C12 | 119.1 (4) |
N1—C1—C2 | 117.6 (5) | C8—C9—C10 | 121.8 (5) |
C3—C2—C1 | 116.2 (5) | C8—C9—H9 | 119.1 |
C3—C2—C6 | 124.1 (5) | C10—C9—H9 | 119.1 |
C1—C2—C6 | 119.0 (5) | C11—C10—C9 | 118.5 (5) |
C2—C3—C4 | 123.3 (5) | C11—C10—H10 | 120.7 |
C2—C3—H3 | 118.4 | C9—C10—H10 | 120.7 |
C4—C3—H3 | 118.4 | N3—C11—C10 | 119.1 (5) |
C5—C4—C3 | 118.6 (5) | N3—C11—H11 | 120.5 |
C5—C4—H4 | 120.7 | C10—C11—H11 | 120.5 |
C3—C4—H4 | 120.7 | C8—C12—H12A | 109.5 |
C4—C5—N1 | 119.8 (6) | C8—C12—H12B | 109.5 |
C4—C5—H5 | 120.1 | H12A—C12—H12B | 109.5 |
N1—C5—H5 | 120.1 | C8—C12—H12C | 109.5 |
C2—C6—H6A | 109.5 | H12A—C12—H12C | 109.5 |
C2—C6—H6B | 109.5 | H12B—C12—H12C | 109.5 |
H6A—C6—H6B | 109.5 | C7—N3—C11 | 124.4 (5) |
C2—C6—H6C | 109.5 | C7—N3—H3A | 117.8 |
H6A—C6—H6C | 109.5 | C11—N3—H3A | 117.8 |
H6B—C6—H6C | 109.5 | C7—N4—H4A | 120.0 |
C1—N1—C5 | 123.3 (5) | C7—N4—H4B | 120.0 |
C1—N1—H1 | 118.3 | H4A—N4—H4B | 120.0 |
C5—N1—H1 | 118.3 | Cl2—Zn1—Cl3 | 113.75 (5) |
C1—N2—H2A | 120.0 | Cl2—Zn1—Cl1 | 109.26 (5) |
C1—N2—H2B | 120.0 | Cl3—Zn1—Cl1 | 110.27 (5) |
H2A—N2—H2B | 120.0 | Cl2—Zn1—Cl4 | 109.40 (5) |
N4—C7—N3 | 119.5 (5) | Cl3—Zn1—Cl4 | 104.48 (5) |
N4—C7—C8 | 122.7 (5) | Cl1—Zn1—Cl4 | 109.55 (5) |
N3—C7—C8 | 117.8 (5) | H1O—O1—H2O | 105.6 |
C9—C8—C7 | 118.3 (5) | | |
| | | |
N2—C1—C2—C3 | −171.5 (7) | N4—C7—C8—C9 | −179.1 (5) |
N1—C1—C2—C3 | 9.1 (12) | N3—C7—C8—C9 | 0.6 (8) |
N2—C1—C2—C6 | −0.9 (13) | N4—C7—C8—C12 | 1.9 (8) |
N1—C1—C2—C6 | 179.8 (7) | N3—C7—C8—C12 | −178.5 (5) |
C1—C2—C3—C4 | −10.1 (12) | C7—C8—C9—C10 | −1.3 (7) |
C6—C2—C3—C4 | 179.9 (7) | C12—C8—C9—C10 | 177.7 (5) |
C2—C3—C4—C5 | 1.5 (11) | C8—C9—C10—C11 | 2.2 (8) |
C3—C4—C5—N1 | 8.0 (13) | C9—C10—C11—N3 | −2.5 (8) |
N2—C1—N1—C5 | −179.6 (8) | N4—C7—N3—C11 | 178.7 (5) |
C2—C1—N1—C5 | −0.2 (12) | C8—C7—N3—C11 | −1.0 (8) |
C4—C5—N1—C1 | −8.8 (14) | C10—C11—N3—C7 | 2.0 (9) |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl4 | 0.88 | 2.35 | 3.134 (5) | 148 |
N2—H2A···Cl1 | 0.88 | 2.54 | 3.375 (4) | 158 |
N2—H2B···O1 | 0.88 | 2.03 | 2.838 (5) | 152 |
N3—H3A···Cl4 | 0.88 | 2.66 | 3.306 (4) | 132 |
N4—H4A···Cl3 | 0.88 | 2.40 | 3.268 (4) | 170 |
N4—H4B···Cl2i | 0.88 | 2.51 | 3.333 (5) | 155 |
O1—H1O···Cl3ii | 0.88 | 2.95 | 3.669 (4) | 141 |
O1—H1O···Cl4ii | 0.88 | 2.98 | 3.675 (4) | 138 |
O1—H2O···Cl1iii | 0.88 | 2.45 | 3.302 (4) | 162 |
C10—H10···Cl3iv | 0.95 | 2.92 | 3.696 (5) | 140 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y−1, z. |
References
Chen, J. Y., Chen, S. Y., Chen, W. T., Yin, M. C. & Wang, C. M. (2022). Chem. Eur. J. 28 article e202200732. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gordon, L. & Harrison, W. T. A. (2004). Inorg. Chem. 43, 1808–1809. Web of Science CSD CrossRef PubMed CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Harrison, W. T. A., Phillips, M. L. F., Stanchfield, J. & Nenoff, T. M. (2001). Inorg. Chem. 40, 895–899. Web of Science CSD CrossRef CAS Google Scholar
Holmes, W., Cordes, D. B., Slawin, A. M. Z. & Harrison, W. T. A. (2018). Acta Cryst. E74, 1411–1416. Web of Science CSD CrossRef IUCr Journals Google Scholar
Katinaitė, J. & Harrison, W. T. A. (2017). Acta Cryst. E73, 759–762. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liang, J., Wang, Y., Yu, J., Li, Y. & Xu, R. (2003). Chem. Commun. pp. 882–883. Web of Science CSD CrossRef Google Scholar
Lin, Z., Nayek, H. & Dehnen, S. (2009). Z. Anorg. Allg. Chem. 635, 2391–2395. Web of Science CSD CrossRef CAS Google Scholar
Lin, Z.-E., Zhang, J., Zheng, S.-T., Wei, Q.-H. & Yang, G.-Y. (2003). Solid State Sci. 5, 1435–1438. Web of Science CSD CrossRef CAS Google Scholar
Ma, Y., Li, N., Xiang, S. & Guan, N. (2007). J. Phys. Chem. C, 111, 18361–18366. Web of Science CrossRef CAS Google Scholar
Mao, Y. M., Dong, X. H., Deng, Y. D., Li, J., Huang, L., Zeng, H. M., Zou, G. H. & Lin, Z. E. (2021). Dalton Trans. 50, 5442–5445. Web of Science CSD CrossRef CAS PubMed Google Scholar
Okuniewski, A., Rosiak, D., Chojnacki, J. & Becker, B. (2015). Polyhedron, 90, 47–57. Web of Science CSD CrossRef CAS Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Phillips, M. L. F., Nenoff, T. M., Thompson, C. T. & Harrison, W. T. A. (2002). J. Solid State Chem. 167, 337–343. CrossRef CAS Google Scholar
Rigaku (2015). CrystalClear, Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Ursu, D., Casut, C. & Miclau, M. (2022). Materials 15, article 7792. Web of Science CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
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