research communications
3,5-Lutidine pentaaqua sulfate complexes of first-row transition metals: [M(3,5-lutidine)(H2O)5]SO4, with M = Mn, Co, Ni, and Zn
aUniversity of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
*Correspondence e-mail: dmanke@umassd.edu
The reactions of MnSO4·H2O, CoSO4·7H2O, NiSO4·6H2O and ZnSO4·7H2O with 3,5-lutidine (3,5-dimethylpyridine) yield crystals of pentaaqua(3,5-dimethylpyridine-κN)manganese(II) sulfate, [Mn(C7H9N)(H2O)5]SO4, (1), pentaaqua(3,5-dimethylpyridine-κN)cobalt(II) sulfate, [Co(C7H9N)(H2O)5]SO4, (2), pentaaqua(3,5-dimethylpyridine-κN)nickel(II) sulfate, [Ni(C7H9N)(H2O)5]SO4, (3), and pentaaqua(3,5-dimethylpyridine-κN)zinc(II) sulfate, [Zn(C7H9N)(H2O)5]SO4, (4), which were characterized by single-crystal X-ray diffraction. The four crystals are isostructural, demonstrating near identical unit-cell parameters and atomic positions. The metal atoms are all octahedrally coordinated, with one lutidine ligand and five water ligands. The sulfate dianion hydrogen bonds with the coordinated water molecules of the dicationic metal complex salts, generating infinite three-dimensional networks.
Keywords: crystal structure; lutidine; sulfate; transition metal; coordination chemistry.
1. Chemical context
Metal–pyridine sulfate complexes have been reported in the literature since the 1880s (Jørgensen, 1886; Reitzenstein, 1898; Manke, 2021), though an extensive and systematic look at the crystal structures of this class of compounds has never been undertaken. In recent years, our laboratory began looking at the structures of first-row transition-metal–pyridine sulfate complexes, first with the parent pyridine (Park et al., 2019; Pham et al., 2018; Roy et al., 2018) and then with picoline ligands (Park et al., 2022; Pham et al., 2019). In our efforts to examine the structural diversity of this class of compounds, we recently expanded to look at lutidine ligands. Herein we report four isostructural first-row transition-metal complexes of 3,5-lutidine.
2. Structural commentary
The four compounds described herein are isostructural, demonstrating near identical unit-cell parameters and atomic positions (Fig. 1). The comprises half of the cation and half of the sulfate anion, both ions having crystallographic mirror symmetry. In the cation, the metal atom, the lutidine ligand and the O1 atom of the trans-aqua ligand lie in the mirror plane, while two independent aqua ligands are in general positions. In each structure, both methyl groups of the lutidine ligand are rotationally disordered between two mirror-related orientations. In the anion, atoms S1, O4 and O6 lie in the mirror plane, while O5 and O5ii are related by it. Reflection generates the full dicationic complex, which exhibits an octahedral coordination with one lutidine and five water ligands bound to the metal, as well as the full sulfate dianion.
The MO3N plane formed by the three crystallographically unique water molecules and the lutidine nitrogen atom is rotated by 45.52 (4)° from the plane of the pyridine ring for Mn, 45.79 (4)° for Co, 45.93 (3)° for Ni, and 45.75 (3)° for Zn. The M—N distances (Table 1) observed in the complexes are all consistent with the ionic radii for the metals (Shannon, 1976). The full sulfate dianions have three near equivalent S—O bonds (S1—O4, S1—O5 and S1—O5ii) with two metal-bound waters hydrogen bonding to each oxygen atom. There is also one slightly longer S—O bond (S1—O6) with four metal-bound waters hydrogen bonding to the oxygen. All S—O distances are listed in Table 1.
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3. Supramolecular features
The ions in all of the compounds described are connected in an extended 3D network through hydrogen bonding. The major hydrogen bonds are between the metal–aqua complexes and the sulfate dianions (Tables 2–5). The extended structure packing of all compounds show π–π stacking between lutidine rings of adjacent complexes. The parameters of the π–π interactions are in Table 6. The crystal packing of the zinc complex is shown in Fig. 2. The crystal packing of the other three compounds is isostructural in nature.
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4. Database survey
While there are many examples of metal–pyridine pentahydrate complexes, there is only one pyridine-based pentahydrate complex of a transition metal with a sulfate counter-ion, which is the dimer of zinc bridged by 1,2-bis(pyridin-3-ylmethylene)hydrazine (YUMVAG; Lozovan et al., 2020). The other similar structures with sulfur-based anions in the literature include a 3-carboxamidepyridine complex of cobalt with a sulfonate counter-ion (CACFAP; Lian et al., 2010), and a pyridine nickel sulfonate complex with a calixarene tetrasulfonate counter-anion (VIWHUE: Atwood et al., 1991). The only similar 3,5-lutidine structures are a tetrakis(3,5-lutidine) copper sulfate complex (IWAWEJ; Bowmaker et al., 2011), and a bis(3,5-lutidine) nickel thiosulfate dimer (BEMNIS; Pladzyk et al., 2012).
5. Synthesis and crystallization
A metal sulfate (44 mg of MnSO4·H2O, 44 mg of CoSO4·7H2O, 217 mg of NiSO4·6H2O, 33 mg of ZnSO4·7H2O) was dissolved in five drops of water and 2.5 mL of 3,5-lutidine. The resulting solution was heated to 338–343 K for twelve hours and allowed to cool slowly to room temperature producing single crystals suitable for X-ray diffraction. The manganese crystals formed as colorless blocks, the cobalt crystals formed as pink blocks, the nickel crystals formed as pale-green plates, and the zinc crystals formed as colorless blocks.
6. Refinement
Crystal data, data collection and structure . The water hydrogen atoms H1, H2A, H2B, H3A, and H3B were found in difference-Fourier maps. These hydrogen atoms were refined isotropically, using DFIX restraints with O—H distances of 0.78 (1) Å. Isotopic displacement parameters were set to 1.5 Ueq of the parent oxygen atom. All other hydrogen atoms were placed in calculated positions [C—H = 0.93 Å (sp2), 0.96 Å (CH3)]. Isotropic displacement parameters were set to 1.2 Ueq of the parent aromatic carbon atoms and 1.5 Ueq of the parent methyl atoms.
details are summarized in Table 7
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Supporting information
https://doi.org/10.1107/S2056989023005261/zv2026sup1.cif
contains datablocks 1, 2, 3, 4. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989023005261/zv20261sup2.hkl
Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989023005261/zv20262sup3.hkl
Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2056989023005261/zv20263sup4.hkl
Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S2056989023005261/zv20264sup5.hkl
For all structures, data collection: APEX4 (Bruker, 2021); cell
SAINT (Bruker, 2021); data reduction: SAINT (Bruker, 2021); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).[Mn(C7H9N)(H2O)5]SO4 | Dx = 1.650 Mg m−3 |
Mr = 348.23 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 7487 reflections |
a = 17.1868 (13) Å | θ = 3.0–25.7° |
b = 7.1278 (5) Å | µ = 1.13 mm−1 |
c = 11.4447 (8) Å | T = 297 K |
V = 1402.02 (17) Å3 | BLOCK, colourless |
Z = 4 | 0.22 × 0.08 × 0.05 mm |
F(000) = 724 |
Bruker D8 Venture CMOS diffractometer | 1265 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.074 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 25.8°, θmin = 3.0° |
Tmin = 0.585, Tmax = 0.745 | h = −20→20 |
27161 measured reflections | k = −8→8 |
1460 independent reflections | l = −13→13 |
Refinement on F2 | 7 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0433P)2 + 0.6101P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
1460 reflections | Δρmax = 0.39 e Å−3 |
128 parameters | Δρmin = −0.42 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mn1 | 0.38853 (3) | 0.750000 | 0.19452 (4) | 0.02628 (16) | |
S1 | 0.33347 (4) | 0.250000 | −0.03698 (6) | 0.02472 (19) | |
O1 | 0.35349 (17) | 0.750000 | 0.0101 (2) | 0.0431 (6) | |
O2 | 0.47201 (10) | 0.9730 (3) | 0.14197 (15) | 0.0370 (4) | |
O3 | 0.30623 (11) | 0.5330 (3) | 0.23922 (17) | 0.0442 (4) | |
O4 | 0.29510 (15) | 0.250000 | 0.0770 (2) | 0.0442 (6) | |
O5 | 0.31258 (11) | 0.0805 (2) | −0.10225 (15) | 0.0433 (4) | |
O6 | 0.41874 (13) | 0.250000 | −0.0163 (2) | 0.0414 (6) | |
N1 | 0.44712 (15) | 0.750000 | 0.3681 (2) | 0.0305 (6) | |
C1 | 0.52514 (18) | 0.750000 | 0.3748 (3) | 0.0335 (7) | |
H1A | 0.553273 | 0.750000 | 0.305376 | 0.040* | |
C2 | 0.56607 (18) | 0.750000 | 0.4786 (3) | 0.0322 (7) | |
C3 | 0.52253 (19) | 0.750000 | 0.5812 (3) | 0.0344 (7) | |
H3 | 0.547891 | 0.750000 | 0.652995 | 0.041* | |
C4 | 0.44230 (19) | 0.750000 | 0.5779 (3) | 0.0327 (7) | |
C5 | 0.40755 (19) | 0.750000 | 0.4686 (3) | 0.0323 (7) | |
H5 | 0.353492 | 0.750000 | 0.465014 | 0.039* | |
C6 | 0.6535 (2) | 0.750000 | 0.4798 (4) | 0.0489 (10) | |
H6A | 0.671766 | 0.681677 | 0.546736 | 0.073* | 0.5 |
H6B | 0.672147 | 0.876855 | 0.483598 | 0.073* | 0.5 |
H6C | 0.672591 | 0.691467 | 0.409899 | 0.073* | 0.5 |
C7 | 0.3933 (2) | 0.750000 | 0.6867 (3) | 0.0500 (10) | |
H7A | 0.420061 | 0.816577 | 0.747595 | 0.075* | 0.5 |
H7B | 0.384142 | 0.623070 | 0.711140 | 0.075* | 0.5 |
H7C | 0.344518 | 0.810353 | 0.670925 | 0.075* | 0.5 |
H1 | 0.3430 (17) | 0.834 (3) | −0.032 (2) | 0.054 (9)* | |
H2A | 0.4583 (16) | 1.057 (3) | 0.103 (2) | 0.056 (10)* | |
H2B | 0.5081 (14) | 0.930 (5) | 0.111 (3) | 0.084 (13)* | |
H3A | 0.2719 (12) | 0.549 (4) | 0.282 (2) | 0.062 (10)* | |
H3B | 0.2951 (17) | 0.451 (3) | 0.197 (2) | 0.062 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0239 (2) | 0.0297 (3) | 0.0253 (3) | 0.000 | −0.00054 (17) | 0.000 |
S1 | 0.0223 (4) | 0.0241 (4) | 0.0278 (4) | 0.000 | −0.0028 (3) | 0.000 |
O1 | 0.0624 (17) | 0.0320 (14) | 0.0347 (14) | 0.000 | −0.0176 (12) | 0.000 |
O2 | 0.0330 (9) | 0.0403 (10) | 0.0378 (9) | −0.0031 (8) | 0.0016 (7) | 0.0063 (8) |
O3 | 0.0413 (10) | 0.0442 (11) | 0.0469 (10) | −0.0143 (9) | 0.0136 (8) | −0.0105 (9) |
O4 | 0.0490 (15) | 0.0410 (14) | 0.0425 (13) | 0.000 | 0.0151 (11) | 0.000 |
O5 | 0.0548 (11) | 0.0305 (9) | 0.0447 (9) | 0.0012 (8) | −0.0186 (8) | −0.0054 (7) |
O6 | 0.0218 (11) | 0.0466 (15) | 0.0558 (15) | 0.000 | −0.0007 (10) | 0.000 |
N1 | 0.0274 (13) | 0.0352 (15) | 0.0290 (13) | 0.000 | −0.0047 (11) | 0.000 |
C1 | 0.0293 (16) | 0.0395 (19) | 0.0315 (16) | 0.000 | 0.0012 (13) | 0.000 |
C2 | 0.0256 (16) | 0.0314 (17) | 0.0396 (18) | 0.000 | −0.0050 (13) | 0.000 |
C3 | 0.0340 (17) | 0.0389 (19) | 0.0303 (16) | 0.000 | −0.0080 (13) | 0.000 |
C4 | 0.0318 (16) | 0.0357 (17) | 0.0307 (16) | 0.000 | −0.0015 (13) | 0.000 |
C5 | 0.0273 (15) | 0.0344 (17) | 0.0351 (17) | 0.000 | −0.0038 (13) | 0.000 |
C6 | 0.0255 (17) | 0.064 (3) | 0.057 (2) | 0.000 | −0.0055 (16) | 0.000 |
C7 | 0.042 (2) | 0.076 (3) | 0.0317 (18) | 0.000 | 0.0010 (15) | 0.000 |
Mn1—O1 | 2.195 (2) | N1—C5 | 1.336 (4) |
Mn1—O2i | 2.2240 (17) | C1—H1A | 0.9300 |
Mn1—O2 | 2.2240 (17) | C1—C2 | 1.381 (5) |
Mn1—O3 | 2.1575 (17) | C2—C3 | 1.392 (5) |
Mn1—O3i | 2.1575 (17) | C2—C6 | 1.504 (4) |
Mn1—N1 | 2.227 (3) | C3—H3 | 0.9300 |
S1—O4 | 1.462 (2) | C3—C4 | 1.379 (5) |
S1—O5ii | 1.4650 (17) | C4—C5 | 1.386 (4) |
S1—O5 | 1.4650 (17) | C4—C7 | 1.503 (5) |
S1—O6 | 1.484 (2) | C5—H5 | 0.9300 |
O1—H1 | 0.786 (10) | C6—H6A | 0.9600 |
O1—H1i | 0.786 (10) | C6—H6B | 0.9600 |
O2—H2A | 0.781 (10) | C6—H6C | 0.9600 |
O2—H2B | 0.776 (10) | C7—H7A | 0.9600 |
O3—H3A | 0.775 (10) | C7—H7B | 0.9600 |
O3—H3B | 0.779 (10) | C7—H7C | 0.9600 |
N1—C1 | 1.343 (4) | ||
O1—Mn1—O2i | 85.24 (7) | C1—N1—Mn1 | 120.2 (2) |
O1—Mn1—O2 | 85.24 (7) | C5—N1—Mn1 | 122.5 (2) |
O1—Mn1—N1 | 169.05 (11) | C5—N1—C1 | 117.3 (3) |
O2i—Mn1—O2 | 91.24 (10) | N1—C1—H1A | 118.0 |
O2i—Mn1—N1 | 87.11 (7) | N1—C1—C2 | 123.9 (3) |
O2—Mn1—N1 | 87.11 (7) | C2—C1—H1A | 118.0 |
O3i—Mn1—O1 | 92.76 (8) | C1—C2—C3 | 116.9 (3) |
O3—Mn1—O1 | 92.76 (8) | C1—C2—C6 | 121.1 (3) |
O3—Mn1—O2 | 177.99 (7) | C3—C2—C6 | 122.0 (3) |
O3i—Mn1—O2 | 88.55 (7) | C2—C3—H3 | 119.5 |
O3—Mn1—O2i | 88.55 (7) | C4—C3—C2 | 120.9 (3) |
O3i—Mn1—O2i | 177.99 (7) | C4—C3—H3 | 119.5 |
O3—Mn1—O3i | 91.59 (11) | C3—C4—C5 | 117.1 (3) |
O3—Mn1—N1 | 94.87 (7) | C3—C4—C7 | 122.5 (3) |
O3i—Mn1—N1 | 94.87 (7) | C5—C4—C7 | 120.4 (3) |
O4—S1—O5ii | 110.15 (9) | N1—C5—C4 | 123.9 (3) |
O4—S1—O5 | 110.15 (10) | N1—C5—H5 | 118.1 |
O4—S1—O6 | 107.66 (15) | C4—C5—H5 | 118.1 |
O5—S1—O5ii | 111.09 (14) | C2—C6—H6A | 109.5 |
O5—S1—O6 | 108.85 (9) | C2—C6—H6B | 109.5 |
O5ii—S1—O6 | 108.86 (9) | C2—C6—H6C | 109.5 |
Mn1—O1—H1i | 130 (2) | H6A—C6—H6B | 109.5 |
Mn1—O1—H1 | 130 (2) | H6A—C6—H6C | 109.5 |
H1—O1—H1i | 99 (4) | H6B—C6—H6C | 109.5 |
Mn1—O2—H2A | 120 (2) | C4—C7—H7A | 109.5 |
Mn1—O2—H2B | 111 (3) | C4—C7—H7B | 109.5 |
H2A—O2—H2B | 106.7 (17) | C4—C7—H7C | 109.5 |
Mn1—O3—H3A | 123 (2) | H7A—C7—H7B | 109.5 |
Mn1—O3—H3B | 123 (2) | H7A—C7—H7C | 109.5 |
H3A—O3—H3B | 108.1 (17) | H7B—C7—H7C | 109.5 |
Mn1—N1—C1—C2 | 180.000 (1) | C2—C3—C4—C5 | 0.000 (1) |
Mn1—N1—C5—C4 | 180.000 (1) | C2—C3—C4—C7 | 180.000 (1) |
N1—C1—C2—C3 | 0.000 (1) | C3—C4—C5—N1 | 0.000 (1) |
N1—C1—C2—C6 | 180.000 (1) | C5—N1—C1—C2 | 0.000 (1) |
C1—N1—C5—C4 | 0.000 (1) | C6—C2—C3—C4 | 180.000 (1) |
C1—C2—C3—C4 | 0.000 (1) | C7—C4—C5—N1 | 180.000 (1) |
Symmetry codes: (i) x, −y+3/2, z; (ii) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5iii | 0.79 (1) | 2.00 (1) | 2.775 (2) | 166 (3) |
O2—H2A···O6iii | 0.78 (1) | 2.06 (1) | 2.832 (3) | 172 (3) |
O2—H2B···O6iv | 0.78 (1) | 2.10 (2) | 2.850 (3) | 162 (4) |
O3—H3A···O5v | 0.78 (1) | 1.98 (1) | 2.752 (2) | 177 (4) |
O3—H3B···O4 | 0.78 (1) | 1.99 (1) | 2.748 (3) | 165 (3) |
Symmetry codes: (iii) x, y+1, z; (iv) −x+1, −y+1, −z; (v) −x+1/2, y+1/2, z+1/2. |
[Co(C7H9N)(H2O)5]SO4 | Dx = 1.708 Mg m−3 |
Mr = 352.22 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 6866 reflections |
a = 17.1238 (10) Å | θ = 3.0–25.3° |
b = 7.1064 (4) Å | µ = 1.44 mm−1 |
c = 11.2576 (6) Å | T = 297 K |
V = 1369.92 (13) Å3 | BLOCK, pink |
Z = 4 | 0.08 × 0.08 × 0.06 mm |
F(000) = 732 |
Bruker D8 Venture CMOS diffractometer | 1194 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.070 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 25.4°, θmin = 3.0° |
Tmin = 0.714, Tmax = 0.745 | h = −20→20 |
32289 measured reflections | k = −8→8 |
1367 independent reflections | l = −13→13 |
Refinement on F2 | 7 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.069 | w = 1/[σ2(Fo2) + (0.033P)2 + 0.9563P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
1367 reflections | Δρmax = 0.43 e Å−3 |
128 parameters | Δρmin = −0.29 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Co1 | 0.38970 (2) | 0.750000 | 0.19737 (4) | 0.02337 (15) | |
S1 | 0.33394 (4) | 0.250000 | −0.03379 (7) | 0.02209 (19) | |
O1 | 0.35093 (18) | 0.750000 | 0.0198 (2) | 0.0394 (6) | |
O2 | 0.46967 (11) | 0.9655 (3) | 0.14383 (16) | 0.0336 (4) | |
O3 | 0.31132 (11) | 0.5387 (3) | 0.24411 (17) | 0.0384 (4) | |
O4 | 0.29778 (16) | 0.250000 | 0.0839 (2) | 0.0427 (7) | |
O5 | 0.31138 (11) | 0.0802 (2) | −0.09856 (16) | 0.0406 (5) | |
O6 | 0.42011 (14) | 0.250000 | −0.0164 (2) | 0.0396 (6) | |
N1 | 0.44535 (16) | 0.750000 | 0.3648 (2) | 0.0251 (6) | |
C1 | 0.5235 (2) | 0.750000 | 0.3707 (3) | 0.0293 (7) | |
H1A | 0.551507 | 0.750000 | 0.299987 | 0.035* | |
C2 | 0.56474 (19) | 0.750000 | 0.4765 (3) | 0.0279 (7) | |
C3 | 0.5217 (2) | 0.750000 | 0.5803 (3) | 0.0315 (8) | |
H3 | 0.547380 | 0.750000 | 0.653096 | 0.038* | |
C4 | 0.4411 (2) | 0.750000 | 0.5776 (3) | 0.0297 (7) | |
C5 | 0.40575 (19) | 0.750000 | 0.4670 (3) | 0.0268 (7) | |
H5 | 0.351489 | 0.750000 | 0.463642 | 0.032* | |
C6 | 0.6528 (2) | 0.750000 | 0.4759 (4) | 0.0439 (10) | |
H6A | 0.671655 | 0.688585 | 0.546196 | 0.066* | 0.5 |
H6B | 0.671452 | 0.877337 | 0.474120 | 0.066* | 0.5 |
H6C | 0.671263 | 0.684078 | 0.406972 | 0.066* | 0.5 |
C7 | 0.3926 (2) | 0.750000 | 0.6890 (3) | 0.0465 (10) | |
H7A | 0.420270 | 0.814262 | 0.751028 | 0.070* | 0.5 |
H7B | 0.382469 | 0.622638 | 0.712901 | 0.070* | 0.5 |
H7C | 0.343972 | 0.813100 | 0.674071 | 0.070* | 0.5 |
H1 | 0.3369 (18) | 0.838 (3) | −0.016 (2) | 0.058 (10)* | |
H2A | 0.4543 (17) | 1.052 (3) | 0.108 (2) | 0.058 (11)* | |
H2B | 0.5060 (14) | 0.928 (5) | 0.108 (3) | 0.079 (14)* | |
H3A | 0.2753 (11) | 0.555 (4) | 0.284 (2) | 0.046 (9)* | |
H3B | 0.3023 (16) | 0.457 (3) | 0.201 (2) | 0.053 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0234 (2) | 0.0267 (2) | 0.0200 (2) | 0.000 | −0.00065 (17) | 0.000 |
S1 | 0.0216 (4) | 0.0213 (4) | 0.0233 (4) | 0.000 | −0.0020 (3) | 0.000 |
O1 | 0.0592 (18) | 0.0293 (15) | 0.0298 (14) | 0.000 | −0.0181 (13) | 0.000 |
O2 | 0.0318 (10) | 0.0375 (10) | 0.0316 (9) | −0.0022 (8) | 0.0004 (8) | 0.0067 (9) |
O3 | 0.0381 (11) | 0.0389 (11) | 0.0382 (10) | −0.0127 (9) | 0.0118 (9) | −0.0095 (9) |
O4 | 0.0531 (17) | 0.0397 (15) | 0.0354 (14) | 0.000 | 0.0166 (12) | 0.000 |
O5 | 0.0531 (11) | 0.0261 (10) | 0.0427 (10) | −0.0013 (8) | −0.0190 (9) | −0.0058 (8) |
O6 | 0.0228 (12) | 0.0426 (15) | 0.0532 (16) | 0.000 | −0.0015 (11) | 0.000 |
N1 | 0.0255 (14) | 0.0280 (15) | 0.0218 (13) | 0.000 | −0.0028 (11) | 0.000 |
C1 | 0.0298 (18) | 0.0311 (18) | 0.0270 (17) | 0.000 | 0.0007 (14) | 0.000 |
C2 | 0.0270 (17) | 0.0258 (17) | 0.0309 (18) | 0.000 | −0.0047 (14) | 0.000 |
C3 | 0.0344 (19) | 0.036 (2) | 0.0245 (16) | 0.000 | −0.0085 (14) | 0.000 |
C4 | 0.0341 (18) | 0.0292 (18) | 0.0258 (17) | 0.000 | 0.0003 (14) | 0.000 |
C5 | 0.0248 (16) | 0.0290 (17) | 0.0266 (17) | 0.000 | −0.0031 (13) | 0.000 |
C6 | 0.0238 (19) | 0.060 (3) | 0.048 (2) | 0.000 | −0.0031 (16) | 0.000 |
C7 | 0.043 (2) | 0.070 (3) | 0.0268 (19) | 0.000 | 0.0016 (17) | 0.000 |
Co1—O1 | 2.106 (3) | N1—C5 | 1.335 (4) |
Co1—O2 | 2.1408 (18) | C1—H1A | 0.9300 |
Co1—O2i | 2.1408 (18) | C1—C2 | 1.384 (5) |
Co1—O3 | 2.0813 (18) | C2—C3 | 1.382 (5) |
Co1—O3i | 2.0813 (18) | C2—C6 | 1.507 (5) |
Co1—N1 | 2.112 (3) | C3—H3 | 0.9300 |
S1—O4 | 1.462 (3) | C3—C4 | 1.380 (5) |
S1—O5ii | 1.4618 (17) | C4—C5 | 1.385 (5) |
S1—O5 | 1.4618 (17) | C4—C7 | 1.504 (5) |
S1—O6 | 1.488 (2) | C5—H5 | 0.9300 |
O1—H1i | 0.778 (10) | C6—H6A | 0.9600 |
O1—H1 | 0.778 (10) | C6—H6B | 0.9600 |
O2—H2A | 0.782 (10) | C6—H6C | 0.9600 |
O2—H2B | 0.784 (10) | C7—H7A | 0.9600 |
O3—H3A | 0.774 (10) | C7—H7B | 0.9600 |
O3—H3B | 0.776 (10) | C7—H7C | 0.9600 |
N1—C1 | 1.339 (4) | ||
O1—Co1—O2i | 86.24 (8) | C1—N1—Co1 | 119.7 (2) |
O1—Co1—O2 | 86.24 (8) | C5—N1—Co1 | 122.7 (2) |
O1—Co1—N1 | 171.55 (11) | C5—N1—C1 | 117.7 (3) |
O2—Co1—O2i | 91.32 (11) | N1—C1—H1A | 118.2 |
O3—Co1—O1 | 92.10 (8) | N1—C1—C2 | 123.6 (3) |
O3i—Co1—O1 | 92.10 (8) | C2—C1—H1A | 118.2 |
O3i—Co1—O2 | 88.15 (8) | C1—C2—C6 | 120.5 (3) |
O3—Co1—O2i | 88.15 (8) | C3—C2—C1 | 117.1 (3) |
O3i—Co1—O2i | 178.29 (8) | C3—C2—C6 | 122.5 (3) |
O3—Co1—O2 | 178.29 (8) | C2—C3—H3 | 119.5 |
O3—Co1—O3i | 92.32 (11) | C4—C3—C2 | 121.0 (3) |
O3i—Co1—N1 | 93.74 (8) | C4—C3—H3 | 119.5 |
O3—Co1—N1 | 93.74 (8) | C3—C4—C5 | 117.2 (3) |
N1—Co1—O2 | 87.86 (7) | C3—C4—C7 | 122.3 (3) |
N1—Co1—O2i | 87.86 (7) | C5—C4—C7 | 120.5 (3) |
O4—S1—O6 | 107.51 (16) | N1—C5—C4 | 123.6 (3) |
O5ii—S1—O4 | 109.87 (10) | N1—C5—H5 | 118.2 |
O5—S1—O4 | 109.87 (10) | C4—C5—H5 | 118.2 |
O5ii—S1—O5 | 111.27 (14) | C2—C6—H6A | 109.5 |
O5ii—S1—O6 | 109.12 (10) | C2—C6—H6B | 109.5 |
O5—S1—O6 | 109.12 (10) | C2—C6—H6C | 109.5 |
Co1—O1—H1 | 126 (2) | H6A—C6—H6B | 109.5 |
Co1—O1—H1i | 126 (2) | H6A—C6—H6C | 109.5 |
H1—O1—H1i | 106 (5) | H6B—C6—H6C | 109.5 |
Co1—O2—H2A | 120 (2) | C4—C7—H7A | 109.5 |
Co1—O2—H2B | 114 (3) | C4—C7—H7B | 109.5 |
H2A—O2—H2B | 105.7 (16) | C4—C7—H7C | 109.5 |
Co1—O3—H3A | 124 (2) | H7A—C7—H7B | 109.5 |
Co1—O3—H3B | 121 (2) | H7A—C7—H7C | 109.5 |
H3A—O3—H3B | 108.7 (17) | H7B—C7—H7C | 109.5 |
Co1—N1—C1—C2 | 180.000 (1) | C2—C3—C4—C5 | 0.000 (1) |
Co1—N1—C5—C4 | 180.000 (1) | C2—C3—C4—C7 | 180.000 (1) |
N1—C1—C2—C3 | 0.000 (1) | C3—C4—C5—N1 | 0.000 (1) |
N1—C1—C2—C6 | 180.000 (1) | C5—N1—C1—C2 | 0.000 (1) |
C1—N1—C5—C4 | 0.000 (1) | C6—C2—C3—C4 | 180.000 (1) |
C1—C2—C3—C4 | 0.000 (1) | C7—C4—C5—N1 | 180.000 (1) |
Symmetry codes: (i) x, −y+3/2, z; (ii) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5iii | 0.78 (1) | 2.01 (1) | 2.782 (2) | 173 (3) |
O2—H2A···O6iii | 0.78 (1) | 2.07 (1) | 2.840 (3) | 169 (3) |
O2—H2B···O6iv | 0.78 (1) | 2.07 (2) | 2.822 (3) | 161 (4) |
O3—H3A···O5v | 0.77 (1) | 1.99 (1) | 2.764 (2) | 174 (3) |
O3—H3B···O4 | 0.78 (1) | 1.97 (1) | 2.742 (3) | 171 (3) |
Symmetry codes: (iii) x, y+1, z; (iv) −x+1, −y+1, −z; (v) −x+1/2, y+1/2, z+1/2. |
[Ni(C7H9N)(H2O)5]SO4 | Dx = 1.723 Mg m−3 |
Mr = 352.00 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 9899 reflections |
a = 17.1196 (8) Å | θ = 3.0–26.3° |
b = 7.0609 (3) Å | µ = 1.62 mm−1 |
c = 11.2233 (5) Å | T = 297 K |
V = 1356.67 (10) Å3 | BLOCK, green |
Z = 4 | 0.17 × 0.04 × 0.03 mm |
F(000) = 736 |
Bruker D8 Venture CMOS diffractometer | 1386 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.049 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 26.4°, θmin = 3.6° |
Tmin = 0.680, Tmax = 0.745 | h = −21→20 |
36924 measured reflections | k = −8→8 |
1499 independent reflections | l = −14→14 |
Refinement on F2 | 7 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.060 | w = 1/[σ2(Fo2) + (0.0308P)2 + 0.6821P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
1499 reflections | Δρmax = 0.44 e Å−3 |
128 parameters | Δρmin = −0.33 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.39091 (2) | 0.750000 | 0.19852 (3) | 0.02146 (11) | |
S1 | 0.33343 (3) | 0.250000 | −0.03397 (5) | 0.02160 (14) | |
O1 | 0.35007 (14) | 0.750000 | 0.02346 (18) | 0.0384 (5) | |
O2 | 0.46878 (7) | 0.9627 (2) | 0.14536 (12) | 0.0309 (3) | |
O3 | 0.31406 (8) | 0.5401 (2) | 0.24601 (12) | 0.0354 (3) | |
O4 | 0.29830 (12) | 0.250000 | 0.08496 (18) | 0.0424 (5) | |
O5 | 0.31029 (8) | 0.0794 (2) | −0.09827 (12) | 0.0410 (3) | |
O6 | 0.41976 (10) | 0.250000 | −0.01750 (19) | 0.0394 (5) | |
N1 | 0.44466 (12) | 0.750000 | 0.36335 (17) | 0.0241 (4) | |
C1 | 0.52308 (14) | 0.750000 | 0.3692 (2) | 0.0277 (5) | |
H1A | 0.551105 | 0.750000 | 0.298181 | 0.033* | |
C2 | 0.56433 (14) | 0.750000 | 0.4753 (2) | 0.0272 (5) | |
C3 | 0.52130 (15) | 0.750000 | 0.5799 (2) | 0.0304 (6) | |
H3 | 0.546992 | 0.750000 | 0.652878 | 0.036* | |
C4 | 0.44033 (15) | 0.750000 | 0.5768 (2) | 0.0282 (5) | |
C5 | 0.40464 (14) | 0.750000 | 0.4658 (2) | 0.0260 (5) | |
H5 | 0.350357 | 0.750000 | 0.462450 | 0.031* | |
C6 | 0.65243 (15) | 0.750000 | 0.4748 (3) | 0.0409 (7) | |
H6A | 0.671277 | 0.686857 | 0.544900 | 0.061* | 0.5 |
H6B | 0.671120 | 0.878180 | 0.474031 | 0.061* | 0.5 |
H6C | 0.670966 | 0.684963 | 0.405226 | 0.061* | 0.5 |
C7 | 0.39189 (17) | 0.750000 | 0.6886 (2) | 0.0429 (7) | |
H7A | 0.418880 | 0.818472 | 0.750001 | 0.064* | 0.5 |
H7B | 0.383346 | 0.621918 | 0.714204 | 0.064* | 0.5 |
H7C | 0.342529 | 0.809610 | 0.673085 | 0.064* | 0.5 |
H1 | 0.3354 (14) | 0.840 (3) | −0.011 (2) | 0.057 (8)* | |
H2A | 0.4540 (12) | 1.048 (2) | 0.1067 (18) | 0.045 (7)* | |
H2B | 0.5056 (10) | 0.923 (3) | 0.1115 (19) | 0.062 (9)* | |
H3A | 0.2777 (9) | 0.557 (3) | 0.2854 (16) | 0.041 (6)* | |
H3B | 0.3050 (12) | 0.460 (3) | 0.2012 (16) | 0.048 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.02095 (16) | 0.02450 (18) | 0.01894 (17) | 0.000 | −0.00045 (11) | 0.000 |
S1 | 0.0213 (3) | 0.0206 (3) | 0.0229 (3) | 0.000 | −0.0023 (2) | 0.000 |
O1 | 0.0564 (13) | 0.0289 (11) | 0.0300 (10) | 0.000 | −0.0187 (9) | 0.000 |
O2 | 0.0301 (7) | 0.0325 (7) | 0.0300 (7) | −0.0018 (6) | 0.0016 (5) | 0.0060 (6) |
O3 | 0.0348 (7) | 0.0370 (8) | 0.0343 (7) | −0.0105 (6) | 0.0108 (6) | −0.0078 (7) |
O4 | 0.0527 (12) | 0.0386 (12) | 0.0357 (11) | 0.000 | 0.0161 (9) | 0.000 |
O5 | 0.0544 (8) | 0.0269 (7) | 0.0417 (8) | 0.0008 (6) | −0.0201 (6) | −0.0060 (6) |
O6 | 0.0232 (9) | 0.0435 (12) | 0.0515 (12) | 0.000 | 0.0003 (8) | 0.000 |
N1 | 0.0243 (9) | 0.0260 (11) | 0.0221 (10) | 0.000 | −0.0029 (8) | 0.000 |
C1 | 0.0252 (11) | 0.0302 (14) | 0.0277 (13) | 0.000 | 0.0008 (10) | 0.000 |
C2 | 0.0244 (12) | 0.0273 (13) | 0.0299 (13) | 0.000 | −0.0044 (10) | 0.000 |
C3 | 0.0330 (13) | 0.0339 (14) | 0.0242 (12) | 0.000 | −0.0086 (10) | 0.000 |
C4 | 0.0323 (12) | 0.0280 (13) | 0.0243 (12) | 0.000 | 0.0004 (10) | 0.000 |
C5 | 0.0251 (11) | 0.0271 (13) | 0.0258 (12) | 0.000 | −0.0022 (9) | 0.000 |
C6 | 0.0219 (12) | 0.0562 (19) | 0.0444 (17) | 0.000 | −0.0065 (11) | 0.000 |
C7 | 0.0392 (15) | 0.064 (2) | 0.0251 (14) | 0.000 | 0.0012 (11) | 0.000 |
Ni1—O1 | 2.0855 (19) | N1—C5 | 1.339 (3) |
Ni1—O2 | 2.0949 (13) | C1—H1A | 0.9300 |
Ni1—O2i | 2.0949 (13) | C1—C2 | 1.384 (3) |
Ni1—O3 | 2.0522 (13) | C2—C3 | 1.386 (4) |
Ni1—O3i | 2.0522 (13) | C2—C6 | 1.508 (3) |
Ni1—N1 | 2.066 (2) | C3—H3 | 0.9300 |
S1—O4 | 1.464 (2) | C3—C4 | 1.387 (4) |
S1—O5ii | 1.4588 (14) | C4—C5 | 1.387 (3) |
S1—O5 | 1.4588 (14) | C4—C7 | 1.505 (4) |
S1—O6 | 1.4895 (19) | C5—H5 | 0.9300 |
O1—H1i | 0.782 (10) | C6—H6A | 0.9600 |
O1—H1 | 0.782 (10) | C6—H6B | 0.9600 |
O2—H2A | 0.782 (9) | C6—H6C | 0.9600 |
O2—H2B | 0.787 (9) | C7—H7A | 0.9600 |
O3—H3A | 0.773 (9) | C7—H7B | 0.9600 |
O3—H3B | 0.774 (9) | C7—H7C | 0.9600 |
N1—C1 | 1.344 (3) | ||
O1—Ni1—O2i | 86.85 (6) | C1—N1—Ni1 | 119.23 (17) |
O1—Ni1—O2 | 86.85 (6) | C5—N1—Ni1 | 122.77 (16) |
O2i—Ni1—O2 | 91.60 (8) | C5—N1—C1 | 118.0 (2) |
O3i—Ni1—O1 | 91.70 (6) | N1—C1—H1A | 118.3 |
O3—Ni1—O1 | 91.70 (6) | N1—C1—C2 | 123.4 (2) |
O3i—Ni1—O2 | 87.95 (6) | C2—C1—H1A | 118.3 |
O3—Ni1—O2 | 178.51 (6) | C1—C2—C3 | 117.2 (2) |
O3—Ni1—O2i | 87.95 (6) | C1—C2—C6 | 120.5 (2) |
O3i—Ni1—O2i | 178.51 (6) | C3—C2—C6 | 122.3 (2) |
O3—Ni1—O3i | 92.46 (8) | C2—C3—H3 | 119.7 |
O3i—Ni1—N1 | 93.04 (6) | C2—C3—C4 | 120.7 (2) |
O3—Ni1—N1 | 93.04 (6) | C4—C3—H3 | 119.7 |
N1—Ni1—O1 | 173.14 (9) | C3—C4—C5 | 117.6 (2) |
N1—Ni1—O2 | 88.38 (5) | C3—C4—C7 | 122.0 (2) |
N1—Ni1—O2i | 88.37 (5) | C5—C4—C7 | 120.4 (2) |
O4—S1—O6 | 107.12 (13) | N1—C5—C4 | 123.1 (2) |
O5ii—S1—O4 | 109.84 (8) | N1—C5—H5 | 118.5 |
O5—S1—O4 | 109.85 (8) | C4—C5—H5 | 118.5 |
O5ii—S1—O5 | 111.30 (11) | C2—C6—H6A | 109.5 |
O5—S1—O6 | 109.32 (8) | C2—C6—H6B | 109.5 |
O5ii—S1—O6 | 109.32 (8) | C2—C6—H6C | 109.5 |
Ni1—O1—H1 | 124.8 (19) | H6A—C6—H6B | 109.5 |
Ni1—O1—H1i | 124.8 (19) | H6A—C6—H6C | 109.5 |
H1—O1—H1i | 108 (4) | H6B—C6—H6C | 109.5 |
Ni1—O2—H2A | 120.2 (17) | C4—C7—H7A | 109.5 |
Ni1—O2—H2B | 113.1 (19) | C4—C7—H7B | 109.5 |
H2A—O2—H2B | 105.3 (15) | C4—C7—H7C | 109.5 |
Ni1—O3—H3A | 123.6 (16) | H7A—C7—H7B | 109.5 |
Ni1—O3—H3B | 119.3 (16) | H7A—C7—H7C | 109.5 |
H3A—O3—H3B | 108.9 (15) | H7B—C7—H7C | 109.5 |
Ni1—N1—C1—C2 | 180.000 (1) | C2—C3—C4—C5 | 0.000 (1) |
Ni1—N1—C5—C4 | 180.000 (1) | C2—C3—C4—C7 | 180.000 (1) |
N1—C1—C2—C3 | 0.000 (1) | C3—C4—C5—N1 | 0.000 (1) |
N1—C1—C2—C6 | 180.000 (1) | C5—N1—C1—C2 | 0.000 (1) |
C1—N1—C5—C4 | 0.000 (1) | C6—C2—C3—C4 | 180.000 (1) |
C1—C2—C3—C4 | 0.000 (1) | C7—C4—C5—N1 | 180.000 (1) |
Symmetry codes: (i) x, −y+3/2, z; (ii) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5iii | 0.78 (1) | 2.00 (1) | 2.7822 (18) | 174 (3) |
O2—H2A···O6iii | 0.78 (1) | 2.08 (1) | 2.857 (2) | 172 (2) |
O2—H2B···O6iv | 0.79 (1) | 2.06 (1) | 2.821 (2) | 163 (3) |
O3—H3A···O5v | 0.77 (1) | 2.00 (1) | 2.7683 (18) | 173 (2) |
O3—H3B···O4 | 0.77 (1) | 1.98 (1) | 2.745 (2) | 172 (2) |
Symmetry codes: (iii) x, y+1, z; (iv) −x+1, −y+1, −z; (v) −x+1/2, y+1/2, z+1/2. |
[Zn(C7H9N)(H2O)5]SO4 | Dx = 1.739 Mg m−3 |
Mr = 358.66 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 9907 reflections |
a = 17.1312 (8) Å | θ = 3.0–26.1° |
b = 7.0826 (3) Å | µ = 1.99 mm−1 |
c = 11.2879 (5) Å | T = 297 K |
V = 1369.60 (11) Å3 | BLOCK, colourless |
Z = 4 | 0.21 × 0.13 × 0.1 mm |
F(000) = 744 |
Bruker D8 Venture CMOS diffractometer | 1414 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.042 |
Absorption correction: multi-scan (SADABS; Bruker, 2021) | θmax = 26.4°, θmin = 3.0° |
Tmin = 0.671, Tmax = 0.745 | h = −21→21 |
46710 measured reflections | k = −8→8 |
1516 independent reflections | l = −14→14 |
Refinement on F2 | 7 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.021 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.0287P)2 + 0.6476P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
1516 reflections | Δρmax = 0.40 e Å−3 |
128 parameters | Δρmin = −0.27 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.38941 (2) | 0.750000 | 0.20029 (2) | 0.02445 (10) | |
S1 | 0.33349 (3) | 0.250000 | −0.03485 (5) | 0.02238 (13) | |
O1 | 0.35283 (14) | 0.750000 | 0.02014 (17) | 0.0411 (5) | |
O2 | 0.46998 (8) | 0.9672 (2) | 0.14481 (11) | 0.0334 (3) | |
O3 | 0.31084 (8) | 0.5381 (2) | 0.24347 (13) | 0.0393 (3) | |
O4 | 0.29751 (12) | 0.250000 | 0.08280 (17) | 0.0435 (5) | |
O5 | 0.31108 (8) | 0.07969 (19) | −0.09923 (12) | 0.0418 (3) | |
O6 | 0.41959 (10) | 0.250000 | −0.01709 (19) | 0.0403 (5) | |
N1 | 0.44544 (12) | 0.750000 | 0.36501 (17) | 0.0258 (4) | |
C1 | 0.52356 (14) | 0.750000 | 0.3709 (2) | 0.0292 (5) | |
H1A | 0.551519 | 0.750000 | 0.300258 | 0.035* | |
C2 | 0.56501 (14) | 0.750000 | 0.4762 (2) | 0.0296 (5) | |
C3 | 0.52173 (15) | 0.750000 | 0.5806 (2) | 0.0314 (5) | |
H3 | 0.547367 | 0.750000 | 0.653242 | 0.038* | |
C4 | 0.44114 (15) | 0.750000 | 0.5775 (2) | 0.0290 (5) | |
C5 | 0.40543 (14) | 0.750000 | 0.4668 (2) | 0.0273 (5) | |
H5 | 0.351191 | 0.750000 | 0.463327 | 0.033* | |
C6 | 0.65285 (15) | 0.750000 | 0.4765 (3) | 0.0440 (7) | |
H6A | 0.671449 | 0.681907 | 0.544387 | 0.066* | 0.5 |
H6B | 0.671527 | 0.877698 | 0.479610 | 0.066* | 0.5 |
H6C | 0.671616 | 0.690396 | 0.405608 | 0.066* | 0.5 |
C7 | 0.39253 (17) | 0.750000 | 0.6883 (2) | 0.0438 (7) | |
H7A | 0.419605 | 0.817081 | 0.749703 | 0.066* | 0.5 |
H7B | 0.383455 | 0.622262 | 0.713159 | 0.066* | 0.5 |
H7C | 0.343476 | 0.810656 | 0.672744 | 0.066* | 0.5 |
H1 | 0.3379 (13) | 0.836 (2) | −0.0171 (18) | 0.052 (7)* | |
H2A | 0.4540 (12) | 1.049 (3) | 0.1049 (18) | 0.050 (7)* | |
H2B | 0.5065 (11) | 0.928 (4) | 0.1108 (19) | 0.068 (9)* | |
H3A | 0.2758 (10) | 0.550 (3) | 0.2857 (16) | 0.050 (7)* | |
H3B | 0.3024 (13) | 0.458 (3) | 0.1986 (16) | 0.049 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02442 (15) | 0.02788 (16) | 0.02103 (15) | 0.000 | −0.00072 (10) | 0.000 |
S1 | 0.0220 (3) | 0.0216 (3) | 0.0235 (3) | 0.000 | −0.0025 (2) | 0.000 |
O1 | 0.0616 (13) | 0.0301 (11) | 0.0317 (10) | 0.000 | −0.0188 (9) | 0.000 |
O2 | 0.0320 (7) | 0.0367 (7) | 0.0314 (6) | −0.0012 (6) | 0.0013 (5) | 0.0063 (6) |
O3 | 0.0387 (7) | 0.0406 (8) | 0.0387 (7) | −0.0129 (6) | 0.0121 (6) | −0.0103 (7) |
O4 | 0.0544 (12) | 0.0396 (11) | 0.0366 (10) | 0.000 | 0.0167 (9) | 0.000 |
O5 | 0.0541 (8) | 0.0274 (7) | 0.0438 (7) | 0.0002 (6) | −0.0201 (6) | −0.0064 (6) |
O6 | 0.0229 (9) | 0.0446 (11) | 0.0533 (12) | 0.000 | 0.0002 (8) | 0.000 |
N1 | 0.0275 (10) | 0.0274 (10) | 0.0226 (9) | 0.000 | −0.0034 (8) | 0.000 |
C1 | 0.0259 (12) | 0.0339 (13) | 0.0278 (12) | 0.000 | 0.0004 (9) | 0.000 |
C2 | 0.0265 (12) | 0.0284 (12) | 0.0340 (13) | 0.000 | −0.0046 (10) | 0.000 |
C3 | 0.0331 (13) | 0.0351 (14) | 0.0259 (12) | 0.000 | −0.0085 (10) | 0.000 |
C4 | 0.0318 (12) | 0.0310 (13) | 0.0242 (11) | 0.000 | 0.0001 (10) | 0.000 |
C5 | 0.0237 (11) | 0.0304 (13) | 0.0277 (12) | 0.000 | −0.0018 (9) | 0.000 |
C6 | 0.0236 (13) | 0.0580 (19) | 0.0504 (17) | 0.000 | −0.0049 (11) | 0.000 |
C7 | 0.0399 (15) | 0.066 (2) | 0.0251 (13) | 0.000 | 0.0028 (11) | 0.000 |
Zn1—O1 | 2.1279 (19) | N1—C5 | 1.337 (3) |
Zn1—O2 | 2.1598 (13) | C1—H1A | 0.9300 |
Zn1—O2i | 2.1598 (13) | C1—C2 | 1.385 (3) |
Zn1—O3 | 2.0742 (13) | C2—C3 | 1.392 (4) |
Zn1—O3i | 2.0742 (13) | C2—C6 | 1.505 (3) |
Zn1—N1 | 2.0924 (19) | C3—H3 | 0.9300 |
S1—O4 | 1.4641 (19) | C3—C4 | 1.381 (4) |
S1—O5ii | 1.4596 (13) | C4—C5 | 1.392 (3) |
S1—O5 | 1.4596 (13) | C4—C7 | 1.502 (3) |
S1—O6 | 1.4886 (18) | C5—H5 | 0.9300 |
O1—H1i | 0.784 (10) | C6—H6A | 0.9600 |
O1—H1 | 0.784 (10) | C6—H6B | 0.9600 |
O2—H2A | 0.784 (9) | C6—H6C | 0.9600 |
O2—H2B | 0.785 (9) | C7—H7A | 0.9600 |
O3—H3A | 0.771 (9) | C7—H7B | 0.9600 |
O3—H3B | 0.773 (9) | C7—H7C | 0.9600 |
N1—C1 | 1.340 (3) | ||
O1—Zn1—O2i | 84.90 (6) | C1—N1—Zn1 | 120.14 (16) |
O1—Zn1—O2 | 84.90 (6) | C5—N1—Zn1 | 121.87 (16) |
O2i—Zn1—O2 | 90.87 (8) | C5—N1—C1 | 118.0 (2) |
O3i—Zn1—O1 | 91.92 (6) | N1—C1—H1A | 118.2 |
O3—Zn1—O1 | 91.92 (6) | N1—C1—C2 | 123.7 (2) |
O3i—Zn1—O2 | 88.13 (6) | C2—C1—H1A | 118.2 |
O3—Zn1—O2 | 176.74 (5) | C1—C2—C3 | 117.0 (2) |
O3—Zn1—O2i | 88.13 (6) | C1—C2—C6 | 120.9 (2) |
O3i—Zn1—O2i | 176.74 (5) | C3—C2—C6 | 122.1 (2) |
O3—Zn1—O3i | 92.71 (8) | C2—C3—H3 | 119.6 |
O3i—Zn1—N1 | 95.10 (6) | C4—C3—C2 | 120.7 (2) |
O3—Zn1—N1 | 95.10 (6) | C4—C3—H3 | 119.6 |
N1—Zn1—O1 | 169.82 (9) | C3—C4—C5 | 117.5 (2) |
N1—Zn1—O2 | 87.97 (5) | C3—C4—C7 | 122.2 (2) |
N1—Zn1—O2i | 87.97 (5) | C5—C4—C7 | 120.3 (2) |
O4—S1—O6 | 107.16 (12) | N1—C5—C4 | 123.1 (2) |
O5ii—S1—O4 | 109.93 (8) | N1—C5—H5 | 118.4 |
O5—S1—O4 | 109.93 (8) | C4—C5—H5 | 118.4 |
O5ii—S1—O5 | 111.46 (11) | C2—C6—H6A | 109.5 |
O5—S1—O6 | 109.12 (7) | C2—C6—H6B | 109.5 |
O5ii—S1—O6 | 109.12 (7) | C2—C6—H6C | 109.5 |
Zn1—O1—H1 | 127.5 (18) | H6A—C6—H6B | 109.5 |
Zn1—O1—H1i | 127.5 (18) | H6A—C6—H6C | 109.5 |
H1—O1—H1i | 102 (4) | H6B—C6—H6C | 109.5 |
Zn1—O2—H2A | 118.1 (17) | C4—C7—H7A | 109.5 |
Zn1—O2—H2B | 114 (2) | C4—C7—H7B | 109.5 |
H2A—O2—H2B | 105.0 (14) | C4—C7—H7C | 109.5 |
Zn1—O3—H3A | 125.1 (17) | H7A—C7—H7B | 109.5 |
Zn1—O3—H3B | 119.8 (16) | H7A—C7—H7C | 109.5 |
H3A—O3—H3B | 109.6 (16) | H7B—C7—H7C | 109.5 |
Zn1—N1—C1—C2 | 180.000 (1) | C2—C3—C4—C5 | 0.000 (1) |
Zn1—N1—C5—C4 | 180.000 (1) | C2—C3—C4—C7 | 180.000 (1) |
N1—C1—C2—C3 | 0.000 (1) | C3—C4—C5—N1 | 0.000 (1) |
N1—C1—C2—C6 | 180.000 (1) | C5—N1—C1—C2 | 0.000 (1) |
C1—N1—C5—C4 | 0.000 (1) | C6—C2—C3—C4 | 180.000 (1) |
C1—C2—C3—C4 | 0.000 (1) | C7—C4—C5—N1 | 180.000 (1) |
Symmetry codes: (i) x, −y+3/2, z; (ii) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5iii | 0.78 (1) | 2.01 (1) | 2.7892 (17) | 172 (3) |
O2—H2A···O6iii | 0.78 (1) | 2.07 (1) | 2.845 (2) | 173 (2) |
O2—H2B···O6iv | 0.79 (1) | 2.08 (1) | 2.833 (2) | 162 (3) |
O3—H3A···O5v | 0.77 (1) | 1.99 (1) | 2.7571 (18) | 177 (2) |
O3—H3B···O4 | 0.77 (1) | 1.97 (1) | 2.7395 (19) | 172 (2) |
Symmetry codes: (iii) x, y+1, z; (iv) −x+1, −y+1, −z; (v) −x+1/2, y+1/2, z+1/2. |
Compound | M—N1 | S1—O4 | S1—O5 | S1—O6 |
(1) | 2.227 (3) | 1.462 (2) | 1.4650 (17) | 1.484 (2) |
(2) | 2.112 (3) | 1.462 (3) | 1.4618 (17) | 1.488 (2) |
(3) | 2.066 (2) | 1.464 (2) | 1.4588 (14) | 1.4895 (19) |
(4) | 2.0924 (19) | 1.4641 (19) | 1.4596 (13) | 1.4886 (18) |
(1) | (2) | (3) | (4) | |
Centroid-to-centroid | 3.6461 (6) | 3.6485 (6) | 3.6337 (5) | 3.6370 (5) |
Plane-to-plane shift | 0.770 (3) | 0.829 (3) | 0.8599 (19) | 0.8290 (19) |
Plane-to-centroid | 3.5639 (3) | 3.5532 (2) | 3.53045 (15) | 3.54130 (15) |
Funding information
Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (grant No. CHE-1429086).
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