research communications
fac-Triaqua(1,10-phenanthroline-κ2N,N′)(sulfato-κO)cobalt(II): Hirshfeld surface analysis and computational study
aDépartement de Technologie, Faculté de Technologie, Université 20 Août 1955-Skikda, BP 26, Route d'El-Hadaiek, Skikda 21000, Algeria, bLaboratoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas Sétif 1, Sétif 19000, Algeria, cResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia, and dDepartment of Chemistry, Université de Montréal, 2900 Edouard-Montpetit Blvd, Montreal, Quebec, H3T1J4, Canada
*Correspondence e-mail: edwardt@sunway.edu.my
The CoII atom in the title complex, [Co(SO4)(C12H8N2)(H2O)3] (or C12H14CoN2O7S), is octahedrally coordinated within a cis-N2O4 donor set defined by the chelating N-donors of the 1,10-phenanthroline ligand, sulfate-O and three aqua-O atoms, the latter occupying an octahedral face. In the crystal, supramolecular layers lying parallel to (110) are sustained by aqua-O—H⋯O(sulfate) hydrogen bonding. The layers stack along the c-axis direction with the closest directional interaction between them being a weak phenanthroline-C—H⋯O(sulfate) contact. There are four significant types of contact contributing to the calculated Hirshfeld surface: at 44.5%, the major contribution comes from O—H⋯O contacts followed by H⋯H (28.6%), H⋯C/C⋯H (19.5%) and C⋯C (5.7%) contacts. The dominance of the electrostatic potential force in the molecular packing is also evident in the calculated energy frameworks. The title complex is isostructural with its manganese, zinc and cadmium containing analogues and isomeric with its mer-triaqua analogue.
CCDC reference: 2002737
1. Chemical context
As a consequence of their ability to link metal ions in a variety of different ways, polynitrile anions, either functioning alone or in combination with neutral co-ligands, provide opportunities for the generation of molecular architectures with varying dimensions and topologies (Benmansour et al., 2012). The presence of other potential donor groups such as those derived from –OH, –SH or –NH2, together with their rigidity and electronic delocalization, mean that polynitrile anions can also lead to new magnetic and luminescent coordination polymers based on transition-metal ions (Benmansour et al., 2010; Kayukov et al., 2017; Lehchili et al., 2017; Setifi et al., 2017). Furthermore, the use of polynitrile anions for the synthesis of interesting discrete and polymeric bistable materials has been described (Setifi et al., 2014; Milin et al., 2016; Pittala et al., 2017). In view of this coordinating ability, these ligands have also been explored for their utility in developing materials capable of magnetic exchange coupling (Addala et al., 2015; Déniel et al., 2017). It was during the course of attempts to prepare such complexes with 1,10-phenanthroline as a co-ligand that the title complex, (I), was unexpectedly obtained. Herein, the crystal and molecular structures of (I) are described, a study complemented by an analysis of the molecular packing by calculating the Hirshfeld surfaces as well as a computational chemistry study.
2. Structural commentary
The molecule of (I) is shown in Fig. 1 and selected geometric parameters are collated in Table 1. The CoII complex features a chelating 1,10-phenanthroline ligand, a monodentate sulfate di-anion and three coordinated water molecules. The resulting N2O4 donor set defines a distorted octahedral coordination geometry for the CoII atom, with the water molecules occupying one octahedral face. The greatest deviations from a regular geometry is seen in the restricted bite angle subtended by the 1,10-phenanthroline ligand, i.e. N1—Co1—N2 = 78.21 (6)°, and in the trans O2W—Co—N2 angle of 166.55 (6)°. The Co—N bond lengths are equal within experimental error but the Co—O(aqua) bonds span an experimentally distinct range, Table 1. The observation that the shortest and longest Co—O(aqua) bonds have each aqua-O atom trans to a nitrogen atom suggests the differences in bond lengths are due to the considerable hydrogen bonding operating in the crystal. Indeed, there is an intramolecular aqua-O1W—H⋯O3(sulfate) hydrogen bond, Table 2. The coordinated sulfate-O1 atom forms the longer of the four sulfate-S—O bonds, Table 1. The S—O bond lengths formed by the non-coordinating sulfate-oxygen atoms spans an experimentally distinct range of 1.4616 (14) Å for S1—O2, to 1.4813 (14) Å for S1—O3. As discussed below, the sulfate-O1–O4 oxygen atoms form, respectively, one, one, two and two hydrogen bonds with the water molecules, which is consistent with the S1—O2 bond length being the shortest of the four bonds. The above notwithstanding, it is likely that the formal negative charge on the SO3 residue is delocalized over the three non-coordinating S—O bonds.
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3. Supramolecular features
Each of the aqua ligands donates two hydrogen bonds to different sulfate-O atoms, one of these hydrogen bonds is intramolecular while the remaining are intermolecular, Table 2. The result of the hydrogen bonding is the formation of a supramolecular layer lying parallel to (110). A simplified view of the hydrogen bonding scheme is shown in Fig. 2(a). The aqua molecule forming the intramolecular O1W—H⋯O3 hydrogen bond forms a second hydrogen bond to the coordinated O1 atom of a symmetry-related molecule, and the O2W aqua ligand of this molecule connects to the O3 atom of the original molecule, leading to the formation of a non-symmetric eight-membered {⋯HOH⋯O⋯HOCoO} synthon. The second hydrogen atom of the O2W ligand forms a connection to a sulfate-O4 atom, which is also hydrogen bonded to an O3W molecule, which forms an additional link to a symmetry related sulfate-O2 atom with the result a {⋯HOH⋯OSO⋯HOH⋯O} non-symmetric ten-membered synthon is formed. Two additional eight-membered synthons, {HOCoOH⋯OSO}, are formed as a result of the hydrogen-bonding scheme as adjacent pairs of aqua molecules effectively bridge two sulfoxide residues. As seen from Fig. 2(b), the 1,10-phenanthroline molecules project to either side of the supramolecular layer. The layers inter-digitate along [001], Fig. 2(c), with the closest connections between layers being phenanthroline-C—H⋯O2(sulfate) interactions, Table 2. A deeper analysis of the molecular packing is found in the next two sections of this paper.
4. Hirshfeld surface analysis
In order to understand further the interactions operating in the crystal of (I), the Hirshfeld surfaces and two-dimensional fingerprint plots were calculated employing the program Crystal Explorer 17 (Turner et al., 2017) and literature procedures (Tan et al., 2019). The intermolecular O—H⋯O hydrogen bonds in (I), Table 2, are characterized as pairs of bright-red spots near the aqua-O and sulfate-O atoms on the Hirshfeld surface mapped over dnorm shown in Fig. 3. The faint-red spots near the phenanthroline-C—H (H1, H3 H6 and H10) atoms on the dnorm-mapped Hirshfeld surface in the two views of Fig. 4 represent the influence of the weak C3—H3⋯O2 and C10—H10⋯O1 interactions as well as H1⋯O3, H6⋯O3W short contacts, Table 3. The donors and acceptors of the weak C—H⋯O interaction are viewed as blue and red regions on the Hirshfeld surface mapped over the calculated electrostatic potential in Fig. 5, and which correspond to positive and negative electrostatic potentials.
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The overall two-dimensional fingerprint plot of (I) is shown in Fig. 6(a). The overall contacts are also delineated into H⋯H, H⋯O/O⋯H, H⋯C/C⋯H and C⋯C contacts, as displayed in Fig. 6(b)–(e), respectively. The short interatomic H⋯H contacts are characterized as the pair of beak-shaped tips at de + di ∼2.3 Å, Fig. 6(b), and contribute 28.6% to the overall surface contacts. The significant O—H⋯O contacts between the aqua- and sulfate-O atoms make the major contribution to the overall contacts (44.5%), and these are represented as pairs of well-defined spikes at de + di ∼1.7 Å in Fig. 6(c). The short interatomic H⋯C/C⋯H (19.5%) and C⋯C (5.7%) contacts are, respectively, characterized as pairs of broad symmetrical wings at de + di ∼2.9 Å in Fig. 6(d), and the vase-shaped distribution of points at de + di ∼3.5 Å in Fig. 6(e). The accumulated contribution of the remaining interatomic contacts is less than 2% and has a negligible effect on the packing.
5. Computational chemistry
In the present analysis, the pairwise interaction energies between the molecules in the crystal were calculated by summing up four different energy components, i.e. the electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energy terms, after Turner et al. (2017). These energies were obtained by applying the wave functions calculated at the B3LYP/6-31G(d,p) level of theory. The benchmarked energies were scaled according to Mackenzie et al. (2017) while Eele, Epol, Edis and Erep were scaled as 1.057, 0.740, 0.871 and 0.618, respectively (Edwards et al., 2017). The intermolecular interaction energies are collated in Table 4. Consistent with the presence of strong O—H⋯O hydrogen-bonding interactions in the crystal, the electrostatic energy component has a major influence in the formation of supramolecular architecture of (I), Table 4. The energy associated with the C—H⋯O interactions involving the sulfate-O atoms (−66.8 and −55.7 kJ mol−1) are greater than for the C—H⋯O interaction involving the aqua-O atoms (−30.6 kJ mol−1). The energy frameworks were also computed and illustrate the above conclusions, Fig. 7. These clearly demonstrate the dominance of the electrostatic in the molecular packing.
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6. Database survey
There are several literature analogues of (I), i.e. molecules conforming to the general formula fac-M(1,10-phenanthroline)(OH2)3OSO3. These include M = Mn (XATNAH; Zheng et al., 2000), M = Zn (IJOQAA; Liu et al., 2011) and M = Cd (RACWUO; Li et al., 2003). The three literature structures are isostructural with (I). Literature analogues are also available for the isomeric mer-M(1,10-phenanthroline)(OH2)3OSO3 species, i.e. M = Mn (UGOJUV; Zheng et al., 2002), M = Fe (MIKJAS; Li et al., 2007), M = Co (FICNOU; Li & Zhou, 1987) and M = Ni (ESUZOH; He et al., 2003). The four mer-isomers are also isostructural, crystallizing in the monoclinic P21/c. There are two pairs of structures (containing Mn and Co) crystallizing in both forms. For the Mn complexes, the authors reporting the structure of the mer-isomer indicated that both forms were formed concomitantly from the slow evaporation of a methanol solution of the complex (Zheng et al., 2002). To a first approximation, the molecular packing in the mer form resembles that for the fac-isomer in that supramolecular layers are formed by hydrogen bonding whereby each aqua ligand hydrogen bonds to two different sulfate-O atoms, i.e. as for (I).
The key difference in the packing between the two isomers arises as one sulfate-O atom in the mer-isomer participates in three hydrogen bonds at the expense of the hydrogen bond involving the coordinated sulfate-O1 atom. The presence of inter-layer phenanthroline-C—H⋯O(sulfate) interactions persist as for the fac-isomer with the crucial difference that π–π stacking interactions are evident in the inter-layer region of the mer-form with the shortest separation being 3.76 Å.
The different packing arrangements result in different densities with that for (I) of 1.776 g cm−3 being greater than 1.723 g cm−3 for the mer-isomer (FICNOU; Li & Zhou, 1987). The calculated packing efficiencies follow this trend being 72.8 and 66.5%, respectively. Similar results are noted for the pair of Mn structures, i.e. 1.690 g cm−3 and 71.1% for the fac-isomer (Zheng et al., 2000) c.f. 1.643 g cm−3 and 68.7% for the mer-isomer (Zheng et al., 2000). The consistency of these parameters may suggest that the fac-isomer in these M(1,10-phenanthroline)(OH2)3OSO3 complexes is the thermodynamically more stable form.
Given the isostructural relationship in the series (I), IJOQAA, RACWUO and XATNAH, it was thought of interest to compare the percentage contributions of the difference intermolecular contacts to the calculated Hirshfeld surfaces. Thus, these were calculated for the three literature structures as were the overall and delineated two-dimensional fingerprint plots. Qualitatively, the fingerprint plots had the same general appearance in accord with expectation (Jotani et al., 2019). The calculated percentage contributions to the Hirshfeld surfaces for the four complexes are collated in Table 5. Clearly and as would be expected, the data in Table 5 reveal a high degree of concordance in the percentage contributions to the Hirshfeld surfaces between the four isostructural complexes.
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7. Synthesis and crystallization
The title compound was synthesized solvothermally under autogenous pressure from a mixture of CoSO4·7H2O (28 mg, 0.1 mmol), 1,10-phenanthroline (18 mg, 0.1 mmol) and K(tcnoet) (45 mg, 0.2 mmol) in water–methanol (4:1v/v, 25 ml); where tcnoet is 1,1,3,3-tetracyano-2-ethoxypropenide. The mixture was sealed in a Teflon-lined autoclave and held at 403 K for 2 days, and then cooled to room temperature at a rate of 10 K h−1; yield: 35%. Light-pink blocks of the title complex suitable for single-crystal X-ray diffraction were selected directly from the synthesized product.
8. Refinement
Crystal data, data collection and structure . The carbon-bound H atoms were placed in calculated positions (C—H = 0.95 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). The oxygen-bound H atoms were located from a difference-Fourier map and refined with O—H = 0.84±0.01 Å, and with Uiso(H) set to 1.5Ueq(O). Owing to poor agreement, four reflections, i.e. (0 1 4), (0 0 2), (0 1 2) and (0 0 4), were omitted from the final cycles of The was determined based on differences in Friedel pairs included in the data set.
details are summarized in Table 6
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Supporting information
CCDC reference: 2002737
https://doi.org/10.1107/S2056989020006271/hb7911sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020006271/hb7911Isup2.hkl
Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Co(SO4)(C12H8N2)(H2O)3] | Dx = 1.776 Mg m−3 |
Mr = 389.24 | Ga Kα radiation, λ = 1.34139 Å |
Orthorhombic, P212121 | Cell parameters from 9840 reflections |
a = 7.9732 (4) Å | θ = 4.0–60.7° |
b = 9.5589 (4) Å | µ = 7.61 mm−1 |
c = 19.0955 (9) Å | T = 150 K |
V = 1455.36 (12) Å3 | Prism, light-pink |
Z = 4 | 0.08 × 0.08 × 0.05 mm |
F(000) = 796 |
Bruker Venture Metaljet diffractometer | 3202 independent reflections |
Radiation source: Metal Jet, Gallium Liquid Metal Jet Source | 3126 reflections with I > 2σ(I) |
Helios MX Mirror Optics monochromator | Rint = 0.033 |
Detector resolution: 10.24 pixels mm-1 | θmax = 60.6°, θmin = 4.5° |
ω and φ scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −12→12 |
Tmin = 0.064, Tmax = 0.155 | l = −24→24 |
25223 measured reflections |
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)] = 0.017 | w = 1/[σ2(Fo2) + (0.0202P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.046 | (Δ/σ)max = 0.001 |
S = 0.99 | Δρmax = 0.51 e Å−3 |
3202 reflections | Δρmin = −0.58 e Å−3 |
227 parameters | Extinction correction: SHELXL-2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
6 restraints | Extinction coefficient: 0.0057 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack x determined using 1194 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013). |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.0101 (17) |
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 | ||
Co | 0.63811 (3) | 0.53373 (3) | 0.31720 (2) | 0.02111 (9) | |
S1 | 0.24258 (5) | 0.56910 (4) | 0.27630 (2) | 0.02212 (11) | |
O1 | 0.40704 (16) | 0.63702 (14) | 0.29351 (7) | 0.0239 (3) | |
O2 | 0.17822 (17) | 0.49545 (15) | 0.33775 (7) | 0.0291 (3) | |
O3 | 0.26932 (17) | 0.46986 (15) | 0.21777 (7) | 0.0289 (3) | |
O4 | 0.12543 (18) | 0.68089 (14) | 0.25463 (7) | 0.0290 (3) | |
O1W | 0.60122 (18) | 0.42633 (14) | 0.22184 (7) | 0.0267 (3) | |
H1W | 0.5005 (18) | 0.431 (3) | 0.2097 (13) | 0.040* | |
H2W | 0.607 (3) | 0.3405 (14) | 0.2144 (14) | 0.040* | |
O2W | 0.77952 (18) | 0.68717 (15) | 0.26762 (8) | 0.0296 (3) | |
H3W | 0.768 (4) | 0.7735 (15) | 0.2743 (14) | 0.044* | |
H4W | 0.8839 (17) | 0.673 (3) | 0.2607 (15) | 0.044* | |
O3W | 0.85965 (17) | 0.41650 (15) | 0.32821 (7) | 0.0281 (3) | |
H5W | 0.874 (4) | 0.353 (2) | 0.2999 (12) | 0.042* | |
H6W | 0.9583 (19) | 0.440 (3) | 0.3324 (14) | 0.042* | |
N1 | 0.6414 (2) | 0.64091 (16) | 0.41532 (8) | 0.0252 (3) | |
N2 | 0.5377 (2) | 0.37822 (16) | 0.38651 (8) | 0.0240 (3) | |
C1 | 0.6826 (3) | 0.7733 (2) | 0.42840 (11) | 0.0307 (4) | |
H1 | 0.716162 | 0.831005 | 0.390391 | 0.037* | |
C2 | 0.6788 (3) | 0.8312 (2) | 0.49569 (12) | 0.0349 (5) | |
H2 | 0.706310 | 0.926898 | 0.502638 | 0.042* | |
C3 | 0.6351 (3) | 0.7487 (2) | 0.55149 (12) | 0.0357 (5) | |
H3 | 0.634774 | 0.786001 | 0.597609 | 0.043* | |
C4 | 0.5906 (3) | 0.6081 (2) | 0.53970 (11) | 0.0311 (4) | |
C5 | 0.5383 (3) | 0.5154 (3) | 0.59456 (11) | 0.0374 (5) | |
H5 | 0.537335 | 0.547683 | 0.641615 | 0.045* | |
C6 | 0.4904 (3) | 0.3828 (3) | 0.58034 (11) | 0.0394 (5) | |
H6 | 0.456658 | 0.323326 | 0.617613 | 0.047* | |
C7 | 0.4897 (3) | 0.3302 (2) | 0.50992 (11) | 0.0315 (4) | |
C8 | 0.4422 (3) | 0.1926 (2) | 0.49259 (12) | 0.0358 (5) | |
H8 | 0.410012 | 0.128509 | 0.528178 | 0.043* | |
C9 | 0.4430 (3) | 0.1523 (2) | 0.42371 (12) | 0.0350 (5) | |
H9 | 0.411464 | 0.059775 | 0.411121 | 0.042* | |
C10 | 0.4904 (3) | 0.2480 (2) | 0.37212 (11) | 0.0290 (4) | |
H10 | 0.488688 | 0.218795 | 0.324580 | 0.035* | |
C11 | 0.5388 (2) | 0.4191 (2) | 0.45479 (10) | 0.0251 (4) | |
C12 | 0.5919 (2) | 0.5600 (2) | 0.46986 (10) | 0.0258 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.02084 (13) | 0.02088 (13) | 0.02160 (13) | −0.00016 (10) | 0.00033 (10) | 0.00127 (10) |
S1 | 0.0203 (2) | 0.0203 (2) | 0.0258 (2) | −0.00016 (15) | −0.00058 (17) | −0.00105 (15) |
O1 | 0.0203 (6) | 0.0225 (6) | 0.0291 (6) | −0.0006 (5) | −0.0005 (5) | −0.0017 (5) |
O2 | 0.0262 (6) | 0.0301 (7) | 0.0311 (7) | −0.0029 (6) | 0.0008 (5) | 0.0037 (5) |
O3 | 0.0282 (6) | 0.0279 (6) | 0.0306 (7) | −0.0006 (6) | −0.0015 (6) | −0.0074 (6) |
O4 | 0.0235 (6) | 0.0256 (6) | 0.0378 (7) | 0.0016 (6) | −0.0023 (6) | 0.0027 (5) |
O1W | 0.0273 (7) | 0.0240 (6) | 0.0287 (7) | 0.0042 (5) | −0.0013 (6) | −0.0016 (5) |
O2W | 0.0244 (7) | 0.0244 (6) | 0.0399 (8) | 0.0008 (6) | 0.0046 (6) | 0.0047 (6) |
O3W | 0.0221 (6) | 0.0250 (6) | 0.0371 (7) | 0.0012 (6) | −0.0018 (6) | −0.0011 (5) |
N1 | 0.0242 (7) | 0.0253 (7) | 0.0259 (7) | 0.0006 (7) | −0.0010 (7) | 0.0000 (6) |
N2 | 0.0225 (7) | 0.0251 (8) | 0.0242 (7) | −0.0003 (6) | 0.0009 (6) | 0.0010 (6) |
C1 | 0.0318 (11) | 0.0275 (9) | 0.0329 (10) | −0.0025 (8) | −0.0020 (8) | −0.0001 (8) |
C2 | 0.0354 (11) | 0.0292 (10) | 0.0402 (11) | −0.0022 (9) | −0.0043 (9) | −0.0074 (8) |
C3 | 0.0365 (11) | 0.0404 (11) | 0.0302 (10) | −0.0001 (10) | −0.0014 (10) | −0.0109 (8) |
C4 | 0.0296 (10) | 0.0363 (10) | 0.0273 (9) | 0.0006 (8) | −0.0011 (8) | −0.0032 (8) |
C5 | 0.0423 (12) | 0.0468 (12) | 0.0231 (9) | −0.0016 (10) | 0.0031 (8) | −0.0016 (9) |
C6 | 0.0461 (13) | 0.0474 (13) | 0.0247 (10) | −0.0035 (11) | 0.0058 (10) | 0.0064 (9) |
C7 | 0.0314 (10) | 0.0347 (10) | 0.0286 (9) | −0.0023 (9) | 0.0038 (8) | 0.0045 (8) |
C8 | 0.0386 (12) | 0.0341 (11) | 0.0348 (11) | −0.0053 (10) | 0.0064 (9) | 0.0084 (9) |
C9 | 0.0381 (11) | 0.0270 (9) | 0.0400 (11) | −0.0056 (9) | 0.0029 (9) | 0.0024 (9) |
C10 | 0.0289 (10) | 0.0288 (9) | 0.0293 (10) | −0.0023 (8) | 0.0015 (8) | −0.0021 (8) |
C11 | 0.0234 (8) | 0.0277 (9) | 0.0244 (8) | 0.0003 (7) | 0.0011 (7) | 0.0008 (7) |
C12 | 0.0236 (8) | 0.0285 (9) | 0.0253 (9) | 0.0011 (7) | −0.0005 (7) | −0.0006 (7) |
Co—O1 | 2.1386 (13) | C1—C2 | 1.399 (3) |
Co—O1W | 2.1110 (14) | C1—H1 | 0.9500 |
Co—O2W | 2.0782 (15) | C2—C3 | 1.371 (3) |
Co—O3W | 2.1024 (14) | C2—H2 | 0.9500 |
Co—N1 | 2.1356 (15) | C3—C4 | 1.408 (3) |
Co—N2 | 2.1453 (16) | C3—H3 | 0.9500 |
S1—O1 | 1.4997 (13) | C4—C12 | 1.411 (3) |
S1—O2 | 1.4616 (14) | C4—C5 | 1.434 (3) |
S1—O3 | 1.4813 (14) | C5—C6 | 1.351 (4) |
S1—O4 | 1.4784 (14) | C5—H5 | 0.9500 |
O1W—H1W | 0.837 (12) | C6—C7 | 1.436 (3) |
O1W—H2W | 0.834 (13) | C6—H6 | 0.9500 |
O2W—H3W | 0.840 (13) | C7—C11 | 1.409 (3) |
O2W—H4W | 0.853 (12) | C7—C8 | 1.408 (3) |
O3W—H5W | 0.822 (12) | C8—C9 | 1.371 (3) |
O3W—H6W | 0.822 (13) | C8—H8 | 0.9500 |
N1—C1 | 1.331 (3) | C9—C10 | 1.397 (3) |
N1—C12 | 1.356 (2) | C9—H9 | 0.9500 |
N2—C10 | 1.329 (3) | C10—H10 | 0.9500 |
N2—C11 | 1.361 (2) | C11—C12 | 1.441 (3) |
O2W—Co—O3W | 88.05 (6) | N1—C1—C2 | 122.9 (2) |
O2W—Co—O1W | 91.48 (6) | N1—C1—H1 | 118.6 |
O3W—Co—O1W | 86.80 (6) | C2—C1—H1 | 118.6 |
O2W—Co—N1 | 93.13 (6) | C3—C2—C1 | 119.5 (2) |
O3W—Co—N1 | 99.08 (6) | C3—C2—H2 | 120.3 |
O2W—Co—O1 | 92.59 (6) | C1—C2—H2 | 120.3 |
O1—Co—O3W | 172.31 (5) | C2—C3—C4 | 119.26 (19) |
O1W—Co—O1 | 85.53 (5) | C2—C3—H3 | 120.4 |
N1—Co—O1 | 88.54 (6) | C4—C3—H3 | 120.4 |
O1W—Co—N1 | 172.65 (6) | C3—C4—C12 | 117.42 (19) |
O2W—Co—N2 | 166.55 (6) | C3—C4—C5 | 123.1 (2) |
O3W—Co—N2 | 83.25 (6) | C12—C4—C5 | 119.4 (2) |
O1W—Co—N2 | 98.23 (6) | C6—C5—C4 | 121.0 (2) |
N1—Co—N2 | 78.21 (6) | C6—C5—H5 | 119.5 |
O1—Co—N2 | 97.41 (6) | C4—C5—H5 | 119.5 |
O2—S1—O4 | 110.56 (8) | C5—C6—C7 | 121.2 (2) |
O2—S1—O3 | 110.35 (8) | C5—C6—H6 | 119.4 |
O4—S1—O3 | 110.04 (8) | C7—C6—H6 | 119.4 |
O2—S1—O1 | 109.85 (8) | C11—C7—C8 | 117.58 (19) |
O4—S1—O1 | 107.51 (8) | C11—C7—C6 | 119.2 (2) |
O3—S1—O1 | 108.47 (8) | C8—C7—C6 | 123.3 (2) |
S1—O1—Co | 126.85 (8) | C9—C8—C7 | 119.13 (19) |
Co—O1W—H1W | 110.3 (18) | C9—C8—H8 | 120.4 |
Co—O1W—H2W | 128.2 (19) | C7—C8—H8 | 120.4 |
H1W—O1W—H2W | 93 (3) | C8—C9—C10 | 119.6 (2) |
Co—O2W—H3W | 125 (2) | C8—C9—H9 | 120.2 |
Co—O2W—H4W | 119 (2) | C10—C9—H9 | 120.2 |
H3W—O2W—H4W | 106 (3) | N2—C10—C9 | 123.01 (19) |
Co—O3W—H5W | 117 (2) | N2—C10—H10 | 118.5 |
Co—O3W—H6W | 132 (2) | C9—C10—H10 | 118.5 |
H5W—O3W—H6W | 97 (3) | N2—C11—C7 | 122.72 (18) |
C1—N1—C12 | 118.04 (17) | N2—C11—C12 | 117.50 (16) |
C1—N1—Co | 128.58 (14) | C7—C11—C12 | 119.78 (18) |
C12—N1—Co | 113.38 (12) | N1—C12—C4 | 122.85 (18) |
C10—N2—C11 | 117.96 (16) | N1—C12—C11 | 117.73 (16) |
C10—N2—Co | 128.85 (14) | C4—C12—C11 | 119.43 (18) |
C11—N2—Co | 112.92 (12) | ||
O2—S1—O1—Co | 67.05 (11) | C10—N2—C11—C7 | −1.0 (3) |
O4—S1—O1—Co | −172.59 (9) | Co—N2—C11—C7 | −175.48 (16) |
O3—S1—O1—Co | −53.64 (11) | C10—N2—C11—C12 | 179.40 (17) |
C12—N1—C1—C2 | 0.7 (3) | Co—N2—C11—C12 | 4.9 (2) |
Co—N1—C1—C2 | 179.75 (16) | C8—C7—C11—N2 | 1.7 (3) |
N1—C1—C2—C3 | 1.7 (3) | C6—C7—C11—N2 | −178.4 (2) |
C1—C2—C3—C4 | −1.6 (3) | C8—C7—C11—C12 | −178.70 (19) |
C2—C3—C4—C12 | −0.7 (3) | C6—C7—C11—C12 | 1.2 (3) |
C2—C3—C4—C5 | −178.1 (2) | C1—N1—C12—C4 | −3.3 (3) |
C3—C4—C5—C6 | 177.4 (2) | Co—N1—C12—C4 | 177.58 (15) |
C12—C4—C5—C6 | 0.0 (4) | C1—N1—C12—C11 | 176.72 (17) |
C4—C5—C6—C7 | −0.2 (4) | Co—N1—C12—C11 | −2.4 (2) |
C5—C6—C7—C11 | −0.4 (4) | C3—C4—C12—N1 | 3.2 (3) |
C5—C6—C7—C8 | 179.5 (2) | C5—C4—C12—N1 | −179.3 (2) |
C11—C7—C8—C9 | −1.1 (3) | C3—C4—C12—C11 | −176.74 (19) |
C6—C7—C8—C9 | 179.0 (2) | C5—C4—C12—C11 | 0.8 (3) |
C7—C8—C9—C10 | −0.1 (4) | N2—C11—C12—N1 | −1.7 (3) |
C11—N2—C10—C9 | −0.3 (3) | C7—C11—C12—N1 | 178.67 (18) |
Co—N2—C10—C9 | 173.15 (16) | N2—C11—C12—C4 | 178.26 (17) |
C8—C9—C10—N2 | 0.9 (4) | C7—C11—C12—C4 | −1.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O3 | 0.84 (2) | 1.89 (2) | 2.680 (2) | 158 (2) |
O1W—H2W···O1i | 0.83 (1) | 1.95 (1) | 2.7818 (19) | 172 (2) |
O2W—H3W···O3ii | 0.84 (2) | 1.91 (2) | 2.744 (2) | 175 (3) |
O2W—H4W···O4iii | 0.85 (1) | 1.93 (1) | 2.770 (2) | 167 (3) |
O3W—H5W···O4i | 0.82 (2) | 1.95 (2) | 2.7548 (19) | 168 (3) |
O3W—H6W···O2iii | 0.82 (2) | 1.84 (2) | 2.6560 (19) | 178 (3) |
C3—H3···O2iv | 0.95 | 2.45 | 3.252 (3) | 142 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x+1, y, z; (iv) x+1/2, −y+3/2, −z+1. |
Contact | Distance | Symmetry operation |
H2W···O1b | 1.81 | -x + 1, y - 1/2, -z + 1/2 |
H3W···O3b | 1.76 | -x + 1, y + 1/2, -z + 1/2 |
H4W···O4b | 1.81 | x + 1, y, z |
H5W···O4b | 1.79 | -x + 1, y - 1/2, -z + 1/2 |
H6W···O2b | 1.67 | x + 1, y, z |
H1···O3 | 2.33 | -x + 1, y + 1/2, -z + 1/2 |
H3···O2 | 2.35 | x + 1/2, -y + 3/2, - z + 1 |
H6···O3W | 2.51 | x - 1/2, -y + 1/2, - z + 1 |
H10···O1 | 2.40 | -x + 1, y - 1/2, - z + 1/2 |
Notes: (a) The interatomic distances are calculated in Crystal Explorer 17 (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values; (b) these interactions correspond to conventional hydrogen bonds. |
Contact | R (Å) | Eele | Epol | Edis | Erep | Etot |
O1W—H2W···O1i + | 6.78 | -330.8 | -116.8 | -49.6 | 180.1 | -368.1 |
O3W—H5W···O4i + | ||||||
O2W—H3W···O3ii + | ||||||
C10—H10···O1i | ||||||
O3W—H6W···O2iii + | 7.97 | -198.3 | -63.8 | -16.4 | 121.0 | -196.4 |
O2W—H4W···O4iii | ||||||
C5—H5···O3v + | 10.47 | -46.2 | -19.3 | -9.8 | 7.8 | -66.8 |
C6—H6···O4v | ||||||
C3—H3···O2iv | 7.64 | -17.3 | -30.2 | -42.3 | 35.3 | -55.7 |
C6—H6···O3Wvi | 8.03 | -2.3 | -13.7 | -37.7 | 24.0 | -30.6 |
Symmetry operations: (i) -x + 1, y - 1/2, -z + 1/2; (ii) - x + 1, y + 1/2, - z + 1/2; (iii) x + 1, y, z; (iv) x + 1/2, -y + 3/2, -z + 1; (v) -x + 1/2, - y + 1, z + 1/2; (vi) x – 1/2, -y + 1/2, -z + 1. |
Contact | Percentage contribution | |||
(I), M = Co | IJOQAA, M = Zn | RACWUO, M = Cd | XATNAH, M = Mn | |
H···H | 28.6 | 30.1 | 27.6 | 27.2 |
H···O/O···H | 44.5 | 43.3 | 45.8 | 45.9 |
H···C/C···H | 19.5 | 19.1 | 19.2 | 19.1 |
C···C | 5.7 | 5.7 | 5.2 | 5.6 |
Others | 1.7 | 1.8 | 2.2 | 2.2 |
Footnotes
‡Additional correspondence author, e-mail: setifi_zouaoui@yahoo.fr.
Funding information
FS gratefully acknowledges the Algerian Ministère de l'Enseignement Supérieur et de la Recherche Scientifique (MESRS), the Direction Générale de la Recherche Scientifique et du Développement Technologique (DG–RSDT) as well as the Université Ferhat Abbas Sétif 1 for financial support. The Canadian Foundation for Innovation is thanked for the support of the Metaljet instrument. Crystallographic research at Sunway University is supported by Sunway University Sdn Bhd (Grant no. STR-RCTR-RCCM-001-2019).
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