Crystal structure and Hirshfeld surface analysis of di­aqua­bis­(N,N-di­ethyl­nicotinamide-κN1)bis­(2,4,6-tri­methyl­benzoato-κO)manganese(II)

Hökelek, T.; Özkaya, S.; Necefoğlu, H.

doi:10.1107/S2056989018003377

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Volume 74| Part 4| April 2018| Pages 422-427

https://doi.org/10.1107/S2056989018003377

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Crystal structure and Hirshfeld surface analysis of diaquabis(N,N-diethylnicotinamide-κN¹)bis(2,4,6-trimethylbenzoato-κO)manganese(II)

Tuncer Hökelek,^a ^* Safiye Özkaya ^b and Hacali Necefoğlu ^b,^c

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, and ^cInternational Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan
^*Correspondence e-mail:

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 16 February 2018; accepted 27 February 2018; online 2 March 2018)

In the title centrosymmetric complex, [Mn(C₁₀H₁₁O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], the Mn^II cation is located on an inversion centre. The four O atoms form a slightly distorted square-planar arrangement around the Mn^II cation, and the distorted octahedral coordination is completed by two pyridine N atoms at distances of 2.3289 (15) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring is 87.73 (16)°, while the benzene and pyridine rings are oriented at a dihedral angle of 43.03 (8)°. In the crystal, the water molecules are involved in both intramolecular (to the non-coordinating carboxylate O atom) and intermolecular (to the amide carbonyl O atom) O—H⋯O hydrogen bonds. The latter lead to the formation of layers parallel to (100). These layers are further linked via weak C—H⋯O hydrogen bonds, resulting in a three-dimensional supramolecular network. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (70.0%), H⋯O/O⋯H (15.5%) and H⋯C/C⋯H (14.0%) interactions. One of the ethyl groups of the diethylnicotinamide ligand is disordered over two sets of sites, with an occupancy ratio of 0.282 (10):0.718 (10).

Keywords: crystal structure; manganese(II); transition metal complexes of benzoic acid and nicotinamide derivatives.

CCDC reference: 1826038

1. Chemical context

Nicotinamide (NA) is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels (Krishnamachari, 1974 ). The nicotinic acid derivative N,N-Diethylnicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972 ). The crystal structure of the complex [Co(CH₃CO₂)₂(DENA)₂(H₂O)₂] (Mikelashvili, 1982 ) is isostructural with the analogous Ni, Mn, Zn and Cd complexes (Sergienko et al., 1980 ). The structures of some complexes obtained from the reactions of transition metal(II) ions with nicotinamide (NA), N,N-Diethylnicotinamide (DENA) and some benzoic acid derivatives as ligands, e.g. [Zn(NA)₂(C₇H₅O₃)₂] [(II); Necefoğlu et al., 2002 ], [Zn(NA)₂(C₈H₈NO₂)₂]·H₂O [(III); Hökelek et al., 2009a ], [Co(NA)(C₉H₁₀NO₂)₂(H₂O)₂] [(IV); Hökelek et al., 2009b ], [Zn₂(DENA)₂(C₁₁H₁₄NO₂)₄] [(V); Hökelek et al., 2009c ], [Mn(DENA)₂(C₇H₄ClO₂)₄(H₂O)₂ [(VI); Hökelek et al., 2009d ], [Mn(DENA)₂(NCS)₂] [(VII); Bigoli et al., 1973a ], [Zn(DENA)₂(NCS)₂(H₂O)₂] [(VIII); Bigoli et al., 1973b ] and [Cd(DENA)(SCN)₂] [(IX); Bigoli et al., 1972] have been determined previously. In complex (VII), DENA is a bidentate ligand, while in complexes (V), (VI), (VIII) and (IX), DENA is a monodentate ligand. In complex (V), the four 4-(diethylamino)benzoate (DEAB) ions act as bidentate ligands bridging the two Zn atoms.

The structure–function–coordination relationships of the arylcarboxylate ion in Mn^II complexes of benzoic acid derivatives may change depending on the nature and position of the substituted groups on the benzene ring, the nature of the additional ligand molecule or solvent, and the pH and temperature of synthesis (Shnulin et al., 1981 ; Nadzhafov et al., 1981 ; Antsyshkina et al., 1980 ; Adiwidjaja et al., 1978 ). When pyridine and its derivatives are used instead of water molecules, the structure is completely different (Catterick et al., 1974 ). In this context, the Mn^II-containing title compound, (I), with 2,4,6-trimethylbenzoate (TMB) and DENA ligands, namely diaquabis(N,N-diethylnicotinamide -κN¹)bis(2,4,6-trimethylbenzoato-κO¹) manganese(II), [Mn(DENA)₂(TMB)₂(H₂O)₂], was synthesized and its crystal structure is reported on herein.

2. Structural commentary

The asymmetric unit of the crystal structure of the mononuclear title complex, contains one Mn^II cation located on an inversion centre, one 2,4,6-trimethylbenzoate (TMB) anion and one N,N-diethylnicotinamide (DENA) molecule together with the one water molecule, with all ligands coordinating to the Mn^II cation in a monodentate manner (Fig. 1).

Figure 1
The molecular structure of the title complex with the atom-numbering scheme for the asymmetric unit. Unlabelled atoms are related to labelled ones by the symmetry operation (−x, −y, −z). Displacement ellipsoids are drawn at the 50% probability level. Intramolecular O—H⋯O hydrogen bonds, enclosing S(6) ring motifs, are shown as dashed lines.

The Mn^II cation is coordinated monodentately through the two carboxylate O atoms (O1 and O1ⁱ) of the two symmetry-related TMB anions and the two symmetry-related water O atoms (O4 and O4ⁱ) at distances of 2.0999 (14) and 2.2230 (15) Å, respectively, to form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination sphere is completed by the two pyridine N atoms (N1 and N1ⁱ) at distances of 2.3289 (15) Å of the two symmetry-related DENA ligands in the axial positions [symmetry code: (i) −x, −y, −z] (Fig. 1).

The near equalities of the C1—O1 [1.254 (3) Å] and C1—O2 [1.243 (3) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The Mn—O bond lengths [2.2230 (15) Å] for water oxygen atoms are by ca 0.1 Å longer than those involving the benzoate oxygen atoms [2.0999 (14) Å]. The Mn—N bond length [2.3289 (15) Å] is the longest one in the MnO₄N₂ octahedron. The Mn1 atom lies 0.0697 (1) Å above the planar (O1/O2/C1) carboxylate group. The O2—C1—O1 bond angle [125.5 (2)°] seems to be significantly increased than that present in a free acid [122.2°], in which the O2—C1—O1 bond angle may be compared with the corresponding values of 123.5 (2) and 120.4 (2)° in (II), 119.2 (3) and 123.8 (2)° in (III), 123.86 (13) and 118.49 (14)° in (IV), 125.11 (13) and 124.80 (14)° in (V) and 126.65 (14)° in (VI), where the benzoate ions are coordinated to the metal atoms only bidentately in (V), only monodentately in (VI) and both monodentately and bidentately in (II), (III) and (IV). The O—Mn—O and O–Mn—N bond angles [range 87.88 (6) to 92.12 (6)° for cis angles; all trans angles are 180° due to symmetry] deviate slightly from ideal values, with same average values of 90.00 (6)°.

The dihedral angle between the planar carboxylate group (O1/O2/C1) and the adjacent benzene A (C2–C7) ring is 87.73 (16)°, while the benzene A and pyridine B (N1/C11–C15) rings are oriented at a dihedral angle of A/B = 43.03 (8)°.

3. Supramolecular features

Intramolecular O—H_w⋯O_c (w = water, c = non-coordinating carboxylate O atom) hydrogen bonds (Table 1) link two of the water ligands to the TMB anions, enclosing an S(6) ring motif (Fig. 1). The other water H atom is involved in intermolecular O—H_w⋯O_DENA (O_DENA = carbonyl O atom of N,N-diethylnicotinamide) hydrogen bonds (Table 1), leading to the formation of layers parallel to (100) (Fig. 2). These layers are further linked into a three-dimensional network structure via weak C—H_TMB⋯O_c (TMB = 2,4,6-trimethylbenzoate) and C—H_DENA⋯O_DENA hdyrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O3ⁱ	0.85 (3)	2.00 (3)	2.838 (2)	171 (3)
O4—H42⋯O2ⁱⁱ	0.80 (3)	1.90 (3)	2.660 (3)	157 (3)
C9—H9C⋯O2^ix	0.96	2.48	3.366 (5)	154
C11—H11⋯O3ⁱ	0.93	2.52	3.447 (3)	179
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y, -z; (ix) $[-x-1, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Figure 2
Part of the crystal structure. Only O—H_W⋯O_TMB and O—H_W⋯O_DENA (W = water, TMB = 2,4,6-trimethylbenzoate and DENA = N,N-diethylnicotinamide) hydrogen bonds, enclosing S(6) ring motifs, are shown as dashed lines. Only one part of the disordered group has been included and the C-bound hydrogen atoms have been omitted for clarity.

4. Hirshfeld surface analysis

Visulization and exploration of intermolecular close contacts in the crystal structure of the title complex is invaluable. Thus, a Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ) was carried out by using CrystalExplorer17.5 (Turner et al., 2017 ) to investigate the locations of atom–atom short contacts with potential to form hydrogen bonds and the quantitative ratios of these interactions and those of the π-stacking interactions. In the HS plotted over d_norm (Fig. 3), the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ). The bright-red spots appearing near DENA-O3, carboxylate-O2, and hydrogen atoms H41, H42, H9C and H11 indicate their roles as the respective donors and acceptors in the dominant O—H⋯O and C—H⋯O hydrogen bonds; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman et al., 2008 ; Jayatilaka et al., 2005 ) as shown in Fig. 4. The blue regions indicate the positive electrostatic potential (hydrogen-bond donors), while the red regions indicate the negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the π–π stacking interactions by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 5 clearly suggests that there are no π⋯π interactions in (I).

Figure 3
View of the three-dimensional Hirshfeld surface of the title complex plotted over d_norm in the range −0.6741 to 1.6440 a.u.

Figure 4
View of the three-dimensional Hirshfeld surface of the title complex plotted over electrostatic potential energy in the range −0.1032 to 0.1415 a.u. using the STO-3G basis set at the Hartree–Fock level of theory. The O—H⋯O and C—H⋯O hydrogen-bond donors and acceptors are viewed as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.

Figure 5
Hirshfeld surface of the title complex plotted over shape-index.

The overall two-dimensional fingerprint plot, Fig. 6a, and those delineated into H⋯H, H⋯O/O⋯H, H⋯C/C⋯H, C⋯C, H⋯N/N⋯H and N⋯C/C⋯N contacts (McKinnon et al., 2007 ) are illustrated in Fig. 6b–g, respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯H, contributing 70.0% to the overall crystal packing, which is reflected in Fig. 6b as widely scattered points of high density due to the large hydrogen content of the molecule. The single spike in the centre at d_e = d_i = 0.96 Å in Fig. 6b is due to a short interatomic H⋯H contact (Table 2). In the fingerprint plot delineated into H⋯O/O⋯H contacts Fig. 6c, the 15.5% contribution to the HS arises from intermolecular O—H⋯O hydrogen bonding and is viewed as pair of spikes with the tip at d_e + d_i ∼1.84 Å. The short H⋯O/O⋯H contacts may be masked by strong O—H⋯O hydrogen bonding in this plot. In the presence of a weak C—H⋯π interaction in the crystal, the two pairs of characteristic wings in the fingerprint plot delineated into H⋯C/C⋯H contacts with 14.0% contribution to the HS, Fig. 6d, and the two pairs of thin and thick edges at d_e + d_i ∼2.91 and 2.89 Å, respectively, result from short interatomic H⋯C/C⋯H contacts (Table 2). The Hirshfeld surface representations with the function d_norm plotted onto the surface are shown for the H⋯H, H⋯O/O⋯H and H⋯C/C⋯H interactions in Fig. 7a–c, respectively.

Table 2
Selected interatomic distances (Å)

O1⋯H10B	2.87	C17A⋯H15	2.78
O1⋯H13ⁱ	2.65	C17B⋯H20B	2.75
O1⋯H8C	2.82	C18A⋯H9B^v	2.87
O2⋯H42ⁱⁱ	1.90 (3)	C18B⋯H8B^vi	2.79
O2⋯H9Cⁱⁱⁱ	2.48	C20⋯H17C	2.76
O3⋯H12^iv	2.85	H4⋯H8A	2.37
O3⋯H11^v	2.52	H4⋯H9A	2.38
O3⋯H41^v	2.00 (3)	H6⋯H10A	2.37
O3⋯H19B	2.35	H6⋯H9C	2.50
O4⋯H15ⁱⁱ	2.62	H8A⋯H20A^vii	2.31
O4⋯H11	2.89	H8B⋯H17A^viii	2.44
C1⋯H42ⁱⁱ	2.61 (3)	H8B⋯H18E^viii	2.14
C1⋯H8C	2.59	H11⋯H41	2.52
C1⋯H10B	2.71	H15⋯H18F	2.48
C14⋯H17D	2.40	H15⋯H17B	2.00
C14⋯H17B	2.74	H17A⋯H19A	1.96
C14⋯H18B	2.82	H17C⋯H20B	2.16
C15⋯H17D	2.88	H18A⋯H9B^v	2.50
C15⋯H17B	2.44	H18E⋯H19A	2.46
C16⋯H18B	2.80
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y, -z; (iii) $[-x-1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vii) x, y, z-1; (viii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 6
The full two-dimensional fingerprint plots for the title complex, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯O/O⋯H, (d) H⋯C/C⋯H, (e) C⋯C, (f) H⋯N/N⋯H and (g) N⋯C/C⋯N interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

Figure 7
The Hirshfeld surface representations with the function d_norm plotted onto the surface for (a) H⋯H, (b) H⋯O/O⋯H and (c) H⋯C/C⋯H interactions.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯O/O⋯H and H⋯C/C⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hartwar et al., 2015 ).

5. Synthesis and crystallization

The title compound was prepared by the reaction of MnSO₄·H₂O (0.85 g, 5 mmol) in H₂O (100 ml) and N,N-diethylnicotinamide (1.78 g, 10 mmol) in H₂O (10 ml) with sodium 2,4,6-trimethylbenzoate (1.86 g, 10 mmol) in H₂O (150 ml). The mixture was filtered and set aside to crystallize at ambient temperature for three weeks, giving colourless single crystals.

6. Refinement

The experimental details including the crystal data, data collection and refinement are summarized in Table 3. Water H atoms H41 and H42 were located in a difference-Fourier map and freely refined. C-bound H atoms were positioned geometrically, with C—H = 0.93, 0.96 and 0.97 Å for aromatic, methyl and methylene H atoms, respectively, and constrained to ride on their parent atoms, with U_iso(H) = k × U_eq(C), where k = 1.5 for methyl H atoms and k = 1.2 for other H atoms. The disordered ethyl group (C17, C18) was refined over two sets of sites with distance restraints and SIMU and DELU restraints (Sheldrick, 2008 ). The refined occupancy ratio of the two orientations is 0.282 (10):0.718 (10).

Table 3
Experimental details

Crystal data
Chemical formula	[Mn(C₁₀H₁₁O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r	773.83
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.1040 (4), 10.8828 (3), 15.7167 (4)
β (°)	111.570 (2)
V (Å³)	2084.37 (10)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.37
Crystal size (mm)	0.45 × 0.37 × 0.35

Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.851, 0.882
No. of measured, independent and observed [I > 2σ(I)] reflections	36139, 5178, 3995
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.144, 1.05
No. of reflections	5178
No. of parameters	274
No. of restraints	42
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.37
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012 ), WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1826038

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018003377/xu5920sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018003377/xu5920Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Diaquabis(N,N-diethylnicotinamide-κN¹)bis(2,4,6-trimethylbenzoato-κO)manganese(II) top

Crystal data top

[Mn(C₁₀H₁₁O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	F(000) = 822
M_r = 773.83	D_x = 1.233 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9985 reflections
a = 13.1040 (4) Å	θ = 2.5–28.2°
b = 10.8828 (3) Å	µ = 0.37 mm⁻¹
c = 15.7167 (4) Å	T = 296 K
β = 111.570 (2)°	Block, translucent light colourless
V = 2084.37 (10) Å³	0.45 × 0.37 × 0.35 mm
Z = 2

Data collection top

Bruker SMART BREEZE CCD diffractometer	5178 independent reflections
Radiation source: fine-focus sealed tube	3995 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 28.3°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −17→17
T_min = 0.851, T_max = 0.882	k = −14→13
36139 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0696P)² + 0.7599P] where P = (F_o² + 2F_c²)/3
5178 reflections	(Δ/σ)_max < 0.001
274 parameters	Δρ_max = 0.51 e Å⁻³
42 restraints	Δρ_min = −0.37 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn1	0.0000	0.0000	0.0000	0.04559 (14)
O1	−0.14717 (12)	0.04378 (15)	−0.10765 (9)	0.0615 (4)
O2	−0.25400 (18)	−0.1155 (2)	−0.11016 (17)	0.1263 (10)
O3	−0.02706 (15)	0.12536 (14)	0.39218 (9)	0.0699 (4)
O4	0.08409 (16)	0.14917 (14)	−0.04553 (11)	0.0590 (4)
H41	0.058 (2)	0.220 (3)	−0.0636 (19)	0.077 (8)*
H42	0.143 (2)	0.153 (2)	−0.005 (2)	0.075 (9)*
N1	−0.04496 (14)	0.13195 (15)	0.09755 (10)	0.0534 (4)
N2	−0.1788 (2)	0.0256 (3)	0.30478 (15)	0.0975 (8)
C1	−0.23618 (19)	−0.0138 (2)	−0.13796 (16)	0.0667 (6)
C2	−0.32465 (17)	0.0468 (2)	−0.21779 (15)	0.0633 (5)
C3	−0.3318 (2)	0.0191 (2)	−0.30595 (17)	0.0696 (6)
C4	−0.4057 (2)	0.0847 (3)	−0.37831 (17)	0.0805 (7)
H4	−0.4101	0.0677	−0.4375	0.097*
C5	−0.4726 (2)	0.1739 (3)	−0.36515 (19)	0.0837 (8)
C6	−0.4672 (2)	0.1957 (3)	−0.2775 (2)	0.0871 (8)
H6	−0.5142	0.2536	−0.2680	0.104*
C7	−0.3934 (2)	0.1337 (3)	−0.20238 (17)	0.0763 (6)
C8	−0.2595 (3)	−0.0781 (3)	−0.3224 (2)	0.0988 (9)
H8A	−0.2585	−0.0688	−0.3828	0.148*
H8B	−0.2875	−0.1579	−0.3166	0.148*
H8C	−0.1862	−0.0697	−0.2781	0.148*
C9	−0.5484 (3)	0.2479 (4)	−0.4452 (3)	0.1240 (14)
H9A	−0.5621	0.2031	−0.5009	0.186*
H9B	−0.5145	0.3251	−0.4483	0.186*
H9C	−0.6165	0.2623	−0.4370	0.186*
C10	−0.3879 (3)	0.1594 (4)	−0.1064 (2)	0.1176 (12)
H10A	−0.4327	0.2295	−0.1070	0.176*
H10B	−0.3134	0.1760	−0.0676	0.176*
H10C	−0.4143	0.0892	−0.0836	0.176*
C11	−0.0577 (2)	0.2526 (2)	0.08377 (14)	0.0671 (6)
H11	−0.0501	0.2856	0.0319	0.081*
C12	−0.0817 (3)	0.3307 (2)	0.14275 (16)	0.0805 (8)
H12	−0.0887	0.4147	0.1311	0.097*
C13	−0.0952 (2)	0.2834 (2)	0.21932 (14)	0.0661 (6)
H13	−0.1108	0.3345	0.2604	0.079*
C14	−0.08498 (16)	0.15840 (18)	0.23330 (11)	0.0508 (4)
C15	−0.05883 (18)	0.08718 (18)	0.17157 (12)	0.0532 (4)
H15	−0.0504	0.0030	0.1822	0.064*
C16	−0.09574 (19)	0.10153 (18)	0.31679 (12)	0.0580 (5)
C17A	−0.2372 (10)	−0.0494 (10)	0.2202 (6)	0.085 (4)	0.282 (10)
H17A	−0.2608	−0.1285	0.2348	0.102*	0.282 (10)
H17B	−0.1926	−0.0612	0.1835	0.102*	0.282 (10)
C17B	−0.2820 (5)	0.0332 (6)	0.2173 (4)	0.0939 (18)	0.718 (10)
H17C	−0.3462	0.0479	0.2326	0.113*	0.718 (10)
H17D	−0.2752	0.1001	0.1790	0.113*	0.718 (10)
C18A	−0.3339 (15)	0.036 (2)	0.1740 (14)	0.155 (8)	0.282 (10)
H18A	−0.3582	0.0269	0.1089	0.233*	0.282 (10)
H18B	−0.3114	0.1199	0.1902	0.233*	0.282 (10)
H18C	−0.3929	0.0165	0.1940	0.233*	0.282 (10)
C18B	−0.2932 (6)	−0.0862 (6)	0.1678 (5)	0.142 (3)	0.718 (10)
H18D	−0.3531	−0.0811	0.1100	0.213*	0.718 (10)
H18E	−0.3071	−0.1507	0.2038	0.213*	0.718 (10)
H18F	−0.2266	−0.1034	0.1579	0.213*	0.718 (10)
C19	−0.1838 (4)	−0.0419 (4)	0.3858 (2)	0.1213 (14)
H19A	−0.2042	−0.1267	0.3691	0.146*
H19B	−0.1118	−0.0415	0.4342	0.146*
C20	−0.2624 (5)	0.0130 (5)	0.4194 (3)	0.171 (3)
H20A	−0.2656	−0.0343	0.4699	0.257*
H20B	−0.3335	0.0141	0.3713	0.257*
H20C	−0.2402	0.0955	0.4392	0.257*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0618 (2)	0.0489 (2)	0.02981 (18)	−0.00067 (16)	0.02117 (16)	0.00058 (13)
O1	0.0652 (9)	0.0672 (8)	0.0465 (7)	−0.0039 (7)	0.0140 (6)	0.0079 (6)
O2	0.0932 (14)	0.1235 (18)	0.1255 (18)	−0.0337 (13)	−0.0030 (13)	0.0690 (15)
O3	0.1131 (12)	0.0614 (8)	0.0348 (7)	−0.0133 (8)	0.0266 (7)	−0.0056 (6)
O4	0.0774 (10)	0.0539 (8)	0.0500 (8)	0.0010 (7)	0.0286 (8)	0.0088 (6)
N1	0.0761 (10)	0.0536 (9)	0.0367 (7)	0.0019 (7)	0.0281 (7)	0.0001 (6)
N2	0.127 (2)	0.1230 (19)	0.0551 (12)	−0.0580 (16)	0.0490 (13)	−0.0147 (12)
C1	0.0634 (12)	0.0778 (15)	0.0558 (12)	−0.0048 (10)	0.0184 (10)	0.0167 (10)
C2	0.0560 (11)	0.0751 (13)	0.0557 (11)	−0.0062 (10)	0.0170 (9)	0.0126 (10)
C3	0.0635 (12)	0.0839 (16)	0.0574 (12)	−0.0026 (11)	0.0178 (10)	0.0092 (10)
C4	0.0739 (15)	0.107 (2)	0.0550 (13)	−0.0008 (14)	0.0166 (11)	0.0126 (12)
C5	0.0642 (14)	0.107 (2)	0.0733 (16)	0.0069 (13)	0.0180 (12)	0.0277 (14)
C6	0.0677 (15)	0.105 (2)	0.0923 (19)	0.0159 (14)	0.0339 (14)	0.0174 (16)
C7	0.0677 (13)	0.0976 (18)	0.0669 (14)	−0.0037 (13)	0.0287 (11)	0.0072 (12)
C8	0.117 (2)	0.098 (2)	0.0807 (19)	0.0161 (18)	0.0365 (17)	0.0007 (16)
C9	0.099 (2)	0.162 (4)	0.100 (2)	0.040 (2)	0.0236 (18)	0.059 (2)
C10	0.123 (3)	0.161 (3)	0.080 (2)	0.015 (2)	0.051 (2)	−0.004 (2)
C11	0.1095 (18)	0.0582 (11)	0.0469 (10)	0.0063 (11)	0.0442 (11)	0.0089 (9)
C12	0.143 (2)	0.0507 (11)	0.0622 (13)	0.0147 (13)	0.0547 (15)	0.0080 (10)
C13	0.1038 (17)	0.0565 (11)	0.0481 (10)	0.0091 (11)	0.0397 (11)	−0.0032 (8)
C14	0.0689 (11)	0.0549 (10)	0.0320 (8)	−0.0057 (8)	0.0224 (8)	−0.0043 (7)
C15	0.0819 (13)	0.0471 (9)	0.0360 (8)	0.0005 (9)	0.0280 (8)	−0.0004 (7)
C16	0.0904 (14)	0.0546 (10)	0.0381 (9)	−0.0074 (10)	0.0344 (9)	−0.0077 (7)
C17A	0.129 (9)	0.068 (6)	0.059 (6)	−0.048 (6)	0.037 (5)	−0.022 (4)
C17B	0.098 (4)	0.109 (4)	0.085 (3)	−0.031 (3)	0.046 (3)	−0.017 (3)
C18A	0.121 (12)	0.197 (19)	0.103 (12)	−0.017 (10)	−0.011 (9)	−0.007 (13)
C18B	0.144 (5)	0.143 (5)	0.142 (5)	−0.059 (4)	0.057 (4)	−0.071 (4)
C19	0.183 (4)	0.124 (3)	0.080 (2)	−0.064 (3)	0.077 (2)	−0.0064 (19)
C20	0.164 (4)	0.283 (7)	0.100 (3)	−0.063 (4)	0.088 (3)	−0.019 (3)

Geometric parameters (Å, º) top

Mn1—O1	2.0999 (14)	C9—H9C	0.9600
Mn1—O1ⁱ	2.0999 (14)	C10—H10A	0.9600
Mn1—O4	2.2230 (15)	C10—H10B	0.9600
Mn1—O4ⁱ	2.2230 (15)	C10—H10C	0.9600
Mn1—N1	2.3289 (15)	C11—C12	1.377 (3)
Mn1—N1ⁱ	2.3289 (15)	C11—H11	0.9300
O1—C1	1.254 (3)	C12—H12	0.9300
O2—C1	1.243 (3)	C13—C12	1.379 (3)
O3—C16	1.224 (3)	C13—H13	0.9300
O4—H41	0.85 (3)	C14—C13	1.376 (3)
O4—H42	0.80 (3)	C14—C15	1.380 (2)
N1—C11	1.331 (3)	C14—C16	1.504 (2)
N1—C15	1.334 (2)	C15—H15	0.9300
N2—C17A	1.506 (9)	C16—N2	1.324 (3)
N2—C17B	1.536 (7)	C17A—C18A	1.526 (17)
N2—C19	1.493 (3)	C17A—H17A	0.9700
C2—C1	1.511 (3)	C17A—H17B	0.9700
C2—C3	1.387 (3)	C17B—C18B	1.493 (8)
C2—C7	1.388 (4)	C17B—H17C	0.9700
C3—C8	1.505 (4)	C17B—H17D	0.9700
C4—C3	1.390 (3)	C18A—H18A	0.9600
C4—C5	1.373 (4)	C18A—H18B	0.9600
C4—H4	0.9300	C18A—H18C	0.9600
C5—C6	1.373 (4)	C18B—H18D	0.9600
C5—C9	1.516 (4)	C18B—H18E	0.9600
C6—H6	0.9300	C18B—H18F	0.9600
C7—C6	1.395 (4)	C19—C20	1.447 (6)
C7—C10	1.510 (4)	C19—H19A	0.9700
C8—H8A	0.9600	C19—H19B	0.9700
C8—H8B	0.9600	C20—H20A	0.9600
C8—H8C	0.9600	C20—H20B	0.9600
C9—H9A	0.9600	C20—H20C	0.9600
C9—H9B	0.9600

O1···H10B	2.87	C16···H18B	2.80
O1···H13ⁱⁱ	2.65	C16···H41^v	2.93 (3)
O1···H8C	2.82	C17A···H15	2.78
O2···H42ⁱ	1.90 (3)	C17B···H20B	2.75
O2···H9Cⁱⁱⁱ	2.48	C18A···H9B^v	2.87
O3···H12^iv	2.85	C18B···H8B^vi	2.79
O3···H11^v	2.52	C18B···H19A	2.97
O3···H41^v	2.00 (3)	C19···H18E	2.97
O3···H19B	2.35	C20···H17C	2.76
O4···H15ⁱ	2.62	H4···H8A	2.37
O4···H11	2.89	H4···H9A	2.38
C1···H10C	2.98	H6···H10A	2.37
C1···H42ⁱ	2.61 (3)	H6···H9C	2.50
C1···H8C	2.59	H8A···H20A^vii	2.31
C1···H10B	2.71	H8B···H17A^viii	2.44
C5···H18Bⁱⁱ	2.98	H8B···H18E^viii	2.14
C13···H17D	2.97	H11···H41	2.52
C14···H17D	2.40	H15···H18F	2.48
C14···H17B	2.74	H15···H17B	2.00
C14···H18B	2.82	H17A···H19A	1.96
C15···H17D	2.88	H17C···H20B	2.16
C15···H17B	2.44	H18A···H9B^v	2.50
C15···H18F	2.97	H18E···H19A	2.46

O1ⁱ—Mn1—O1	180.00 (7)	H9A—C9—H9B	109.5
O1—Mn1—O4	89.54 (6)	H9A—C9—H9C	109.5
O1ⁱ—Mn1—O4	90.46 (6)	H9B—C9—H9C	109.5
O1—Mn1—O4ⁱ	90.46 (6)	C7—C10—H10A	109.5
O1ⁱ—Mn1—O4ⁱ	89.54 (6)	C7—C10—H10B	109.5
O1—Mn1—N1	90.62 (6)	C7—C10—H10C	109.5
O1ⁱ—Mn1—N1	89.38 (6)	H10A—C10—H10B	109.5
O1—Mn1—N1ⁱ	89.38 (6)	H10A—C10—H10C	109.5
O1ⁱ—Mn1—N1ⁱ	90.62 (6)	H10B—C10—H10C	109.5
O4ⁱ—Mn1—O4	180.00 (9)	N1—C11—C12	123.08 (18)
O4—Mn1—N1	92.12 (6)	N1—C11—H11	118.5
O4ⁱ—Mn1—N1	87.88 (6)	C12—C11—H11	118.5
O4—Mn1—N1ⁱ	87.88 (6)	C11—C12—C13	119.4 (2)
O4ⁱ—Mn1—N1ⁱ	92.12 (6)	C11—C12—H12	120.3
N1—Mn1—N1ⁱ	180.00 (7)	C13—C12—H12	120.3
Mn1—O4—H41	126.1 (18)	C12—C13—H13	120.9
Mn1—O4—H42	103 (2)	C14—C13—C12	118.18 (18)
H41—O4—H42	111 (3)	C14—C13—H13	120.9
C1—O1—Mn1	130.03 (14)	C13—C14—C15	118.53 (17)
C11—N1—Mn1	123.24 (12)	C13—C14—C16	120.74 (16)
C11—N1—C15	116.92 (16)	C15—C14—C16	120.64 (17)
C15—N1—Mn1	119.84 (12)	N1—C15—C14	123.83 (18)
C16—N2—C17A	126.0 (4)	N1—C15—H15	118.1
C16—N2—C17B	120.1 (3)	C14—C15—H15	118.1
C16—N2—C19	118.5 (2)	O3—C16—N2	122.95 (19)
C19—N2—C17A	108.6 (4)	O3—C16—C14	119.10 (19)
C19—N2—C17B	119.3 (3)	N2—C16—C14	117.94 (18)
O1—C1—C2	114.81 (19)	N2—C17A—C18A	98.7 (12)
O2—C1—O1	125.5 (2)	N2—C17A—H17A	112.0
O2—C1—C2	119.7 (2)	N2—C17A—H17B	112.0
C3—C2—C1	118.9 (2)	C18A—C17A—H17A	112.0
C3—C2—C7	120.9 (2)	C18A—C17A—H17B	112.0
C7—C2—C1	120.1 (2)	H17A—C17A—H17B	109.7
C2—C3—C4	118.4 (2)	N2—C17B—H17C	110.1
C2—C3—C8	120.6 (2)	N2—C17B—H17D	110.1
C4—C3—C8	121.0 (2)	C18B—C17B—N2	107.8 (6)
C3—C4—H4	118.9	C18B—C17B—H17C	110.1
C5—C4—C3	122.1 (3)	C18B—C17B—H17D	110.1
C5—C4—H4	118.9	H17C—C17B—H17D	108.5
C4—C5—C6	118.2 (2)	C17B—C18B—H18D	109.5
C4—C5—C9	120.7 (3)	C17B—C18B—H18E	109.5
C6—C5—C9	121.1 (3)	C17B—C18B—H18F	109.5
C5—C6—C7	122.0 (3)	H18D—C18B—H18E	109.5
C5—C6—H6	119.0	H18D—C18B—H18F	109.5
C7—C6—H6	119.0	H18E—C18B—H18F	109.5
C2—C7—C6	118.3 (2)	N2—C19—H19A	109.3
C2—C7—C10	120.4 (3)	N2—C19—H19B	109.3
C6—C7—C10	121.3 (3)	C20—C19—N2	111.6 (4)
C3—C8—H8A	109.5	C20—C19—H19A	109.3
C3—C8—H8B	109.5	C20—C19—H19B	109.3
C3—C8—H8C	109.5	H19A—C19—H19B	108.0
H8A—C8—H8B	109.5	C19—C20—H20A	109.5
H8A—C8—H8C	109.5	C19—C20—H20B	109.5
H8B—C8—H8C	109.5	C19—C20—H20C	109.5
C5—C9—H9A	109.5	H20A—C20—H20B	109.5
C5—C9—H9B	109.5	H20A—C20—H20C	109.5
C5—C9—H9C	109.5	H20B—C20—H20C	109.5

O4—Mn1—O1—C1	168.4 (2)	C1—C2—C3—C8	5.5 (4)
O4ⁱ—Mn1—O1—C1	−11.6 (2)	C7—C2—C3—C4	3.1 (4)
N1—Mn1—O1—C1	−99.5 (2)	C7—C2—C3—C8	−178.0 (2)
N1ⁱ—Mn1—O1—C1	80.5 (2)	C1—C2—C7—C6	174.2 (2)
O1—Mn1—N1—C11	−62.66 (19)	C1—C2—C7—C10	−6.0 (4)
O1ⁱ—Mn1—N1—C11	117.34 (19)	C3—C2—C7—C6	−2.3 (4)
O1—Mn1—N1—C15	117.53 (16)	C3—C2—C7—C10	177.6 (3)
O1ⁱ—Mn1—N1—C15	−62.47 (16)	C5—C4—C3—C2	−1.1 (4)
O4—Mn1—N1—C11	26.91 (19)	C5—C4—C3—C8	−179.9 (3)
O4ⁱ—Mn1—N1—C11	−153.09 (19)	C3—C4—C5—C6	−1.7 (4)
O4—Mn1—N1—C15	−152.91 (16)	C3—C4—C5—C9	177.1 (3)
O4ⁱ—Mn1—N1—C15	27.09 (16)	C4—C5—C6—C7	2.6 (4)
Mn1—O1—C1—O2	−2.5 (4)	C9—C5—C6—C7	−176.2 (3)
Mn1—O1—C1—C2	−179.51 (14)	C2—C7—C6—C5	−0.6 (4)
Mn1—N1—C11—C12	−178.4 (2)	C10—C7—C6—C5	179.5 (3)
C15—N1—C11—C12	1.4 (4)	N1—C11—C12—C13	−1.1 (4)
Mn1—N1—C15—C14	179.68 (16)	C14—C13—C12—C11	−0.6 (4)
C11—N1—C15—C14	−0.1 (3)	C15—C14—C13—C12	1.7 (4)
C16—N2—C17A—C18A	−96.6 (11)	C16—C14—C13—C12	178.3 (2)
C17B—N2—C17A—C18A	−0.4 (10)	C13—C14—C15—N1	−1.5 (3)
C19—N2—C17A—C18A	113.2 (10)	C16—C14—C15—N1	−178.04 (19)
C16—N2—C17B—C18B	117.7 (4)	C13—C14—C16—O3	−65.7 (3)
C17A—N2—C17B—C18B	6.0 (7)	C13—C14—C16—N2	115.6 (3)
C19—N2—C17B—C18B	−78.9 (5)	C15—C14—C16—O3	110.9 (2)
C16—N2—C19—C20	102.2 (4)	C15—C14—C16—N2	−67.9 (3)
C17A—N2—C19—C20	−105.0 (7)	O3—C16—N2—C17A	−152.8 (7)
C17B—N2—C19—C20	−61.5 (5)	O3—C16—N2—C17B	158.4 (3)
C3—C2—C1—O1	89.8 (3)	O3—C16—N2—C19	−5.2 (4)
C3—C2—C1—O2	−87.4 (3)	C14—C16—N2—C17A	26.0 (8)
C7—C2—C1—O1	−86.7 (3)	C14—C16—N2—C17B	−22.9 (4)
C7—C2—C1—O2	96.0 (3)	C14—C16—N2—C19	173.5 (3)
C1—C2—C3—C4	−173.4 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O3ⁱⁱ	0.85 (3)	2.00 (3)	2.838 (2)	171 (3)
O4—H42···O2ⁱ	0.80 (3)	1.90 (3)	2.660 (3)	157 (3)
C9—H9C···O2^ix	0.96	2.48	3.366 (5)	154
C11—H11···O3ⁱⁱ	0.93	2.52	3.447 (3)	179

Symmetry codes: (i) −x, −y, −z; (ii) x, −y+1/2, z−1/2; (ix) −x−1, y+1/2, −z−1/2.

Acknowledgements

The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010K120480 of the State of Planning Organization).

References

Adiwidjaja, G., Rossmanith, E. & Küppers, H. (1978). Acta Cryst. B34, 3079–3083. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Antsyshkina, A. S., Chiragov, F. M. & Poray-Koshits, M. A. (1980). Koord. Khim. 15, 1098–1103. Google Scholar
Bigoli, F., Braibanti, A., Pellinghelli, M. A. & Tiripicchio, A. (1972). Acta Cryst. B28, 962–966. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bigoli, F., Braibanti, A., Pellinghelli, M. A. & Tiripicchio, A. (1973a). Acta Cryst. B29, 39–43. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bigoli, F., Braibanti, A., Pellinghelli, M. A. & Tiripicchio, A. (1973b). Acta Cryst. B29, 2344–2348. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Catterick (neé Drew), J., Hursthouse, M. B., New, D. B. & Thornton, P. (1974). J. Chem. Soc. Chem. Commun. pp. 843–844. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hathwar, V. R., Sist, M., Jørgensen, M. R. V., Mamakhel, A. H., Wang, X., Hoffmann, C. M., Sugimoto, K., Overgaard, J. & Iversen, B. B. (2015). IUCrJ, 2, 563–574. Web of Science CSD CrossRef CAS PubMed IUCr Journals Google Scholar
Hirshfeld, H. L. (1977). Theor. Chim. Acta, 44, 129–138. CrossRef CAS Web of Science Google Scholar
Hökelek, T., Dal, H., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009a). Acta Cryst. E65, m1365–m1366. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009b). Acta Cryst. E65, m627–m628. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009d). Acta Cryst. E65, m513–m514. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Yılmaz, F., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009c). Acta Cryst. E65, m955–m956. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). TONTO – A System for Computational Chemistry. Available at: https://hirshfeldsurface.net/ Google Scholar
Krishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108–111. CrossRef CAS PubMed Web of Science Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814. Google Scholar
Mikelashvili, Z. A. (1982). Dissertation, Tbilisi State University, Georgia. Google Scholar
Nadzhafov, G. N., Shnulin, A. N. & Mamedov, Kh. S. (1981). Zh. Strukt. Khim. 22, 124–128. CAS Google Scholar
Necefoğlu, H., Hökelek, T., Ersanlı, C. C. & Erdönmez, A. (2002). Acta Cryst. E58, m758–m761. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sergienko, V. S., Shurkina, V. N., Khodashova, T. S., Poray-Koshits, M. A. & Tsintsadze, G. V. (1980). Koord. Khim. 6, 1606–1609. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shnulin, A. N., Nadzhafov, G. N., Amiraslanov, I. R., Usubaliev, B. T. & Mamedov, Kh. S. (1981). Koord. Khim. 7, 1409–1416. CAS Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm 10, 377–388. CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. The University of Western Australia. Google Scholar
Venkatesan, P., Thamotharan, S., Ilangovan, A., Liang, H. & Sundius, T. (2016). Spectrochim. Acta Part A 153, 625–636. Web of Science CSD CrossRef CAS Google Scholar

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