Crystal structure of aqua­tris­(isonicotinamide-κN)bis­(thio­cyanato-κN)cobalt(II) 2.5-hydrate

Neumann, T.; Jess, I.; Näther, C.

doi:10.1107/S2056989016012470

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ISSN: 2056-9890

Volume 72| Part 9| September 2016| Pages 1263-1266

https://doi.org/10.1107/S2056989016012470

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Crystal structure of aquatris(isonicotinamide-κN)bis(thiocyanato-κN)cobalt(II) 2.5-hydrate

Tristan Neumann,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany
^*Correspondence e-mail: t.neumann@ac.uni-kiel.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 27 July 2016; accepted 2 August 2016; online 9 August 2016)

The asymmetric unit of the title compound, [Co(NCS)₂(C₆H₆N₂O)₃(H₂O)]·2.5H₂O, comprises one Co^II cation, three isonicotinamide ligands, two thiocyanate anions, one aqua ligand and two water solvent molecules in general positions, as well as one water solvent molecule that is located on a twofold rotation axis. The Co^II cations are octahedrally coordinated by two terminally N-bonded thiocyanate anions, one water molecule and three isonicotinamide ligands, each coordinating via the pyridine N atom. The discrete complexes are linked by intermolecular O—H⋯O, N—H⋯O and N—H⋯S hydrogen bonding into a three-dimensional network that contains cavities in which the solvent water molecules are located. The latter are linked by further O—H⋯O hydrogen bonds to the network. There are additional short contacts present in the crystal, indicative of weak C—H⋯S, C—H⋯O and C—H⋯N interactions.

Keywords: crystal structure; discrete complex; cobalt(II) thiocyanate; isonicotinamide; hydrogen bonding.

CCDC reference: 1497322

1. Chemical context

The synthesis of new coordination polymers with cooperative magnetic properties is still a major field in coordination chemistry. In this context, compounds that show a slow relaxation of the magnetization, such as, for example, single chain magnets, are of special interest because of their potential for future applications (Dhers et al., 2015 ; Caneschi et al., 2001 ; Liu et al., 2010 ). To trigger such behavior, cations of large magnetic anisotropy, such as, for example, Mn^II, Fe^II or Co^II, must be linked by ligands into chains that can mediate a magnetic exchange. Therefore, we are generally interested in the synthesis and the magnetic properties of Co- and Fe-containing thio- and selenocyanate coordination polymers (Werner et al., 2014 , 2015a ,b ,c ; Boeckmann et al., 2012 ; Wöhlert et al., 2014 ). This also includes the synthesis of discrete complexes with a terminal coordination because such compounds can be transformed into the desired polymeric compounds by thermal decomposition reactions (Näther et al., 2013 ). In the course of our investigations, we attempted to prepare Co-containing thiocyanate coordination compounds with isonicotinamide as ligand and obtained crystals of the title compound, [Co(NCS)₂(C₆H₆N₂O)₃(H₂O)]·2.5H₂O. However, this phase could not be prepared as a pure phase. To identify these crystals, a single crystal structure analysis was performed and the results are reported herein.

2. Structural commentary

The asymmetric unit comprises one cobalt(II) cation, two thiocyanate anions, three isonicotinamide ligands and three water molecules (one as a ligand and two as solvent molecules) that occupy general positions as well as one water solvent molecule that is located on a twofold rotation axis (Fig. 1). The Co^II cation is coordinated by one water molecule, two terminal N-bonded thiocyanate anions and three terminal isonicotinamide ligands bonded through the pyridine N atom. The Co—N distances to the negatively charged anionic ligands of 2.0746 (1) and 2.0834 (17) Å are shorter than that to the neutral isonicotinamide ligands [Co—N: 2.1725 (16)–2.2059 (15) Å]. The bond angles around the Co^II atom deviate slightly from the ideal values [cis angles: 85.81 (6)–92.60 (7)°; trans angles: 173.17 (7)–177.74 (6)°]. The resulting coordination polyhedron can be described as a slightly distorted octahedron (Fig. 1)

Figure 1
View of the asymmetric unit of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

In the crystal structure, four symmetry-related complexes are linked by intermolecular O—H⋯O hydrogen bonding between the water H atoms of the coordinating water molecules of two complexes and the carbonyl O acceptor atoms of two additional complexes into eight-membered rings that are located on centres of inversion (Fig. 2). These tetramers are further connected by intermolecular O—H⋯O and N—H⋯O hydrogen bonding between water molecules and amide H atoms, respectively, and the carbonyl as well as water acceptor-O atoms into a three-dimensional network (Fig. 2). There are additional hydrogen bonds between the amide H atoms and the S atoms of the anionic ligands. The N—H⋯S angles deviate only slightly from 180°. Within this network cavities are formed, in which additional water molecules are embedded. These solvent molecules are linked by (water)O—H⋯O(water) hydrogen bonding into chain-like aggregates that consist of five water molecules each, whereby the aggregates are located on twofold rotation axes. These water aggregates are linked by additional O—H⋯O hydrogen bonds involving the carbonyl O acceptor atoms of the isonicotinamide ligands to the network. Finally, there are several short contacts indicative of weak C—H⋯S, C—H⋯O and C—H⋯N interactions. Numerical values of the hydrogen-bonding interactions are collated in Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯S2ⁱ	0.95	2.96	3.646 (2)	130
C14—H14⋯S1ⁱⁱ	0.95	2.84	3.785 (2)	172
C15—H15⋯O21ⁱⁱⁱ	0.95	2.45	3.324 (3)	153
N12—H12A⋯O31^iv	0.88	2.07	2.922 (2)	163
N12—H12B⋯S1ⁱⁱ	0.88	2.74	3.592 (2)	164
C21—H21⋯N2	0.95	2.65	3.245 (3)	122
C22—H22⋯O4	0.95	2.49	3.234 (2)	136
C24—H24⋯O2	0.95	2.58	3.423 (3)	149
C25—H25⋯N1	0.95	2.49	3.107 (2)	122
N22—H22A⋯S1^v	0.88	2.79	3.6484 (18)	165
N22—H22B⋯O2	0.88	2.04	2.873 (2)	158
C32—H32⋯S2ⁱⁱⁱ	0.95	3.00	3.826 (2)	146
N32—H32A⋯O2^vi	0.88	2.25	3.121 (2)	172
N32—H32B⋯S2ⁱⁱⁱ	0.88	2.57	3.4083 (19)	160
O1—H1O1⋯O21ⁱⁱⁱ	0.84	1.96	2.7858 (19)	166
O1—H2O1⋯O21^vii	0.84	2.01	2.8106 (19)	158
O2—H1O2⋯O3^viii	0.84	1.83	2.650 (3)	164
O2—H2O2⋯N1^ix	0.84	2.60	3.337 (2)	148
O2—H2O2⋯N31^ix	0.84	2.66	3.363 (2)	143
O3—H1O3⋯O31	0.84	2.17	2.966 (3)	158
O3—H2O3⋯O4^x	0.84	2.20	2.963 (2)	152
O4—H1O4⋯O11^xi	0.84	1.91	2.723 (2)	163
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (vi) x, y-1, z; (vii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (viii) x, y+1, z; (ix) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (x) -x+1, -y+1, -z+1; (xi) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 2
The packing in the crystal structure of the title compound in a view along the b axis. Intermolecular hydrogen bonding is shown as dashed lines.

4. Database survey

Some metal compounds based on isonicotinamide ligands and thiocyanates anions are reported in the Cambridge Structure Database (Version 5.37, last update 2015; Groom et al., 2016 ). Two Ni-clathrates, one with 9,10-anthraquinone and the other with pyrene, in which Ni^II cations are connected by μ-1,3-bridging thiocyanate ligands into coordination polymers (Sekiya et al., 2009 ) and one very similar cadmium compound with 9,10-dichloroanthracene as clathrate molecule (Sekiya & Nishikiori, 2005 ). Moreover, one compound comprising a three-dimensional coordination network based on Cd(SCN)₂ (Yang et al., 2001 ) and a compound built up of Cu–NCS layers are also reported (Đaković et al., 2010 ). Very recently we reported two discrete complexes with isonicotinamide as co-ligand, one of which is based on Zn(NCS)₂ with the Zn^II cation in tetrahedral coordination (Neumann et al., 2016a ) while the other is based on Co(NCS)₂ in which the Co^II cation is octahedrally coordinated (Neumann et al., 2016b ).

5. Synthesis and crystallization

Cobalt thiocyanate and 4-isonicotinamide were obtained from Alfa Aesar and were used without any further purification. Crystals suitable for single crystal structure analysis were obtained from a mixture of 26.3 mg Co(NCS)₂ (0.15 mmol) and 73.3 mg 4-isonicotinamide (0.6 mmol) in demineralized water (1.5 ml) within three days. The title compound could not be prepared as a single phase and was always contaminated with a second crystalline phase which could not be identified so far.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C—H and N—H hydrogen atoms were positioned in calculated positions with U_iso(H) = 1.2U_eq(C, N) using a riding model with C—H = 0.95 Å for aromatic and N—H = 0.88 Å for amide H atoms. The water hydrogen atoms were located in a difference map, and their bond lengths were constrained to O—H = 0.84 Å and with U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₆H₆N₂O)₃(H₂O)]·2.5H₂O
M_r	604.53
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	19.2539 (16), 13.1442 (8), 20.7913 (16)
β (°)	97.327 (10)
V (Å³)	5218.8 (7)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.87
Crystal size (mm)	0.11 × 0.08 × 0.06

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe, 2008 )
T_min, T_max	0.775, 0.920
No. of measured, independent and observed [I > 2σ(I)] reflections	29661, 6260, 5098
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.094, 1.01
No. of reflections	6260
No. of parameters	339
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.55
Computer programs: X-AREA (Stoe, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1497322

Crystal structure: contains datablocks I, kw171. DOI: https://doi.org/10.1107/S2056989016012470/wm5313sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016012470/wm5313Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Aquatris(isonicotinamide-κN)bis(thiocyanato-κN)cobalt(II) 2.5-hydrate top

Crystal data top

[Co(NCS)₂(C₆H₆N₂O)₃(H₂O)]·2.5H₂O	F(000) = 2496
M_r = 604.53	D_x = 1.539 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.2539 (16) Å	Cell parameters from 6260 reflections
b = 13.1442 (8) Å	θ = 4.3–56°
c = 20.7913 (16) Å	µ = 0.87 mm⁻¹
β = 97.327 (10)°	T = 200 K
V = 5218.8 (7) Å³	Block, red-brown
Z = 8	0.11 × 0.08 × 0.06 mm

Data collection top

Stoe IPDS-2 diffractometer	5098 reflections with I > 2σ(I)
ω–scans	R_int = 0.060
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	θ_max = 28.0°, θ_min = 2.6°
T_min = 0.775, T_max = 0.920	h = −25→25
29661 measured reflections	k = −17→17
6260 independent reflections	l = −27→27

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0525P)² + 5.523P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
6260 reflections	Δρ_max = 0.33 e Å⁻³
339 parameters	Δρ_min = −0.55 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.

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

	x	y	z	U_iso*/U_eq
Co1	0.18635 (2)	0.67227 (2)	0.31272 (2)	0.01581 (7)
N1	0.14313 (9)	0.70880 (14)	0.39620 (8)	0.0246 (3)
C1	0.10950 (9)	0.72960 (14)	0.43682 (9)	0.0186 (3)
S1	0.06154 (3)	0.75764 (4)	0.49356 (3)	0.02889 (12)
N2	0.22147 (9)	0.62103 (13)	0.22769 (8)	0.0233 (3)
C2	0.25664 (10)	0.61371 (14)	0.18638 (9)	0.0201 (4)
S2	0.30765 (3)	0.60830 (4)	0.12936 (3)	0.02793 (12)
N11	0.12709 (8)	0.79048 (12)	0.25649 (8)	0.0209 (3)
C11	0.12791 (11)	0.88801 (16)	0.27443 (10)	0.0262 (4)
H11	0.1524	0.9059	0.3155	0.031*
C12	0.09489 (11)	0.96437 (16)	0.23626 (10)	0.0269 (4)
H12	0.0975	1.0329	0.2509	0.032*
C13	0.05785 (10)	0.94012 (15)	0.17636 (9)	0.0206 (4)
C14	0.05573 (11)	0.83848 (16)	0.15789 (10)	0.0264 (4)
H14	0.0305	0.8182	0.1177	0.032*
C15	0.09093 (11)	0.76706 (15)	0.19885 (10)	0.0263 (4)
H15	0.0894	0.6979	0.1855	0.032*
C16	0.02360 (11)	1.02471 (16)	0.13489 (10)	0.0250 (4)
N12	−0.01376 (10)	0.99985 (14)	0.07899 (9)	0.0324 (4)
H12A	−0.0341	1.0476	0.0536	0.039*
H12B	−0.0182	0.9356	0.0673	0.039*
O11	0.03115 (10)	1.11340 (12)	0.15299 (8)	0.0415 (4)
N21	0.27358 (8)	0.77939 (12)	0.33884 (8)	0.0187 (3)
C21	0.32723 (10)	0.78644 (16)	0.30338 (10)	0.0246 (4)
H21	0.3289	0.7402	0.2685	0.030*
C22	0.38017 (10)	0.85805 (16)	0.31536 (10)	0.0235 (4)
H22	0.4164	0.8613	0.2884	0.028*
C23	0.37979 (9)	0.92477 (14)	0.36683 (9)	0.0174 (3)
C24	0.32564 (10)	0.91704 (15)	0.40465 (9)	0.0207 (4)
H24	0.3239	0.9609	0.4407	0.025*
C25	0.27411 (10)	0.84428 (15)	0.38891 (9)	0.0212 (4)
H25	0.2371	0.8400	0.4150	0.025*
C26	0.43638 (9)	1.00411 (14)	0.37791 (9)	0.0187 (4)
N22	0.45023 (9)	1.04280 (14)	0.43691 (8)	0.0252 (4)
H22A	0.4825	1.0902	0.4449	0.030*
H22B	0.4272	1.0212	0.4682	0.030*
O21	0.46730 (7)	1.03177 (11)	0.33192 (7)	0.0231 (3)
N31	0.24699 (8)	0.55232 (12)	0.36533 (7)	0.0182 (3)
C31	0.24100 (10)	0.45608 (15)	0.34455 (9)	0.0222 (4)
H31	0.2135	0.4428	0.3042	0.027*
C32	0.27278 (10)	0.37491 (15)	0.37887 (10)	0.0235 (4)
H32	0.2667	0.3076	0.3625	0.028*
C33	0.31380 (9)	0.39326 (14)	0.43780 (9)	0.0183 (3)
C34	0.32139 (10)	0.49318 (15)	0.45905 (10)	0.0238 (4)
H34	0.3497	0.5088	0.4986	0.029*
C35	0.28715 (11)	0.56976 (15)	0.42182 (10)	0.0245 (4)
H35	0.2924	0.6378	0.4370	0.029*
C36	0.35105 (10)	0.31096 (15)	0.47912 (9)	0.0203 (4)
N32	0.32523 (10)	0.21708 (13)	0.47146 (9)	0.0283 (4)
H32A	0.3452	0.1668	0.4949	0.034*
H32B	0.2882	0.2054	0.4430	0.034*
O31	0.40296 (7)	0.33185 (11)	0.51840 (7)	0.0257 (3)
O1	0.09982 (7)	0.56631 (11)	0.29295 (7)	0.0226 (3)
H1O1	0.0844	0.5474	0.2552	0.034*
H2O1	0.0639	0.5683	0.3120	0.034*
O2	0.38171 (8)	1.02681 (13)	0.55143 (7)	0.0324 (3)
H1O2	0.4007	1.0670	0.5798	0.049*
H2O2	0.3617	0.9813	0.5707	0.049*
O3	0.43909 (14)	0.17955 (15)	0.62254 (12)	0.0672 (7)
H1O3	0.4391	0.2301	0.5978	0.101*
H2O3	0.4411	0.2036	0.6602	0.101*
O4	0.5000	0.73797 (19)	0.2500	0.0451 (6)
H1O4	0.5181	0.7008	0.2238	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01664 (12)	0.01500 (12)	0.01570 (12)	−0.00072 (9)	0.00174 (9)	0.00114 (9)
N1	0.0253 (8)	0.0258 (9)	0.0237 (8)	−0.0016 (7)	0.0075 (7)	−0.0018 (7)
C1	0.0190 (8)	0.0162 (8)	0.0196 (8)	−0.0020 (7)	−0.0014 (7)	0.0010 (7)
S1	0.0318 (3)	0.0333 (3)	0.0232 (2)	0.0063 (2)	0.0099 (2)	−0.0006 (2)
N2	0.0264 (8)	0.0240 (9)	0.0200 (8)	−0.0008 (7)	0.0048 (6)	−0.0017 (6)
C2	0.0245 (9)	0.0144 (8)	0.0202 (9)	0.0006 (7)	−0.0012 (7)	0.0016 (7)
S2	0.0301 (3)	0.0310 (3)	0.0243 (2)	0.0070 (2)	0.0096 (2)	0.0061 (2)
N11	0.0225 (8)	0.0187 (8)	0.0205 (8)	0.0005 (6)	−0.0010 (6)	0.0020 (6)
C11	0.0303 (10)	0.0226 (10)	0.0230 (9)	0.0048 (8)	−0.0067 (8)	−0.0034 (8)
C12	0.0331 (10)	0.0188 (9)	0.0267 (10)	0.0045 (8)	−0.0044 (8)	−0.0048 (8)
C13	0.0208 (9)	0.0199 (9)	0.0205 (9)	0.0029 (7)	0.0009 (7)	0.0016 (7)
C14	0.0316 (10)	0.0222 (10)	0.0222 (9)	0.0012 (8)	−0.0084 (8)	0.0000 (8)
C15	0.0342 (10)	0.0158 (9)	0.0259 (10)	−0.0007 (8)	−0.0083 (8)	0.0000 (8)
C16	0.0282 (10)	0.0209 (10)	0.0256 (10)	0.0060 (8)	0.0020 (8)	0.0015 (8)
N12	0.0417 (10)	0.0221 (9)	0.0294 (9)	0.0076 (8)	−0.0105 (8)	0.0027 (7)
O11	0.0673 (12)	0.0199 (8)	0.0337 (9)	0.0107 (8)	−0.0072 (8)	−0.0019 (7)
N21	0.0172 (7)	0.0158 (7)	0.0227 (8)	−0.0023 (6)	0.0012 (6)	0.0014 (6)
C21	0.0255 (9)	0.0214 (10)	0.0279 (10)	−0.0026 (8)	0.0071 (8)	−0.0058 (8)
C22	0.0221 (9)	0.0225 (10)	0.0273 (10)	−0.0032 (7)	0.0083 (7)	−0.0022 (8)
C23	0.0160 (8)	0.0147 (8)	0.0209 (9)	−0.0002 (6)	0.0000 (6)	0.0041 (7)
C24	0.0204 (8)	0.0212 (9)	0.0205 (9)	−0.0032 (7)	0.0027 (7)	−0.0025 (7)
C25	0.0189 (8)	0.0222 (10)	0.0228 (9)	−0.0041 (7)	0.0041 (7)	−0.0011 (7)
C26	0.0163 (8)	0.0171 (9)	0.0223 (9)	0.0011 (7)	0.0010 (7)	0.0027 (7)
N22	0.0237 (8)	0.0284 (9)	0.0235 (8)	−0.0098 (7)	0.0031 (6)	−0.0026 (7)
O21	0.0214 (6)	0.0260 (7)	0.0220 (7)	−0.0043 (5)	0.0026 (5)	0.0057 (6)
N31	0.0199 (7)	0.0159 (7)	0.0185 (7)	0.0005 (6)	0.0007 (6)	0.0015 (6)
C31	0.0256 (9)	0.0195 (9)	0.0197 (9)	0.0016 (7)	−0.0043 (7)	−0.0037 (7)
C32	0.0292 (10)	0.0159 (9)	0.0239 (9)	−0.0003 (7)	−0.0024 (8)	−0.0017 (7)
C33	0.0178 (8)	0.0163 (9)	0.0206 (9)	0.0008 (6)	0.0016 (7)	0.0008 (7)
C34	0.0270 (9)	0.0190 (9)	0.0231 (9)	0.0007 (7)	−0.0058 (7)	−0.0013 (7)
C35	0.0297 (10)	0.0160 (9)	0.0252 (10)	−0.0007 (7)	−0.0068 (8)	−0.0011 (7)
C36	0.0212 (8)	0.0189 (9)	0.0209 (9)	0.0032 (7)	0.0026 (7)	−0.0009 (7)
N32	0.0318 (9)	0.0162 (8)	0.0337 (10)	0.0011 (7)	−0.0085 (7)	0.0036 (7)
O31	0.0254 (7)	0.0227 (7)	0.0267 (7)	0.0016 (6)	−0.0057 (6)	−0.0004 (6)
O1	0.0187 (6)	0.0271 (7)	0.0220 (7)	−0.0063 (5)	0.0023 (5)	−0.0021 (6)
O2	0.0374 (8)	0.0337 (9)	0.0272 (8)	−0.0031 (7)	0.0085 (6)	0.0033 (7)
O3	0.1016 (18)	0.0296 (10)	0.0598 (14)	−0.0097 (11)	−0.0299 (13)	0.0075 (9)
O4	0.0690 (18)	0.0284 (13)	0.0415 (14)	0.000	0.0211 (13)	0.000

Geometric parameters (Å, º) top

Co1—N1	2.0746 (17)	C23—C24	1.387 (3)
Co1—N2	2.0834 (17)	C23—C26	1.505 (2)
Co1—O1	2.1703 (13)	C24—C25	1.387 (3)
Co1—N31	2.1725 (16)	C24—H24	0.9500
Co1—N11	2.1778 (16)	C25—H25	0.9500
Co1—N21	2.2059 (15)	C26—O21	1.244 (2)
N1—C1	1.161 (3)	C26—N22	1.323 (3)
C1—S1	1.6304 (19)	N22—H22A	0.8800
N2—C2	1.164 (3)	N22—H22B	0.8800
C2—S2	1.635 (2)	N31—C31	1.337 (2)
N11—C11	1.335 (3)	N31—C35	1.341 (2)
N11—C15	1.343 (3)	C31—C32	1.382 (3)
C11—C12	1.383 (3)	C31—H31	0.9500
C11—H11	0.9500	C32—C33	1.392 (3)
C12—C13	1.391 (3)	C32—H32	0.9500
C12—H12	0.9500	C33—C34	1.387 (3)
C13—C14	1.389 (3)	C33—C36	1.505 (3)
C13—C16	1.506 (3)	C34—C35	1.384 (3)
C14—C15	1.385 (3)	C34—H34	0.9500
C14—H14	0.9500	C35—H35	0.9500
C15—H15	0.9500	C36—O31	1.238 (2)
C16—O11	1.228 (3)	C36—N32	1.332 (3)
C16—N12	1.327 (3)	N32—H32A	0.8800
N12—H12A	0.8800	N32—H32B	0.8800
N12—H12B	0.8800	O1—H1O1	0.8401
N21—C25	1.345 (2)	O1—H2O1	0.8398
N21—C21	1.347 (2)	O2—H1O2	0.8401
C21—C22	1.386 (3)	O2—H2O2	0.8400
C21—H21	0.9500	O3—H1O3	0.8400
C22—C23	1.384 (3)	O3—H2O3	0.8400
C22—H22	0.9500	O4—H1O4	0.8400

N1—Co1—N2	173.17 (7)	C22—C21—H21	118.5
N1—Co1—O1	85.81 (6)	C23—C22—C21	119.53 (18)
N2—Co1—O1	87.49 (6)	C23—C22—H22	120.2
N1—Co1—N31	89.65 (6)	C21—C22—H22	120.2
N2—Co1—N31	88.90 (6)	C22—C23—C24	118.04 (17)
O1—Co1—N31	88.85 (6)	C22—C23—C26	118.85 (16)
N1—Co1—N11	92.60 (7)	C24—C23—C26	123.08 (17)
N2—Co1—N11	88.83 (7)	C25—C24—C23	118.91 (18)
O1—Co1—N11	91.10 (6)	C25—C24—H24	120.5
N31—Co1—N11	177.74 (6)	C23—C24—H24	120.5
N1—Co1—N21	91.16 (6)	N21—C25—C24	123.68 (17)
N2—Co1—N21	95.51 (6)	N21—C25—H25	118.2
O1—Co1—N21	176.67 (6)	C24—C25—H25	118.2
N31—Co1—N21	89.76 (6)	O21—C26—N22	122.75 (17)
N11—Co1—N21	90.41 (6)	O21—C26—C23	119.55 (17)
C1—N1—Co1	169.72 (16)	N22—C26—C23	117.69 (16)
N1—C1—S1	179.25 (19)	C26—N22—H22A	120.0
C2—N2—Co1	159.31 (16)	C26—N22—H22B	120.0
N2—C2—S2	177.44 (19)	H22A—N22—H22B	120.0
C11—N11—C15	117.13 (17)	C31—N31—C35	117.46 (16)
C11—N11—Co1	123.26 (13)	C31—N31—Co1	120.35 (12)
C15—N11—Co1	119.48 (13)	C35—N31—Co1	121.99 (13)
N11—C11—C12	123.26 (18)	N31—C31—C32	123.31 (17)
N11—C11—H11	118.4	N31—C31—H31	118.3
C12—C11—H11	118.4	C32—C31—H31	118.3
C11—C12—C13	119.55 (19)	C31—C32—C33	119.01 (18)
C11—C12—H12	120.2	C31—C32—H32	120.5
C13—C12—H12	120.2	C33—C32—H32	120.5
C14—C13—C12	117.48 (18)	C34—C33—C32	117.99 (17)
C14—C13—C16	123.79 (18)	C34—C33—C36	118.40 (17)
C12—C13—C16	118.71 (18)	C32—C33—C36	123.60 (17)
C15—C14—C13	119.15 (18)	C35—C34—C33	119.14 (18)
C15—C14—H14	120.4	C35—C34—H34	120.4
C13—C14—H14	120.4	C33—C34—H34	120.4
N11—C15—C14	123.41 (19)	N31—C35—C34	123.07 (18)
N11—C15—H15	118.3	N31—C35—H35	118.5
C14—C15—H15	118.3	C34—C35—H35	118.5
O11—C16—N12	122.13 (19)	O31—C36—N32	122.80 (18)
O11—C16—C13	119.94 (19)	O31—C36—C33	120.18 (17)
N12—C16—C13	117.93 (18)	N32—C36—C33	117.02 (17)
C16—N12—H12A	120.0	C36—N32—H32A	120.0
C16—N12—H12B	120.0	C36—N32—H32B	120.0
H12A—N12—H12B	120.0	H32A—N32—H32B	120.0
C25—N21—C21	116.72 (16)	Co1—O1—H1O1	122.5
C25—N21—Co1	121.72 (12)	Co1—O1—H2O1	123.2
C21—N21—Co1	121.48 (13)	H1O1—O1—H2O1	103.7
N21—C21—C22	123.09 (18)	H1O2—O2—H2O2	107.4
N21—C21—H21	118.5	H1O3—O3—H2O3	105.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···S2ⁱ	0.95	2.96	3.646 (2)	130
C14—H14···S1ⁱⁱ	0.95	2.84	3.785 (2)	172
C15—H15···O21ⁱⁱⁱ	0.95	2.45	3.324 (3)	153
N12—H12A···O31^iv	0.88	2.07	2.922 (2)	163
N12—H12B···S1ⁱⁱ	0.88	2.74	3.592 (2)	164
C21—H21···N2	0.95	2.65	3.245 (3)	122
C22—H22···O4	0.95	2.49	3.234 (2)	136
C24—H24···O2	0.95	2.58	3.423 (3)	149
C25—H25···N1	0.95	2.49	3.107 (2)	122
N22—H22A···S1^v	0.88	2.79	3.6484 (18)	165
N22—H22B···O2	0.88	2.04	2.873 (2)	158
C32—H32···S2ⁱⁱⁱ	0.95	3.00	3.826 (2)	146
N32—H32A···O2^vi	0.88	2.25	3.121 (2)	172
N32—H32B···S2ⁱⁱⁱ	0.88	2.57	3.4083 (19)	160
O1—H1O1···O21ⁱⁱⁱ	0.84	1.96	2.7858 (19)	166
O1—H2O1···O21^vii	0.84	2.01	2.8106 (19)	158
O2—H1O2···O3^viii	0.84	1.83	2.650 (3)	164
O2—H2O2···N1^ix	0.84	2.60	3.337 (2)	148
O2—H2O2···N31^ix	0.84	2.66	3.363 (2)	143
O3—H1O3···O31	0.84	2.17	2.966 (3)	158
O3—H2O3···O4^x	0.84	2.20	2.963 (2)	152
O4—H1O4···O11^xi	0.84	1.91	2.723 (2)	163

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x, y, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) x−1/2, −y+3/2, z−1/2; (v) x+1/2, y+1/2, z; (vi) x, y−1, z; (vii) x−1/2, y−1/2, z; (viii) x, y+1, z; (ix) −x+1/2, −y+3/2, −z+1; (x) −x+1, −y+1, −z+1; (xi) x+1/2, y−1/2, z.

Acknowledgements

This project was supported by the Deutsche Forschungsgemeinschaft (project No. NA 720/5–1) and the State of Schleswig-Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

References

Boeckmann, J., Wriedt, M. & Näther, C. (2012). Chem. Eur. J. 18, 5284–5289. Web of Science CSD CrossRef CAS PubMed Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Caneschi, A., Gatteschi, D., Lalioti, N., Sangregorio, C., Sessoli, R., Venturi, G., Vindigni, A. R., Rettori, A., Pini, M. G. & Novak, M. A. (2001). Angew. Chem. Int. Ed. 40, 1760–1763. CrossRef CAS Google Scholar
Đaković, M., Jagličić, Z., Kozlevčar, B. & Popović, Z. (2010). Polyhedron, 29, 1910–1917. Google Scholar
Dhers, S., Feltham, H. L. C. & Brooker, S. (2015). Coord. Chem. Rev. 296, 24–44. Web of Science CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, R., Li, L., Wang, X., Yang, P., Wang, C., Liao, D. & Sutter, J.-P. (2010). Chem. Commun. 46, 2566–2568. Web of Science CSD CrossRef Google Scholar
Näther, C., Wöhlert, S., Boeckmann, J., Wriedt, M. & Jess, I. (2013). Z. Anorg. Allg. Chem. 639, 2696–2714. Google Scholar
Neumann, T., Jess, I. & Näther, C. (2016a). Acta Cryst. E72, 922–925. Web of Science CSD CrossRef IUCr Journals Google Scholar
Neumann, T., Jess, I. & Näther, C. (2016b). Acta Cryst. E72, 1077–1080. CSD CrossRef IUCr Journals Google Scholar
Sekiya, R. & Nishikiori, S. (2005). Chem. Lett. 34, 1076–1077. Web of Science CSD CrossRef CAS Google Scholar
Sekiya, R., Nishikiori, S. & Kuroda, R. (2009). CrystEngComm, 11, 2251–2253. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Werner, J., Rams, M., Tomkowicz, Z. & Näther, C. (2014). Dalton Trans. 43, 17333–17342. Web of Science CSD CrossRef CAS PubMed Google Scholar
Werner, J., Rams, M., Tomkowicz, Z., Runčevski, T., Dinnebier, R. E., Suckert, S. & Näther, C. (2015a). Inorg. Chem. 54, 2893–2901. Web of Science CSD CrossRef CAS PubMed Google Scholar
Werner, J., Runčevski, T., Dinnebier, R. E., Ebbinghaus, S. G., Suckert, S. & Näther, C. (2015c). Eur. J. Inorg. Chem. 2015, 3236–3245. Web of Science CSD CrossRef CAS Google Scholar
Werner, J., Tomkowicz, Z., Rams, M., Ebbinghaus, S. G., Neumann, T. & Näther, C. (2015b). Dalton Trans. 44, 14149–14158. Web of Science CSD CrossRef CAS PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wöhlert, S., Tomkowicz, Z., Rams, M., Ebbinghaus, S. G., Fink, L., Schmidt, M. U. & Näther, C. (2014). Inorg. Chem. 53, 8298–8310. Web of Science PubMed Google Scholar
Yang, G., Zhu, H.-G., Liang, B.-H. & Chen, X.-M. (2001). J. Chem. Soc. Dalton Trans. pp. 580–585. Web of Science CSD CrossRef Google Scholar

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