Crystal structure of a looped-chain CoII coordination polymer: catena-poly[[bis­(nitrato-κO)cobalt(II)]bis­[μ-bis­(pyridin-3-ylmeth­yl)sulfane-κ2N:N′]]

Moon, S.-H.; Seo, J.; Park, K.-M.

doi:10.1107/S2056989017014980

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Volume 73| Part 11| November 2017| Pages 1700-1703

https://doi.org/10.1107/S2056989017014980

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Crystal structure of a looped-chain Co^II coordination polymer: catena-poly[[bis(nitrato-κO)cobalt(II)]bis[μ-bis(pyridin-3-ylmethyl)sulfane-κ²N:N′]]

Suk-Hee Moon,^a Joobeom Seo ^b ^* and Ki-Min Park ^c ^*

^aDepartment of Food and Nutrition, Kyungnam College of Information and Technology, Busan 47011, Republic of Korea, ^bMineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon 34132, Republic of Korea, and ^cResearch institute of Natural Science, Gyeongsang National University, Jinju 52828, Republic of Korea
^*Correspondence e-mail: joobeomi@kigam.re.kr, kmpark@gnu.ac.kr

Edited by P. C. Healy, Griffith University, Australia (Received 14 October 2017; accepted 16 October 2017; online 20 October 2017)

The asymmetric unit of the title compound, [Co(NO₃)₂(C₁₂H₁₂N₂S)₂]_n, contains a bis(pyridin-3-ylmethyl)sulfane (L) ligand, an NO₃⁻ anion and half a Co^II cation, which lies on an inversion centre. The Co^II cation is six-coordinated, being bound to four pyridine N atoms from four symmetry-related L ligands. The remaining coordination sites are occupied by two O atoms from two symmetry-related nitrate anions in a monodentate manner. Thus, the Co^II centre adopts a distorted octahedral geometry. Two symmetry-related L ligands are connected by two symmetry-related Co^II cations, forming a 20-membered cyclic dimer, in which the Co^II atoms are separated by 10.2922 (7) Å. The cyclic dimers are connected to each other by sharing Co^II atoms, giving rise to the formation of an infinite looped chain propagating along the [101] direction. Intermolecular C—H⋯π (H⋯ring centroid = 2.89 Å) interactions between one pair of corresponding L ligands and C—H⋯O hydrogen bonds between the L ligands and the nitrate anions occur in the looped chain. In the crystal, adjacent looped chains are connected by intermolecular π–π stacking interactions [centroid-to-centroid distance = 3.8859 (14) Å] and C—H⋯π hydrogen bonds (H⋯ring centroid = 2.65 Å), leading to the formation of layers parallel to (101). These layers are further connected through C—H⋯O hydrogen bonds between the layers, resulting in the formation of a three-dimensional supramolecular architecture.

Keywords: crystal structure; cobalt(II); dipyridyl ligand; looped chain; hydrogen bonding; π–π interactions.

CCDC reference: 1580230

1. Chemical context

Over the last two decades, numerous one-dimensional coordination polymers have been developed, not only because of their fascinating architectures but also their potential applications as functional materials (Furukawa et al., 2014 ; Silva et al., 2015 ). In this area of research, dipyridyl-type molecules as organic building blocks have been widely used to construct diverse one-dimensional self-assembled coordination polymers with intriguing structural topologies (Leong & Vittal, 2011 ; Wang et al., 2012 ). Our group has also developed several one-dimensional coordination polymers with fascinating topologies such as zigzag (Lee et al., 2013 ; Moon et al., 2016 ), helical (Moon et al., 2014 , 2015 ), double helical (Lee et al., 2015 ), looped chain (Ju et al., 2014 ) and ribbon-type double-stranded (Moon et al., 2017 ; Park et al., 2010 ) structures using dipyridyl-type ligands. In an extension of our research, the title compound was prepared by the reaction of cobalt(II) nitrate with bis(pyridin-3-ylmethyl)sulfane (L) as a flexible dipyridyl-type ligand, synthesized using a literature procedure (Park et al., 2010; Lee et al., 2012 ). Herein, we report the crystal structure of the title compound, which adopts a one-dimensional looped-chain structure.

2. Structural commentary

As illustrated in Fig. 1, the asymmetric unit of the title compound consists of one Co^II cation located on an inversion centre, one (pyridin-3-ylmethyl)sulfane ligand, L, and one NO₃⁻ anion. The Co^II cation is coordinated by four pyridine N atoms from four symmetry-related L ligands. In addition, the Co^II cation binds to two O atoms of two symmetry-related monodentate nitrate anions, forming a distorted octahedral CoN₄O₂ coordination. Selected bond lengths and angles around the Co1 atom are listed in Table 1. The N1- and N2-pyridine rings coordinated to the Co^II centre are tilted by 70.75 (7)° with respect to each other (Fig. 1).

Table 1
Selected geometric parameters (Å, °)

Co1—O1	2.1414 (16)	Co1—N2ⁱ	2.1907 (18)
Co1—N1	2.1571 (17)

O1ⁱⁱ—Co1—O1	180.0	N1—Co1—N2ⁱ	92.32 (6)
O1—Co1—N1	85.34 (7)	O1—Co1—N2ⁱⁱⁱ	88.21 (7)
O1—Co1—N1ⁱⁱ	94.66 (7)	N1—Co1—N2ⁱⁱⁱ	87.68 (6)
N1—Co1—N1ⁱⁱ	180.0	N2ⁱ—Co1—N2ⁱⁱⁱ	180.0
O1—Co1—N2ⁱ	91.79 (7)
Symmetry codes: (i) x+1, y, z+1; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z.

Figure 1
View of the cyclic dimer structure of the title compound, showing the geometry around Co^II centre and the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Intermolecular C—H⋯π and C—H⋯O hydrogen bonds are represented by yellow and black dashed lines, respectively [symmetry codes: (i) x + 1, y, z + 1; (ii) −x + 1, −y + 1, −z + 1; (iii) −x, −y + 1, −z; (iv) x − 1, y, z − 1].

Two symmetry-related L ligands bridge two Co^II atoms, resulting in the formation of a 20-membered cyclic dimer with a Co⋯Co separation of 10.2922 (7) Å. The cyclic dimers are connected by sharing Co^II atoms, leading to the formation of an infinite looped chain propagating along the [101] direction. An intermolecular C7—H7B⋯ Cg2ⁱ interactions [H⋯π = 2.89 Å; Table 2; yellow dashed lines in Fig. 1; Cg2 is the centroid of atoms N2/C8–C12; symmetry code: (i) −x, −y + 1, −z] between one pair of corresponding L ligands and several C—H⋯O hydrogen bonds between the L ligands and the NO₃⁻ anions (Table 2; black dashed lines in Fig. 1) contribute to the stabilization of the looped chain.

Table 2
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the N2/C8–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O3^iv	0.93	2.60	3.466 (3)	155
C5—H5⋯O2ⁱⁱ	0.93	2.30	3.171 (3)	157
C9—H9⋯O2ⁱⁱ	0.93	2.54	3.373 (3)	149
C11—H11⋯O1ⁱⁱⁱ	0.93	2.43	3.032 (3)	122
C12—H12⋯O1^v	0.93	2.53	3.134 (3)	123
C12—H12⋯O2^v	0.93	2.59	3.219 (3)	125
C6—H6A⋯Cg2^vi	0.97	2.65	3.546 (3)	154
C7—H7B⋯Cg2ⁱⁱⁱ	0.97	2.89	3.565 (3)	127
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z; (iv) -x+2, -y+1, -z+1; (v) x-1, y, z-1; (vi) -x, -y+2, -z.

3. Supramolecular features

Adjacent looped chains in the structure are connected by intermolecular π–π stacking interactions between the N1-pyridine rings [Cg1⋯Cg1ⁱⁱ = 3.8859 (14) Å; yellow dashed lines in Fig. 2; Cg1 is the centroid of atoms N1/C1–C5; symmetry code: (ii) −x + 1, −y + 2, −z + 1] together with intermolecular C6—H6A⋯Cg2ⁱⁱⁱ hydrogen bonds [H⋯π = 2.65 Å; Table 2; black dashed lines in Fig. 2; symmetry code: (iii) −x, −y + 2, −z], generating layers parallel to (101). Neighboring layers are packed by C1—H1⋯O3^iv hydrogen bonds [H⋯O = 2.60 Å; Table 2; yellow dashed lines in Fig. 3; symmetry code: (iv) −x + 2, −y + 1, −z + 1] between pyridine H atoms and nitrogen O atoms, resulting in the formation of a three-dimensional supramolecular architecture.

Figure 2
The supramolecular layer formed by intermolecular π–π stacking interactions (yellow dashed lines) and C—H⋯π hydrogen bonds (black dashed lines) between the looped chains. H atoms not involved in intermolecular interactions have been omitted for clarity.

Figure 3
The three-dimensional supramolecular network formed via intermolecular C—H⋯O hydrogen bonds (yellow dashed lines) between the layers. H atoms not involved in intermolecular interactions have been omitted for clarity.

4. Synthesis and crystallization

The L ligand was synthesized according to a literature method (Park et al., 2010; Lee et al., 2012). Crystals of the title compound were grown by slow evaporation of a methanol/H₂O (2:1) solution of the L ligand with Co(NO₃)₂·6H₂O in a 2:1 molar ratio.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and refined as riding: C—H = 0.93 Å for Csp²—H and 0.97 Å for methylene C—H with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[Co(NO₃)₂(C₁₂H₁₂N₂S)₂]
M_r	615.54
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	298
a, b, c (Å)	8.1620 (7), 8.8158 (8), 9.5078 (8)
α, β, γ (°)	98.531 (2), 109.218 (2), 92.062 (2)
V (Å³)	636.22 (10)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.89
Crystal size (mm)	0.45 × 0.30 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.634, 0.896
No. of measured, independent and observed [I > 2σ(I)] reflections	3659, 2456, 2082
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.088, 1.04
No. of reflections	2456
No. of parameters	178
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.37
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1580230

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989017014980/hg5499sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017014980/hg5499Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

catena-Poly[[bis(nitrato-κO)cobalt(II)]bis[µ-bis(pyridin-3-ylmethyl)sulfane-κ²N:N']] top

Crystal data top

[Co(NO₃)₂(C₁₂H₁₂N₂S)₂]	Z = 1
M_r = 615.54	F(000) = 317
Triclinic, P1	D_x = 1.607 Mg m⁻³
a = 8.1620 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8158 (8) Å	Cell parameters from 3659 reflections
c = 9.5078 (8) Å	θ = 2.3–26.0°
α = 98.531 (2)°	µ = 0.89 mm⁻¹
β = 109.218 (2)°	T = 298 K
γ = 92.062 (2)°	Plate, violet
V = 636.22 (10) Å³	0.45 × 0.30 × 0.15 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	2082 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.040
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 26.0°, θ_min = 2.3°
T_min = 0.634, T_max = 0.896	h = −7→10
3659 measured reflections	k = −10→10
2456 independent reflections	l = −11→7

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0488P)² + 0.1617P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2456 reflections	Δρ_max = 0.33 e Å⁻³
178 parameters	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.

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

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.5000	0.5000	0.02620 (13)
S1	0.20509 (7)	0.89446 (7)	−0.01804 (7)	0.03834 (17)
N1	0.5427 (2)	0.7131 (2)	0.42595 (19)	0.0294 (4)
N2	−0.3498 (2)	0.5946 (2)	−0.2639 (2)	0.0294 (4)
N3	0.8472 (2)	0.3452 (2)	0.4702 (2)	0.0353 (4)
O1	0.7307 (2)	0.4382 (2)	0.4536 (2)	0.0459 (4)
O2	0.9392 (2)	0.3314 (3)	0.5987 (2)	0.0623 (6)
O3	0.8698 (3)	0.2729 (2)	0.3594 (2)	0.0600 (5)
C1	0.7012 (3)	0.7803 (3)	0.4459 (3)	0.0359 (5)
H1	0.7992	0.7378	0.5020	0.043*
C2	0.7239 (3)	0.9093 (3)	0.3867 (3)	0.0419 (6)
H2	0.8356	0.9533	0.4041	0.050*
C3	0.5807 (3)	0.9731 (3)	0.3014 (3)	0.0377 (5)
H3	0.5945	1.0595	0.2595	0.045*
C4	0.4158 (3)	0.9065 (2)	0.2792 (2)	0.0293 (4)
C5	0.4044 (3)	0.7788 (2)	0.3446 (2)	0.0288 (4)
H5	0.2939	0.7352	0.3316	0.035*
C6	0.2546 (3)	0.9672 (3)	0.1822 (3)	0.0345 (5)
H6A	0.2707	1.0788	0.1994	0.041*
H6B	0.1566	0.9379	0.2119	0.041*
C7	0.1232 (3)	0.6961 (3)	−0.0308 (3)	0.0345 (5)
H7A	0.1544	0.6312	−0.1080	0.041*
H7B	0.1802	0.6624	0.0648	0.041*
C8	−0.0710 (3)	0.6735 (2)	−0.0675 (2)	0.0298 (5)
C9	−0.1533 (3)	0.7008 (3)	0.0387 (3)	0.0390 (5)
H9	−0.0889	0.7344	0.1402	0.047*
C10	−0.3334 (3)	0.6773 (3)	−0.0089 (3)	0.0425 (6)
H10	−0.3915	0.6973	0.0603	0.051*
C11	−0.4259 (3)	0.6242 (3)	−0.1590 (3)	0.0369 (5)
H11	−0.5466	0.6082	−0.1889	0.044*
C12	−0.1752 (3)	0.6202 (2)	−0.2167 (2)	0.0292 (4)
H12	−0.1205	0.6011	−0.2885	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0226 (2)	0.0291 (2)	0.0237 (2)	0.00094 (15)	0.00236 (16)	0.00769 (16)
S1	0.0360 (3)	0.0407 (3)	0.0324 (3)	−0.0055 (2)	0.0012 (2)	0.0141 (2)
N1	0.0260 (9)	0.0313 (9)	0.0286 (9)	0.0012 (7)	0.0049 (7)	0.0082 (7)
N2	0.0280 (9)	0.0285 (9)	0.0279 (9)	−0.0005 (7)	0.0039 (7)	0.0067 (7)
N3	0.0288 (10)	0.0424 (11)	0.0357 (11)	−0.0022 (8)	0.0122 (8)	0.0074 (9)
O1	0.0323 (9)	0.0589 (11)	0.0496 (10)	0.0161 (8)	0.0135 (8)	0.0168 (9)
O2	0.0407 (10)	0.1040 (17)	0.0441 (11)	0.0230 (11)	0.0094 (9)	0.0258 (11)
O3	0.0686 (13)	0.0642 (13)	0.0510 (12)	0.0086 (10)	0.0314 (10)	−0.0046 (10)
C1	0.0243 (11)	0.0422 (13)	0.0367 (12)	0.0025 (9)	0.0023 (9)	0.0114 (10)
C2	0.0292 (12)	0.0469 (14)	0.0478 (14)	−0.0051 (10)	0.0093 (11)	0.0133 (11)
C3	0.0368 (12)	0.0334 (12)	0.0398 (13)	−0.0066 (9)	0.0077 (10)	0.0113 (10)
C4	0.0308 (11)	0.0282 (10)	0.0247 (10)	0.0002 (8)	0.0044 (9)	0.0040 (8)
C5	0.0238 (10)	0.0331 (11)	0.0274 (10)	−0.0003 (8)	0.0056 (8)	0.0067 (9)
C6	0.0337 (12)	0.0285 (11)	0.0370 (12)	0.0035 (9)	0.0042 (10)	0.0100 (9)
C7	0.0305 (11)	0.0330 (11)	0.0311 (11)	0.0001 (9)	−0.0008 (9)	0.0047 (9)
C8	0.0315 (11)	0.0254 (10)	0.0276 (11)	−0.0008 (8)	0.0027 (9)	0.0071 (8)
C9	0.0440 (13)	0.0419 (13)	0.0249 (11)	−0.0050 (10)	0.0051 (10)	0.0037 (9)
C10	0.0441 (14)	0.0520 (15)	0.0334 (12)	−0.0032 (11)	0.0181 (11)	0.0039 (11)
C11	0.0321 (12)	0.0444 (13)	0.0347 (12)	−0.0005 (10)	0.0117 (10)	0.0083 (10)
C12	0.0294 (11)	0.0279 (10)	0.0282 (11)	0.0004 (8)	0.0072 (9)	0.0052 (8)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.1414 (16)	C2—H2	0.9300
Co1—O1	2.1414 (16)	C3—C4	1.386 (3)
Co1—N1	2.1571 (17)	C3—H3	0.9300
Co1—N1ⁱ	2.1571 (17)	C4—C5	1.378 (3)
Co1—N2ⁱⁱ	2.1907 (18)	C4—C6	1.505 (3)
Co1—N2ⁱⁱⁱ	2.1907 (18)	C5—H5	0.9300
S1—C6	1.820 (2)	C6—H6A	0.9700
S1—C7	1.822 (2)	C6—H6B	0.9700
N1—C1	1.346 (3)	C7—C8	1.505 (3)
N1—C5	1.346 (3)	C7—H7A	0.9700
N2—C11	1.338 (3)	C7—H7B	0.9700
N2—C12	1.345 (3)	C8—C9	1.384 (3)
N2—Co1^iv	2.1907 (17)	C8—C12	1.392 (3)
N3—O3	1.219 (3)	C9—C10	1.386 (3)
N3—O2	1.232 (3)	C9—H9	0.9300
N3—O1	1.264 (2)	C10—C11	1.376 (3)
C1—C2	1.374 (3)	C10—H10	0.9300
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.378 (3)	C12—H12	0.9300

O1ⁱ—Co1—O1	180.0	C4—C3—H3	120.5
O1ⁱ—Co1—N1	94.66 (7)	C5—C4—C3	117.63 (19)
O1—Co1—N1	85.34 (7)	C5—C4—C6	120.95 (19)
O1ⁱ—Co1—N1ⁱ	85.34 (7)	C3—C4—C6	121.38 (19)
O1—Co1—N1ⁱ	94.66 (7)	N1—C5—C4	124.37 (19)
N1—Co1—N1ⁱ	180.0	N1—C5—H5	117.8
O1ⁱ—Co1—N2ⁱⁱ	88.21 (7)	C4—C5—H5	117.8
O1—Co1—N2ⁱⁱ	91.79 (7)	C4—C6—S1	112.23 (16)
N1—Co1—N2ⁱⁱ	92.32 (6)	C4—C6—H6A	109.2
N1ⁱ—Co1—N2ⁱⁱ	87.68 (6)	S1—C6—H6A	109.2
O1ⁱ—Co1—N2ⁱⁱⁱ	91.79 (7)	C4—C6—H6B	109.2
O1—Co1—N2ⁱⁱⁱ	88.21 (7)	S1—C6—H6B	109.2
N1—Co1—N2ⁱⁱⁱ	87.68 (6)	H6A—C6—H6B	107.9
N1ⁱ—Co1—N2ⁱⁱⁱ	92.32 (6)	C8—C7—S1	113.88 (15)
N2ⁱⁱ—Co1—N2ⁱⁱⁱ	180.0	C8—C7—H7A	108.8
C6—S1—C7	101.13 (11)	S1—C7—H7A	108.8
C1—N1—C5	116.71 (18)	C8—C7—H7B	108.8
C1—N1—Co1	123.98 (14)	S1—C7—H7B	108.8
C5—N1—Co1	119.10 (13)	H7A—C7—H7B	107.7
C11—N2—C12	116.94 (19)	C9—C8—C12	117.5 (2)
C11—N2—Co1^iv	121.87 (15)	C9—C8—C7	124.0 (2)
C12—N2—Co1^iv	121.15 (14)	C12—C8—C7	118.5 (2)
O3—N3—O2	120.9 (2)	C8—C9—C10	118.8 (2)
O3—N3—O1	119.8 (2)	C8—C9—H9	120.6
O2—N3—O1	119.3 (2)	C10—C9—H9	120.6
N3—O1—Co1	145.89 (15)	C11—C10—C9	119.7 (2)
N1—C1—C2	122.6 (2)	C11—C10—H10	120.2
N1—C1—H1	118.7	C9—C10—H10	120.2
C2—C1—H1	118.7	N2—C11—C10	122.9 (2)
C1—C2—C3	119.8 (2)	N2—C11—H11	118.6
C1—C2—H2	120.1	C10—C11—H11	118.6
C3—C2—H2	120.1	N2—C12—C8	124.2 (2)
C2—C3—C4	118.9 (2)	N2—C12—H12	117.9
C2—C3—H3	120.5	C8—C12—H12	117.9

O3—N3—O1—Co1	122.6 (3)	C7—S1—C6—C4	73.67 (17)
O2—N3—O1—Co1	−59.0 (4)	C6—S1—C7—C8	91.15 (17)
C5—N1—C1—C2	−0.2 (3)	S1—C7—C8—C9	−82.8 (2)
Co1—N1—C1—C2	174.55 (18)	S1—C7—C8—C12	98.0 (2)
N1—C1—C2—C3	−0.9 (4)	C12—C8—C9—C10	−1.4 (3)
C1—C2—C3—C4	1.0 (4)	C7—C8—C9—C10	179.4 (2)
C2—C3—C4—C5	0.1 (3)	C8—C9—C10—C11	1.5 (4)
C2—C3—C4—C6	−177.6 (2)	C12—N2—C11—C10	−0.5 (3)
C1—N1—C5—C4	1.4 (3)	Co1^iv—N2—C11—C10	177.10 (18)
Co1—N1—C5—C4	−173.66 (16)	C9—C10—C11—N2	−0.6 (4)
C3—C4—C5—N1	−1.3 (3)	C11—N2—C12—C8	0.6 (3)
C6—C4—C5—N1	176.39 (19)	Co1^iv—N2—C12—C8	−177.01 (15)
C5—C4—C6—S1	−95.4 (2)	C9—C8—C12—N2	0.4 (3)
C3—C4—C6—S1	82.2 (2)	C7—C8—C12—N2	179.61 (19)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z+1; (iii) −x, −y+1, −z; (iv) x−1, y, z−1.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the N2/C8–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3^v	0.93	2.60	3.466 (3)	155
C5—H5···O2ⁱ	0.93	2.30	3.171 (3)	157
C9—H9···O2ⁱ	0.93	2.54	3.373 (3)	149
C11—H11···O1ⁱⁱⁱ	0.93	2.43	3.032 (3)	122
C12—H12···O1^iv	0.93	2.53	3.134 (3)	123
C12—H12···O2^iv	0.93	2.59	3.219 (3)	125
C6—H6A···Cg2^vi	0.97	2.65	3.546 (3)	154
C7—H7B···Cg2ⁱⁱⁱ	0.97	2.89	3.565 (3)	127

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

Funding information

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2015R1D1A3A01020410).

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