Crystal structure of a CoII coordination polymer with a dipyridyl ligand: catena-poly[[bis­(nitrato-κ2O,O′)cobalt(II)]-μ-N-(pyridin-2-ylmeth­yl)pyridine-3-amine-κ3N,N′:N′′]

Moon, S.-H.; Kang, Y.; Park, K.-M.

doi:10.1107/S205698901701475X

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 73| Part 11| November 2017| Pages 1696-1699

https://doi.org/10.1107/S205698901701475X

Open

access

Crystal structure of a Co^II coordination polymer with a dipyridyl ligand: catena-poly[[bis(nitrato-κ²O,O′)cobalt(II)]-μ-N-(pyridin-2-ylmethyl)pyridine-3-amine-κ³N,N′:N′′]

Suk-Hee Moon,^a Youngjin Kang ^b ^* and Ki-Min Park ^c ^*

^aDepartment of Food and Nutrition, Kyungnam College of Information and Technology, Busan 47011, Republic of Korea, ^bDivision of Science Education, Kangwon National University, Chuncheon 24341, Republic of Korea, and ^cResearch institute of Natural Science, Gyeongsang National University, Jinju 52828, Republic of Korea
^*Correspondence e-mail: kangy@kangwon.ac.kr, kmpark@gnu.ac.kr

Edited by G. S. Nichol, University of Edinburgh, Scotland (Received 6 September 2017; accepted 12 October 2017; online 20 October 2017)

The asymmetric unit of the title compound, [Co(NO₃)₂L]_n, L = N-(pyridine-2-ylmethyl)pyridine-3-amine (C₁₁H₁₁N₃), contains one Co^II centre, two nitrate anions and one L ligand in which the C_py—C—N—C_py moiety adopts a trans conformation with a torsion angle of −173.1 (3) Å. The coordination geometry of the Co^II atom is a distorted pentagonal bipyramid. One amine N atom from the L ligand and four O atoms from two η²-nitrato ligands form the basal plane and two pyridyl N atoms from two symmetry-related L ligands occupy the apical positions [N—Co—N = 171.86 (11)°]. The displacement of the central Co^II atom from the basal plane (r.m.s. deviation = 0.085 Å) is 0.1491 (12) Å. Each bidentate nitrate group is bonded asymmetrically to the cobalt atom in an chelating fashion. The Co^II ions are linked by the L ligands to form a zigzag chain propagating along the c-axis direction. Within the zigzag chain, C—H⋯O hydrogen bonds between the ligands and the nitrate anions are observed. Adjacent zigzag chains are connected via intermolecular π–π stacking interactions [centroid-to-centroid distance = 3.844 (2) Å] between the pyridine rings together with N/C—H⋯O hydrogen bonds.

Keywords: crystal structure; dipyridyl-type ligand; cobalt(II); zigzag chain; metal-organic framework.

CCDC reference: 1579473

1. Chemical context

Over the past few decades, the continuous efforts have been devoted to the design and development of metal–organic frameworks (MOFs) obtained by linking transition metal centers with several organic bridging ligands. In particular, rigid or flexible dipyridyl-type ligands have been widely used to construct MOFs with attractive structures and potential applications in materials chemistry (Silva et al., 2015 ; Furukawa et al., 2014 ; Wang et al., 2012 ; Leong & Vittal, 2011 ). Our group has also tried to develop diverse dipyridyl-type MOFs with intriguing topologies including a cyclic dimer (Moon et al., 2011 ), zigzag chain (Moon et al., 2016 ), double helical chain (Lee et al., 2015 ), helical looped-chain (Ju et al., 2014 ) and two-dimensional pseudo-polyrotaxane network (Im et al., 2017 ), and reported their crystal structures. As a part of our ongoing efforts to develop dipyridyl-type MOFs with different structural motifs, we prepared the title compound obtained by the reaction of cobalt(II) nitrate with a dipyridyl ligand, namely N-(pyridine-2-ylmethyl)pyridine-3-amine. Herein, we report its crystal structure, which is the first example of a Co^II complex with an N-(pyridine-2-ylmethyl)pyridine-3-amine ligand.

2. Structural commentary

The asymmetric unit of the title compound comprises one Co^II atom, one L ligand and two nitrate anions, which coordinate the cobalt ion in a bidentate chelating fashion. The coordination geometry of the Co^II atom is distorted pentagonal bipyramidal with the five basal sites being occupied by one amine N atom from the L ligand and four O atoms from two η²-nitrato ligands and the two apical positions occupied by two pyridyl N atoms from two symmetry-related L ligands [N1—Co1—N3ⁱ = 171.86 (11)°; symmetry code: (i) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ] (Fig. 1). The central Co^II atom is displaced by 0.1491 (12) Å from the basal plane (r.m.s. deviation = 0.085 Å). The Co—N distances in apical positions [Co1—N1 = 2.120 (3), Co1—N3ⁱ = 2.125 (3) Å] are slightly shorter than that of the basal [Co1—N2 = 2.191 (3) Å]. The largest deviations from the NO₄ basal plane around the cobalt center involve the angles O2—Co1—O3 [55.81 (11)°] and N2—Co1—O5 [84.19 (9)°]. This distortion may reflect the narrow bite angles of the bidentate nitrate ions.

Figure 1
A view of the molecular structure of the title compound, showing the atom-numbering scheme [symmetry codes: (i) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (ii) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ]. Displacement ellipsoids are drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radius.

The L ligand adopts a stretched trans conformation with the C5—C6—N2—C7 torsion angle being −173.1 (3) Å. The terminal pyridine rings of the L ligand are nearly perpendicular to each other, with the dihedral angle between their mean planes being 76.74 (12)°. Each bidentate nitrate group is bonded asymmetrically to the cobalt atom [Co1—O2 = 2.139 (3), Co1—O3 = 2.327 (3), Co1—O5 = 2.365 (2) and Co1—O6 = 2.167 (2) Å]. Each L ligand is bridged by the Co^II ions, forming –(Co-L)_n– zigzag chains propagating along the c-axis direction (Figs. 2 and 3). The zigzag chain is reinforced by several C—H⋯O hydrogen bonds (Table 2; green dashed lines in Fig. 2) between the L ligands and the nitrate O atoms.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O5ⁱⁱ	0.96	2.11	2.987 (4)	151
C1—H1⋯O2ⁱⁱⁱ	0.93	2.57	3.186 (5)	124
C6—H6A⋯O6^iv	0.97	2.54	3.413 (4)	149
C8—H8⋯O3^v	0.93	2.53	3.163 (4)	126
C9—H9⋯O5^v	0.93	2.49	3.164 (4)	130
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z; (iv) x, y, z+1; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
The zigzag chain formed through C—H⋯O hydrogen bonds (green dashed lines). H atoms not involved in intermolecular interactions have been omitted for clarity.

Figure 3
The three-dimensional structure formed through intermolecular π–π stacking interactions (black dashed lines) and N/C—H⋯O hydrogen bonds (green dashed lines). H atoms not involved in intermolecular interactions have been omitted for clarity.

3. Supramolecular features

In the crystal of the title compound, adjacent zigzag chains are linked by intermolecular π–π stacking interactions [black dashed lines in Fig. 3; Cg1⋯Cg1ⁱⁱ = 3.844 (2) Å; Cg1 is the centroid of the N1/C1–C5 ring; symmetry code: (ii) −x, −y + 1, −z + 1] between the pyridine rings and C—H⋯O hydrogen bonds between pyridyl H atoms and nitrate O atoms (Table 1; green dashed lines in Fig. 3), forming layers extending parallel to the (100) plane. The layers are further connected by intermolecular N—H⋯O hydrogen bonds (Table 2; green dashed lines in Fig. 3) between amine H atoms and nitrate O atoms.

Table 1
Selected geometric parameters (Å, °)

Co1—N1	2.120 (3)	Co1—N2	2.191 (3)
Co1—N3ⁱ	2.125 (3)	Co1—O3	2.327 (3)
Co1—O2	2.139 (3)	Co1—O5	2.365 (2)
Co1—O6	2.167 (2)

N1—Co1—N3ⁱ	171.86 (11)	N3ⁱ—Co1—O3	92.35 (10)
N1—Co1—O2	90.67 (11)	O2—Co1—O3	55.81 (11)
N3ⁱ—Co1—O2	97.46 (11)	O6—Co1—O3	135.30 (10)
N1—Co1—O6	90.57 (10)	N2—Co1—O3	84.11 (10)
N3ⁱ—Co1—O6	90.67 (10)	N1—Co1—O5	81.99 (10)
O2—Co1—O6	79.58 (11)	N3ⁱ—Co1—O5	92.07 (10)
N1—Co1—N2	77.43 (10)	O2—Co1—O5	134.56 (10)
N3ⁱ—Co1—N2	96.52 (10)	O6—Co1—O5	55.89 (9)
O2—Co1—N2	137.86 (11)	N2—Co1—O5	84.19 (9)
O6—Co1—N2	139.71 (10)	O3—Co1—O5	167.89 (10)
N1—Co1—O3	92.42 (10)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

4. Database survey

A search of the Cambridge Structural Database (Version 5.38, update May 2017; Groom et al., 2016 ) for the compounds obtained by the reaction of transition metal ions and the L ligand gave 11 hits. Three (AQEGAG, AQEGEK, AQEGIO) are Hg^II complexes and seven (CEZPAA, DURFON, POFKUS, PONTUJ, VIPTOF, WIHWUH, WIHXOC) of them are Ag^I complexes. The remaining one is a Zn^II complex (DUVPER). There are no metal complexes that are similar to the structure of the Co^II complex described above. Therefore, the title compound is the first example of a Co^II complex with an L ligand.

5. Synthesis and crystallization

The L ligand was synthesized according to a literature method (Lee et al., 2013 ). X-ray-quality single crystals of the title compound were obtained by slow evaporation of an acetonitrile solution of the L ligand with Co(NO₃)₂·6H₂O in the molar ratio 1:1.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The amine H atom was located from a difference-Fourier map and refined with riding constraints [d(N—H) = 0.96 Å]. All other H atoms were positioned geometrically and refined as riding, with d(C—H) = 0.93 Å for Csp²—H and 0.97 Å for methylene C—H. For all H atoms, U_iso(H) = 1.2U_eq of the parent atom.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(NO₃)₂(C₁₁H₁₁N₃)]
M_r	368.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.4550 (13), 17.662 (2), 7.9653 (10)
β (°)	108.160 (3)
V (Å³)	1397.6 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.27
Crystal size (mm)	0.32 × 0.27 × 0.23

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.644, 0.725
No. of measured, independent and observed [I > 2σ(I)] reflections	7841, 2737, 1695
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.087, 0.96
No. of reflections	2737
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.31
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2010 ), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1579473

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S205698901701475X/nk2241sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901701475X/nk2241Isup2.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 (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-κ²O,O')cobalt(II)]-µ-N-(pyridin-2-ylmethyl)pyridine-3-amine-κ³N,N':N''] top

Crystal data top

[Co(NO₃)₂(C₁₁H₁₁N₃)]	F(000) = 748
M_r = 368.18	D_x = 1.750 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.4550 (13) Å	Cell parameters from 2739 reflections
b = 17.662 (2) Å	θ = 2.1–26.0°
c = 7.9653 (10) Å	µ = 1.27 mm⁻¹
β = 108.160 (3)°	T = 298 K
V = 1397.6 (3) Å³	Block, violet
Z = 4	0.32 × 0.27 × 0.23 mm

Data collection top

Bruker APEXII CCD diffractometer	1695 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.070
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 26.0°, θ_min = 2.4°
T_min = 0.644, T_max = 0.725	h = −8→12
7841 measured reflections	k = −21→18
2737 independent reflections	l = −9→9

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0331P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max < 0.001
2737 reflections	Δρ_max = 0.26 e Å⁻³
208 parameters	Δρ_min = −0.31 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	0.27153 (4)	0.39860 (2)	0.26458 (6)	0.03391 (16)
N1	0.1788 (3)	0.48757 (15)	0.3629 (3)	0.0358 (7)
N2	0.3601 (3)	0.38625 (14)	0.5512 (3)	0.0326 (7)
H2N	0.4398	0.4164	0.5764	0.039*
N3	0.3901 (3)	0.18597 (14)	0.6941 (3)	0.0343 (7)
C1	0.1212 (4)	0.54840 (19)	0.2707 (5)	0.0431 (9)
H1	0.1017	0.5474	0.1486	0.052*
C2	0.0893 (4)	0.6122 (2)	0.3468 (5)	0.0471 (10)
H2	0.0516	0.6541	0.2786	0.057*
C3	0.1144 (4)	0.6125 (2)	0.5272 (5)	0.0471 (10)
H3	0.0940	0.6550	0.5829	0.056*
C4	0.1700 (3)	0.5495 (2)	0.6242 (5)	0.0398 (9)
H4	0.1869	0.5488	0.7459	0.048*
C5	0.2005 (3)	0.48701 (18)	0.5379 (4)	0.0330 (8)
C6	0.2606 (4)	0.41626 (18)	0.6310 (4)	0.0383 (9)
H6A	0.3042	0.4268	0.7552	0.046*
H6B	0.1905	0.3790	0.6213	0.046*
C7	0.4171 (3)	0.31400 (18)	0.6103 (4)	0.0303 (8)
C8	0.3417 (3)	0.25586 (18)	0.6498 (4)	0.0345 (8)
H8	0.2533	0.2660	0.6453	0.041*
C9	0.5162 (4)	0.1726 (2)	0.6967 (5)	0.0453 (9)
H9	0.5501	0.1238	0.7224	0.054*
C10	0.5989 (4)	0.2273 (2)	0.6632 (5)	0.0489 (10)
H10	0.6870	0.2160	0.6689	0.059*
C11	0.5489 (4)	0.2985 (2)	0.6216 (5)	0.0427 (9)
H11	0.6035	0.3366	0.6008	0.051*
N4	0.0418 (3)	0.32781 (17)	0.1539 (4)	0.0423 (8)
O1	−0.0745 (3)	0.30287 (19)	0.0943 (4)	0.0832 (10)
O2	0.0852 (3)	0.37335 (16)	0.0660 (4)	0.0661 (8)
O3	0.1166 (3)	0.30993 (15)	0.2978 (4)	0.0628 (8)
N5	0.3877 (3)	0.50903 (17)	0.1413 (4)	0.0412 (8)
O4	0.4248 (3)	0.56412 (17)	0.0738 (4)	0.0752 (9)
O5	0.4407 (3)	0.49125 (14)	0.2962 (3)	0.0500 (7)
O6	0.2877 (3)	0.47059 (14)	0.0518 (3)	0.0517 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0436 (3)	0.0265 (2)	0.0319 (3)	0.0006 (2)	0.0121 (2)	−0.0005 (2)
N1	0.0423 (18)	0.0294 (16)	0.0357 (18)	0.0051 (13)	0.0120 (14)	−0.0007 (14)
N2	0.0346 (16)	0.0276 (16)	0.0370 (16)	0.0011 (12)	0.0132 (13)	0.0031 (13)
N3	0.044 (2)	0.0293 (16)	0.0318 (17)	0.0018 (13)	0.0147 (14)	0.0016 (13)
C1	0.052 (2)	0.039 (2)	0.040 (2)	0.0139 (17)	0.0157 (18)	0.0057 (18)
C2	0.054 (2)	0.033 (2)	0.053 (3)	0.0097 (17)	0.015 (2)	0.0066 (18)
C3	0.049 (2)	0.037 (2)	0.056 (3)	0.0076 (17)	0.019 (2)	−0.0097 (19)
C4	0.042 (2)	0.042 (2)	0.037 (2)	0.0042 (16)	0.0146 (18)	−0.0065 (17)
C5	0.034 (2)	0.0311 (19)	0.036 (2)	0.0020 (14)	0.0133 (16)	0.0005 (16)
C6	0.047 (2)	0.035 (2)	0.035 (2)	0.0059 (16)	0.0164 (17)	0.0011 (16)
C7	0.034 (2)	0.0294 (19)	0.0264 (18)	−0.0007 (15)	0.0080 (15)	−0.0005 (15)
C8	0.034 (2)	0.032 (2)	0.040 (2)	0.0017 (15)	0.0142 (17)	0.0049 (16)
C9	0.058 (3)	0.031 (2)	0.049 (2)	0.0120 (18)	0.020 (2)	0.0066 (17)
C10	0.041 (2)	0.043 (2)	0.070 (3)	0.0103 (18)	0.028 (2)	0.013 (2)
C11	0.044 (3)	0.036 (2)	0.053 (2)	−0.0016 (17)	0.0217 (19)	0.0038 (18)
N4	0.047 (2)	0.0347 (19)	0.047 (2)	−0.0007 (15)	0.0167 (18)	−0.0056 (16)
O1	0.057 (2)	0.088 (3)	0.096 (3)	−0.0211 (18)	0.0120 (18)	−0.014 (2)
O2	0.065 (2)	0.067 (2)	0.0587 (19)	−0.0084 (15)	0.0074 (15)	0.0029 (16)
O3	0.064 (2)	0.061 (2)	0.061 (2)	0.0070 (15)	0.0166 (17)	−0.0011 (16)
N5	0.057 (2)	0.0290 (18)	0.043 (2)	−0.0088 (15)	0.0227 (17)	−0.0023 (15)
O4	0.102 (3)	0.059 (2)	0.066 (2)	−0.0244 (17)	0.0285 (18)	0.0130 (16)
O5	0.0670 (19)	0.0443 (16)	0.0382 (16)	−0.0091 (12)	0.0155 (14)	0.0042 (13)
O6	0.0631 (19)	0.0502 (17)	0.0423 (16)	−0.0101 (14)	0.0173 (14)	−0.0049 (13)

Geometric parameters (Å, º) top

Co1—N1	2.120 (3)	C3—H3	0.9300
Co1—N3ⁱ	2.125 (3)	C4—C5	1.389 (4)
Co1—O2	2.139 (3)	C4—H4	0.9300
Co1—O6	2.167 (2)	C5—C6	1.488 (4)
Co1—N2	2.191 (3)	C6—H6A	0.9700
Co1—O3	2.327 (3)	C6—H6B	0.9700
Co1—O5	2.365 (2)	C7—C11	1.381 (4)
N1—C1	1.334 (4)	C7—C8	1.389 (4)
N1—C5	1.341 (4)	C8—H8	0.9300
N2—C7	1.425 (4)	C9—C10	1.378 (5)
N2—C6	1.475 (4)	C9—H9	0.9300
N2—H2N	0.9565	C10—C11	1.362 (5)
N3—C9	1.334 (4)	C10—H10	0.9300
N3—C8	1.339 (4)	C11—H11	0.9300
N3—Co1ⁱⁱ	2.125 (3)	N4—O3	1.211 (4)
C1—C2	1.368 (4)	N4—O1	1.240 (4)
C1—H1	0.9300	N4—O2	1.241 (4)
C2—C3	1.378 (5)	N5—O5	1.226 (3)
C2—H2	0.9300	N5—O4	1.232 (3)
C3—C4	1.376 (5)	N5—O6	1.263 (4)

N1—Co1—N3ⁱ	171.86 (11)	C4—C3—H3	120.2
N1—Co1—O2	90.67 (11)	C2—C3—H3	120.2
N3ⁱ—Co1—O2	97.46 (11)	C3—C4—C5	119.1 (3)
N1—Co1—O6	90.57 (10)	C3—C4—H4	120.4
N3ⁱ—Co1—O6	90.67 (10)	C5—C4—H4	120.4
O2—Co1—O6	79.58 (11)	N1—C5—C4	121.2 (3)
N1—Co1—N2	77.43 (10)	N1—C5—C6	115.6 (3)
N3ⁱ—Co1—N2	96.52 (10)	C4—C5—C6	123.2 (3)
O2—Co1—N2	137.86 (11)	N2—C6—C5	109.4 (3)
O6—Co1—N2	139.71 (10)	N2—C6—H6A	109.8
N1—Co1—O3	92.42 (10)	C5—C6—H6A	109.8
N3ⁱ—Co1—O3	92.35 (10)	N2—C6—H6B	109.8
O2—Co1—O3	55.81 (11)	C5—C6—H6B	109.8
O6—Co1—O3	135.30 (10)	H6A—C6—H6B	108.2
N2—Co1—O3	84.11 (10)	C11—C7—C8	117.7 (3)
N1—Co1—O5	81.99 (10)	C11—C7—N2	120.4 (3)
N3ⁱ—Co1—O5	92.07 (10)	C8—C7—N2	121.9 (3)
O2—Co1—O5	134.56 (10)	N3—C8—C7	123.1 (3)
O6—Co1—O5	55.89 (9)	N3—C8—H8	118.4
N2—Co1—O5	84.19 (9)	C7—C8—H8	118.4
O3—Co1—O5	167.89 (10)	N3—C9—C10	123.3 (3)
C1—N1—C5	118.6 (3)	N3—C9—H9	118.3
C1—N1—Co1	125.0 (2)	C10—C9—H9	118.3
C5—N1—Co1	115.4 (2)	C11—C10—C9	118.6 (3)
C7—N2—C6	117.2 (2)	C11—C10—H10	120.7
C7—N2—Co1	115.52 (19)	C9—C10—H10	120.7
C6—N2—Co1	106.71 (19)	C10—C11—C7	119.9 (3)
C7—N2—H2N	100.5	C10—C11—H11	120.0
C6—N2—H2N	113.2	C7—C11—H11	120.0
Co1—N2—H2N	102.7	O3—N4—O1	122.4 (3)
C9—N3—C8	117.3 (3)	O3—N4—O2	117.5 (3)
C9—N3—Co1ⁱⁱ	121.8 (2)	O1—N4—O2	120.1 (4)
C8—N3—Co1ⁱⁱ	120.9 (2)	N4—O2—Co1	97.3 (2)
N1—C1—C2	123.4 (3)	N4—O3—Co1	89.1 (2)
N1—C1—H1	118.3	O5—N5—O4	122.4 (3)
C2—C1—H1	118.3	O5—N5—O6	117.7 (3)
C1—C2—C3	118.1 (3)	O4—N5—O6	119.7 (3)
C1—C2—H2	120.9	N5—O5—Co1	88.92 (19)
C3—C2—H2	120.9	N5—O6—Co1	97.3 (2)
C4—C3—C2	119.5 (3)

C5—N1—C1—C2	3.5 (5)	C9—N3—C8—C7	−1.1 (5)
Co1—N1—C1—C2	−165.0 (3)	Co1ⁱⁱ—N3—C8—C7	177.1 (2)
N1—C1—C2—C3	−2.0 (5)	C11—C7—C8—N3	−1.4 (5)
C1—C2—C3—C4	−0.1 (5)	N2—C7—C8—N3	175.4 (3)
C2—C3—C4—C5	0.5 (5)	C8—N3—C9—C10	2.6 (5)
C1—N1—C5—C4	−3.0 (5)	Co1ⁱⁱ—N3—C9—C10	−175.6 (3)
Co1—N1—C5—C4	166.5 (2)	N3—C9—C10—C11	−1.5 (6)
C1—N1—C5—C6	177.9 (3)	C9—C10—C11—C7	−1.3 (5)
Co1—N1—C5—C6	−12.5 (4)	C8—C7—C11—C10	2.6 (5)
C3—C4—C5—N1	1.1 (5)	N2—C7—C11—C10	−174.2 (3)
C3—C4—C5—C6	−179.9 (3)	O3—N4—O2—Co1	−6.4 (3)
C7—N2—C6—C5	−173.1 (3)	O1—N4—O2—Co1	173.0 (3)
Co1—N2—C6—C5	−41.8 (3)	O1—N4—O3—Co1	−173.5 (3)
N1—C5—C6—N2	37.5 (4)	O2—N4—O3—Co1	5.8 (3)
C4—C5—C6—N2	−141.5 (3)	O4—N5—O5—Co1	173.0 (3)
C6—N2—C7—C11	−145.9 (3)	O6—N5—O5—Co1	−4.0 (3)
Co1—N2—C7—C11	87.0 (3)	O5—N5—O6—Co1	4.4 (3)
C6—N2—C7—C8	37.4 (4)	O4—N5—O6—Co1	−172.7 (3)
Co1—N2—C7—C8	−89.8 (3)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) 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
N2—H2N···O5ⁱⁱⁱ	0.96	2.11	2.987 (4)	151
C1—H1···O2^iv	0.93	2.57	3.186 (5)	124
C6—H6A···O6^v	0.97	2.54	3.413 (4)	149
C8—H8···O3ⁱⁱ	0.93	2.53	3.163 (4)	126
C9—H9···O5ⁱⁱ	0.93	2.49	3.164 (4)	130

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

Funding information

This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2015R1D1A3A01020410 and NRF-2016R1D1A1B01012630).

References

Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Furukawa, S., Reboul, J., Diring, S., Sumida, K. & Kitagawa, S. (2014). Chem. Soc. Rev. 43, 5700–5734. Web of Science CrossRef CAS PubMed
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
Im, H., Lee, E., Moon, S.-H., Lee, S. S., Kim, T. H. & Park, K.-M. (2017). Bull. Korean Chem. Soc. 38, 127–129. CSD CrossRef CAS
Ju, H., Lee, E., Moon, S.-H., Lee, S. S. & Park, K.-M. (2014). Bull. Korean Chem. Soc. 35, 3658–3660. Web of Science CSD CrossRef CAS
Lee, E., Ju, H., Moon, S.-H., Lee, S. S. & Park, K.-M. (2015). Bull. Korean Chem. Soc. 36, 1532–1535. Web of Science CrossRef CAS
Lee, E., Ryu, H., Moon, S.-H. & Park, K.-M. (2013). Bull. Korean Chem. Soc. 34, 3477–3480. Web of Science CSD CrossRef CAS
Leong, W. L. & Vittal, J. J. (2011). Chem. Rev. 111, 688–764. Web of Science CrossRef CAS PubMed
Moon, S.-H., Kang, D. & Park, K.-M. (2016). Acta Cryst. E72, 1513–1516. Web of Science CSD CrossRef IUCr Journals
Moon, S.-H., Kim, T. H. & Park, K.-M. (2011). Acta Cryst. E67, m1769–m1770. CSD CrossRef IUCr Journals
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals
Silva, P., Vilela, S. M. F., Tomé, J. P. C. & Almeida Paz, F. A. (2015). Chem. Soc. Rev. 44, 6774–6803. Web of Science CrossRef CAS PubMed
Wang, C., Zhang, T. & Lin, W. (2012). Chem. Rev. 112, 1084–1104. Web of Science CrossRef CAS PubMed
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.