Poly[[(μ-aqua)[μ4-4-(carboxyl­atometh­yl)ben­zo­ato]cobalt(II)] hemi[1,4-bis­(pyridin-4-ylmeth­yl)piper­azine] hemihydrate]

Gaskin, G.J.; LaDuca, R.L.

doi:10.1107/S241431462300648X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 7| July 2023| x230648

https://doi.org/10.1107/S241431462300648X

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Poly[[(μ-aqua)[μ₄-4-(carboxylatomethyl)benzoato]cobalt(II)] hemi[1,4-bis(pyridin-4-ylmethyl)piperazine] hemihydrate]

Gabrielle J. Gaskin ^a and Robert L. LaDuca ^a ^*

^aE-35 Holmes Hall, Michigan State University, Lyman Briggs College, 919 E. Shaw Lane, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 21 July 2023; accepted 25 July 2023; online 28 July 2023)

In the title compound, {[Co(C₉H₆O₄)(H₂O)]·0.5C₁₆H₂₀N₄·0.5H₂O}_n, two-dimensional coordination polymer slabs are held together in the three-dimensional crystal structure by means of O—H⋯N hydrogen bonding between bound water molecules and pyridyl N atoms of cocrystallized 1,4-bis(pyridin-4-ylmethyl)piperazine molecules.

Keywords: crystal structure; coordination polymer; piperazine; cobalt.

CCDC reference: 1946425

Structure description

Our group has demonstrated the utility of 1,4-bis(pyridin-4-ylmethyl)piperazine (bpmp) for the construction of divalent metal coordination polymers with a striking variety of interesting topologies (Robinson et al., 2015 ). For instance, the cobalt oxalate (ox) bpmp phase {[Co(H₂O)₄(bpmp)](ox)}_n displays cationic one-dimensional chain motifs with unligated ox moieties. A higher temperature polymorph, {[Co(ox)(bpmp)]·3H₂O}_n, manifests a threefold interpenetrated three-dimensional dia topology. Use of isophthalate (iph) as the dicarboxylate ligand afforded {[Co(iph)(bpmp)]·H₂O}_n, which exhibits a dimer-based two-dimensional layered structure (Martin et al., 2007 ). The title compound was isolated during an attempt to prepare a divalent cobalt coordination polymer containing both bpmp and 4-(carboxylatomethyl)benzoate (cmb) ligands.

The asymmetric unit of the title compound contains a divalent Co atom, a fully deprotonated cmb ligand, a bound water molecule, a cocrystallized water molecule best refined at half-occupancy, and half of an unligated bpmp molecule whose central piperazine ring is sited on a crystallographic inversion center. The Co atom is coordinated in a {CoO₆} distorted octahedral fashion (Fig. 1) with carboxylate O-atom donors from four cmb ligands in the nominal equatorial plane. The two nominally axial positions are taken up by bound water molecules. Pertinent bond distances and angles for the coordination sphere are listed in Table 1.

Table 1
Selected geometric parameters (Å, °)

Co1—O1	2.011 (2)	Co1—O4ⁱⁱⁱ	2.140 (2)
Co1—O2ⁱ	2.029 (2)	Co1—O5	2.139 (2)
Co1—O4ⁱⁱ	2.094 (2)	Co1—O5ⁱ	2.169 (2)

O1—Co1—O2ⁱ	177.55 (9)	O2ⁱ—Co1—O5ⁱ	87.29 (9)
O1—Co1—O4ⁱⁱⁱ	92.37 (9)	O4ⁱⁱ—Co1—O4ⁱⁱⁱ	170.65 (6)
O1—Co1—O4ⁱⁱ	95.23 (9)	O4ⁱⁱⁱ—Co1—O5ⁱ	93.25 (8)
O1—Co1—O5ⁱ	93.31 (9)	O4ⁱⁱ—Co1—O5ⁱ	80.90 (9)
O1—Co1—O5	92.67 (9)	O4ⁱⁱ—Co1—O5	104.48 (9)
O2ⁱ—Co1—O4ⁱⁱⁱ	85.22 (9)	O5—Co1—O4ⁱⁱⁱ	80.55 (9)
O2ⁱ—Co1—O4ⁱⁱ	87.21 (9)	O5—Co1—O5ⁱ	171.56 (4)
O2ⁱ—Co1—O5	86.49 (9)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Figure 1
The cobalt coordination environment in the title compound with a full cmb ligand and cocrystallized species. Displacement ellipsoids are drawn at the 50% probability level. Water molecule O1W has been omitted. Color code: Co dark blue, O red, N light blue, C black, and H pink. The symmetry codes are as listed in Table 1

The bound water molecules bridge adjacent Co atoms to construct [Co(μ-H₂O)]_n one-dimensional chain submotifs arranged parallel to the b crystal axis, in which the Co⋯Co internuclear distance measures 3.170 (1) Å. Carboxylate groups from cmb ligands and single carboxylate O atoms from other cmb ligands also bridge the same Co⋯Co internuclear distance, thereby affording [Co(OCO)(μ-H₂O)(μ-O)]_n chain motifs oriented along the b crystal direction (Fig. 2). One carboxylate terminus of the cmb ligands bridges two Co atoms in a chelating syn–syn fashion, while the other carboxylate group donates a single O atom to two adjacent Co atoms. One carboxylate O atom (O3) of each cmb ligand remains unligated. The chain motifs are connected into [Co₂(μ-H₂O)₂(cmb)]_n two-dimensional slabs by the exo-tetradentate cmb ligands; these slabs are oriented parallel to the bc crystal planes (Fig. 3).

Figure 2
The [Co(OCO)(μ-H₂O)(μ-O)]_n coordination polymer chain in the title compound.

Figure 3
A [Co(μ-H₂O)(cmb)]_n coordination polymer slab in the title compound.

[Co(μ-H₂O)(cmb)]_n layers are connected into the three-dimensional crystal structure by hydrogen bonding mediated by the unligated bpmp molecules in the interlamellar regions. The pyridyl termini of the cocrystallized bpmp molecules accept hydrogen bonds from the bridging water molecules in two adjacent layer motifs (Fig. 4). Cocrystallized water molecules are held in the crystal by donating hydrogen bonds to the bpmp piperazine N atoms. Details regarding the hydrogen-bonding patterns in the title compound are listed in Table 2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯N2	0.95	2.53	2.860 (5)	101
O1W—H1WA⋯N2	0.87	2.16	2.847 (10)	136
O5—H5A⋯O3ⁱ	0.85 (2)	1.79 (2)	2.619 (3)	164 (4)
O5—H5B⋯N1	0.86 (2)	1.82 (2)	2.672 (4)	175 (5)
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 4
The supramolecular three-dimensional structure formed by O—H⋯N hydrogen bonding (hatched bonds) between [Co(cmb)(μ-H₂O)]_n slabs and cocrystallized bpmp molecules.

Synthesis and crystallization

Co(NO₃)₂·6H₂O (108 mg, 0.37 mmol), 4-(carboxymethyl)benzoic acid (cmbH₂) (67 mg, 0.37 mmol), 1,4-bis(pyridin-4-ylmethyl)piperazine (bpmp) (99 mg, 0.37 mmol), and 0.75 ml of a 1.0 M NaOH solution were placed in 10 ml distilled H₂O in a Teflon-lined acid digestion bomb. The bomb was sealed and heated in an oven at 393 K for 48 h and then cooled slowly to 273 K. Pink crystals of the title complex were obtained in 68% yield.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms attached to C atoms were placed in calculated positions and refined with a riding model. The H atoms bound to the water O5 atom were found via a difference map and were refined freely with a restraint of 0.85 Å for the O—H distances, but those bound to atom O1W were positioned geometrically and refined using a riding model.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(C₉H₆O₄)(H₂O)]·0.5C₁₆H₂₀N₄·0.5H₂O
M_r	796.54
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	27.036 (6), 6.3093 (13), 20.653 (5)
β (°)	105.536 (6)
V (Å³)	3394.2 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.05
Crystal size (mm)	0.27 × 0.14 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.669, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	8691, 3089, 2334
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.113, 1.06
No. of reflections	3089
No. of parameters	243
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.66
Computer programs: COSMO (Bruker, 2009 ), SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015 ), SHELXL (Sheldrick, 2008 ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1946425

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S241431462300648X/bt4140sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462300648X/bt4140Isup2.hkl

checkCIF report

Computing details top

Data collection: COSMO (Bruker, 2009); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[[(µ-aqua)[µ₄-4-(carboxylatomethyl)benzoato]cobalt(II)] hemi[1,4-bis(pyridin-4-ylmethyl)piperazine] hemihydrate] top

Crystal data top

[Co(C₉H₆O₄)(H₂O)]·0.5C₁₆H₂₀N₄·0.5H₂O	F(000) = 1648
M_r = 796.54	D_x = 1.559 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.036 (6) Å	Cell parameters from 3416 reflections
b = 6.3093 (13) Å	θ = 2.1–25.4°
c = 20.653 (5) Å	µ = 1.05 mm⁻¹
β = 105.536 (6)°	T = 173 K
V = 3394.2 (13) Å³	Block, pink
Z = 4	0.27 × 0.14 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	3089 independent reflections
Radiation source: sealed tube	2334 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 8.36 pixels mm^-1	θ_max = 25.4°, θ_min = 2.1°
ω scans	h = −31→32
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −7→7
T_min = 0.669, T_max = 0.745	l = −24→24
8691 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0475P)² + 5.8489P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
3089 reflections	Δρ_max = 0.65 e Å⁻³
243 parameters	Δρ_min = −0.66 e Å⁻³
3 restraints

Special details top

Experimental. Data was collected using a BRUKER CCD (charge coupled device) based diffractometer equipped with an Oxford low-temperature apparatus operating at 173 K. A suitable crystal was chosen and mounted on a nylon loop using Paratone oil. Data were measured using omega scans of 0.5° per frame for 30 s. The total number of images were based on results from the program COSMO where redundancy was expected to be 4 and completeness to 0.83Å to 100%. Cell parameters were retrieved using APEX II software and refined using SAINT on all observed reflections.Data reduction was performed using the SAINT software which corrects for Lp. Scaling and absorption corrections were applied using SADABS6 multi-scan technique, supplied by George Sheldrick. The structure was solved by the direct method using the SHELXT program and refined by least squares method on F2, SHELXL, incorporated in OLEX2.

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. The structure was refined by Least Squares using version 2018/3 of XL (Sheldrick, 2015) incorporated in Olex2 (Dolomanov et al., 2009). All non-hydrogen atoms were refined anisotropically. Hydrogen atom positions were calculated geometrically and refined using the riding model, except for the Hydrogen atom on the nitrogen atom which was found by difference Fourier methods and refined isotropically.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.74834 (2)	0.12245 (6)	0.74217 (2)	0.01613 (16)
O1	0.77518 (9)	0.2010 (3)	0.66350 (10)	0.0218 (5)
O2	0.77731 (9)	0.5545 (3)	0.67641 (10)	0.0214 (5)
O3	0.84413 (9)	0.8638 (3)	0.37647 (11)	0.0251 (6)
O4	0.79387 (8)	0.6398 (3)	0.30472 (10)	0.0177 (5)
O5	0.69426 (9)	0.3776 (3)	0.72357 (11)	0.0176 (5)
N1	0.61639 (12)	0.3261 (5)	0.77903 (15)	0.0320 (7)
N2	0.50168 (11)	0.4195 (5)	0.93570 (14)	0.0300 (7)
C1	0.78312 (12)	0.3868 (5)	0.64604 (14)	0.0174 (7)
C2	0.80076 (12)	0.4150 (5)	0.58368 (15)	0.0200 (7)
C3	0.80611 (13)	0.6162 (5)	0.56001 (16)	0.0222 (7)
H3	0.799069	0.736233	0.583858	0.027*
C4	0.82169 (14)	0.6449 (5)	0.50162 (16)	0.0272 (8)
H4	0.824641	0.784229	0.485601	0.033*
C5	0.83291 (12)	0.4727 (5)	0.46672 (14)	0.0185 (7)
C6	0.82768 (13)	0.2713 (5)	0.49056 (16)	0.0255 (8)
H6	0.835191	0.151654	0.466903	0.031*
C7	0.81175 (13)	0.2408 (5)	0.54812 (16)	0.0251 (8)
H7	0.808268	0.101157	0.563545	0.030*
C8	0.85144 (13)	0.4970 (5)	0.40366 (14)	0.0202 (7)
H8A	0.889229	0.513829	0.417283	0.024*
H8B	0.843514	0.364930	0.377015	0.024*
C9	0.82837 (13)	0.6809 (5)	0.35940 (15)	0.0195 (7)
C10	0.60190 (15)	0.4890 (7)	0.81086 (19)	0.0395 (10)
H10	0.617359	0.623322	0.809065	0.047*
C11	0.56540 (16)	0.4711 (6)	0.8464 (2)	0.0419 (10)
H11	0.556036	0.591621	0.867983	0.050*
C12	0.54265 (14)	0.2779 (6)	0.85029 (17)	0.0304 (8)
C13	0.55802 (15)	0.1093 (6)	0.81812 (19)	0.0355 (9)
H13	0.543538	−0.027144	0.819787	0.043*
C14	0.59459 (15)	0.1393 (6)	0.78341 (19)	0.0354 (9)
H14	0.604698	0.020841	0.761580	0.043*
C15	0.50169 (15)	0.2492 (7)	0.88805 (19)	0.0373 (10)
H15A	0.467525	0.242547	0.855163	0.045*
H15B	0.507536	0.112621	0.912525	0.045*
C16	0.54563 (14)	0.4017 (6)	0.99510 (18)	0.0345 (9)
H16A	0.577929	0.403010	0.981173	0.041*
H16B	0.543748	0.265931	1.018344	0.041*
C17	0.45449 (14)	0.4153 (7)	0.95746 (19)	0.0371 (10)
H17A	0.452101	0.279572	0.980461	0.045*
H17B	0.424369	0.426346	0.917854	0.045*
O1W	0.4535 (4)	0.7370 (16)	0.8420 (5)	0.131 (4)	0.5
H1WA	0.455906	0.672793	0.879981	0.196*	0.5
H1WB	0.468736	0.858073	0.853331	0.196*	0.5
H5A	0.6813 (14)	0.440 (6)	0.6864 (13)	0.044 (12)*
H5B	0.6705 (14)	0.359 (7)	0.743 (2)	0.072 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0225 (3)	0.0114 (2)	0.0161 (2)	−0.00011 (18)	0.00797 (18)	0.00042 (16)
O1	0.0344 (15)	0.0149 (12)	0.0194 (11)	0.0002 (10)	0.0130 (10)	0.0009 (9)
O2	0.0313 (14)	0.0169 (12)	0.0196 (11)	−0.0004 (10)	0.0132 (10)	0.0000 (9)
O3	0.0346 (15)	0.0200 (13)	0.0178 (11)	−0.0065 (11)	0.0019 (10)	0.0005 (9)
O4	0.0228 (13)	0.0150 (12)	0.0127 (10)	−0.0003 (9)	0.0003 (9)	−0.0008 (8)
O5	0.0221 (13)	0.0143 (12)	0.0168 (11)	0.0021 (10)	0.0061 (10)	0.0019 (9)
N1	0.0281 (19)	0.0404 (19)	0.0293 (16)	0.0012 (15)	0.0109 (14)	0.0035 (14)
N2	0.0225 (17)	0.0423 (19)	0.0271 (15)	−0.0019 (14)	0.0101 (13)	−0.0023 (13)
C1	0.0181 (18)	0.0184 (17)	0.0152 (15)	0.0010 (14)	0.0037 (13)	0.0017 (13)
C2	0.0214 (19)	0.0233 (18)	0.0160 (15)	0.0024 (14)	0.0059 (13)	0.0013 (13)
C3	0.034 (2)	0.0137 (16)	0.0223 (16)	0.0006 (15)	0.0127 (15)	−0.0021 (13)
C4	0.045 (2)	0.0169 (18)	0.0232 (17)	−0.0018 (16)	0.0160 (16)	0.0033 (14)
C5	0.0194 (18)	0.0206 (17)	0.0148 (14)	−0.0006 (14)	0.0034 (13)	−0.0001 (13)
C6	0.036 (2)	0.0184 (18)	0.0257 (17)	0.0017 (16)	0.0138 (16)	−0.0015 (14)
C7	0.037 (2)	0.0154 (17)	0.0270 (17)	0.0014 (16)	0.0160 (16)	0.0031 (14)
C8	0.0246 (19)	0.0197 (17)	0.0171 (15)	0.0014 (15)	0.0069 (14)	0.0028 (13)
C9	0.0214 (19)	0.0230 (18)	0.0172 (15)	−0.0015 (14)	0.0104 (14)	−0.0021 (13)
C10	0.046 (3)	0.035 (2)	0.043 (2)	−0.004 (2)	0.022 (2)	0.0025 (19)
C11	0.053 (3)	0.034 (2)	0.050 (2)	−0.002 (2)	0.032 (2)	−0.006 (2)
C12	0.028 (2)	0.035 (2)	0.0288 (18)	−0.0014 (18)	0.0088 (16)	0.0007 (16)
C13	0.038 (2)	0.030 (2)	0.042 (2)	−0.0035 (18)	0.0172 (18)	0.0008 (17)
C14	0.040 (2)	0.034 (2)	0.036 (2)	0.0052 (19)	0.0168 (18)	−0.0008 (17)
C15	0.036 (2)	0.043 (2)	0.037 (2)	−0.005 (2)	0.0162 (18)	−0.0036 (18)
C16	0.022 (2)	0.050 (3)	0.033 (2)	0.0060 (18)	0.0099 (16)	−0.0004 (18)
C17	0.020 (2)	0.061 (3)	0.0313 (19)	−0.0041 (19)	0.0076 (16)	−0.0082 (18)
O1W	0.165 (10)	0.120 (8)	0.115 (8)	−0.008 (8)	0.052 (7)	0.013 (7)

Geometric parameters (Å, º) top

Co1—O1	2.011 (2)	C5—C8	1.523 (4)
Co1—O2ⁱ	2.029 (2)	C6—H6	0.9500
Co1—O4ⁱⁱ	2.094 (2)	C6—C7	1.382 (4)
Co1—O4ⁱⁱⁱ	2.140 (2)	C7—H7	0.9500
Co1—O5	2.139 (2)	C8—H8A	0.9900
Co1—O5ⁱ	2.169 (2)	C8—H8B	0.9900
O1—C1	1.262 (4)	C8—C9	1.505 (4)
O2—C1	1.261 (4)	C10—H10	0.9500
O3—C9	1.248 (4)	C10—C11	1.383 (5)
O4—C9	1.284 (4)	C11—H11	0.9500
O5—H5A	0.851 (19)	C11—C12	1.377 (5)
O5—H5B	0.855 (19)	C12—C13	1.376 (5)
N1—C10	1.334 (5)	C12—C15	1.526 (5)
N1—C14	1.332 (5)	C13—H13	0.9500
N2—C15	1.457 (5)	C13—C14	1.381 (5)
N2—C16	1.466 (5)	C14—H14	0.9500
N2—C17	1.462 (4)	C15—H15A	0.9900
C1—C2	1.499 (4)	C15—H15B	0.9900
C2—C3	1.382 (4)	C16—H16A	0.9900
C2—C7	1.397 (4)	C16—H16B	0.9900
C3—H3	0.9500	C16—C17^iv	1.515 (5)
C3—C4	1.392 (4)	C17—H17A	0.9900
C4—H4	0.9500	C17—H17B	0.9900
C4—C5	1.382 (4)	O1W—H1WA	0.8698
C5—C6	1.384 (5)	O1W—H1WB	0.8699

O1—Co1—O2ⁱ	177.55 (9)	C7—C6—H6	119.4
O1—Co1—O4ⁱⁱⁱ	92.37 (9)	C2—C7—H7	119.9
O1—Co1—O4ⁱⁱ	95.23 (9)	C6—C7—C2	120.1 (3)
O1—Co1—O5ⁱ	93.31 (9)	C6—C7—H7	119.9
O1—Co1—O5	92.67 (9)	C5—C8—H8A	108.6
O2ⁱ—Co1—O4ⁱⁱⁱ	85.22 (9)	C5—C8—H8B	108.6
O2ⁱ—Co1—O4ⁱⁱ	87.21 (9)	H8A—C8—H8B	107.5
O2ⁱ—Co1—O5	86.49 (9)	C9—C8—C5	114.8 (3)
O2ⁱ—Co1—O5ⁱ	87.29 (9)	C9—C8—H8A	108.6
O4ⁱⁱ—Co1—O4ⁱⁱⁱ	170.65 (6)	C9—C8—H8B	108.6
O4ⁱⁱⁱ—Co1—O5ⁱ	93.25 (8)	O3—C9—O4	123.2 (3)
O4ⁱⁱ—Co1—O5ⁱ	80.90 (9)	O3—C9—C8	119.1 (3)
O4ⁱⁱ—Co1—O5	104.48 (9)	O4—C9—C8	117.7 (3)
O5—Co1—O4ⁱⁱⁱ	80.55 (9)	N1—C10—H10	118.5
O5—Co1—O5ⁱ	171.56 (4)	N1—C10—C11	122.9 (4)
C1—O1—Co1	125.86 (19)	C11—C10—H10	118.5
C1—O2—Co1^v	134.8 (2)	C10—C11—H11	120.1
Co1ⁱⁱ—O4—Co1^vi	96.93 (8)	C12—C11—C10	119.8 (4)
C9—O4—Co1ⁱⁱ	138.0 (2)	C12—C11—H11	120.1
C9—O4—Co1^vi	123.7 (2)	C11—C12—C15	122.1 (3)
Co1—O5—Co1^v	94.73 (9)	C13—C12—C11	117.3 (3)
Co1—O5—H5A	127 (3)	C13—C12—C15	120.6 (3)
Co1^v—O5—H5A	93 (3)	C12—C13—H13	120.2
Co1^v—O5—H5B	120 (3)	C12—C13—C14	119.7 (4)
Co1—O5—H5B	112 (3)	C14—C13—H13	120.2
H5A—O5—H5B	108 (4)	N1—C14—C13	123.2 (4)
C14—N1—C10	117.0 (3)	N1—C14—H14	118.4
C15—N2—C16	111.2 (3)	C13—C14—H14	118.4
C15—N2—C17	110.6 (3)	N2—C15—C12	112.9 (3)
C17—N2—C16	108.7 (3)	N2—C15—H15A	109.0
O1—C1—C2	118.3 (3)	N2—C15—H15B	109.0
O2—C1—O1	125.7 (3)	C12—C15—H15A	109.0
O2—C1—C2	116.0 (3)	C12—C15—H15B	109.0
C3—C2—C1	120.0 (3)	H15A—C15—H15B	107.8
C3—C2—C7	118.7 (3)	N2—C16—H16A	109.7
C7—C2—C1	121.3 (3)	N2—C16—H16B	109.7
C2—C3—H3	119.6	N2—C16—C17^iv	110.0 (3)
C2—C3—C4	120.7 (3)	H16A—C16—H16B	108.2
C4—C3—H3	119.6	C17^iv—C16—H16A	109.7
C3—C4—H4	119.7	C17^iv—C16—H16B	109.7
C5—C4—C3	120.6 (3)	N2—C17—C16^iv	109.8 (3)
C5—C4—H4	119.7	N2—C17—H17A	109.7
C4—C5—C6	118.6 (3)	N2—C17—H17B	109.7
C4—C5—C8	122.4 (3)	C16^iv—C17—H17A	109.7
C6—C5—C8	119.0 (3)	C16^iv—C17—H17B	109.7
C5—C6—H6	119.4	H17A—C17—H17B	108.2
C7—C6—C5	121.3 (3)	H1WA—O1W—H1WB	104.5

Co1—O1—C1—O2	2.7 (5)	C5—C6—C7—C2	−0.3 (5)
Co1—O1—C1—C2	−176.9 (2)	C5—C8—C9—O3	76.4 (4)
Co1^v—O2—C1—O1	−3.5 (5)	C5—C8—C9—O4	−105.1 (3)
Co1^v—O2—C1—C2	176.2 (2)	C6—C5—C8—C9	145.6 (3)
Co1^vi—O4—C9—O3	−11.0 (4)	C7—C2—C3—C4	0.6 (5)
Co1ⁱⁱ—O4—C9—O3	−174.2 (2)	C8—C5—C6—C7	179.0 (3)
Co1^vi—O4—C9—C8	170.56 (19)	C10—N1—C14—C13	0.8 (6)
Co1ⁱⁱ—O4—C9—C8	7.3 (4)	C10—C11—C12—C13	0.3 (6)
O1—C1—C2—C3	175.1 (3)	C10—C11—C12—C15	−179.3 (4)
O1—C1—C2—C7	−4.5 (5)	C11—C12—C13—C14	−0.5 (6)
O2—C1—C2—C3	−4.6 (5)	C11—C12—C15—N2	−18.8 (5)
O2—C1—C2—C7	175.8 (3)	C12—C13—C14—N1	−0.1 (6)
N1—C10—C11—C12	0.5 (6)	C13—C12—C15—N2	161.7 (3)
C1—C2—C3—C4	−179.0 (3)	C14—N1—C10—C11	−1.0 (6)
C1—C2—C7—C6	179.6 (3)	C15—N2—C16—C17^iv	178.2 (3)
C2—C3—C4—C5	−1.0 (5)	C15—N2—C17—C16^iv	−177.9 (3)
C3—C2—C7—C6	0.1 (5)	C15—C12—C13—C14	179.1 (4)
C3—C4—C5—C6	0.8 (5)	C16—N2—C15—C12	−73.7 (4)
C3—C4—C5—C8	−178.3 (3)	C16—N2—C17—C16^iv	59.7 (4)
C4—C5—C6—C7	−0.2 (5)	C17—N2—C15—C12	165.4 (3)
C4—C5—C8—C9	−35.2 (5)	C17—N2—C16—C17^iv	−59.8 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···N2	0.95	2.53	2.860 (5)	101
O1W—H1WA···N2	0.87	2.16	2.847 (10)	136
O5—H5A···O3^vii	0.85 (2)	1.79 (2)	2.619 (3)	164 (4)
O5—H5B···N1	0.86 (2)	1.82 (2)	2.672 (4)	175 (5)

Symmetry code: (vii) −x+3/2, −y+3/2, −z+1.

Funding information

Funding for this research was provided by: Lyman Briggs College of Science at Michigan State University.

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