Poly[di­aqua­[μ-1,4-bis­(pyridin-4-ylmeth­yl)pip­era­zine][μ-4-(carboxyl­atoeth­yl)benzoato]nickel(II)]

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

doi:10.1107/S2414314623007885

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 9| September 2023| x230788

https://doi.org/10.1107/S2414314623007885

Open

access

Poly[diaqua[μ-1,4-bis(pyridin-4-ylmethyl)piperazine][μ-4-(carboxylatoethyl)benzoato]nickel(II)]

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. Weil, Vienna University of Technology, Austria (Received 26 July 2023; accepted 8 September 2023; online 22 September 2023)

The title compound, [Ni(C₁₀H₈O₄)(C₁₆H₂₀N₄)(H₂O)₂]_n, contains Ni^II cations octahedrally surrounded within an [O₄N₂] coordination set. The cations are linked by 4-(carboxyethyl)benzoate (ceb) and 1,4-bis(pyridin-4-ylmethyl)piperazine (bpmp) ligands into tri-periodic diamondoid (dia) networks. The fivefold interpenetrated dia networks are held into the crystal structure by means of O—H⋯O hydrogen bonding between bound water molecules and unligated carboxylate O atoms of the ceb ligands.

Keywords: crystal structure; nickel; coordination polymer; diamondoid network..

CCDC reference: 1946427

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 remarkable variety of interesting topologies (Robinson et al., 2015 ). For instance, the cobalt oxalate (ox) bpmp phase {[Co(ox)(bpmp)]^.3H₂O}_n, manifests a threefold interpenetrated tri-periodic diamondoid (dia) topology. Use of the dicarboxylate ligand oxy(bis)benzoate (oba) afforded {[Co₃(oba)₃(bpmp)₂]_n, which exhibits a striking self-penetrated tri-periodic network with 4⁴5¹⁷6⁷ topology (Martin et al., 2008 ). The title compound was isolated during an attempt to prepare a divalent nickel coordination polymer containing both bpmp and 4-(carboxylatoethyl)benzoato (ceb) ligands.

The asymmetric unit of the title compound contains a divalent nickel atom, a fully deprotonated ceb ligand, two bound water molecules, and a bpmp ligand. The nickel atom is coordinated in an [O₄N₂] distorted octahedral fashion (Fig. 1) with two cis-oriented aqua ligands, two trans-oriented carboxylate O atom donors from two ceb ligands, and two cis-oriented pyridyl N atom donors from two bpmp ligands. Pertinent bond length and angle information for the coordination sphere is listed in Table 1.

Table 1
Selected geometric parameters (Å, °)

Ni1—O1	2.068 (10)	Ni1—O6	2.089 (11)
Ni1—O4ⁱ	2.071 (10)	Ni1—N1	2.089 (12)
Ni1—O5	2.112 (9)	Ni1—N4ⁱⁱ	2.109 (10)

O1—Ni1—O4ⁱ	174.77 (15)	O4ⁱ—Ni1—N4ⁱⁱ	89.8 (4)
O1—Ni1—O5	90.3 (4)	O6—Ni1—O5	90.47 (17)
O1—Ni1—O6	85.0 (4)	O6—Ni1—N4ⁱⁱ	178.3 (4)
O1—Ni1—N1	89.5 (4)	N1—Ni1—O5	179.7 (5)
O1—Ni1—N4ⁱⁱ	93.6 (4)	N1—Ni1—O6	89.3 (4)
O4ⁱ—Ni1—O5	85.8 (4)	N1—Ni1—N4ⁱⁱ	89.56 (16)
O4ⁱ—Ni1—O6	91.6 (3)	N4ⁱⁱ—Ni1—O5	90.6 (4)
O4ⁱ—Ni1—N1	94.4 (4)
Symmetry codes: (i) $[x+1, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{3\over 2}}]$ .

Figure 1
Nickel coordination environment in the title compound with full ceb and bpmp ligands. Displacement ellipsoids are drawn at the 50% probability level. Color code: Co, dark blue; O, red; N, light blue; C, black; H, pink. Symmetry codes are as listed in Table 1

The ceb ligands bridge adjacent nickel(II) atoms in a bis(monodentate) fashion to construct [Ni(ceb)(H₂O)₂]_n chain submotifs arranged parallel to [201], in which the Ni⋯Ni internuclear distance measures 13.996 (4) Å (Fig. 2). These chain motifs are connected into [Ni(ceb)(bpmp)(H₂O)₂]_n 6⁶ dia topology (Blatov et al., 2014 ) coordination polymer networks (Fig. 3). Incipient void space within a single [Ni(ceb)(bpmp)(H₂O)₂]_n network allows interpenetration of four additional networks to instill a fivefold system of interpenetrated dia networks in the title compound (Fig. 4).

Figure 2
[Ni(ceb)(H₂O)₂]_n coordination polymer chain in the title compound.

Figure 3
A single [Ni(ceb)(bpmp)(H₂O)₂]_n dia coordination polymer network in the title compound with unit cell outlines shown.

Figure 4
Fivefold interpenetration of dia polymer networks in the title compound. The linking ligands are shown as rods.

The [Ni(ceb)(H₂O)₂]_n chain submotifs are stabilized by internal O—H⋯O hydrogen bonding between the bound water molecules and unligated ceb carboxylate O atoms (O5—H5A⋯O2). Adjacent [Ni(ceb)(bpmp)(H₂O)₂]_n coordination polymer networks are held into the fivefold interpenetrated structure by similar O—H⋯O hydrogen bonding patterns between the bound water molecules (O5, O6) and unligated ceb carboxylate O atoms (O2^iv, O3ⁱⁱⁱ). Numerical details regarding the hydrogen bonding 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
O5—H5A⋯O2	0.84 (3)	1.82 (4)	2.621 (15)	158 (9)
O5—H5B⋯O3ⁱⁱⁱ	0.83 (3)	2.30 (7)	2.894 (14)	129 (6)
O6—H6B⋯O2^iv	0.85 (3)	2.05 (4)	2.880 (15)	166 (9)
Symmetry codes: (iii) x+1, y, z+1; (iv) $[x, -y+1, z-{\script{1\over 2}}]$ .

Synthesis and crystallization

Ni(NO₃)₂^.6H₂O (108 mg, 0.37 mmol), 4-(carboxyethyl)benzoic acid (cebH₂) (72 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 into 10 ml distilled water 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. Green crystals of the title complex were obtained in 72% yield.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The crystal was twinned by non-merohedry. Only data from the major twin component was used in solution and refinement. Additionally, the structure refined best as an inversion twin in space group Cc with a refined BASF parameter of 0.39 (4). The H atoms bound to the O atoms of the water molecules were found by difference-Fourier maps, restrained with DFIX commands at 0.84 (2) Å, and refined with U_iso(H) = 1.2U_eq(O).

Table 3
Experimental details

Crystal data
Chemical formula	[Ni(C₁₀H₈O₄)(C₁₆H₂₀N₄)(H₂O)₂]
M_r	555.26
Crystal system, space group	Monoclinic, Cc
Temperature (K)	173
a, b, c (Å)	17.282 (3), 16.324 (3), 12.698 (4)
β (°)	131.754 (2)
V (Å³)	2672.3 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.77
Crystal size (mm)	0.32 × 0.21 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.519, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	21011, 4903, 3946
R_int	0.118
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.149, 1.05
No. of reflections	4903
No. of parameters	311
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.46, −0.65
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.39 (4)
Computer programs: COSMO (Bruker, 2009 ), SAINT (Bruker, 2014 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), CrystalMaker X (Palmer, 2020 ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1946427

Crystal structure: contains datablocks I, 1R. DOI: https://doi.org/10.1107/S2414314623007885/wm4194sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623007885/wm4194Isup2.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, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: CrystalMaker X (Palmer, 2020); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Poly[diaqua[µ-1,4-bis(pyridin-4-ylmethyl)piperazine][µ-4-(carboxylatoethyl)benzoato]nickel(II)] top

Crystal data top

[Ni(C₁₀H₈O₄)(C₁₆H₂₀N₄)(H₂O)₂]	F(000) = 1168
M_r = 555.26	D_x = 1.380 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 17.282 (3) Å	Cell parameters from 7345 reflections
b = 16.324 (3) Å	θ = 2.5–25.1°
c = 12.698 (4) Å	µ = 0.77 mm⁻¹
β = 131.754 (2)°	T = 173 K
V = 2672.3 (11) Å³	Chunk, green
Z = 4	0.32 × 0.21 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	4903 independent reflections
Radiation source: sealed tube	3946 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.118
Detector resolution: 8.36 pixels mm^-1	θ_max = 25.4°, θ_min = 2.0°
ω scans	h = −20→20
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −19→19
T_min = 0.519, T_max = 0.745	l = −15→15
21011 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.057	w = 1/[σ²(F_o²) + (0.0734P)² + 2.7583P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.149	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 1.46 e Å⁻³
4903 reflections	Δρ_min = −0.64 e Å⁻³
311 parameters	Absolute structure: Refined as an inversion twin
8 restraints	Absolute structure parameter: 0.39 (4)
Primary atom site location: dual

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
Ni1	0.9080 (2)	0.44647 (4)	1.1095 (3)	0.0249 (3)
O1	0.7548 (7)	0.4520 (6)	1.0183 (9)	0.031 (3)
O2	0.7660 (7)	0.5196 (6)	1.1810 (9)	0.039 (3)
O3	0.0511 (7)	0.4808 (7)	0.5374 (10)	0.042 (3)
O4	0.0617 (7)	0.5475 (5)	0.7020 (8)	0.028 (3)
O5	0.9473 (7)	0.5383 (6)	1.2552 (9)	0.029 (2)
O6	0.8654 (7)	0.5358 (7)	0.9613 (10)	0.035 (3)
N1	0.8685 (8)	0.3559 (7)	0.9646 (11)	0.026 (3)
N2	0.7051 (9)	0.2250 (7)	0.5017 (11)	0.030 (3)
N3	0.6112 (9)	0.2750 (7)	0.2218 (11)	0.034 (3)
N4	0.4467 (8)	0.1455 (7)	−0.2456 (11)	0.025 (3)
C1	0.7170 (12)	0.4855 (9)	1.0645 (17)	0.035 (2)
C2	0.5985 (10)	0.4809 (8)	0.9613 (13)	0.035 (2)
H2A	0.570123	0.503193	0.869034	0.042*
H2B	0.577580	0.422672	0.946978	0.042*
C3	0.5517 (11)	0.5259 (8)	1.0082 (14)	0.035 (2)
H3A	0.586039	0.507320	1.104771	0.042*
H3B	0.568175	0.584794	1.014318	0.042*
C4	0.4387 (11)	0.5181 (9)	0.9203 (18)	0.039 (4)
C5	0.3753 (13)	0.4740 (9)	0.7964 (17)	0.043 (4)
H5	0.405671	0.444413	0.767356	0.051*
C6	0.2662 (11)	0.4715 (8)	0.7110 (15)	0.041 (3)
H6	0.224770	0.440385	0.626232	0.049*
C7	0.2181 (8)	0.5153 (8)	0.7515 (12)	0.0261 (18)
C8	0.2775 (7)	0.5557 (5)	0.8700 (9)	0.042 (2)
H8	0.247516	0.583759	0.900809	0.050*
C9	0.3845 (7)	0.5582 (5)	0.9521 (9)	0.0390 (19)
H9	0.424024	0.589608	1.036478	0.047*
C10	0.1021 (10)	0.5149 (9)	0.6574 (14)	0.0261 (18)
C11	0.9436 (10)	0.3177 (9)	0.9745 (14)	0.034 (4)
H11	1.014340	0.329718	1.052678	0.041*
C12	0.9193 (12)	0.2603 (9)	0.8714 (15)	0.037 (4)
H12	0.973385	0.233259	0.883407	0.045*
C13	0.8190 (11)	0.2445 (10)	0.7565 (15)	0.034 (4)
C14	0.7419 (11)	0.2820 (9)	0.7461 (15)	0.034 (4)
H14	0.670952	0.269867	0.669043	0.041*
C15	0.7697 (11)	0.3374 (10)	0.8497 (14)	0.039 (4)
H15	0.715707	0.363767	0.838687	0.046*
C16	0.7929 (12)	0.1936 (10)	0.6390 (14)	0.037 (4)
H16A	0.853783	0.191376	0.646851	0.044*
H16B	0.777492	0.137020	0.648371	0.044*
C17	0.7384 (12)	0.2994 (9)	0.4741 (15)	0.0340 (7)
H17A	0.795601	0.285564	0.477098	0.041*
H17B	0.763878	0.341043	0.547575	0.041*
C18	0.6462 (11)	0.3335 (8)	0.3286 (13)	0.0340 (7)
H18A	0.589034	0.347020	0.325883	0.041*
H18B	0.667120	0.384459	0.310988	0.041*
C19	0.6673 (11)	0.1634 (8)	0.3875 (13)	0.0340 (7)
H19A	0.725343	0.147538	0.393179	0.041*
H19B	0.642672	0.113524	0.401786	0.041*
C20	0.5811 (12)	0.1987 (8)	0.2451 (15)	0.0340 (7)
H20A	0.560144	0.158647	0.171595	0.041*
H20B	0.520475	0.208814	0.236221	0.041*
C21	0.5270 (12)	0.3104 (9)	0.0812 (14)	0.036 (4)
H21A	0.549806	0.363581	0.072359	0.044*
H21B	0.465634	0.320556	0.070690	0.044*
C22	0.3756 (11)	0.1827 (9)	−0.2542 (13)	0.031 (3)
H22	0.305146	0.173130	−0.336325	0.037*
C23	0.3944 (11)	0.2335 (8)	−0.1559 (15)	0.032 (3)
H23	0.338597	0.256557	−0.167464	0.039*
C24	0.4971 (11)	0.2519 (9)	−0.0363 (14)	0.029 (3)
C25	0.5714 (12)	0.2170 (10)	−0.0316 (16)	0.041 (4)
H25	0.642522	0.228510	0.045559	0.050*
C26	0.5443 (10)	0.1653 (8)	−0.1371 (12)	0.030 (3)
H26	0.597494	0.143039	−0.131876	0.036*
H5A	0.898 (4)	0.537 (6)	1.254 (8)	0.036*
H6A	0.928 (3)	0.545 (6)	1.007 (7)	0.036*
H5B	1.000 (4)	0.514 (5)	1.323 (6)	0.036*
H6B	0.830 (5)	0.527 (5)	0.874 (4)	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0212 (4)	0.0340 (4)	0.0202 (4)	−0.0002 (11)	0.0140 (3)	−0.0002 (11)
O1	0.008 (4)	0.049 (7)	0.025 (6)	0.003 (4)	0.007 (4)	0.002 (5)
O2	0.032 (5)	0.055 (7)	0.021 (6)	0.009 (5)	0.013 (4)	−0.006 (5)
O3	0.025 (5)	0.074 (8)	0.035 (6)	0.003 (5)	0.024 (5)	−0.002 (6)
O4	0.032 (5)	0.036 (6)	0.024 (6)	0.002 (4)	0.022 (5)	−0.006 (4)
O5	0.020 (5)	0.039 (5)	0.019 (5)	0.000 (4)	0.010 (4)	−0.010 (4)
O6	0.030 (6)	0.046 (6)	0.036 (6)	0.005 (5)	0.025 (5)	−0.001 (5)
N1	0.019 (6)	0.035 (6)	0.024 (6)	−0.001 (5)	0.014 (5)	0.007 (5)
N2	0.043 (7)	0.025 (6)	0.027 (7)	−0.010 (5)	0.026 (6)	−0.009 (5)
N3	0.042 (8)	0.035 (7)	0.026 (7)	0.002 (6)	0.024 (6)	0.000 (5)
N4	0.028 (6)	0.029 (6)	0.017 (6)	0.004 (5)	0.015 (5)	−0.001 (5)
C1	0.034 (4)	0.030 (4)	0.044 (5)	0.004 (3)	0.027 (4)	0.014 (3)
C2	0.034 (4)	0.030 (4)	0.044 (5)	0.004 (3)	0.027 (4)	0.014 (3)
C3	0.034 (4)	0.030 (4)	0.044 (5)	0.004 (3)	0.027 (4)	0.014 (3)
C4	0.033 (7)	0.028 (7)	0.068 (9)	0.008 (6)	0.039 (7)	0.011 (7)
C5	0.060 (9)	0.034 (7)	0.054 (9)	0.002 (7)	0.046 (8)	−0.005 (7)
C6	0.026 (5)	0.044 (6)	0.054 (7)	−0.008 (4)	0.027 (5)	−0.030 (5)
C7	0.016 (4)	0.034 (4)	0.025 (4)	0.003 (3)	0.012 (3)	0.002 (3)
C8	0.035 (4)	0.055 (5)	0.039 (5)	−0.001 (4)	0.026 (4)	−0.011 (4)
C9	0.034 (4)	0.049 (5)	0.032 (4)	−0.002 (3)	0.021 (4)	−0.008 (4)
C10	0.016 (4)	0.034 (4)	0.025 (4)	0.003 (3)	0.012 (3)	0.002 (3)
C11	0.021 (7)	0.052 (9)	0.028 (9)	0.000 (7)	0.016 (7)	−0.003 (7)
C12	0.044 (9)	0.038 (8)	0.039 (9)	0.004 (6)	0.032 (8)	−0.001 (7)
C13	0.040 (9)	0.038 (8)	0.025 (9)	−0.005 (7)	0.022 (7)	0.001 (6)
C14	0.031 (8)	0.047 (9)	0.024 (8)	−0.005 (7)	0.018 (7)	−0.007 (7)
C15	0.026 (8)	0.062 (10)	0.030 (8)	−0.005 (7)	0.019 (7)	−0.002 (7)
C16	0.044 (9)	0.035 (8)	0.033 (9)	−0.006 (7)	0.026 (7)	−0.008 (6)
C17	0.0454 (17)	0.0312 (15)	0.0290 (14)	−0.0073 (12)	0.0263 (14)	−0.0071 (12)
C18	0.0454 (17)	0.0312 (15)	0.0290 (14)	−0.0073 (12)	0.0263 (14)	−0.0071 (12)
C19	0.0454 (17)	0.0312 (15)	0.0290 (14)	−0.0073 (12)	0.0263 (14)	−0.0071 (12)
C20	0.0454 (17)	0.0312 (15)	0.0290 (14)	−0.0073 (12)	0.0263 (14)	−0.0071 (12)
C21	0.050 (9)	0.033 (8)	0.028 (8)	0.005 (7)	0.027 (7)	0.006 (6)
C22	0.026 (7)	0.037 (8)	0.024 (8)	0.003 (7)	0.014 (7)	−0.003 (7)
C23	0.024 (7)	0.037 (7)	0.031 (8)	0.002 (6)	0.017 (6)	−0.002 (6)
C24	0.039 (9)	0.025 (7)	0.025 (8)	0.004 (6)	0.022 (7)	0.004 (6)
C25	0.029 (8)	0.052 (10)	0.028 (9)	−0.005 (7)	0.013 (7)	−0.007 (7)
C26	0.023 (7)	0.045 (8)	0.021 (7)	0.004 (6)	0.014 (6)	−0.006 (6)

Geometric parameters (Å, º) top

Ni1—O1	2.068 (10)	C7—C8	1.302 (14)
Ni1—O4ⁱ	2.071 (10)	C7—C10	1.501 (17)
Ni1—O5	2.112 (9)	C8—H8	0.9500
Ni1—O6	2.089 (11)	C8—C9	1.393 (11)
Ni1—N1	2.089 (12)	C9—H9	0.9500
Ni1—N4ⁱⁱ	2.109 (10)	C11—H11	0.9500
O1—C1	1.258 (18)	C11—C12	1.43 (2)
O2—C1	1.243 (18)	C12—H12	0.9500
O3—C10	1.272 (16)	C12—C13	1.35 (2)
O4—C10	1.273 (16)	C13—C14	1.39 (2)
O5—H5A	0.84 (3)	C13—C16	1.490 (19)
O5—H5B	0.83 (3)	C14—H14	0.9500
O6—H6A	0.83 (3)	C14—C15	1.39 (2)
O6—H6B	0.85 (3)	C15—H15	0.9500
N1—C11	1.368 (18)	C16—H16A	0.9900
N1—C15	1.349 (17)	C16—H16B	0.9900
N2—C16	1.442 (17)	C17—H17A	0.9900
N2—C17	1.482 (18)	C17—H17B	0.9900
N2—C19	1.510 (15)	C17—C18	1.530 (19)
N3—C18	1.423 (15)	C18—H18A	0.9900
N3—C20	1.454 (17)	C18—H18B	0.9900
N3—C21	1.476 (16)	C19—H19A	0.9900
N4—C22	1.309 (18)	C19—H19B	0.9900
N4—C26	1.323 (16)	C19—C20	1.495 (19)
C1—C2	1.531 (19)	C20—H20A	0.9900
C2—H2A	0.9900	C20—H20B	0.9900
C2—H2B	0.9900	C21—H21A	0.9900
C2—C3	1.479 (19)	C21—H21B	0.9900
C3—H3A	0.9900	C21—C24	1.543 (19)
C3—H3B	0.9900	C22—H22	0.9500
C3—C4	1.47 (2)	C22—C23	1.347 (19)
C4—C5	1.377 (10)	C23—H23	0.9500
C4—C9	1.404 (17)	C23—C24	1.40 (2)
C5—H5	0.9500	C24—C25	1.37 (2)
C5—C6	1.42 (2)	C25—H25	0.9500
C6—H6	0.9500	C25—C26	1.37 (2)
C6—C7	1.427 (16)	C26—H26	0.9500

O1—Ni1—O4ⁱ	174.77 (15)	O3—C10—C7	116.7 (12)
O1—Ni1—O5	90.3 (4)	O4—C10—C7	118.8 (12)
O1—Ni1—O6	85.0 (4)	N1—C11—H11	118.9
O1—Ni1—N1	89.5 (4)	N1—C11—C12	122.3 (13)
O1—Ni1—N4ⁱⁱ	93.6 (4)	C12—C11—H11	118.9
O4ⁱ—Ni1—O5	85.8 (4)	C11—C12—H12	120.1
O4ⁱ—Ni1—O6	91.6 (3)	C13—C12—C11	119.9 (15)
O4ⁱ—Ni1—N1	94.4 (4)	C13—C12—H12	120.1
O4ⁱ—Ni1—N4ⁱⁱ	89.8 (4)	C12—C13—C14	118.4 (15)
O6—Ni1—O5	90.47 (17)	C12—C13—C16	120.2 (15)
O6—Ni1—N4ⁱⁱ	178.3 (4)	C14—C13—C16	121.2 (13)
N1—Ni1—O5	179.7 (5)	C13—C14—H14	120.3
N1—Ni1—O6	89.3 (4)	C13—C14—C15	119.4 (14)
N1—Ni1—N4ⁱⁱ	89.56 (16)	C15—C14—H14	120.3
N4ⁱⁱ—Ni1—O5	90.6 (4)	N1—C15—C14	124.0 (15)
C1—O1—Ni1	128.8 (10)	N1—C15—H15	118.0
C10—O4—Ni1ⁱⁱⁱ	130.1 (9)	C14—C15—H15	118.0
Ni1—O5—H5A	103 (7)	N2—C16—C13	112.7 (13)
Ni1—O5—H5B	93 (6)	N2—C16—H16A	109.1
H5A—O5—H5B	114 (6)	N2—C16—H16B	109.1
Ni1—O6—H6A	89 (6)	C13—C16—H16A	109.1
Ni1—O6—H6B	125 (6)	C13—C16—H16B	109.1
H6A—O6—H6B	115 (6)	H16A—C16—H16B	107.8
C11—N1—Ni1	120.6 (9)	N2—C17—H17A	109.8
C15—N1—Ni1	123.2 (11)	N2—C17—H17B	109.8
C15—N1—C11	115.9 (13)	N2—C17—C18	109.2 (12)
C16—N2—C17	108.4 (12)	H17A—C17—H17B	108.3
C16—N2—C19	111.0 (11)	C18—C17—H17A	109.8
C17—N2—C19	107.8 (10)	C18—C17—H17B	109.8
C18—N3—C20	111.3 (10)	N3—C18—C17	110.2 (11)
C18—N3—C21	109.9 (12)	N3—C18—H18A	109.6
C20—N3—C21	112.5 (12)	N3—C18—H18B	109.6
C22—N4—Ni1^iv	121.5 (9)	C17—C18—H18A	109.6
C22—N4—C26	116.6 (12)	C17—C18—H18B	109.6
C26—N4—Ni1^iv	121.8 (10)	H18A—C18—H18B	108.1
O1—C1—C2	113.2 (14)	N2—C19—H19A	109.6
O2—C1—O1	126.6 (14)	N2—C19—H19B	109.6
O2—C1—C2	120.2 (14)	H19A—C19—H19B	108.1
C1—C2—H2A	108.7	C20—C19—N2	110.5 (11)
C1—C2—H2B	108.7	C20—C19—H19A	109.6
H2A—C2—H2B	107.6	C20—C19—H19B	109.6
C3—C2—C1	114.1 (12)	N3—C20—C19	111.9 (13)
C3—C2—H2A	108.7	N3—C20—H20A	109.2
C3—C2—H2B	108.7	N3—C20—H20B	109.2
C2—C3—H3A	108.0	C19—C20—H20A	109.2
C2—C3—H3B	108.0	C19—C20—H20B	109.2
H3A—C3—H3B	107.3	H20A—C20—H20B	107.9
C4—C3—C2	117.1 (13)	N3—C21—H21A	109.5
C4—C3—H3A	108.0	N3—C21—H21B	109.5
C4—C3—H3B	108.0	N3—C21—C24	110.6 (12)
C5—C4—C3	123.7 (10)	H21A—C21—H21B	108.1
C5—C4—C9	113.4 (8)	C24—C21—H21A	109.5
C9—C4—C3	122.9 (14)	C24—C21—H21B	109.5
C4—C5—H5	119.0	N4—C22—H22	117.4
C4—C5—C6	122.0 (10)	N4—C22—C23	125.1 (13)
C6—C5—H5	119.0	C23—C22—H22	117.4
C5—C6—H6	119.8	C22—C23—H23	120.4
C5—C6—C7	120.5 (12)	C22—C23—C24	119.1 (14)
C7—C6—H6	119.8	C24—C23—H23	120.4
C6—C7—C10	120.0 (11)	C23—C24—C21	123.2 (14)
C8—C7—C6	118.0 (11)	C25—C24—C21	121.0 (13)
C8—C7—C10	122.0 (11)	C25—C24—C23	115.7 (14)
C7—C8—H8	119.6	C24—C25—H25	119.6
C7—C8—C9	120.8 (8)	C24—C25—C26	120.8 (14)
C9—C8—H8	119.6	C26—C25—H25	119.6
C4—C9—H9	117.4	N4—C26—C25	122.4 (14)
C8—C9—C4	125.3 (9)	N4—C26—H26	118.8
C8—C9—H9	117.4	C25—C26—H26	118.8
O3—C10—O4	124.6 (12)

Ni1—O1—C1—O2	−4 (2)	C9—C4—C5—C6	0.7 (13)
Ni1—O1—C1—C2	176.3 (8)	C10—C7—C8—C9	−176.9 (11)
Ni1ⁱⁱⁱ—O4—C10—O3	3 (2)	C11—N1—C15—C14	1 (2)
Ni1ⁱⁱⁱ—O4—C10—C7	−176.3 (8)	C11—C12—C13—C14	−3 (2)
Ni1—N1—C11—C12	−174.9 (10)	C11—C12—C13—C16	171.6 (13)
Ni1—N1—C15—C14	174.7 (11)	C12—C13—C14—C15	3 (2)
Ni1^iv—N4—C22—C23	170.4 (11)	C12—C13—C16—N2	−139.0 (15)
Ni1^iv—N4—C26—C25	−171.1 (11)	C13—C14—C15—N1	−2 (2)
O1—C1—C2—C3	−175.1 (11)	C14—C13—C16—N2	36 (2)
O2—C1—C2—C3	5 (2)	C15—N1—C11—C12	−1 (2)
N1—C11—C12—C13	2 (2)	C16—N2—C17—C18	179.9 (11)
N2—C17—C18—N3	−61.5 (14)	C16—N2—C19—C20	−176.2 (13)
N2—C19—C20—N3	55.7 (15)	C16—C13—C14—C15	−171.7 (14)
N3—C21—C24—C23	134.8 (15)	C17—N2—C16—C13	73.5 (16)
N3—C21—C24—C25	−48 (2)	C17—N2—C19—C20	−57.6 (13)
N4—C22—C23—C24	3 (2)	C18—N3—C20—C19	−56.5 (14)
C1—C2—C3—C4	−174.7 (12)	C18—N3—C21—C24	173.1 (11)
C2—C3—C4—C5	−2.3 (16)	C19—N2—C16—C13	−168.2 (11)
C2—C3—C4—C9	−179.4 (11)	C19—N2—C17—C18	59.7 (13)
C3—C4—C5—C6	−176.6 (19)	C20—N3—C18—C17	58.4 (14)
C3—C4—C9—C8	177.3 (11)	C20—N3—C21—C24	−62.3 (16)
C4—C5—C6—C7	0 (2)	C21—N3—C18—C17	−176.2 (13)
C5—C4—C9—C8	−0.1 (13)	C21—N3—C20—C19	179.7 (11)
C5—C6—C7—C8	−2 (2)	C21—C24—C25—C26	−179.6 (14)
C5—C6—C7—C10	177.5 (14)	C22—N4—C26—C25	5 (2)
C6—C7—C8—C9	2.1 (17)	C22—C23—C24—C21	179.0 (13)
C6—C7—C10—O3	−6 (2)	C22—C23—C24—C25	1 (2)
C6—C7—C10—O4	173.1 (13)	C23—C24—C25—C26	−2 (2)
C7—C8—C9—C4	−1.4 (15)	C24—C25—C26—N4	−1 (3)
C8—C7—C10—O3	172.7 (12)	C26—N4—C22—C23	−6 (2)
C8—C7—C10—O4	−8 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2	0.84 (3)	1.82 (4)	2.621 (15)	158 (9)
O5—H5B···O3^v	0.83 (3)	2.30 (7)	2.894 (14)	129 (6)
O6—H6B···O2^vi	0.85 (3)	2.05 (4)	2.880 (15)	166 (9)

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

Funding information

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

References

Blatov, V. A., Shevchenko, A. P. & Proserpio, D. M. (2014). Cryst. Growth Des. 14, 3576–3586. Web of Science CrossRef CAS Google Scholar
Bruker (2009). COSMO. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2014). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Martin, D. P., Staples, R. J. & LaDuca, R. L. (2008). Inorg. Chem. 47, 9754–9756. Web of Science CSD CrossRef PubMed CAS Google Scholar
Palmer, D. (2020). CrystalMaker X. CrystalMaker Software, Begbroke, England. Google Scholar
Robinson, M. E., Mizzi, J. E., Staples, R. J. & LaDuca, R. L. (2015). Cryst. Growth Des. 15, 2260–2271. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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.