trans-Di­aqua­bis­(N,N,N′-tri­methyl­ethylenedi­amine)­nickel(II) dichloride

Miecznikowski, J.R.; Jasinski, J.P.; Flaherty, N.F.; Mircovich, E.E.; Smolinsky, A.N.; Bertolotti, N.R.

doi:10.1107/S2414314620011827

metal-organic compounds

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ISSN: 2414-3146

Volume 5| Part 9| September 2020| x201182

https://doi.org/10.1107/S2414314620011827

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trans-Diaquabis(N,N,N′-trimethylethylenediamine)nickel(II) dichloride

John R. Miecznikowski,^a ^* Jerry P. Jasinski,^b ^* Nicole F. Flaherty,^a Emma E. Mircovich,^a Allison N. Smolinsky ^a and Natalia R. Bertolotti ^a

^aDepartment of Chemistry & Biochemistry, Fairfield Univerity, 1073 North Benson Road, Fairfield, CT 06824, USA, and ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435, USA
^*Correspondence e-mail: jmiecznikowski@fairfield.edu, jjasinski@keene.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 3 August 2020; accepted 27 August 2020; online 8 September 2020)

In the title salt, [Ni(C₅H₁₂N₂)₂(H₂O)₂]Cl₂, the asymmetric unit is comprised of half of the complex cation and a chloride ion with the Ni^II atom of the cation situated about a twofold rotation axis. The six-coordinate Ni^II atom of the cation is connected to four N atoms from two methyl-substituted ethyelenediamine ligands and two water molecules in a slightly distorted octahedral environment. The five-membered chelate ring is in a slight envelope conformation. The crystal packing features O—H⋯Cl and N—H⋯Cl intermolecular interactions with the Cl⁻ ion forming weak bifurcated hydrogen bonds with nearby water molecules and N—H interactions, leading to a three-dimensional supramolecular network structure.

Keywords: Ligand precursor; crystal structure; substituted ethylenediamine ligand.

CCDC reference: 2025810

Structure description

Previously, a tris-ethylenediaminenickel(II) complex has been reported (Swink & Atoji, 1960 ). Since then, such tris-ethylenediamine complexes have been reported for nearly all of the first row transition metals as well: scandium(III) (Wagner & Melson, 1973 ), titanium(II) (McDonald et al., 1968 ), vanadium(II) (Daniels et al., 1995 ), and vanadium(III) (Clark & Greenfield, 1967 ), chromium(III) (Whuler et al., 1975 ), iron(II) (Girard et al., 1998 ), iron(III) (Renovitch & Baker, 1968 ), cobalt(III) (Nakatsu, 1962 ), copper(II) (Cullen & Lingafelter, 1970 ) and zinc(II) (Emsley et al., 1989 ). Substituted tris-ethylenediamine complexes with methyl groups instead of hydrogen atoms bonded to the nitrogen atoms have not been reported, to the best of our knowledge. In this communication, we report the preparation, spectroscopic characterization and single-crystal structure analysis of a nickel(II) complex that contains an N,N,N'-trimethylendiamine ligand.

In the title salt, the asymmetric unit is comprised of half of the cationic complex and a chloride ion with the Ni^II atom of the cation situated about a twofold rotation axis (Fig. 1). The chelate ring (Fig. 2) is in a slight envelope conformation on C1 with puckering parameters Q2 = 0.476 (2)^° and φ2 = 79.8 (2)°. The six-coordinate Ni^II atom of the cation is connected to four N atoms from two methyl-substituted ethelenediamine ligands and two water molecules in a slightly distorted octahedral environment, with the two substituted ethylenediamine ligands and two water molecules each coordinating trans to each other. The Ni—N bond lengths of 2.1906 (18) and 2.1245 (18) Å compare well to those of 2.120 (13) Å in the literature (Swink & Atoji, 1960); the Ni—O bond of 2.1189 (15) Å is the shortest of the metal–ligand bonds.

Figure 1
A view of [Ni(C₅H₁₆N₄O₂]²⁺2Cl⁻, showing its structure generated from two asymmetric units containing half of the cation complex and a chloride ion situated about a twofold rotation axis on the Ni^II ion. The green dotted lines represent hydrogen bonds.

Figure 2
The molecular structure of the asymmetric unit of [Ni(C₅H₁₆N₄O₂]²⁺2Cl⁻, showing the atom-labeling scheme with displacement ellipsoids drawn at the 50% probability level.

The crystal packing features O—H⋯Cl and N—H⋯Cl intermolecular interactions with the Cl⁻ ions forming weak bifurcated hydrogen bonds with nearby water molecules and N—H interactions from the en moieties (Fig. 3, Table 1). Chains then form along [010], [001] and [100], generating a three-dimensional supramolecular network structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl1ⁱ	1.00	2.31	3.296 (2)	169
O1—H1A⋯Cl1ⁱⁱ	0.75 (3)	2.36 (3)	3.1065 (16)	172 (4)
O1—H1B⋯Cl1	0.85 (4)	2.24 (5)	3.0836 (19)	172 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (ii) $[-x+{\script{3\over 4}}, y-{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Figure 3
A partial packing diagram of the title compound viewed along the c axis showing the O—H⋯Cl and N—H⋯Cl intermolecular interactions (dashed lines) with the Cl⁻ ion, forming weak bifurcated hydrogen bonds.

Synthesis and crystallization

N,N,N′-Trimethylethylenediamine (0.47 g, 0.0046 mol) was added to 10 ml of 95%_vol ethanol in a round-bottom flask. To this solution, 0.32 g (0.0013 mol) of NiCl₂·6H₂O were added. The reaction mixture became green in color. The reaction contents were then refluxed for 18 h. After the reaction time, the solvent was removed under reduced pressure. The product was then re-dissolved in acetonitrile and then the acetonitrile was removed under reduced pressure in order to determine the yield of the product. (0.41 g, 82%). Single crystals of the product were obtained by dissolving the product in acetonitrile and then allowing a diethyl ether vapor to slowly diffuse into the acetonitrile solution which contained the product. Analysis calculated for [C₁₀H₃₂N₄NiO₂]Cl₂: C: 32.46; H: 8.72; N: 15.14. Found: C: 32.29; H: 8.59; N: 14.96. UV–Visible data: λ (nm), (∊ (M⁻¹cm⁻¹) (2.4 mM in MeCN) 390.00 (24); 228.00 (1600); 222.00 (1700).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(C₅H₁₂N₂)₂(H₂O)₂]Cl₂
M_r	370.00
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	173
a, b, c (Å)	24.7168 (8), 16.6156 (5), 8.3805 (3)
V (Å³)	3441.75 (19)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	1.44
Crystal size (mm)	0.38 × 0.22 × 0.12

Data collection
Diffractometer	Rigaku Oxford Diffraction Gemini Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 )
T_min, T_max	0.718, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3481, 1940, 1866
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.758

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.064, 1.03
No. of reflections	1940
No. of parameters	98
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.28
Absolute structure	Classical Flack method (Flack, 1983 ) preferred over Parsons because s.u. lower
Absolute structure parameter	0.011 (14)
Computer programs: CrysAlis PRO (Rigaku OD, 2020), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2025810

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620011827/wm4136sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620011827/wm4136Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

trans-Diaquabis(N,N,N'-trimethylethylenediamine)nickel(II) dichloride top

Crystal data top

[Ni(C₅H₁₂N₂)₂(H₂O)₂]Cl₂	D_x = 1.428 Mg m⁻³
M_r = 370.00	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 1975 reflections
a = 24.7168 (8) Å	θ = 4.5–32.7°
b = 16.6156 (5) Å	µ = 1.44 mm⁻¹
c = 8.3805 (3) Å	T = 173 K
V = 3441.75 (19) Å³	Plate, clear light blue
Z = 8	0.38 × 0.22 × 0.12 mm
F(000) = 1584

Data collection top

Rigaku Oxford Diffraction Gemini Eos diffractometer	1940 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1866 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 16.0416 pixels mm^-1	θ_max = 32.6°, θ_min = 3.7°
ω scans	h = −36→22
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	k = −13→23
T_min = 0.718, T_max = 1.000	l = −12→5
3481 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)] = 0.025	w = 1/[σ²(F_o²) + (0.0416P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.064	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.45 e Å⁻³
1940 reflections	Δρ_min = −0.28 e Å⁻³
98 parameters	Absolute structure: Classical Flack method (Flack, 1983) preferred over Parsons because s.u. lower
1 restraint	Absolute structure parameter: 0.011 (14)
Primary atom site location: dual

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.

Refinement. All of the H atoms were placed in their calculated positions and then refined with lengths of 0.99 Å (CH); 0.98 Å (CH₃) using a riding model with U_iso(H) = 1.2U_eq(CH, NH) or 1.5U_eq(CH₃) of the parent atom. The idealized methyl group was refined as a rotating group. O-bound H atoms were located from a difference Fourier map and were refined freely.

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

	x	y	z	U_iso*/U_eq
Ni1	0.250000	0.750000	0.50037 (3)	0.01242 (9)
O1	0.32782 (6)	0.69655 (9)	0.4955 (2)	0.0176 (3)
N1	0.21604 (8)	0.66367 (11)	0.6707 (2)	0.0168 (3)
N2	0.22374 (8)	0.66391 (11)	0.3297 (2)	0.0178 (4)
H2	0.190094	0.686465	0.280789	0.021*
C1	0.17897 (9)	0.61499 (13)	0.5691 (3)	0.0220 (4)
H1C	0.146266	0.646888	0.543559	0.026*
H1D	0.167461	0.566293	0.628112	0.026*
C2	0.20698 (10)	0.59057 (13)	0.4165 (3)	0.0218 (4)
H2A	0.239070	0.557186	0.441324	0.026*
H2B	0.182077	0.558369	0.349569	0.026*
C3	0.25933 (11)	0.64123 (16)	0.1951 (3)	0.0259 (5)
H3A	0.273671	0.689984	0.144676	0.039*
H3B	0.238542	0.610325	0.116619	0.039*
H3C	0.289369	0.608359	0.234850	0.039*
C4	0.18262 (11)	0.69845 (14)	0.8001 (3)	0.0247 (4)
H4A	0.206073	0.726192	0.876681	0.037*
H4B	0.162891	0.655298	0.854570	0.037*
H4C	0.156786	0.736879	0.754674	0.037*
C5	0.25562 (9)	0.60896 (13)	0.7464 (3)	0.0216 (4)
H5A	0.274396	0.577959	0.663706	0.032*
H5B	0.236689	0.572070	0.818502	0.032*
H5C	0.282020	0.640596	0.807014	0.032*
Cl1	0.39455 (2)	0.76479 (3)	0.21560 (8)	0.02448 (13)
H1A	0.3323 (12)	0.6516 (18)	0.495 (5)	0.026 (7)*
H1B	0.3469 (19)	0.720 (2)	0.424 (5)	0.049 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01210 (15)	0.01247 (14)	0.01270 (14)	0.00142 (12)	0.000	0.000
O1	0.0163 (6)	0.0152 (6)	0.0213 (7)	0.0030 (5)	0.0004 (7)	−0.0003 (6)
N1	0.0184 (9)	0.0149 (7)	0.0172 (8)	0.0004 (6)	0.0018 (7)	0.0014 (6)
N2	0.0180 (9)	0.0181 (8)	0.0173 (8)	0.0037 (7)	−0.0023 (7)	−0.0020 (7)
C1	0.0193 (10)	0.0191 (9)	0.0274 (10)	−0.0050 (8)	0.0010 (9)	0.0010 (9)
C2	0.0223 (10)	0.0162 (8)	0.0270 (11)	−0.0012 (8)	−0.0050 (9)	−0.0036 (8)
C3	0.0315 (12)	0.0275 (11)	0.0187 (10)	0.0038 (10)	−0.0005 (10)	−0.0054 (9)
C4	0.0287 (12)	0.0233 (10)	0.0220 (9)	0.0038 (9)	0.0081 (9)	0.0024 (8)
C5	0.0237 (10)	0.0191 (9)	0.0219 (10)	0.0026 (7)	−0.0004 (10)	0.0064 (9)
Cl1	0.0205 (2)	0.0189 (2)	0.0340 (3)	−0.00289 (18)	0.0101 (2)	−0.0041 (2)

Geometric parameters (Å, º) top

Ni1—O1ⁱ	2.1189 (15)	C1—H1C	0.9900
Ni1—O1	2.1189 (15)	C1—H1D	0.9900
Ni1—N1ⁱ	2.1906 (18)	C1—C2	1.509 (3)
Ni1—N1	2.1906 (18)	C2—H2A	0.9900
Ni1—N2	2.1245 (18)	C2—H2B	0.9900
Ni1—N2ⁱ	2.1245 (18)	C3—H3A	0.9800
O1—H1A	0.75 (3)	C3—H3B	0.9800
O1—H1B	0.85 (4)	C3—H3C	0.9800
N1—C1	1.489 (3)	C4—H4A	0.9800
N1—C4	1.481 (3)	C4—H4B	0.9800
N1—C5	1.478 (3)	C4—H4C	0.9800
N2—H2	1.0000	C5—H5A	0.9800
N2—C2	1.479 (3)	C5—H5B	0.9800
N2—C3	1.479 (3)	C5—H5C	0.9800

O1ⁱ—Ni1—O1	177.80 (10)	N1—C1—H1C	109.6
O1—Ni1—N1	94.93 (7)	N1—C1—H1D	109.6
O1ⁱ—Ni1—N1ⁱ	94.93 (7)	N1—C1—C2	110.35 (18)
O1ⁱ—Ni1—N1	86.51 (7)	H1C—C1—H1D	108.1
O1—Ni1—N1ⁱ	86.51 (7)	C2—C1—H1C	109.6
O1ⁱ—Ni1—N2	89.54 (7)	C2—C1—H1D	109.6
O1ⁱ—Ni1—N2ⁱ	88.98 (7)	N2—C2—C1	108.91 (16)
O1—Ni1—N2ⁱ	89.54 (7)	N2—C2—H2A	109.9
O1—Ni1—N2	88.98 (7)	N2—C2—H2B	109.9
N1ⁱ—Ni1—N1	98.69 (10)	C1—C2—H2A	109.9
N2—Ni1—N1ⁱ	175.26 (8)	C1—C2—H2B	109.9
N2—Ni1—N1	83.15 (7)	H2A—C2—H2B	108.3
N2ⁱ—Ni1—N1	175.26 (8)	N2—C3—H3A	109.5
N2ⁱ—Ni1—N1ⁱ	83.15 (7)	N2—C3—H3B	109.5
N2—Ni1—N2ⁱ	95.36 (11)	N2—C3—H3C	109.5
Ni1—O1—H1A	123 (2)	H3A—C3—H3B	109.5
Ni1—O1—H1B	109 (3)	H3A—C3—H3C	109.5
H1A—O1—H1B	111 (4)	H3B—C3—H3C	109.5
C1—N1—Ni1	102.65 (14)	N1—C4—H4A	109.5
C4—N1—Ni1	115.81 (13)	N1—C4—H4B	109.5
C4—N1—C1	106.69 (19)	N1—C4—H4C	109.5
C5—N1—Ni1	115.38 (14)	H4A—C4—H4B	109.5
C5—N1—C1	108.56 (17)	H4A—C4—H4C	109.5
C5—N1—C4	107.15 (18)	H4B—C4—H4C	109.5
Ni1—N2—H2	106.1	N1—C5—H5A	109.5
C2—N2—Ni1	108.00 (13)	N1—C5—H5B	109.5
C2—N2—H2	106.1	N1—C5—H5C	109.5
C2—N2—C3	109.40 (18)	H5A—C5—H5B	109.5
C3—N2—Ni1	120.21 (16)	H5A—C5—H5C	109.5
C3—N2—H2	106.1	H5B—C5—H5C	109.5

Ni1—N1—C1—C2	46.67 (19)	C3—N2—C2—C1	170.25 (19)
Ni1—N2—C2—C1	37.8 (2)	C4—N1—C1—C2	168.89 (17)
N1—C1—C2—N2	−59.4 (2)	C5—N1—C1—C2	−75.9 (2)

Symmetry code: (i) −x+1/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱ	1.00	2.31	3.296 (2)	169
O1—H1A···Cl1ⁱⁱ	0.75 (3)	2.36 (3)	3.1065 (16)	172 (4)
O1—H1B···Cl1	0.85 (4)	2.24 (5)	3.0836 (19)	172 (4)

Symmetry codes: (i) −x+1/2, −y+3/2, z; (ii) −x+3/4, y−1/4, z+1/4.

Funding information

JRM acknowledges support from The Science Institute of the College of Arts and Sciences at Fairfield University for this work. Jerry P. Jasinski expresses thanks to the National Science Foundation Major Research Instrumentation Program (grant No. CHE-1039027) for funds to purchase an X-ray diffractometer. ANS and NRB acknowledge financial support from the Klimas Fund to support their summer research at Fairfield University.

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