metal-organic compounds
trans-Diaquabis(N,N,N′-trimethylethylenediamine)nickel(II) dichloride
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
In the title salt, [Ni(C5H12N2)2(H2O)2]Cl2, the is comprised of half of the complex cation and a chloride ion with the NiII atom of the cation situated about a twofold rotation axis. The six-coordinate NiII 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 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.
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 II atom of the cation situated about a twofold rotation axis (Fig. 1). The chelate ring (Fig. 2) is in a slight on C1 with puckering parameters Q2 = 0.476 (2)° and φ2 = 79.8 (2)°. The six-coordinate NiII 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.
is comprised of half of the cationic complex and a chloride ion with the NiThe 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.
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 .
details are summarized in Table 2Structural data
CCDC reference: 2025810
https://doi.org/10.1107/S2414314620011827/wm4136sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620011827/wm4136Isup2.hkl
Data collection: CrysAlis PRO (Rigaku OD, 2020); cell
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).[Ni(C5H12N2)2(H2O)2]Cl2 | Dx = 1.428 Mg m−3 |
Mr = 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 |
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 | Rint = 0.018 |
Detector resolution: 16.0416 pixels mm-1 | θmax = 32.6°, θmin = 3.7° |
ω scans | h = −36→22 |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020) | k = −13→23 |
Tmin = 0.718, Tmax = 1.000 | l = −12→5 |
3481 measured reflections |
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(Fo2) + (0.0416P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.064 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.45 e Å−3 |
1940 reflections | Δρmin = −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 |
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 Uiso(H) = 1.2Ueq(CH, NH) or 1.5Ueq(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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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. |
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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