Bis[2-(2-amino­ethyl­amino)­ethanol]copper(II) dinitrate

Abstract

In the title compound, [Cu(C₄H₁₂N₂O)₂](NO₃)₂, the central Cu^II atom has a distorted octa­hedral coordination geometry and is surrounded by four N atoms and two O atoms from the two inversion-related 2-(2-amino­ethyl­amino)­ethanol ligands. In the crystal, mol­ecules are held together by inter­molecular O—H⋯O and N—H⋯O hydrogen bonds, leading to the formation of a three-dimensional network.

Related literature

For crystal structures of related complexes, see: Qu et al. (2004 ▶); Uçar & Bulut (2005 ▶); Chastain & Dominick (1973 ▶).

Experimental

Crystal data

• [Cu(C₄H₁₂N₂O)₂](NO₃)₂

• M _r = 395.87

• Tetragonal,

• a = 14.6640 (1) Å

• c = 29.8298 (7) Å

• V = 6414.39 (16) ų

• Z = 16

• Mo Kα radiation

• μ = 1.41 mm⁻¹

• T = 296 K

• 0.45 × 0.36 × 0.23 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.532, T _max = 0.741

• 224935 measured reflections

• 4172 independent reflections

• 3346 reflections with I > 2σ(I)

• R _int = 0.047

Refinement

• R[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 0.121

• S = 1.04

• 4172 reflections

• 109 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.67 e Å⁻³

• Δρ_min = −0.72 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3i	0.90	2.14	2.9963 (17)	159
O1—H1⋯O4ii	0.93	2.28	3.1256 (16)	152
N2—H2B⋯O4iii	0.90	2.58	3.3356 (18)	141
N1—H2⋯O4iv	0.92 (2)	2.49 (2)	3.2449 (18)	139.8 (18)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

Metal alkanolamines complexes are among the most investigated compounds in coordination chemistry. As an extension of the work, we report here the crystal structure of the title compound, (I), a Cu^II complex incorporating the ligand N-(2-hydroxyethyl)ethylenediamine. The structure of bis [N-(2-hydroxyethyl)ethylenediamine] copper(II) nitrate consists of discrete [Cu(L)2]2+cations and nitrate anions. The closest distance between Cu and O of NO3 is 5.85 Å. The ORTEP diagram of the cation with the atom numbering scheme is shown in Fig. 1. The Ligand (L) coordinates in a tridentate manner via two nitrogen atoms and one oxygen atom, as shown in Fig. 1, providing a distorted octahedral arrangement about copper. The two O atoms coordinate to the Cu^II atom in trans positions, while the four N atoms occupy the equatorial positions. The three trans angles at the Cu^II atom are about 172° and the other angles subtended at the Cu^II atom are close to 90°, varying from 81.26 (15) to 95.15 (15)°. The two O atoms coordinate to the Cu^II atom in trans positions. The secondary-amine N-atoms and primary-amine N-atoms coordinate to the Cu^II atom in trans positions. In the crystal structure, the molecules are held together by intermolecular O—-H—O and N—-H—-O hydrogen bonds, leading to the formation of a three-dimensional network (Fig. 2 and Table 2).

Experimental

Copper(II) nitrate dihydrate (0.5 mol) in 50 ml of methanol was slowly mixed with N-(2-hydroxyethyl)ethylenediamine (1 mol) in 50 ml of methanol. The reaction was refluxed for a further 2 h. The solution volume was then reduced to 10 ml by roto-evaporation. Vapour diffusion of ether into this solution afforded pink crystals.

Refinement

The H-atoms were included in calculated positions and treated as riding atoms: O—H = 0.93 Å, C—-H=0.97 Å, N—H = 0.93and 0.90 Å for NH and NH2, respectively, with U_iso(H) = k × U_eq(C), where k = 1.5 for OH and CH3 H-atoms and k = 1.2 for all other H-atoms.

Figures

Fig. 1.

The structure of title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Fig. 2.

The crystal packing of title compound, viewed along the a axis. Hydrogen bonds are indicated by dashed lines.

Crystal data

[Cu(C4H12N2O)2](NO3)2	Dx = 1.640 Mg m−3
Mr = 395.87	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/acd	Cell parameters from 9080 reflections
Hall symbol: -I 4bd 2c	θ = 3.1–36.4°
a = 14.6640 (1) Å	µ = 1.41 mm−1
c = 29.8298 (7) Å	T = 296 K
V = 6414.39 (16) Å3	Regular, pink
Z = 16	0.45 × 0.36 × 0.23 mm
F(000) = 3312

Data collection

Bruker APEXII CCD diffractometer	4172 independent reflections
Radiation source: fine-focus sealed tube	3346 reflections with I > 2σ(I)
graphite	Rint = 0.047
φ and ω scans	θmax = 37.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −24→24
Tmin = 0.532, Tmax = 0.741	k = −24→24
224935 measured reflections	l = −50→50

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0796P)2 + 2.0215P] where P = (Fo2 + 2Fc2)/3
4172 reflections	(Δ/σ)max = 0.001
109 parameters	Δρmax = 0.67 e Å−3
0 restraints	Δρmin = −0.72 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu	0.7500	0.309239 (12)	0.0000	0.02305 (7)
O1	0.61649 (7)	0.29396 (8)	−0.02849 (4)	0.0422 (2)
H1	0.5640	0.3209	−0.0170	0.051*
O2	0.77057 (12)	0.25081 (15)	0.19377 (6)	0.0770 (5)
O3	0.71878 (11)	0.38235 (9)	0.21338 (6)	0.0619 (4)
O4	0.62849 (9)	0.26916 (9)	0.20917 (4)	0.0566 (3)
N1	0.71690 (7)	0.21768 (7)	0.05303 (3)	0.02816 (17)
N2	0.79384 (7)	0.40760 (7)	−0.04633 (4)	0.03194 (19)
H2A	0.7556	0.4556	−0.0460	0.038*
H2B	0.8499	0.4275	−0.0388	0.038*
N3	0.70700 (9)	0.29975 (8)	0.20544 (4)	0.0358 (2)
C1	0.66926 (10)	0.27016 (10)	0.08834 (4)	0.0377 (3)
H1A	0.6779	0.2401	0.1170	0.045*
H1B	0.6044	0.2710	0.0819	0.045*
C2	0.79595 (10)	0.36737 (10)	−0.09140 (5)	0.0388 (3)
H2C	0.8356	0.4029	−0.1107	0.047*
H2D	0.7352	0.3678	−0.1042	0.047*
C3	0.61890 (9)	0.23541 (11)	−0.06844 (5)	0.0411 (3)
H3A	0.6231	0.2731	−0.0951	0.049*
H3B	0.5629	0.2004	−0.0702	0.049*
C4	0.80093 (10)	0.17140 (11)	0.06673 (6)	0.0441 (3)
H4A	0.8140	0.1225	0.0458	0.053*
H4B	0.7921	0.1444	0.0961	0.053*
H2	0.6816 (15)	0.1700 (17)	0.0429 (7)	0.054 (6)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu	0.01921 (9)	0.02340 (9)	0.02654 (10)	0.000	0.00019 (5)	0.000
O1	0.0266 (4)	0.0506 (5)	0.0494 (6)	0.0057 (4)	−0.0040 (4)	−0.0110 (5)
O2	0.0687 (9)	0.0947 (13)	0.0675 (9)	0.0433 (9)	−0.0148 (7)	−0.0199 (9)
O3	0.0572 (7)	0.0336 (5)	0.0948 (11)	−0.0136 (5)	−0.0136 (7)	0.0028 (6)
O4	0.0502 (6)	0.0520 (7)	0.0675 (7)	−0.0214 (5)	−0.0097 (5)	0.0097 (6)
N1	0.0238 (3)	0.0278 (4)	0.0328 (4)	−0.0029 (3)	0.0010 (3)	0.0025 (3)
N2	0.0318 (4)	0.0264 (4)	0.0376 (5)	−0.0005 (3)	0.0019 (4)	0.0050 (3)
N3	0.0378 (5)	0.0323 (5)	0.0374 (5)	−0.0004 (4)	−0.0086 (4)	0.0040 (4)
C1	0.0393 (6)	0.0418 (7)	0.0321 (5)	−0.0039 (5)	0.0098 (4)	0.0012 (5)
C2	0.0428 (6)	0.0409 (6)	0.0326 (5)	−0.0011 (5)	0.0032 (5)	0.0098 (5)
C3	0.0274 (5)	0.0523 (8)	0.0435 (6)	−0.0019 (5)	−0.0058 (4)	−0.0132 (6)
C4	0.0338 (6)	0.0386 (7)	0.0598 (9)	0.0033 (5)	0.0007 (6)	0.0213 (6)

Geometric parameters (Å, °)

Cu—N2	2.0984 (10)	N2—H2A	0.9000
Cu—N2i	2.0984 (10)	N2—H2B	0.9000
Cu—N1i	2.1308 (10)	C1—C2i	1.517 (2)
Cu—N1	2.1308 (10)	C1—H1A	0.9700
Cu—O1	2.1460 (10)	C1—H1B	0.9700
Cu—O1i	2.1460 (10)	C2—C1i	1.517 (2)
O1—C3	1.4693 (17)	C2—H2C	0.9700
O1—H1	0.9300	C2—H2D	0.9700
O2—N3	1.2269 (19)	C3—C4i	1.505 (2)
O3—N3	1.2462 (16)	C3—H3A	0.9700
O4—N3	1.2406 (17)	C3—H3B	0.9700
N1—C4	1.4649 (17)	C4—C3i	1.505 (2)
N1—C1	1.4798 (17)	C4—H4A	0.9700
N1—H2	0.92 (2)	C4—H4B	0.9700
N2—C2	1.4684 (18)
N2—Cu—N2i	93.16 (6)	H2A—N2—H2B	108.2
N2—Cu—N1i	82.79 (4)	O2—N3—O4	121.27 (17)
N2i—Cu—N1i	172.64 (4)	O2—N3—O3	121.15 (17)
N2—Cu—N1	172.64 (4)	O4—N3—O3	117.58 (15)
N2i—Cu—N1	82.79 (4)	N1—C1—C2i	111.89 (10)
N1i—Cu—N1	101.88 (6)	N1—C1—H1A	109.2
N2—Cu—O1	95.19 (5)	C2i—C1—H1A	109.2
N2i—Cu—O1	93.04 (4)	N1—C1—H1B	109.2
N1i—Cu—O1	81.26 (4)	C2i—C1—H1B	109.2
N1—Cu—O1	91.17 (4)	H1A—C1—H1B	107.9
N2—Cu—O1i	93.04 (4)	N2—C2—C1i	109.24 (10)
N2i—Cu—O1i	95.19 (5)	N2—C2—H2C	109.8
N1i—Cu—O1i	91.17 (4)	C1i—C2—H2C	109.8
N1—Cu—O1i	81.26 (4)	N2—C2—H2D	109.8
O1—Cu—O1i	168.02 (6)	C1i—C2—H2D	109.8
C3—O1—Cu	111.12 (7)	H2C—C2—H2D	108.3
C3—O1—H1	124.4	O1—C3—C4i	110.83 (11)
Cu—O1—H1	124.4	O1—C3—H3A	109.5
C4—N1—C1	116.07 (12)	C4i—C3—H3A	109.5
C4—N1—Cu	107.91 (8)	O1—C3—H3B	109.5
C1—N1—Cu	107.95 (8)	C4i—C3—H3B	109.5
C4—N1—H2	102.3 (14)	H3A—C3—H3B	108.1
C1—N1—H2	111.3 (14)	N1—C4—C3i	112.19 (11)
Cu—N1—H2	111.2 (14)	N1—C4—H4A	109.2
C2—N2—Cu	109.47 (8)	C3i—C4—H4A	109.2
C2—N2—H2A	109.8	N1—C4—H4B	109.2
Cu—N2—H2A	109.8	C3i—C4—H4B	109.2
C2—N2—H2B	109.8	H4A—C4—H4B	107.9
Cu—N2—H2B	109.8
N2—Cu—O1—C3	79.30 (10)	O1i—Cu—N1—C1	105.41 (9)
N2i—Cu—O1—C3	172.76 (10)	N2i—Cu—N2—C2	−157.09 (10)
N1i—Cu—O1—C3	−2.56 (10)	N1i—Cu—N2—C2	16.74 (8)
N1—Cu—O1—C3	−104.40 (10)	O1—Cu—N2—C2	−63.74 (9)
O1i—Cu—O1—C3	−53.89 (10)	O1i—Cu—N2—C2	107.54 (9)
N2i—Cu—N1—C4	−117.16 (10)	C4—N1—C1—C2i	88.06 (14)
N1i—Cu—N1—C4	68.61 (10)	Cu—N1—C1—C2i	−33.15 (13)
O1—Cu—N1—C4	149.92 (10)	Cu—N2—C2—C1i	−38.94 (13)
O1i—Cu—N1—C4	−20.75 (10)	Cu—O1—C3—C4i	25.17 (15)
N2i—Cu—N1—C1	9.00 (8)	C1—N1—C4—C3i	−79.92 (15)
N1i—Cu—N1—C1	−165.23 (9)	Cu—N1—C4—C3i	41.32 (15)
O1—Cu—N1—C1	−83.92 (8)

Symmetry codes: (i) −x+3/2, y, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ii	0.90	2.14	2.9963 (17)	159.
O1—H1···O4iii	0.93	2.28	3.1256 (16)	152.
N2—H2B···O4iv	0.90	2.58	3.3356 (18)	141.
N1—H2···O4v	0.92 (2)	2.49 (2)	3.2449 (18)	139.8 (18)

Symmetry codes: (ii) y+1/4, −x+5/4, z−1/4; (iii) −y+3/4, x−1/4, −z+1/4; (iv) y+3/4, x−1/4, z−1/4; (v) y+1/4, −x+3/4, −z+1/4.