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

Azadbakht, R.; Amiri Rudbari, H.; Bruno, G.

doi:10.1107/S1600536811030637

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page m1203

doi:10.1107/S1600536811030637

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

Reza Azadbakht,^a ^* Hadi Amiri Rudbari ^b and Giuseppe Bruno ^b

^aDepartment of Chemistry, Payame Noor University, Hamedan, Iran, and ^bDipartimento di Chimica Inorganica, Vill. S. Agata, Salita Sperone 31, Università di Messina 98166 Messina, Italy
^*Correspondence e-mail: r_azadbakht@yahoo.com

(Received 24 July 2011; accepted 29 July 2011; online 6 August 2011)

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, I 4₁ /a c d
a = 14.6640 (1) Å
c = 29.8298 (7) Å
V = 6414.39 (16) Å³
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[F² > 2σ(F²)] = 0.035
wR(F²) = 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

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⋯O4^iv	0.92 (2)	2.49 (2)	3.2449 (18)	139.8 (18)
Symmetry codes: (i) $[y+{\script{1\over 4}}, -x+{\script{5\over 4}}, z-{\script{1\over 4}}]$ ; (ii) $[-y+{\script{3\over 4}}, x-{\script{1\over 4}}, -z+{\script{1\over 4}}]$ ; (iii) $[y+{\script{3\over 4}}, x-{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (iv) $[y+{\script{1\over 4}}, -x+{\script{3\over 4}}, -z+{\script{1\over 4}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811030637/qm2020sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030637/qm2020Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 (Sheldrick, 2008).

Figures top

	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.

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

Crystal data top

[Cu(C₄H₁₂N₂O)₂](NO₃)₂	D_x = 1.640 Mg m⁻³
M_r = 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 top

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

Refinement top

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(F_o²) + (0.0796P)² + 2.0215P] where P = (F_o² + 2F_c²)/3
4172 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

[Cu(C₄H₁₂N₂O)₂](NO₃)₂	Z = 16
M_r = 395.87	Mo Kα radiation
Tetragonal, I4₁/acd	µ = 1.41 mm⁻¹
a = 14.6640 (1) Å	T = 296 K
c = 29.8298 (7) Å	0.45 × 0.36 × 0.23 mm
V = 6414.39 (16) Å³

Data collection top

Bruker APEXII CCD diffractometer	4172 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	3346 reflections with I > 2σ(I)
T_min = 0.532, T_max = 0.741	R_int = 0.047
224935 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.67 e Å⁻³
4172 reflections	Δρ_min = −0.72 e Å⁻³
109 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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 code: (i) −x+3/2, y, −z.

Hydrogen-bond geometry (Å, º) top

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···O4^iv	0.90	2.58	3.3356 (18)	141
N1—H2···O4^v	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.

Experimental details

Crystal data
Chemical formula	[Cu(C₄H₁₂N₂O)₂](NO₃)₂
M_r	395.87
Crystal system, space group	Tetragonal, I4₁/acd
Temperature (K)	296
a, c (Å)	14.6640 (1), 29.8298 (7)
V (Å³)	6414.39 (16)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	1.41
Crystal size (mm)	0.45 × 0.36 × 0.23

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.532, 0.741
No. of measured, independent and observed [I > 2σ(I)] reflections	224935, 4172, 3346
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.856

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.121, 1.04
No. of reflections	4172
No. of parameters	109
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.72

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.90	2.14	2.9963 (17)	159.0
O1—H1···O4ⁱⁱ	0.93	2.28	3.1256 (16)	151.6
N2—H2B···O4ⁱⁱⁱ	0.90	2.58	3.3356 (18)	141.4
N1—H2···O4^iv	0.92 (2)	2.49 (2)	3.2449 (18)	139.8 (18)

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

Acknowledgements

We are grateful to Payame Noor University (PNU) for financial support.

References

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