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

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.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.121
• Data-to-parameter ratio = 38.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT143_ALERT_4_C su on c - Axis Small or Missing ................    0.00010 Ang.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     --  C3      ..        6.4 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          N3
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          7
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         41
PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc)          3

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu     --  O1      ..       14.4 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu     --  N1      ..        5.0 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu     --  N2      ..        5.0 su
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.13 Ratio
PLAT793_ALERT_4_G The Model has Chirality at N1      (Verify) ....          R
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu      (II)          2.06

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. 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).

Related literature

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

S2. 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.

S3. 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.

Computing details

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

	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

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) Å^3	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 monochromator	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 F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0796P)^2 + 2.0215P] where P = (Fo^2 + 2Fc^2)/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)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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

Symmetry code: (i) −x+3/2, y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3^ii	0.90	2.14	2.9963 (17)	159
O1—H1···O4^iii	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.