catena-Poly[[(2-{1-[2-(2-amino­ethyl­amino)ethyl­imino]­eth­yl}-5-methoxy­phenolato-κ4N,N′,N′′,O)copper(II)]-μ-nitrato-κ2O:O′]

Wang, S.; Li, Z.; Wang, X.; Yu, X.

doi:10.1107/S1600536808021880

catena-Poly[[(2-{1-[2-(2-aminoethylamino)ethylimino]ethyl}-5-methoxyphenolato-κ⁴N,N′,N′′,O)copper(II)]-μ-nitrato-κ²O:O′]

In the title compound, [Cu(C₁₃H₂₀N₃O₂)(NO₃)]_n, the Cu^II atom is chelated by the Schiff base ligand via three N atoms and one O atom lying in an approximate square plane (r.m.s. deviation = 0.04 Å). The complex molecules are linked into a polymeric chain by bridging nitrate anions, forming axial Cu—O bonds of 2.535 (6) and 2.676 (7) Å, completing a distorted octahedral coordination geometry. The NH groups of the ligand form hydrogen bonds to the nitrate anions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808021880/bi2290sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808021880/bi2290Isup2.hkl Contains datablock I

CCDC reference: 702423

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.009 Å
R factor = 0.060
wR factor = 0.160
Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O4
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         N3
PLAT412_ALERT_2_B Short Intra XH3 .. XHn     H4     ..  H9B     ..       1.75 Ang.

Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.17
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O3     --  N3      ..       5.29 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O4     --  N3      ..       6.56 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    --  N4      ..       5.40 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cu1
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       2000 Deg.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1     ..  O3      ..       2.65 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4B    ..  O4      ..       2.66 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT793_ALERT_4_G Check the Absolute Configuration of N2     .....          R

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Schiff bases have been studied as ligands for a long time due to instant and enduring popularity from their easy synthesis and versatility in complexes. They play an important role in the development of coordination chemistry as well as inorganic biochemistry, catalysis, optical materials and so on (Garnovskii et al., 1993; Huang et al., 2002). Considerable attention has been focused on the syntheses and structures of Cu^II and Ni^II complexes. The Ni^II complexes with multidentate Schiff-base ligands have aroused particular interest because Ni can exhibit several oxidation states and may provide the basis of models for active sites of biological systems. On the other hand, the main attention in the optically active Schiff-base complexes is concentrated on their catalytic abilities in stereoselective synthesis (Bhadbhade & Srinivas, 1993; Bunce et al., 1998).

Related literature top

For related literature, see: Garnovskii et al. (1993); Huang et al. (2002); Bhadbhade & Srinivas (1993); Bunce et al. (1998).

Experimental top

A mixture of copper(II) nitrate hemi(pentahydrate) (1 mmol) and N-(2-hydroxy-4-methoxybenzyl)bisethylenetriamine (1 mmol) in 20 ml methanol was refluxed for two hours. The resulting solution was cooled and filtered and the filtrate was evaporated naturally at room temperature. Two day later, blue blocks were obtained with a yield of 16 %. Elemental analysis calculated: C 41.60, H 5.07, N 14.93 %; found: C 41.51, H 5.08, N 14.85 %.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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 asymmetric unit of the title compound drawn with 30% probability displacement ellipsoids for the non-hydrogen atoms.

catena-Poly[[(2-{1-[2-(2-aminoethylamino)ethylimino]ethyl}-5- methoxyphenolato-κ⁴N,N',N'',O)copper(II)]-µ- nitrato-κ²O:O'] top

Crystal data top

[Cu(C₁₃H₂₀N₃O₂)(NO₃)]	Z = 2
M_r = 375.87	F(000) = 390
Triclinic, P1	D_x = 1.587 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2012 (10) Å	Cell parameters from 2739 reflections
b = 10.095 (2) Å	θ = 2.2–25.0°
c = 11.581 (2) Å	µ = 1.42 mm⁻¹
α = 69.15 (2)°	T = 293 K
β = 89.73 (2)°	Block, blue
γ = 89.95 (2)°	0.43 × 0.28 × 0.22 mm
V = 786.8 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	2739 independent reflections
Radiation source: fine-focus sealed tube	1896 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
T_min = 0.569, T_max = 0.730	k = −11→12
4891 measured reflections	l = −13→13

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.107P)² + 0.9393P] where P = (F_o² + 2F_c²)/3
2739 reflections	(Δ/σ)_max = 0.016
213 parameters	Δρ_max = 0.91 e Å⁻³
1 restraint	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Cu(C₁₃H₂₀N₃O₂)(NO₃)]	γ = 89.95 (2)°
M_r = 375.87	V = 786.8 (3) Å³
Triclinic, P1	Z = 2
a = 7.2012 (10) Å	Mo Kα radiation
b = 10.095 (2) Å	µ = 1.42 mm⁻¹
c = 11.581 (2) Å	T = 293 K
α = 69.15 (2)°	0.43 × 0.28 × 0.22 mm
β = 89.73 (2)°

Data collection top

Bruker APEXII CCD diffractometer	2739 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1896 reflections with I > 2σ(I)
T_min = 0.569, T_max = 0.730	R_int = 0.029
4891 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	1 restraint
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.91 e Å⁻³
2739 reflections	Δρ_min = −0.42 e Å⁻³
213 parameters

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. 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 > σ(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
Cu1	0.72893 (13)	0.60509 (7)	0.61951 (6)	0.0396 (3)
C2	0.7556 (9)	0.9968 (6)	0.1737 (5)	0.0428 (13)
C3	0.7606 (11)	1.1062 (6)	0.2212 (6)	0.0533 (16)
H3	0.7675	1.2001	0.1682	0.064*
C4	0.7551 (10)	1.0737 (7)	0.3470 (6)	0.0511 (16)
H4	0.7594	1.1475	0.3772	0.061*
C5	0.7434 (8)	0.9336 (6)	0.4323 (5)	0.0355 (12)
C6	0.7281 (8)	0.8240 (6)	0.3825 (5)	0.0379 (12)
C7	0.7387 (9)	0.8620 (6)	0.2511 (6)	0.0430 (14)
H7	0.7337	0.7905	0.2181	0.052*
C8	0.7388 (8)	0.9117 (6)	0.5646 (5)	0.0364 (12)
C9	0.7516 (10)	1.0377 (7)	0.6051 (6)	0.0503 (15)
H9A	0.6518	1.0342	0.6614	0.075*
H9B	0.7428	1.1235	0.5342	0.075*
H9C	0.8682	1.0357	0.6455	0.075*
C10	0.7303 (11)	0.7615 (7)	0.7821 (5)	0.0519 (16)
H10A	0.6546	0.8307	0.8011	0.062*
H10B	0.8577	0.7716	0.8046	0.062*
C11	0.6598 (11)	0.6117 (8)	0.8535 (6)	0.0625 (19)
H11A	0.6895	0.5850	0.9404	0.075*
H11B	0.5260	0.6079	0.8456	0.075*
C12	0.6772 (13)	0.3710 (8)	0.8405 (7)	0.0637 (19)
H12A	0.5426	0.3719	0.8441	0.076*
H12B	0.7233	0.3152	0.9219	0.076*
C13	0.7406 (11)	0.3068 (7)	0.7474 (6)	0.0562 (17)
H13A	0.8729	0.2881	0.7557	0.067*
H13B	0.6766	0.2177	0.7620	0.067*
N1	0.7187 (7)	0.7844 (5)	0.6477 (4)	0.0402 (11)
N2	0.7485 (8)	0.5147 (5)	0.8029 (4)	0.0415 (11)
H1	0.871 (2)	0.517 (7)	0.816 (6)	0.050*
N3	0.2005 (9)	0.5570 (6)	0.6866 (6)	0.0550 (14)
N4	0.6991 (8)	0.4070 (5)	0.6214 (5)	0.0500 (13)
H4A	0.5822	0.3937	0.6006	0.060*
H4B	0.7773	0.3921	0.5664	0.060*
O1	0.7593 (8)	1.0387 (5)	0.0493 (4)	0.0616 (13)
O2	0.7129 (9)	0.6914 (4)	0.4468 (4)	0.0633 (15)
O3	0.0805 (9)	0.5939 (7)	0.6146 (6)	0.0869 (18)
O4	0.3604 (9)	0.5871 (7)	0.6519 (7)	0.096 (2)
O5	0.1656 (9)	0.4935 (8)	0.7984 (6)	0.098 (2)
C1	0.7476 (17)	0.9303 (8)	−0.0054 (6)	0.080 (3)
H1A	0.8518	0.8674	0.0206	0.121*
H1B	0.7488	0.9741	−0.0938	0.121*
H1C	0.6346	0.8776	0.0207	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0575 (5)	0.0319 (4)	0.0322 (4)	−0.0024 (3)	0.0031 (3)	−0.0149 (3)
C2	0.040 (3)	0.038 (3)	0.048 (3)	−0.004 (2)	0.000 (3)	−0.013 (3)
C3	0.076 (5)	0.029 (3)	0.046 (3)	0.007 (3)	−0.016 (3)	0.000 (2)
C4	0.070 (4)	0.035 (3)	0.048 (3)	−0.004 (3)	0.013 (3)	−0.015 (3)
C5	0.032 (3)	0.033 (3)	0.048 (3)	−0.006 (2)	0.013 (2)	−0.022 (2)
C6	0.045 (3)	0.033 (3)	0.035 (3)	−0.006 (2)	−0.003 (2)	−0.011 (2)
C7	0.050 (4)	0.038 (3)	0.048 (3)	−0.005 (3)	0.015 (3)	−0.025 (3)
C8	0.031 (3)	0.030 (3)	0.051 (3)	0.001 (2)	0.006 (2)	−0.018 (2)
C9	0.058 (4)	0.046 (3)	0.060 (4)	−0.001 (3)	−0.001 (3)	−0.034 (3)
C10	0.077 (5)	0.048 (3)	0.037 (3)	0.001 (3)	0.002 (3)	−0.022 (3)
C11	0.064 (5)	0.078 (5)	0.053 (4)	−0.009 (4)	0.010 (3)	−0.033 (4)
C12	0.087 (6)	0.053 (4)	0.053 (4)	−0.005 (4)	−0.007 (4)	−0.021 (3)
C13	0.072 (5)	0.044 (4)	0.053 (4)	0.000 (3)	0.016 (3)	−0.020 (3)
N1	0.046 (3)	0.044 (3)	0.038 (2)	−0.001 (2)	0.005 (2)	−0.025 (2)
N2	0.046 (3)	0.049 (3)	0.032 (2)	−0.003 (2)	0.002 (2)	−0.018 (2)
N3	0.055 (4)	0.055 (3)	0.057 (4)	−0.002 (3)	0.004 (3)	−0.022 (3)
N4	0.055 (3)	0.046 (3)	0.049 (3)	−0.005 (2)	0.006 (2)	−0.017 (2)
O1	0.098 (4)	0.042 (2)	0.040 (2)	−0.006 (2)	−0.007 (2)	−0.0085 (19)
O2	0.125 (5)	0.029 (2)	0.036 (2)	−0.005 (2)	0.000 (2)	−0.0107 (17)
O3	0.065 (4)	0.108 (5)	0.078 (4)	−0.005 (3)	0.020 (3)	−0.022 (3)
O4	0.060 (4)	0.100 (5)	0.147 (6)	0.018 (3)	−0.040 (4)	−0.067 (5)
O5	0.071 (4)	0.137 (6)	0.076 (4)	0.003 (4)	−0.010 (3)	−0.026 (4)
C1	0.155 (9)	0.052 (4)	0.038 (3)	−0.008 (5)	−0.003 (4)	−0.020 (3)

Geometric parameters (Å, º) top

Cu1—N1	1.952 (5)	C10—C11	1.529 (10)
Cu1—N2	1.997 (5)	C10—H10A	0.970
Cu1—N4	2.004 (5)	C10—H10B	0.970
Cu1—O2	1.880 (4)	C11—N2	1.453 (9)
Cu1—O3ⁱ	2.535 (6)	C11—H11A	0.970
Cu1—O4	2.676 (7)	C11—H11B	0.970
C2—C7	1.342 (8)	C12—N2	1.451 (9)
C2—O1	1.350 (7)	C12—C13	1.511 (10)
C2—C3	1.398 (9)	C12—H12A	0.970
C3—C4	1.374 (9)	C12—H12B	0.970
C3—H3	0.930	C13—N4	1.481 (9)
C4—C5	1.410 (8)	C13—H13A	0.970
C4—H4	0.930	C13—H13B	0.970
C5—C6	1.422 (8)	N2—H1	0.90 (1)
C5—C8	1.468 (8)	N3—O3	1.169 (9)
C6—O2	1.284 (7)	N3—O4	1.220 (9)
C6—C7	1.433 (8)	N3—O5	1.248 (8)
C7—H7	0.930	N4—H4A	0.900
C8—N1	1.310 (7)	N4—H4B	0.900
C8—C9	1.508 (8)	O1—C1	1.449 (9)
C9—H9A	0.960	C1—H1A	0.960
C9—H9B	0.960	C1—H1B	0.960
C9—H9C	0.960	C1—H1C	0.960
C10—N1	1.493 (7)

O2—Cu1—N1	93.98 (19)	N2—C11—H11A	110.0
O2—Cu1—N2	179.4 (3)	C10—C11—H11A	110.0
N1—Cu1—N2	85.7 (2)	N2—C11—H11B	110.0
O2—Cu1—N4	95.0 (2)	C10—C11—H11B	110.0
N1—Cu1—N4	167.3 (2)	H11A—C11—H11B	108.4
N2—Cu1—N4	85.4 (2)	N2—C12—C13	108.5 (6)
O2—Cu1—O4	93.8 (3)	N2—C12—H12A	110.0
N1—Cu1—O4	87.8 (2)	C13—C12—H12A	110.0
N2—Cu1—O4	86.7 (2)	N2—C12—H12B	110.0
N4—Cu1—O4	82.8 (2)	C13—C12—H12B	110.0
C7—C2—O1	124.9 (5)	H12A—C12—H12B	108.4
C7—C2—C3	119.6 (6)	N4—C13—C12	109.0 (6)
O1—C2—C3	115.4 (5)	N4—C13—H13A	109.9
C4—C3—C2	119.5 (6)	C12—C13—H13A	109.9
C4—C3—H3	120.3	N4—C13—H13B	109.9
C2—C3—H3	120.3	C12—C13—H13B	109.9
C3—C4—C5	123.1 (6)	H13A—C13—H13B	108.3
C3—C4—H4	118.5	C8—N1—C10	120.5 (5)
C5—C4—H4	118.5	C8—N1—Cu1	126.7 (4)
C4—C5—C6	116.8 (5)	C10—N1—Cu1	111.3 (4)
C4—C5—C8	118.2 (5)	C12—N2—C11	118.0 (6)
C6—C5—C8	124.9 (5)	C12—N2—Cu1	108.8 (4)
O2—C6—C5	124.9 (5)	C11—N2—Cu1	106.1 (4)
O2—C6—C7	116.7 (5)	C12—N2—H1	112 (4)
C5—C6—C7	118.3 (5)	C11—N2—H1	108 (4)
C2—C7—C6	122.5 (5)	Cu1—N2—H1	103 (4)
C2—C7—H7	118.7	O3—N3—O4	119.1 (6)
C6—C7—H7	118.7	O3—N3—O5	120.6 (7)
N1—C8—C5	120.8 (5)	O4—N3—O5	120.2 (7)
N1—C8—C9	119.6 (5)	C13—N4—Cu1	108.5 (4)
C5—C8—C9	119.6 (5)	C13—N4—H4A	110.0
C8—C9—H9A	109.5	Cu1—N4—H4A	110.0
C8—C9—H9B	109.5	C13—N4—H4B	110.0
H9A—C9—H9B	109.5	Cu1—N4—H4B	110.0
C8—C9—H9C	109.5	H4A—N4—H4B	108.4
H9A—C9—H9C	109.5	C2—O1—C1	117.9 (5)
H9B—C9—H9C	109.5	C6—O2—Cu1	127.1 (4)
N1—C10—C11	107.4 (5)	N3—O4—Cu1	167.6 (6)
N1—C10—H10A	110.2	O1—C1—H1A	109.5
C11—C10—H10A	110.2	O1—C1—H1B	109.5
N1—C10—H10B	110.2	H1A—C1—H1B	109.5
C11—C10—H10B	110.2	O1—C1—H1C	109.5
H10A—C10—H10B	108.5	H1A—C1—H1C	109.5
N2—C11—C10	108.5 (6)	H1B—C1—H1C	109.5

Symmetry code: (i) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O5ⁱ	0.90 (1)	2.15 (2)	3.013 (8)	161 (6)
N2—H1···O3ⁱ	0.90 (1)	2.65 (6)	3.134 (8)	115 (5)
N4—H4A···O2ⁱⁱ	0.90	2.43	3.316 (9)	168
N4—H4B···O3ⁱⁱ	0.90	2.29	3.157 (8)	162
N4—H4B···O4ⁱⁱ	0.90	2.66	3.175 (9)	118

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₃H₂₀N₃O₂)(NO₃)]
M_r	375.87
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.2012 (10), 10.095 (2), 11.581 (2)
α, β, γ (°)	69.15 (2), 89.73 (2), 89.95 (2)
V (Å³)	786.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.42
Crystal size (mm)	0.43 × 0.28 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.569, 0.730
No. of measured, independent and observed [I > 2σ(I)] reflections	4891, 2739, 1896
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.160, 1.00
No. of reflections	2739
No. of parameters	213
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)	0.91, −0.42

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).