{2-[2-(Ethyl­amino)ethyl­imino­meth­yl]-5-methoxy­phenolato}(thio­cyanato-κN)­copper(II)

In the title mononuclear copper(II) complex, [Cu(C₁₂H₁₇N₂O₂)(NCS)], the Cu^II atom is four-coordinated by an NNO-donor set of the tridentate Schiff base ligand and the N atom of a terminal thio­cyanate ligand in a slightly distorted square-planar geometry.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.044
• wR factor = 0.129
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          7
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2N    ...          ?
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        112

Alert level G
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ..           2
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

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

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

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S1. Comment

Copper(II) complexes with Schiff base ligands have received much attention in coordination chemistry (Rai, 2010; Roy & Manassero, 2010; Rajasekar et al., 2010; Dede et al., 2009). In the present work, we report the the crystal structure of a new copper(II) complex, the title compound, with the Schiff base ligand 2-[(2-ethylaminoethylimino)methyl]-5-methoxyphenolate.

The Cu^II atom in the title complex is four-coordinated by the NNO donor set of the Schiff base ligand, and the N atom of the terminal thiocyanate ligand, in a square-planar geometry. The coordination bond distances (Table 1) are within normal ranges and comparable to those in related complexes (Roper et al., 1989; Adams et al., 2003).

Related literature

For Cu^II complexes with Schiff base ligands, see: Dede et al. (2009); Rai (2010); Rajasekar et al. (2010); Roper et al. (1989). For related structures, see: Adams et al. (2003); Roy & Manassero (2010).

S2. Experimental

Equimolar quantities (1 mmol each) of 2-hydroxy-4-methoxybenzaldehyde, N-ethylethylenediamine, ammonium thiocyanate, and copper nitrate were mixed and stirred in a methanol-acetonitrile (2:1 v/v) solution at room temperature for 3 h. The solution was allowed to evaporate slowly to give needle-shaped single crystals.

S3. Refinement

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C–H = 0.93–0.97 Å, N–H = 0.91 Å, and U_iso(H) = 1.2U_eq(C,N) and 1.5U_eq(C_methyl).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 molecular structure of the title compound, showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level.

{2-[2-(Ethylamino)ethyliminomethyl]-5-methoxyphenolato}(thiocyanato-κN) copper(II)

Crystal data

[Cu(C12H17N2O2)(NCS)]	F(000) = 708
Mr = 342.90	Dx = 1.533 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2310 reflections
a = 12.296 (6) Å	θ = 2.6–25.0°
b = 10.582 (5) Å	µ = 1.61 mm^−1
c = 12.480 (6) Å	T = 293 K
β = 113.810 (7)°	Block cut from needle, blue
V = 1485.7 (12) Å^3	0.30 × 0.27 × 0.27 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3282 independent reflections
Radiation source: fine-focus sealed tube	2123 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scan	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.643, Tmax = 0.670	k = −13→13
8523 measured reflections	l = −16→10

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0551P)^2 + 1.5145P] where P = (Fo^2 + 2Fc^2)/3
3282 reflections	(Δ/σ)max = 0.001
183 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.55890 (4)	0.38272 (4)	0.94272 (4)	0.04744 (18)
N1	0.6492 (3)	0.3114 (3)	1.0844 (3)	0.0465 (8)
N2	0.4301 (3)	0.2831 (3)	0.9449 (3)	0.0596 (9)
H2N	0.3686	0.3382	0.9287	0.072*
N3	0.4579 (3)	0.4525 (3)	0.7995 (3)	0.0488 (8)
O1	0.6770 (2)	0.4836 (3)	0.9392 (2)	0.0543 (7)
O2	1.0326 (3)	0.7210 (3)	1.0840 (3)	0.0718 (9)
S1	0.30391 (13)	0.57348 (14)	0.60132 (10)	0.0790 (4)
C1	0.7807 (3)	0.5063 (4)	1.0246 (3)	0.0460 (9)
C2	0.8513 (4)	0.5995 (4)	1.0075 (3)	0.0516 (10)
H2	0.8249	0.6414	0.9360	0.062*
C3	0.9598 (4)	0.6314 (4)	1.0944 (4)	0.0552 (10)
C4	0.9978 (5)	0.7842 (5)	0.9760 (4)	0.0858 (17)
H4A	0.9877	0.7240	0.9152	0.129*
H4B	1.0578	0.8443	0.9801	0.129*
H4C	0.9240	0.8276	0.9590	0.129*
C5	1.0006 (4)	0.5683 (5)	1.2010 (4)	0.0664 (12)
H5	1.0740	0.5885	1.2598	0.080*
C6	0.9326 (4)	0.4776 (4)	1.2183 (4)	0.0629 (12)
H6	0.9605	0.4365	1.2904	0.075*
C7	0.8217 (4)	0.4421 (4)	1.1327 (3)	0.0480 (9)
C8	0.7542 (4)	0.3458 (4)	1.1546 (3)	0.0510 (10)
H8	0.7884	0.3035	1.2258	0.061*
C9	0.5884 (4)	0.2097 (4)	1.1177 (4)	0.0597 (11)
H9A	0.6175	0.2042	1.2023	0.072*
H9B	0.6024	0.1293	1.0880	0.072*
C10	0.4593 (4)	0.2402 (4)	1.0658 (4)	0.0630 (12)
H10A	0.4129	0.1660	1.0658	0.076*
H10B	0.4421	0.3062	1.1106	0.076*
C11	0.3850 (5)	0.1848 (5)	0.8565 (4)	0.0792 (15)
H11A	0.4379	0.1126	0.8819	0.095*
H11B	0.3879	0.2159	0.7845	0.095*
C12	0.2620 (5)	0.1410 (5)	0.8301 (4)	0.0816 (16)
H12A	0.2569	0.1124	0.9009	0.122*
H12B	0.2422	0.0727	0.7748	0.122*
H12C	0.2074	0.2095	0.7976	0.122*
C13	0.3932 (4)	0.5018 (4)	0.7173 (3)	0.0459 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0569 (3)	0.0430 (3)	0.0396 (3)	−0.0019 (2)	0.0166 (2)	0.00224 (19)
N1	0.063 (2)	0.0397 (17)	0.0379 (16)	0.0056 (15)	0.0213 (15)	0.0010 (13)
N2	0.077 (3)	0.0499 (19)	0.0485 (19)	−0.0137 (18)	0.0216 (18)	0.0024 (15)
N3	0.055 (2)	0.0471 (18)	0.0396 (17)	−0.0061 (16)	0.0142 (15)	0.0017 (14)
O1	0.0489 (16)	0.0666 (18)	0.0378 (14)	−0.0067 (14)	0.0073 (12)	0.0121 (12)
O2	0.0598 (19)	0.089 (2)	0.0557 (19)	−0.0252 (18)	0.0123 (15)	−0.0104 (16)
S1	0.0831 (9)	0.1010 (10)	0.0463 (6)	0.0400 (8)	0.0192 (6)	0.0180 (6)
C1	0.046 (2)	0.050 (2)	0.0409 (19)	0.0040 (18)	0.0167 (17)	−0.0023 (17)
C2	0.048 (2)	0.063 (3)	0.040 (2)	−0.002 (2)	0.0142 (17)	−0.0014 (18)
C3	0.052 (2)	0.060 (3)	0.051 (2)	−0.004 (2)	0.0181 (19)	−0.0141 (19)
C4	0.078 (4)	0.106 (4)	0.069 (3)	−0.044 (3)	0.024 (3)	−0.008 (3)
C5	0.051 (3)	0.078 (3)	0.054 (3)	0.002 (2)	0.004 (2)	−0.007 (2)
C6	0.063 (3)	0.068 (3)	0.045 (2)	0.010 (2)	0.008 (2)	0.003 (2)
C7	0.047 (2)	0.050 (2)	0.043 (2)	0.0092 (19)	0.0146 (17)	0.0009 (17)
C8	0.064 (3)	0.048 (2)	0.038 (2)	0.018 (2)	0.0180 (19)	0.0068 (17)
C9	0.087 (3)	0.044 (2)	0.047 (2)	0.001 (2)	0.025 (2)	0.0102 (18)
C10	0.086 (4)	0.052 (2)	0.052 (2)	−0.018 (2)	0.029 (2)	0.002 (2)
C11	0.103 (4)	0.073 (3)	0.065 (3)	−0.030 (3)	0.037 (3)	−0.011 (3)
C12	0.078 (3)	0.093 (4)	0.057 (3)	−0.029 (3)	0.009 (2)	−0.002 (3)
C13	0.054 (2)	0.046 (2)	0.038 (2)	−0.0007 (19)	0.0193 (18)	−0.0025 (17)

Geometric parameters (Å, º)

Cu1—O1	1.817 (3)	C4—H4B	0.96
Cu1—N1	1.828 (3)	C4—H4C	0.96
Cu1—N3	1.868 (3)	C5—C6	1.346 (6)
Cu1—N2	1.912 (4)	C5—H5	0.93
N1—C8	1.286 (5)	C6—C7	1.402 (6)
N1—C9	1.463 (5)	C6—H6	0.93
N2—C11	1.453 (6)	C7—C8	1.410 (6)
N2—C10	1.474 (5)	C8—H8	0.93
N2—H2N	0.91	C9—C10	1.488 (6)
N3—C13	1.139 (5)	C9—H9A	0.97
O1—C1	1.313 (4)	C9—H9B	0.97
O2—C3	1.346 (5)	C10—H10A	0.97
O2—C4	1.409 (6)	C10—H10B	0.97
S1—C13	1.610 (4)	C11—C12	1.487 (7)
C1—C2	1.386 (6)	C11—H11A	0.97
C1—C7	1.409 (5)	C11—H11B	0.97
C2—C3	1.379 (6)	C12—H12A	0.96
C2—H2	0.93	C12—H12B	0.96
C3—C5	1.389 (6)	C12—H12C	0.96
C4—H4A	0.96
O1—Cu1—N1	94.97 (13)	C3—C5—H5	120.4
O1—Cu1—N3	88.49 (13)	C5—C6—C7	122.9 (4)
N1—Cu1—N3	176.29 (15)	C5—C6—H6	118.5
O1—Cu1—N2	177.40 (14)	C7—C6—H6	118.5
N1—Cu1—N2	86.67 (15)	C6—C7—C1	117.6 (4)
N3—Cu1—N2	89.82 (15)	C6—C7—C8	120.9 (4)
C8—N1—C9	120.1 (3)	C1—C7—C8	121.6 (4)
C8—N1—Cu1	126.4 (3)	N1—C8—C7	125.5 (3)
C9—N1—Cu1	113.4 (3)	N1—C8—H8	117.3
C11—N2—C10	114.7 (3)	C7—C8—H8	117.3
C11—N2—Cu1	116.6 (3)	N1—C9—C10	107.1 (3)
C10—N2—Cu1	108.9 (3)	N1—C9—H9A	110.3
C11—N2—H2N	105.2	C10—C9—H9A	110.3
C10—N2—H2N	105.2	N1—C9—H9B	110.3
Cu1—N2—H2N	105.2	C10—C9—H9B	110.3
C13—N3—Cu1	174.4 (3)	H9A—C9—H9B	108.5
C1—O1—Cu1	127.7 (2)	N2—C10—C9	106.8 (4)
C3—O2—C4	118.0 (3)	N2—C10—H10A	110.4
O1—C1—C2	118.0 (3)	C9—C10—H10A	110.4
O1—C1—C7	122.9 (4)	N2—C10—H10B	110.4
C2—C1—C7	119.1 (4)	C9—C10—H10B	110.4
C3—C2—C1	121.3 (4)	H10A—C10—H10B	108.6
C3—C2—H2	119.3	N2—C11—C12	115.7 (4)
C1—C2—H2	119.3	N2—C11—H11A	108.4
O2—C3—C2	124.5 (4)	C12—C11—H11A	108.4
O2—C3—C5	115.7 (4)	N2—C11—H11B	108.4
C2—C3—C5	119.8 (4)	C12—C11—H11B	108.4
O2—C4—H4A	109.5	H11A—C11—H11B	107.4
O2—C4—H4B	109.5	C11—C12—H12A	109.5
H4A—C4—H4B	109.5	C11—C12—H12B	109.5
O2—C4—H4C	109.5	H12A—C12—H12B	109.5
H4A—C4—H4C	109.5	C11—C12—H12C	109.5
H4B—C4—H4C	109.5	H12A—C12—H12C	109.5
C6—C5—C3	119.3 (4)	H12B—C12—H12C	109.5
C6—C5—H5	120.4	N3—C13—S1	178.8 (4)