{6-[(2-Anilinoeth­yl)imino­meth­yl]-2-eth­oxyphenolato}(thio­cyanato-κN)­copper(II)

In the title complex, [Cu(C₁₇H₁₉N₂O₂)(NCS)], the Cu^II atom is chelated by the phenolate O atom, the imine N atom and the amine N atom of the N,N′,O-tridentate 2-eth­oxy-6-[(2-anilino­ethyl)­iminometh­yl]phenolate ligand, and by the N atom of a thio­cyanate anion, forming a distorted CuON₃ square-planar geometry. The dihedral angle between the aromatic rings of the ligand is 67.9 (4)°. In the crystal, inversion dimers linked by pairs of N—H...O hydrogen bonds occur, generating R₂²(8) loops.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.055
• wR factor = 0.182
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT241_ALERT_2_A Check High      Ueq as Compared to Neighbors for        C16

Author Response: This is caused by the disorder of the ethoxy and benzene groups.

Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.11 Ratio
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O2     --  C16     ..       7.75 su
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C10
PLAT331_ALERT_2_B Small Average Phenyl   C-C Dist. C10    -C15           1.35 Ang.

Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.79 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C16    --  C17     ..       5.43 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C5

Author Response: This is caused by the disorder of the ethoxy and benzene groups.

PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C11

Author Response: This is caused by the disorder of the ethoxy and benzene groups.

PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C12

Author Response: This is caused by the disorder of the ethoxy and benzene groups.

PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C14

Author Response: This is caused by the disorder of the ethoxy and benzene groups.

PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C15

Author Response: This is caused by the disorder of the ethoxy and benzene groups.

PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C18
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         12
PLAT234_ALERT_4_C Large Hirshfeld Difference O2     --  C3      ..       0.16 Ang.
PLAT731_ALERT_1_C Bond    Calc     0.90(4), Rep   0.901(10) ......       4.00 su-Ra
              N2   -H2      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(4), Rep   0.901(10) ......       4.00 su-Ra
              N2   -H2      1.555   1.555
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         11

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         13
PLAT793_ALERT_4_G The Model has Chirality at N2      (Verify) ....          R

   1 ALERT level A = In general: serious problem
   5 ALERT level B = Potentially serious problem
  14 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  14 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 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

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S1. Comment

Copper(II) complexes have been received much attention for their versatile biological activities and interesting structures (Collinson & Fenton, 1996; Hossain et al., 1996; Tarafder et al., 2002; Musie et al., 2003; García-Raso et al., 2003). Considerable effort has been made to construct a variety of copper(II) complexes in an attempt to model the physical and chemical behaviour of copper-containing enzymes (Reddy et al., 2000). The peculiarity of copper lies in its ability to form complexes with coordination number four, five, and six (Ray et al., 2003; Arnold et al., 2003; Raptopoulou et al., 1998).

As part of our onging investigations into urease inhibitors (Wang et al., 2009a,b; Wang, 2009), we have synthesized the title compound, (I), a new Cu^II complex, and its crystal structure is reported here. The Cu^II atom in the complex is chelated by the phenolate O atom, imine N atom, and the amine N atom of 2-ethoxy-6-[(2-phenylaminoethylimino)methyl]phenolate, and by the N atom of a thiocyanate ligand, giving a square planar geometry (Fig. 1). The coordinate bond lengths and angles (Table 1) are typical and are comparable with those observed in other related copper(II) complexes (Hebbachi & Benali-Cherif, 2005; Butcher et al., 2003; Elmali et al., 2000; Warda et al., 1997).

Related literature

For background to the structures and properties of copper complexes, see: Collinson & Fenton (1996); Hossain et al. (1996); Tarafder et al. (2002); Musie et al. (2003); García-Raso et al. (2003); Reddy et al. (2000); Ray et al. (2003); Arnold et al. (2003); Raptopoulou et al. (1998). For related structures, see: Wang et al. (2009a,b); Wang (2009); Hebbachi & Benali-Cherif (2005); Butcher et al. (2003); Elmali et al. (2000); Warda et al. (1997).

S2. Experimental

3-Ethoxysalicylaldehyde (1.0 mmol, 166 mg), N-phenyl-1,2-diaminoethane (1.0 mmol, 136 mg), ammonium thiocyanate (1.0 mmol, 76 mg), and Cu(CH₃COO)₂.H₂O (1.0 mmol, 200 mg) were dissolved in methanol (80 ml). The mixture was stirred at room temperature for about 1 h to give a blue solution. After keeping the solution in air for a few days, blue blocks of (I) were formed.

S3. Refinement

H2 was located from a difference Fourier map and refined isotropically, with N—H distance of 0.90 (1) Å. Other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93-0.97 Å, and with U_iso(H) set at 1.2U_eq(C) and 1.5U_eq(C17).

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 (I), showing displacement ellipsoids drawn at the 30% probability level.

{6-[(2-Anilinoethyl)iminomethyl]-2-ethoxyphenolato}(thiocyanato- κN)copper(II)

Crystal data

[Cu(C17H19N2O2)(NCS)]	F(000) = 1672
Mr = 404.96	Dx = 1.484 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2506 reflections
a = 13.6786 (5) Å	θ = 2.4–24.9°
b = 10.4938 (4) Å	µ = 1.34 mm^−1
c = 25.2618 (10) Å	T = 298 K
V = 3626.1 (2) Å^3	Block, blue
Z = 8	0.30 × 0.27 × 0.27 mm

Data collection

Bruker SMART CCD diffractometer	3746 independent reflections
Radiation source: fine-focus sealed tube	2041 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
ω scan	θmax = 26.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→16
Tmin = 0.690, Tmax = 0.714	k = −13→12
19741 measured reflections	l = −26→31

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.182	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0843P)^2 + 3.6378P] where P = (Fo^2 + 2Fc^2)/3
3746 reflections	(Δ/σ)max = 0.001
229 parameters	Δρmax = 1.25 e Å^−3
13 restraints	Δρmin = −0.64 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	0.88473 (4)	0.07765 (5)	0.49939 (2)	0.0424 (2)
O1	0.9189 (3)	0.0617 (3)	0.57256 (13)	0.0498 (9)
O2	0.9226 (4)	−0.0030 (7)	0.67464 (19)	0.0976 (17)
S1	0.82168 (12)	−0.35452 (14)	0.52360 (11)	0.1050 (8)
N1	0.9061 (3)	0.2590 (4)	0.50007 (17)	0.0454 (10)
N2	0.9049 (3)	0.0938 (4)	0.41821 (16)	0.0468 (10)
N3	0.8557 (4)	−0.1032 (4)	0.49588 (17)	0.0568 (12)
C1	0.9081 (4)	0.2849 (6)	0.5943 (2)	0.0625 (15)
C2	0.9123 (4)	0.1538 (6)	0.6078 (2)	0.0528 (14)
C3	0.9115 (5)	0.1206 (8)	0.6623 (2)	0.0731 (18)
C4	0.9057 (6)	0.2158 (12)	0.7003 (3)	0.108 (3)
H4	0.9043	0.1930	0.7358	0.130*
C5	0.9020 (7)	0.3417 (12)	0.6870 (4)	0.123 (4)
H5	0.8990	0.4034	0.7134	0.148*
C6	0.9027 (5)	0.3772 (8)	0.6348 (4)	0.094 (3)
H6	0.8995	0.4631	0.6260	0.113*
C7	0.9110 (4)	0.3275 (5)	0.5412 (3)	0.0585 (15)
H7	0.9172	0.4149	0.5360	0.070*
C8	0.9046 (4)	0.3177 (5)	0.4472 (2)	0.0597 (16)
H8A	0.9436	0.3948	0.4471	0.072*
H8B	0.8382	0.3397	0.4374	0.072*
C9	0.9458 (4)	0.2233 (5)	0.4086 (2)	0.0567 (14)
H9A	0.9303	0.2500	0.3728	0.068*
H9B	1.0163	0.2207	0.4121	0.068*
C10	0.8236 (4)	0.0581 (6)	0.3843 (2)	0.0529 (14)
C11	0.7402 (5)	0.1237 (8)	0.3838 (3)	0.110 (3)
H11	0.7344	0.1955	0.4052	0.132*
C12	0.6615 (6)	0.0878 (10)	0.3522 (5)	0.124 (3)
H12	0.6035	0.1339	0.3538	0.149*
C13	0.6683 (6)	−0.0091 (11)	0.3208 (3)	0.092 (3)
H13	0.6174	−0.0291	0.2978	0.110*
C14	0.7499 (7)	−0.0807 (10)	0.3217 (3)	0.117 (3)
H14	0.7538	−0.1532	0.3006	0.141*
C15	0.8299 (6)	−0.0466 (9)	0.3544 (3)	0.105 (3)
H15	0.8861	−0.0964	0.3551	0.126*
C16	0.8566 (12)	−0.0681 (15)	0.6821 (7)	0.215 (7)
H16A	0.8254	−0.0841	0.6483	0.258*
H16B	0.8102	−0.0210	0.7036	0.258*
C17	0.8735 (8)	−0.1978 (12)	0.7090 (4)	0.154 (4)
H17A	0.8550	−0.2650	0.6853	0.232*
H17B	0.8348	−0.2029	0.7406	0.232*
H17C	0.9414	−0.2065	0.7180	0.232*
C18	0.8418 (4)	−0.2070 (5)	0.5072 (2)	0.0523 (13)
H2	0.952 (3)	0.035 (4)	0.413 (2)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0542 (4)	0.0294 (3)	0.0437 (4)	−0.0002 (2)	−0.0047 (3)	0.0060 (3)
O1	0.058 (2)	0.048 (2)	0.0435 (19)	0.0116 (17)	−0.0025 (16)	0.0050 (16)
O2	0.076 (3)	0.147 (5)	0.069 (3)	0.005 (4)	0.018 (3)	0.042 (3)
S1	0.0524 (9)	0.0341 (8)	0.228 (2)	−0.0038 (7)	−0.0174 (12)	0.0304 (11)
N1	0.042 (2)	0.033 (2)	0.061 (3)	0.0013 (16)	0.000 (2)	0.006 (2)
N2	0.047 (3)	0.051 (3)	0.042 (2)	0.003 (2)	−0.0037 (19)	0.006 (2)
N3	0.074 (3)	0.034 (2)	0.063 (3)	−0.002 (2)	−0.006 (2)	0.004 (2)
C1	0.053 (4)	0.065 (4)	0.069 (4)	0.000 (3)	0.006 (3)	−0.018 (3)
C2	0.047 (3)	0.065 (4)	0.047 (3)	0.001 (3)	0.002 (2)	−0.005 (3)
C3	0.063 (4)	0.102 (5)	0.054 (4)	0.001 (4)	0.004 (3)	0.006 (4)
C4	0.087 (6)	0.182 (10)	0.056 (4)	−0.012 (7)	0.016 (4)	−0.040 (6)
C5	0.115 (8)	0.140 (9)	0.115 (8)	−0.022 (7)	0.028 (6)	−0.067 (8)
C6	0.092 (6)	0.083 (5)	0.106 (6)	−0.011 (4)	0.028 (5)	−0.049 (5)
C7	0.054 (3)	0.036 (3)	0.086 (5)	0.003 (2)	0.005 (3)	−0.007 (3)
C8	0.058 (4)	0.043 (3)	0.078 (4)	0.001 (3)	0.004 (3)	0.028 (3)
C9	0.045 (3)	0.064 (4)	0.061 (3)	0.000 (3)	0.003 (3)	0.022 (3)
C10	0.045 (3)	0.072 (4)	0.042 (3)	−0.003 (3)	−0.003 (2)	0.012 (3)
C11	0.062 (5)	0.122 (7)	0.146 (7)	0.022 (5)	−0.032 (5)	−0.036 (6)
C12	0.068 (6)	0.140 (9)	0.164 (9)	0.010 (5)	−0.048 (6)	−0.012 (7)
C13	0.068 (5)	0.152 (8)	0.056 (4)	−0.039 (6)	−0.019 (4)	0.032 (5)
C14	0.092 (6)	0.166 (9)	0.095 (6)	−0.021 (6)	−0.019 (5)	−0.057 (6)
C15	0.067 (5)	0.140 (8)	0.108 (6)	0.007 (5)	−0.015 (4)	−0.053 (6)
C16	0.199 (10)	0.184 (10)	0.261 (11)	0.002 (8)	0.075 (8)	−0.001 (8)
C17	0.148 (7)	0.157 (8)	0.158 (7)	−0.017 (6)	0.054 (6)	0.036 (6)
C18	0.046 (3)	0.034 (3)	0.077 (4)	0.001 (2)	−0.007 (3)	0.004 (3)

Geometric parameters (Å, º)

Cu1—O1	1.914 (3)	C7—H7	0.9300
Cu1—N1	1.926 (4)	C8—C9	1.499 (8)
Cu1—N3	1.941 (4)	C8—H8A	0.9700
Cu1—N2	2.076 (4)	C8—H8B	0.9700
O1—C2	1.316 (6)	C9—H9A	0.9700
O2—C16	1.148 (15)	C9—H9B	0.9700
O2—C3	1.342 (9)	C10—C11	1.332 (9)
S1—C18	1.627 (5)	C10—C15	1.336 (9)
N1—C7	1.265 (7)	C11—C12	1.392 (11)
N1—C8	1.470 (6)	C11—H11	0.9300
N2—C10	1.452 (7)	C12—C13	1.294 (12)
N2—C9	1.489 (7)	C12—H12	0.9300
N2—H2	0.901 (10)	C13—C14	1.346 (12)
N3—C18	1.142 (7)	C13—H13	0.9300
C1—C6	1.411 (9)	C14—C15	1.419 (10)
C1—C7	1.414 (8)	C14—H14	0.9300
C1—C2	1.419 (8)	C15—H15	0.9300
C2—C3	1.420 (8)	C16—C17	1.538 (17)
C3—C4	1.388 (11)	C16—H16A	0.9700
C4—C5	1.364 (13)	C16—H16B	0.9700
C4—H4	0.9300	C17—H17A	0.9600
C5—C6	1.371 (13)	C17—H17B	0.9600
C5—H5	0.9300	C17—H17C	0.9600
C6—H6	0.9300
O1—Cu1—N1	92.33 (17)	C9—C8—H8A	110.1
O1—Cu1—N3	90.50 (16)	N1—C8—H8B	110.1
N1—Cu1—N3	176.25 (19)	C9—C8—H8B	110.1
O1—Cu1—N2	158.24 (17)	H8A—C8—H8B	108.4
N1—Cu1—N2	84.73 (18)	N2—C9—C8	110.9 (4)
N3—Cu1—N2	93.54 (17)	N2—C9—H9A	109.5
C2—O1—Cu1	124.9 (3)	C8—C9—H9A	109.5
C16—O2—C3	121.6 (10)	N2—C9—H9B	109.5
C7—N1—C8	120.6 (5)	C8—C9—H9B	109.5
C7—N1—Cu1	125.2 (4)	H9A—C9—H9B	108.1
C8—N1—Cu1	113.8 (3)	C11—C10—C15	118.3 (6)
C10—N2—C9	115.3 (4)	C11—C10—N2	121.9 (6)
C10—N2—Cu1	117.4 (3)	C15—C10—N2	119.7 (6)
C9—N2—Cu1	106.5 (3)	C10—C11—C12	121.9 (8)
C10—N2—H2	107 (4)	C10—C11—H11	119.0
C9—N2—H2	109 (4)	C12—C11—H11	119.0
Cu1—N2—H2	100 (4)	C13—C12—C11	120.6 (9)
C18—N3—Cu1	162.8 (5)	C13—C12—H12	119.7
C6—C1—C7	118.2 (7)	C11—C12—H12	119.7
C6—C1—C2	119.6 (7)	C12—C13—C14	119.2 (7)
C7—C1—C2	122.2 (5)	C12—C13—H13	120.4
O1—C2—C1	123.5 (5)	C14—C13—H13	120.4
O1—C2—C3	118.4 (6)	C13—C14—C15	120.6 (8)
C1—C2—C3	118.1 (6)	C13—C14—H14	119.7
O2—C3—C4	122.7 (7)	C15—C14—H14	119.7
O2—C3—C2	117.5 (6)	C10—C15—C14	119.2 (8)
C4—C3—C2	119.6 (8)	C10—C15—H15	120.4
C5—C4—C3	122.0 (9)	C14—C15—H15	120.4
C5—C4—H4	119.0	O2—C16—C17	118.8 (15)
C3—C4—H4	119.0	O2—C16—H16A	107.6
C4—C5—C6	119.9 (9)	C17—C16—H16A	107.6
C4—C5—H5	120.0	O2—C16—H16B	107.6
C6—C5—H5	120.0	C17—C16—H16B	107.6
C5—C6—C1	120.8 (9)	H16A—C16—H16B	107.1
C5—C6—H6	119.6	C16—C17—H17A	109.5
C1—C6—H6	119.6	C16—C17—H17B	109.5
N1—C7—C1	126.7 (5)	H17A—C17—H17B	109.5
N1—C7—H7	116.7	C16—C17—H17C	109.5
C1—C7—H7	116.7	H17A—C17—H17C	109.5
N1—C8—C9	108.0 (4)	H17B—C17—H17C	109.5
N1—C8—H8A	110.1	N3—C18—S1	179.6 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.90 (1)	2.07 (3)	2.920 (6)	157 (5)

Symmetry code: (i) −x+2, −y, −z+1.