{4-Bromo-2-[2-(ethyl­amino)ethyl­imino­meth­yl]phenolato-κ³N,N′,O}(thio­cyanato-κN)copper(II)

In the title compound, [Cu(C₁₁H₁₄BrN₂O)(NCS)], the Cu atom is four-coordinated by the NNO donor set of the Schiff base ligand and by the terminal N atom of the thio­cyanate anion, forming a square-planar geometry. An N—H...S hydrogen bond helps to establish the packing.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.061
• wR factor = 0.148
• Data-to-parameter ratio = 19.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  S1      ..       3.48 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C7     ..  C12     ..       3.19 Ang.
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      38.00 A   3 

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.75
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

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

---

S1. Comment

Recently, we have reported a Schiff base-nickel(II) complex (Zhou & Xiao, 2007). As an extensive of our work, we report herein the crystal structure of the title mononuclear copper(II) complex, (I), (Fig. 1).

The Cu atom in (I) is four-coordinated by the NNO donor set of the Schiff base ligand and by the terminal N atom of the thiocyante anion, forming a square-planar geometry. The bond lengths and bond angles (Table 1) subtended at the metal centre are comparable to the values in similar copper(II) complexes (Xu et al., 2005; Wang & Li, 2005; Wang et al., 2006; Li et al., 2007).

An N—H···S hydrogen bond helps to establish the packing (Table 2).

Related literature

For related structures, see: Li et al. (2007); Wang et al. (2006); Wang & Li (2005); Xu et al. (2005); Zhou & Xiao (2007).

S2. Experimental

5-Bromosalicylaldehyde (0.1 mmol, 20.1 mg), N-ethylethane-1,2-diamine (0.1 mmol, 8.8 mg), ammonium thiocyanate (0.1 mmol, 7.6 mg) and copper acetate (0.1 mmol, 20.0 mg) were mixed in a methanol solution (10 ml). The mixture was stirred at room temperature for 30 min to give a deep blue solution. Blue blocks of (I) were formed by slow evaporation of the solution in air.

S3. Refinement

The N-bound H atom was located in a difference map and freely refined.

The C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with U_iso(H) = 1.2 or 1.5 times U_eq(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures

Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids (arbitrary spheres for the H atoms).

{4-Bromo-2-[2-(ethylamino)ethyliminomethyl]phenolato- κ³N,N',O}(thiocyanato-κN)copper(II)

Crystal data

[Cu(C11H14BrN2O)(NCS)]	F(000) = 780
Mr = 391.77	Dx = 1.771 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1356 reflections
a = 6.3368 (12) Å	θ = 2.4–24.9°
b = 19.163 (4) Å	µ = 4.34 mm^−1
c = 12.308 (2) Å	T = 298 K
β = 100.601 (3)°	Block, blue
V = 1469.1 (5) Å^3	0.15 × 0.13 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEXII CCD diffractometer	3350 independent reflections
Radiation source: fine-focus sealed tube	2054 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −8→8
Tmin = 0.562, Tmax = 0.671	k = −24→24
12464 measured reflections	l = −15→15

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0585P)^2 + 0.919P] where P = (Fo^2 + 2Fc^2)/3
3350 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.74 e Å^−3
1 restraint	Δρmin = −0.59 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > 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	0.76392 (11)	0.19400 (4)	0.04069 (6)	0.0411 (2)
Br1	1.26434 (12)	−0.06356 (4)	−0.27110 (7)	0.0665 (3)
S1	0.0947 (3)	0.28292 (10)	−0.10857 (15)	0.0584 (5)
O1	0.6977 (6)	0.1300 (2)	−0.0701 (3)	0.0427 (10)
N1	1.0370 (7)	0.1586 (2)	0.0899 (4)	0.0374 (11)
N2	0.8306 (9)	0.2596 (3)	0.1625 (4)	0.0514 (14)
N3	0.4882 (8)	0.2303 (3)	−0.0064 (4)	0.0461 (13)
C1	1.0482 (9)	0.0795 (3)	−0.0614 (5)	0.0367 (13)
C2	0.8301 (9)	0.0898 (3)	−0.1105 (4)	0.0351 (13)
C3	0.7508 (10)	0.0525 (3)	−0.2095 (5)	0.0497 (16)
H3	0.6083	0.0578	−0.2439	0.060*
C4	0.8822 (10)	0.0090 (3)	−0.2544 (6)	0.0501 (16)
H4	0.8279	−0.0152	−0.3190	0.060*
C5	1.0960 (10)	0.0003 (3)	−0.2050 (6)	0.0471 (15)
C6	1.1782 (10)	0.0347 (3)	−0.1109 (5)	0.0423 (14)
H6	1.3217	0.0287	−0.0787	0.051*
C7	1.1358 (9)	0.1143 (3)	0.0405 (5)	0.0433 (15)
H7	1.2763	0.1034	0.0731	0.052*
C8	1.1484 (10)	0.1894 (3)	0.1934 (5)	0.0490 (16)
H8A	1.3019	0.1908	0.1947	0.059*
H8B	1.1224	0.1621	0.2559	0.059*
C9	1.0620 (10)	0.2614 (3)	0.1986 (6)	0.0549 (18)
H9A	1.0969	0.2789	0.2737	0.066*
H9B	1.1260	0.2923	0.1513	0.066*
C10	0.7238 (12)	0.3277 (4)	0.1615 (6)	0.0610 (19)
H10A	0.7791	0.3516	0.2303	0.073*
H10B	0.5714	0.3201	0.1584	0.073*
C11	0.7524 (13)	0.3740 (4)	0.0674 (7)	0.078 (2)
H11A	0.9028	0.3801	0.0674	0.117*
H11B	0.6881	0.4186	0.0755	0.117*
H11C	0.6848	0.3531	−0.0011	0.117*
C12	0.3270 (9)	0.2526 (3)	−0.0482 (5)	0.0391 (14)
H2	0.801 (11)	0.237 (3)	0.222 (4)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0367 (4)	0.0458 (5)	0.0390 (4)	−0.0040 (3)	0.0024 (3)	−0.0002 (3)
Br1	0.0680 (5)	0.0485 (4)	0.0901 (6)	−0.0006 (3)	0.0334 (4)	−0.0116 (4)
S1	0.0429 (10)	0.0786 (13)	0.0543 (11)	0.0118 (8)	0.0104 (8)	0.0249 (9)
O1	0.034 (2)	0.043 (2)	0.047 (2)	−0.0003 (18)	−0.0052 (18)	−0.0099 (19)
N1	0.034 (3)	0.041 (3)	0.035 (3)	−0.004 (2)	0.000 (2)	0.004 (2)
N2	0.052 (3)	0.057 (3)	0.042 (3)	−0.004 (3)	0.001 (3)	−0.010 (3)
N3	0.034 (3)	0.058 (3)	0.045 (3)	0.004 (2)	0.004 (2)	−0.011 (2)
C1	0.033 (3)	0.031 (3)	0.046 (4)	−0.005 (2)	0.008 (3)	0.006 (3)
C2	0.038 (3)	0.029 (3)	0.035 (3)	−0.003 (2)	−0.001 (3)	0.005 (2)
C3	0.045 (4)	0.037 (3)	0.059 (4)	0.004 (3)	−0.010 (3)	−0.009 (3)
C4	0.047 (4)	0.045 (4)	0.055 (4)	−0.010 (3)	0.001 (3)	−0.010 (3)
C5	0.051 (4)	0.033 (3)	0.059 (4)	0.000 (3)	0.015 (3)	0.002 (3)
C6	0.041 (3)	0.034 (3)	0.054 (4)	0.002 (3)	0.014 (3)	0.007 (3)
C7	0.032 (3)	0.044 (4)	0.051 (4)	−0.004 (3)	−0.001 (3)	0.015 (3)
C8	0.048 (4)	0.058 (4)	0.037 (3)	−0.013 (3)	−0.003 (3)	0.002 (3)
C9	0.048 (4)	0.065 (4)	0.050 (4)	−0.013 (3)	0.003 (3)	−0.023 (3)
C10	0.068 (5)	0.061 (5)	0.056 (4)	0.001 (4)	0.015 (4)	−0.014 (4)
C11	0.090 (6)	0.058 (5)	0.080 (6)	0.002 (4)	−0.001 (5)	−0.014 (4)
C12	0.034 (3)	0.048 (4)	0.038 (3)	−0.007 (3)	0.013 (3)	−0.009 (3)

Geometric parameters (Å, º)

Cu1—O1	1.825 (4)	C3—H3	0.9300
Cu1—N1	1.853 (5)	C4—C5	1.389 (8)
Cu1—N3	1.870 (5)	C4—H4	0.9300
Cu1—N2	1.942 (5)	C5—C6	1.351 (8)
Br1—C5	1.902 (6)	C6—H6	0.9300
S1—C12	1.629 (6)	C7—H7	0.9300
O1—C2	1.304 (6)	C8—C9	1.491 (8)
N1—C7	1.274 (7)	C8—H8A	0.9700
N1—C8	1.462 (7)	C8—H8B	0.9700
N2—C9	1.452 (8)	C9—H9A	0.9700
N2—C10	1.471 (8)	C9—H9B	0.9700
N2—H2	0.90 (5)	C10—C11	1.496 (10)
N3—C12	1.140 (7)	C10—H10A	0.9700
C1—C6	1.404 (8)	C10—H10B	0.9700
C1—C2	1.417 (7)	C11—H11A	0.9600
C1—C7	1.438 (8)	C11—H11B	0.9600
C2—C3	1.422 (8)	C11—H11C	0.9600
C3—C4	1.364 (8)
O1—Cu1—N1	94.06 (19)	C5—C6—C1	120.4 (6)
O1—Cu1—N3	86.84 (19)	C5—C6—H6	119.8
N1—Cu1—N3	179.0 (2)	C1—C6—H6	119.8
O1—Cu1—N2	177.8 (2)	N1—C7—C1	125.5 (5)
N1—Cu1—N2	85.8 (2)	N1—C7—H7	117.3
N3—Cu1—N2	93.3 (2)	C1—C7—H7	117.3
C2—O1—Cu1	127.4 (3)	N1—C8—C9	106.8 (5)
C7—N1—C8	118.9 (5)	N1—C8—H8A	110.4
C7—N1—Cu1	126.8 (4)	C9—C8—H8A	110.4
C8—N1—Cu1	114.2 (4)	N1—C8—H8B	110.4
C9—N2—C10	114.7 (5)	C9—C8—H8B	110.4
C9—N2—Cu1	108.5 (4)	H8A—C8—H8B	108.6
C10—N2—Cu1	122.3 (4)	N2—C9—C8	108.8 (5)
C9—N2—H2	96 (5)	N2—C9—H9A	109.9
C10—N2—H2	105 (5)	C8—C9—H9A	109.9
Cu1—N2—H2	106 (5)	N2—C9—H9B	109.9
C12—N3—Cu1	171.2 (5)	C8—C9—H9B	109.9
C6—C1—C2	120.3 (5)	H9A—C9—H9B	108.3
C6—C1—C7	119.9 (5)	N2—C10—C11	114.3 (6)
C2—C1—C7	119.8 (5)	N2—C10—H10A	108.7
O1—C2—C1	124.4 (5)	C11—C10—H10A	108.7
O1—C2—C3	118.3 (5)	N2—C10—H10B	108.7
C1—C2—C3	117.3 (5)	C11—C10—H10B	108.7
C4—C3—C2	120.5 (6)	H10A—C10—H10B	107.6
C4—C3—H3	119.7	C10—C11—H11A	109.5
C2—C3—H3	119.7	C10—C11—H11B	109.5
C3—C4—C5	121.0 (6)	H11A—C11—H11B	109.5
C3—C4—H4	119.5	C10—C11—H11C	109.5
C5—C4—H4	119.5	H11A—C11—H11C	109.5
C6—C5—C4	120.5 (6)	H11B—C11—H11C	109.5
C6—C5—Br1	121.5 (5)	N3—C12—S1	178.8 (6)
C4—C5—Br1	117.9 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1^i	0.90 (5)	2.68 (3)	3.520 (6)	155 (6)

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.