{4-Bromo-2-[(2-diethyl­amino­ethyl­imino)methyl]phenolato}thio­cyanato­copper(II)

The title compound, [Cu(C₁₃H₁₈BrN₂O)(NCS)], is a mononuclear Schiff base copper(II) complex. The Cu^II atom is coordinated by one O and two N atoms of the Schiff base ligand, and by one N atom of the thio­cyanate ligand, forming a square-planar coordination.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.091
• Data-to-parameter ratio = 18.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.16 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.64 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Recently, we have reported a series of Schiff base complexes (You, 2005a,b,c). As an extension of this work on the structural characterization of Schiff base complexes, we describe here the synthesis and structure of the title new copper(II) compound, (I).

The molecular structure of compound (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. Compound (I) is structurally similar to the copper(II) compounds reported recently (You, 2005d,e). The Cu^II atom is four-coordinated, in a square-planar arrangement, by one O and two N atoms of the Schiff base ligand, and by one N atom of the thiocyanate anion. The values of the trans angles in the CuON₃ square plane are 176.48 (12) and 176.09 (10)°, indicating a slightly distorted square-planar coordination. The Cu—O and Cu—N bond lengths (Table 1) are comparable with the corresponding values observed in other Schiff base copper(II) complexes (You & Zhu, 2004) and, as expected, the bond involving amine atom N2 [2.071 (3) Å] is longer than that involving imine atom N1 [1.925 (3) Å] (Mondal et al., 2001).

In the crystal strucrure, the molecules stack along the a axis; the crystal packing is shown in Fig. 2.

S2. Experimental

5-Bromosalicylaldehy (0.1 mmol, 20.1 mg) and N,N'-diethylethane-1,2-diamine (0.1 mmol, 11.6 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 20 min to give a yellow solution. To this solution were added an aqueous solution (2 ml) of NH₄NCS (0.1 mmol, 6.5 mg) and a MeOH solution (3 ml) of Cu(CH₃COO)₂·H₂O (0.1 mmol, 19.9 mg), with stirring. The mixture was stirred for a further 20 min at room temperature and then filtered. The filtrate was kept in air for 5 d, during which time blue block-shaped crystals of (I) were formed.

S3. Refinement

The H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with U_iso(H) = 1.2 or 1.5U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of compound (I), viewed along the a axis.

{4-Bromo-2-[(2-diethylaminoethylimino)methyl]phenolato}thiocyanatocopper(II)

Crystal data

[Cu(C13H18BrN2O)(NCS)]	F(000) = 844
Mr = 419.82	Dx = 1.726 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3328 reflections
a = 7.052 (1) Å	θ = 2.4–24.6°
b = 16.688 (2) Å	µ = 3.96 mm^−1
c = 13.775 (2) Å	T = 298 K
β = 94.79 (1)°	Block, blue
V = 1615.4 (4) Å^3	0.25 × 0.18 × 0.17 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3564 independent reflections
Radiation source: fine-focus sealed tube	2787 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
Tmin = 0.404, Tmax = 0.510	k = −21→21
11427 measured reflections	l = −16→17

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0453P)^2 + 0.4325P] where P = (Fo^2 + 2Fc^2)/3
3564 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.41 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	0.24192 (5)	0.72498 (2)	1.01867 (3)	0.03673 (12)
Br1	0.93758 (5)	0.40802 (2)	1.16694 (3)	0.05364 (13)
S1	−0.29725 (14)	0.82260 (8)	1.15452 (8)	0.0719 (3)
O1	0.2750 (3)	0.63306 (12)	1.09990 (15)	0.0410 (5)
N1	0.4757 (4)	0.70606 (14)	0.95910 (17)	0.0352 (5)
N2	0.2110 (4)	0.82183 (15)	0.92092 (18)	0.0390 (6)
N3	0.0115 (4)	0.75086 (19)	1.0795 (2)	0.0588 (8)
C1	0.5849 (4)	0.59285 (16)	1.0572 (2)	0.0324 (6)
C2	0.4214 (4)	0.58535 (16)	1.1096 (2)	0.0323 (6)
C3	0.4193 (4)	0.52132 (18)	1.1767 (2)	0.0375 (7)
H3	0.3135	0.5145	1.2119	0.045*
C4	0.5687 (4)	0.46902 (17)	1.1913 (2)	0.0382 (7)
H4	0.5629	0.4271	1.2355	0.046*
C5	0.7289 (4)	0.47863 (17)	1.1403 (2)	0.0359 (7)
C6	0.7373 (4)	0.53849 (17)	1.0741 (2)	0.0358 (6)
H6	0.8445	0.5437	1.0396	0.043*
C7	0.6001 (4)	0.65218 (17)	0.9838 (2)	0.0348 (6)
H7	0.7099	0.6517	0.9508	0.042*
C8	0.5146 (5)	0.7638 (2)	0.8834 (3)	0.0514 (9)
H8A	0.5804	0.7376	0.8330	0.062*
H8B	0.5946	0.8067	0.9111	0.062*
C9	0.3304 (5)	0.7965 (2)	0.8414 (2)	0.0501 (8)
H9A	0.2633	0.7561	0.8013	0.060*
H9B	0.3531	0.8422	0.8004	0.060*
C10	0.2880 (6)	0.8978 (2)	0.9632 (3)	0.0696 (12)
H10A	0.4241	0.8914	0.9776	0.083*
H10B	0.2692	0.9392	0.9139	0.083*
C11	0.2081 (8)	0.9266 (3)	1.0516 (4)	0.1023 (18)
H11A	0.0741	0.9358	1.0382	0.153*
H11B	0.2695	0.9757	1.0724	0.153*
H11C	0.2283	0.8871	1.1021	0.153*
C12	0.0093 (5)	0.8275 (2)	0.8795 (3)	0.0513 (9)
H12A	−0.0680	0.8425	0.9316	0.062*
H12B	−0.0314	0.7745	0.8575	0.062*
C13	−0.0328 (5)	0.8853 (2)	0.7963 (3)	0.0573 (10)
H13A	−0.0020	0.9388	0.8179	0.086*
H13B	−0.1655	0.8825	0.7743	0.086*
H13C	0.0421	0.8714	0.7437	0.086*
C14	−0.1159 (5)	0.7801 (2)	1.1115 (2)	0.0465 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0362 (2)	0.0425 (2)	0.0329 (2)	0.00864 (15)	0.01138 (15)	0.00463 (15)
Br1	0.0387 (2)	0.0456 (2)	0.0759 (3)	0.00827 (14)	0.00099 (17)	0.00703 (16)
S1	0.0446 (5)	0.1075 (9)	0.0651 (7)	0.0174 (5)	0.0135 (5)	−0.0313 (6)
O1	0.0387 (12)	0.0458 (12)	0.0412 (12)	0.0094 (9)	0.0189 (10)	0.0113 (9)
N1	0.0358 (13)	0.0378 (12)	0.0333 (13)	0.0006 (10)	0.0106 (11)	0.0022 (10)
N2	0.0379 (14)	0.0433 (14)	0.0358 (14)	0.0047 (11)	0.0037 (11)	0.0045 (11)
N3	0.0573 (19)	0.0691 (19)	0.0540 (19)	0.0265 (16)	0.0284 (15)	0.0197 (16)
C1	0.0330 (15)	0.0321 (14)	0.0323 (15)	0.0012 (11)	0.0030 (12)	−0.0046 (12)
C2	0.0326 (15)	0.0356 (14)	0.0291 (15)	−0.0005 (12)	0.0052 (12)	−0.0038 (12)
C3	0.0373 (16)	0.0409 (16)	0.0354 (16)	−0.0037 (13)	0.0091 (13)	0.0000 (13)
C4	0.0409 (17)	0.0346 (15)	0.0389 (17)	−0.0021 (13)	0.0018 (14)	0.0010 (12)
C5	0.0295 (15)	0.0360 (15)	0.0414 (17)	0.0037 (12)	−0.0026 (13)	−0.0063 (13)
C6	0.0284 (14)	0.0397 (15)	0.0400 (17)	−0.0002 (12)	0.0065 (12)	−0.0064 (13)
C7	0.0291 (14)	0.0386 (15)	0.0383 (16)	−0.0027 (12)	0.0115 (12)	−0.0039 (12)
C8	0.052 (2)	0.0501 (19)	0.056 (2)	0.0058 (16)	0.0244 (17)	0.0156 (16)
C9	0.050 (2)	0.060 (2)	0.0425 (19)	0.0082 (16)	0.0150 (16)	0.0133 (16)
C10	0.068 (3)	0.064 (2)	0.073 (3)	0.007 (2)	−0.011 (2)	−0.009 (2)
C11	0.127 (5)	0.089 (3)	0.095 (4)	0.002 (3)	0.032 (4)	−0.037 (3)
C12	0.0409 (19)	0.060 (2)	0.053 (2)	0.0056 (16)	0.0010 (16)	0.0171 (17)
C13	0.049 (2)	0.074 (2)	0.048 (2)	0.0158 (18)	0.0028 (17)	0.0182 (18)
C14	0.0428 (19)	0.059 (2)	0.0388 (18)	0.0077 (16)	0.0101 (15)	0.0062 (15)

Geometric parameters (Å, º)

Cu1—O1	1.902 (2)	C5—C6	1.357 (4)
Cu1—N1	1.928 (3)	C6—H6	0.9300
Cu1—N3	1.938 (3)	C7—H7	0.9300
Cu1—N2	2.103 (2)	C8—C9	1.482 (5)
Br1—C5	1.897 (3)	C8—H8A	0.9700
S1—C14	1.617 (4)	C8—H8B	0.9700
O1—C2	1.302 (3)	C9—H9A	0.9700
N1—C7	1.282 (4)	C9—H9B	0.9700
N1—C8	1.463 (4)	C10—C11	1.464 (6)
N2—C10	1.480 (5)	C10—H10A	0.9700
N2—C12	1.490 (4)	C10—H10B	0.9700
N2—C9	1.497 (4)	C11—H11A	0.9600
N3—C14	1.143 (4)	C11—H11B	0.9600
C1—C6	1.411 (4)	C11—H11C	0.9600
C1—C2	1.416 (4)	C12—C13	1.509 (4)
C1—C7	1.426 (4)	C12—H12A	0.9700
C2—C3	1.414 (4)	C12—H12B	0.9700
C3—C4	1.370 (4)	C13—H13A	0.9600
C3—H3	0.9300	C13—H13B	0.9600
C4—C5	1.389 (4)	C13—H13C	0.9600
C4—H4	0.9300
O1—Cu1—N1	92.93 (9)	N1—C8—C9	108.1 (3)
O1—Cu1—N3	89.52 (11)	N1—C8—H8A	110.1
N1—Cu1—N3	176.48 (12)	C9—C8—H8A	110.1
O1—Cu1—N2	176.09 (10)	N1—C8—H8B	110.1
N1—Cu1—N2	84.27 (10)	C9—C8—H8B	110.1
N3—Cu1—N2	93.41 (11)	H8A—C8—H8B	108.4
C2—O1—Cu1	127.65 (19)	C8—C9—N2	110.3 (3)
C7—N1—C8	119.1 (3)	C8—C9—H9A	109.6
C7—N1—Cu1	126.3 (2)	N2—C9—H9A	109.6
C8—N1—Cu1	114.43 (19)	C8—C9—H9B	109.6
C10—N2—C12	113.8 (3)	N2—C9—H9B	109.6
C10—N2—C9	108.6 (3)	H9A—C9—H9B	108.1
C12—N2—C9	108.3 (3)	C11—C10—N2	117.0 (4)
C10—N2—Cu1	113.0 (2)	C11—C10—H10A	108.0
C12—N2—Cu1	109.78 (19)	N2—C10—H10A	108.0
C9—N2—Cu1	102.55 (18)	C11—C10—H10B	108.0
C14—N3—Cu1	167.6 (3)	N2—C10—H10B	108.0
C6—C1—C2	120.0 (3)	H10A—C10—H10B	107.3
C6—C1—C7	117.5 (3)	C10—C11—H11A	109.5
C2—C1—C7	122.4 (3)	C10—C11—H11B	109.5
O1—C2—C3	118.5 (3)	H11A—C11—H11B	109.5
O1—C2—C1	124.5 (3)	C10—C11—H11C	109.5
C3—C2—C1	117.0 (3)	H11A—C11—H11C	109.5
C4—C3—C2	121.9 (3)	H11B—C11—H11C	109.5
C4—C3—H3	119.1	N2—C12—C13	116.9 (3)
C2—C3—H3	119.1	N2—C12—H12A	108.1
C3—C4—C5	120.0 (3)	C13—C12—H12A	108.1
C3—C4—H4	120.0	N2—C12—H12B	108.1
C5—C4—H4	120.0	C13—C12—H12B	108.1
C6—C5—C4	120.5 (3)	H12A—C12—H12B	107.3
C6—C5—Br1	120.7 (2)	C12—C13—H13A	109.5
C4—C5—Br1	118.7 (2)	C12—C13—H13B	109.5
C5—C6—C1	120.6 (3)	H13A—C13—H13B	109.5
C5—C6—H6	119.7	C12—C13—H13C	109.5
C1—C6—H6	119.7	H13A—C13—H13C	109.5
N1—C7—C1	125.8 (3)	H13B—C13—H13C	109.5
N1—C7—H7	117.1	N3—C14—S1	178.6 (3)
C1—C7—H7	117.1