{4-Bromo-2-[2-(isopropyl­amino)ethyl­imino­meth­yl]phenolato}thio­cyanato­copper(II)

In the title mononuclear Schiff base copper(II) complex, [Cu(C₁₂H₁₆BrN₂O)(NCS)], the Cu^II ion is coordinated by two N atoms and one O atom from a Schiff base ligand, and by one N atom from a thio­cyanate anion, giving a square-planar geometry. There are long-range inter­actions between the Cu atom and S [3.151 (5) Å] and Br [3.929 (5) Å] atoms above and below the square plane.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.056
• wR factor = 0.154
• Data-to-parameter ratio = 19.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.98 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.39 Ratio

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.71
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        C10
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      ..       3.54 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.715
            Tmax scaled      0.229 Tmin scaled      0.214
PLAT793_ALERT_2_G Check the Absolute Configuration of N2     .....          S

   0 ALERT level A = In general: serious problem
   2 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
   5 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Recently, we have reported some metal complexes derived from the Schiff base ligands (Ma, Lv et al., 2006; Ma, Gu et al., 2006; Ma, Wu et al., 2006; Ma et al., 2005). As part of a further investigation of the structures of such complexes, the title mononuclear copper(II) complex, is reported in this paper.

In the complex the Cu atom is coordinated by two nitrogen atoms and one oxygen atom from a Schiff base ligand, and by one nitrogen atom from a thiocyanate anion, giving a square planar geometry (Fig. 1). There exist long range interactions between the Cu and S (3.151 (5) Å; symmetry code: 1 + x, y, z) and Br (3.929 (5) Å; symmetry code: 1 - x, - y, 1 - z) atoms above and below the square plane. All the bond lengths and angles (Table 1) related to the Cu atom in the complex are within normal ranges. The four coordinating atoms around the Cu centre are approximately coplanar, giving a square-planar geometry with an average deviation of 0.047 (4) Å; the Cu atom lies 0.089 (2) Å above this plane. The C8—C9—N2—C10 torsion angle is 2.0 (3)°.

Related literature

For related literature, see: Ma et al. (2005); Ma, Gu, Guo et al. (2006); Ma, Lv et al. (2006); Ma, Wu et al. (2006).

S2. Experimental

N-Isopropylethane-1,2-diamine (0.5 mmol, 51.0 mg) and 5-bromosalicylaldehyde (0.5 mmol, 100.5 mg) were dissolved in methanol (30 ml). The mixture was stirred for 1 h to obtain a clear yellow solution. To the solution was added with stirring a methanol solution (20 ml) of copper(II) acetate (0.5 mmol, 99.6 mg) and a methanol solution (10 ml) of ammonium thiocyanate (0.5 mmol, 38.0 mg). After keeping the resulting solution in air for a few days, blue block-shaped crystals were formed.

S3. Refinement

All 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 with Uĩso~(H) = 1.2U~eq~(C,N) and 1.5U~eq~(methyl C).

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure at the 30% probability level ellipsoids.

{4-Bromo-2-[2-(isopropylamino)ethyliminomethyl]phenolato}thiocyanatocopper(II)

Crystal data

[Cu(C12H16BrN2O)(NCS)]	F(000) = 812
Mr = 405.80	Dx = 1.680 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1880 reflections
a = 6.161 (2) Å	θ = 2.5–24.3°
b = 20.223 (3) Å	µ = 3.98 mm^−1
c = 12.930 (3) Å	T = 298 K
β = 95.332 (5)°	Block, blue
V = 1604.0 (7) Å^3	0.40 × 0.38 × 0.37 mm
Z = 4

Data collection

Bruker SMART 1000 diffractometer	3474 independent reflections
Radiation source: fine-focus sealed tube	2126 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ω scans	θmax = 27.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.299, Tmax = 0.321	k = −25→25
11914 measured reflections	l = −16→16

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) = 0.153	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0682P)^2] where P = (Fo^2 + 2Fc^2)/3
3474 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.81 e Å^−3
0 restraints	Δρmin = −0.49 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	0.26493 (10)	0.20760 (3)	0.47898 (5)	0.0450 (2)
N1	0.5364 (7)	0.1721 (2)	0.5425 (3)	0.0408 (10)
N2	0.3292 (7)	0.2854 (2)	0.5819 (4)	0.0534 (12)
H2A	0.2664	0.2729	0.6397	0.064*
N3	−0.0164 (8)	0.2425 (3)	0.4201 (4)	0.0616 (14)
O1	0.2003 (6)	0.1286 (2)	0.4022 (3)	0.0551 (10)
S1	−0.4273 (2)	0.25260 (9)	0.31058 (11)	0.0566 (4)
Br1	0.80195 (10)	−0.08910 (3)	0.28530 (5)	0.0677 (3)
C1	0.6219 (9)	−0.0194 (3)	0.3274 (4)	0.0475 (13)
C2	0.6939 (9)	0.0269 (3)	0.3994 (4)	0.0466 (13)
H2	0.8364	0.0245	0.4299	0.056*
C3	0.5578 (8)	0.0781 (2)	0.4285 (4)	0.0382 (12)
C4	0.3387 (8)	0.0829 (3)	0.3822 (4)	0.0418 (12)
C5	0.2699 (9)	0.0321 (3)	0.3099 (4)	0.0532 (15)
H5	0.1270	0.0326	0.2795	0.064*
C6	0.4065 (10)	−0.0175 (3)	0.2836 (5)	0.0552 (15)
H6	0.3554	−0.0499	0.2365	0.066*
C7	0.6414 (9)	0.1221 (3)	0.5099 (4)	0.0436 (12)
H7	0.7808	0.1140	0.5413	0.052*
C8	0.6326 (9)	0.2117 (3)	0.6316 (4)	0.0544 (15)
H8A	0.7902	0.2077	0.6376	0.065*
H8B	0.5801	0.1957	0.6955	0.065*
C9	0.5675 (9)	0.2829 (3)	0.6140 (4)	0.0536 (15)
H9A	0.6006	0.3081	0.6773	0.064*
H9B	0.6478	0.3019	0.5602	0.064*
C10	0.2371 (15)	0.3525 (4)	0.5575 (6)	0.092 (2)
H10	0.0818	0.3447	0.5376	0.111*
C11	0.242 (2)	0.3952 (5)	0.6475 (9)	0.150 (4)
H11A	0.2122	0.3697	0.7072	0.225*
H11B	0.1328	0.4290	0.6354	0.225*
H11C	0.3828	0.4154	0.6596	0.225*
C12	0.319 (2)	0.3811 (5)	0.4651 (7)	0.152 (5)
H12A	0.2246	0.4165	0.4396	0.228*
H12B	0.3221	0.3477	0.4125	0.228*
H12C	0.4633	0.3979	0.4824	0.228*
C13	−0.1851 (9)	0.2472 (3)	0.3741 (4)	0.0457 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0348 (4)	0.0592 (5)	0.0396 (4)	0.0019 (3)	−0.0042 (3)	−0.0043 (3)
N1	0.038 (2)	0.048 (3)	0.035 (2)	−0.006 (2)	−0.0057 (18)	0.002 (2)
N2	0.051 (3)	0.066 (3)	0.044 (3)	0.010 (2)	0.007 (2)	−0.005 (2)
N3	0.042 (3)	0.079 (4)	0.061 (3)	0.011 (3)	−0.008 (2)	−0.015 (3)
O1	0.036 (2)	0.066 (3)	0.061 (3)	0.0002 (19)	−0.0087 (17)	−0.011 (2)
S1	0.0407 (8)	0.0800 (11)	0.0466 (8)	−0.0024 (8)	−0.0086 (6)	0.0161 (8)
Br1	0.0639 (5)	0.0571 (4)	0.0838 (5)	−0.0015 (3)	0.0157 (4)	−0.0128 (3)
C1	0.043 (3)	0.045 (3)	0.055 (3)	−0.004 (3)	0.007 (3)	0.000 (3)
C2	0.043 (3)	0.046 (3)	0.050 (3)	−0.002 (3)	−0.001 (2)	0.007 (3)
C3	0.039 (3)	0.038 (3)	0.037 (3)	−0.004 (2)	0.000 (2)	0.005 (2)
C4	0.037 (3)	0.046 (3)	0.041 (3)	−0.006 (2)	−0.001 (2)	0.004 (2)
C5	0.040 (3)	0.062 (4)	0.054 (4)	−0.009 (3)	−0.011 (3)	−0.007 (3)
C6	0.058 (4)	0.052 (4)	0.054 (4)	−0.013 (3)	0.001 (3)	−0.007 (3)
C7	0.038 (3)	0.048 (3)	0.044 (3)	0.001 (3)	−0.003 (2)	0.015 (3)
C8	0.049 (3)	0.063 (4)	0.048 (3)	−0.006 (3)	−0.013 (3)	−0.009 (3)
C9	0.056 (4)	0.057 (4)	0.049 (3)	−0.002 (3)	0.006 (3)	−0.014 (3)
C10	0.121 (7)	0.082 (5)	0.073 (5)	0.032 (5)	0.002 (5)	−0.017 (4)
C11	0.248 (14)	0.083 (7)	0.124 (9)	0.029 (7)	0.039 (9)	−0.018 (6)
C12	0.280 (15)	0.099 (7)	0.084 (6)	0.089 (9)	0.055 (8)	0.028 (6)
C13	0.046 (3)	0.049 (3)	0.043 (3)	0.002 (3)	0.007 (3)	0.002 (3)

Geometric parameters (Å, º)

Cu1—O1	1.903 (4)	C4—C5	1.426 (7)
Cu1—N1	1.932 (4)	C5—C6	1.372 (8)
Cu1—N3	1.959 (5)	C5—H5	0.9300
Cu1—N2	2.075 (5)	C6—H6	0.9300
N1—C7	1.292 (6)	C7—H7	0.9300
N1—C8	1.481 (6)	C8—C9	1.507 (8)
N2—C9	1.489 (7)	C8—H8A	0.9700
N2—C10	1.493 (9)	C8—H8B	0.9700
N2—H2A	0.9100	C9—H9A	0.9700
N3—C13	1.152 (6)	C9—H9B	0.9700
O1—C4	1.300 (6)	C10—C11	1.448 (11)
S1—C13	1.639 (6)	C10—C12	1.458 (12)
Br1—C1	1.905 (5)	C10—H10	0.9800
C1—C2	1.364 (7)	C11—H11A	0.9600
C1—C6	1.394 (8)	C11—H11B	0.9600
C2—C3	1.406 (7)	C11—H11C	0.9600
C2—H2	0.9300	C12—H12A	0.9600
C3—C4	1.428 (7)	C12—H12B	0.9600
C3—C7	1.436 (7)	C12—H12C	0.9600
O1—Cu1—N1	92.32 (17)	N1—C7—C3	124.6 (5)
O1—Cu1—N3	87.98 (19)	N1—C7—H7	117.7
N1—Cu1—N3	177.5 (2)	C3—C7—H7	117.7
O1—Cu1—N2	171.59 (18)	N1—C8—C9	108.5 (5)
N1—Cu1—N2	84.45 (18)	N1—C8—H8A	110.0
N3—Cu1—N2	94.91 (19)	C9—C8—H8A	110.0
C7—N1—C8	120.1 (4)	N1—C8—H8B	110.0
C7—N1—Cu1	126.3 (3)	C9—C8—H8B	110.0
C8—N1—Cu1	113.5 (3)	H8A—C8—H8B	108.4
C9—N2—C10	115.9 (5)	N2—C9—C8	108.5 (5)
C9—N2—Cu1	106.1 (3)	N2—C9—H9A	110.0
C10—N2—Cu1	120.5 (4)	C8—C9—H9A	110.0
C9—N2—H2A	104.2	N2—C9—H9B	110.0
C10—N2—H2A	104.2	C8—C9—H9B	110.0
Cu1—N2—H2A	104.2	H9A—C9—H9B	108.4
C13—N3—Cu1	162.4 (5)	C11—C10—C12	116.1 (9)
C4—O1—Cu1	126.3 (3)	C11—C10—N2	113.2 (7)
C2—C1—C6	119.7 (5)	C12—C10—N2	112.3 (6)
C2—C1—Br1	122.8 (4)	C11—C10—H10	104.6
C6—C1—Br1	117.5 (4)	C12—C10—H10	104.6
C1—C2—C3	121.6 (5)	N2—C10—H10	104.6
C1—C2—H2	119.2	C10—C11—H11A	109.5
C3—C2—H2	119.2	C10—C11—H11B	109.5
C2—C3—C4	120.1 (5)	H11A—C11—H11B	109.5
C2—C3—C7	118.1 (5)	C10—C11—H11C	109.5
C4—C3—C7	121.8 (5)	H11A—C11—H11C	109.5
O1—C4—C5	118.8 (5)	H11B—C11—H11C	109.5
O1—C4—C3	125.2 (5)	C10—C12—H12A	109.5
C5—C4—C3	116.0 (5)	C10—C12—H12B	109.5
C6—C5—C4	122.4 (5)	H12A—C12—H12B	109.5
C6—C5—H5	118.8	C10—C12—H12C	109.5
C4—C5—H5	118.8	H12A—C12—H12C	109.5
C5—C6—C1	120.2 (5)	H12B—C12—H12C	109.5
C5—C6—H6	119.9	N3—C13—S1	178.7 (6)
C1—C6—H6	119.9