Di-μ-thocyanato-bis­{2-bromo-4-chloro-6-[(2-methyl­amino­ethyl­imino)methyl]­phenolato­copper(II)}

The title compound, [Cu₂(C₁₀H₁₁BrClN₂O)₂(NCS)₂], is a centrosymmetric dithio­cyanate-bridged binuclear copper(II) complex. The Cu^II atoms are penta­coordinated by the N,N′,O-donor atoms of the Schiff base ligand 2-bromo-4-chloro-6-[(2-methyl­amino­ethyl­imino)meth­yl]phenol (HBCP), and by one N and one S atom from two symmetry-related thio­cyanate anions, so forming a slightly distorted square-pyramidal coordination configuration. The Cu...Cu distance is 5.480 (2) Å.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.048
• wR factor = 0.115
• Data-to-parameter ratio = 19.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.88
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  Br1     ..       3.50 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  BR1     ..       3.09 Ang.
PLAT731_ALERT_1_C Bond    Calc     0.90(3), Rep   0.899(10) ......       3.00 su-Ra
              N2   -H2      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(3), Rep   0.899(10) ......       3.00 su-Ra
              N2   -H2      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(3), Rep   0.899(10) ......       3.00 su-Ra
              N2   -H2      1.555   1.555

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      0.876
            Tmax scaled      0.414 Tmin scaled      0.377
PLAT793_ALERT_1_G Check the Absolute Configuration of N2     = ...          S
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.22
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
  11 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   1 ALERT type 5 Informative message, check

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S1. Comment

Recently, we has reported the crystal structure of a mononuclear copper(II) complex derived from the Schiff base ligand 1-[3-(cyclohexylamino)propyliminomethyl]-2-naphthol (Zhang, 2004). As an extension of this work on the structural characterization of Schiff base copper(II) compounds, we report on the crystal structure of the new title binuclear complex.

The title compound is a centrosymmetric dithiocyanato-bridged binuclear copper(II) complex, as shown in Fig. 1. The Cu^II atoms are pentacoordinated by the NNO donor atoms of the Schiff base ligand, 2-bromo-4-chloro-6-[(2-methylaminoethylimino)methyl]phenol (HBCP), and by one N and one S atom, from symmetry related thiocyanate anions, forming a slightly distorted square pyramidal coordination configuration. The Cu···Cu distance is 5.480 (2) Å. The bond lengths and angles (Table 1) are within normal ranges and comparable to the values found in the complex mentioned above.

Related literature

For related literature, see: Zhang (2004).

S2. Experimental

N-Methyl-1,2-diaminoethane (0.1 mmol, 7.4 mg) and 3-bromo-5-chlorosalicylaldehyde (0.1 mmol, 23.5 mg) were dissolved in ethanol (10 cm³). The mixture was stirred for 10 min to give a clear yellow solution. To the solution was added an aqueous solution (2 cm³) of ammonium thiocyanate (0.1 mmol, 7.6 mg) and CuCl₂.2H₂O (0.1 mmol, 17.1 mg), with stirring. The mixture was stirred at room temperature for 1 h and then filtered. After keeping the brown filtrate in air for seven days, blue block-shaped crystals were formed with high yield (73% based on 3-bromo-5-chlorosalicylaldehyde).

S3. Refinement

The H2 atom was located in a difference Fourier map and refined isotropically, with the N—H distance restrained to 0.90 (1) Å. The other H atoms were placed in geometrically 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) = 1.2U_eq(C) and 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Sheldrick, 1997b).

Figures

Fig. 1. The structure of the complex, showing the atom-numbering scheme with displacement ellipsoids drawn at the 30% probability level.

Di-µ-thocyanato-bis{2-bromo-4-chloro-6-[(2- methylaminoethylimino)methyl]phenolatocopper(II)}

Crystal data

[Cu2(C10H11BrClN2O)2(NCS)2]	F(000) = 1624
Mr = 824.38	Dx = 1.817 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.2440 (14) Å	Cell parameters from 1694 reflections
b = 19.693 (4) Å	θ = 2.4–24.5°
c = 21.128 (4) Å	µ = 4.41 mm^−1
β = 90.98 (3)°	T = 298 K
V = 3013.6 (10) Å^3	Block, blue
Z = 4	0.23 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3443 independent reflections
Radiation source: fine-focus sealed tube	2187 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.430, Tmax = 0.472	k = −25→25
12868 measured reflections	l = −27→27

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0472P)^2] where P = (Fo^2 + 2Fc^2)/3
3443 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.51 e Å^−3
1 restraint	Δρmin = −0.44 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	0.08641 (8)	0.23561 (3)	0.44417 (3)	0.03910 (18)
Br1	0.10518 (8)	0.48082 (3)	0.42831 (3)	0.0597 (2)
Cl1	0.30665 (19)	0.45169 (8)	0.17930 (7)	0.0700 (4)
S1	−0.2341 (2)	0.28910 (9)	0.62831 (7)	0.0673 (4)
O1	0.1260 (4)	0.32908 (14)	0.42352 (13)	0.0400 (8)
N1	0.1986 (5)	0.20430 (18)	0.36694 (17)	0.0404 (9)
N2	0.1020 (6)	0.13676 (19)	0.4707 (2)	0.0489 (10)
N3	−0.0142 (6)	0.2635 (2)	0.52432 (18)	0.0475 (10)
C1	0.2193 (6)	0.3142 (2)	0.3153 (2)	0.0374 (10)
C2	0.1652 (6)	0.3537 (2)	0.3687 (2)	0.0363 (10)
C3	0.1652 (6)	0.4246 (2)	0.3588 (2)	0.0410 (11)
C4	0.2047 (6)	0.4542 (3)	0.3019 (2)	0.0505 (13)
H4	0.1992	0.5011	0.2972	0.061*
C5	0.2524 (6)	0.4136 (3)	0.2519 (2)	0.0495 (13)
C6	0.2593 (7)	0.3449 (3)	0.2576 (2)	0.0479 (12)
H6	0.2906	0.3183	0.2230	0.057*
C7	0.2399 (6)	0.2413 (2)	0.3195 (2)	0.0430 (12)
H7	0.2877	0.2193	0.2845	0.052*
C8	0.2424 (8)	0.1311 (2)	0.3683 (3)	0.0628 (15)
H8A	0.3704	0.1247	0.3812	0.075*
H8B	0.2255	0.1120	0.3263	0.075*
C9	0.1205 (8)	0.0960 (2)	0.4131 (2)	0.0623 (15)
H9A	−0.0002	0.0891	0.3936	0.075*
H9B	0.1719	0.0519	0.4238	0.075*
C10	−0.0439 (8)	0.1095 (3)	0.5115 (3)	0.0659 (16)
H10A	−0.1620	0.1155	0.4910	0.099*
H10B	−0.0421	0.1333	0.5511	0.099*
H10C	−0.0224	0.0620	0.5189	0.099*
C11	−0.1063 (6)	0.2737 (2)	0.5673 (2)	0.0447 (12)
H2	0.211 (4)	0.132 (3)	0.491 (2)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0502 (4)	0.0315 (3)	0.0357 (3)	−0.0015 (3)	0.0049 (2)	0.0000 (2)
Br1	0.0834 (4)	0.0382 (3)	0.0574 (4)	0.0070 (3)	−0.0037 (3)	−0.0075 (2)
Cl1	0.0670 (9)	0.0903 (11)	0.0529 (8)	0.0032 (8)	0.0099 (7)	0.0358 (8)
S1	0.0625 (9)	0.0938 (12)	0.0463 (8)	0.0121 (8)	0.0181 (7)	0.0091 (8)
O1	0.059 (2)	0.0303 (17)	0.0310 (17)	−0.0028 (15)	0.0085 (15)	0.0012 (13)
N1	0.047 (2)	0.032 (2)	0.043 (2)	−0.0035 (17)	0.0084 (19)	−0.0033 (18)
N2	0.062 (3)	0.037 (2)	0.047 (3)	−0.002 (2)	0.000 (2)	0.0011 (19)
N3	0.059 (3)	0.045 (2)	0.038 (2)	−0.003 (2)	0.009 (2)	0.0016 (19)
C1	0.037 (3)	0.040 (3)	0.036 (3)	0.000 (2)	0.006 (2)	0.002 (2)
C2	0.031 (2)	0.039 (3)	0.039 (3)	−0.003 (2)	−0.004 (2)	−0.002 (2)
C3	0.042 (3)	0.039 (3)	0.042 (3)	0.002 (2)	−0.002 (2)	−0.003 (2)
C4	0.043 (3)	0.047 (3)	0.061 (4)	−0.001 (2)	−0.003 (3)	0.015 (3)
C5	0.043 (3)	0.068 (4)	0.037 (3)	0.001 (3)	0.006 (2)	0.018 (3)
C6	0.044 (3)	0.061 (4)	0.039 (3)	0.000 (2)	0.008 (2)	0.000 (2)
C7	0.042 (3)	0.043 (3)	0.043 (3)	−0.001 (2)	0.008 (2)	−0.015 (2)
C8	0.080 (4)	0.033 (3)	0.076 (4)	0.002 (3)	0.020 (3)	−0.007 (3)
C9	0.093 (4)	0.036 (3)	0.058 (4)	0.003 (3)	−0.001 (3)	−0.003 (3)
C10	0.083 (4)	0.041 (3)	0.074 (4)	−0.013 (3)	0.003 (3)	0.010 (3)
C11	0.047 (3)	0.045 (3)	0.043 (3)	−0.004 (2)	−0.002 (2)	0.008 (2)

Geometric parameters (Å, º)

Cu1—O1	1.914 (3)	C1—C7	1.445 (6)
Cu1—N3	1.935 (4)	C2—C3	1.412 (6)
Cu1—N1	1.936 (4)	C3—C4	1.370 (6)
Cu1—N2	2.028 (4)	C4—C5	1.374 (7)
Br1—C3	1.896 (4)	C4—H4	0.9300
Cl1—C5	1.758 (5)	C5—C6	1.359 (6)
S1—C11	1.628 (5)	C6—H6	0.9300
O1—C2	1.291 (5)	C7—H7	0.9300
N1—C7	1.278 (6)	C8—C9	1.478 (7)
N1—C8	1.475 (6)	C8—H8A	0.9700
N2—C9	1.464 (6)	C8—H8B	0.9700
N2—C10	1.476 (6)	C9—H9A	0.9700
N2—H2	0.899 (10)	C9—H9B	0.9700
N3—C11	1.154 (6)	C10—H10A	0.9600
C1—C6	1.397 (6)	C10—H10B	0.9600
C1—C2	1.430 (6)	C10—H10C	0.9600
O1—Cu1—N3	89.25 (14)	C6—C5—C4	121.4 (4)
O1—Cu1—N1	92.72 (14)	C6—C5—Cl1	119.6 (4)
N3—Cu1—N1	176.34 (16)	C4—C5—Cl1	119.0 (4)
O1—Cu1—N2	167.94 (16)	C5—C6—C1	120.1 (5)
N3—Cu1—N2	92.91 (17)	C5—C6—H6	120.0
N1—Cu1—N2	84.53 (16)	C1—C6—H6	120.0
C2—O1—Cu1	126.9 (3)	N1—C7—C1	126.1 (4)
C7—N1—C8	121.3 (4)	N1—C7—H7	117.0
C7—N1—Cu1	125.9 (3)	C1—C7—H7	117.0
C8—N1—Cu1	112.8 (3)	N1—C8—C9	109.8 (4)
C9—N2—C10	111.2 (4)	N1—C8—H8A	109.7
C9—N2—Cu1	107.6 (3)	C9—C8—H8A	109.7
C10—N2—Cu1	118.2 (3)	N1—C8—H8B	109.7
C9—N2—H2	104 (3)	C9—C8—H8B	109.7
C10—N2—H2	108 (3)	H8A—C8—H8B	108.2
Cu1—N2—H2	106 (3)	N2—C9—C8	109.9 (4)
C11—N3—Cu1	166.0 (4)	N2—C9—H9A	109.7
C6—C1—C2	121.1 (4)	C8—C9—H9A	109.7
C6—C1—C7	117.4 (4)	N2—C9—H9B	109.7
C2—C1—C7	121.4 (4)	C8—C9—H9B	109.7
O1—C2—C3	120.3 (4)	H9A—C9—H9B	108.2
O1—C2—C1	124.8 (4)	N2—C10—H10A	109.5
C3—C2—C1	114.9 (4)	N2—C10—H10B	109.5
C4—C3—C2	123.5 (4)	H10A—C10—H10B	109.5
C4—C3—Br1	119.0 (4)	N2—C10—H10C	109.5
C2—C3—Br1	117.5 (3)	H10A—C10—H10C	109.5
C3—C4—C5	119.1 (5)	H10B—C10—H10C	109.5
C3—C4—H4	120.5	N3—C11—S1	179.1 (5)
C5—C4—H4	120.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Br1^i	0.90 (1)	3.09 (4)	3.777 (4)	135 (4)
N2—H2···O1^i	0.90 (1)	2.27 (3)	3.031 (5)	142 (4)

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