{4-Chloro-2-[(2-dimethyl­amino­ethyl­imino)meth­yl]phenolato}thio­cyanato­copper(II)

The title compound, [Cu(C₁₁H₁₄ClN₂O)(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. The mol­ecule possesses crystallographic mirror symmetry.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.035
• wR factor = 0.100
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT412_ALERT_2_B Short Intra XH3 .. XHn     H9A    ..  H10A    ..       1.74 Ang.

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.66 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.11 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N3
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.51
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   8 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
   6 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

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S1. Comment

Recently, the author has reported on a series of Schiff base complexes (You, 2005a,d,e). As an extension of the work on the structural characterization of Schiff base complexes, the synthesis and structure of a new copper(II) compound, (I), is reported here.

The molecular structure of complex (I), a mononuclear copper(II) compound, 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, 2005b,c). The Cu 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 molecule possesses crystallographic mirror symmetry, with atoms Cu1, Cl1, S1, O1, C1–C8, C11, H3, H4, H6 and H7 lying in the crystallographic mirror plane. The values of the trans angles in the CuON₃ square plane are, respectively, 175.41 (12) and 177.79 (11)°, indicating a slightly distorted square-planar coordination. The Cu–O and Cu–N bond lengths (Table 1) are comparable to the corresponding values observed in other Schiff base copper(II) complexes (MacLachlan et al., 1996; Colacio et al., 2000) 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 structure, the molecules stack back-to-back along the b axis and the crystal packing is shown in Fig. 2.

S2. Experimental

5-Chlorosalicylaldehy (0.1 mmol, 15.6 mg) and N,N'-dimethylethane-1,2-diamine (0.1 mmol, 8.8 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 20 min to give a yellow solution. To the above solution was added an aqueous solution (2 ml) of NH₄NCS (0.1 mmol, 6.5 mg) and an MeOH solution (3 ml) of Cu(CH₃COO)₂·H₂O (0.1 mmol, 19.9 mg), with stirring. The mixture was stirred for another 20 min at room temperature. The filtrate was kept in air for 9 d, during which time blue block-shaped crystals were formed.

S3. Refinement

All non-H atoms except C9 and C10 lie in a crystallographic mirror plane. Atom C9 is disordered across the mirror plane and as a result the occupancy factor for the disordered components were fixed at 0.50 each. The H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.96 Å, and with U_iso(H) = 1.2U_eq(C) 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 and displacement ellipsoids drawn at the 30% probability level. The atom labelled with the suffix A is at the symmetry position (x, 1/2 − y, z). Only one component of the disordered C9 group is shown.
	Fig. 2. The crystal packing of compound (I), viewed along the b axis.

{4-Chloro-2-[(2-dimethylaminoethylimino)methyl]phenolato}thiocyanatocopper(II)

Crystal data

[Cu(C11H14ClN2O)(NCS)]	F(000) = 708
Mr = 347.31	Dx = 1.570 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 4650 reflections
a = 19.172 (2) Å	θ = 2.8–27.2°
b = 6.764 (1) Å	µ = 1.80 mm^−1
c = 11.334 (1) Å	T = 298 K
V = 1469.8 (3) Å^3	Block, blue
Z = 4	0.22 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1827 independent reflections
Radiation source: fine-focus sealed tube	1558 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.692, Tmax = 0.714	k = −8→8
12043 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 0.9005P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1827 reflections	Δρmax = 0.77 e Å^−3
117 parameters	Δρmin = −0.60 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (8)

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	Occ. (<1)
Cu1	0.316105 (18)	0.2500	0.13768 (3)	0.04083 (16)
Cl1	0.65292 (5)	0.2500	−0.15121 (9)	0.0592 (3)
S1	0.08076 (5)	0.2500	0.04135 (13)	0.1106 (7)
O1	0.35797 (11)	0.2500	−0.01487 (19)	0.0456 (5)
N1	0.40484 (14)	0.2500	0.2172 (2)	0.0462 (7)
N2	0.27443 (15)	0.2500	0.3063 (3)	0.0615 (9)
N3	0.22355 (15)	0.2500	0.0701 (3)	0.0680 (10)
C1	0.47828 (15)	0.2500	0.0449 (3)	0.0351 (6)
C2	0.42428 (15)	0.2500	−0.0404 (3)	0.0363 (6)
C3	0.44440 (18)	0.2500	−0.1602 (3)	0.0472 (8)
H3	0.4100	0.2500	−0.2180	0.057*
C4	0.51288 (18)	0.2500	−0.1941 (3)	0.0482 (8)
H4	0.5245	0.2500	−0.2738	0.058*
C5	0.56501 (16)	0.2500	−0.1085 (3)	0.0426 (7)
C6	0.54859 (15)	0.2500	0.0085 (3)	0.0379 (6)
H6	0.5840	0.2500	0.0646	0.045*
C7	0.46528 (16)	0.2500	0.1685 (3)	0.0429 (7)
H7	0.5039	0.2500	0.2182	0.052*
C8	0.3988 (2)	0.2500	0.3458 (3)	0.0844 (18)
H8A	0.4020	0.3832	0.3745	0.101*	0.50
H8B	0.4367	0.1758	0.3788	0.101*	0.50
C9	0.3345 (3)	0.1673 (11)	0.3827 (4)	0.0646 (17)	0.50
H9A	0.3364	0.0261	0.3748	0.077*	0.50
H9B	0.3263	0.1982	0.4642	0.077*	0.50
C10	0.2307 (2)	0.0760 (5)	0.3279 (3)	0.0935 (13)
H10A	0.2570	−0.0417	0.3119	0.140*
H10B	0.1906	0.0803	0.2772	0.140*
H10C	0.2158	0.0754	0.4088	0.140*
C11	0.16454 (18)	0.2500	0.0584 (3)	0.0614 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0279 (2)	0.0560 (3)	0.0386 (2)	0.000	0.00528 (14)	0.000
Cl1	0.0374 (4)	0.0766 (6)	0.0636 (6)	0.000	0.0194 (4)	0.000
S1	0.0299 (5)	0.229 (2)	0.0725 (8)	0.000	0.0026 (5)	0.000
O1	0.0290 (10)	0.0694 (15)	0.0384 (11)	0.000	0.0023 (9)	0.000
N1	0.0354 (13)	0.0697 (19)	0.0335 (13)	0.000	0.0039 (11)	0.000
N2	0.0365 (14)	0.102 (3)	0.0457 (16)	0.000	0.0131 (13)	0.000
N3	0.0339 (15)	0.117 (3)	0.0533 (19)	0.000	0.0028 (13)	0.000
C1	0.0320 (13)	0.0366 (14)	0.0366 (14)	0.000	0.0035 (11)	0.000
C2	0.0324 (14)	0.0404 (15)	0.0360 (15)	0.000	0.0035 (11)	0.000
C3	0.0398 (16)	0.066 (2)	0.0363 (16)	0.000	0.0020 (13)	0.000
C4	0.0489 (18)	0.060 (2)	0.0360 (16)	0.000	0.0119 (14)	0.000
C5	0.0346 (15)	0.0452 (17)	0.0480 (17)	0.000	0.0121 (13)	0.000
C6	0.0316 (14)	0.0397 (16)	0.0424 (16)	0.000	0.0020 (12)	0.000
C7	0.0313 (14)	0.059 (2)	0.0385 (15)	0.000	−0.0009 (12)	0.000
C8	0.049 (2)	0.169 (6)	0.0348 (19)	0.000	0.0051 (16)	0.000
C9	0.048 (2)	0.109 (5)	0.036 (2)	0.001 (3)	0.008 (2)	0.010 (2)
C10	0.122 (3)	0.068 (2)	0.090 (2)	0.016 (2)	0.061 (2)	0.0184 (19)
C11	0.0345 (17)	0.110 (3)	0.0395 (18)	0.000	0.0062 (14)	0.000

Geometric parameters (Å, º)

Cu1—O1	1.906 (2)	C3—C4	1.368 (5)
Cu1—N1	1.925 (3)	C3—H3	0.9300
Cu1—N3	1.932 (3)	C4—C5	1.393 (5)
Cu1—N2	2.071 (3)	C4—H4	0.9300
Cl1—C5	1.754 (3)	C5—C6	1.363 (5)
S1—C11	1.618 (4)	C6—H6	0.9300
O1—C2	1.304 (4)	C7—H7	0.9300
N1—C7	1.284 (4)	C8—C9	1.416 (6)
N1—C8	1.462 (4)	C8—C9^i	1.416 (6)
N2—C10	1.466 (4)	C8—H8A	0.9601
N2—C10^i	1.466 (4)	C8—H8B	0.9599
N2—C9^i	1.546 (6)	C9—C9^i	1.118 (14)
N2—C9	1.546 (6)	C9—H9A	0.9600
N3—C11	1.139 (5)	C9—H9B	0.9600
C1—C6	1.410 (4)	C10—H10A	0.9600
C1—C2	1.417 (4)	C10—H10B	0.9600
C1—C7	1.423 (4)	C10—H10C	0.9600
C2—C3	1.411 (4)
O1—Cu1—N1	93.02 (10)	C4—C5—Cl1	119.8 (3)
O1—Cu1—N3	91.56 (12)	C5—C6—C1	120.4 (3)
N1—Cu1—N3	175.41 (12)	C5—C6—H6	119.8
O1—Cu1—N2	177.79 (11)	C1—C6—H6	119.8
N1—Cu1—N2	84.76 (12)	N1—C7—C1	125.6 (3)
N3—Cu1—N2	90.65 (13)	N1—C7—H7	117.2
C2—O1—Cu1	127.7 (2)	C1—C7—H7	117.2
C7—N1—C8	120.1 (3)	C9—C8—C9^i	46.5 (6)
C7—N1—Cu1	126.6 (2)	C9—C8—N1	111.3 (3)
C8—N1—Cu1	113.4 (2)	C9^i—C8—N1	111.3 (3)
C10—N2—C10^i	106.8 (3)	C9—C8—H8A	109.0
C10—N2—C9^i	128.5 (4)	C9^i—C8—H8A	65.5
C10^i—N2—C9^i	92.4 (3)	N1—C8—H8A	109.4
C10—N2—C9	92.4 (3)	C9—C8—H8B	109.7
C10^i—N2—C9	128.5 (4)	C9^i—C8—H8B	138.6
C10—N2—Cu1	112.0 (2)	N1—C8—H8B	109.2
C10^i—N2—Cu1	112.0 (2)	H8A—C8—H8B	108.0
C9^i—N2—Cu1	103.3 (2)	C9^i—C9—C8	66.8 (3)
C9—N2—Cu1	103.3 (2)	C9^i—C9—N2	68.8 (3)
C11—N3—Cu1	163.3 (3)	C8—C9—N2	109.9 (4)
C6—C1—C2	119.9 (3)	C9^i—C9—H9A	174.2
C6—C1—C7	117.1 (3)	C8—C9—H9A	109.4
C2—C1—C7	123.0 (3)	N2—C9—H9A	109.6
O1—C2—C3	118.7 (3)	C9^i—C9—H9B	77.4
O1—C2—C1	124.1 (3)	C8—C9—H9B	110.0
C3—C2—C1	117.2 (3)	N2—C9—H9B	109.7
C4—C3—C2	122.2 (3)	H9A—C9—H9B	108.2
C4—C3—H3	118.9	N2—C10—H10A	109.5
C2—C3—H3	118.9	N2—C10—H10B	109.5
C3—C4—C5	119.5 (3)	H10A—C10—H10B	109.5
C3—C4—H4	120.2	N2—C10—H10C	109.5
C5—C4—H4	120.2	H10A—C10—H10C	109.5
C6—C5—C4	120.8 (3)	H10B—C10—H10C	109.5
C6—C5—Cl1	119.4 (3)	N3—C11—S1	179.8 (4)
N1—Cu1—O1—C2	0.0	C3—C4—C5—C6	0.0
N3—Cu1—O1—C2	180.0	C3—C4—C5—Cl1	180.0
O1—Cu1—N1—C7	0.0	C4—C5—C6—C1	0.0
N2—Cu1—N1—C7	180.0	Cl1—C5—C6—C1	180.0
O1—Cu1—N1—C8	180.0	C2—C1—C6—C5	0.0
N2—Cu1—N1—C8	0.0	C7—C1—C6—C5	180.0
N1—Cu1—N2—C10	−120.0 (2)	C8—N1—C7—C1	180.0
N3—Cu1—N2—C10	60.0 (2)	Cu1—N1—C7—C1	0.0
N1—Cu1—N2—C10^i	120.0 (2)	C6—C1—C7—N1	180.0
N3—Cu1—N2—C10^i	−60.0 (2)	C2—C1—C7—N1	0.0
N1—Cu1—N2—C9^i	21.8 (3)	C7—N1—C8—C9	−154.9 (3)
N3—Cu1—N2—C9^i	−158.2 (3)	Cu1—N1—C8—C9	25.1 (3)
N1—Cu1—N2—C9	−21.8 (3)	C7—N1—C8—C9^i	154.9 (3)
N3—Cu1—N2—C9	158.2 (3)	Cu1—N1—C8—C9^i	−25.1 (3)
O1—Cu1—N3—C11	180.0	N1—C8—C9—C9^i	−99.7 (2)
N2—Cu1—N3—C11	0.0	C9^i—C8—C9—N2	55.0 (4)
Cu1—O1—C2—C3	180.0	N1—C8—C9—N2	−44.7 (5)
Cu1—O1—C2—C1	0.0	C10—N2—C9—C9^i	−151.5 (2)
C6—C1—C2—O1	180.0	C10^i—N2—C9—C9^i	−37.6 (3)
C7—C1—C2—O1	0.0	Cu1—N2—C9—C9^i	95.25 (11)
C6—C1—C2—C3	0.0	C10—N2—C9—C8	154.7 (4)
C7—C1—C2—C3	180.0	C10^i—N2—C9—C8	−91.4 (4)
O1—C2—C3—C4	180.0	C9^i—N2—C9—C8	−53.8 (4)
C1—C2—C3—C4	0.0	Cu1—N2—C9—C8	41.4 (4)
C2—C3—C4—C5	0.0

Symmetry code: (i) x, −y+1/2, z.