Chlorido{4-chloro-2-[(2-morpholinoeth­yl)imino­meth­yl]phenolato-κ3N,N′,O}copper(II)

Ikmal Hisham, N.A.; Mohd Ali, H.; Ng, S.W.

doi:10.1107/S1600536809025215

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m870

doi:10.1107/S1600536809025215

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Chlorido{4-chloro-2-[(2-morpholinoethyl)iminomethyl]phenolato-κ³N,N′,O}copper(II)

Nurul Azimah Ikmal Hisham,^a Hapipah Mohd Ali ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 29 June 2009; accepted 30 June 2009; online 4 July 2009)

The Cu^II atom in the title compound, [Cu(C₁₃H₁₆ClN₂O₂)Cl], exists in a distorted square-planar coordination environment as the deprotonated Schiff base chelates to the Cu^II atom through three atom sites. In the crystal structure, adjacent molecules are linked by a Cu⋯Cl [3.011 (1) Å] bridge, generating a linear chain running along the b axis of the orthorhombic unit cell.

Related literature

A similar deprotonated Schiff base is bidentate in bis{5-methoxy-2-[(2-morpholinoethyl)iminomethyl]phenolato}nickel; see: Mohd Lair et al. (2009 ).

Experimental

Crystal data

[Cu(C₁₃H₁₆ClN₂O₂)Cl]
M_r = 366.72
Orthorhombic, P b c n
a = 23.0936 (6) Å
b = 8.4890 (2) Å
c = 14.0582 (3) Å
V = 2756.0 (1) Å³
Z = 8
Mo Kα radiation
μ = 1.97 mm⁻¹
T = 140 K
0.40 × 0.10 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.506, T_max = 0.962
17248 measured reflections
3156 independent reflections
2416 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.113
S = 1.09
3156 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.907 (2)
Cu1—N1	1.947 (3)
Cu1—N2	2.105 (3)
Cu1—Cl1	2.2620 (9)

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025215/xu2547sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025215/xu2547Isup2.hkl

checkCIF report

Related literature top

A similar deprotonated Schiff base is bidentate in bis{5-methoxy-2-[(2-morpholinoethyl)iminomethyl]phenolato}nickel; see: Mohd Lair et al. (2009).

Experimental top

The Schiff base was synthesized by condensing N-2-(aminoethyl)morpholine (0.80 g, 6.1 mmol) and 5-chlorosalicylaldehyde (0.96 g, 6.1 mmol) in ethanol; the reactants were heated for 2 hours. Copper(II) chloride (1.00 g, 6.1 mmol) was added and the heating continued for another 5 hour. The solvent was removed and the product recrystallized from methanol.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the CuCl(C₁₃H₁₆ClN₂O₂) at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Chlorido{4-chloro-2-[(2-morpholinoethyl)iminomethyl]phenolato- κ³N,N',O}copper(II) top

Crystal data top

[Cu(C₁₃H₁₆ClN₂O₂)Cl]	F(000) = 1496
M_r = 366.72	D_x = 1.768 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4043 reflections
a = 23.0936 (6) Å	θ = 2.6–28.1°
b = 8.4890 (2) Å	µ = 1.97 mm⁻¹
c = 14.0582 (3) Å	T = 140 K
V = 2756.0 (1) Å³	Plate, green
Z = 8	0.40 × 0.10 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	3156 independent reflections
Radiation source: fine-focus sealed tube	2416 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→30
T_min = 0.506, T_max = 0.962	k = −10→10
17248 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0476P)² + 6.7938P] where P = (F_o² + 2F_c²)/3
3156 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.76 e Å⁻³
0 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

[Cu(C₁₃H₁₆ClN₂O₂)Cl]	V = 2756.0 (1) Å³
M_r = 366.72	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 23.0936 (6) Å	µ = 1.97 mm⁻¹
b = 8.4890 (2) Å	T = 140 K
c = 14.0582 (3) Å	0.40 × 0.10 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	3156 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2416 reflections with I > 2σ(I)
T_min = 0.506, T_max = 0.962	R_int = 0.050
17248 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.09	Δρ_max = 0.76 e Å⁻³
3156 reflections	Δρ_min = −0.84 e Å⁻³
181 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.229938 (18)	0.65838 (5)	0.49762 (3)	0.01385 (13)
Cl1	0.24525 (4)	0.85643 (10)	0.39295 (6)	0.0181 (2)
Cl2	0.43295 (4)	0.32750 (12)	0.83746 (7)	0.0253 (2)
O1	0.30890 (10)	0.6693 (3)	0.53670 (17)	0.0159 (5)
O2	0.03792 (12)	0.7569 (3)	0.36877 (18)	0.0225 (6)
N1	0.20874 (13)	0.5357 (3)	0.60938 (19)	0.0141 (6)
N2	0.14182 (13)	0.6347 (3)	0.46204 (19)	0.0131 (6)
C1	0.33436 (15)	0.5909 (4)	0.6049 (2)	0.0131 (7)
C2	0.39494 (16)	0.6087 (4)	0.6170 (2)	0.0158 (7)
H2	0.4156	0.6769	0.5756	0.019*
C3	0.42459 (16)	0.5294 (4)	0.6873 (2)	0.0157 (7)
H3	0.4652	0.5438	0.6942	0.019*
C4	0.39495 (16)	0.4279 (4)	0.7485 (2)	0.0169 (7)
C5	0.33647 (16)	0.4082 (4)	0.7404 (2)	0.0158 (7)
H5	0.3168	0.3396	0.7829	0.019*
C6	0.30502 (15)	0.4889 (4)	0.6696 (2)	0.0139 (7)
C7	0.24355 (16)	0.4685 (4)	0.6681 (2)	0.0149 (7)
H7	0.2271	0.3998	0.7141	0.018*
C8	0.14665 (15)	0.5035 (4)	0.6176 (2)	0.0147 (7)
H8A	0.1272	0.5891	0.6531	0.018*
H8B	0.1401	0.4030	0.6517	0.018*
C9	0.12305 (15)	0.4933 (4)	0.5171 (2)	0.0147 (7)
H9A	0.1376	0.3966	0.4859	0.018*
H9B	0.0802	0.4882	0.5189	0.018*
C10	0.11098 (16)	0.7815 (4)	0.4921 (2)	0.0168 (7)
H10A	0.1293	0.8732	0.4607	0.020*
H10B	0.1155	0.7949	0.5617	0.020*
C11	0.04724 (17)	0.7799 (5)	0.4681 (3)	0.0209 (8)
H11A	0.0280	0.6943	0.5040	0.025*
H11B	0.0296	0.8810	0.4879	0.025*
C12	0.06457 (16)	0.6146 (5)	0.3373 (3)	0.0202 (8)
H12A	0.0585	0.6029	0.2679	0.024*
H12B	0.0459	0.5239	0.3693	0.024*
C13	0.12914 (16)	0.6129 (5)	0.3585 (2)	0.0173 (7)
H13A	0.1457	0.5114	0.3371	0.021*
H13B	0.1482	0.6981	0.3220	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0132 (2)	0.0170 (2)	0.0113 (2)	−0.00069 (18)	−0.00083 (15)	0.00270 (17)
Cl1	0.0202 (4)	0.0186 (4)	0.0154 (4)	−0.0010 (4)	−0.0009 (3)	0.0058 (3)
Cl2	0.0222 (5)	0.0295 (5)	0.0243 (5)	−0.0005 (4)	−0.0077 (4)	0.0126 (4)
O1	0.0146 (13)	0.0158 (13)	0.0174 (11)	0.0000 (10)	−0.0020 (10)	0.0069 (10)
O2	0.0209 (14)	0.0274 (15)	0.0193 (13)	0.0077 (12)	−0.0033 (11)	0.0008 (11)
N1	0.0152 (15)	0.0145 (15)	0.0126 (13)	−0.0010 (12)	−0.0018 (11)	−0.0015 (11)
N2	0.0163 (15)	0.0126 (14)	0.0103 (12)	0.0011 (12)	−0.0014 (11)	−0.0013 (11)
C1	0.0171 (18)	0.0117 (17)	0.0106 (15)	0.0007 (14)	−0.0021 (13)	−0.0006 (12)
C2	0.0173 (19)	0.0149 (17)	0.0151 (16)	−0.0030 (15)	0.0029 (13)	−0.0001 (13)
C3	0.0154 (18)	0.0144 (18)	0.0173 (16)	−0.0016 (14)	−0.0018 (13)	−0.0031 (13)
C4	0.0221 (19)	0.0159 (18)	0.0126 (15)	0.0024 (15)	−0.0035 (14)	0.0028 (13)
C5	0.0225 (19)	0.0127 (18)	0.0121 (15)	0.0002 (15)	0.0005 (13)	0.0006 (13)
C6	0.0191 (18)	0.0119 (16)	0.0106 (15)	0.0005 (14)	0.0001 (13)	−0.0007 (12)
C7	0.0205 (19)	0.0142 (17)	0.0100 (14)	0.0009 (14)	0.0029 (13)	−0.0002 (13)
C8	0.0140 (17)	0.0166 (17)	0.0133 (15)	−0.0007 (14)	−0.0002 (13)	0.0032 (13)
C9	0.0146 (17)	0.0161 (17)	0.0135 (16)	0.0003 (14)	−0.0030 (12)	0.0022 (13)
C10	0.0194 (18)	0.0146 (17)	0.0164 (16)	0.0035 (15)	0.0008 (14)	−0.0009 (14)
C11	0.022 (2)	0.0218 (19)	0.0191 (17)	0.0042 (17)	0.0028 (15)	−0.0031 (15)
C12	0.020 (2)	0.0238 (19)	0.0171 (17)	0.0009 (16)	−0.0031 (14)	−0.0020 (15)
C13	0.0191 (19)	0.0198 (18)	0.0130 (15)	0.0019 (15)	−0.0011 (13)	−0.0012 (14)

Geometric parameters (Å, º) top

Cu1—O1	1.907 (2)	C4—C5	1.366 (5)
Cu1—N1	1.947 (3)	C5—C6	1.410 (5)
Cu1—N2	2.105 (3)	C5—H5	0.9500
Cu1—Cl1	2.2620 (9)	C6—C7	1.430 (5)
Cu1—Cl1ⁱ	3.0107 (10)	C7—H7	0.9500
Cl2—C4	1.750 (3)	C8—C9	1.516 (4)
O1—C1	1.307 (4)	C8—H8A	0.9900
O2—C11	1.427 (4)	C8—H8B	0.9900
O2—C12	1.426 (5)	C9—H9A	0.9900
N1—C7	1.285 (4)	C9—H9B	0.9900
N1—C8	1.464 (4)	C10—C11	1.510 (5)
N2—C9	1.492 (4)	C10—H10A	0.9900
N2—C13	1.496 (4)	C10—H10B	0.9900
N2—C10	1.497 (4)	C11—H11A	0.9900
C1—C2	1.417 (5)	C11—H11B	0.9900
C1—C6	1.427 (5)	C12—C13	1.521 (5)
C2—C3	1.378 (5)	C12—H12A	0.9900
C2—H2	0.9500	C12—H12B	0.9900
C3—C4	1.396 (5)	C13—H13A	0.9900
C3—H3	0.9500	C13—H13B	0.9900

O1—Cu1—N1	91.95 (11)	N1—C7—C6	125.2 (3)
O1—Cu1—N2	176.00 (11)	N1—C7—H7	117.4
N1—Cu1—N2	84.12 (12)	C6—C7—H7	117.4
O1—Cu1—Cl1	90.10 (7)	N1—C8—C9	106.8 (3)
N1—Cu1—Cl1	164.06 (9)	N1—C8—H8A	110.4
N2—Cu1—Cl1	93.88 (8)	C9—C8—H8A	110.4
O1—Cu1—Cl1ⁱ	90.02 (8)	N1—C8—H8B	110.4
N1—Cu1—Cl1ⁱ	89.25 (9)	C9—C8—H8B	110.4
N2—Cu1—Cl1ⁱ	89.22 (8)	H8A—C8—H8B	108.6
Cl1—Cu1—Cl1ⁱ	106.56 (3)	N2—C9—C8	109.5 (3)
C1—O1—Cu1	128.1 (2)	N2—C9—H9A	109.8
C11—O2—C12	110.8 (3)	C8—C9—H9A	109.8
C7—N1—C8	118.6 (3)	N2—C9—H9B	109.8
C7—N1—Cu1	126.7 (3)	C8—C9—H9B	109.8
C8—N1—Cu1	114.2 (2)	H9A—C9—H9B	108.2
C9—N2—C13	110.4 (3)	N2—C10—C11	113.1 (3)
C9—N2—C10	112.6 (3)	N2—C10—H10A	109.0
C13—N2—C10	106.5 (3)	C11—C10—H10A	109.0
C9—N2—Cu1	103.6 (2)	N2—C10—H10B	109.0
C13—N2—Cu1	115.6 (2)	C11—C10—H10B	109.0
C10—N2—Cu1	108.2 (2)	H10A—C10—H10B	107.8
O1—C1—C2	118.5 (3)	O2—C11—C10	111.5 (3)
O1—C1—C6	124.3 (3)	O2—C11—H11A	109.3
C2—C1—C6	117.2 (3)	C10—C11—H11A	109.3
C3—C2—C1	121.6 (3)	O2—C11—H11B	109.3
C3—C2—H2	119.2	C10—C11—H11B	109.3
C1—C2—H2	119.2	H11A—C11—H11B	108.0
C2—C3—C4	120.0 (3)	O2—C12—C13	111.7 (3)
C2—C3—H3	120.0	O2—C12—H12A	109.3
C4—C3—H3	120.0	C13—C12—H12A	109.3
C5—C4—C3	120.6 (3)	O2—C12—H12B	109.3
C5—C4—Cl2	119.7 (3)	C13—C12—H12B	109.3
C3—C4—Cl2	119.7 (3)	H12A—C12—H12B	107.9
C4—C5—C6	120.5 (3)	N2—C13—C12	112.4 (3)
C4—C5—H5	119.7	N2—C13—H13A	109.1
C6—C5—H5	119.7	C12—C13—H13A	109.1
C5—C6—C7	117.6 (3)	N2—C13—H13B	109.1
C5—C6—C1	120.0 (3)	C12—C13—H13B	109.1
C7—C6—C1	122.4 (3)	H13A—C13—H13B	107.8

N1—Cu1—O1—C1	11.0 (3)	Cl2—C4—C5—C6	179.6 (3)
Cl1—Cu1—O1—C1	175.2 (3)	C4—C5—C6—C7	−177.2 (3)
Cl1ⁱ—Cu1—O1—C1	−78.2 (3)	C4—C5—C6—C1	0.6 (5)
O1—Cu1—N1—C7	−12.6 (3)	O1—C1—C6—C5	179.4 (3)
N2—Cu1—N1—C7	166.6 (3)	C2—C1—C6—C5	−1.3 (5)
Cl1—Cu1—N1—C7	−109.8 (4)	O1—C1—C6—C7	−2.9 (5)
Cl1ⁱ—Cu1—N1—C7	77.4 (3)	C2—C1—C6—C7	176.3 (3)
O1—Cu1—N1—C8	175.5 (2)	C8—N1—C7—C6	−179.5 (3)
N2—Cu1—N1—C8	−5.2 (2)	Cu1—N1—C7—C6	9.0 (5)
Cl1—Cu1—N1—C8	78.3 (4)	C5—C6—C7—N1	178.7 (3)
Cl1ⁱ—Cu1—N1—C8	−94.5 (2)	C1—C6—C7—N1	1.0 (5)
N1—Cu1—N2—C9	−21.8 (2)	C7—N1—C8—C9	−141.6 (3)
Cl1—Cu1—N2—C9	174.03 (19)	Cu1—N1—C8—C9	30.9 (3)
Cl1ⁱ—Cu1—N2—C9	67.48 (19)	C13—N2—C9—C8	169.0 (3)
N1—Cu1—N2—C13	−142.8 (3)	C10—N2—C9—C8	−72.1 (3)
Cl1—Cu1—N2—C13	53.1 (2)	Cu1—N2—C9—C8	44.6 (3)
Cl1ⁱ—Cu1—N2—C13	−53.4 (2)	N1—C8—C9—N2	−50.7 (4)
N1—Cu1—N2—C10	97.9 (2)	C9—N2—C10—C11	−67.4 (4)
Cl1—Cu1—N2—C10	−66.2 (2)	C13—N2—C10—C11	53.8 (4)
Cl1ⁱ—Cu1—N2—C10	−172.8 (2)	Cu1—N2—C10—C11	178.7 (2)
Cu1—O1—C1—C2	175.2 (2)	C12—O2—C11—C10	57.0 (4)
Cu1—O1—C1—C6	−5.6 (5)	N2—C10—C11—O2	−57.2 (4)
O1—C1—C2—C3	−179.9 (3)	C11—O2—C12—C13	−57.2 (4)
C6—C1—C2—C3	0.8 (5)	C9—N2—C13—C12	69.1 (4)
C1—C2—C3—C4	0.4 (5)	C10—N2—C13—C12	−53.5 (4)
C2—C3—C4—C5	−1.2 (5)	Cu1—N2—C13—C12	−173.8 (2)
C2—C3—C4—Cl2	179.9 (3)	O2—C12—C13—N2	57.4 (4)
C3—C4—C5—C6	0.7 (5)

Symmetry code: (i) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₃H₁₆ClN₂O₂)Cl]
M_r	366.72
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	140
a, b, c (Å)	23.0936 (6), 8.4890 (2), 14.0582 (3)
V (Å³)	2756.0 (1)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.97
Crystal size (mm)	0.40 × 0.10 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.506, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	17248, 3156, 2416
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.113, 1.09
No. of reflections	3156
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.84

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Selected bond lengths (Å) top

Cu1—O1	1.907 (2)	Cu1—N2	2.105 (3)
Cu1—N1	1.947 (3)	Cu1—Cl1	2.2620 (9)

Acknowledgements

We thank the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar

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