{2,2′-[1,2-Phenyl­enebis­(nitrilo­methyl­idyne)]­diphenolato}copper(II) di­chloro­methane solvate

Baggio, R.; Garland, M.T.; Atria, A.M.; Hidalgo, O.; Solezi, S.

doi:10.1107/S1600536800019668

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{2,2'-[1,2-Phenylenebis(nitrilomethylidyne)]diphenolato}copper(II) dichloromethane solvate

R. Baggio, M. T. Garland, A. M. Atria, O. Hidalgo and S. Solezi

The title compound, [Cu(C₂₀H₁₄N₂O₂)]·CH₂Cl₂, crystallizes as a monomer, with the copper ion in a square-planar environment provided by the tetradentate 2,2'-[1,2-phenylenebis(nitrilomethylidyne)]diphenolate (L18) ligand. The planar molecules pack parallel to the (101) crystallographic planes.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019668/cf6024sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019668/cf6024Isup2.hkl Contains datablock I

CCDC reference: 155838

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.016 Å
R factor = 0.048
wR factor = 0.108
Data-to-parameter ratio = 6.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               1718
         Count of symmetry unique reflns         1703
         Completeness (_total/calc)            100.88%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured        15
         Fraction of Friedel pairs measured     0.009
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure

Comment top

2,2'-[1,2-Phenylenebis(nitrilomethylidyne)]diphenol (L18) is a well known Schiff base which can act as a tetradentate ligand, and its square-planar copper complex has been described as an isolated molecule in a number of crystalline forms, both on its own (Suresh et al., 1996), (1), as well as stabilized by a variety of different solvates, e.g. water [(2); Yao et al., 1997], thiourea [(3); Ferrari et al., 1976] and tetracyanoquinodimethane [(4); Cassoux & Gleizes, 1980]. During the synthesis of a heteronuclear Cu–Gd(L18) complex, we obtained some crystals which happened to be a new unreported form of the Cu(L18) complex, (I), this time stabilized by a molecule of CH₂Cl₂, and which we report herein.

The molecular structure of (I) is quite similar to those described previously (Fig. 1), in spite of the very different crystalline forms, and a least-squares fit showed that the extreme differences were found when comparing it with the two independent moieties in (2), with a minimum mean-squares deviation of 0.079 Å and a maximum of 0.158 Å. The largest misfit appeared as deviations of the ligand from its planar character, rather than from the intrinsic bond lengths and angles, which remained fairly stable.

The planar molecules pack parallel to each other and to the (101) planes (Fig. 2), with no obvious interaction besides the usual van der Waals forces.

The CH₂Cl₂ solvate molecule attaches to the complex through a medium strength C—H···O interaction [H1XB···O1 2.313 (3) Å and C1X—H1XB···O1 171 (3)°].

Experimental top

To a solution containing 1 mmol of Cu(NO₃)₂·2H₂O in CH₂Cl₂, 1 mm mol of Gd(NO₃)₂ and 1 mm mol of L18 were added. The Cu(L18)·CH₂Cl₂ complex precipitated as a polycrystalline brown powder, which by filtering was separated from the solution containing the heteronuclear species.

Computing details top

Data collection: P3/P4-PC (Siemens, 1991); cell refinement: P3/P4-PC; data reduction: XDISK in SHELXTL/PC (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXTL and PARST (Nardelli, 1983).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom numbering and displacement ellipsoids at the 50% probability level.
	Fig. 2. Packing diagram showing the way in which the molecules organize parallel to (101).

{2,2'-[1,2-Phenylenebis(nitrilomethylidyne)]diphenolato}copper(II) dichloromethane solvate top

Crystal data top

[Cu(C₂₀H₁₄N₂O₂)]·CH₂Cl₂	F(000) = 940
M_r = 462.80	D_x = 1.591 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 15.787 (3) Å	Cell parameters from 25 reflections
b = 14.359 (3) Å	θ = 7.5–12.5°
c = 9.1630 (15) Å	µ = 1.43 mm⁻¹
β = 111.59 (2)°	T = 293 K
V = 1931.5 (6) Å³	Prism, red–brown
Z = 4	0.15 × 0.12 × 0.10 mm

Data collection top

Siemens R3m diffractometer	1308 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 25.0°, θ_min = 2.0°
ω/2θ scans	h = −18→18
Absorption correction: ψ scan (SHELXTL/PC; Sheldrick, 1994)	k = −17→17
T_min = 0.80, T_max = 0.84	l = 0→10
3419 measured reflections	2 standard reflections every 98 reflections
1718 independent reflections	intensity decay: 4.8%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.061P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
1718 reflections	Δρ_max = 0.49 e Å⁻³
262 parameters	Δρ_min = −0.34 e Å⁻³
3 restraints	Absolute structure: Flack (1983); 119 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (3)

Crystal data top

[Cu(C₂₀H₁₄N₂O₂)]·CH₂Cl₂	V = 1931.5 (6) Å³
M_r = 462.80	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 15.787 (3) Å	µ = 1.43 mm⁻¹
b = 14.359 (3) Å	T = 293 K
c = 9.1630 (15) Å	0.15 × 0.12 × 0.10 mm
β = 111.59 (2)°

Data collection top

Siemens R3m diffractometer	1308 reflections with I > 2σ(I)
Absorption correction: ψ scan (SHELXTL/PC; Sheldrick, 1994)	R_int = 0.043
T_min = 0.80, T_max = 0.84	2 standard reflections every 98 reflections
3419 measured reflections	intensity decay: 4.8%
1718 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.108	Δρ_max = 0.49 e Å⁻³
S = 1.02	Δρ_min = −0.34 e Å⁻³
1718 reflections	Absolute structure: Flack (1983); 119 Friedel pairs
262 parameters	Absolute structure parameter: −0.01 (3)
3 restraints

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.02223 (9)	0.42130 (7)	0.18066 (14)	0.0481 (3)
O1	0.1030 (4)	0.4909 (5)	0.1118 (9)	0.060 (2)
O2	0.0606 (5)	0.3127 (5)	0.1040 (9)	0.059 (2)
N1	−0.0269 (5)	0.5305 (7)	0.2483 (10)	0.049 (2)
N2	−0.0589 (5)	0.3541 (6)	0.2600 (10)	0.048 (2)
C1	0.1104 (6)	0.5799 (7)	0.1092 (12)	0.055 (3)
C2	0.1680 (7)	0.6185 (7)	0.0354 (13)	0.058 (3)
H2A	0.1977	0.5783	−0.0095	0.070*
C3	0.1811 (7)	0.7127 (8)	0.0285 (14)	0.070 (3)
H3A	0.2197	0.7359	−0.0189	0.083*
C4	0.1356 (7)	0.7729 (8)	0.0937 (14)	0.073 (3)
H4A	0.1448	0.8367	0.0905	0.088*
C5	0.0788 (7)	0.7413 (7)	0.1610 (13)	0.070 (3)
H5A	0.0487	0.7834	0.2020	0.083*
C6	0.0640 (7)	0.6447 (7)	0.1704 (13)	0.047 (3)
C7	0.0005 (6)	0.6155 (7)	0.2412 (13)	0.049 (3)
H7A	−0.0231	0.6618	0.2862	0.058*
C8	−0.0939 (6)	0.5089 (7)	0.3089 (12)	0.050 (2)
C9	−0.1442 (7)	0.5740 (7)	0.3569 (13)	0.060 (3)
H9A	−0.1330	0.6374	0.3536	0.072*
C10	−0.2102 (6)	0.5433 (8)	0.4086 (13)	0.066 (3)
H10A	−0.2437	0.5869	0.4396	0.079*
C11	−0.2284 (7)	0.4518 (8)	0.4163 (15)	0.069 (3)
H11A	−0.2745	0.4334	0.4506	0.083*
C12	−0.1783 (6)	0.3856 (7)	0.3731 (13)	0.058 (3)
H12A	−0.1895	0.3226	0.3809	0.069*
C13	−0.1107 (5)	0.4140 (7)	0.3176 (10)	0.045 (2)
C14	−0.0631 (6)	0.2633 (7)	0.2629 (12)	0.054 (2)
H14A	−0.1016	0.2376	0.3085	0.064*
C15	−0.0168 (8)	0.2024 (9)	0.2056 (15)	0.054 (3)
C16	−0.0296 (8)	0.1040 (9)	0.2224 (18)	0.074 (4)
H16A	−0.0697	0.0855	0.2701	0.089*
C17	0.0142 (10)	0.0367 (6)	0.172 (2)	0.082 (3)
H17A	0.0064	−0.0260	0.1893	0.098*
C18	0.0706 (9)	0.0638 (8)	0.0941 (16)	0.074 (4)
H18A	0.0999	0.0188	0.0568	0.089*
C19	0.0834 (6)	0.1548 (7)	0.0720 (14)	0.065 (3)
H19A	0.1207	0.1708	0.0175	0.078*
C20	0.0427 (8)	0.2264 (8)	0.1276 (16)	0.058 (4)
C1X	0.2638 (9)	0.3553 (14)	0.112 (2)	0.133 (6)
H1XA	0.241 (2)	0.297 (2)	0.0918 (15)	0.40 (13)*
H1XB	0.2240 (19)	0.397 (3)	0.1198 (19)	0.11 (3)*
Cl1X	0.3001 (3)	0.3872 (4)	−0.0303 (6)	0.1333 (16)
Cl2X	0.3454 (3)	0.3480 (4)	0.2994 (6)	0.1506 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0462 (4)	0.0484 (5)	0.0553 (6)	−0.0015 (6)	0.0254 (4)	−0.0020 (7)
O1	0.062 (4)	0.048 (4)	0.076 (5)	−0.008 (3)	0.031 (4)	0.002 (4)
O2	0.065 (4)	0.046 (4)	0.079 (6)	0.004 (3)	0.042 (4)	0.002 (4)
N1	0.050 (5)	0.054 (5)	0.043 (5)	−0.002 (4)	0.019 (4)	−0.003 (4)
N2	0.044 (5)	0.052 (5)	0.050 (5)	−0.006 (3)	0.022 (4)	−0.004 (4)
C1	0.047 (5)	0.055 (6)	0.063 (7)	−0.009 (5)	0.021 (5)	0.007 (6)
C2	0.058 (6)	0.053 (6)	0.069 (8)	−0.008 (5)	0.029 (6)	0.000 (6)
C3	0.064 (6)	0.083 (8)	0.069 (8)	−0.019 (5)	0.034 (6)	−0.003 (6)
C4	0.077 (7)	0.069 (7)	0.072 (8)	−0.039 (6)	0.025 (6)	−0.003 (6)
C5	0.072 (7)	0.067 (7)	0.069 (8)	−0.006 (6)	0.026 (6)	−0.009 (6)
C6	0.050 (6)	0.043 (6)	0.045 (7)	−0.019 (5)	0.014 (5)	−0.012 (5)
C7	0.046 (6)	0.046 (6)	0.045 (7)	0.009 (5)	0.006 (5)	−0.010 (5)
C8	0.043 (4)	0.062 (7)	0.047 (6)	0.012 (5)	0.020 (4)	−0.005 (5)
C9	0.067 (6)	0.054 (6)	0.069 (8)	0.010 (5)	0.039 (6)	−0.002 (6)
C10	0.049 (5)	0.080 (7)	0.072 (8)	0.014 (5)	0.029 (5)	−0.012 (6)
C11	0.053 (6)	0.080 (7)	0.082 (9)	0.002 (5)	0.036 (6)	−0.003 (7)
C12	0.051 (5)	0.067 (6)	0.064 (7)	−0.009 (4)	0.030 (5)	−0.009 (5)
C13	0.041 (4)	0.057 (6)	0.042 (5)	0.001 (4)	0.023 (4)	−0.006 (5)
C14	0.052 (5)	0.057 (6)	0.058 (7)	−0.007 (5)	0.027 (5)	−0.007 (5)
C15	0.058 (6)	0.054 (6)	0.061 (8)	0.004 (5)	0.033 (6)	−0.004 (6)
C16	0.072 (8)	0.053 (6)	0.107 (12)	−0.013 (6)	0.045 (8)	−0.010 (7)
C17	0.102 (8)	0.050 (5)	0.107 (9)	−0.009 (9)	0.054 (8)	−0.003 (9)
C18	0.083 (8)	0.064 (7)	0.080 (10)	0.013 (6)	0.036 (7)	0.001 (7)
C19	0.069 (6)	0.061 (6)	0.071 (8)	0.009 (5)	0.035 (6)	0.009 (6)
C20	0.057 (7)	0.067 (8)	0.049 (7)	0.000 (5)	0.018 (6)	−0.015 (6)
C1X	0.072 (8)	0.180 (17)	0.170 (19)	0.035 (10)	0.071 (11)	0.055 (13)
Cl1X	0.130 (3)	0.171 (4)	0.110 (4)	0.006 (3)	0.057 (3)	−0.019 (3)
Cl2X	0.138 (3)	0.188 (4)	0.113 (4)	0.007 (3)	0.031 (3)	0.030 (3)

Geometric parameters (Å, º) top

Cu1—O2	1.899 (7)	C9—H9A	0.9300
Cu1—O1	1.902 (7)	C10—C11	1.353 (14)
Cu1—N2	1.945 (8)	C10—H10A	0.9300
Cu1—N1	1.949 (9)	C11—C12	1.383 (14)
O1—C1	1.285 (12)	C11—H11A	0.9300
O2—C20	1.306 (14)	C12—C13	1.402 (12)
N1—C7	1.305 (14)	C12—H12A	0.9300
N1—C8	1.397 (12)	C14—C15	1.363 (16)
N2—C14	1.306 (13)	C14—H14A	0.9300
N2—C13	1.416 (12)	C15—C20	1.416 (14)
C1—C6	1.422 (16)	C15—C16	1.444 (18)
C1—C2	1.428 (14)	C16—C17	1.36 (2)
C2—C3	1.374 (14)	C16—H16A	0.9300
C2—H2A	0.9300	C17—C18	1.385 (19)
C3—C4	1.392 (15)	C17—H17A	0.9300
C3—H3A	0.9300	C18—C19	1.350 (15)
C4—C5	1.340 (14)	C18—H18A	0.9300
C4—H4A	0.9300	C19—C20	1.403 (15)
C5—C6	1.413 (14)	C19—H19A	0.9300
C5—H5A	0.9300	C1X—Cl1X	1.671 (17)
C6—C7	1.442 (13)	C1X—Cl2X	1.729 (19)
C7—H7A	0.9300	C1X—H1XA	0.90 (3)
C8—C9	1.399 (13)	C1X—H1XB	0.89 (4)
C8—C13	1.397 (13)	Cl2X—H1XA	2.135 (17)
C9—C10	1.365 (14)

O2—Cu1—O1	88.0 (3)	C11—C10—C9	122.4 (10)
O2—Cu1—N2	94.2 (4)	C11—C10—H10A	118.8
O1—Cu1—N2	177.2 (4)	C9—C10—H10A	118.8
O2—Cu1—N1	175.5 (4)	C10—C11—C12	119.8 (11)
O1—Cu1—N1	94.4 (4)	C10—C11—H11A	120.1
N2—Cu1—N1	83.5 (4)	C12—C11—H11A	120.1
C1—O1—Cu1	127.3 (8)	C11—C12—C13	119.8 (9)
C20—O2—Cu1	126.9 (8)	C11—C12—H12A	120.1
C7—N1—C8	122.8 (9)	C13—C12—H12A	120.1
C7—N1—Cu1	123.9 (7)	C8—C13—C12	119.3 (8)
C8—N1—Cu1	113.3 (7)	C8—C13—N2	115.1 (8)
C14—N2—C13	123.9 (9)	C12—C13—N2	125.5 (8)
C14—N2—Cu1	123.3 (7)	N2—C14—C15	126.4 (11)
C13—N2—Cu1	112.8 (6)	N2—C14—H14A	116.8
O1—C1—C6	125.5 (10)	C15—C14—H14A	116.8
O1—C1—C2	118.2 (11)	C14—C15—C20	126.0 (13)
C6—C1—C2	116.3 (10)	C14—C15—C16	118.0 (12)
C3—C2—C1	122.4 (11)	C20—C15—C16	116.0 (12)
C3—C2—H2A	118.7	C17—C16—C15	123.2 (13)
C1—C2—H2A	118.8	C17—C16—H16A	118.4
C2—C3—C4	118.7 (10)	C15—C16—H16A	118.4
C2—C3—H3A	120.7	C16—C17—C18	118.5 (11)
C4—C3—H3A	120.6	C16—C17—H17A	120.8
C5—C4—C3	121.8 (10)	C18—C17—H17A	120.7
C5—C4—H4A	119.1	C19—C18—C17	120.6 (12)
C3—C4—H4A	119.2	C19—C18—H18A	119.7
C4—C5—C6	120.9 (11)	C17—C18—H18A	119.7
C4—C5—H5A	119.6	C18—C19—C20	122.8 (12)
C6—C5—H5A	119.5	C18—C19—H19A	118.7
C5—C6—C1	119.8 (11)	C20—C19—H19A	118.5
C5—C6—C7	118.1 (11)	O2—C20—C19	118.7 (13)
C1—C6—C7	122.1 (9)	O2—C20—C15	122.6 (12)
N1—C7—C6	126.4 (9)	C19—C20—C15	118.8 (13)
N1—C7—H7A	116.8	Cl1X—C1X—Cl2X	116.6 (8)
C6—C7—H7A	116.8	Cl1X—C1X—H1XA	108.5 (17)
C9—C8—C13	119.5 (9)	Cl2X—C1X—H1XA	104.1 (17)
C9—C8—N1	125.2 (9)	Cl1X—C1X—H1XB	109.2 (17)
C13—C8—N1	115.3 (8)	Cl2X—C1X—H1XB	104.5 (17)
C10—C9—C8	119.2 (9)	H1XA—C1X—H1XB	114 (3)
C10—C9—H9A	120.5	C1X—Cl2X—H1XA	24.2 (10)
C8—C9—H9A	120.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1X—H1XB···O1	0.89 (4)	2.32 (4)	3.20 (2)	171 (3)

Experimental details

Crystal data
Chemical formula	[Cu(C₂₀H₁₄N₂O₂)]·CH₂Cl₂
M_r	462.80
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	15.787 (3), 14.359 (3), 9.1630 (15)
β (°)	111.59 (2)
V (Å³)	1931.5 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.43
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Siemens R3m diffractometer
Absorption correction	ψ scan (SHELXTL/PC; Sheldrick, 1994)
T_min, T_max	0.80, 0.84
No. of measured, independent and observed [I > 2σ(I)] reflections	3419, 1718, 1308
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.108, 1.02
No. of reflections	1718
No. of parameters	262
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.34
Absolute structure	Flack (1983); 119 Friedel pairs
Absolute structure parameter	−0.01 (3)

Computer programs: P3/P4-PC (Siemens, 1991), P3/P4-PC, XDISK in SHELXTL/PC (Sheldrick, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1994), SHELXTL and PARST (Nardelli, 1983).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1X—H1XB···O1	0.89 (4)	2.32 (4)	3.20 (2)	171 (3)

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{2,2'-[1,2-Phenyl­enebis­(nitrilo­methyl­idyne)]­diphenolato}copper(II) di­chloro­methane solvate