Bis[4-(1-imino­eth­yl)-3-methyl-1-phenyl-1H-pyrazol-5-olato-κ2O,N4]copper(II)

Zhu, H.; Wang, Z.; Wei, Z.; Bai, Y.; Xv, X.

doi:10.1107/S1600536811030753

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page m1208

doi:10.1107/S1600536811030753

Open

access

Bis[4-(1-iminoethyl)-3-methyl-1-phenyl-1H-pyrazol-5-olato-κ²O,N⁴]copper(II)

Hualing Zhu,^a Zhan Wang,^a Zhen Wei,^a Yanan Bai ^a and Xiaoping Xv ^a ^*

^aDepartment of Basic Science, Tianjin Agriculturial College, Tianjin Jinjing Road No. 22, Tianjin 300384, People's Republic of China
^*Correspondence e-mail: zhuhualing2004@126.com

(Received 27 July 2011; accepted 31 July 2011; online 6 August 2011)

In the title complex, [Cu(C₁₂H₁₂N₃O)₂], the Cu^II ion is tetracoordinated by two N atoms and two O atoms from two bis-chelating 4-(1-iminoethyl)-3-methyl-1-phenyl-1H-pyrazol-5-olate ligands in a square-planar geometry. The two N atoms and two O atoms around the Cu^II atom are trans to each other, as the Cu^II atom lies on an inversion centre. The six-membered ring composed of the Cu, an O, an N and three C atoms of the ligand and the pyrazole ring is nearly planar, the largest deviation being 0.037 (4) Å for an N atom. In the crystal, weak intermolecular C—H⋯N hydrogen-bonding interactions link the molecules into chains along the c axis.

Related literature

For our ongoing studies on pyrazolone derivatives, see: Zhu, Shi et al. (2010 ); Zhu, Wei et al. (2010 ). For related structures, see: Parsons et al. (2004 ); Shi et al. (2005 ).

Experimental

Crystal data

[Cu(C₁₂H₁₂N₃O)₂]
M_r = 492.03
Monoclinic, P 2₁ /n
a = 6.391 (6) Å
b = 9.010 (8) Å
c = 18.772 (17) Å
β = 98.701 (17)°
V = 1068.5 (16) Å³
Z = 2
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 113 K
0.10 × 0.10 × 0.10 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2008) T_min = 0.902, T_max = 0.902
8871 measured reflections
1888 independent reflections
1636 reflections with I > 2σ(I)
R_int = 0.130

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.136
S = 1.08
1888 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −1.64 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯N1ⁱ	0.95	2.61	3.366 (6)	137
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; 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: CrystalStructure (Rigaku/MSC, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811030753/pv2436sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030753/pv2436Isup2.hkl

checkCIF report

Comment top

As a part of our onging studies on pyrazolone derivatives as potential ligands (Zhu, Shi et al., 2010; Zhu, Wei et al., 2010) we report the structure of the title complex in this article.

In the title complex (Fig. 1.), the central Cu^II ion is tetracoordinated by two N atoms and two O atoms from two bis-chelating 4-(2-methyl iminomethyl)-3-methyl- 1- phenyl-1H-pyrazol-5(4H)-onato ligands in a square-planar geometry. The two N atoms and two O atoms around the Cu^II atom are trans to each other, as the Cu^II atom lies on an inversion centre. The six membered chelate ring (Cu1/O1/N3/C1/C2/C5) / and the pyrazol ring are nearly coplannar with the largest deviation 0.037 (4)Å for N2 atom. In the crystal structure, weak intermolecular hydrogen bonding interactions (C11—H11···N1) link molecules into one-dimensional chains (Fig. 2).

Related literature top

For oour ongoing studies on pyrazolone derivatives, see: Zhu, Shi et al. (2010); Zhu, Wei et al. (2010). For related structures: Parsons et al. (2004); Shi et al. (2005).

Experimental top

The title compound was synthesized by dropping a copper acetate (15 mmol) ethanolic solution into an ethanolic solution of 4-[(3,4-dihydro-5-methyl-3-oxo-2-phenyl-2H-pyrazol-4–ylidene)(methyl) methylamino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one(30 mmol) and stirring for about 7 h at room temperature. The dark green blocks which were obtained were dried in air. The product was recrystallized from N,N-dimethylformamide which afforded crystals suitable for X–ray analysis.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2008); cell refinement: CrystalClear (Rigaku/MSC, 2008); data reduction: CrystalClear (Rigaku/MSC, 2008); 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: CrystalStructure (Rigaku/MSC, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code: ⁱ: -x + 1/2, -y + 1/2, -z + 1/2).
	Fig. 2. Part of the crystal structure showing intermolecular hydrogen bonding interactions (C—H···N) as dashed lines.

Bis[4-(1-iminoethyl)-3-methyl-1-phenyl-1H-pyrazol-5-olato- κ²O,N⁴]copper(II) top

Crystal data top

[Cu(C₁₂H₁₂N₃O)₂]	F(000) = 510
M_r = 492.03	D_x = 1.529 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3203 reflections
a = 6.391 (6) Å	θ = 2.2–27.9°
b = 9.010 (8) Å	µ = 1.06 mm⁻¹
c = 18.772 (17) Å	T = 113 K
β = 98.701 (17)°	Block, dark green
V = 1068.5 (16) Å³	0.10 × 0.10 × 0.10 mm
Z = 2

Data collection top

Rigaku Saturn724 CCD diffractometer	1888 independent reflections
Radiation source: rotating anode	1636 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.130
Detector resolution: 14.22 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω and ϕ scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2008)	k = −10→10
T_min = 0.902, T_max = 0.902	l = −22→21
8871 measured reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.043P)² + 2.9195P] where P = (F_o² + 2F_c²)/3
1888 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −1.64 e Å⁻³

Crystal data top

[Cu(C₁₂H₁₂N₃O)₂]	V = 1068.5 (16) Å³
M_r = 492.03	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.391 (6) Å	µ = 1.06 mm⁻¹
b = 9.010 (8) Å	T = 113 K
c = 18.772 (17) Å	0.10 × 0.10 × 0.10 mm
β = 98.701 (17)°

Data collection top

Rigaku Saturn724 CCD diffractometer	1888 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2008)	1636 reflections with I > 2σ(I)
T_min = 0.902, T_max = 0.902	R_int = 0.130
8871 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.08	Δρ_max = 0.62 e Å⁻³
1888 reflections	Δρ_min = −1.64 e Å⁻³
154 parameters

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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	1.0000	0.0000	0.0000	0.0168 (2)
O1	0.8267 (5)	0.0256 (3)	0.07637 (14)	0.0180 (6)
N1	0.5337 (5)	0.1293 (4)	0.11912 (17)	0.0175 (8)
N2	0.3649 (5)	0.2250 (4)	0.09578 (18)	0.0181 (8)
N3	0.8317 (5)	0.1373 (4)	−0.06383 (17)	0.0174 (8)
H3	0.8788	0.1521	−0.1049	0.018 (11)*
C1	0.6638 (6)	0.1120 (4)	0.0678 (2)	0.0149 (8)
C2	0.5770 (6)	0.2036 (4)	0.0094 (2)	0.0147 (8)
C3	0.3932 (6)	0.2692 (4)	0.0303 (2)	0.0172 (9)
C4	0.2369 (7)	0.3782 (5)	−0.0080 (2)	0.0226 (9)
H4A	0.1279	0.4000	0.0220	0.034*
H4B	0.1704	0.3356	−0.0540	0.034*
H4C	0.3105	0.4701	−0.0171	0.034*
C5	0.6613 (7)	0.2121 (4)	−0.0571 (2)	0.0186 (9)
C6	0.5517 (7)	0.3040 (5)	−0.1183 (2)	0.0248 (10)
H6A	0.6266	0.2943	−0.1599	0.037*
H6B	0.5513	0.4083	−0.1035	0.037*
H6C	0.4056	0.2694	−0.1314	0.037*
C7	0.5388 (7)	0.0532 (4)	0.1862 (2)	0.0171 (9)
C8	0.3507 (7)	0.0359 (5)	0.2136 (2)	0.0217 (9)
H8	0.2236	0.0788	0.1896	0.026*
C9	0.3505 (7)	−0.0449 (5)	0.2766 (2)	0.0242 (10)
H9	0.2219	−0.0586	0.2953	0.029*
C10	0.5372 (7)	−0.1061 (5)	0.3124 (2)	0.0239 (10)
H10	0.5354	−0.1621	0.3552	0.029*
C11	0.7253 (7)	−0.0854 (5)	0.2858 (2)	0.0220 (9)
H11	0.8529	−0.1265	0.3105	0.026*
C12	0.7277 (7)	−0.0043 (4)	0.2227 (2)	0.0182 (9)
H12	0.8570	0.0117	0.2046	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0155 (4)	0.0184 (4)	0.0171 (4)	0.0023 (3)	0.0047 (3)	−0.0003 (3)
O1	0.0137 (14)	0.0223 (15)	0.0186 (14)	0.0057 (12)	0.0044 (11)	0.0013 (12)
N1	0.0137 (17)	0.0185 (18)	0.0205 (17)	0.0046 (14)	0.0034 (14)	0.0012 (14)
N2	0.0151 (17)	0.0160 (17)	0.0240 (18)	0.0013 (14)	0.0057 (14)	−0.0006 (14)
N3	0.0184 (18)	0.0208 (18)	0.0140 (16)	−0.0009 (15)	0.0055 (14)	−0.0024 (14)
C1	0.0136 (19)	0.015 (2)	0.0166 (18)	−0.0032 (16)	0.0036 (16)	−0.0009 (15)
C2	0.015 (2)	0.0124 (19)	0.0170 (19)	−0.0017 (16)	0.0030 (16)	0.0006 (16)
C3	0.017 (2)	0.0125 (19)	0.022 (2)	−0.0026 (16)	0.0029 (17)	−0.0026 (16)
C4	0.020 (2)	0.020 (2)	0.027 (2)	0.0031 (18)	0.0017 (19)	0.0018 (18)
C5	0.021 (2)	0.016 (2)	0.018 (2)	−0.0043 (17)	0.0006 (17)	−0.0016 (17)
C6	0.030 (3)	0.024 (2)	0.020 (2)	0.004 (2)	0.0029 (19)	0.0001 (18)
C7	0.023 (2)	0.015 (2)	0.0138 (18)	0.0005 (17)	0.0044 (17)	−0.0034 (16)
C8	0.016 (2)	0.027 (2)	0.023 (2)	0.0053 (18)	0.0069 (18)	0.0012 (18)
C9	0.019 (2)	0.031 (2)	0.025 (2)	−0.0016 (19)	0.0104 (18)	−0.0015 (19)
C10	0.026 (2)	0.028 (2)	0.020 (2)	−0.004 (2)	0.0087 (19)	−0.0007 (18)
C11	0.020 (2)	0.026 (2)	0.019 (2)	0.0035 (19)	0.0014 (17)	−0.0021 (18)
C12	0.015 (2)	0.019 (2)	0.022 (2)	−0.0018 (17)	0.0058 (17)	−0.0016 (17)

Geometric parameters (Å, º) top

Cu1—N3ⁱ	1.932 (4)	C4—H4C	0.9800
Cu1—N3	1.932 (4)	C5—C6	1.502 (6)
Cu1—O1	1.953 (3)	C6—H6A	0.9800
Cu1—O1ⁱ	1.953 (3)	C6—H6B	0.9800
O1—C1	1.290 (5)	C6—H6C	0.9800
N1—C1	1.373 (5)	C7—C8	1.385 (6)
N1—N2	1.399 (5)	C7—C12	1.395 (6)
N1—C7	1.430 (5)	C8—C9	1.389 (6)
N2—C3	1.330 (5)	C8—H8	0.9500
N3—C5	1.303 (5)	C9—C10	1.392 (6)
N3—H3	0.8800	C9—H9	0.9500
C1—C2	1.418 (5)	C10—C11	1.383 (6)
C2—C3	1.422 (6)	C10—H10	0.9500
C2—C5	1.435 (6)	C11—C12	1.395 (6)
C3—C4	1.505 (6)	C11—H11	0.9500
C4—H4A	0.9800	C12—H12	0.9500
C4—H4B	0.9800

N3ⁱ—Cu1—N3	180.0 (2)	H4B—C4—H4C	109.5
N3ⁱ—Cu1—O1	86.83 (14)	N3—C5—C2	119.1 (4)
N3—Cu1—O1	93.17 (14)	N3—C5—C6	120.7 (4)
N3ⁱ—Cu1—O1ⁱ	93.17 (14)	C2—C5—C6	120.1 (4)
N3—Cu1—O1ⁱ	86.83 (14)	C5—C6—H6A	109.5
O1—Cu1—O1ⁱ	180.00 (14)	C5—C6—H6B	109.5
C1—O1—Cu1	121.1 (2)	H6A—C6—H6B	109.5
C1—N1—N2	111.8 (3)	C5—C6—H6C	109.5
C1—N1—C7	128.9 (3)	H6A—C6—H6C	109.5
N2—N1—C7	119.0 (3)	H6B—C6—H6C	109.5
C3—N2—N1	105.5 (3)	C8—C7—C12	120.7 (4)
C5—N3—Cu1	131.7 (3)	C8—C7—N1	118.4 (4)
C5—N3—H3	114.1	C12—C7—N1	120.9 (4)
Cu1—N3—H3	114.1	C7—C8—C9	119.2 (4)
O1—C1—N1	123.0 (3)	C7—C8—H8	120.4
O1—C1—C2	131.4 (4)	C9—C8—H8	120.4
N1—C1—C2	105.6 (3)	C8—C9—C10	120.5 (4)
C1—C2—C3	105.8 (3)	C8—C9—H9	119.7
C1—C2—C5	123.3 (4)	C10—C9—H9	119.7
C3—C2—C5	130.8 (4)	C11—C10—C9	120.0 (4)
N2—C3—C2	111.4 (4)	C11—C10—H10	120.0
N2—C3—C4	117.7 (4)	C9—C10—H10	120.0
C2—C3—C4	131.0 (4)	C10—C11—C12	120.0 (4)
C3—C4—H4A	109.5	C10—C11—H11	120.0
C3—C4—H4B	109.5	C12—C11—H11	120.0
H4A—C4—H4B	109.5	C11—C12—C7	119.5 (4)
C3—C4—H4C	109.5	C11—C12—H12	120.3
H4A—C4—H4C	109.5	C7—C12—H12	120.3

N3ⁱ—Cu1—O1—C1	−178.9 (3)	C1—C2—C3—C4	178.8 (4)
N3—Cu1—O1—C1	1.1 (3)	C5—C2—C3—C4	−5.6 (7)
C1—N1—N2—C3	−1.2 (4)	Cu1—N3—C5—C2	3.6 (6)
C7—N1—N2—C3	−175.0 (3)	Cu1—N3—C5—C6	−175.4 (3)
O1—Cu1—N3—C5	−2.5 (4)	C1—C2—C5—N3	−3.1 (6)
O1ⁱ—Cu1—N3—C5	177.5 (4)	C3—C2—C5—N3	−178.0 (4)
Cu1—O1—C1—N1	177.7 (3)	C1—C2—C5—C6	175.9 (4)
Cu1—O1—C1—C2	−1.4 (6)	C3—C2—C5—C6	0.9 (7)
N2—N1—C1—O1	−178.0 (3)	C1—N1—C7—C8	−151.2 (4)
C7—N1—C1—O1	−4.9 (6)	N2—N1—C7—C8	21.4 (5)
N2—N1—C1—C2	1.3 (4)	C1—N1—C7—C12	27.8 (6)
C7—N1—C1—C2	174.4 (4)	N2—N1—C7—C12	−159.6 (4)
O1—C1—C2—C3	178.3 (4)	C12—C7—C8—C9	−2.6 (6)
N1—C1—C2—C3	−1.0 (4)	N1—C7—C8—C9	176.4 (4)
O1—C1—C2—C5	2.3 (7)	C7—C8—C9—C10	0.9 (7)
N1—C1—C2—C5	−177.0 (4)	C8—C9—C10—C11	0.6 (7)
N1—N2—C3—C2	0.5 (4)	C9—C10—C11—C12	−0.5 (6)
N1—N2—C3—C4	−178.2 (3)	C10—C11—C12—C7	−1.1 (6)
C1—C2—C3—N2	0.3 (5)	C8—C7—C12—C11	2.7 (6)
C5—C2—C3—N2	175.9 (4)	N1—C7—C12—C11	−176.3 (4)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.88	2.47	2.670 (5)	94
C4—H4B···N3ⁱⁱ	0.98	2.79	3.419 (6)	123
C9—H9···N2ⁱⁱⁱ	0.95	2.94	3.596 (6)	128
C11—H11···N1^iv	0.95	2.61	3.366 (6)	137
C11—H11···N2^iv	0.95	2.68	3.599 (6)	163
C12—H12···O1	0.95	2.39	2.923 (5)	115

Symmetry codes: (i) −x+2, −y, −z; (ii) x−1, y, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₂N₃O)₂]
M_r	492.03
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	6.391 (6), 9.010 (8), 18.772 (17)
β (°)	98.701 (17)
V (Å³)	1068.5 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.06
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Rigaku Saturn724 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2008)
T_min, T_max	0.902, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	8871, 1888, 1636
R_int	0.130
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.136, 1.08
No. of reflections	1888
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −1.64

Computer programs: CrystalClear (Rigaku/MSC, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku/MSC, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···N1ⁱ	0.95	2.61	3.366 (6)	136.6

Symmetry code: (i) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

The authors are grateful for financial support from the Spark Program Foundation of the Science and Technology Department of China (research Nos. 09ZHXHNC07900 and 2010 GA610009).

References

Parsons, S., Emeleus, L., Tasker, P. & Wood, P. (2004). Private communication (refcode XAJREG). CCDC, Cambridge, England. Google Scholar
Rigaku/MSC (2008). CrystalClear and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, J. M., Zhang, F. X., Wu, C. J. & Liu, L. D. (2005). Acta Cryst. E61, m2320–m2321. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhu, H., Shi, J., Wei, Z., Bai, Y. & Bu, L. (2010). Acta Cryst. E66, o1583. CrossRef IUCr Journals Google Scholar
Zhu, H., Wei, Z., Bu, L., Xu, X. & Shi, J. (2010). Acta Cryst. E66, m904. Web of Science CrossRef IUCr Journals Google Scholar