Bis[4-(1-imino-eth-yl)-3-methyl-1-phenyl-1H-pyrazol-5-olato-κO,N]copper(II).

In the title complex, [Cu(C(12)H(12)N(3)O)(2)], the Cu(II) ion is tetra-coordinated by two N atoms and two O atoms from two bis-chelating 4-(1-imino-eth-yl)-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 inter-molecular C-H⋯N hydrogen-bonding inter-actions link the mol-ecules 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 = 492.03

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.136

S = 1.08

1888 reflections

154 parameters

H-atom parameters constrained

Δρmax = 0.62 e Å−3

Δρmin = −1.64 e Å−3

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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811030753/pv2436sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C12H12N3O)2]	F(000) = 510
Mr = 492.03	Dx = 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

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

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(Fo2) + (0.043P)2 + 2.9195P] where P = (Fo2 + 2Fc2)/3
1888 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.62 e Å−3
0 restraints	Δρmin = −1.64 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···N1iv	0.95	2.61	3.366 (6)	137.
C11—H11···N2iv	0.95	2.68	3.599 (6)	163.
C12—H12···O1	0.95	2.39	2.923 (5)	115.

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) .