{N'-[1-(2-Pyrid-yl)ethyl-idene-κN]benzo-hydrazidato-κN',O}{N'-[1-(2-pyrid-yl)ethyl-idene-κN]benzohydrazide-κN',O}copper(II) trichloro-acetate.

In the title complex, [Cu(C(14)H(13)N(3)O)(C(14)H(12)N(3)O)](CCl(3)COO), the central Cu(II) ion exhibits a distorted octa-hedral geometry with the two ligands coordinating in an meridional format. The N(4)O(2) ligand environment is defined by two benzoyl O atoms, two pyridyl N atoms and imino N atoms. As evidenced by the bond lengths, the two benzohydrazone ligands exist in distinctively different forms, one of them as a regular neutral ligand and the other as an anionic enolate arising from deprotonation. The much longer Cu-O bond and longer Cu-N bond lengths in the neutral benzohydrazone ligand imply weak ligation in comparison with the anionic enolate form. The acute angles of the five-membered rings cause a significant deviation from a regular octa-hedral geometry.

Related literature

For related complexes of the same precursor ligand, see: Patole et al. (2003 ▶); Sen et al. (2005 ▶, 2007a ▶,b ▶); Ray et al. (2008 ▶); Datta et al. (2010 ▶).

Experimental

Crystal data

[Cu(C14H13N3O)(C14H12N3O)](C2Cl3O2)

M = 703.45

Triclinic,

a = 8.3341 (6) Å

b = 13.0470 (9) Å

c = 16.0729 (12) Å

α = 107.737 (1)°

β = 102.541 (1)°

γ = 95.259 (1)°

V = 1601.3 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.98 mm−1

T = 295 K

0.30 × 0.27 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.799, T max = 0.875

9034 measured reflections

6180 independent reflections

4962 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.189

S = 1.03

6180 reflections

399 parameters

1 restraint

H-atom parameters constrained

Δρmax = 1.16 e Å−3

Δρmin = −0.52 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811036592/zk2027sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036592/zk2027Isup2.hkl

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

[Cu(C14H13N3O)(C14H12N3O)](C2Cl3O2)	V = 1601.3 (2) Å3
Mr = 703.45	Z = 2
Triclinic, P1	F(000) = 718
Hall symbol: -P 1	Dx = 1.459 Mg m−3
a = 8.3341 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.0470 (9) Å	µ = 0.98 mm−1
c = 16.0729 (12) Å	T = 295 K
α = 107.737 (1)°	Square, green
β = 102.541 (1)°	0.30 × 0.27 × 0.25 mm
γ = 95.259 (1)°

Bruker APEXII CCD area-detector diffractometer	6180 independent reflections
Radiation source: fine-focus sealed tube	4962 reflections with I > 2σ(I)
graphite	Rint = 0.016
phi and ω scans	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.799, Tmax = 0.875	k = −15→16
9034 measured reflections	l = −17→19

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.189	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.1266P)2 + 0.7166P] where P = (Fo2 + 2Fc2)/3
6180 reflections	(Δ/σ)max = 0.001
399 parameters	Δρmax = 1.16 e Å−3
1 restraint	Δρmin = −0.52 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
C1	0.8662 (5)	0.7231 (4)	0.8172 (3)	0.0642 (10)
H1	0.9207	0.7952	0.8428	0.077*
C2	0.8171 (6)	0.6703 (5)	0.8729 (3)	0.0779 (12)
H2	0.8365	0.7069	0.9346	0.094*
C3	0.7401 (6)	0.5639 (5)	0.8359 (4)	0.0810 (14)
H3	0.7067	0.5271	0.8722	0.097*
C4	0.7121 (5)	0.5114 (4)	0.7440 (3)	0.0707 (12)
H4	0.6604	0.4387	0.7180	0.085*
C5	0.7614 (4)	0.5676 (3)	0.6908 (3)	0.0524 (8)
C6	0.7387 (4)	0.5210 (3)	0.5918 (3)	0.0521 (8)
C7	0.6495 (6)	0.4074 (3)	0.5377 (3)	0.0740 (12)
H7A	0.6098	0.4019	0.4755	0.111*
H7B	0.5568	0.3907	0.5606	0.111*
H7C	0.7247	0.3567	0.5422	0.111*
C8	0.8707 (4)	0.6479 (3)	0.4554 (2)	0.0478 (7)
C9	0.8752 (4)	0.6359 (3)	0.3610 (2)	0.0501 (8)
C10	1.0003 (5)	0.7006 (3)	0.3449 (3)	0.0596 (9)
H10	1.0787	0.7523	0.3933	0.072*
C11	1.0075 (6)	0.6879 (4)	0.2581 (3)	0.0723 (11)
H11	1.0934	0.7292	0.2479	0.087*
C12	0.8891 (7)	0.6145 (4)	0.1860 (3)	0.0810 (13)
H12	0.8925	0.6080	0.1272	0.097*
C13	0.7658 (7)	0.5509 (4)	0.2012 (3)	0.0834 (14)
H13	0.6871	0.5002	0.1524	0.100*
C14	0.7575 (5)	0.5614 (3)	0.2868 (3)	0.0642 (10)
H14	0.6723	0.5183	0.2960	0.077*
C15	1.2778 (5)	0.7146 (3)	0.7063 (3)	0.0568 (9)
H15	1.2450	0.6421	0.6691	0.068*
C16	1.4413 (5)	0.7497 (4)	0.7564 (3)	0.0677 (11)
H16	1.5173	0.7016	0.7527	0.081*
C17	1.4910 (5)	0.8573 (4)	0.8123 (3)	0.0693 (11)
H17	1.6000	0.8826	0.8478	0.083*
C18	1.3744 (5)	0.9265 (3)	0.8142 (3)	0.0622 (10)
H18	1.4044	0.9996	0.8505	0.075*
C19	1.2123 (4)	0.8857 (3)	0.7613 (2)	0.0490 (8)
C20	1.0801 (4)	0.9549 (3)	0.7556 (3)	0.0533 (8)
C21	1.1254 (6)	1.0762 (3)	0.8015 (4)	0.0950 (19)
H21A	1.2375	1.1002	0.8011	0.142*
H21B	1.1173	1.0944	0.8628	0.142*
H21C	1.0503	1.1118	0.7700	0.142*
C22	0.6592 (4)	0.9005 (3)	0.6336 (2)	0.0445 (7)
C23	0.5230 (4)	0.9641 (3)	0.6162 (2)	0.0428 (7)
C24	0.3589 (4)	0.9092 (3)	0.5859 (2)	0.0496 (8)
H24	0.3367	0.8353	0.5785	0.060*
C25	0.2288 (5)	0.9639 (3)	0.5669 (3)	0.0595 (9)
H25	0.1193	0.9275	0.5484	0.071*
C26	0.2622 (5)	1.0744 (3)	0.5757 (3)	0.0634 (10)
H26	0.1751	1.1113	0.5622	0.076*
C27	0.4247 (5)	1.1279 (3)	0.6045 (3)	0.0624 (10)
H27	0.4472	1.2013	0.6105	0.075*
C28	0.5548 (5)	1.0737 (3)	0.6245 (3)	0.0520 (8)
H28	0.6641	1.1107	0.6437	0.062*
C29	0.3176 (6)	0.7394 (4)	0.0606 (3)	0.0661 (10)
C30	0.2374 (6)	0.8395 (4)	0.1034 (4)	0.0753 (12)
N1	0.8380 (4)	0.6743 (3)	0.7289 (2)	0.0526 (7)
N2	0.8012 (3)	0.5880 (2)	0.5580 (2)	0.0468 (6)
N3	0.7924 (4)	0.5618 (2)	0.4679 (2)	0.0521 (7)
N4	1.1651 (3)	0.7807 (2)	0.7093 (2)	0.0478 (6)
N5	0.9358 (3)	0.9034 (2)	0.70525 (19)	0.0456 (6)
N6	0.8058 (3)	0.9593 (2)	0.6930 (2)	0.0500 (7)
H6	0.8162	1.0281	0.7214	0.060*
O1	0.9407 (3)	0.73837 (19)	0.51784 (18)	0.0564 (6)
O2	0.6418 (3)	0.80149 (19)	0.59581 (19)	0.0558 (6)
O3	0.2322 (5)	0.8536 (3)	0.1794 (3)	0.1018 (12)
O4	0.1930 (14)	0.8931 (8)	0.0589 (6)	0.261 (5)
Cu	0.90049 (5)	0.73603 (3)	0.63528 (3)	0.05047 (18)
Cl1	0.16329 (19)	0.61979 (11)	0.01824 (10)	0.0956 (4)
Cl2	0.4774 (2)	0.71845 (14)	0.14101 (15)	0.1265 (7)
Cl3	0.3983 (5)	0.7551 (2)	−0.02666 (19)	0.1990 (15)

	U11	U22	U33	U12	U13	U23
C1	0.057 (2)	0.068 (2)	0.061 (2)	0.0066 (18)	0.0097 (18)	0.017 (2)
C2	0.078 (3)	0.097 (4)	0.063 (3)	0.021 (3)	0.013 (2)	0.034 (3)
C3	0.081 (3)	0.096 (4)	0.087 (3)	0.021 (3)	0.023 (3)	0.059 (3)
C4	0.071 (3)	0.067 (3)	0.091 (3)	0.017 (2)	0.024 (2)	0.047 (2)
C5	0.0419 (17)	0.0469 (18)	0.074 (2)	0.0123 (14)	0.0144 (16)	0.0269 (17)
C6	0.0478 (18)	0.0364 (17)	0.070 (2)	0.0089 (14)	0.0104 (16)	0.0179 (16)
C7	0.085 (3)	0.0380 (19)	0.088 (3)	−0.0057 (19)	0.010 (2)	0.018 (2)
C8	0.0435 (17)	0.0360 (16)	0.059 (2)	0.0079 (13)	0.0117 (15)	0.0091 (14)
C9	0.0549 (19)	0.0355 (16)	0.057 (2)	0.0135 (14)	0.0140 (16)	0.0098 (14)
C10	0.064 (2)	0.0476 (19)	0.066 (2)	0.0114 (17)	0.0211 (19)	0.0144 (17)
C11	0.087 (3)	0.065 (3)	0.074 (3)	0.018 (2)	0.036 (2)	0.024 (2)
C12	0.110 (4)	0.077 (3)	0.064 (3)	0.024 (3)	0.034 (3)	0.025 (2)
C13	0.103 (4)	0.069 (3)	0.057 (3)	0.011 (3)	0.005 (2)	0.003 (2)
C14	0.066 (2)	0.052 (2)	0.064 (2)	0.0067 (18)	0.0079 (19)	0.0127 (18)
C15	0.056 (2)	0.0482 (19)	0.071 (2)	0.0183 (16)	0.0217 (18)	0.0201 (18)
C16	0.054 (2)	0.068 (3)	0.088 (3)	0.0254 (19)	0.021 (2)	0.031 (2)
C17	0.044 (2)	0.077 (3)	0.082 (3)	0.0107 (19)	0.0065 (19)	0.026 (2)
C18	0.0436 (19)	0.060 (2)	0.072 (2)	0.0040 (16)	0.0085 (17)	0.0109 (19)
C19	0.0405 (17)	0.0453 (18)	0.058 (2)	0.0058 (13)	0.0128 (14)	0.0125 (15)
C20	0.0430 (18)	0.0400 (17)	0.065 (2)	0.0068 (14)	0.0089 (16)	0.0049 (16)
C21	0.056 (2)	0.045 (2)	0.143 (5)	0.0061 (18)	0.001 (3)	−0.008 (3)
C22	0.0430 (16)	0.0393 (16)	0.0497 (18)	0.0053 (13)	0.0122 (14)	0.0132 (14)
C23	0.0410 (16)	0.0403 (16)	0.0454 (17)	0.0072 (12)	0.0109 (13)	0.0121 (13)
C24	0.0452 (17)	0.0432 (17)	0.058 (2)	0.0037 (14)	0.0114 (15)	0.0161 (15)
C25	0.0426 (18)	0.060 (2)	0.072 (2)	0.0059 (16)	0.0120 (17)	0.0183 (19)
C26	0.058 (2)	0.062 (2)	0.069 (2)	0.0254 (18)	0.0090 (19)	0.020 (2)
C27	0.069 (2)	0.0408 (18)	0.074 (3)	0.0121 (17)	0.008 (2)	0.0217 (18)
C28	0.0500 (19)	0.0409 (17)	0.058 (2)	0.0009 (14)	0.0075 (15)	0.0135 (15)
C29	0.077 (3)	0.059 (2)	0.062 (2)	0.008 (2)	0.025 (2)	0.0147 (19)
C30	0.086 (3)	0.066 (3)	0.082 (3)	0.024 (2)	0.022 (3)	0.030 (2)
N1	0.0419 (15)	0.0540 (17)	0.0612 (18)	0.0060 (12)	0.0107 (13)	0.0206 (14)
N2	0.0452 (15)	0.0338 (13)	0.0583 (17)	0.0058 (11)	0.0126 (12)	0.0118 (12)
N3	0.0571 (17)	0.0368 (14)	0.0568 (17)	0.0048 (12)	0.0127 (14)	0.0099 (12)
N4	0.0423 (14)	0.0393 (14)	0.0611 (17)	0.0074 (11)	0.0156 (13)	0.0143 (13)
N5	0.0413 (14)	0.0385 (14)	0.0512 (15)	0.0087 (11)	0.0106 (12)	0.0073 (12)
N6	0.0418 (14)	0.0362 (14)	0.0612 (17)	0.0111 (11)	0.0069 (12)	0.0043 (12)
O1	0.0632 (15)	0.0387 (12)	0.0574 (15)	−0.0042 (11)	0.0175 (12)	0.0046 (11)
O2	0.0510 (13)	0.0346 (12)	0.0705 (16)	0.0058 (10)	0.0059 (12)	0.0087 (11)
O3	0.109 (3)	0.096 (3)	0.079 (2)	0.042 (2)	0.023 (2)	−0.008 (2)
O4	0.395 (13)	0.307 (10)	0.265 (9)	0.269 (10)	0.187 (9)	0.224 (9)
Cu	0.0526 (3)	0.0376 (3)	0.0532 (3)	−0.00343 (18)	0.0129 (2)	0.00748 (19)
Cl1	0.0939 (9)	0.0706 (8)	0.0948 (9)	−0.0064 (6)	0.0015 (7)	0.0103 (7)
Cl2	0.0788 (9)	0.0975 (11)	0.1661 (17)	0.0305 (8)	−0.0130 (10)	0.0181 (11)
Cl3	0.336 (4)	0.1402 (18)	0.171 (2)	0.017 (2)	0.189 (3)	0.0433 (16)

Cu—N1	2.046 (3)	C14—H14	0.9300
N2—N3	1.367 (4)	C15—N4	1.330 (4)
Cu—N2	1.938 (3)	C15—C16	1.378 (6)
Cu—N4	2.196 (3)	C15—H15	0.9300
N5—N6	1.373 (4)	C16—C17	1.383 (6)
Cu—N5	2.088 (3)	C16—H16	0.9300
N6—H6	0.8600	C17—C18	1.385 (6)
Cu—O1	1.996 (3)	C17—H17	0.9300
Cu—O2	2.420 (2)	C18—C19	1.388 (5)
C1—N1	1.324 (5)	C18—H18	0.9300
C1—C2	1.389 (6)	C19—N4	1.338 (4)
C1—H1	0.9300	C19—C20	1.493 (5)
C2—C3	1.364 (7)	C20—N5	1.285 (4)
C2—H2	0.9300	C20—C21	1.500 (5)
C3—C4	1.383 (7)	C21—H21A	0.9600
C3—H3	0.9300	C21—H21B	0.9600
C4—C5	1.385 (6)	C21—H21C	0.9600
C4—H4	0.9300	C22—O2	1.228 (4)
C5—N1	1.367 (5)	C22—N6	1.367 (4)
C5—C6	1.481 (6)	C22—C23	1.494 (4)
C6—N2	1.289 (5)	C23—C28	1.390 (5)
C6—C7	1.496 (5)	C23—C24	1.393 (5)
C7—H7A	0.9600	C24—C25	1.382 (5)
C7—H7B	0.9600	C24—H24	0.9300
C7—H7C	0.9600	C25—C26	1.400 (6)
O1—C8	1.280 (4)	C25—H25	0.9300
C8—N3	1.338 (4)	C26—C27	1.376 (6)
C8—C9	1.485 (5)	C26—H26	0.9300
C9—C14	1.393 (5)	C27—C28	1.381 (5)
C9—C10	1.398 (5)	C27—H27	0.9300
C10—C11	1.370 (6)	C28—H28	0.9300
C10—H10	0.9300	C29—C30	1.561 (6)
C11—C12	1.374 (7)	C29—Cl3	1.738 (4)
C11—H11	0.9300	C29—Cl2	1.747 (5)
C12—C13	1.370 (7)	C29—Cl1	1.777 (5)
C12—H12	0.9300	C30—O4	1.173 (7)
C13—C14	1.360 (7)	C30—O3	1.189 (6)
C13—H13	0.9300
N1—C1—C2	122.2 (4)	C20—C21—H21C	109.5
N1—C1—H1	118.9	H21A—C21—H21C	109.5
C2—C1—H1	118.9	H21B—C21—H21C	109.5
C3—C2—C1	119.1 (5)	O2—C22—N6	121.8 (3)
C3—C2—H2	120.5	O2—C22—C23	122.1 (3)
C1—C2—H2	120.5	N6—C22—C23	116.1 (3)
C2—C3—C4	119.4 (4)	C28—C23—C24	119.3 (3)
C2—C3—H3	120.3	C28—C23—C22	122.4 (3)
C4—C3—H3	120.3	C24—C23—C22	118.2 (3)
C3—C4—C5	119.6 (4)	C25—C24—C23	120.3 (3)
C3—C4—H4	120.2	C25—C24—H24	119.9
C5—C4—H4	120.2	C23—C24—H24	119.9
N1—C5—C4	120.3 (4)	C24—C25—C26	120.0 (3)
N1—C5—C6	114.8 (3)	C24—C25—H25	120.0
C4—C5—C6	125.0 (4)	C26—C25—H25	120.0
N2—C6—C5	113.4 (3)	C27—C26—C25	119.5 (3)
N2—C6—C7	124.2 (4)	C27—C26—H26	120.3
C5—C6—C7	122.4 (3)	C25—C26—H26	120.3
C6—C7—H7A	109.5	C26—C27—C28	120.7 (3)
C6—C7—H7B	109.5	C26—C27—H27	119.7
H7A—C7—H7B	109.5	C28—C27—H27	119.7
C6—C7—H7C	109.5	C27—C28—C23	120.3 (3)
H7A—C7—H7C	109.5	C27—C28—H28	119.9
H7B—C7—H7C	109.5	C23—C28—H28	119.9
O1—C8—N3	125.2 (3)	C30—C29—Cl3	111.7 (3)
O1—C8—C9	118.4 (3)	C30—C29—Cl2	111.6 (3)
N3—C8—C9	116.4 (3)	Cl3—C29—Cl2	108.5 (3)
C14—C9—C10	118.2 (4)	C30—C29—Cl1	108.9 (3)
C14—C9—C8	121.9 (3)	Cl3—C29—Cl1	109.4 (3)
C10—C9—C8	119.9 (3)	Cl2—C29—Cl1	106.7 (2)
C11—C10—C9	120.1 (4)	O4—C30—O3	127.5 (6)
C11—C10—H10	119.9	O4—C30—C29	117.5 (6)
C9—C10—H10	119.9	O3—C30—C29	115.0 (4)
C10—C11—C12	120.6 (4)	C1—N1—C5	119.5 (3)
C10—C11—H11	119.7	C1—N1—Cu	128.5 (3)
C12—C11—H11	119.7	C5—N1—Cu	112.0 (2)
C13—C12—C11	119.7 (5)	C6—N2—N3	122.9 (3)
C13—C12—H12	120.2	C6—N2—Cu	119.6 (3)
C11—C12—H12	120.2	N3—N2—Cu	117.4 (2)
C14—C13—C12	120.7 (5)	C8—N3—N2	107.9 (3)
C14—C13—H13	119.7	C15—N4—C19	119.1 (3)
C12—C13—H13	119.7	C15—N4—Cu	126.5 (2)
C13—C14—C9	120.7 (4)	C19—N4—Cu	114.4 (2)
C13—C14—H14	119.6	C20—N5—N6	120.0 (3)
C9—C14—H14	119.6	C20—N5—Cu	120.5 (2)
N4—C15—C16	122.4 (4)	N6—N5—Cu	119.4 (2)
N4—C15—H15	118.8	C22—N6—N5	116.8 (3)
C16—C15—H15	118.8	C22—N6—H6	121.6
C15—C16—C17	119.2 (4)	N5—N6—H6	121.6
C15—C16—H16	120.4	C8—O1—Cu	109.8 (2)
C17—C16—H16	120.4	C22—O2—Cu	110.6 (2)
C16—C17—C18	118.4 (4)	N2—Cu—O1	79.25 (11)
C16—C17—H17	120.8	N2—Cu—N1	80.17 (12)
C18—C17—H17	120.8	O1—Cu—N1	159.01 (12)
C17—C18—C19	119.2 (4)	N2—Cu—N5	162.98 (12)
C17—C18—H18	120.4	O1—Cu—N5	100.25 (11)
C19—C18—H18	120.4	N1—Cu—N5	100.64 (12)
N4—C19—C18	121.7 (3)	N2—Cu—N4	122.15 (11)
N4—C19—C20	115.2 (3)	O1—Cu—N4	94.88 (11)
C18—C19—C20	123.1 (3)	N1—Cu—N4	92.52 (11)
N5—C20—C19	115.0 (3)	N5—Cu—N4	74.87 (10)
N5—C20—C21	125.4 (3)	N2—Cu—O2	91.71 (10)
C19—C20—C21	119.4 (3)	O1—Cu—O2	88.33 (11)
C20—C21—H21A	109.5	N1—Cu—O2	96.41 (11)
C20—C21—H21B	109.5	N5—Cu—O2	71.28 (9)
H21A—C21—H21B	109.5	N4—Cu—O2	146.02 (9)

Table 1

Selected bond lengths (Å)

Cu—N1	2.046 (3)
Cu—N2	1.938 (3)
Cu—N4	2.196 (3)
Cu—N5	2.088 (3)
Cu—O1	1.996 (3)
Cu—O2	2.420 (2)