Tetra-μ-acetato-κ⁸ O:O′-bis­{[2-(m-tolyl­amino)pyridine-κN]copper(II)}

Abstract

In the crystal structure of the title compound, [Cu₂(C₂H₃O₂)₄(C₁₂H₁₂N₂)₂], the binuclear mol­ecule lies about a center of inversion; the four acetate groups each bridge a pair of Cu^II atoms. The coordination of the metal atom is distorted square-pyramidal, with the bonding O atoms comprising a square basal plane and the coordinating N atom of the N-heterocycle occupying the apical position. The pyridine ring is twisted with respect to the benzene ring at a dihedral angle of 45.68 (16)°. Intra­molecular N—H⋯O hydrogen bonding is present between the imino and carb­oxy groups.

Related literature

There are many examples of tetra­kisacetatobis[(substituted pyridine)copper] complexes. For examples of 2-amino­pyridyl derivatives, see: Barquín et al. (2004 ▶); Seco et al. (2004 ▶); Sieroń (2004 ▶).

Experimental

Crystal data

• [Cu₂(C₂H₃O₂)₄(C₁₂H₁₂N₂)₂]

• M _r = 731.73

• Triclinic,

• a = 7.7143 (2) Å

• b = 10.5625 (3) Å

• c = 11.2413 (3) Å

• α = 66.531 (2)°

• β = 85.740 (2)°

• γ = 78.568 (2)°

• V = 823.51 (4) ų

• Z = 1

• Mo Kα radiation

• μ = 1.35 mm⁻¹

• T = 293 K

• 0.25 × 0.15 × 0.05 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.730, T _max = 0.936

• 6451 measured reflections

• 3678 independent reflections

• 2915 reflections with I > 2σ(I)

• R _int = 0.023

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.098

• S = 1.07

• 3678 reflections

• 211 parameters

• H-atom parameters constrained

• Δρ_max = 0.49 e Å⁻³

• Δρ_min = −0.59 e Å⁻³

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 ▶).

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Cu1—O1	1.9762 (19)
Cu1—O2i	1.9866 (19)
Cu1—O3	1.967 (2)
Cu1—O4i	1.966 (2)
Cu1—N1	2.197 (2)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2i	0.86	2.17	2.913 (3)	145

Symmetry code: (i) .

supplementary crystallographic information

Experimental

Copper acetate (0.1 g, 0.5 mmol) was dissolved in acetonitrile (5 ml). The solution was mixed with a solution of 3-tolylamino-2-pyridine (0.2 g, 1.1 mmol) dissolved in acetonitrile (15 ml). The green precipitate that formed was recrystallized from acetonitrile.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C). The amino H-atom was similarly treated.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of Cu2(C2H3O2)4(C12H12N2)2 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Dashed lines indicate the hydrogen bonding.

Crystal data

[Cu2(C2H3O2)4(C12H12N2)2]	Z = 1
Mr = 731.73	F(000) = 378
Triclinic, P1	Dx = 1.475 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7143 (2) Å	Cell parameters from 2561 reflections
b = 10.5625 (3) Å	θ = 2.3–27.6°
c = 11.2413 (3) Å	µ = 1.35 mm−1
α = 66.531 (2)°	T = 293 K
β = 85.740 (2)°	Prism, green
γ = 78.568 (2)°	0.25 × 0.15 × 0.05 mm
V = 823.51 (4) Å3

Data collection

Bruker SMART APEX diffractometer	3678 independent reflections
Radiation source: fine-focus sealed tube	2915 reflections with I > 2σ(I)
graphite	Rint = 0.023
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
Tmin = 0.730, Tmax = 0.936	k = −13→13
6451 measured reflections	l = −14→14

Refinement

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0426P)2 + 0.4239P] where P = (Fo2 + 2Fc2)/3
3678 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.59 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.58894 (4)	0.46743 (4)	0.60797 (3)	0.03044 (12)
O1	0.6955 (3)	0.6324 (2)	0.50147 (18)	0.0439 (5)
O2	0.5505 (3)	0.6857 (2)	0.31997 (18)	0.0419 (5)
O3	0.7582 (3)	0.3494 (2)	0.53769 (19)	0.0460 (5)
O4	0.6100 (3)	0.4052 (2)	0.35536 (19)	0.0436 (5)
N1	0.7506 (3)	0.4120 (2)	0.7806 (2)	0.0304 (5)
N2	0.5409 (3)	0.3175 (3)	0.9254 (2)	0.0446 (6)
H2	0.4771	0.3436	0.8573	0.053*
C1	0.6579 (4)	0.7076 (3)	0.3856 (3)	0.0342 (6)
C2	0.7467 (5)	0.8317 (4)	0.3197 (3)	0.0570 (9)
H2A	0.8448	0.8237	0.3717	0.085*
H2B	0.6637	0.9162	0.3091	0.085*
H2C	0.7885	0.8346	0.2363	0.085*
C3	0.7354 (4)	0.3375 (3)	0.4329 (3)	0.0378 (6)
C4	0.8709 (5)	0.2335 (4)	0.4000 (3)	0.0578 (9)
H4A	0.9175	0.1573	0.4784	0.087*
H4B	0.9652	0.2787	0.3520	0.087*
H4C	0.8169	0.1979	0.3485	0.087*
C5	0.9143 (4)	0.4436 (3)	0.7539 (3)	0.0389 (7)
H5	0.9471	0.4835	0.6675	0.047*
C6	1.0348 (4)	0.4198 (3)	0.8479 (3)	0.0438 (7)
H6	1.1454	0.4446	0.8259	0.053*
C7	0.9871 (4)	0.3582 (3)	0.9752 (3)	0.0403 (7)
H7	1.0662	0.3400	1.0411	0.048*
C8	0.8228 (4)	0.3236 (3)	1.0051 (3)	0.0395 (7)
H8	0.7896	0.2817	1.0912	0.047*
C9	0.7059 (3)	0.3518 (3)	0.9053 (2)	0.0309 (6)
C10	0.4629 (4)	0.2444 (3)	1.0447 (2)	0.0339 (6)
C11	0.3760 (4)	0.1388 (3)	1.0512 (3)	0.0365 (6)
H11	0.3785	0.1149	0.9799	0.044*
C12	0.2858 (4)	0.0682 (3)	1.1613 (3)	0.0417 (7)
C13	0.2886 (5)	0.1024 (4)	1.2678 (3)	0.0513 (8)
H13	0.2327	0.0539	1.3440	0.062*
C14	0.3736 (5)	0.2078 (4)	1.2618 (3)	0.0522 (8)
H14	0.3734	0.2302	1.3339	0.063*
C15	0.4592 (4)	0.2808 (3)	1.1506 (3)	0.0420 (7)
H15	0.5137	0.3533	1.1468	0.050*
C16	0.1823 (5)	−0.0390 (4)	1.1628 (4)	0.0658 (10)
H16A	0.2210	−0.0685	1.0932	0.099*
H16B	0.0587	0.0016	1.1522	0.099*
H16C	0.2012	−0.1187	1.2440	0.099*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu1	0.02917 (19)	0.0399 (2)	0.02439 (17)	−0.01136 (14)	0.00032 (12)	−0.01252 (14)
O1	0.0492 (13)	0.0523 (13)	0.0312 (10)	−0.0263 (10)	−0.0027 (9)	−0.0090 (9)
O2	0.0452 (12)	0.0516 (13)	0.0325 (10)	−0.0246 (10)	−0.0018 (9)	−0.0125 (9)
O3	0.0414 (12)	0.0601 (14)	0.0384 (11)	−0.0004 (10)	−0.0021 (9)	−0.0250 (10)
O4	0.0412 (12)	0.0558 (13)	0.0376 (11)	−0.0023 (10)	−0.0020 (9)	−0.0251 (10)
N1	0.0282 (12)	0.0365 (13)	0.0277 (11)	−0.0101 (10)	−0.0003 (9)	−0.0118 (10)
N2	0.0374 (14)	0.0714 (18)	0.0249 (11)	−0.0241 (13)	−0.0002 (10)	−0.0123 (12)
C1	0.0330 (15)	0.0411 (16)	0.0309 (14)	−0.0141 (12)	0.0046 (11)	−0.0138 (12)
C2	0.065 (2)	0.058 (2)	0.0484 (19)	−0.0362 (19)	−0.0014 (16)	−0.0094 (16)
C3	0.0370 (16)	0.0418 (17)	0.0353 (15)	−0.0110 (13)	0.0082 (12)	−0.0154 (13)
C4	0.058 (2)	0.062 (2)	0.051 (2)	0.0063 (18)	0.0032 (16)	−0.0289 (18)
C5	0.0349 (16)	0.0487 (18)	0.0323 (14)	−0.0123 (14)	0.0022 (12)	−0.0133 (13)
C6	0.0298 (15)	0.0532 (19)	0.0489 (18)	−0.0094 (14)	−0.0038 (13)	−0.0191 (15)
C7	0.0344 (16)	0.0476 (18)	0.0387 (16)	−0.0007 (13)	−0.0117 (12)	−0.0179 (14)
C8	0.0398 (17)	0.0489 (18)	0.0277 (14)	−0.0074 (14)	−0.0039 (12)	−0.0125 (13)
C9	0.0293 (14)	0.0353 (15)	0.0289 (13)	−0.0068 (11)	−0.0014 (10)	−0.0129 (11)
C10	0.0299 (14)	0.0421 (16)	0.0272 (13)	−0.0056 (12)	0.0013 (10)	−0.0117 (12)
C11	0.0327 (15)	0.0406 (16)	0.0362 (15)	−0.0027 (12)	0.0003 (11)	−0.0171 (13)
C12	0.0366 (16)	0.0317 (16)	0.0494 (18)	−0.0040 (13)	0.0041 (13)	−0.0100 (13)
C13	0.052 (2)	0.055 (2)	0.0358 (16)	−0.0099 (16)	0.0131 (14)	−0.0090 (15)
C14	0.058 (2)	0.068 (2)	0.0357 (16)	−0.0142 (18)	0.0102 (14)	−0.0261 (16)
C15	0.0450 (18)	0.0476 (18)	0.0385 (16)	−0.0129 (15)	0.0054 (13)	−0.0210 (14)
C16	0.065 (3)	0.047 (2)	0.080 (3)	−0.0220 (19)	0.006 (2)	−0.0163 (19)

Geometric parameters (Å, °)

Cu1—O1	1.9762 (19)	C4—H4C	0.9600
Cu1—O2i	1.9866 (19)	C5—C6	1.372 (4)
Cu1—O3	1.967 (2)	C5—H5	0.9300
Cu1—O4i	1.966 (2)	C6—C7	1.372 (4)
Cu1—N1	2.197 (2)	C6—H6	0.9300
Cu1—Cu1i	2.6532 (6)	C7—C8	1.370 (4)
O1—C1	1.246 (3)	C7—H7	0.9300
O2—C1	1.259 (3)	C8—C9	1.393 (4)
O2—Cu1i	1.9866 (19)	C8—H8	0.9300
O3—C3	1.261 (3)	C10—C11	1.387 (4)
O4—C3	1.250 (4)	C10—C15	1.385 (4)
O4—Cu1i	1.966 (2)	C11—C12	1.384 (4)
N1—C9	1.339 (3)	C11—H11	0.9300
N1—C5	1.352 (3)	C12—C13	1.385 (4)
N2—C9	1.370 (3)	C12—C16	1.503 (4)
N2—C10	1.413 (3)	C13—C14	1.377 (5)
N2—H2	0.8600	C13—H13	0.9300
C1—C2	1.498 (4)	C14—C15	1.380 (4)
C2—H2A	0.9600	C14—H14	0.9300
C2—H2B	0.9600	C15—H15	0.9300
C2—H2C	0.9600	C16—H16A	0.9600
C3—C4	1.500 (4)	C16—H16B	0.9600
C4—H4A	0.9600	C16—H16C	0.9600
C4—H4B	0.9600
O4i—Cu1—O3	167.64 (8)	H4A—C4—H4C	109.5
O4i—Cu1—O1	88.77 (9)	H4B—C4—H4C	109.5
O3—Cu1—O1	90.33 (9)	N1—C5—C6	123.4 (3)
O4i—Cu1—O2i	89.16 (9)	N1—C5—H5	118.3
O3—Cu1—O2i	89.01 (9)	C6—C5—H5	118.3
O1—Cu1—O2i	167.27 (8)	C5—C6—C7	118.1 (3)
O4i—Cu1—N1	98.40 (8)	C5—C6—H6	121.0
O3—Cu1—N1	93.96 (8)	C7—C6—H6	121.0
O1—Cu1—N1	94.60 (8)	C8—C7—C6	119.8 (3)
O2i—Cu1—N1	98.13 (8)	C8—C7—H7	120.1
O4i—Cu1—Cu1i	84.47 (6)	C6—C7—H7	120.1
O3—Cu1—Cu1i	83.19 (6)	C7—C8—C9	119.3 (3)
O1—Cu1—Cu1i	83.69 (6)	C7—C8—H8	120.3
O2i—Cu1—Cu1i	83.61 (6)	C9—C8—H8	120.3
N1—Cu1—Cu1i	176.65 (6)	N1—C9—N2	115.0 (2)
C1—O1—Cu1	124.57 (18)	N1—C9—C8	121.4 (2)
C1—O2—Cu1i	123.80 (18)	N2—C9—C8	123.6 (2)
C3—O3—Cu1	124.0 (2)	C11—C10—C15	119.4 (3)
C3—O4—Cu1i	122.82 (18)	C11—C10—N2	117.7 (2)
C9—N1—C5	118.0 (2)	C15—C10—N2	122.7 (3)
C9—N1—Cu1	127.85 (17)	C10—C11—C12	121.6 (3)
C5—N1—Cu1	114.18 (17)	C10—C11—H11	119.2
C9—N2—C10	127.9 (2)	C12—C11—H11	119.2
C9—N2—H2	116.1	C13—C12—C11	118.2 (3)
C10—N2—H2	116.1	C13—C12—C16	121.2 (3)
O1—C1—O2	124.3 (2)	C11—C12—C16	120.6 (3)
O1—C1—C2	117.9 (2)	C14—C13—C12	120.5 (3)
O2—C1—C2	117.8 (3)	C14—C13—H13	119.8
C1—C2—H2A	109.5	C12—C13—H13	119.8
C1—C2—H2B	109.5	C13—C14—C15	121.2 (3)
H2A—C2—H2B	109.5	C13—C14—H14	119.4
C1—C2—H2C	109.5	C15—C14—H14	119.4
H2A—C2—H2C	109.5	C14—C15—C10	119.1 (3)
H2B—C2—H2C	109.5	C14—C15—H15	120.5
O4—C3—O3	125.3 (3)	C10—C15—H15	120.5
O4—C3—C4	118.0 (3)	C12—C16—H16A	109.5
O3—C3—C4	116.7 (3)	C12—C16—H16B	109.5
C3—C4—H4A	109.5	H16A—C16—H16B	109.5
C3—C4—H4B	109.5	C12—C16—H16C	109.5
H4A—C4—H4B	109.5	H16A—C16—H16C	109.5
C3—C4—H4C	109.5	H16B—C16—H16C	109.5
O4i—Cu1—O1—C1	−84.3 (2)	C9—N1—C5—C6	−1.4 (4)
O3—Cu1—O1—C1	83.4 (2)	Cu1—N1—C5—C6	178.8 (2)
O2i—Cu1—O1—C1	−3.6 (6)	N1—C5—C6—C7	1.3 (5)
N1—Cu1—O1—C1	177.4 (2)	C5—C6—C7—C8	−0.5 (5)
Cu1i—Cu1—O1—C1	0.3 (2)	C6—C7—C8—C9	−0.1 (5)
O4i—Cu1—O3—C3	0.2 (6)	C5—N1—C9—N2	−177.5 (3)
O1—Cu1—O3—C3	−85.6 (2)	Cu1—N1—C9—N2	2.2 (4)
O2i—Cu1—O3—C3	81.7 (2)	C5—N1—C9—C8	0.7 (4)
N1—Cu1—O3—C3	179.8 (2)	Cu1—N1—C9—C8	−179.6 (2)
Cu1i—Cu1—O3—C3	−2.0 (2)	C10—N2—C9—N1	175.0 (3)
O4i—Cu1—N1—C9	58.8 (2)	C10—N2—C9—C8	−3.2 (5)
O3—Cu1—N1—C9	−121.1 (2)	C7—C8—C9—N1	0.0 (4)
O1—Cu1—N1—C9	148.2 (2)	C7—C8—C9—N2	178.1 (3)
O2i—Cu1—N1—C9	−31.6 (2)	C9—N2—C10—C11	−134.6 (3)
O4i—Cu1—N1—C5	−121.5 (2)	C9—N2—C10—C15	50.2 (5)
O3—Cu1—N1—C5	58.6 (2)	C15—C10—C11—C12	−0.2 (4)
O1—Cu1—N1—C5	−32.0 (2)	N2—C10—C11—C12	−175.6 (3)
O2i—Cu1—N1—C5	148.2 (2)	C10—C11—C12—C13	−2.0 (4)
Cu1—O1—C1—O2	−2.2 (4)	C10—C11—C12—C16	175.8 (3)
Cu1—O1—C1—C2	178.1 (2)	C11—C12—C13—C14	2.4 (5)
Cu1i—O2—C1—O1	3.4 (4)	C16—C12—C13—C14	−175.4 (3)
Cu1i—O2—C1—C2	−176.9 (2)	C12—C13—C14—C15	−0.6 (5)
Cu1i—O4—C3—O3	−5.7 (4)	C13—C14—C15—C10	−1.6 (5)
Cu1i—O4—C3—C4	174.4 (2)	C11—C10—C15—C14	2.0 (4)
Cu1—O3—C3—O4	5.2 (4)	N2—C10—C15—C14	177.2 (3)
Cu1—O3—C3—C4	−175.0 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2i	0.86	2.17	2.913 (3)	145

Symmetry codes: (i) −x+1, −y+1, −z+1.