Redetermination of bis{[(2-hydroxy­phenyl­methyl)­bis(2-pyridyl­methyl)­aminato]copper(II)} diperchlorate

The structure of the title compound, [Cu₂(C₁₉H₁₈N₃O)₂](ClO₄)₂, was reported with insufficient accuracy because of a twinning problem by Adams, Bailey, Campbell, Fenton & He [J. Chem. Soc. Dalton Trans. (1996), pp. 2233-2237]. The dinuclear phenolate-bridged Cu^II complex has an inversion centre.

S1. Comment

The title copper(II) complex, [Cu₂(phpy)₂](ClO₄)₂ [phpy is (2-hydroxyphenylmethyl)bis(2-pyridylmethyl)aminate], (I), which has a long Cu–phenolic O atom bond, can be considered as a nobel model compound for galactose oxidase (Ito et al., 1998).

Adams et al. (1996) noted that the structure was difficult to refine because of a twinning problem.

S2. Experimental

In the present study, single crystals of (I) were grown from an acetonitrile solution as needles elongated along a.

S3. Refinement

Positional parameters of all the H atoms were calculated geometrically and fixed with U(H) = 1.2U_eq(parent atom).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

(I)

Crystal data

[Cu2(C19H18N3O)2](ClO4)2	Dx = 1.642 Mg m^−3
Mr = 934.74	Mo Kα radiation, λ = 0.71073 Å
Monoclinic, P21/n	Cell parameters from 25 reflections
a = 11.380 (1) Å	θ = 10–15°
b = 9.877 (2) Å	µ = 1.33 mm^−1
c = 17.400 (2) Å	T = 298 K
β = 104.79 (1)°	Needle, green
V = 1891.0 (5) Å^3	0.7 × 0.15 × 0.1 mm
Z = 2

Data collection

Rigaku AFC-5S diffractometer	Rint = 0.059
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→15
Tmin = 0.662, Tmax = 0.897	k = 0→13
4819 measured reflections	l = −23→23
4338 independent reflections	3 standard reflections every 100 reflections
2393 reflections with I > 2σ(I)	intensity decay: 5.5%

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.063	w = 1/[σ^2(Fo^2) + (0.1(Fo^2 + 2Fc^2)/3)^2]
wR(F^2) = 0.185	(Δ/σ)max = 0.009
S = 0.98	Δρmax = 0.59 e Å^−3
4338 reflections	Δρmin = −0.63 e Å^−3
262 parameters

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

	x	y	z	Uiso*/Ueq
Cu1	0.54358 (6)	0.02660 (8)	0.42187 (4)	0.0373 (2)
Cl1	0.4955 (1)	0.2387 (2)	0.1692 (1)	0.0603 (5)
O1	0.6029 (3)	−0.0563 (4)	0.5432 (2)	0.043 (1)
O2	0.5814 (5)	0.1502 (6)	0.1495 (4)	0.085 (2)
O3	0.4568 (5)	0.179 (1)	0.2322 (4)	0.142 (3)
O4	0.3945 (6)	0.2534 (9)	0.1043 (4)	0.126 (3)
O5	0.5546 (7)	0.3610 (9)	0.1932 (7)	0.160 (4)
N1	0.6163 (4)	0.2133 (6)	0.4286 (3)	0.045 (1)
N2	0.7031 (4)	−0.0249 (6)	0.3969 (3)	0.043 (1)
N3	0.4837 (4)	−0.1444 (5)	0.3634 (3)	0.038 (1)
C1	0.5920 (5)	0.3222 (6)	0.4677 (4)	0.045 (2)
C2	0.6567 (7)	0.4417 (7)	0.4739 (4)	0.059 (2)
C3	0.7500 (7)	0.4480 (9)	0.4364 (5)	0.071 (3)
C4	0.7756 (6)	0.3392 (9)	0.3949 (4)	0.064 (2)
C5	0.7093 (5)	0.2212 (7)	0.3932 (4)	0.050 (2)
C6	0.7315 (5)	0.0962 (8)	0.3523 (4)	0.057 (2)
C7	0.6918 (6)	−0.1505 (8)	0.3492 (4)	0.062 (2)
C8	0.5683 (5)	−0.2142 (7)	0.3366 (3)	0.044 (2)
C9	0.5431 (6)	−0.3391 (7)	0.3010 (4)	0.053 (2)
C10	0.4301 (7)	−0.3950 (7)	0.2919 (4)	0.060 (2)
C11	0.3438 (6)	−0.3230 (7)	0.3184 (4)	0.054 (2)
C12	0.3731 (5)	−0.1988 (7)	0.3528 (3)	0.044 (2)
C13	0.8019 (4)	−0.0359 (7)	0.4726 (3)	0.043 (2)
C14	0.7886 (5)	−0.1479 (6)	0.5270 (4)	0.043 (2)
C15	0.8802 (5)	−0.2459 (7)	0.5490 (4)	0.049 (2)
C16	0.8783 (6)	−0.3425 (7)	0.6050 (5)	0.058 (2)
C17	0.7859 (5)	−0.3416 (7)	0.6435 (4)	0.051 (2)
C18	0.6940 (5)	−0.2455 (6)	0.6239 (3)	0.043 (2)
C19	0.6923 (4)	−0.1495 (6)	0.5647 (3)	0.036 (1)
H1	0.5260	0.3169	0.4927	0.0543*
H2	0.6377	0.5175	0.5031	0.0707*
H3	0.7970	0.5294	0.4395	0.0847*
H4	0.8388	0.3444	0.3675	0.0764*
H5	0.8152	0.0931	0.3507	0.0682*
H6	0.6803	0.0956	0.2991	0.0682*
H7	0.7055	−0.1293	0.2984	0.0744*
H8	0.7520	−0.2140	0.3764	0.0744*
H9	0.6043	−0.3867	0.2827	0.0633*
H10	0.4112	−0.4824	0.2676	0.0720*
H11	0.2639	−0.3598	0.3125	0.0646*
H12	0.3120	−0.1490	0.3700	0.0533*
H13	0.8776	−0.0486	0.4587	0.0515*
H14	0.8043	0.0478	0.5011	0.0515*
H15	0.9463	−0.2452	0.5239	0.0588*
H16	0.9407	−0.4104	0.6175	0.0699*
H17	0.7853	−0.4077	0.6839	0.0617*
H18	0.6308	−0.2451	0.6514	0.0520*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0240 (3)	0.0473 (4)	0.0441 (4)	0.0030 (3)	0.0155 (2)	−0.0071 (4)
Cl1	0.0362 (8)	0.084 (1)	0.066 (1)	−0.0073 (8)	0.0239 (7)	−0.0120 (9)
O1	0.031 (2)	0.055 (3)	0.046 (2)	0.011 (2)	0.018 (2)	−0.006 (2)
O2	0.074 (3)	0.068 (4)	0.132 (5)	−0.007 (3)	0.063 (3)	−0.011 (3)
O3	0.054 (3)	0.30 (1)	0.078 (4)	−0.010 (5)	0.031 (3)	0.034 (6)
O4	0.071 (4)	0.187 (9)	0.104 (5)	0.017 (5)	−0.004 (4)	0.041 (5)
O5	0.106 (5)	0.122 (7)	0.28 (1)	−0.033 (5)	0.098 (7)	−0.113 (7)
N1	0.030 (2)	0.054 (3)	0.049 (3)	0.003 (2)	0.012 (2)	0.003 (2)
N2	0.029 (2)	0.059 (3)	0.045 (3)	0.001 (2)	0.015 (2)	−0.009 (3)
N3	0.034 (2)	0.050 (3)	0.034 (2)	0.006 (2)	0.015 (2)	−0.005 (2)
C1	0.044 (3)	0.041 (4)	0.050 (3)	0.003 (3)	0.010 (3)	0.004 (3)
C2	0.062 (4)	0.040 (4)	0.069 (4)	0.005 (3)	0.006 (3)	−0.004 (3)
C3	0.060 (4)	0.063 (6)	0.087 (5)	−0.012 (4)	0.015 (4)	0.017 (4)
C4	0.045 (4)	0.083 (6)	0.063 (4)	−0.008 (4)	0.015 (3)	0.024 (4)
C5	0.033 (3)	0.069 (5)	0.047 (4)	0.004 (3)	0.011 (3)	0.016 (3)
C6	0.036 (3)	0.093 (6)	0.047 (4)	0.005 (3)	0.020 (3)	0.009 (4)
C7	0.038 (3)	0.077 (5)	0.076 (5)	0.002 (3)	0.024 (3)	−0.031 (4)
C8	0.039 (3)	0.056 (4)	0.041 (3)	0.010 (3)	0.016 (2)	−0.002 (3)
C9	0.056 (4)	0.056 (4)	0.051 (4)	0.012 (3)	0.022 (3)	−0.007 (3)
C10	0.064 (4)	0.050 (4)	0.066 (4)	0.005 (3)	0.017 (4)	−0.011 (3)
C11	0.044 (3)	0.054 (4)	0.064 (4)	−0.003 (3)	0.013 (3)	−0.001 (3)
C12	0.036 (3)	0.055 (4)	0.044 (3)	0.006 (3)	0.013 (2)	−0.001 (3)
C13	0.021 (2)	0.061 (4)	0.050 (3)	0.005 (3)	0.015 (2)	0.002 (3)
C14	0.031 (3)	0.042 (3)	0.059 (4)	0.006 (3)	0.017 (3)	0.001 (3)
C15	0.032 (3)	0.049 (4)	0.070 (4)	0.010 (3)	0.022 (3)	−0.002 (3)
C16	0.042 (3)	0.050 (4)	0.085 (5)	0.011 (3)	0.022 (3)	0.003 (4)
C17	0.042 (3)	0.050 (4)	0.061 (4)	0.002 (3)	0.010 (3)	0.001 (3)
C18	0.033 (3)	0.051 (4)	0.046 (3)	−0.004 (3)	0.009 (2)	−0.004 (3)
C19	0.026 (2)	0.043 (3)	0.041 (3)	0.007 (2)	0.011 (2)	−0.005 (3)

Geometric parameters (Å, º)

Cu1—O1	2.203 (4)	C6—H5	0.960
Cu1—O1^i	1.938 (3)	C6—H6	0.960
Cu1—N1	2.013 (5)	C7—C8	1.503 (9)
Cu1—N2	2.037 (4)	C7—H7	0.959
Cu1—N3	2.000 (5)	C7—H8	0.960
Cl1—O2	1.416 (6)	C8—C9	1.377 (9)
Cl1—O3	1.411 (7)	C9—C10	1.371 (10)
Cl1—O4	1.398 (6)	C9—H9	0.960
Cl1—O5	1.393 (7)	C10—C11	1.383 (9)
O1—C19	1.352 (6)	C10—H10	0.961
N1—C1	1.338 (8)	C11—C12	1.368 (9)
N1—C5	1.357 (7)	C11—H11	0.960
N2—C6	1.505 (9)	C12—H12	0.960
N2—C7	1.479 (8)	C13—C14	1.488 (8)
N2—C13	1.502 (7)	C13—H13	0.960
N3—C8	1.359 (7)	C13—H14	0.960
N3—C12	1.338 (7)	C14—C15	1.402 (8)
C1—C2	1.381 (9)	C14—C19	1.414 (7)
C1—H1	0.960	C15—C16	1.368 (10)
C2—C3	1.38 (1)	C15—H15	0.961
C2—H2	0.960	C16—C17	1.383 (9)
C3—C4	1.37 (1)	C16—H16	0.960
C3—H3	0.960	C17—C18	1.389 (8)
C4—C5	1.384 (10)	C17—H17	0.961
C4—H4	0.960	C18—C19	1.396 (8)
C5—C6	1.48 (1)	C18—H18	0.960
Cu1···O3	3.531 (7)	O4···C13^v	3.594 (10)
O2···C7^ii	3.242 (8)	O5···C7^ii	3.158 (10)
O2···C3^iii	3.372 (9)	O5···C10^vi	3.465 (10)
O2···C6	3.547 (9)	O5···C9^vi	3.527 (9)
O3···C11^iv	3.308 (8)	O5···C6^ii	3.60 (1)
O3···C6	3.387 (9)	C3···C9^vi	3.56 (1)
O3···C18^i	3.441 (9)	C3···C16^vi	3.58 (1)
O3···N1	3.453 (8)	C10···C17^vii	3.56 (1)
O3···C5	3.487 (8)	C11···C17^vii	3.364 (10)
O4···C12^iv	3.349 (9)	C11···C18^vii	3.446 (9)
O4···C11^iv	3.41 (1)	C12···C17^vii	3.545 (9)
O4···C3^v	3.57 (1)
O1—Cu1—O1^i	80.4 (2)	C5—C6—H5	109.5
O1—Cu1—N1	105.3 (2)	C5—C6—H6	109.5
O1—Cu1—N2	92.3 (2)	H5—C6—H6	109.5
O1—Cu1—N3	98.9 (2)	N2—C7—C8	112.2 (5)
O1^i—Cu1—N1	102.5 (2)	N2—C7—H7	108.8
O1^i—Cu1—N2	172.1 (2)	N2—C7—H8	108.8
O1^i—Cu1—N3	94.5 (2)	C8—C7—H7	108.8
N1—Cu1—N2	82.3 (2)	C8—C7—H8	108.7
N1—Cu1—N3	152.3 (2)	H7—C7—H8	109.5
N2—Cu1—N3	83.5 (2)	N3—C8—C7	117.1 (6)
O2—Cl1—O3	107.6 (5)	N3—C8—C9	121.6 (6)
O2—Cl1—O4	110.2 (5)	C7—C8—C9	121.3 (5)
O2—Cl1—O5	107.3 (4)	C8—C9—C10	119.6 (6)
O3—Cl1—O4	108.4 (4)	C8—C9—H9	120.2
O3—Cl1—O5	110.5 (6)	C10—C9—H9	120.2
O4—Cl1—O5	112.7 (6)	C9—C10—C11	118.6 (6)
Cu1—O1—Cu1^i	99.6 (2)	C9—C10—H10	120.7
Cu1—O1—C19	122.9 (3)	C11—C10—H10	120.6
Cu1^i—O1—C19	131.5 (4)	C10—C11—C12	119.5 (6)
Cu1—N1—C1	129.1 (4)	C10—C11—H11	120.3
Cu1—N1—C5	112.5 (4)	C12—C11—H11	120.3
C1—N1—C5	118.2 (6)	N3—C12—C11	122.4 (6)
Cu1—N2—C6	103.4 (4)	N3—C12—H12	118.8
Cu1—N2—C7	112.0 (4)	C11—C12—H12	118.8
Cu1—N2—C13	109.8 (3)	N2—C13—C14	115.9 (5)
C6—N2—C7	112.1 (5)	N2—C13—H13	107.9
C6—N2—C13	107.4 (5)	N2—C13—H14	107.8
C7—N2—C13	111.7 (5)	C14—C13—H13	107.8
Cu1—N3—C8	115.1 (4)	C14—C13—H14	107.8
Cu1—N3—C12	126.6 (4)	H13—C13—H14	109.4
C8—N3—C12	118.2 (5)	C13—C14—C15	119.8 (5)
N1—C1—C2	123.4 (6)	C13—C14—C19	121.3 (5)
N1—C1—H1	118.3	C15—C14—C19	118.4 (6)
C2—C1—H1	118.3	C14—C15—C16	122.0 (5)
C1—C2—C3	117.5 (7)	C14—C15—H15	119.0
C1—C2—H2	121.3	C16—C15—H15	119.0
C3—C2—H2	121.3	C15—C16—C17	119.5 (6)
C2—C3—C4	120.5 (7)	C15—C16—H16	120.3
C2—C3—H3	119.8	C17—C16—H16	120.3
C4—C3—H3	119.8	C16—C17—C18	120.2 (6)
C3—C4—C5	119.0 (7)	C16—C17—H17	119.9
C3—C4—H4	120.5	C18—C17—H17	119.9
C5—C4—H4	120.5	C17—C18—C19	120.8 (5)
N1—C5—C4	121.5 (7)	C17—C18—H18	119.6
N1—C5—C6	114.8 (6)	C19—C18—H18	119.6
C4—C5—C6	123.7 (6)	O1—C19—C14	118.7 (5)
N2—C6—C5	109.3 (5)	O1—C19—C18	122.3 (5)
N2—C6—H5	109.6	C14—C19—C18	118.9 (5)
N2—C6—H6	109.6

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