Acetonitrile-{3-[bis-(2-pyridyl-methyl-κN)amino-κN]propanol-κO}(perchlorato-κO)copper(II) perchlorate.

In the title compound, [Cu(ClO(4))(C(2)H(3)N)(C(15)H(19)N(3)O)]ClO(4), the Cu(II) ion is coordinated by three N atoms and a hydroxyl-O atom of the tetra-dentate ligand, an O atom of a perchlorate ion and an N atom of an acetonitrile ligand giving a tetra-gonally distorted octa-hedral environment around the copper(II) atom. There is an offset inter-complex face-to-face π-π inter-action [centroid-centroid distance = 3.718 (2) Å] involving one of the pyridine rings of the ligand as well as an intra-complex O-H⋯O hydrogen-bonding inter-action between the coordinated hydroxyl group of the ligand and the perchlorate counter-ion.

Related literature

The preparation and characterization of polyamine complexes have allowed the elucidatation of the mechanisms of metalloenzyme reactions, see: Tshuva & Lippard (2004 ▶). For studies of complexes with bis­(2-pyridyl­meth­yl)amine moieties, see: Bebout et al. (1998 ▶); Shin et al. (2010 ▶). For potential biological applications of the tridentate unit, see: van Staveren et al. (2002 ▶). Examples include the use of PdII and PtII complexes with bis­(2-pyridyl­meth­yl)amine or its derivatives as anti­cancer agents, e.g. cis-platin (Rauterkus et al., 2003 ▶). For inter­complex π–π stacking inter­actions, see: Shetty et al. (1996 ▶). For the preparation of N,N-bis­(2-pyridyl­meth­yl)-3-amino­propanol, see: Young et al. (1995 ▶).

Experimental

Crystal data

[Cu(ClO4)(C2H3N)(C15H19N3O)]ClO4

M = 560.83

Monoclinic,

a = 18.8394 (16) Å

b = 10.6049 (9) Å

c = 23.171 (2) Å

β = 102.998 (2)°

V = 4510.7 (7) Å3

Z = 8

Mo Kα radiation

μ = 1.26 mm−1

T = 200 K

0.20 × 0.17 × 0.08 mm

Data collection

Siemens SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.777, T max = 0.904

16472 measured reflections

5616 independent reflections

3249 reflections with I > 2σ(I)

R int = 0.066

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.188

S = 1.11

5616 reflections

303 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.66 e Å−3

Δρmin = −1.16 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810053985/zs2085sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053985/zs2085Isup2.hkl

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

[Cu(ClO4)(C2H3N)(C15H19N3O)]ClO4	F(000) = 2296
Mr = 560.83	Dx = 1.652 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3827 reflections
a = 18.8394 (16) Å	θ = 2.2–27.2°
b = 10.6049 (9) Å	µ = 1.26 mm−1
c = 23.171 (2) Å	T = 200 K
β = 102.998 (2)°	Block, blue
V = 4510.7 (7) Å3	0.20 × 0.17 × 0.08 mm
Z = 8

Siemens SMART CCD diffractometer	5616 independent reflections
Radiation source: fine-focus sealed tube	3249 reflections with I > 2σ(I)
graphite	Rint = 0.066
φ and ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
Tmin = 0.777, Tmax = 0.904	k = −14→14
16472 measured reflections	l = −26→30

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.188	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ2(Fo2) + (0.0574P)2 + 23.552P] where P = (Fo2 + 2Fc2)/3
5616 reflections	(Δ/σ)max = 0.004
303 parameters	Δρmax = 1.66 e Å−3
0 restraints	Δρmin = −1.16 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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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	0.13311 (3)	0.19042 (6)	0.63867 (3)	0.0267 (2)
Cl1	0.35845 (8)	0.20097 (13)	0.70690 (6)	0.0348 (3)
Cl2	−0.11763 (8)	0.33890 (14)	0.50981 (7)	0.0397 (4)
N1	0.1499 (2)	0.1811 (4)	0.55716 (19)	0.0263 (9)
N2	0.1661 (2)	0.0086 (4)	0.6439 (2)	0.0279 (10)
N3	0.1492 (2)	0.1799 (4)	0.72643 (18)	0.0266 (9)
N4	0.1036 (3)	0.3717 (4)	0.6338 (2)	0.0352 (11)
O1	0.0140 (2)	0.1484 (4)	0.6184 (2)	0.0464 (12)
H1A	−0.016 (3)	0.176 (5)	0.596 (2)	0.056 (16)*
O2	0.4077 (3)	0.2983 (5)	0.7002 (3)	0.0691 (15)
O3	0.2870 (2)	0.2349 (4)	0.67406 (19)	0.0432 (11)
O4	0.3794 (2)	0.0851 (4)	0.6847 (2)	0.0569 (13)
O5	0.3560 (3)	0.1857 (5)	0.76703 (18)	0.0567 (13)
O6	−0.1520 (3)	0.3725 (7)	0.4524 (2)	0.085 (2)
O7	−0.1319 (4)	0.4221 (6)	0.5530 (3)	0.092 (2)
O8	−0.1411 (9)	0.2274 (8)	0.5240 (4)	0.247 (8)
O9	−0.0464 (4)	0.3278 (15)	0.5138 (3)	0.230 (7)
C1	0.1296 (3)	0.2643 (5)	0.5134 (2)	0.0325 (12)
H1	0.1038	0.3377	0.5203	0.039*
C2	0.1449 (3)	0.2472 (6)	0.4586 (3)	0.0367 (13)
H2	0.1300	0.3076	0.4280	0.044*
C3	0.1825 (3)	0.1403 (5)	0.4491 (3)	0.0362 (13)
H3	0.1942	0.1269	0.4117	0.043*
C4	0.2031 (3)	0.0532 (5)	0.4936 (2)	0.0339 (13)
H4	0.2278	−0.0218	0.4872	0.041*
C5	0.1870 (3)	0.0769 (5)	0.5481 (2)	0.0254 (11)
C6	0.2135 (3)	−0.0071 (5)	0.6006 (2)	0.0314 (12)
H6A	0.2124	−0.0961	0.5876	0.038*
H6B	0.2644	0.0147	0.6198	0.038*
C7	0.2068 (3)	−0.0160 (5)	0.7060 (2)	0.0296 (12)
H7A	0.2598	−0.0110	0.7080	0.035*
H7B	0.1958	−0.1024	0.7176	0.035*
C8	0.1873 (3)	0.0770 (5)	0.7490 (2)	0.0288 (12)
C9	0.2105 (3)	0.0616 (6)	0.8098 (3)	0.0370 (13)
H9	0.2383	−0.0101	0.8257	0.044*
C10	0.1923 (3)	0.1526 (6)	0.8468 (3)	0.0402 (15)
H10	0.2082	0.1449	0.8886	0.048*
C11	0.1511 (3)	0.2539 (6)	0.8227 (3)	0.0379 (14)
H11	0.1364	0.3153	0.8475	0.045*
C12	0.1315 (3)	0.2653 (5)	0.7627 (3)	0.0334 (13)
H12	0.1041	0.3370	0.7461	0.040*
C13	0.1030 (3)	−0.0805 (5)	0.6262 (3)	0.0394 (14)
H13A	0.0839	−0.0730	0.5829	0.047*
H13B	0.1215	−0.1676	0.6343	0.047*
C14	0.0411 (4)	−0.0619 (6)	0.6559 (3)	0.0504 (18)
H14A	0.0601	−0.0263	0.6959	0.061*
H14B	0.0189	−0.1448	0.6607	0.061*
C15	−0.0177 (4)	0.0262 (6)	0.6211 (4)	0.058 (2)
H15A	−0.0363	−0.0070	0.5806	0.070*
H15B	−0.0589	0.0319	0.6410	0.070*
C16	0.0700 (3)	0.4605 (5)	0.6291 (2)	0.0291 (12)
C17	0.0256 (3)	0.5744 (5)	0.6235 (3)	0.0404 (14)
H17A	0.0255	0.6155	0.5856	0.061*
H17B	0.0459	0.6322	0.6561	0.061*
H17C	−0.0244	0.5521	0.6252	0.061*

	U11	U22	U33	U12	U13	U23
Cu1	0.0314 (4)	0.0225 (3)	0.0273 (4)	0.0038 (3)	0.0086 (3)	0.0016 (3)
Cl1	0.0357 (8)	0.0375 (7)	0.0332 (7)	−0.0068 (6)	0.0120 (6)	−0.0047 (6)
Cl2	0.0440 (9)	0.0379 (8)	0.0365 (8)	0.0053 (6)	0.0074 (7)	0.0025 (6)
N1	0.030 (2)	0.020 (2)	0.030 (2)	0.0003 (18)	0.0085 (19)	−0.0011 (18)
N2	0.022 (2)	0.032 (2)	0.030 (2)	−0.0014 (19)	0.0068 (19)	−0.002 (2)
N3	0.036 (2)	0.027 (2)	0.017 (2)	0.0041 (19)	0.0062 (18)	0.0031 (18)
N4	0.041 (3)	0.032 (3)	0.033 (3)	0.008 (2)	0.009 (2)	−0.001 (2)
O1	0.021 (2)	0.044 (3)	0.068 (3)	0.004 (2)	−0.003 (2)	0.011 (2)
O2	0.053 (3)	0.069 (3)	0.082 (4)	−0.030 (3)	0.007 (3)	0.012 (3)
O3	0.031 (2)	0.045 (2)	0.051 (3)	−0.0031 (19)	0.0049 (19)	0.009 (2)
O4	0.044 (3)	0.055 (3)	0.074 (3)	0.006 (2)	0.018 (2)	−0.026 (3)
O5	0.072 (3)	0.077 (3)	0.021 (2)	0.001 (3)	0.010 (2)	0.000 (2)
O6	0.072 (4)	0.147 (6)	0.034 (3)	0.040 (4)	0.005 (3)	0.016 (3)
O7	0.128 (6)	0.089 (4)	0.060 (4)	0.026 (4)	0.025 (4)	−0.015 (3)
O8	0.53 (2)	0.092 (6)	0.131 (9)	−0.135 (10)	0.107 (12)	−0.010 (6)
O9	0.078 (5)	0.55 (2)	0.059 (5)	0.122 (9)	0.014 (4)	0.020 (8)
C1	0.038 (3)	0.031 (3)	0.029 (3)	0.003 (2)	0.007 (2)	0.005 (2)
C2	0.041 (3)	0.042 (3)	0.027 (3)	−0.002 (3)	0.006 (3)	0.003 (3)
C3	0.041 (3)	0.039 (3)	0.029 (3)	0.000 (3)	0.011 (3)	0.000 (3)
C4	0.033 (3)	0.036 (3)	0.033 (3)	0.004 (2)	0.007 (2)	−0.003 (3)
C5	0.022 (3)	0.024 (2)	0.027 (3)	−0.006 (2)	0.000 (2)	0.001 (2)
C6	0.031 (3)	0.030 (3)	0.033 (3)	0.007 (2)	0.007 (2)	0.001 (2)
C7	0.029 (3)	0.029 (3)	0.032 (3)	0.005 (2)	0.007 (2)	0.004 (2)
C8	0.024 (3)	0.033 (3)	0.029 (3)	−0.006 (2)	0.008 (2)	0.002 (2)
C9	0.039 (3)	0.038 (3)	0.035 (3)	0.001 (3)	0.009 (3)	0.005 (3)
C10	0.053 (4)	0.044 (3)	0.024 (3)	−0.011 (3)	0.009 (3)	0.003 (3)
C11	0.044 (4)	0.036 (3)	0.036 (3)	−0.008 (3)	0.013 (3)	0.000 (3)
C12	0.042 (3)	0.031 (3)	0.031 (3)	0.002 (3)	0.016 (3)	0.002 (2)
C13	0.034 (3)	0.028 (3)	0.055 (4)	−0.002 (2)	0.006 (3)	0.007 (3)
C14	0.044 (4)	0.034 (3)	0.077 (5)	−0.007 (3)	0.023 (4)	0.010 (3)
C15	0.032 (4)	0.043 (4)	0.099 (6)	−0.002 (3)	0.013 (4)	0.004 (4)
C16	0.034 (3)	0.030 (3)	0.023 (3)	0.002 (2)	0.007 (2)	0.001 (2)
C17	0.036 (3)	0.032 (3)	0.052 (4)	0.010 (3)	0.010 (3)	−0.001 (3)

Cu1—N1	1.986 (4)	C3—H3	0.9500
Cu1—N3	1.991 (4)	C4—C5	1.386 (7)
Cu1—N4	1.997 (5)	C4—H4	0.9500
Cu1—N2	2.021 (4)	C5—C6	1.500 (7)
Cu1—O1	2.232 (4)	C6—H6A	0.9900
Cu1—O3	2.868 (4)	C6—H6B	0.9900
Cl1—O5	1.413 (4)	C7—C8	1.505 (7)
Cl1—O2	1.420 (5)	C7—H7A	0.9900
Cl1—O4	1.421 (4)	C7—H7B	0.9900
Cl1—O3	1.436 (4)	C8—C9	1.387 (8)
Cl2—O8	1.330 (8)	C9—C10	1.385 (8)
Cl2—O9	1.330 (7)	C9—H9	0.9500
Cl2—O6	1.389 (5)	C10—C11	1.368 (8)
Cl2—O7	1.405 (5)	C10—H10	0.9500
N1—C1	1.333 (7)	C11—C12	1.363 (8)
N1—C5	1.349 (6)	C11—H11	0.9500
N2—C7	1.493 (7)	C12—H12	0.9500
N2—C6	1.495 (7)	C13—C14	1.496 (8)
N2—C13	1.501 (7)	C13—H13A	0.9900
N3—C12	1.328 (7)	C13—H13B	0.9900
N3—C8	1.346 (7)	C14—C15	1.532 (9)
N4—C16	1.126 (7)	C14—H14A	0.9900
O1—C15	1.434 (8)	C14—H14B	0.9900
O1—H1A	0.73 (6)	C15—H15A	0.9900
C1—C2	1.377 (8)	C15—H15B	0.9900
C1—H1	0.9500	C16—C17	1.459 (7)
C2—C3	1.381 (8)	C17—H17A	0.9800
C2—H2	0.9500	C17—H17B	0.9800
C3—C4	1.374 (8)	C17—H17C	0.9800
N1—Cu1—N3	161.51 (18)	N2—C6—C5	109.8 (4)
N1—Cu1—N4	95.48 (18)	N2—C6—H6A	109.7
N3—Cu1—N4	95.08 (18)	C5—C6—H6A	109.7
N1—Cu1—N2	84.12 (17)	N2—C6—H6B	109.7
N3—Cu1—N2	84.88 (17)	C5—C6—H6B	109.7
N4—Cu1—N2	178.30 (19)	H6A—C6—H6B	108.2
N1—Cu1—O1	99.08 (19)	N2—C7—C8	112.0 (4)
N3—Cu1—O1	96.80 (19)	N2—C7—H7A	109.2
N4—Cu1—O1	85.79 (19)	C8—C7—H7A	109.2
N2—Cu1—O1	95.91 (17)	N2—C7—H7B	109.2
O5—Cl1—O2	111.0 (3)	C8—C7—H7B	109.2
O5—Cl1—O4	109.3 (3)	H7A—C7—H7B	107.9
O2—Cl1—O4	110.3 (3)	N3—C8—C9	120.6 (5)
O5—Cl1—O3	108.4 (3)	N3—C8—C7	117.5 (5)
O2—Cl1—O3	108.6 (3)	C9—C8—C7	121.8 (5)
O4—Cl1—O3	109.2 (3)	C10—C9—C8	118.8 (6)
O8—Cl2—O9	106.9 (9)	C10—C9—H9	120.6
O8—Cl2—O6	110.8 (6)	C8—C9—H9	120.6
O9—Cl2—O6	109.5 (4)	C11—C10—C9	119.4 (6)
O8—Cl2—O7	104.8 (6)	C11—C10—H10	120.3
O9—Cl2—O7	111.0 (6)	C9—C10—H10	120.3
O6—Cl2—O7	113.5 (4)	C12—C11—C10	119.1 (6)
C1—N1—C5	119.6 (5)	C12—C11—H11	120.5
C1—N1—Cu1	127.6 (4)	C10—C11—H11	120.5
C5—N1—Cu1	112.8 (3)	N3—C12—C11	122.4 (5)
C7—N2—C6	111.8 (4)	N3—C12—H12	118.8
C7—N2—C13	111.0 (4)	C11—C12—H12	118.8
C6—N2—C13	107.5 (4)	C14—C13—N2	116.2 (5)
C7—N2—Cu1	108.0 (3)	C14—C13—H13A	108.2
C6—N2—Cu1	106.7 (3)	N2—C13—H13A	108.2
C13—N2—Cu1	111.8 (3)	C14—C13—H13B	108.2
C12—N3—C8	119.7 (5)	N2—C13—H13B	108.2
C12—N3—Cu1	127.3 (4)	H13A—C13—H13B	107.4
C8—N3—Cu1	112.9 (3)	C13—C14—C15	112.6 (6)
C16—N4—Cu1	162.4 (5)	C13—C14—H14A	109.1
C15—O1—Cu1	125.4 (4)	C15—C14—H14A	109.1
C15—O1—H1A	98 (4)	C13—C14—H14B	109.1
Cu1—O1—H1A	130 (5)	C15—C14—H14B	109.1
N1—C1—C2	122.0 (5)	H14A—C14—H14B	107.8
N1—C1—H1	119.0	O1—C15—C14	108.4 (5)
C2—C1—H1	119.0	O1—C15—H15A	110.0
C1—C2—C3	118.5 (5)	C14—C15—H15A	110.0
C1—C2—H2	120.8	O1—C15—H15B	110.0
C3—C2—H2	120.8	C14—C15—H15B	110.0
C4—C3—C2	120.0 (5)	H15A—C15—H15B	108.4
C4—C3—H3	120.0	N4—C16—C17	179.1 (6)
C2—C3—H3	120.0	C16—C17—H17A	109.5
C3—C4—C5	118.7 (5)	C16—C17—H17B	109.5
C3—C4—H4	120.7	H17A—C17—H17B	109.5
C5—C4—H4	120.7	C16—C17—H17C	109.5
N1—C5—C4	121.1 (5)	H17A—C17—H17C	109.5
N1—C5—C6	116.8 (5)	H17B—C17—H17C	109.5
C4—C5—C6	122.0 (5)
N3—Cu1—N1—C1	−137.9 (6)	N4—Cu1—O1—C15	−170.7 (6)
N4—Cu1—N1—C1	−13.4 (5)	N2—Cu1—O1—C15	9.4 (6)
N2—Cu1—N1—C1	168.3 (5)	Cu1—N1—C1—C2	179.7 (4)
O1—Cu1—N1—C1	73.2 (5)	Cu1—N1—C5—C4	179.2 (4)
N3—Cu1—N1—C5	41.3 (7)	C1—N1—C5—C6	175.0 (5)
N4—Cu1—N1—C5	165.9 (4)	Cu1—N1—C5—C6	−4.3 (6)
N2—Cu1—N1—C5	−12.5 (3)	C3—C4—C5—C6	−174.2 (5)
O1—Cu1—N1—C5	−107.5 (3)	C7—N2—C6—C5	−151.1 (4)
N1—Cu1—N2—C7	145.7 (3)	C13—N2—C6—C5	86.9 (5)
N3—Cu1—N2—C7	−19.4 (3)	Cu1—N2—C6—C5	−33.2 (5)
O1—Cu1—N2—C7	−115.7 (3)	N1—C5—C6—N2	25.8 (6)
N1—Cu1—N2—C6	25.3 (3)	C4—C5—C6—N2	−157.7 (5)
N3—Cu1—N2—C6	−139.8 (3)	C6—N2—C7—C8	139.1 (4)
O1—Cu1—N2—C6	123.9 (3)	C13—N2—C7—C8	−100.9 (5)
N1—Cu1—N2—C13	−91.9 (4)	Cu1—N2—C7—C8	21.9 (5)
N3—Cu1—N2—C13	103.0 (4)	C12—N3—C8—C9	−2.4 (8)
O1—Cu1—N2—C13	6.6 (4)	Cu1—N3—C8—C9	172.8 (4)
N1—Cu1—N3—C12	134.6 (6)	C12—N3—C8—C7	−179.2 (5)
N4—Cu1—N3—C12	10.0 (5)	N2—C7—C8—N3	−12.6 (7)
N2—Cu1—N3—C12	−171.7 (5)	N2—C7—C8—C9	170.7 (5)
O1—Cu1—N3—C12	−76.3 (5)	C7—C8—C9—C10	178.1 (5)
N1—Cu1—N3—C8	−40.2 (7)	C9—C10—C11—C12	−2.7 (9)
N4—Cu1—N3—C8	−164.8 (4)	Cu1—N3—C12—C11	−173.7 (4)
N2—Cu1—N3—C8	13.5 (4)	C7—N2—C13—C14	69.5 (6)
O1—Cu1—N3—C8	108.9 (4)	C6—N2—C13—C14	−168.0 (5)
N1—Cu1—N4—C16	102.7 (16)	Cu1—N2—C13—C14	−51.2 (6)
N3—Cu1—N4—C16	−92.5 (16)	N2—C13—C14—C15	91.7 (7)
N1—Cu1—O1—C15	94.4 (6)	Cu1—O1—C15—C14	15.4 (9)
N3—Cu1—O1—C15	−76.1 (6)	C13—C14—C15—O1	−63.0 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O9	0.74 (5)	2.46 (5)	3.090 (12)	145 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O9	0.74 (5)	2.46 (5)	3.090 (12)	145 (5)