{N,N'-Bis[1-(pyridin-2-yl)ethyl-idene]-propane-1,3-diamine}-(thio-cyanato-κN)copper(II) tetra-fluoridoborate.

In the title compound, [Cu(NCS)(C(17)H(20)N(4))]BF(4), the Cu(II) ion is five-coordinated by the four N atoms of the tetra-dentate Schiff base ligand and one N atom of a thio-cyanate ligand, thereby forming a square-pyramidal CuN(5) ccoordination geometry. The dihedral angle between the pyridine rings of the Schiff base is 55.58 (14)°. The F atoms of the tetra-fluoridoborate anion are disordered over two sets of sites with occupancies of 0.614 (3) and 0.386 (3). In the crystal, the components are linked by C-H⋯F inter-actions.

Related literature

For background on the use of copper(II) complexes with Schiff bases in coordination chemistry and biological chemistry, see: Adhikary et al. (2009 ▶); Al-Karawi (2009 ▶); Xiao & Zhang (2009 ▶); Rajasekar et al. (2010 ▶); Sang & Lin (2010 ▶); Qin et al. (2010 ▶). For a related copper(II) complex that we reported recently, see: Liu (2010 ▶). For related copper complexes with square-pyramidal coordination, see: Liu et al. (1997 ▶); Chattopadhyay et al. (2006 ▶); Rahaman et al. (2005 ▶).

Experimental

Crystal data

[Cu(NCS)(C17H20N4)]BF4

M = 488.80

Monoclinic,

a = 9.5057 (7) Å

b = 13.7527 (11) Å

c = 16.1902 (13) Å

β = 101.200 (1)°

V = 2076.2 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.20 mm−1

T = 298 K

0.33 × 0.30 × 0.28 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.692, T max = 0.729

17908 measured reflections

5059 independent reflections

3368 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.107

S = 1.03

5059 reflections

310 parameters

56 restraints

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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) global, I. DOI: 10.1107/S1600536811021040/hb5899sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021040/hb5899Isup2.hkl

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

[Cu(NCS)(C17H20N4)]BF4	F(000) = 996
Mr = 488.80	Dx = 1.564 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.5057 (7) Å	Cell parameters from 4043 reflections
b = 13.7527 (11) Å	θ = 2.5–25.1°
c = 16.1902 (13) Å	µ = 1.20 mm−1
β = 101.200 (1)°	T = 298 K
V = 2076.2 (3) Å3	Block, blue
Z = 4	0.33 × 0.30 × 0.28 mm

Bruker APEXII CCD diffractometer	5059 independent reflections
Radiation source: fine-focus sealed tube	3368 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→12
Tmin = 0.692, Tmax = 0.729	k = −18→18
17908 measured reflections	l = −21→21

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0515P)2 + 0.3601P] where P = (Fo2 + 2Fc2)/3
5059 reflections	(Δ/σ)max = 0.001
310 parameters	Δρmax = 0.35 e Å−3
56 restraints	Δρmin = −0.28 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	Occ. (<1)
Cu1	0.86559 (4)	0.35520 (2)	0.20844 (2)	0.04286 (12)
S1	1.20466 (9)	0.30423 (6)	0.02388 (5)	0.0610 (2)
N1	0.8455 (2)	0.22227 (15)	0.26403 (13)	0.0417 (5)
N2	0.7105 (2)	0.29716 (16)	0.12272 (13)	0.0443 (5)
N3	0.7727 (2)	0.48651 (16)	0.19522 (13)	0.0445 (5)
N4	0.9890 (2)	0.42656 (15)	0.30527 (13)	0.0431 (5)
N5	1.0234 (3)	0.33564 (18)	0.13614 (17)	0.0594 (7)
C1	0.7394 (3)	0.16805 (18)	0.21868 (16)	0.0409 (6)
C2	0.7017 (3)	0.0789 (2)	0.24686 (18)	0.0506 (7)
H2	0.6281	0.0427	0.2149	0.061*
C3	0.7750 (4)	0.0439 (2)	0.3233 (2)	0.0594 (8)
H3	0.7513	−0.0160	0.3435	0.071*
C4	0.8819 (4)	0.0983 (2)	0.36833 (19)	0.0593 (8)
H4	0.9333	0.0757	0.4195	0.071*
C5	0.9139 (3)	0.1878 (2)	0.33747 (18)	0.0523 (7)
H5	0.9861	0.2253	0.3694	0.063*
C6	0.6669 (3)	0.21236 (19)	0.13808 (16)	0.0424 (6)
C7	0.5498 (3)	0.1593 (2)	0.0812 (2)	0.0595 (8)
H7A	0.4592	0.1888	0.0838	0.089*
H7B	0.5491	0.0926	0.0986	0.089*
H7C	0.5656	0.1623	0.0244	0.089*
C8	0.6416 (4)	0.3483 (2)	0.04519 (18)	0.0578 (8)
H8A	0.5383	0.3446	0.0393	0.069*
H8B	0.6676	0.3166	−0.0032	0.069*
C9	0.6869 (3)	0.4539 (2)	0.04699 (17)	0.0540 (7)
H9A	0.7885	0.4569	0.0459	0.065*
H9B	0.6358	0.4856	−0.0035	0.065*
C10	0.6597 (3)	0.5092 (2)	0.12256 (17)	0.0572 (8)
H10A	0.6588	0.5785	0.1112	0.069*
H10B	0.5670	0.4912	0.1345	0.069*
C11	0.8076 (3)	0.54422 (19)	0.25782 (17)	0.0455 (6)
C12	0.7350 (4)	0.6387 (2)	0.2680 (2)	0.0727 (10)
H12A	0.7947	0.6915	0.2568	0.109*
H12B	0.7187	0.6439	0.3245	0.109*
H12C	0.6448	0.6414	0.2291	0.109*
C13	0.9330 (3)	0.51342 (18)	0.32143 (16)	0.0421 (6)
C14	0.9964 (3)	0.5691 (2)	0.38931 (17)	0.0520 (7)
H14	0.9556	0.6280	0.4002	0.062*
C15	1.1200 (3)	0.5373 (2)	0.44084 (18)	0.0569 (8)
H15	1.1627	0.5738	0.4874	0.068*
C16	1.1795 (3)	0.4511 (2)	0.42266 (18)	0.0564 (8)
H16	1.2640	0.4286	0.4560	0.068*
C17	1.1114 (3)	0.3979 (2)	0.35371 (19)	0.0526 (7)
H17	1.1529	0.3401	0.3408	0.063*
C18	1.0978 (3)	0.32353 (18)	0.08884 (17)	0.0418 (6)
B1	0.5510 (4)	0.3543 (3)	0.3428 (2)	0.0678 (11)	0.614 (8)
F1	0.5253 (15)	0.3475 (8)	0.2600 (4)	0.138 (4)	0.614 (8)
F2	0.6776 (6)	0.3143 (6)	0.3830 (3)	0.130 (3)	0.614 (8)
F3	0.4436 (7)	0.3062 (7)	0.3717 (3)	0.140 (3)	0.614 (8)
F4	0.5594 (10)	0.4452 (3)	0.3778 (4)	0.153 (3)	0.614 (8)
B1'	0.5510 (4)	0.3543 (3)	0.3428 (2)	0.0678 (11)	0.386 (8)
F1'	0.527 (2)	0.3819 (11)	0.2591 (5)	0.116 (4)	0.386 (8)
F2'	0.5547 (12)	0.2555 (4)	0.3521 (5)	0.110 (3)	0.386 (8)
F3'	0.4465 (10)	0.3895 (9)	0.3752 (5)	0.112 (4)	0.386 (8)
F4'	0.6822 (10)	0.3896 (10)	0.3720 (6)	0.140 (5)	0.386 (8)

	U11	U22	U33	U12	U13	U23
Cu1	0.0456 (2)	0.03860 (18)	0.0420 (2)	0.00179 (14)	0.00258 (14)	−0.00137 (13)
S1	0.0590 (5)	0.0726 (5)	0.0545 (5)	0.0038 (4)	0.0188 (4)	0.0015 (4)
N1	0.0429 (13)	0.0401 (11)	0.0416 (12)	0.0034 (10)	0.0073 (10)	0.0000 (9)
N2	0.0466 (14)	0.0464 (13)	0.0386 (12)	0.0007 (10)	0.0055 (10)	0.0018 (10)
N3	0.0445 (13)	0.0446 (12)	0.0440 (12)	0.0077 (10)	0.0078 (10)	0.0055 (10)
N4	0.0427 (13)	0.0398 (11)	0.0458 (12)	0.0009 (10)	0.0059 (10)	−0.0008 (9)
N5	0.0611 (17)	0.0551 (15)	0.0660 (17)	−0.0031 (13)	0.0226 (15)	−0.0104 (13)
C1	0.0391 (15)	0.0404 (14)	0.0455 (15)	0.0049 (11)	0.0141 (12)	−0.0029 (11)
C2	0.0499 (17)	0.0439 (15)	0.0594 (18)	−0.0006 (13)	0.0140 (14)	−0.0017 (13)
C3	0.066 (2)	0.0422 (16)	0.072 (2)	0.0067 (15)	0.0195 (17)	0.0127 (15)
C4	0.066 (2)	0.0563 (18)	0.0538 (18)	0.0100 (16)	0.0063 (15)	0.0111 (14)
C5	0.0571 (19)	0.0519 (16)	0.0443 (15)	0.0035 (14)	0.0012 (13)	0.0039 (13)
C6	0.0376 (15)	0.0458 (15)	0.0449 (15)	0.0022 (12)	0.0109 (12)	−0.0044 (12)
C7	0.0503 (19)	0.0624 (19)	0.0613 (19)	−0.0083 (15)	−0.0005 (15)	0.0012 (15)
C8	0.059 (2)	0.0634 (19)	0.0449 (16)	−0.0037 (15)	−0.0039 (14)	0.0073 (14)
C9	0.0571 (19)	0.0591 (18)	0.0427 (15)	0.0018 (14)	0.0020 (13)	0.0125 (13)
C10	0.0585 (19)	0.0557 (17)	0.0535 (17)	0.0154 (15)	0.0006 (15)	0.0094 (14)
C11	0.0482 (16)	0.0412 (14)	0.0502 (16)	0.0020 (12)	0.0171 (13)	0.0019 (12)
C12	0.077 (2)	0.0548 (19)	0.084 (2)	0.0179 (17)	0.009 (2)	−0.0135 (17)
C13	0.0466 (16)	0.0378 (13)	0.0450 (14)	−0.0036 (11)	0.0163 (12)	−0.0003 (11)
C14	0.065 (2)	0.0424 (14)	0.0514 (17)	−0.0083 (14)	0.0187 (15)	−0.0076 (13)
C15	0.066 (2)	0.0581 (18)	0.0460 (16)	−0.0184 (16)	0.0084 (15)	−0.0048 (14)
C16	0.0533 (18)	0.0627 (19)	0.0493 (16)	−0.0093 (15)	0.0002 (14)	0.0076 (14)
C17	0.0503 (18)	0.0466 (15)	0.0583 (18)	0.0014 (13)	0.0039 (14)	−0.0017 (13)
C18	0.0446 (16)	0.0311 (12)	0.0472 (15)	−0.0029 (11)	0.0025 (13)	0.0000 (11)
B1	0.072 (3)	0.071 (3)	0.064 (3)	0.023 (2)	0.021 (2)	0.008 (2)
F1	0.180 (6)	0.172 (8)	0.065 (4)	−0.003 (6)	0.029 (4)	−0.006 (3)
F2	0.109 (5)	0.147 (6)	0.138 (4)	0.076 (5)	0.034 (4)	0.016 (4)
F3	0.116 (5)	0.208 (8)	0.098 (3)	−0.066 (6)	0.027 (3)	−0.015 (4)
F4	0.190 (7)	0.075 (3)	0.175 (5)	0.035 (4)	−0.011 (4)	−0.017 (3)
B1'	0.072 (3)	0.071 (3)	0.064 (3)	0.023 (2)	0.021 (2)	0.008 (2)
F1'	0.142 (7)	0.129 (8)	0.084 (7)	0.010 (6)	0.038 (5)	0.041 (5)
F2'	0.128 (7)	0.077 (4)	0.122 (5)	0.005 (4)	0.013 (5)	0.011 (4)
F3'	0.111 (7)	0.145 (7)	0.094 (5)	0.073 (6)	0.059 (4)	0.020 (5)
F4'	0.114 (7)	0.169 (8)	0.127 (6)	−0.055 (7)	0.001 (5)	0.000 (6)

Cu1—N2	1.986 (2)	C7—H7C	0.9600
Cu1—N3	2.003 (2)	C8—C9	1.513 (4)
Cu1—N4	2.021 (2)	C8—H8A	0.9700
Cu1—N1	2.063 (2)	C8—H8B	0.9700
Cu1—N5	2.091 (3)	C9—C10	1.505 (4)
S1—C18	1.620 (3)	C9—H9A	0.9700
N1—C5	1.327 (3)	C9—H9B	0.9700
N1—C1	1.351 (3)	C10—H10A	0.9700
N2—C6	1.278 (3)	C10—H10B	0.9700
N2—C8	1.477 (3)	C11—C13	1.478 (4)
N3—C11	1.279 (3)	C11—C12	1.496 (4)
N3—C10	1.464 (3)	C12—H12A	0.9600
N4—C17	1.330 (3)	C12—H12B	0.9600
N4—C13	1.354 (3)	C12—H12C	0.9600
N5—C18	1.151 (4)	C13—C14	1.378 (4)
C1—C2	1.380 (4)	C14—C15	1.373 (4)
C1—C6	1.483 (4)	C14—H14	0.9300
C2—C3	1.383 (4)	C15—C16	1.371 (4)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.355 (4)	C16—C17	1.385 (4)
C3—H3	0.9300	C16—H16	0.9300
C4—C5	1.385 (4)	C17—H17	0.9300
C4—H4	0.9300	B1—F1	1.320 (7)
C5—H5	0.9300	B1—F2	1.367 (5)
C6—C7	1.491 (4)	B1—F4	1.368 (5)
C7—H7A	0.9600	B1—F3	1.372 (5)
C7—H7B	0.9600
N2—Cu1—N3	92.05 (9)	N2—C8—H8A	109.4
N2—Cu1—N4	167.96 (9)	C9—C8—H8A	109.4
N3—Cu1—N4	79.77 (9)	N2—C8—H8B	109.4
N2—Cu1—N1	80.19 (9)	C9—C8—H8B	109.4
N3—Cu1—N1	140.31 (9)	H8A—C8—H8B	108.0
N4—Cu1—N1	100.42 (8)	C10—C9—C8	114.0 (3)
N2—Cu1—N5	94.19 (10)	C10—C9—H9A	108.7
N3—Cu1—N5	113.90 (9)	C8—C9—H9A	108.7
N4—Cu1—N5	97.20 (9)	C10—C9—H9B	108.7
N1—Cu1—N5	105.51 (9)	C8—C9—H9B	108.7
C5—N1—C1	118.3 (2)	H9A—C9—H9B	107.6
C5—N1—Cu1	129.53 (19)	N3—C10—C9	109.3 (2)
C1—N1—Cu1	112.00 (17)	N3—C10—H10A	109.8
C6—N2—C8	119.6 (2)	C9—C10—H10A	109.8
C6—N2—Cu1	117.11 (18)	N3—C10—H10B	109.8
C8—N2—Cu1	123.28 (18)	C9—C10—H10B	109.8
C11—N3—C10	122.8 (2)	H10A—C10—H10B	108.3
C11—N3—Cu1	115.70 (18)	N3—C11—C13	115.1 (2)
C10—N3—Cu1	121.13 (18)	N3—C11—C12	124.9 (3)
C17—N4—C13	118.6 (2)	C13—C11—C12	120.0 (3)
C17—N4—Cu1	128.55 (19)	C11—C12—H12A	109.5
C13—N4—Cu1	112.82 (17)	C11—C12—H12B	109.5
C18—N5—Cu1	172.4 (3)	H12A—C12—H12B	109.5
N1—C1—C2	121.7 (2)	C11—C12—H12C	109.5
N1—C1—C6	115.0 (2)	H12A—C12—H12C	109.5
C2—C1—C6	123.3 (3)	H12B—C12—H12C	109.5
C1—C2—C3	119.1 (3)	N4—C13—C14	121.1 (3)
C1—C2—H2	120.4	N4—C13—C11	114.3 (2)
C3—C2—H2	120.4	C14—C13—C11	124.4 (2)
C4—C3—C2	119.0 (3)	C15—C14—C13	119.8 (3)
C4—C3—H3	120.5	C15—C14—H14	120.1
C2—C3—H3	120.5	C13—C14—H14	120.1
C3—C4—C5	119.4 (3)	C16—C15—C14	119.0 (3)
C3—C4—H4	120.3	C16—C15—H15	120.5
C5—C4—H4	120.3	C14—C15—H15	120.5
N1—C5—C4	122.5 (3)	C15—C16—C17	118.8 (3)
N1—C5—H5	118.8	C15—C16—H16	120.6
C4—C5—H5	118.8	C17—C16—H16	120.6
N2—C6—C1	115.7 (2)	N4—C17—C16	122.5 (3)
N2—C6—C7	123.9 (2)	N4—C17—H17	118.8
C1—C6—C7	120.4 (2)	C16—C17—H17	118.8
C6—C7—H7A	109.5	N5—C18—S1	178.5 (3)
C6—C7—H7B	109.5	F1—B1—F2	115.3 (7)
H7A—C7—H7B	109.5	F1—B1—F4	118.0 (6)
C6—C7—H7C	109.5	F2—B1—F4	101.3 (5)
H7A—C7—H7C	109.5	F1—B1—F3	108.0 (7)
H7B—C7—H7C	109.5	F2—B1—F3	106.8 (5)
N2—C8—C9	111.3 (2)	F4—B1—F3	106.7 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···F4i	0.93	2.49	3.416 (8)	176
C7—H7B···F4i	0.96	2.34	3.234 (6)	155

Table 1

Selected bond lengths (Å)

Cu1—N2	1.986 (2)
Cu1—N3	2.003 (2)
Cu1—N4	2.021 (2)
Cu1—N1	2.063 (2)
Cu1—N5	2.091 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯F4i	0.93	2.49	3.416 (8)	176
C7—H7B⋯F4i	0.96	2.34	3.234 (6)	155

Symmetry code: (i) .