Aqua-{4,4',6,6'-tetra-fluoro-2,2'-[(piperazine-1,4-di-yl)dimethyl-ene]diphenolato}copper(II).

In the title compound, [Cu(C(18)H(16)F(4)N(2)O(2))(H(2)O)], the Cu(II) atom shows a distorted square-pyramidal coordination geometry with the N,N',O,O'-tetra-dentate piperazine-diphenolate ligand forming the basal plane. The apical site is occupied by the O atom of a coordinated water mol-ecule. Neighbouring complexes are associated through inter-molecular O-H⋯O and O-H⋯F hydrogen bonds between the water mol-ecule and a phenolate O atom or an F atom from an adjacent ligand, respectively, forming a centrosymmetric dimer. Dimers are linked by additional inter-molecular C-H⋯O and C-H⋯F hydrogen bonds, giving infinite chains propagating along the a axis.

Related literature

For related stuctures, see: Kubono et al. (2003 ▶, 2009 ▶); Loukiala et al. (1997 ▶); Mukhopadhyay et al. (2004 ▶); Weinberger et al. (2000 ▶). For the supra­molecular chemistry of complexes with piperazine-based ligands, see: Tsai et al. (2008 ▶); Zhao et al. (2004 ▶). For graph-set analysis in the crystal structures of organometallic compounds, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Cu(C18H16F4N2O2)(H2O)]

M = 449.89

Triclinic,

a = 8.0157 (17) Å

b = 9.6873 (10) Å

c = 11.7693 (12) Å

α = 83.743 (9)°

β = 87.763 (12)°

γ = 74.420 (11)°

V = 875.0 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.31 mm−1

T = 296 K

0.30 × 0.20 × 0.10 mm

Data collection

Rigaku AFC-7R diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.737, T max = 0.877

4895 measured reflections

4015 independent reflections

3120 reflections with I > 2σ(I)

R int = 0.051

3 standard reflections every 150 reflections intensity decay: 1.1%

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.108

S = 1.05

4015 reflections

262 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.61 e Å−3

Data collection: WinAFC (Rigaku/MSC, 2006 ▶); cell refinement: WinAFC; data reduction: CrystalStructure (Rigaku/MSC, 2006 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810040080/im2234sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040080/im2234Isup2.hkl

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

[Cu(C18H16F4N2O2)(H2O)]	Z = 2
Mr = 449.89	F(000) = 458.00
Triclinic, P1	Dx = 1.708 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 8.0157 (17) Å	Cell parameters from 25 reflections
b = 9.6873 (10) Å	θ = 15.2–16.8°
c = 11.7693 (12) Å	µ = 1.31 mm−1
α = 83.743 (9)°	T = 296 K
β = 87.763 (12)°	Prismatic, blue
γ = 74.420 (11)°	0.30 × 0.20 × 0.10 mm
V = 875.0 (2) Å3

Rigaku AFC-7R diffractometer	Rint = 0.051
ω–2θ scans	θmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −10→5
Tmin = 0.737, Tmax = 0.877	k = −12→12
4895 measured reflections	l = −15→15
4015 independent reflections	3 standard reflections every 150 reflections
3120 reflections with F2 > 2σ(F2)	intensity decay: 1.1%

Refinement on F2	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.039	w = 1/[σ2(Fo2) + (0.0368P)2 + 1.0373P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.108	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.54 e Å−3
4015 reflections	Δρmin = −0.61 e Å−3
262 parameters

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
Cu1	0.26597 (5)	0.08830 (4)	0.58962 (3)	0.03020 (12)
F1	0.1709 (2)	−0.0061 (2)	0.24903 (17)	0.0463 (4)
F2	0.1403 (3)	0.4645 (2)	0.0841 (2)	0.0726 (7)
F3	0.3363 (3)	−0.3057 (2)	1.10318 (18)	0.0675 (7)
F4	0.3025 (3)	−0.3709 (2)	0.71553 (17)	0.0510 (5)
O1	0.3198 (3)	0.0354 (2)	0.43752 (17)	0.0367 (4)
O2	0.2095 (3)	−0.0851 (2)	0.65512 (17)	0.0352 (4)
O3	−0.0692 (4)	0.1793 (3)	0.5321 (2)	0.0542 (7)
N1	0.3452 (3)	0.2713 (2)	0.5630 (2)	0.0296 (5)
N2	0.2158 (3)	0.1861 (2)	0.7367 (2)	0.0302 (5)
C1	0.2816 (3)	0.1421 (3)	0.3534 (2)	0.0311 (6)
C2	0.2011 (4)	0.1248 (3)	0.2551 (2)	0.0352 (6)
C3	0.1514 (4)	0.2286 (4)	0.1652 (2)	0.0439 (7)
C4	0.1890 (4)	0.3584 (4)	0.1722 (2)	0.0456 (8)
C5	0.2728 (4)	0.3836 (3)	0.2633 (2)	0.0398 (7)
C6	0.3215 (4)	0.2762 (3)	0.3542 (2)	0.0335 (6)
C7	0.4255 (4)	0.2979 (3)	0.4507 (2)	0.0337 (6)
C8	0.1833 (4)	0.3809 (3)	0.5837 (2)	0.0368 (6)
C9	0.1110 (4)	0.3332 (3)	0.6997 (2)	0.0374 (6)
C10	0.3909 (4)	0.1940 (3)	0.7660 (2)	0.0385 (7)
C11	0.4658 (4)	0.2616 (3)	0.6585 (2)	0.0347 (6)
C12	0.1324 (4)	0.1160 (3)	0.8309 (2)	0.0369 (6)
C13	0.2144 (4)	−0.0436 (3)	0.8547 (2)	0.0344 (6)
C14	0.2497 (4)	−0.1032 (3)	0.9671 (2)	0.0423 (7)
C15	0.3025 (5)	−0.2496 (4)	0.9919 (2)	0.0450 (8)
C16	0.3221 (4)	−0.3418 (3)	0.9091 (3)	0.0429 (7)
C17	0.2888 (4)	−0.2811 (3)	0.7984 (2)	0.0358 (6)
C18	0.2376 (4)	−0.1328 (3)	0.7648 (2)	0.0318 (6)
H1	0.0950	0.2124	0.1024	0.053*
H2	0.2974	0.4718	0.2649	0.048*
H3	0.5409	0.2332	0.4482	0.040*
H4	0.4364	0.3958	0.4413	0.040*
H5	0.1010	0.3881	0.5237	0.044*
H6	0.2057	0.4742	0.5853	0.044*
H7	0.1181	0.3983	0.7553	0.045*
H8	−0.0094	0.3341	0.6925	0.045*
H9	0.4641	0.0984	0.7889	0.046*
H10	0.3838	0.2527	0.8286	0.046*
H11	0.4753	0.3568	0.6704	0.042*
H12	0.5802	0.2023	0.6410	0.042*
H13	0.0113	0.1312	0.8128	0.044*
H14	0.1370	0.1617	0.8997	0.044*
H15	0.2374	−0.0434	1.0253	0.051*
H16	0.3564	−0.4412	0.9270	0.052*
H17	−0.108 (6)	0.180 (5)	0.473 (4)	0.064 (14)*
H18	−0.093 (8)	0.120 (6)	0.572 (5)	0.10 (2)*

	U11	U22	U33	U12	U13	U23
Cu1	0.0424 (2)	0.02358 (18)	0.02562 (18)	−0.00841 (14)	−0.00367 (14)	−0.00654 (12)
F1	0.0546 (12)	0.0506 (11)	0.0397 (10)	−0.0196 (9)	−0.0076 (8)	−0.0136 (8)
F2	0.0874 (18)	0.0779 (16)	0.0472 (13)	−0.0242 (14)	−0.0234 (12)	0.0307 (11)
F3	0.0991 (19)	0.0711 (15)	0.0371 (11)	−0.0354 (14)	−0.0242 (12)	0.0138 (10)
F4	0.0811 (15)	0.0334 (9)	0.0425 (10)	−0.0203 (10)	0.0101 (10)	−0.0120 (8)
O1	0.0559 (14)	0.0271 (10)	0.0261 (10)	−0.0075 (9)	−0.0072 (9)	−0.0048 (7)
O2	0.0538 (13)	0.0314 (10)	0.0254 (9)	−0.0181 (9)	−0.0004 (9)	−0.0077 (8)
O3	0.0628 (18)	0.0647 (18)	0.0454 (15)	−0.0315 (15)	−0.0090 (13)	−0.0105 (14)
N1	0.0328 (12)	0.0258 (11)	0.0303 (12)	−0.0057 (9)	−0.0062 (10)	−0.0062 (9)
N2	0.0333 (12)	0.0278 (11)	0.0303 (12)	−0.0066 (10)	−0.0027 (9)	−0.0097 (9)
C1	0.0314 (15)	0.0322 (14)	0.0277 (13)	−0.0045 (11)	0.0009 (11)	−0.0051 (11)
C2	0.0330 (15)	0.0418 (16)	0.0318 (14)	−0.0096 (13)	0.0002 (12)	−0.0090 (12)
C3	0.0389 (17)	0.062 (2)	0.0282 (15)	−0.0089 (15)	−0.0055 (13)	−0.0022 (14)
C4	0.0456 (19)	0.054 (2)	0.0313 (16)	−0.0077 (16)	−0.0032 (14)	0.0097 (14)
C5	0.0410 (17)	0.0366 (16)	0.0398 (17)	−0.0095 (13)	0.0000 (13)	0.0027 (13)
C6	0.0343 (15)	0.0336 (14)	0.0312 (14)	−0.0069 (12)	−0.0003 (12)	−0.0027 (11)
C7	0.0381 (16)	0.0301 (14)	0.0351 (15)	−0.0122 (12)	−0.0017 (12)	−0.0044 (11)
C8	0.0363 (16)	0.0256 (13)	0.0457 (17)	−0.0011 (12)	−0.0074 (13)	−0.0077 (12)
C9	0.0366 (16)	0.0295 (14)	0.0437 (17)	−0.0018 (12)	−0.0030 (13)	−0.0106 (12)
C10	0.0375 (16)	0.0448 (17)	0.0349 (15)	−0.0111 (14)	−0.0095 (12)	−0.0070 (13)
C11	0.0340 (15)	0.0336 (14)	0.0382 (15)	−0.0090 (12)	−0.0086 (12)	−0.0081 (12)
C12	0.0452 (18)	0.0361 (15)	0.0311 (15)	−0.0103 (13)	0.0027 (13)	−0.0139 (12)
C13	0.0400 (16)	0.0378 (15)	0.0289 (14)	−0.0151 (13)	−0.0007 (12)	−0.0062 (12)
C14	0.054 (2)	0.0484 (19)	0.0301 (15)	−0.0218 (16)	−0.0024 (14)	−0.0067 (13)
C15	0.054 (2)	0.054 (2)	0.0309 (16)	−0.0227 (17)	−0.0102 (14)	0.0056 (14)
C16	0.0480 (19)	0.0357 (16)	0.0442 (18)	−0.0126 (14)	−0.0030 (15)	0.0044 (13)
C17	0.0409 (17)	0.0338 (15)	0.0357 (15)	−0.0146 (13)	0.0056 (13)	−0.0074 (12)
C18	0.0335 (15)	0.0340 (14)	0.0309 (14)	−0.0137 (12)	0.0010 (11)	−0.0054 (11)

Cu1—O1	1.917 (2)	C12—C13	1.508 (4)
Cu1—O2	1.929 (2)	C13—C14	1.392 (4)
Cu1—O3	2.682 (3)	C13—C18	1.413 (4)
Cu1—N1	2.028 (2)	C14—C15	1.369 (5)
Cu1—N2	2.038 (2)	C15—C16	1.369 (5)
F1—C2	1.363 (4)	C16—C17	1.375 (4)
F2—C4	1.366 (4)	C17—C18	1.400 (4)
F3—C15	1.370 (3)	O3—H17	0.77 (5)
F4—C17	1.359 (3)	O3—H18	0.76 (6)
O1—C1	1.331 (3)	C3—H1	0.930
O2—C18	1.330 (3)	C5—H2	0.930
N1—C7	1.474 (3)	C7—H3	0.970
N1—C8	1.470 (3)	C7—H4	0.970
N1—C11	1.490 (4)	C8—H5	0.970
N2—C9	1.475 (3)	C8—H6	0.970
N2—C10	1.482 (4)	C9—H7	0.970
N2—C12	1.470 (4)	C9—H8	0.970
C1—C2	1.393 (4)	C10—H9	0.970
C1—C6	1.420 (4)	C10—H10	0.970
C2—C3	1.370 (4)	C11—H11	0.970
C3—C4	1.381 (5)	C11—H12	0.970
C4—C5	1.365 (5)	C12—H13	0.970
C5—C6	1.396 (4)	C12—H14	0.970
C6—C7	1.500 (4)	C14—H15	0.930
C8—C9	1.535 (4)	C16—H16	0.930
C10—C11	1.537 (4)
O1—Cu1—O2	98.05 (9)	F3—C15—C16	118.9 (3)
O1—Cu1—N1	94.92 (9)	C14—C15—C16	122.1 (3)
O1—Cu1—O3	88.73 (10)	C15—C16—C17	117.1 (3)
O1—Cu1—N2	167.68 (9)	F4—C17—C16	117.9 (2)
O2—Cu1—N1	165.01 (9)	F4—C17—C18	117.3 (2)
O2—Cu1—N2	94.21 (9)	C16—C17—C18	124.8 (3)
O2—Cu1—O3	85.04 (10)	O2—C18—C13	124.6 (2)
O3—Cu1—N1	102.79 (10)	O2—C18—C17	120.0 (2)
O3—Cu1—N2	91.14 (10)	C13—C18—C17	115.3 (2)
N1—Cu1—N2	73.10 (10)	H17—O3—H18	108 (6)
Cu1—O1—C1	116.27 (17)	C2—C3—H1	121.6
Cu1—O2—C18	121.3 (2)	C4—C3—H1	121.6
Cu1—N1—C7	116.32 (19)	C4—C5—H2	120.1
Cu1—N1—C8	101.17 (19)	C6—C5—H2	120.1
Cu1—N1—C11	104.88 (17)	N1—C7—H3	109.2
C7—N1—C8	113.5 (2)	N1—C7—H4	109.2
C7—N1—C11	111.7 (2)	C6—C7—H3	109.2
C8—N1—C11	108.4 (2)	C6—C7—H4	109.2
Cu1—N2—C9	104.26 (18)	H3—C7—H4	107.9
Cu1—N2—C10	101.31 (17)	N1—C8—H5	110.3
Cu1—N2—C12	117.3 (2)	N1—C8—H6	110.3
C9—N2—C10	108.3 (2)	C9—C8—H5	110.3
C9—N2—C12	112.0 (2)	C9—C8—H6	110.3
C10—N2—C12	112.8 (2)	H5—C8—H6	108.6
O1—C1—C2	120.1 (2)	N2—C9—H7	110.2
O1—C1—C6	124.4 (2)	N2—C9—H8	110.2
C2—C1—C6	115.5 (2)	C8—C9—H7	110.2
F1—C2—C1	116.8 (2)	C8—C9—H8	110.2
F1—C2—C3	118.2 (3)	H7—C9—H8	108.5
C1—C2—C3	125.0 (3)	N2—C10—H9	110.3
C2—C3—C4	116.9 (3)	N2—C10—H10	110.3
F2—C4—C3	118.3 (3)	C11—C10—H9	110.3
F2—C4—C5	119.4 (3)	C11—C10—H10	110.3
C3—C4—C5	122.3 (3)	H9—C10—H10	108.5
C4—C5—C6	119.7 (3)	N1—C11—H11	110.3
C1—C6—C5	120.5 (3)	N1—C11—H12	110.3
C1—C6—C7	119.0 (2)	C10—C11—H11	110.3
C5—C6—C7	120.4 (3)	C10—C11—H12	110.3
N1—C7—C6	112.0 (2)	H11—C11—H12	108.5
N1—C8—C9	107.1 (2)	N2—C12—H13	108.8
N2—C9—C8	107.6 (2)	N2—C12—H14	108.8
N2—C10—C11	107.1 (2)	C13—C12—H13	108.8
N1—C11—C10	107.2 (2)	C13—C12—H14	108.8
N2—C12—C13	113.7 (2)	H13—C12—H14	107.7
C12—C13—C14	119.2 (2)	C13—C14—H15	120.0
C12—C13—C18	119.8 (2)	C15—C14—H15	120.0
C14—C13—C18	120.6 (2)	C15—C16—H16	121.5
C13—C14—C15	120.0 (3)	C17—C16—H16	121.5
F3—C15—C14	119.0 (3)
O1—Cu1—O2—C18	149.2 (2)	C9—N2—C12—C13	167.7 (2)
O2—Cu1—O1—C1	147.0 (2)	C12—N2—C9—C8	−165.5 (2)
O1—Cu1—N1—C7	−4.8 (2)	C10—N2—C12—C13	−69.9 (3)
O1—Cu1—N1—C8	118.61 (18)	C12—N2—C10—C11	177.0 (2)
O1—Cu1—N1—C11	−128.73 (17)	O1—C1—C2—F1	−2.3 (4)
N1—Cu1—O1—C1	−40.5 (2)	O1—C1—C2—C3	178.0 (2)
O1—Cu1—N2—C9	40.3 (5)	O1—C1—C6—C5	−178.5 (2)
O1—Cu1—N2—C10	−72.0 (5)	O1—C1—C6—C7	5.0 (4)
O1—Cu1—N2—C12	164.8 (4)	C2—C1—C6—C5	3.2 (4)
N2—Cu1—O1—C1	−27.3 (6)	C2—C1—C6—C7	−173.3 (2)
O2—Cu1—N1—C7	145.0 (3)	C6—C1—C2—F1	176.1 (2)
O2—Cu1—N1—C8	−91.5 (3)	C6—C1—C2—C3	−3.6 (4)
O2—Cu1—N1—C11	21.1 (4)	F1—C2—C3—C4	−177.8 (2)
N1—Cu1—O2—C18	−0.4 (4)	C1—C2—C3—C4	1.9 (4)
O2—Cu1—N2—C9	−134.0 (2)	C2—C3—C4—F2	−179.6 (2)
O2—Cu1—N2—C10	113.62 (17)	C2—C3—C4—C5	0.5 (5)
O2—Cu1—N2—C12	−9.5 (2)	F2—C4—C5—C6	179.3 (2)
N2—Cu1—O2—C18	−32.0 (2)	C3—C4—C5—C6	−0.8 (5)
N1—Cu1—N2—C9	54.1 (2)	C4—C5—C6—C1	−1.2 (4)
N1—Cu1—N2—C10	−58.25 (17)	C4—C5—C6—C7	175.3 (2)
N1—Cu1—N2—C12	178.6 (2)	C1—C6—C7—N1	−55.8 (3)
N2—Cu1—N1—C7	178.1 (2)	C5—C6—C7—N1	127.6 (2)
N2—Cu1—N1—C8	−58.47 (18)	N1—C8—C9—N2	−8.7 (3)
N2—Cu1—N1—C11	54.19 (16)	N2—C10—C11—N1	−8.6 (3)
Cu1—O1—C1—C2	−135.5 (2)	N2—C12—C13—C14	133.7 (3)
Cu1—O1—C1—C6	46.3 (3)	N2—C12—C13—C18	−52.9 (4)
Cu1—O2—C18—C13	37.3 (4)	C12—C13—C14—C15	171.3 (3)
Cu1—O2—C18—C17	−144.8 (2)	C12—C13—C18—O2	7.7 (5)
Cu1—N1—C7—C6	47.3 (2)	C12—C13—C18—C17	−170.3 (3)
Cu1—N1—C8—C9	51.3 (2)	C14—C13—C18—O2	−179.0 (3)
Cu1—N1—C11—C10	−38.0 (2)	C14—C13—C18—C17	3.0 (4)
C7—N1—C8—C9	176.6 (2)	C18—C13—C14—C15	−2.0 (5)
C8—N1—C7—C6	−69.4 (3)	C13—C14—C15—F3	−179.9 (2)
C7—N1—C11—C10	−164.8 (2)	C13—C14—C15—C16	−0.1 (4)
C11—N1—C7—C6	167.7 (2)	F3—C15—C16—C17	−179.3 (3)
C8—N1—C11—C10	69.4 (2)	C14—C15—C16—C17	1.0 (5)
C11—N1—C8—C9	−58.7 (3)	C15—C16—C17—F4	−178.0 (3)
Cu1—N2—C9—C8	−37.7 (3)	C15—C16—C17—C18	0.3 (5)
Cu1—N2—C10—C11	50.8 (2)	F4—C17—C18—O2	−2.0 (4)
Cu1—N2—C12—C13	47.2 (3)	F4—C17—C18—C13	176.1 (2)
C9—N2—C10—C11	−58.5 (3)	C16—C17—C18—O2	179.6 (3)
C10—N2—C9—C8	69.6 (3)	C16—C17—C18—C13	−2.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H17···O2i	0.77 (5)	2.14 (5)	2.852 (4)	154 (5)
O3—H18···F1i	0.76 (6)	2.41 (6)	3.122 (3)	156 (6)
C7—H3···O2ii	0.97	2.49	3.376 (3)	152 (1)
C11—H12···O1ii	0.97	2.50	3.226 (3)	132 (1)
C8—H6···F4iii	0.97	2.54	3.356 (4)	143 (1)
C12—H13···F1i	0.97	2.32	3.117 (4)	140 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H17⋯O2i	0.77 (5)	2.14 (5)	2.852 (4)	154 (5)
O3—H18⋯F1i	0.76 (6)	2.41 (6)	3.122 (3)	156 (6)
C7—H3⋯O2ii	0.97	2.49	3.376 (3)	152 (1)
C11—H12⋯O1ii	0.97	2.50	3.226 (3)	132 (1)
C8—H6⋯F4iii	0.97	2.54	3.356 (4)	143 (1)
C12—H13⋯F1i	0.97	2.32	3.117 (4)	140 (1)

Symmetry codes: (i) ; (ii) ; (iii) .