Bis[μ-2-(2,4-difluoro­phen­yl)-1,3-bis­(1H-1,2,4-triazol-1-yl)propan-2-olato]dicopper(II) bis­(perchlorate)

The title complex, [Cu₂(C₁₃H₁₁F₂N₆O)₂](ClO₄)₂, which was hydro­thermally synthesized, contains a binuclear copper cluster (2 symmetry) with a Cu₂O₂ rhombus [Cu—O = 1.927 (2) Å] formed by donation of two O atoms from two chelate rings. The tridentate function of each ligand is completed by two N atoms coordinated to the two Cu^II atoms [Cu—N = 1.933 (2) Å]. The separation distance of two Cu^II atoms in a cluster is 2.988 (1) Å. The dihedral angle between the six-membered chelate rings is 2.13 (9)°. The perchlorate counter-anion is disordered over two sites in a 0.58 (10):0.42 (10) ratio.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• Disorder in main residue
• R factor = 0.040
• wR factor = 0.129
• Data-to-parameter ratio = 10.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.99
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       3.25 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cu1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cl1
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          9
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ          ?
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT158_ALERT_4_C The Input Unitcell is NOT Standard/Reduced .....          ?
PLAT927_ALERT_1_C Reported and Calculated  wR2 * 100.0 Differ by .      -0.34

Alert level G
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................      11.00 Perc.
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          5
            O1  -CU1 -N2  -C1    121.80  0.90   5.565   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          9
            O1  -CU1 -N2  -N1    -37.00  1.00   5.565   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         15
            N2  -CU1 -O1  -C4   -151.20  0.80   2.565   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         19
            N2  -CU1 -O1  -CU1    13.50  1.00   2.565   1.555   1.555   5.565
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ......      33.10 Deg.
              O3   -CL1  -O3'     1.555   1.555   1.555
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ......      33.10 Deg.
              O3   -CL1  -O3'     2.575   1.555   2.575
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ......      28.00 Deg.
              O2'  -CL1  -O2      1.555   1.555   1.555
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ......      28.00 Deg.
              O2'  -CL1  -O2      2.575   1.555   2.575

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   9 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
  10 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

1,2,4-triazole and its derivatives, being used in pharmaceuticals and agricultural chemicals, have attracted ever-increasing attention in coordination chemistry (Haasnoot et al., 2000, Zhao et al., 2007). The coordination versatility of 1, 2, 4-triazole as a reliable bridging ligand, i.e. adopting diverse binding fashions upon metal complexation, will be responsible for structural diversity of the resulting coordination frameworks (Liu et al., 2003, Park et al., 2006, Yi et al., 2004, Garcia et al., 2005). Now, we present the synthesis and structure analysis of the title Hflu complex derived from bis-fluconazolato-di-copper diperchlorate. The distinct binding modes of the ligands (Scheme 1) and the coordination preferences of the metal ion are discussed. The title binuclear copper(II) compound, C₂₆H₂₂Cl₂Cu₂F₄N₁₂O₁₀, reveals a centro-symmetric arrangement. The coordination of Cu1 is achieved by 1, 2, 4-triazole-N and flu-O ligands (Fig. 1); two oxygen atoms of fluconazole molecule form rhombus with two copper atoms with Cu-O1 bond of 1.927 (2) Å, forming a Z-style structure. The perchlorate ion is not coordinated to Cu^II atom. It take a part in formation of an ornament of 'palace lantern-style'geometry (Fig. 2). The perchlorate anions adopt two crystallographic orientations in the crystal lattice with occupancy factors of 0.576 and 0.424. The dihedral angle between two 1, 2, 4-triazole groups in the same fluconazole ligand is 68.25 (9) ° and the dihedral angle between two ipso-lateral 1, 2, 4-triazole groups in the same molecular binuclear copper cluster is 68.25 (9) ° (Fig. 1). In order to achieve the optimum coordination, fluconazole molecules were adjusted into epsilon-type arrangement.

Related literature

For the use of 1,2,4-triazole and its derivatives in coordination chemistry, see: Haasnoot et al. (2000); Zhao et al. (2007). For 1,2,4-triazole as a bridging ligand, see: Liu et al. (2003); Park et al. (2006); Yi et al. (2004); Garcia et al. (2005).

S2. Experimental

A methanolic solution (15 ml) containing the Hflu ligand (0.5 mmol, 0.153 g) was added dropwise to a water solution (10 ml) containing Cu(ClO₄)₂ (0.5 mmol, 0.131 g). After stirring for 4 h, the solution was filtered. The filtered solution were evaporated for several days in the air and obtained deep-blue block-shaped crystals that was suitable for single-crystal X-ray diffraction (yield: 65.6% based on the ligand). Anal calc (%). for C₂₆H₂₂Cl₂Cu₂F₄N₁₂O₁₀: H, 2.37; C, 33.34; N, 17.95. Found: H, 2.45; C,33.41; N, 17.81.

S3. Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene H atoms. The thermalfactors being set 1.5 times of their carrier atoms.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).

Figures

	Fig. 1. The structure of the title compound and the atom-numbering scheme. The H atoms have been omitted for clarity. [Symmetry code: (i) -x, 1-y, -z.]
	Fig. 2. The packing diagram of the title compound.
	Fig. 3. The structure of Hfcz, the distinct binding mode of the ligand and the title compound.

Bis[µ-2-(2,4-difluorophenyl)-1,3-bis(1H-1,2,4-triazol-1-yl)propan-2- olato]dicopper(II) bis(perchlorate)

Crystal data

[Cu2(C13H11F2N6O)2](ClO4)2	Dx = 1.778 Mg m^−3
Mr = 936.54	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnnm	Cell parameters from 3901 reflections
a = 15.4464 (18) Å	θ = 2.6–26.9°
b = 7.9532 (10) Å	µ = 1.46 mm^−1
c = 14.2407 (15) Å	T = 298 K
V = 1749.4 (4) Å^3	Block, blue
Z = 2	0.49 × 0.45 × 0.43 mm
F(000) = 940

Data collection

Bruker SMART 1000 diffractometer	1618 independent reflections
Radiation source: fine-focus sealed tube	1169 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
phi and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→18
Tmin = 0.534, Tmax = 0.572	k = −9→9
7867 measured reflections	l = −16→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0552P)^2 + 3.7317P] where P = (Fo^2 + 2Fc^2)/3
1618 reflections	(Δ/σ)max = 0.001
162 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.0000	0.5000	0.10491 (4)	0.0387 (3)
Cl1	0.0000	1.0000	0.1949 (2)	0.0786 (7)
F1	0.3498 (3)	0.3943 (7)	0.0000	0.112 (2)
F2	0.3994 (4)	0.9719 (7)	0.0000	0.110 (2)
N1	0.1704 (2)	0.4153 (4)	0.1725 (2)	0.0412 (8)
N2	0.0936 (2)	0.4883 (4)	0.1947 (2)	0.0394 (8)
N3	0.1944 (3)	0.5620 (5)	0.2995 (3)	0.0595 (11)
O1	0.0783 (2)	0.4823 (5)	0.0000	0.0339 (8)
O2	0.009 (3)	0.8525 (18)	0.126 (2)	0.097 (7)	0.58 (10)
O3	0.0787 (17)	1.020 (6)	0.232 (3)	0.110 (11)	0.58 (10)
O2'	0.047 (4)	0.884 (6)	0.151 (3)	0.106 (13)	0.42 (10)
O3'	0.055 (3)	1.093 (8)	0.261 (3)	0.109 (11)	0.42 (10)
C1	0.1119 (3)	0.5755 (6)	0.2716 (3)	0.0503 (11)
H1	0.0711	0.6402	0.3033	0.060*
C2	0.2285 (3)	0.4627 (6)	0.2355 (3)	0.0546 (12)
H2	0.2863	0.4298	0.2346	0.066*
C3	0.1787 (3)	0.3154 (5)	0.0873 (3)	0.0433 (10)
H3A	0.1359	0.2260	0.0878	0.052*
H3B	0.2357	0.2641	0.0853	0.052*
C4	0.1658 (3)	0.4248 (7)	0.0000	0.0352 (12)
C5	0.2277 (4)	0.5736 (7)	0.0000	0.0395 (13)
C6	0.3173 (4)	0.5544 (9)	0.0000	0.0640 (19)
C7	0.3745 (5)	0.6848 (12)	0.0000	0.079 (2)
H7	0.4339	0.6656	0.0000	0.095*
C8	0.3431 (5)	0.8399 (11)	0.0000	0.069 (2)
C9	0.2571 (5)	0.8714 (9)	0.0000	0.0640 (19)
H9	0.2369	0.9815	0.0000	0.077*
C10	0.1993 (4)	0.7384 (7)	0.0000	0.0448 (14)
H10	0.1402	0.7604	0.0000	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0307 (4)	0.0620 (5)	0.0232 (3)	−0.0056 (3)	0.000	0.000
Cl1	0.0398 (9)	0.0638 (12)	0.132 (2)	0.0021 (9)	0.000	0.000
F1	0.049 (3)	0.078 (3)	0.208 (7)	0.022 (2)	0.000	0.000
F2	0.115 (4)	0.105 (4)	0.111 (4)	−0.075 (3)	0.000	0.000
N1	0.0453 (19)	0.0394 (18)	0.0390 (18)	−0.0007 (16)	−0.0119 (15)	0.0017 (16)
N2	0.0415 (18)	0.049 (2)	0.0276 (16)	−0.0035 (16)	−0.0047 (14)	0.0001 (15)
N3	0.061 (2)	0.064 (3)	0.054 (2)	−0.004 (2)	−0.022 (2)	−0.012 (2)
O1	0.0277 (18)	0.047 (2)	0.0268 (18)	0.0006 (16)	0.000	0.000
O2	0.073 (13)	0.066 (6)	0.153 (12)	−0.002 (6)	0.008 (10)	−0.014 (6)
O3	0.068 (8)	0.101 (17)	0.162 (17)	0.005 (9)	−0.027 (9)	−0.003 (15)
O2'	0.08 (2)	0.087 (15)	0.152 (17)	0.024 (16)	0.009 (16)	−0.013 (13)
O3'	0.078 (14)	0.10 (2)	0.151 (15)	0.002 (14)	−0.022 (11)	−0.018 (13)
C1	0.054 (3)	0.056 (3)	0.041 (2)	0.000 (2)	−0.010 (2)	−0.006 (2)
C2	0.049 (3)	0.059 (3)	0.056 (3)	0.002 (2)	−0.021 (2)	−0.004 (2)
C3	0.051 (2)	0.036 (2)	0.042 (2)	0.0042 (19)	−0.007 (2)	0.0003 (18)
C4	0.031 (3)	0.033 (3)	0.041 (3)	0.000 (2)	0.000	0.000
C5	0.035 (3)	0.039 (3)	0.045 (3)	0.001 (3)	0.000	0.000
C6	0.047 (4)	0.059 (4)	0.086 (5)	0.000 (3)	0.000	0.000
C7	0.047 (4)	0.089 (7)	0.101 (7)	−0.015 (4)	0.000	0.000
C8	0.068 (5)	0.067 (5)	0.071 (5)	−0.036 (4)	0.000	0.000
C9	0.080 (5)	0.045 (4)	0.067 (5)	−0.010 (4)	0.000	0.000
C10	0.048 (3)	0.042 (3)	0.045 (3)	−0.002 (3)	0.000	0.000

Geometric parameters (Å, º)

Cu1—O1^i	1.927 (2)	N3—C1	1.340 (6)
Cu1—O1	1.927 (2)	O1—C4	1.427 (6)
Cu1—N2	1.933 (3)	O1—Cu1^i	1.927 (2)
Cu1—N2^ii	1.933 (3)	C1—H1	0.9300
Cu1—Cu1^i	2.9880 (13)	C2—H2	0.9300
Cl1—O2'	1.33 (2)	C3—C4	1.531 (5)
Cl1—O2'^iii	1.33 (2)	C3—H3A	0.9700
Cl1—O3^iii	1.336 (12)	C3—H3B	0.9700
Cl1—O3	1.336 (12)	C4—C5	1.522 (8)
Cl1—O3'	1.47 (3)	C4—C3^iv	1.531 (5)
Cl1—O3'^iii	1.47 (3)	C5—C10	1.382 (8)
Cl1—O2	1.53 (2)	C5—C6	1.392 (9)
Cl1—O2^iii	1.53 (2)	C6—C7	1.364 (10)
F1—C6	1.368 (9)	C7—C8	1.326 (12)
F2—C8	1.364 (8)	C7—H7	0.9300
N1—C2	1.324 (5)	C8—C9	1.352 (11)
N1—N2	1.358 (5)	C9—C10	1.383 (9)
N1—C3	1.456 (5)	C9—H9	0.9300
N2—C1	1.326 (5)	C10—H10	0.9300
N3—C2	1.316 (6)
O1^i—Cu1—O1	78.33 (16)	C1—N2—Cu1	132.8 (3)
O1^i—Cu1—N2	170.37 (12)	N1—N2—Cu1	121.3 (2)
O1—Cu1—N2	92.30 (13)	C2—N3—C1	102.9 (4)
O1^i—Cu1—N2^ii	92.30 (13)	C4—O1—Cu1^i	128.15 (10)
O1—Cu1—N2^ii	170.37 (12)	C4—O1—Cu1	128.15 (10)
N2—Cu1—N2^ii	97.2 (2)	Cu1^i—O1—Cu1	101.67 (16)
O1^i—Cu1—Cu1^i	39.16 (8)	N2—C1—N3	113.9 (4)
O1—Cu1—Cu1^i	39.16 (8)	N2—C1—H1	123.0
N2—Cu1—Cu1^i	131.42 (10)	N3—C1—H1	123.0
N2^ii—Cu1—Cu1^i	131.42 (10)	N3—C2—N1	111.7 (4)
O2'—Cl1—O2'^iii	124 (3)	N3—C2—H2	124.2
O2'—Cl1—O3^iii	127 (2)	N1—C2—H2	124.2
O2'^iii—Cl1—O3^iii	76.9 (12)	N1—C3—C4	110.8 (3)
O2'—Cl1—O3	76.9 (12)	N1—C3—H3A	109.5
O2'^iii—Cl1—O3	127 (2)	C4—C3—H3A	109.5
O3^iii—Cl1—O3	133 (4)	N1—C3—H3B	109.5
O2'—Cl1—O3'	110.0 (11)	C4—C3—H3B	109.5
O2'^iii—Cl1—O3'	105.2 (13)	H3A—C3—H3B	108.1
O3^iii—Cl1—O3'	109 (3)	O1—C4—C5	110.2 (4)
O3—Cl1—O3'	33.1 (6)	O1—C4—C3^iv	107.8 (3)
O2'—Cl1—O3'^iii	105.2 (13)	C5—C4—C3^iv	111.1 (3)
O2'^iii—Cl1—O3'^iii	110.0 (11)	O1—C4—C3	107.8 (3)
O3^iii—Cl1—O3'^iii	33.1 (6)	C5—C4—C3	111.1 (3)
O3—Cl1—O3'^iii	109 (3)	C3^iv—C4—C3	108.6 (4)
O3'—Cl1—O3'^iii	100 (2)	C10—C5—C6	114.8 (6)
O2'—Cl1—O2	28 (2)	C10—C5—C4	122.6 (5)
O2'^iii—Cl1—O2	106.2 (16)	C6—C5—C4	122.6 (6)
O3^iii—Cl1—O2	104.1 (11)	C7—C6—F1	118.0 (7)
O3—Cl1—O2	105.3 (11)	C7—C6—C5	124.1 (7)
O3'—Cl1—O2	138.4 (14)	F1—C6—C5	117.8 (6)
O3'^iii—Cl1—O2	94.2 (13)	C8—C7—C6	118.0 (7)
O2'—Cl1—O2^iii	106.2 (16)	C8—C7—H7	121.0
O2'^iii—Cl1—O2^iii	28 (2)	C6—C7—H7	121.0
O3^iii—Cl1—O2^iii	105.3 (11)	C7—C8—C9	122.2 (7)
O3—Cl1—O2^iii	104.1 (11)	C7—C8—F2	118.8 (8)
O3'—Cl1—O2^iii	94.2 (13)	C9—C8—F2	119.0 (8)
O3'^iii—Cl1—O2^iii	138.4 (14)	C8—C9—C10	119.5 (7)
O2—Cl1—O2^iii	101 (2)	C8—C9—H9	120.2
C2—N1—N2	108.2 (3)	C10—C9—H9	120.2
C2—N1—C3	131.3 (4)	C5—C10—C9	121.4 (6)
N2—N1—C3	120.3 (3)	C5—C10—H10	119.3
C1—N2—N1	103.3 (3)	C9—C10—H10	119.3
C2—N1—N2—C1	−0.3 (4)	Cu1—O1—C4—C5	−99.6 (3)
C3—N1—N2—C1	−176.2 (4)	Cu1^i—O1—C4—C3^iv	−21.8 (5)
C2—N1—N2—Cu1	163.9 (3)	Cu1—O1—C4—C3^iv	138.9 (3)
C3—N1—N2—Cu1	−12.0 (5)	Cu1^i—O1—C4—C3	−138.9 (3)
O1^i—Cu1—N2—C1	121.8 (9)	Cu1—O1—C4—C3	21.8 (5)
O1—Cu1—N2—C1	135.0 (4)	N1—C3—C4—O1	−65.7 (4)
N2^ii—Cu1—N2—C1	−46.9 (4)	N1—C3—C4—C5	55.2 (5)
Cu1^i—Cu1—N2—C1	133.1 (4)	N1—C3—C4—C3^iv	177.8 (2)
O1^i—Cu1—N2—N1	−37.0 (10)	O1—C4—C5—C10	0.0
O1—Cu1—N2—N1	−23.8 (3)	C3^iv—C4—C5—C10	119.5 (3)
N2^ii—Cu1—N2—N1	154.3 (3)	C3—C4—C5—C10	−119.5 (3)
Cu1^i—Cu1—N2—N1	−25.7 (3)	O1—C4—C5—C6	180.0
O1^i—Cu1—O1—C4	−164.6 (5)	C3^iv—C4—C5—C6	−60.5 (3)
N2—Cu1—O1—C4	17.6 (4)	C3—C4—C5—C6	60.5 (3)
N2^ii—Cu1—O1—C4	−151.2 (8)	C10—C5—C6—C7	0.0
Cu1^i—Cu1—O1—C4	−164.6 (5)	C4—C5—C6—C7	180.0
O1^i—Cu1—O1—Cu1^i	0.0	C10—C5—C6—F1	180.0
N2—Cu1—O1—Cu1^i	−177.77 (17)	C4—C5—C6—F1	0.0
N2^ii—Cu1—O1—Cu1^i	13.5 (10)	F1—C6—C7—C8	180.0
N1—N2—C1—N3	−0.3 (5)	C5—C6—C7—C8	0.0
Cu1—N2—C1—N3	−161.8 (3)	C6—C7—C8—C9	0.0
C2—N3—C1—N2	0.8 (6)	C6—C7—C8—F2	180.0
C1—N3—C2—N1	−0.9 (6)	C7—C8—C9—C10	0.0
N2—N1—C2—N3	0.8 (5)	F2—C8—C9—C10	180.0
C3—N1—C2—N3	176.1 (4)	C6—C5—C10—C9	0.0
C2—N1—C3—C4	−110.2 (5)	C4—C5—C10—C9	180.0
N2—N1—C3—C4	64.5 (5)	C8—C9—C10—C5	0.0
Cu1^i—O1—C4—C5	99.6 (3)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, z; (iii) −x, −y+2, z; (iv) x, y, −z.