Di-μ-chlorido-1:2κ2Cl,2:3κ2Cl-tetra­chlorido-1κCl,2κ2Cl,3κCl-bis­[N,N′′-bis­(2-furylmethylene)diethyl­ene­triamine]-1κ3N,N′,N′′;3κ3N,N′,N′′-tricopper(II)

Wang, Q.; Wang, D.-Q.; Sun, Y.-Y.

doi:10.1107/S1600536807056838

Buy article online - an online subscription or single-article purchase is required to access this article.

Di-μ-chlorido-1:2κ²Cl,2:3κ²Cl-tetrachlorido-1κCl,2κ²Cl,3κCl-bis[N,N′′-bis(2-furylmethylene)diethylenetriamine]-1κ³N,N′,N′′;3κ³N,N′,N′′-tricopper(II)

Q. Wang, D.-Q. Wang and Y.-Y. Sun

The complete title trinuclear Cu^II complex, [Cu₃Cl₆(C₁₄H₁₆N₃O₂)₂], is generated by twofold symmetry with one Cu atom lying on the rotation axis. The central Cu atom adopts a distorted tetrahedral CuCl₄ geometry. The terminal Cu atom is five-coordinated in a distorted square-pyramidal coordination environment consisting of three N atoms of the ligand, one bridging Cl atom and one terminal Cl atom. Intermolecular C—H

Cl hydrogen bonds help to establish the packing.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056838/hb2633sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056838/hb2633Isup2.hkl Contains datablock I

CCDC reference: 672656

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.008 Å
R factor = 0.047
wR factor = 0.088
Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT128_ALERT_4_C Non-standard setting of Space group P2/c    ....    P2/n
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cu2
PLAT324_ALERT_2_C Check for Possibly Missing H on Coordinating....         N2
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.04
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu2         (2)       2.02

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

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

Comment top

Transition metals complexed with multidentate Schiff base ligands result in homo and/or heteronuclear metal complexes with insteresting stereochemistry (e.g. Erxleben et al., 2001). Such species can be used as biological models, catalysis, and molecular ferromagnets (Mukherjee et al., 2002). The Schiff base N,N'-bis(2-furylmethylene)diethylenetriamine is considered to be a good chelating ligand, which can coordinate to transition metals as a tridentate, tetradentate or pentadentate ligand, with consequent variable chemical properties. We report here the synthesis and crystal structure of the title compound, (I), a new copper(II) complex, with a multidentate Schiff base ligand derived from the condensation of 2-furaldehyde and diethylenetriamine.

The complete molecule of (I) (Fig. 1) is generated by 2-fold symmetry. The terminal Cu1 atom is five-coordinated in a distorted square-pyramidal coordination environment consisting of three N atoms of the ligand, one bridging Cl atom and one terminal Cl atom. Cu2 (site symmetry 2) is tetrahedrally coordinated by two bridging Cl atoms and two terminal Cl atoms (Table 1). The two five-membered rings Cu1—N1—C11—C12—N2 and Cu1—N2—C13—C14—N3 form a dihedral angle of 5.7 (3)°, and the dihedral angle between the mean planes of the furan rings is 25.7 (3) °. The Cu1···Cu2 separation is 4.6059 (9) Å.

In the crystal, intermolecular C—H···Cl hydrogen bonds lead to a three-dimensional network (Table 2).

Related literature top

For background, see: Erxleben et al. (2001); Mukherjee et al. (2002).

Experimental top

2-Furaldehyde (4 mmol, 384.4 mg) was added dropwise to a dichloromethane (20 ml) solution of diethylenetriamine (2 mmol, 206.4 mg). The mixture was heated under reflux with stirring for 1.5 h. An absolute ethanol solution (5 ml) of cupric chloride dihydrate (3 mmol, 511.4 mg) was then added dropwise, and the mixture was stirred at room temperature for another 15 h. The solution was filtered off, the filterate was kept at room temperature for about 12 days, after which large pale blue blocks of (I) were obtained.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. Atoms labelled with the suffix A are generated by the symmetry operation (-x + 1/2, y, -z + 3/2). H atoms have been omitted for clarity.

Di-µ-chlorido-1:2κ²Cl,2:3κ²Cl-tetrachlorido-1κCl,2κ²Cl,3κCl- bis[N,N''-bis(2-furylmethylene)diethylenetriamine]- 1κ³N,N',N'';3κ³N,N',N''-tricopper(II) top

Crystal data top

[Cu₃Cl₆(C₁₄H₁₆N₃O₂)₂]	F(000) = 926
M_r = 919.92	D_x = 1.676 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 1576 reflections
a = 10.9456 (15) Å	θ = 2.9–20.0°
b = 7.5287 (10) Å	µ = 2.22 mm⁻¹
c = 22.248 (2) Å	T = 298 K
β = 96.048 (2)°	Block, pale blue
V = 1823.1 (4) Å³	0.26 × 0.14 × 0.05 mm
Z = 2

Data collection top

Siemens SMART CCD diffractometer	3200 independent reflections
Radiation source: fine-focus sealed tube	1749 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→13
T_min = 0.597, T_max = 0.897	k = −6→8
8801 measured reflections	l = −21→26

Refinement top

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0225P)²] where P = (F_o² + 2F_c²)/3
3200 reflections	(Δ/σ)_max = 0.002
213 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Cu₃Cl₆(C₁₄H₁₆N₃O₂)₂]	V = 1823.1 (4) Å³
M_r = 919.92	Z = 2
Monoclinic, P2/n	Mo Kα radiation
a = 10.9456 (15) Å	µ = 2.22 mm⁻¹
b = 7.5287 (10) Å	T = 298 K
c = 22.248 (2) Å	0.26 × 0.14 × 0.05 mm
β = 96.048 (2)°

Data collection top

Siemens SMART CCD diffractometer	3200 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1749 reflections with I > 2σ(I)
T_min = 0.597, T_max = 0.897	R_int = 0.066
8801 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 0.99	Δρ_max = 0.64 e Å⁻³
3200 reflections	Δρ_min = −0.42 e Å⁻³
213 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C13	0.4074 (5)	−0.2812 (7)	0.6330 (2)	0.0646 (16)
H13A	0.3969	−0.3504	0.6689	0.077*
H13B	0.4537	−0.3517	0.6068	0.077*
Cu1	0.45072 (5)	0.05268 (9)	0.58051 (3)	0.0527 (2)
Cu2	0.2500	0.13781 (14)	0.7500	0.0624 (3)
Cl1	0.42526 (12)	0.2454 (2)	0.50298 (6)	0.0691 (5)
Cl2	0.32170 (13)	0.2627 (2)	0.66945 (6)	0.0689 (4)
Cl3	0.07882 (15)	−0.0122 (2)	0.71301 (7)	0.0956 (6)
C11	0.6627 (5)	0.0402 (8)	0.6707 (2)	0.0605 (16)
H11A	0.6451	0.0961	0.7082	0.073*
H11B	0.7511	0.0297	0.6711	0.073*
C7	0.1142 (5)	−0.1623 (8)	0.4910 (2)	0.0537 (15)
C2	0.7637 (5)	0.3940 (8)	0.6357 (3)	0.0523 (15)
O2	0.0691 (3)	−0.1249 (5)	0.43235 (18)	0.0719 (12)
O1	0.8276 (4)	0.3279 (6)	0.68845 (18)	0.0753 (12)
C6	0.2281 (5)	−0.0728 (7)	0.5094 (2)	0.0513 (14)
H6	0.2500	0.0148	0.4831	0.062*
C1	0.6602 (5)	0.2975 (8)	0.6072 (2)	0.0528 (15)
H1	0.6204	0.3552	0.5737	0.063*
C5	0.9170 (6)	0.4454 (11)	0.7032 (3)	0.086 (2)
H5	0.9746	0.4347	0.7369	0.104*
C14	0.2835 (5)	−0.2341 (7)	0.6005 (2)	0.0596 (15)
H14A	0.2462	−0.3378	0.5802	0.071*
H14B	0.2292	−0.1911	0.6291	0.071*
C3	0.8128 (5)	0.5445 (8)	0.6198 (2)	0.0615 (16)
H3	0.7868	0.6141	0.5864	0.074*
C8	0.0327 (5)	−0.2627 (8)	0.5169 (3)	0.0640 (16)
H8	0.0412	−0.3054	0.5564	0.077*
C9	−0.0679 (6)	−0.2912 (9)	0.4730 (3)	0.078 (2)
H9	−0.1392	−0.3544	0.4779	0.093*
C4	0.9142 (6)	0.5794 (10)	0.6643 (3)	0.085 (2)
H4	0.9673	0.6761	0.6657	0.101*
C10	−0.0405 (6)	−0.2098 (9)	0.4234 (3)	0.074 (2)
H10	−0.0904	−0.2108	0.3869	0.088*
N1	0.6121 (3)	0.1490 (6)	0.61850 (17)	0.0478 (11)
N3	0.3035 (4)	−0.0958 (6)	0.55647 (19)	0.0488 (12)
N2	0.4730 (4)	−0.1175 (6)	0.64975 (17)	0.0529 (12)
C12	0.6046 (5)	−0.1397 (8)	0.6653 (2)	0.0672 (17)
H12A	0.6392	−0.2077	0.6341	0.081*
H12B	0.6202	−0.2033	0.7032	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C13	0.077 (4)	0.051 (4)	0.066 (4)	0.003 (3)	0.006 (3)	0.012 (3)
Cu1	0.0446 (4)	0.0592 (5)	0.0538 (4)	−0.0022 (4)	0.0024 (3)	0.0115 (4)
Cu2	0.0607 (7)	0.0705 (8)	0.0559 (6)	0.000	0.0051 (5)	0.000
Cl1	0.0545 (9)	0.0818 (12)	0.0691 (10)	−0.0113 (8)	−0.0027 (7)	0.0301 (8)
Cl2	0.0692 (10)	0.0623 (11)	0.0764 (10)	−0.0040 (8)	0.0138 (8)	0.0099 (8)
Cl3	0.0959 (13)	0.1257 (18)	0.0656 (11)	−0.0453 (12)	0.0108 (9)	−0.0127 (10)
C11	0.055 (4)	0.067 (5)	0.057 (4)	0.002 (3)	−0.005 (3)	0.013 (3)
C7	0.050 (4)	0.056 (4)	0.054 (4)	0.007 (3)	−0.003 (3)	−0.011 (3)
C2	0.043 (3)	0.058 (5)	0.057 (4)	0.002 (3)	0.008 (3)	−0.003 (3)
O2	0.057 (3)	0.088 (3)	0.069 (3)	0.002 (2)	−0.003 (2)	−0.007 (2)
O1	0.066 (3)	0.083 (4)	0.075 (3)	−0.008 (3)	−0.003 (2)	−0.007 (2)
C6	0.050 (3)	0.050 (4)	0.056 (4)	0.005 (3)	0.014 (3)	−0.005 (3)
C1	0.045 (4)	0.065 (5)	0.049 (3)	0.015 (3)	0.010 (3)	0.002 (3)
C5	0.070 (5)	0.102 (7)	0.084 (5)	−0.019 (5)	−0.004 (4)	−0.020 (5)
C14	0.063 (4)	0.054 (4)	0.061 (4)	−0.009 (3)	0.005 (3)	0.000 (3)
C3	0.058 (4)	0.056 (4)	0.073 (4)	−0.001 (4)	0.014 (3)	0.002 (3)
C8	0.056 (4)	0.065 (5)	0.071 (4)	−0.012 (3)	0.008 (3)	−0.004 (3)
C9	0.052 (4)	0.066 (5)	0.115 (6)	−0.005 (3)	0.003 (4)	−0.017 (4)
C4	0.064 (4)	0.075 (6)	0.117 (6)	−0.029 (4)	0.023 (4)	−0.033 (5)
C10	0.051 (4)	0.078 (6)	0.087 (5)	0.011 (4)	−0.013 (4)	−0.033 (4)
N1	0.043 (3)	0.057 (3)	0.044 (3)	0.005 (2)	0.006 (2)	0.008 (2)
N3	0.049 (3)	0.048 (3)	0.052 (3)	−0.001 (2)	0.013 (2)	0.001 (2)
N2	0.053 (3)	0.048 (3)	0.055 (3)	−0.008 (2)	−0.009 (2)	0.009 (2)
C12	0.080 (5)	0.052 (5)	0.069 (4)	0.010 (4)	0.004 (3)	0.014 (3)

Geometric parameters (Å, º) top

C13—N2	1.455 (6)	O2—C10	1.356 (6)
C13—C14	1.510 (6)	O1—C5	1.334 (7)
C13—H13A	0.9700	C6—N3	1.274 (5)
C13—H13B	0.9700	C6—H6	0.9300
Cu1—N3	1.988 (4)	C1—N1	1.273 (6)
Cu1—N2	1.999 (4)	C1—H1	0.9300
Cu1—N1	2.011 (4)	C5—C4	1.327 (8)
Cu1—Cl1	2.2489 (15)	C5—H5	0.9300
Cu1—Cl2	2.9998 (16)	C14—N3	1.462 (6)
Cu2—Cl2	2.2379 (14)	C14—H14A	0.9700
Cu2—Cl2ⁱ	2.2379 (14)	C14—H14B	0.9700
Cu2—Cl3	2.2668 (16)	C3—C4	1.432 (7)
Cu2—Cl3ⁱ	2.2668 (16)	C3—H3	0.9300
C11—N1	1.481 (6)	C8—C9	1.409 (7)
C11—C12	1.495 (7)	C8—H8	0.9300
C11—H11A	0.9700	C9—C10	1.324 (8)
C11—H11B	0.9700	C9—H9	0.9300
C7—C8	1.344 (7)	C4—H4	0.9300
C7—O2	1.376 (5)	C10—H10	0.9300
C7—C6	1.439 (7)	N2—C12	1.455 (6)
C2—C3	1.318 (7)	C12—H12A	0.9700
C2—O1	1.393 (6)	C12—H12B	0.9700
C2—C1	1.436 (7)

N2—C13—C14	108.6 (4)	C2—C1—H1	113.6
N2—C13—H13A	110.0	C4—C5—O1	112.2 (6)
C14—C13—H13A	110.0	C4—C5—H5	123.9
N2—C13—H13B	110.0	O1—C5—H5	123.9
C14—C13—H13B	110.0	N3—C14—C13	107.3 (4)
H13A—C13—H13B	108.4	N3—C14—H14A	110.3
N3—Cu1—N2	82.91 (18)	C13—C14—H14A	110.3
N3—Cu1—N1	165.25 (18)	N3—C14—H14B	110.3
N2—Cu1—N1	82.92 (17)	C13—C14—H14B	110.3
N3—Cu1—Cl1	97.19 (13)	H14A—C14—H14B	108.5
N2—Cu1—Cl1	179.66 (14)	C2—C3—C4	106.3 (6)
N1—Cu1—Cl1	97.01 (13)	C2—C3—H3	126.9
N1—Cu1—Cl2	89.22 (12)	C4—C3—H3	126.9
N2—Cu1—Cl2	81.79 (13)	C7—C8—C9	107.1 (6)
N3—Cu1—Cl2	92.83 (13)	C7—C8—H8	126.4
Cl1—Cu1—Cl2	97.87 (5)	C9—C8—H8	126.4
Cl2—Cu2—Cl2ⁱ	130.30 (9)	C10—C9—C8	106.2 (6)
Cl2—Cu2—Cl3	105.36 (5)	C10—C9—H9	126.9
Cl2ⁱ—Cu2—Cl3	98.85 (6)	C8—C9—H9	126.9
Cl2—Cu2—Cl3ⁱ	98.85 (5)	C5—C4—C3	105.9 (6)
Cl2ⁱ—Cu2—Cl3ⁱ	105.36 (5)	C5—C4—H4	127.1
Cl3—Cu2—Cl3ⁱ	120.23 (11)	C3—C4—H4	127.1
N1—C11—C12	108.5 (4)	C9—C10—O2	111.7 (6)
N1—C11—H11A	110.0	C9—C10—H10	124.1
C12—C11—H11A	110.0	O2—C10—H10	124.1
N1—C11—H11B	110.0	C1—N1—C11	120.9 (5)
C12—C11—H11B	110.0	C1—N1—Cu1	126.7 (4)
H11A—C11—H11B	108.4	C11—N1—Cu1	111.7 (3)
C8—C7—O2	109.5 (5)	C6—N3—C14	121.2 (4)
C8—C7—C6	137.4 (6)	C6—N3—Cu1	125.5 (4)
O2—C7—C6	112.8 (5)	C14—N3—Cu1	113.2 (3)
C3—C2—O1	110.5 (5)	C12—N2—C13	114.4 (5)
C3—C2—C1	129.9 (6)	C12—N2—Cu1	107.1 (3)
O1—C2—C1	119.6 (5)	C13—N2—Cu1	109.2 (3)
C10—O2—C7	105.5 (5)	N2—C12—C11	108.5 (5)
C5—O1—C2	105.1 (5)	N2—C12—H12A	110.0
N3—C6—C7	129.5 (5)	C11—C12—H12A	110.0
N3—C6—H6	115.2	N2—C12—H12B	110.0
C7—C6—H6	115.2	C11—C12—H12B	110.0
N1—C1—C2	132.9 (5)	H12A—C12—H12B	108.4
N1—C1—H1	113.6

Symmetry code: (i) −x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cl3ⁱⁱ	0.93	2.80	3.669 (7)	156
C10—H10···Cl3ⁱⁱⁱ	0.93	2.80	3.451 (8)	128

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

Experimental details

Crystal data
Chemical formula	[Cu₃Cl₆(C₁₄H₁₆N₃O₂)₂]
M_r	919.92
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	298
a, b, c (Å)	10.9456 (15), 7.5287 (10), 22.248 (2)
β (°)	96.048 (2)
V (Å³)	1823.1 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.22
Crystal size (mm)	0.26 × 0.14 × 0.05

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.597, 0.897
No. of measured, independent and observed [I > 2σ(I)] reflections	8801, 3200, 1749
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.088, 0.99
No. of reflections	3200
No. of parameters	213
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.42

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Selected bond lengths (Å) top

Cu1—N3	1.988 (4)	Cu1—Cl2	2.9998 (16)
Cu1—N2	1.999 (4)	Cu2—Cl2	2.2379 (14)
Cu1—N1	2.011 (4)	Cu2—Cl3	2.2668 (16)
Cu1—Cl1	2.2489 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cl3ⁱ	0.93	2.80	3.669 (7)	156
C10—H10···Cl3ⁱⁱ	0.93	2.80	3.451 (8)	128

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

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.

E-mail address*
Repeat e-mail address* (for error checking)

Format*	PDF (US $40)
	HTML (US $40)
	PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number (non-UK EC countries only)
Country*

Terms and conditions of use
Contact us

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page