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Acta Cryst. (2007). E63, m1995    [ doi:10.1107/S1600536807030449 ]

Di-[mu]-chlorido-bis[2,2'-(propane-1,3-diyl)bis(2H-benzotriazole)-[kappa]2N1,N1']copper(I)]

X.-L. Zhou, L.-P. Wang, X.-R. Meng and S. W. Ng

Abstract top

Cupric chloride undergoes reduction in its reaction with 2,2'-(propane-1,3-diyl)bis(2H-benzotriazole) to form the centrosymmetic title compound, [Cu2Cl2(C15H14N6)2]. The organic ligand chelates the CuI atom and two adducts are linked through two chloride bridges into a dinuclear molecule. The metal atom shows tetrahedral coordination.

Comment top

The 2,2'-(propane-1,3-diyl)bis(2H-benzotriazole) heterocycle binds to two copper(I) atoms in the 1:1 adduct with copper(I) chloride to furnish a linear chain structure. The copper atom shows tetrahedral coordination (Table 1) as is covalently bonded to one chlorine atom and datively bonded to the adjacent one (Borsting & Steel, 2004). The present compound is a 1:1 adduct but the compound exists as a monomeric dinculear molecule as the heterocycle functions instead as a bidentate chelate (Fig. 1). However, bond dimensions involving the copper atom are not significantly difference, so that the different architectures reflect the flexible nature of the ligand, which possess three methylene linkages separating the fused-rings.

Related literature top

For the isomeric chain structure, see Borsting & Steel (2004). For related literature, see: Xie et al. (2000).

Experimental top

A methanol solution (5 ml) of 2,2'-(propane-1,3-diyl)bis(2H-benzotriazole) (Xie et al., 2000) (55.6 mg, 0.2 mmol) was added to methanol solution (5 ml) of copper(II) dichloride dihydrate (17.1 mg, 0.1 mmol). The clear solution was set aside for a week for the growth of crystals. The yellow copper(I) chloride adduct is air stable.

Refinement top

The carbon-bound H atoms were placed in calculated positions [C—H = 0.93 to 0.97 Å], and were included in the refinement in the riding model approximation with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of (C15H14N6)2Cl2Cu2; displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radius. Symmetry code i: 1 – x, 1 – y, 1 – z.
Di-µ-chlorido-bis[2,2'-(propane-1,3-diyl)bis(2H-benzotriazole)-\ κ2N1,N1']copper(I)] top
Crystal data top
[Cu2Cl2(C15H14N6)2]F000 = 768
Mr = 754.62Dx = 1.655 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3803 reflections
a = 9.886 (3) Åθ = 2.1–27.9º
b = 10.055 (3) ŵ = 1.63 mm−1
c = 15.876 (4) ÅT = 295 (2) K
β = 106.401 (4)ºPrism, yellow
V = 1514.0 (7) Å30.23 × 0.20 × 0.19 mm
Z = 2
Data collection top
Rigaku Saturn
diffractometer		3592 independent reflections
Radiation source: fine-focus sealed tube3425 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 295(2) Kθmax = 27.9º
ω scansθmin = 2.8º
Absorption correction: Multi-scan
(CrystalClear; Rigaku/MSC, 2006)		h = −13→12
Tmin = 0.592, Tmax = 0.748k = −12→13
17855 measured reflectionsl = −20→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.104  w = 1/[σ2(Fo2) + (0.0602P)2 + 0.7057P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
3592 reflectionsΔρmax = 0.59 e Å−3
208 parametersΔρmin = −0.81 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2Cl2(C15H14N6)2]V = 1514.0 (7) Å3
Mr = 754.62Z = 2
Monoclinic, P21/nMo Kα
a = 9.886 (3) ŵ = 1.63 mm−1
b = 10.055 (3) ÅT = 295 (2) K
c = 15.876 (4) Å0.23 × 0.20 × 0.19 mm
β = 106.401 (4)º
Data collection top
Rigaku Saturn
diffractometer		3592 independent reflections
Absorption correction: Multi-scan
(CrystalClear; Rigaku/MSC, 2006)		3425 reflections with I > 2σ(I)
Tmin = 0.592, Tmax = 0.748Rint = 0.033
17855 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036208 parameters
wR(F2) = 0.104H-atom parameters constrained
S = 1.06Δρmax = 0.59 e Å−3
3592 reflectionsΔρmin = −0.81 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.37039 (3)0.44465 (3)0.431367 (18)0.04155 (11)
Cl10.53996 (5)0.58239 (5)0.40490 (3)0.03700 (13)
N10.16588 (17)0.50352 (17)0.40525 (10)0.0339 (3)
N20.06485 (18)0.42252 (17)0.41610 (11)0.0364 (4)
N3−0.06712 (19)0.4634 (2)0.38526 (13)0.0444 (4)
N40.38999 (18)0.25130 (16)0.39053 (11)0.0352 (3)
N50.29088 (18)0.16622 (17)0.34729 (10)0.0366 (3)
N60.3327 (2)0.04471 (17)0.33617 (13)0.0431 (4)
C10.0923 (2)0.6102 (2)0.36354 (12)0.0348 (4)
C20.1380 (2)0.7295 (2)0.33471 (13)0.0412 (4)
H20.23330.74810.34400.049*
C30.0357 (3)0.8171 (2)0.29235 (15)0.0504 (5)
H30.06230.89680.27190.060*
C4−0.1112 (3)0.7899 (3)0.27846 (16)0.0568 (6)
H4−0.17730.85170.24840.068*
C5−0.1564 (3)0.6767 (3)0.30800 (16)0.0537 (6)
H5−0.25180.66050.30020.064*
C6−0.0523 (2)0.5844 (2)0.35115 (14)0.0401 (4)
C70.0958 (2)0.2884 (2)0.45160 (13)0.0398 (4)
H7A0.04140.27030.49250.048*
H7B0.19510.28160.48320.048*
C80.0595 (2)0.1869 (2)0.37756 (14)0.0425 (4)
H8A−0.04020.19370.34710.051*
H8B0.07670.09840.40260.051*
C90.1437 (2)0.2046 (2)0.31134 (13)0.0398 (4)
H9A0.10140.15110.25980.048*
H9B0.13910.29700.29310.048*
C100.4737 (2)0.04905 (19)0.37568 (14)0.0390 (4)
C110.5774 (3)−0.0498 (2)0.38292 (17)0.0509 (6)
H110.5546−0.13540.36130.061*
C120.7128 (3)−0.0132 (3)0.42332 (16)0.0509 (5)
H120.7843−0.07540.42860.061*
C130.7485 (2)0.1159 (2)0.45750 (16)0.0474 (5)
H130.84250.13540.48500.057*
C140.6498 (2)0.2130 (2)0.45152 (15)0.0429 (4)
H140.67400.29780.47420.052*
C150.5096 (2)0.17771 (19)0.40924 (12)0.0348 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.03493 (17)0.03753 (17)0.04959 (18)−0.00308 (9)0.00770 (12)−0.00336 (10)
Cl10.0374 (2)0.0393 (2)0.0299 (2)−0.01079 (18)0.00249 (17)0.00473 (17)
N10.0309 (8)0.0358 (8)0.0344 (8)−0.0022 (6)0.0080 (6)−0.0020 (6)
N20.0313 (8)0.0411 (9)0.0367 (8)−0.0042 (7)0.0093 (6)−0.0022 (7)
N30.0321 (9)0.0526 (11)0.0486 (10)−0.0010 (8)0.0115 (8)−0.0040 (8)
N40.0374 (8)0.0316 (8)0.0344 (8)−0.0036 (6)0.0064 (6)−0.0065 (6)
N50.0399 (9)0.0339 (8)0.0335 (7)−0.0058 (7)0.0063 (6)−0.0061 (6)
N60.0503 (11)0.0310 (8)0.0444 (9)−0.0062 (7)0.0073 (8)−0.0058 (7)
C10.0350 (9)0.0379 (10)0.0295 (8)0.0014 (8)0.0060 (7)−0.0053 (7)
C20.0478 (11)0.0374 (10)0.0380 (10)0.0001 (9)0.0115 (8)−0.0031 (8)
C30.0694 (16)0.0388 (11)0.0416 (11)0.0080 (10)0.0134 (10)−0.0009 (9)
C40.0585 (14)0.0567 (14)0.0488 (12)0.0221 (12)0.0049 (11)−0.0015 (11)
C50.0389 (11)0.0632 (15)0.0533 (13)0.0137 (11)0.0038 (10)−0.0044 (11)
C60.0341 (10)0.0472 (11)0.0374 (10)0.0032 (8)0.0077 (8)−0.0065 (8)
C70.0425 (11)0.0401 (10)0.0370 (9)−0.0067 (8)0.0114 (8)0.0033 (8)
C80.0383 (10)0.0421 (11)0.0445 (10)−0.0086 (9)0.0076 (8)−0.0023 (9)
C90.0382 (10)0.0445 (11)0.0317 (9)−0.0064 (8)0.0019 (7)−0.0062 (8)
C100.0486 (12)0.0297 (9)0.0366 (9)−0.0023 (8)0.0088 (8)−0.0011 (7)
C110.0640 (15)0.0319 (10)0.0518 (13)0.0067 (10)0.0082 (11)−0.0037 (9)
C120.0564 (14)0.0431 (12)0.0510 (12)0.0149 (11)0.0112 (11)0.0020 (10)
C130.0411 (11)0.0490 (13)0.0496 (12)0.0023 (10)0.0086 (9)−0.0012 (10)
C140.0416 (11)0.0369 (10)0.0471 (11)−0.0024 (8)0.0073 (9)−0.0069 (8)
C150.0403 (10)0.0323 (9)0.0314 (8)−0.0011 (8)0.0093 (7)−0.0026 (7)
Geometric parameters (Å, °) top
Cu1—N12.034 (2)C4—H40.9300
Cu1—N42.076 (2)C5—C61.411 (3)
Cu1—Cl12.3028 (7)C5—H50.9300
Cu1—Cl1i2.5131 (8)C7—C81.521 (3)
Cl1—Cu1i2.5131 (8)C7—H7A0.9700
N1—N21.337 (2)C7—H7B0.9700
N1—C11.359 (3)C8—C91.524 (3)
N2—N31.323 (3)C8—H8A0.9700
N2—C71.460 (3)C8—H8B0.9700
N3—C61.356 (3)C9—H9A0.9700
N4—N51.335 (2)C9—H9B0.9700
N4—C151.355 (3)C10—C151.406 (3)
N5—N61.318 (2)C10—C111.409 (3)
N5—C91.457 (3)C11—C121.361 (4)
N6—C101.358 (3)C11—H110.9300
C1—C21.404 (3)C12—C131.413 (4)
C1—C61.411 (3)C12—H120.9300
C2—C31.366 (3)C13—C141.365 (3)
C2—H20.9300C13—H130.9300
C3—C41.433 (4)C14—C151.405 (3)
C3—H30.9300C14—H140.9300
C4—C51.354 (4)
N1—Cu1—N4112.58 (7)C1—C6—C5121.2 (2)
N1—Cu1—Cl1121.38 (5)N2—C7—C8110.08 (17)
N1—Cu1—Cl1i106.40 (5)N2—C7—H7A109.6
N4—Cu1—Cl1111.68 (5)C8—C7—H7A109.6
N4—Cu1—Cl1i100.66 (5)N2—C7—H7B109.6
Cl1—Cu1—Cl1i101.04 (2)C8—C7—H7B109.6
Cu1—Cl1—Cu1i78.957 (19)H7A—C7—H7B108.2
N2—N1—C1103.12 (16)C7—C8—C9113.52 (17)
N2—N1—Cu1122.15 (13)C7—C8—H8A108.9
C1—N1—Cu1133.93 (14)C9—C8—H8A108.9
N3—N2—N1117.21 (17)C7—C8—H8B108.9
N3—N2—C7120.49 (17)C9—C8—H8B108.9
N1—N2—C7121.96 (17)H8A—C8—H8B107.7
N2—N3—C6102.74 (17)N5—C9—C8112.22 (17)
N5—N4—C15103.35 (16)N5—C9—H9A109.2
N5—N4—Cu1129.87 (13)C8—C9—H9A109.2
C15—N4—Cu1126.57 (13)N5—C9—H9B109.2
N6—N5—N4116.77 (17)C8—C9—H9B109.2
N6—N5—C9120.65 (17)H9A—C9—H9B107.9
N4—N5—C9122.56 (17)N6—C10—C15108.71 (18)
N5—N6—C10103.20 (16)N6—C10—C11130.0 (2)
N1—C1—C2131.01 (19)C15—C10—C11121.2 (2)
N1—C1—C6107.76 (18)C12—C11—C10116.3 (2)
C2—C1—C6121.2 (2)C12—C11—H11121.9
C3—C2—C1116.7 (2)C10—C11—H11121.9
C3—C2—H2121.6C11—C12—C13122.4 (2)
C1—C2—H2121.6C11—C12—H12118.8
C2—C3—C4122.0 (2)C13—C12—H12118.8
C2—C3—H3119.0C14—C13—C12122.3 (2)
C4—C3—H3119.0C14—C13—H13118.8
C5—C4—C3121.8 (2)C12—C13—H13118.8
C5—C4—H4119.1C13—C14—C15116.2 (2)
C3—C4—H4119.1C13—C14—H14121.9
C4—C5—C6117.0 (2)C15—C14—H14121.9
C4—C5—H5121.5N4—C15—C14130.47 (19)
C6—C5—H5121.5N4—C15—C10107.97 (18)
N3—C6—C1109.17 (19)C14—C15—C10121.54 (19)
N3—C6—C5129.6 (2)
N1—Cu1—Cl1—Cu1i117.13 (6)C2—C3—C4—C51.1 (4)
N4—Cu1—Cl1—Cu1i−106.28 (5)C3—C4—C5—C6−1.7 (4)
Cl1i—Cu1—Cl1—Cu1i0.0N2—N3—C6—C10.2 (2)
N4—Cu1—N1—N240.36 (16)N2—N3—C6—C5179.3 (2)
Cl1—Cu1—N1—N2176.60 (12)N1—C1—C6—N30.3 (2)
Cl1i—Cu1—N1—N2−68.98 (14)C2—C1—C6—N3−179.66 (18)
N4—Cu1—N1—C1−127.53 (17)N1—C1—C6—C5−178.99 (19)
Cl1—Cu1—N1—C18.7 (2)C2—C1—C6—C51.1 (3)
Cl1i—Cu1—N1—C1123.13 (17)C4—C5—C6—N3−178.5 (2)
C1—N1—N2—N30.7 (2)C4—C5—C6—C10.6 (3)
Cu1—N1—N2—N3−170.33 (14)N3—N2—C7—C872.4 (2)
C1—N1—N2—C7174.18 (17)N1—N2—C7—C8−100.8 (2)
Cu1—N1—N2—C73.1 (2)N2—C7—C8—C961.2 (2)
N1—N2—N3—C6−0.6 (2)N6—N5—C9—C893.2 (2)
C7—N2—N3—C6−174.12 (18)N4—N5—C9—C8−88.6 (2)
N1—Cu1—N4—N53.63 (19)C7—C8—C9—N571.6 (2)
Cl1—Cu1—N4—N5−136.92 (15)N5—N6—C10—C15−0.1 (2)
Cl1i—Cu1—N4—N5116.54 (16)N5—N6—C10—C11−177.7 (2)
N1—Cu1—N4—C15−170.15 (15)N6—C10—C11—C12176.9 (2)
Cl1—Cu1—N4—C1549.30 (17)C15—C10—C11—C12−0.5 (3)
Cl1i—Cu1—N4—C15−57.23 (16)C10—C11—C12—C130.9 (4)
C15—N4—N5—N60.4 (2)C11—C12—C13—C14−0.7 (4)
Cu1—N4—N5—N6−174.49 (14)C12—C13—C14—C150.0 (4)
C15—N4—N5—C9−177.89 (17)N5—N4—C15—C14177.8 (2)
Cu1—N4—N5—C97.2 (3)Cu1—N4—C15—C14−7.1 (3)
N4—N5—N6—C10−0.2 (2)N5—N4—C15—C10−0.4 (2)
C9—N5—N6—C10178.15 (17)Cu1—N4—C15—C10174.66 (13)
N2—N1—C1—C2179.3 (2)C13—C14—C15—N4−177.6 (2)
Cu1—N1—C1—C2−11.2 (3)C13—C14—C15—C100.4 (3)
N2—N1—C1—C6−0.6 (2)N6—C10—C15—N40.4 (2)
Cu1—N1—C1—C6168.93 (14)C11—C10—C15—N4178.2 (2)
N1—C1—C2—C3178.5 (2)N6—C10—C15—C14−178.04 (19)
C6—C1—C2—C3−1.7 (3)C11—C10—C15—C14−0.2 (3)
C1—C2—C3—C40.6 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N12.034 (2)Cu1—Cl12.3028 (7)
Cu1—N42.076 (2)Cu1—Cl1i2.5131 (8)
N1—Cu1—N4112.58 (7)N4—Cu1—Cl1111.68 (5)
N1—Cu1—Cl1121.38 (5)N4—Cu1—Cl1i100.66 (5)
N1—Cu1—Cl1i106.40 (5)Cl1—Cu1—Cl1i101.04 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

The authors thank the Education Department of Henan Province, China (grant No. 2006150035), Zhengzhou University, China, and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Borsting, P. & Steel, P. J. (2004). Eur. J. Inorg. Chem. pp. 376–380.

Rigaku/MSC (2006). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Westrip, S. P. (2007). PublCIF. In preparation.

Xie, X.-J., Cheng, L., Zheng, A.-H. & Yang, Y.-L. (2000). Chin. J. Synth. Chem. 8, 252–255.