Bromido(meso-5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-1,7-diene)copper(II) bromide dihydrate

Fei-Fei Shi; Xiu-Li He

doi:10.1107/S1600536811012852

. 2011 Apr 16;67(Pt 5):m607. doi: 10.1107/S1600536811012852

Bromido(meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-1,7-diene)copper(II) bromide dihydrate

Fei-Fei Shi ^a,^*, Xiu-Li He ^a

PMCID: PMC3089360 PMID: 21754325

Abstract

There are two formula units (Z′ = 2) in the asymmmetric unit of the title compound, [CuBr(C₁₆H₃₂N₄)]Br·2H₂O. The title crystal consists of two [Cu(C₁₆H₃₂N₄)]²⁺ cations, two Br⁻ anions and four uncoordinated water molecules. The metal atom is five-coordinate square pyramidal, with a long apical Cu—Br bond [2.9734 (11) and 2.9229 (11) Å in the two cations]. The two cations form a loosely associated dimer through the formation of hydrogen bonds between both N—H and O—H and Br⁻. In addition, there is a network of N—H⋯Br, O—H⋯Br and N—H⋯O hydrogen bonds, leading to the formation of a chain structure.

Related literature

For the structure of the ligand, see: Maurya et al. (1991 ▶); Spirlet et al. (1991 ▶). For related macrocyclic complexes, see: Szalda et al. (1989 ▶); Tebbe et al. (1985 ▶); Whimp et al. (1970 ▶) For a description of the geometry of complexes with five-coordnate metal atoms, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[CuBr(C₁₆H₃₂N₄)]Br·2H₂O
M _r = 539.85
Monoclinic,
a = 17.8747 (16) Å
b = 15.5118 (13) Å
c = 17.2528 (19) Å
β = 112.073 (1)°
V = 4433.0 (7) Å³
Z = 8
Mo Kα radiation
μ = 4.61 mm⁻¹
T = 298 K
0.47 × 0.42 × 0.32 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.221, T _max = 0.320
7814 measured reflections
7814 independent reflections
3668 reflections with I > 2σ(I)
R _int = 0.1005

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.099
S = 0.87
7814 reflections
487 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012852/bv2173sup1.cif

e-67-0m607-sup1.cif^{(36KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012852/bv2173Isup2.hkl

e-67-0m607-Isup2.hkl^{(382.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯Br1	0.82 (2)	2.46 (2)	3.274 (5)	173 (8)
O1W—H1W2⋯Br2	0.83 (2)	2.58 (3)	3.395 (6)	170 (7)
O2W—H2W1⋯Br2	0.80 (2)	2.61 (8)	3.238 (6)	136 (9)
O2W—H2W2⋯Br1	0.81 (2)	2.53 (3)	3.328 (7)	168 (10)
O3W—H3W1⋯Br4	0.81 (2)	2.62 (3)	3.417 (6)	169 (10)
O3W—H3W2⋯Br3	0.80 (2)	2.61 (4)	3.362 (6)	156 (8)
O4W—H4W1⋯Br3	0.81 (2)	2.66 (2)	3.461 (6)	170 (8)
O4W—H4W2⋯Br4	0.81 (2)	2.58 (4)	3.327 (5)	155 (7)
N1—H1⋯O1W	0.91	2.44	3.317 (8)	161
N1—H1⋯Br1	0.91	2.99	3.519 (5)	119
N3—H3⋯Br3ⁱ	0.91	2.57	3.457 (5)	166
N5—H5⋯Br4	0.91	2.53	3.432 (5)	170
N7—H7⋯O2W	0.91	2.40	3.257 (9)	158
N7—H7⋯Br2	0.91	3.14	3.612 (5)	115

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

The structures of several related macrocyclic complexes have been reported (Whimp et al., 1970; Tebbe et al., 1985). The unsubstituted parent compound exists in the zwitterionic form (Maurya et al., 1991; Spirlet et al., 1991). The copper teraazamacrocyclic complex cation, [Cu(C₁₆H₃₂N₄ Br)]+, can combine with different anions to form many kinds of structures.

The title compound, [Cu(C₁₆H₃₂N₄Br)]Br^.2H₂O, was synthesized by reaction of CuSO₄^.5H₂O and the complex C₁₈H₃₂N₄^.2HBr^.2H₂O in methanol solution. The two similar macrocycles are linked via N—H···O (water) and O—H···Br hydrogen bonds to form a loosely associated dimer (see Fig. 1). One of the macrocycle units is further associated with the remaining Br anions and water solvent molecules. In the two macrocyclic cations each Cu is square pyramidal five coordinate [τ = 0.07 and 0.11, respectively (Addison et al. 1984)] with long Cu—Br bonds [Cu(1)—Br(1), 2.9734 (11); Cu(2)—Br(2), 2.9229 (11)]. The six-membered rings contain double bonds between N(4)—C(4) and N(2)—C(10); N(6)—C(26) and N(8)—C(20) [distances of 1.273 (7) Å and 1.279 (7) Å in molecule 1 and 1.282 (7) and 1.287 (7) Å in molecule 2, respectively]. The average Cu—N(amine) and Cu—N(imine) bond distances are similar to those found previously (Szalda et al., 1989). The Cu and 4 N atoms are coplanar (r.m.s. average deviation of 0.06 Å). The dihedral "fold" angle between the planes formed by N1, N2, N3 and N1, N4, N3 is 4.39 (2)°. In the crystal structure, the cations, anions and water molecules are linked via intermolecular N—H···Br, O— H···Br and N—H···O hydrogen bonds forming discrete chains, and the structure is stabilized by intramolecular hydrogen bonds. (see Fig. 2).

Experimental

All chemicals were of reagent grade and were used as received with out further purification. The precursor complex C₁₈H₃₂N₄^.2HBr^.2H₂O was prepared previously. To a 10 ml me thanol solution of CuSO₄^.5H₂O (0.2 mmol,0.087 g), a 5 ml me thanol solution of C₁₈H₃₂N₄^.2HBr^.2H₂O (0.2 mmol, 0.0957 g) was added dropwise with stirring. The resulting solution was continuously stirred for about 30 min. Purple crystals suitable for X-ray analysis were obtained by slow evaporation at room temperature over several days.