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Acta Cryst. (2011). E67, 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

F.-F. Shi and X.-L. He

Abstract top

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.

Comment top

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).

Related literature top

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-coordinate metal atoms, see: Addison et al. (1984).

Experimental top

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.

Refinement top

(type here to add refinement details)

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 top
[Figure 1] Fig. 1. The asymmetric structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Crystal packing of the compound (I). Hydrogen bonds are shown as dashed lines.
Bromido(meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca- 1,7-diene)copper(II) bromide dihydrate top
Crystal data top
[CuBr(C16H32N4)]Br·2H2OF(000) = 2200
Mr = 539.85Dx = 1.618 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3476 reflections
a = 17.8747 (16) Åθ = 2.3–27.5°
b = 15.5118 (13) ŵ = 4.61 mm−1
c = 17.2528 (19) ÅT = 298 K
β = 112.073 (1)°Prism, green
V = 4433.0 (7) Å30.47 × 0.42 × 0.32 mm
Z = 8
Data collection top
Rigaku SCXmini
diffractometer		7814 independent reflections
Radiation source: fine-focus sealed tube3668 reflections with I > 2σ(I)
graphiteRint = 0.101
Detector resolution: 13.6612 pixels mm-1θmax = 25.0°, θmin = 1.8°
Thin–slice ω scansh = −21→19
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = 0→18
Tmin = 0.221, Tmax = 0.320l = 0→20
7814 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 0.87 w = 1/[σ2(Fo2) + (0.0269P)2]
where P = (Fo2 + 2Fc2)/3
7814 reflections(Δ/σ)max = 0.001
487 parametersΔρmax = 0.67 e Å−3
12 restraintsΔρmin = −0.82 e Å−3
Crystal data top
[CuBr(C16H32N4)]Br·2H2OV = 4433.0 (7) Å3
Mr = 539.85Z = 8
Monoclinic, P21/cMo Kα radiation
a = 17.8747 (16) ŵ = 4.61 mm−1
b = 15.5118 (13) ÅT = 298 K
c = 17.2528 (19) Å0.47 × 0.42 × 0.32 mm
β = 112.073 (1)°
Data collection top
Rigaku SCXmini
diffractometer		7814 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		3668 reflections with I > 2σ(I)
Tmin = 0.221, Tmax = 0.320Rint = 0.101
7814 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099Δρmax = 0.67 e Å−3
S = 0.87Δρmin = −0.82 e Å−3
7814 reflectionsAbsolute structure: ?
487 parametersFlack parameter: ?
12 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Br10.68214 (4)0.55475 (5)0.65807 (5)0.0576 (2)
Br20.56344 (4)0.42590 (5)0.83988 (5)0.0558 (2)
Br30.10334 (5)0.61103 (5)0.85539 (5)0.0623 (3)
Br40.14785 (5)0.40766 (5)0.65419 (5)0.0564 (2)
Cu10.85587 (5)0.50884 (4)0.73900 (5)0.0322 (2)
Cu20.39711 (4)0.48668 (4)0.76047 (5)0.0311 (2)
O1W0.6265 (4)0.3601 (3)0.6868 (4)0.0777 (17)
H1W10.638 (5)0.408 (3)0.675 (5)0.117*
H1W20.608 (5)0.370 (5)0.723 (4)0.117*
O2W0.6219 (4)0.6163 (3)0.8101 (5)0.097 (2)
H2W10.627 (6)0.578 (4)0.843 (5)0.145*
H2W20.644 (6)0.602 (6)0.779 (5)0.145*
O3W0.0601 (5)0.4038 (4)0.7992 (5)0.0903 (19)
H3W10.075 (6)0.408 (5)0.761 (4)0.135*
H3W20.058 (6)0.451 (3)0.817 (6)0.135*
O4W0.1901 (4)0.6135 (3)0.7066 (4)0.0819 (18)
H4W10.165 (5)0.609 (5)0.737 (5)0.123*
H4W20.191 (6)0.566 (3)0.686 (5)0.123*
N10.8212 (3)0.4034 (3)0.7847 (3)0.0315 (13)
H10.76630.40450.76270.038*
N20.8619 (3)0.4314 (3)0.6499 (3)0.0300 (13)
N30.9094 (3)0.6081 (3)0.7058 (3)0.0307 (13)
H30.96280.60330.73840.037*
N40.8610 (3)0.5833 (3)0.8355 (3)0.0290 (13)
N50.3402 (3)0.3978 (3)0.8025 (3)0.0316 (13)
H50.28720.40260.76890.038*
N60.3864 (3)0.4004 (3)0.6719 (3)0.0305 (13)
N70.4310 (3)0.5837 (3)0.7016 (3)0.0297 (13)
H70.48590.58220.72140.036*
N80.3920 (3)0.5763 (3)0.8397 (3)0.0283 (13)
C10.8070 (4)0.3185 (4)0.9007 (4)0.056 (2)
H1A0.74960.31900.87070.084*
H1B0.81860.31870.95970.084*
H1C0.82950.26760.88620.084*
C20.8440 (4)0.3981 (4)0.8775 (4)0.0353 (17)
C30.8082 (4)0.4773 (4)0.9036 (4)0.0356 (17)
H3A0.75060.47690.87140.043*
H3B0.81540.46960.96180.043*
C40.8388 (4)0.5647 (4)0.8955 (4)0.0360 (18)
C50.8401 (4)0.6287 (4)0.9606 (4)0.056 (2)
H5A0.86970.67890.95630.083*
H5B0.86570.60351.01510.083*
H5C0.78590.64490.95250.083*
C60.9357 (4)0.3966 (4)0.9225 (4)0.050 (2)
H6A0.95620.34180.91350.075*
H6B0.94930.40510.98130.075*
H6C0.95920.44170.90100.075*
C70.9612 (4)0.6862 (4)0.6111 (4)0.049 (2)
H7A0.94160.74020.62300.074*
H7B0.96110.68750.55540.074*
H7C1.01520.67670.65040.074*
C80.9063 (4)0.6128 (4)0.6181 (4)0.0257 (15)
C90.9413 (4)0.5281 (3)0.6002 (4)0.0354 (17)
H9A0.94400.53340.54530.042*
H9B0.99650.52390.64020.042*
C100.9008 (4)0.4439 (4)0.6020 (4)0.0301 (16)
C110.9109 (4)0.3765 (4)0.5437 (4)0.056 (2)
H11A0.88690.32330.55130.083*
H11B0.96730.36760.55580.083*
H11C0.88480.39550.48690.083*
C120.8204 (3)0.6267 (4)0.5564 (4)0.0390 (17)
H12A0.78510.58640.56780.059*
H12B0.81820.61800.50050.059*
H12C0.80370.68440.56190.059*
C130.8442 (4)0.3282 (4)0.7449 (4)0.0408 (18)
H13A0.81470.27740.74990.049*
H13B0.90150.31660.77250.049*
C140.8244 (4)0.3485 (4)0.6540 (4)0.0407 (18)
H14A0.84530.30380.62830.049*
H14B0.76640.35190.62440.049*
C150.8811 (4)0.6858 (4)0.7374 (4)0.0436 (19)
H15A0.82490.69700.70330.052*
H15B0.91250.73570.73410.052*
C160.8905 (4)0.6707 (4)0.8273 (4)0.0445 (19)
H16A0.94680.67610.86370.053*
H16B0.85980.71350.84390.053*
C170.2880 (4)0.3393 (4)0.9064 (4)0.047 (2)
H17A0.23350.34700.86750.071*
H17B0.28980.34570.96240.071*
H17C0.30640.28270.89970.071*
C180.3426 (4)0.4072 (4)0.8898 (4)0.0311 (17)
C190.3091 (4)0.4961 (4)0.8974 (4)0.0382 (18)
H19A0.25390.49820.85700.046*
H19B0.30630.49920.95240.046*
C200.3499 (4)0.5763 (4)0.8861 (4)0.0319 (17)
C210.3361 (4)0.6534 (4)0.9306 (4)0.053 (2)
H21A0.36920.64940.98900.080*
H21B0.28030.65580.92370.080*
H21C0.35000.70460.90770.080*
C220.4281 (4)0.3979 (4)0.9541 (4)0.0451 (19)
H22A0.44600.33960.95420.068*
H22B0.42890.41221.00860.068*
H22C0.46340.43620.94020.068*
C230.4381 (4)0.6507 (4)0.5737 (4)0.058 (2)
H23A0.41410.70400.58060.087*
H23B0.42640.64100.51540.087*
H23C0.49550.65340.60340.087*
C240.4033 (4)0.5764 (4)0.6086 (4)0.0347 (17)
C250.4387 (4)0.4924 (4)0.5897 (4)0.0379 (17)
H25A0.42890.49210.53050.045*
H25B0.49670.49450.61950.045*
C260.4094 (4)0.4076 (4)0.6102 (4)0.0332 (17)
C270.4104 (4)0.3350 (4)0.5538 (4)0.050 (2)
H27A0.46510.31700.56620.076*
H27B0.38690.35370.49670.076*
H27C0.37980.28750.56220.076*
C280.3121 (4)0.5763 (4)0.5687 (4)0.048 (2)
H28A0.29080.53760.59870.072*
H28B0.29550.55790.51160.072*
H28C0.29230.63350.57050.072*
C290.3663 (4)0.3148 (4)0.7806 (4)0.048 (2)
H29A0.33390.26860.78970.058*
H29B0.42240.30430.81560.058*
C300.3563 (4)0.3175 (4)0.6898 (4)0.0461 (19)
H30A0.38610.27050.67790.055*
H30B0.29970.31080.65450.055*
C310.4096 (4)0.6656 (4)0.7330 (4)0.0411 (18)
H31A0.35230.67710.70530.049*
H31B0.43930.71330.72190.049*
C320.4314 (4)0.6557 (3)0.8265 (4)0.0370 (17)
H32A0.48950.65130.85500.044*
H32B0.41280.70530.84840.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0473 (5)0.0711 (5)0.0510 (5)0.0010 (4)0.0144 (4)0.0231 (5)
Br20.0455 (5)0.0689 (5)0.0543 (6)0.0040 (4)0.0203 (4)0.0207 (4)
Br30.0591 (6)0.0778 (6)0.0436 (5)0.0077 (4)0.0121 (4)−0.0088 (5)
Br40.0582 (6)0.0606 (5)0.0447 (5)0.0065 (4)0.0130 (4)−0.0054 (4)
Cu10.0531 (6)0.0252 (4)0.0226 (5)−0.0017 (4)0.0191 (5)0.0000 (4)
Cu20.0488 (6)0.0245 (4)0.0220 (5)−0.0025 (4)0.0156 (4)0.0000 (4)
O1W0.097 (5)0.052 (3)0.093 (5)−0.008 (3)0.046 (4)−0.014 (3)
O2W0.110 (5)0.047 (3)0.163 (7)0.010 (3)0.084 (5)0.009 (4)
O3W0.104 (5)0.091 (4)0.089 (6)−0.009 (4)0.051 (4)0.025 (4)
O4W0.092 (5)0.068 (4)0.088 (5)−0.006 (4)0.036 (4)0.020 (4)
N10.039 (4)0.032 (3)0.019 (3)0.005 (2)0.006 (3)0.005 (3)
N20.044 (4)0.022 (3)0.025 (3)−0.001 (2)0.015 (3)0.000 (3)
N30.044 (4)0.023 (3)0.025 (3)0.004 (2)0.013 (3)0.003 (3)
N40.040 (4)0.023 (3)0.027 (3)−0.002 (2)0.016 (3)−0.003 (3)
N50.039 (3)0.030 (3)0.020 (3)0.000 (2)0.005 (3)0.001 (3)
N60.038 (4)0.025 (3)0.031 (3)−0.001 (2)0.015 (3)0.004 (3)
N70.037 (3)0.030 (3)0.022 (3)0.002 (2)0.011 (3)−0.001 (3)
N80.038 (4)0.024 (3)0.025 (3)0.000 (2)0.014 (3)0.006 (3)
C10.089 (6)0.047 (5)0.039 (5)0.003 (4)0.034 (5)0.010 (4)
C20.049 (5)0.033 (4)0.021 (4)0.002 (3)0.010 (4)0.008 (3)
C30.038 (4)0.047 (5)0.024 (4)0.003 (3)0.013 (3)0.001 (4)
C40.034 (4)0.045 (5)0.033 (5)0.006 (3)0.017 (4)0.003 (4)
C50.076 (6)0.059 (5)0.044 (5)−0.007 (4)0.037 (4)−0.017 (4)
C60.054 (5)0.062 (5)0.027 (4)0.025 (4)0.007 (4)0.005 (4)
C70.067 (5)0.042 (4)0.045 (5)−0.011 (4)0.028 (4)0.009 (4)
C80.035 (4)0.034 (4)0.014 (4)0.000 (3)0.016 (3)0.004 (3)
C90.045 (5)0.035 (4)0.031 (4)0.000 (3)0.020 (4)−0.005 (3)
C100.027 (4)0.037 (4)0.021 (4)0.005 (3)0.003 (3)0.003 (3)
C110.066 (6)0.062 (5)0.048 (5)−0.011 (4)0.031 (4)−0.024 (4)
C120.037 (4)0.053 (4)0.026 (4)0.003 (3)0.010 (4)0.005 (4)
C130.067 (5)0.022 (4)0.042 (5)−0.003 (3)0.030 (4)0.003 (4)
C140.066 (5)0.029 (4)0.030 (5)−0.006 (3)0.021 (4)−0.003 (3)
C150.072 (6)0.024 (4)0.045 (5)0.004 (3)0.033 (4)0.002 (4)
C160.068 (5)0.040 (4)0.035 (5)−0.005 (4)0.031 (4)−0.011 (4)
C170.054 (5)0.050 (5)0.041 (5)−0.003 (4)0.022 (4)0.007 (4)
C180.030 (4)0.033 (4)0.035 (5)0.002 (3)0.017 (4)0.007 (3)
C190.048 (5)0.048 (5)0.027 (4)0.004 (4)0.023 (4)0.003 (4)
C200.037 (5)0.034 (4)0.015 (4)0.011 (3)−0.001 (3)−0.001 (3)
C210.061 (5)0.055 (5)0.051 (5)0.005 (4)0.029 (4)−0.012 (4)
C220.042 (5)0.055 (5)0.030 (4)0.007 (3)0.004 (4)0.008 (4)
C230.085 (6)0.055 (5)0.038 (5)−0.007 (4)0.028 (4)0.019 (4)
C240.049 (5)0.041 (4)0.011 (4)0.002 (3)0.008 (4)0.010 (3)
C250.043 (4)0.047 (4)0.024 (4)0.001 (4)0.014 (3)0.004 (4)
C260.029 (4)0.038 (4)0.029 (4)0.005 (3)0.005 (4)0.002 (4)
C270.070 (6)0.048 (5)0.030 (5)0.004 (4)0.015 (4)−0.009 (4)
C280.056 (5)0.051 (5)0.021 (4)0.005 (4)−0.001 (4)0.001 (4)
C290.090 (6)0.023 (4)0.048 (5)−0.003 (4)0.043 (5)0.005 (4)
C300.071 (5)0.032 (4)0.046 (5)−0.010 (4)0.034 (4)−0.008 (4)
C310.064 (5)0.026 (4)0.033 (5)−0.004 (3)0.018 (4)0.000 (3)
C320.061 (5)0.021 (4)0.031 (4)−0.002 (3)0.020 (4)−0.007 (3)
Geometric parameters (Å, °) top
Br1—Cu12.9734 (11)C9—H9A0.9700
Br2—Cu22.9229 (11)C9—H9B0.9700
Cu1—N21.986 (5)C10—C111.509 (8)
Cu1—N42.000 (5)C11—H11A0.9600
Cu1—N32.007 (4)C11—H11B0.9600
Cu1—N12.011 (4)C11—H11C0.9600
Cu2—N81.977 (5)C12—H12A0.9600
Cu2—N61.986 (5)C12—H12B0.9600
Cu2—N52.004 (5)C12—H12C0.9600
Cu2—N72.032 (4)C13—C141.506 (7)
O1W—H1W10.824 (19)C13—H13A0.9700
O1W—H1W20.83 (2)C13—H13B0.9700
O2W—H2W10.80 (2)C14—H14A0.9700
O2W—H2W20.81 (2)C14—H14B0.9700
O3W—H3W10.81 (2)C15—C161.515 (8)
O3W—H3W20.80 (2)C15—H15A0.9700
O4W—H4W10.81 (2)C15—H15B0.9700
O4W—H4W20.813 (19)C16—H16A0.9700
N1—C131.488 (7)C16—H16B0.9700
N1—C21.499 (7)C17—C181.535 (8)
N1—H10.9100C17—H17A0.9600
N2—C101.279 (7)C17—H17B0.9600
N2—C141.464 (7)C17—H17C0.9600
N3—C151.488 (7)C18—C221.522 (8)
N3—C81.496 (7)C18—C191.529 (8)
N3—H30.9108C19—C201.491 (8)
N4—C41.273 (7)C19—H19A0.9700
N4—C161.479 (7)C19—H19B0.9700
N5—C291.465 (7)C20—C211.491 (8)
N5—C181.498 (7)C21—H21A0.9600
N5—H50.9089C21—H21B0.9600
N6—C261.282 (7)C21—H21C0.9600
N6—C301.471 (7)C22—H22A0.9600
N7—C311.486 (7)C22—H22B0.9600
N7—C241.494 (7)C22—H22C0.9600
N7—H70.9101C23—C241.535 (8)
N8—C201.287 (7)C23—H23A0.9600
N8—C321.479 (7)C23—H23B0.9600
C1—C21.523 (8)C23—H23C0.9600
C1—H1A0.9600C24—C281.513 (8)
C1—H1B0.9600C24—C251.536 (8)
C1—H1C0.9600C25—C261.506 (8)
C2—C61.528 (8)C25—H25A0.9700
C2—C31.528 (8)C25—H25B0.9700
C3—C41.488 (8)C26—C271.493 (8)
C3—H3A0.9700C27—H27A0.9600
C3—H3B0.9700C27—H27B0.9600
C4—C51.493 (8)C27—H27C0.9600
C5—H5A0.9600C28—H28A0.9600
C5—H5B0.9600C28—H28B0.9600
C5—H5C0.9600C28—H28C0.9600
C6—H6A0.9600C29—C301.509 (8)
C6—H6B0.9600C29—H29A0.9700
C6—H6C0.9600C29—H29B0.9700
C7—C81.538 (7)C30—H30A0.9700
C7—H7A0.9600C30—H30B0.9700
C7—H7B0.9600C31—C321.518 (8)
C7—H7C0.9600C31—H31A0.9700
C8—C121.518 (7)C31—H31B0.9700
C8—C91.536 (7)C32—H32A0.9700
C9—C101.499 (8)C32—H32B0.9700
N2—Cu1—N4174.3 (2)C8—C12—H12A109.5
N2—Cu1—N394.19 (19)C8—C12—H12B109.5
N4—Cu1—N385.20 (19)H12A—C12—H12B109.5
N2—Cu1—N185.73 (19)C8—C12—H12C109.5
N4—Cu1—N193.92 (19)H12A—C12—H12C109.5
N3—Cu1—N1170.3 (2)H12B—C12—H12C109.5
N2—Cu1—Br197.60 (14)N1—C13—C14108.6 (5)
N4—Cu1—Br188.02 (14)N1—C13—H13A110.0
N3—Cu1—Br1102.03 (14)C14—C13—H13A110.0
N1—Cu1—Br187.58 (14)N1—C13—H13B110.0
N8—Cu2—N6172.1 (2)C14—C13—H13B110.0
N8—Cu2—N594.13 (19)H13A—C13—H13B108.4
N6—Cu2—N584.2 (2)N2—C14—C13107.5 (5)
N8—Cu2—N785.69 (19)N2—C14—H14A110.2
N6—Cu2—N794.32 (19)C13—C14—H14A110.2
N5—Cu2—N7168.0 (2)N2—C14—H14B110.2
N8—Cu2—Br2101.90 (14)C13—C14—H14B110.2
N6—Cu2—Br286.00 (14)H14A—C14—H14B108.5
N5—Cu2—Br299.99 (14)N3—C15—C16109.1 (5)
N7—Cu2—Br291.81 (14)N3—C15—H15A109.9
H1W1—O1W—H1W2103 (8)C16—C15—H15A109.9
H2W1—O2W—H2W2108 (10)N3—C15—H15B109.9
H3W1—O3W—H3W2109 (9)C16—C15—H15B109.9
H4W1—O4W—H4W2108 (9)H15A—C15—H15B108.3
C13—N1—C2116.0 (5)N4—C16—C15109.5 (5)
C13—N1—Cu1106.1 (3)N4—C16—H16A109.8
C2—N1—Cu1117.6 (4)C15—C16—H16A109.8
C13—N1—H1105.3N4—C16—H16B109.8
C2—N1—H1105.3C15—C16—H16B109.8
Cu1—N1—H1105.3H16A—C16—H16B108.2
C10—N2—C14122.3 (5)C18—C17—H17A109.5
C10—N2—Cu1127.5 (4)C18—C17—H17B109.5
C14—N2—Cu1109.6 (4)H17A—C17—H17B109.5
C15—N3—C8116.3 (4)C18—C17—H17C109.5
C15—N3—Cu1104.6 (4)H17A—C17—H17C109.5
C8—N3—Cu1119.0 (3)H17B—C17—H17C109.5
C15—N3—H3105.2N5—C18—C22111.4 (5)
C8—N3—H3105.2N5—C18—C19108.1 (5)
Cu1—N3—H3105.2C22—C18—C19110.0 (5)
C4—N4—C16121.1 (5)N5—C18—C17109.9 (5)
C4—N4—Cu1127.9 (4)C22—C18—C17109.5 (5)
C16—N4—Cu1110.9 (4)C19—C18—C17107.8 (5)
C29—N5—C18117.0 (5)C20—C19—C18120.9 (5)
C29—N5—Cu2104.9 (4)C20—C19—H19A107.1
C18—N5—Cu2118.0 (4)C18—C19—H19A107.1
C29—N5—H5105.3C20—C19—H19B107.1
C18—N5—H5105.2C18—C19—H19B107.1
Cu2—N5—H5105.2H19A—C19—H19B106.8
C26—N6—C30120.5 (5)N8—C20—C21124.6 (6)
C26—N6—Cu2127.7 (4)N8—C20—C19120.7 (5)
C30—N6—Cu2111.4 (4)C21—C20—C19114.7 (6)
C31—N7—C24115.5 (5)C20—C21—H21A109.5
C31—N7—Cu2106.5 (3)C20—C21—H21B109.5
C24—N7—Cu2116.1 (4)H21A—C21—H21B109.5
C31—N7—H7105.9C20—C21—H21C109.5
C24—N7—H7106.0H21A—C21—H21C109.5
Cu2—N7—H7106.0H21B—C21—H21C109.5
C20—N8—C32121.4 (5)C18—C22—H22A109.5
C20—N8—Cu2128.3 (4)C18—C22—H22B109.5
C32—N8—Cu2109.2 (4)H22A—C22—H22B109.5
C2—C1—H1A109.5C18—C22—H22C109.5
C2—C1—H1B109.5H22A—C22—H22C109.5
H1A—C1—H1B109.5H22B—C22—H22C109.5
C2—C1—H1C109.5C24—C23—H23A109.5
H1A—C1—H1C109.5C24—C23—H23B109.5
H1B—C1—H1C109.5H23A—C23—H23B109.5
N1—C2—C1110.8 (5)C24—C23—H23C109.5
N1—C2—C6110.6 (5)H23A—C23—H23C109.5
C1—C2—C6110.0 (5)H23B—C23—H23C109.5
N1—C2—C3107.2 (5)N7—C24—C28110.7 (5)
C1—C2—C3107.7 (5)N7—C24—C23110.1 (5)
C6—C2—C3110.5 (5)C28—C24—C23110.3 (5)
C4—C3—C2119.7 (5)N7—C24—C25107.2 (5)
C4—C3—H3A107.4C28—C24—C25111.2 (5)
C2—C3—H3A107.4C23—C24—C25107.1 (5)
C4—C3—H3B107.4C26—C25—C24119.0 (5)
C2—C3—H3B107.4C26—C25—H25A107.6
H3A—C3—H3B106.9C24—C25—H25A107.6
N4—C4—C3121.4 (6)C26—C25—H25B107.6
N4—C4—C5122.6 (6)C24—C25—H25B107.6
C3—C4—C5116.0 (6)H25A—C25—H25B107.0
C4—C5—H5A109.5N6—C26—C27124.2 (6)
C4—C5—H5B109.5N6—C26—C25121.2 (6)
H5A—C5—H5B109.5C27—C26—C25114.6 (6)
C4—C5—H5C109.5C26—C27—H27A109.5
H5A—C5—H5C109.5C26—C27—H27B109.5
H5B—C5—H5C109.5H27A—C27—H27B109.5
C2—C6—H6A109.5C26—C27—H27C109.5
C2—C6—H6B109.5H27A—C27—H27C109.5
H6A—C6—H6B109.5H27B—C27—H27C109.5
C2—C6—H6C109.5C24—C28—H28A109.5
H6A—C6—H6C109.5C24—C28—H28B109.5
H6B—C6—H6C109.5H28A—C28—H28B109.5
C8—C7—H7A109.5C24—C28—H28C109.5
C8—C7—H7B109.5H28A—C28—H28C109.5
H7A—C7—H7B109.5H28B—C28—H28C109.5
C8—C7—H7C109.5N5—C29—C30108.5 (5)
H7A—C7—H7C109.5N5—C29—H29A110.0
H7B—C7—H7C109.5C30—C29—H29A110.0
N3—C8—C12111.1 (5)N5—C29—H29B110.0
N3—C8—C9107.4 (5)C30—C29—H29B110.0
C12—C8—C9111.2 (5)H29A—C29—H29B108.4
N3—C8—C7109.4 (5)N6—C30—C29109.4 (5)
C12—C8—C7110.3 (5)N6—C30—H30A109.8
C9—C8—C7107.3 (5)C29—C30—H30A109.8
C10—C9—C8120.2 (5)N6—C30—H30B109.8
C10—C9—H9A107.3C29—C30—H30B109.8
C8—C9—H9A107.3H30A—C30—H30B108.2
C10—C9—H9B107.3N7—C31—C32107.6 (5)
C8—C9—H9B107.3N7—C31—H31A110.2
H9A—C9—H9B106.9C32—C31—H31A110.2
N2—C10—C9122.0 (6)N7—C31—H31B110.2
N2—C10—C11123.7 (6)C32—C31—H31B110.2
C9—C10—C11114.2 (6)H31A—C31—H31B108.5
C10—C11—H11A109.5N8—C32—C31107.6 (5)
C10—C11—H11B109.5N8—C32—H32A110.2
H11A—C11—H11B109.5C31—C32—H32A110.2
C10—C11—H11C109.5N8—C32—H32B110.2
H11A—C11—H11C109.5C31—C32—H32B110.2
H11B—C11—H11C109.5H32A—C32—H32B108.5
N2—Cu1—N1—C1317.1 (4)C2—C3—C4—C5−146.2 (6)
N4—Cu1—N1—C13−157.3 (4)C15—N3—C8—C12−60.5 (6)
Br1—Cu1—N1—C13114.9 (4)Cu1—N3—C8—C1266.1 (5)
N2—Cu1—N1—C2148.9 (4)C15—N3—C8—C9177.7 (5)
N4—Cu1—N1—C2−25.5 (4)Cu1—N3—C8—C9−55.8 (6)
Br1—Cu1—N1—C2−113.3 (4)C15—N3—C8—C761.5 (7)
N3—Cu1—N2—C1010.1 (6)Cu1—N3—C8—C7−171.9 (4)
N1—Cu1—N2—C10−160.2 (6)N3—C8—C9—C1062.6 (7)
Br1—Cu1—N2—C10112.8 (5)C12—C8—C9—C10−59.1 (7)
N3—Cu1—N2—C14−178.6 (4)C7—C8—C9—C10−179.8 (5)
N1—Cu1—N2—C1411.1 (4)C14—N2—C10—C9−177.9 (5)
Br1—Cu1—N2—C14−75.9 (4)Cu1—N2—C10—C9−7.7 (9)
N2—Cu1—N3—C15155.8 (4)C14—N2—C10—C111.3 (10)
N4—Cu1—N3—C15−29.9 (4)Cu1—N2—C10—C11171.6 (4)
Br1—Cu1—N3—C1557.1 (4)C8—C9—C10—N2−30.9 (9)
N2—Cu1—N3—C823.9 (4)C8—C9—C10—C11149.8 (6)
N4—Cu1—N3—C8−161.8 (4)C2—N1—C13—C14−174.3 (5)
Br1—Cu1—N3—C8−74.8 (4)Cu1—N1—C13—C14−41.6 (6)
N3—Cu1—N4—C4−177.4 (6)C10—N2—C14—C13135.2 (6)
N1—Cu1—N4—C4−7.1 (6)Cu1—N2—C14—C13−36.6 (6)
Br1—Cu1—N4—C480.3 (6)N1—C13—C14—N252.3 (7)
N3—Cu1—N4—C166.4 (4)C8—N3—C15—C16−178.6 (5)
N1—Cu1—N4—C16176.7 (4)Cu1—N3—C15—C1647.9 (6)
Br1—Cu1—N4—C16−95.8 (4)C4—N4—C16—C15−157.7 (6)
N8—Cu2—N5—C29−155.8 (4)Cu1—N4—C16—C1518.7 (6)
N6—Cu2—N5—C2931.9 (4)N3—C15—C16—N4−44.7 (7)
N7—Cu2—N5—C29115.4 (9)C29—N5—C18—C2261.9 (7)
Br2—Cu2—N5—C29−53.0 (4)Cu2—N5—C18—C22−64.8 (6)
N8—Cu2—N5—C18−23.5 (4)C29—N5—C18—C19−177.1 (5)
N6—Cu2—N5—C18164.2 (4)Cu2—N5—C18—C1956.2 (6)
N7—Cu2—N5—C18−112.2 (9)C29—N5—C18—C17−59.7 (7)
Br2—Cu2—N5—C1879.4 (4)Cu2—N5—C18—C17173.6 (4)
N5—Cu2—N6—C26178.8 (6)N5—C18—C19—C20−62.3 (7)
N7—Cu2—N6—C2610.8 (6)C22—C18—C19—C2059.6 (7)
Br2—Cu2—N6—C26−80.7 (5)C17—C18—C19—C20178.9 (5)
N5—Cu2—N6—C30−8.4 (4)C32—N8—C20—C210.1 (9)
N7—Cu2—N6—C30−176.4 (4)Cu2—N8—C20—C21−166.6 (4)
Br2—Cu2—N6—C3092.1 (4)C32—N8—C20—C19178.7 (5)
N8—Cu2—N7—C31−16.3 (4)Cu2—N8—C20—C1912.0 (9)
N6—Cu2—N7—C31155.8 (4)C18—C19—C20—N827.5 (9)
N5—Cu2—N7—C3173.3 (10)C18—C19—C20—C21−153.8 (6)
Br2—Cu2—N7—C31−118.1 (4)C31—N7—C24—C28−64.3 (7)
N8—Cu2—N7—C24−146.5 (4)Cu2—N7—C24—C2861.5 (6)
N6—Cu2—N7—C2425.6 (4)C31—N7—C24—C2358.0 (7)
N5—Cu2—N7—C24−56.9 (11)Cu2—N7—C24—C23−176.2 (4)
Br2—Cu2—N7—C24111.7 (4)C31—N7—C24—C25174.3 (5)
N5—Cu2—N8—C20−12.6 (5)Cu2—N7—C24—C25−60.0 (6)
N7—Cu2—N8—C20155.3 (5)N7—C24—C25—C2667.1 (7)
Br2—Cu2—N8—C20−113.7 (5)C28—C24—C25—C26−54.1 (7)
N5—Cu2—N8—C32179.4 (4)C23—C24—C25—C26−174.7 (5)
N7—Cu2—N8—C32−12.6 (4)C30—N6—C26—C27−1.8 (9)
Br2—Cu2—N8—C3278.3 (4)Cu2—N6—C26—C27170.3 (4)
C13—N1—C2—C1−57.8 (7)C30—N6—C26—C25178.6 (5)
Cu1—N1—C2—C1175.1 (4)Cu2—N6—C26—C25−9.2 (9)
C13—N1—C2—C664.5 (6)C24—C25—C26—N6−31.2 (9)
Cu1—N1—C2—C6−62.7 (6)C24—C25—C26—C27149.2 (6)
C13—N1—C2—C3−175.0 (5)C18—N5—C29—C30177.8 (5)
Cu1—N1—C2—C357.9 (6)Cu2—N5—C29—C30−49.3 (6)
N1—C2—C3—C4−66.2 (7)C26—N6—C30—C29156.6 (6)
C1—C2—C3—C4174.6 (6)Cu2—N6—C30—C29−16.8 (6)
C6—C2—C3—C454.5 (8)N5—C29—C30—N644.1 (7)
C16—N4—C4—C3179.4 (5)C24—N7—C31—C32171.8 (5)
Cu1—N4—C4—C33.6 (9)Cu2—N7—C31—C3241.3 (5)
C16—N4—C4—C50.5 (10)C20—N8—C32—C31−130.3 (6)
Cu1—N4—C4—C5−175.3 (4)Cu2—N8—C32—C3138.6 (6)
C2—C3—C4—N434.9 (9)N7—C31—C32—N8−53.3 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···Br10.82 (2)2.46 (2)3.274 (5)173 (8)
O1W—H1W2···Br20.83 (2)2.58 (3)3.395 (6)170 (7)
O2W—H2W1···Br20.80 (2)2.61 (8)3.238 (6)136 (9)
O2W—H2W2···Br10.81 (2)2.53 (3)3.328 (7)168 (10)
O3W—H3W1···Br40.81 (2)2.62 (3)3.417 (6)169 (10)
O3W—H3W2···Br30.80 (2)2.61 (4)3.362 (6)156 (8)
O4W—H4W1···Br30.81 (2)2.66 (2)3.461 (6)170 (8)
O4W—H4W2···Br40.81 (2)2.58 (4)3.327 (5)155 (7)
N1—H1···O1W0.912.443.317 (8)161
N1—H1···Br10.912.993.519 (5)119
N3—H3···Br3i0.912.573.457 (5)166
N5—H5···Br40.912.533.432 (5)170
N7—H7···O2W0.912.403.257 (9)158
N7—H7···Br20.913.143.612 (5)115
Symmetry codes: (i) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···Br10.82 (2)2.46 (2)3.274 (5)173 (8)
O1W—H1W2···Br20.83 (2)2.58 (3)3.395 (6)170 (7)
O2W—H2W1···Br20.80 (2)2.61 (8)3.238 (6)136 (9)
O2W—H2W2···Br10.81 (2)2.53 (3)3.328 (7)168 (10)
O3W—H3W1···Br40.81 (2)2.62 (3)3.417 (6)169 (10)
O3W—H3W2···Br30.80 (2)2.61 (4)3.362 (6)156 (8)
O4W—H4W1···Br30.81 (2)2.66 (2)3.461 (6)170 (8)
O4W—H4W2···Br40.81 (2)2.58 (4)3.327 (5)155 (7)
N1—H1···O1W0.912.443.317 (8)161
N1—H1···Br10.912.993.519 (5)119
N3—H3···Br3i0.912.573.457 (5)166
N5—H5···Br40.912.533.432 (5)170
N7—H7···O2W0.912.403.257 (9)158
N7—H7···Br20.913.143.612 (5)115
Symmetry codes: (i) x+1, y, z.
references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

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