Bromidobis[2-(pyridin-2-yl)methanol-j2N,O]copper(II) bromide mono-hydrate

Nina Lah* and Katja Lapanje

University of Ljubljana, Faculty of Chemistry and Chemical Technology,

Askerceva 5, 1000 Ljubljana, Slovenia

Correspondence e-mail: nina.lah@fkkt.uni-lj.si

Received 13 May 2013

Accepted 15 May 2013

The title compound, [CuBr(C6H7NO)2]Br�H2O, is an ionic

mononuclear complex in which the [CuBr(C6H7NO)2]+ cation

possesses distorted square-pyramidal geometry. The CuII

centre is coordinated by two neutral 2-(pyridin-2-yl)methanol

(2-pyMeOH) ligands and a terminal bromide ligand. The

2-pyMeOH ligands are coordinated in a bidentate chelating

manner through the pyridine N and hydroxy O atoms, forming

a five-membered chelate ring with the CuII centre. The planes

of the pyridine rings are twisted by 58.71 (14)� with respect to

each other. The charge is balanced by a noncoordinating

bromide anion which, together with a solvent water molecule,

links the components through hydrogen bonds into infinite

chains propagating along the a axis. The mononuclear cations

appear to associate in pairs through weak interactions

between the metal atom of one cation and the halogen atom

of an adjacent cation.

Comment

The preparation of coordination polymers remains an attrac-

tive field of research in coordination chemistry. We have been

interested for some time in the use of simple pyridyl-substi-

tuted alcohols as organic linker ligands (Lah et al., 2006; Lah &

Leban, 2010; Lapanje et al., 2012; Trdin & Lah, 2012). While

preparing new CuII complexes with 2-(pyridin-2-yl)methanol

(2-pyMeOH) and various carboxylic acids, the reaction with

CuBr2 was carried out in methanol. Surprisingly, the resulting

product did not contain any of the itaconic acid species that

was present in the reaction mixture. Crystal structure deter-

mination revealed the product to be the title ionic compound,

[CuBr(2-pyMeOH)2]Br�H2O, (I) (Fig. 1).

The [CuBr(C6H7NO)2]+ cation of (I) shows a distorted

square-pyramidal geometry, in which the CuII centre is coor-

dinated by two neutral and crystallographically distinct

2-pyMeOH molecules in a bidentate chelating manner, and by

a Br atom as a terminal ligand. The basal plane consists of the

CuN2OBr chromophore and the axial site is occupied by the

remaining O atom of one of the two 2-pyMeOH ligands. The

charge is balanced by a noncoordinating bromide anion. Some

geometric parameters are listed in Table 1.

In addition, the structure contains solvent water molecules

which are involved in the formation of infinite hydrogen-

bonded chains oriented along the a axis (Fig. 2). Each water

molecule is a hydrogen-bond donor to two neighbouring

bromide anions and a hydrogen-bond acceptor from the hy-

droxy group of one of the two distinct 2-pyMeOH ligands. The

remaining hydroxy group is involved in hydrogen-bond

formation with the bromide counter-ion. Thus, each

noncoordinating bromide anion acts as an acceptor of three

metal-organic compounds

624 # 2013 International Union of Crystallography doi:10.1107/S0108270113013437 Acta Cryst. (2013). C69, 624–626

Acta Crystallographica Section C

Crystal StructureCommunications

ISSN 0108-2701

Figure 1A view of (I), showing the atom-numbering scheme. Displacementellipsoids are drawn at the 50% probability level.

Figure 2Part of the crystal structure of (I), showing the formation of hydrogen-bonded chains. Hydrogen bonds are shown as dashed lines. (Colour keyfor the electronic version of the paper: water molecules are red, bromidecounter-ions are orange spheres and complex cations are grey.)

hydrogen bonds (Table 2). The chains are held together by

weak �–� stacking interactions (Fig. 3).

In a comparison of the structure of (I) with those of known

ionic halide complexes of transition metals with simple pyri-

dine alcohols, six structures need to be mentioned. Three CuII

complexes are reported as mononuclear ionic compounds with

the stoichiometry [CuXL2]X: X = Cl and L = 2-pyMeOH

(Antonioli et al., 2007), X = Cl and L = 2-pyEtOH (Hamamci

et al., 2004), and X = Br and L = 2-pyEtOH (Lah & Leban,

2010). All three crystallize as anhydrous compounds and

contain cations with a similar arrangement of ligands around

the CuII centre. Three further structures deserve a closer look:

(a) a chloride complex with 2-pyMeOH, described as a

dinuclear ionic complex with the formulation [Cu2Cl2-

(2-pyMeOH)4]Cl2�2H2O, (II) (Lah & Leban, 2010); (b) an

analogous cobalt complex, [Co2Cl2(2-pyMeOH)4]Cl2�2H2O,

(III) (Yilmaz et al., 2004); (c) a chloride complex of CuII and

the 4-bromo derivative of 2-pyMeOH with the formulation

[CuCl(2-pyMeOH)2]Cl�H2O, (IV) (Hubrich et al., 2010).

These last three compounds are closely related to (I) so that

their unit-cell parameters agree reasonably well [allowing for

the additional Br atom on the 2-pyMeOH ligand in (IV)]. A

comparison of the unit-cell parameters is given in Table 3.

Nevertheless, two of them are described as dinuclear [(II) and

(III)], while (IV) is described as a mononuclear ionic

compound.

The mononuclear cations appear to associate in pairs across

centres of inversion as a result of an additional weaker

interaction between the halogen atom of one cation and the

metal atom of an adjacent cation. This gives rise to asymmetric

M—X—M double bridges (Fig. 4) for (I), (II) and (IV), and an

almost symmetric bridge for (III). Thus, the coordination

environment around the metal centre becomes distorted

octahedral. Closer inspection of the coordination environment

in all the reported structures reveals that the M—X distances

(M = metal cation and X = halogenide anion) vary from

structure to structure (Table 4). A strong coordinative bond of

the second halogen atom of the M—X—M bridge is only

observed in the case of (III), whereas in the other structures a

significant difference in the M—X distances for the ‘bonded’

halogenide anions is observed. Considering the sum of the van

der Waals radii for the present atoms (Bondi, 1964), there is an

attractive interaction between the metal centre and the halo-

genide atom of the neighbouring unit in (II) and (III), and the

description of (IV) as a mononuclear ionic compound is

justified. Being aware that, in (I), the M—Br distance

[3.2129 (6) A] is just below the sum of the van der Waals radii

(3.25 A), the structure described here can also be described as

a dinuclear ionic compound with the formulation [Cu2Br2(2-

pyMeOH)4]Br2�2H2O (Fig. 4).

Experimental

CuBr2 (120 mg, 5.4 mmol) was dissolved in methanol (15 ml) while

mixing and heating to boiling. Itaconic acid (2-methylidenebutane-

dioic acid; 70 mg, 5.4 mmol) and 2-pyMeOH (0,15 ml, 1.5 mmol) were

added. The resulting solution was left under ambient conditions for

slow evaporation of the solvent. Light-blue crystals of (I) appeared

within a few days.

metal-organic compounds

Acta Cryst. (2013). C69, 624–626 Lah and Lapanje � [CuBr(C6H7NO)2]Br�H2O 625

Figure 3A packing diagram for (I), showing the orientation of the hydrogen-bonded chains. Hydrogen bonds are shown as dashed lines.

Figure 4A view of the assembly of two cations of (I) through weak Cu� � �Brinteractions (dashed lines).

Table 1Selected geometric parameters (A, �).

Br1—Cu1 2.4194 (6) Cu1—O2B 2.037 (3)Cu1—N11 1.983 (3) Cu1—O2A 2.247 (3)Cu1—N21 1.987 (3) Cu1—Br1i 3.2129 (6)

N11—Cu1—N21 168.98 (12) O2B—Cu1—Br1 166.09 (9)N11—Cu1—O2B 90.14 (11) O2A—Cu1—Br1 100.21 (7)N21—Cu1—O2B 81.45 (12) N11—Cu1—Br1i 99.40 (9)N11—Cu1—O2A 77.10 (11) N21—Cu1—Br1i 86.10 (8)N21—Cu1—O2A 96.24 (11) O2B—Cu1—Br1i 79.31 (9)O2B—Cu1—O2A 93.69 (11) O2A—Cu1—Br1i 172.24 (8)N11—Cu1—Br1 92.47 (8) Br1—Cu1—Br1i 86.785 (17)N21—Cu1—Br1 97.41 (9)

Symmetry code: (i) �x þ 1;�y;�zþ 1.

Crystal data

[CuBr(C6H7NO)2]Br�H2OMr = 459.63Triclinic, P1a = 7.9681 (6) Ab = 9.8543 (6) Ac = 11.1812 (8) A� = 74.974 (6)�

� = 72.481 (6)�

� = 76.590 (6)�

V = 797.24 (10) A3

Z = 2Mo K� radiation� = 6.39 mm�1

T = 150 K0.3 � 0.2 � 0.2 mm

Data collection

Agilent SuperNova (Dual, Cu atzero, Atlas) diffractometer

Absorption correction: multi-scan(CrysAlis PRO; Agilent, 2011)Tmin = 0.073, Tmax = 1.000

6592 measured reflections3668 independent reflections3086 reflections with I > 2�(I)Rint = 0.037

Refinement

R[F 2 > 2�(F 2)] = 0.041wR(F 2) = 0.092S = 1.043668 reflections197 parameters

H atoms treated by a mixture ofindependent and constrainedrefinement

��max = 0.92 e A�3

��min = �0.85 e A�3

All C-bound H atoms were initially found in a difference Fourier

map, but they were repositioned at their calculated positions and

refined using a riding model. Aromatic H atoms were permitted to

ride, with C—H = 0.93 A and Uiso(H) = 1.2Ueq(C), and those of the

CH2 group were constrained, with C—H = 0.97 A and Uiso(H) =

1.2Ueq(C). The H atoms of the hydroxy groups and the water mol-

ecule were positioned from a difference Fourier map and refined

freely.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement:

CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to

solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to

refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics:

ORTEP-3 (Farrugia, (2012); software used to prepare material for

publication: SHELXL97.

This work was supported by the Slovenian Ministry of

Education, Science, Culture and Sport through grant No. P1-

0175. The EN–FIST Centre of Excellence is acknowledged for

the use of the SuperNova diffractometer.

Supplementary data for this paper are available from the IUCr electronicarchives (Reference: SK3487). Services for accessing these data aredescribed at the back of the journal.

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire,England.

Antonioli, B., Bray, D., Clegg, J. K., Jolliffe, K. A., Gloe, K., Gloe, K. & Lindoy,L. F. (2007). Polyhedron, 26, 673–678.

Bondi, A. (1964). J. Phys. Chem. 68, 441–451.Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.Hamamci, S., Yilmaz, V. T. & Thone, C. (2004). Acta Cryst. E60, m159–

m161.Hubrich, M., Peukert, M., Seichter, W. & Weber, E. (2010). Polyhedron, 29,

1854–1862.Lah, N. & Leban, I. (2010). Struct. Chem. 21, 263–267.Lah, N., Leban, I. & Clerac, R. (2006). Eur. J. Inorg. Chem. 23, 4888–4894.Lapanje, K., Leban, I. & Lah, N. (2012). Acta Cryst. E68, m599.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Trdin, M. & Lah, N. (2012). Acta Cryst. C68, m359–m362.Yilmaz, V. T., Hamamci, S. & Thone, C. (2004). Polyhedron, 23, 841–848.

metal-organic compounds

626 Lah and Lapanje � [CuBr(C6H7NO)2]Br�H2O Acta Cryst. (2013). C69, 624–626

Table 2Hydrogen-bond geometry (A, �).

D—H� � �A D—H H� � �A D� � �A D—H� � �A

O2B—H2B� � �O1W ii 0.71 (4) 1.86 (4) 2.573 (5) 175 (5)O2A—H2A� � �Br2 0.78 (5) 2.39 (5) 3.163 (3) 173 (4)O1W—H1W� � �Br2iii 0.75 (5) 2.60 (5) 3.319 (4) 162 (5)O1W—H2W� � �Br2 0.84 (6) 2.44 (6) 3.271 (3) 169 (5)

Symmetry codes: (ii) x� 1; y; z; (iii) �xþ 2;�y þ 1;�z.

Table 3Comparison of unit-cell parameters of (I) with those of relatedcompounds (II), (III) and (IV).

Parameter (I) (II) (III) (IV)

T (K) 150 150 133 90a (A) 7.9681 (6) 7.71430 (10) 7.9154 (6) 7.9333 (3)b (A) 9.8543 (6) 9.7359 (2) 9.5718 (6) 11.1019 (3)c (�) 11.1812 (8) 11.0072 (2) 11.1614 (8) 11.2436 (4)� (�) 74.974 (6) 74.570 (1) 72.121 (3) 102.670 (2)� (�) 72.481 (6) 72.311 (1) 70.460 (3) 102.670 (2)� (�) 76.590 (6) 77.405 (1) 76.231 (3) 101.724 (1)V (A3) 797.24 (10) 750.71 (2) 749.77 (9) 862.52 (5)

Table 4Comparison of the coordination environment (A) of the metal centre in(I) (X = Br) with those of related compounds (II), (III) and (IV) (X = Cl).

Bond (I) (II) (III) (IV)

M—N 1.983 (3) 1.9883 (13) 2.0988 (8) 1.97282)1.987 (3) 1.9858 (13) 2.1004 (8) 1.971 (2)

M—O 2.037 (3) 2.0382 (12) 2.1209 (7) 2.029 (2)2.247 (3) 2.2466 (4) 2.1224 (8) 2.179 (2)

M—X 2.4194 (6) 2.2764 (4) 2.4212 (3) 2.2581 (2)3.2129 (6) 3.0434 (5) 2.4620 (3) 3.475 (5)

supplementary materials

sup-1Acta Cryst. (2013). C69, 624-626

supplementary materials

Acta Cryst. (2013). C69, 624-626 [doi:10.1107/S0108270113013437]

Bromidobis[2-(pyridin-2-yl)methanol-κ2N,O]copper(II) bromide monohydrate

Nina Lah and Katja Lapanje

Bromidobis[2-(pyridin-2-yl)methanol-κ2N,O]copper(II) bromide monohydrate

Crystal data

[CuBr(C6H7NO)2]Br·H2OMr = 459.63Triclinic, P1Hall symbol: -P 1a = 7.9681 (6) Åb = 9.8543 (6) Åc = 11.1812 (8) Åα = 74.974 (6)°β = 72.481 (6)°γ = 76.590 (6)°V = 797.24 (10) Å3

Z = 2F(000) = 450Dx = 1.915 Mg m−3

Mo Kα radiation, λ = 0.71073 ÅCell parameters from 3806 reflectionsθ = 2.9–30.4°µ = 6.39 mm−1

T = 150 KPrismatic, light blue0.3 × 0.2 × 0.2 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer

Radiation source: SuperNova (Mo) X-ray Source

Mirror monochromatorDetector resolution: 10.4933 pixels mm-1

ω scansAbsorption correction: multi-scan

(CrysAlis PRO; Agilent, 2011)

Tmin = 0.073, Tmax = 1.0006592 measured reflections3668 independent reflections3086 reflections with I > 2σ(I)Rint = 0.037θmax = 27.5°, θmin = 2.9°h = −10→9k = −12→12l = −14→14

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.041wR(F2) = 0.092S = 1.033668 reflections197 parameters0 restraintsPrimary atom site location: structure-invariant

direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2(Fo2) + (0.0382P)2]

where P = (Fo2 + 2Fc

2)/3(Δ/σ)max = 0.001Δρmax = 0.92 e Å−3

Δρmin = −0.84 e Å−3

Special details

Experimental. Abdorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

supplementary materials

sup-2Acta Cryst. (2013). C69, 624-626

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

x y z Uiso*/Ueq

Br1 0.69276 (5) 0.11173 (4) 0.41782 (4) 0.02072 (12)Br2 0.82213 (5) 0.33174 (4) −0.01707 (4) 0.02657 (13)Cu1 0.41848 (6) 0.15156 (4) 0.35337 (4) 0.01644 (13)O2B 0.1749 (4) 0.1436 (3) 0.3342 (3) 0.0216 (6)O2A 0.4565 (4) 0.3461 (3) 0.1964 (3) 0.0233 (6)O1W 1.0781 (5) 0.3461 (4) 0.1580 (3) 0.0412 (9)H1W 1.120 (7) 0.408 (5) 0.117 (4) 0.033 (15)*H2W 1.000 (9) 0.344 (6) 0.122 (5) 0.065 (19)*N21 0.4958 (4) 0.0118 (3) 0.2393 (3) 0.0165 (6)C22 0.3623 (5) −0.0388 (4) 0.2233 (3) 0.0186 (8)C25 0.7064 (6) −0.1302 (4) 0.0995 (4) 0.0284 (9)H25 0.8243 −0.1591 0.0573 0.034*N11 0.3099 (4) 0.3101 (3) 0.4460 (3) 0.0174 (6)C24 0.5702 (6) −0.1840 (4) 0.0866 (4) 0.0292 (10)H24 0.5952 −0.2519 0.0367 0.035*C1B 0.1767 (5) 0.0183 (4) 0.2924 (4) 0.0243 (9)H1B1 0.0985 0.0402 0.2357 0.029*H1B2 0.1322 −0.0536 0.3658 0.029*C26 0.6636 (6) −0.0318 (4) 0.1770 (4) 0.0241 (9)H26 0.7551 0.0054 0.1862 0.029*C12 0.3498 (5) 0.4406 (4) 0.3872 (4) 0.0212 (8)C14 0.1854 (6) 0.5329 (4) 0.5740 (4) 0.0282 (9)H14 0.1450 0.6081 0.6170 0.034*C15 0.1414 (6) 0.3995 (4) 0.6338 (4) 0.0278 (9)H15 0.0698 0.3834 0.7171 0.033*C13 0.2896 (6) 0.5526 (4) 0.4504 (4) 0.0273 (9)H13 0.3198 0.6418 0.4090 0.033*C1A 0.4647 (6) 0.4577 (4) 0.2527 (4) 0.0262 (9)H1A1 0.4239 0.5492 0.2029 0.031*H1A2 0.5871 0.4552 0.2527 0.031*C16 0.2069 (5) 0.2909 (4) 0.5663 (4) 0.0234 (8)H16 0.1783 0.2009 0.6060 0.028*C23 0.3979 (6) −0.1375 (4) 0.1472 (4) 0.0260 (9)H23 0.3049 −0.1722 0.1373 0.031*H2A 0.542 (7) 0.346 (5) 0.139 (4) 0.032 (14)*H2B 0.149 (6) 0.203 (4) 0.288 (4) 0.017 (13)*

supplementary materials

sup-3Acta Cryst. (2013). C69, 624-626

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Br1 0.0136 (2) 0.0230 (2) 0.0271 (2) 0.00025 (15) −0.00721 (18) −0.00840 (16)Br2 0.0208 (2) 0.0361 (2) 0.0236 (2) −0.00661 (18) −0.00253 (19) −0.00954 (18)Cu1 0.0117 (2) 0.0178 (2) 0.0205 (3) 0.00292 (18) −0.0042 (2) −0.00993 (18)O2B 0.0158 (14) 0.0239 (15) 0.0269 (16) 0.0029 (12) −0.0088 (14) −0.0101 (13)O2A 0.0216 (16) 0.0280 (15) 0.0184 (15) −0.0041 (12) 0.0019 (15) −0.0097 (12)O1W 0.053 (2) 0.0335 (19) 0.047 (2) −0.0148 (18) −0.032 (2) 0.0030 (17)N21 0.0157 (16) 0.0164 (15) 0.0160 (15) 0.0014 (12) −0.0043 (14) −0.0043 (12)C22 0.024 (2) 0.0152 (18) 0.0172 (18) −0.0002 (15) −0.0082 (18) −0.0032 (14)C25 0.029 (2) 0.030 (2) 0.017 (2) 0.0125 (18) −0.002 (2) −0.0089 (17)N11 0.0127 (16) 0.0185 (16) 0.0198 (16) 0.0021 (12) −0.0024 (15) −0.0082 (13)C24 0.048 (3) 0.018 (2) 0.022 (2) 0.0029 (19) −0.011 (2) −0.0094 (16)C1B 0.017 (2) 0.027 (2) 0.031 (2) −0.0027 (16) −0.007 (2) −0.0103 (18)C26 0.021 (2) 0.026 (2) 0.021 (2) 0.0029 (17) −0.0044 (19) −0.0058 (16)C12 0.017 (2) 0.0212 (19) 0.023 (2) 0.0016 (16) −0.0070 (18) −0.0039 (16)C14 0.028 (2) 0.027 (2) 0.031 (2) 0.0087 (18) −0.009 (2) −0.0185 (18)C15 0.027 (2) 0.032 (2) 0.020 (2) 0.0051 (18) −0.001 (2) −0.0138 (17)C13 0.029 (2) 0.0173 (19) 0.037 (2) −0.0002 (17) −0.009 (2) −0.0094 (17)C1A 0.028 (2) 0.022 (2) 0.026 (2) −0.0070 (17) 0.000 (2) −0.0061 (17)C16 0.021 (2) 0.022 (2) 0.024 (2) 0.0009 (16) −0.0022 (19) −0.0063 (16)C23 0.039 (3) 0.0183 (19) 0.025 (2) −0.0054 (18) −0.011 (2) −0.0066 (16)

Geometric parameters (Å, º)

Br1—Cu1 2.4194 (6) N11—C16 1.339 (5)Cu1—N11 1.983 (3) N11—C12 1.346 (4)Cu1—N21 1.987 (3) C24—C23 1.365 (6)Cu1—O2B 2.037 (3) C24—H24 0.9300Cu1—O2A 2.247 (3) C1B—H1B1 0.9700Cu1—Br1i 3.2129 (6) C1B—H1B2 0.9700O2B—C1B 1.425 (4) C26—H26 0.9300O2B—H2B 0.71 (4) C12—C13 1.379 (5)O2A—C1A 1.424 (4) C12—C1A 1.497 (5)O2A—H2A 0.78 (5) C14—C13 1.372 (6)O1W—H1W 0.75 (5) C14—C15 1.383 (6)O1W—H2W 0.84 (6) C14—H14 0.9300N21—C26 1.336 (5) C15—C16 1.382 (5)N21—C22 1.348 (4) C15—H15 0.9300C22—C23 1.381 (5) C13—H13 0.9300C22—C1B 1.501 (5) C1A—H1A1 0.9700C25—C24 1.371 (6) C1A—H1A2 0.9700C25—C26 1.382 (5) C16—H16 0.9300C25—H25 0.9300 C23—H23 0.9300

N11—Cu1—N21 168.98 (12) C23—C24—H24 120.1N11—Cu1—O2B 90.14 (11) C25—C24—H24 120.1N21—Cu1—O2B 81.45 (12) O2B—C1B—C22 110.7 (3)N11—Cu1—O2A 77.10 (11) O2B—C1B—H1B1 109.5

supplementary materials

sup-4Acta Cryst. (2013). C69, 624-626

N21—Cu1—O2A 96.24 (11) C22—C1B—H1B1 109.5O2B—Cu1—O2A 93.69 (11) O2B—C1B—H1B2 109.5N11—Cu1—Br1 92.47 (8) C22—C1B—H1B2 109.5N21—Cu1—Br1 97.41 (9) H1B1—C1B—H1B2 108.1O2B—Cu1—Br1 166.09 (9) N21—C26—C25 122.5 (4)O2A—Cu1—Br1 100.21 (7) N21—C26—H26 118.7N11—Cu1—Br1i 99.40 (9) C25—C26—H26 118.7N21—Cu1—Br1i 86.10 (8) N11—C12—C13 120.8 (3)O2B—Cu1—Br1i 79.31 (9) N11—C12—C1A 117.4 (3)O2A—Cu1—Br1i 172.24 (8) C13—C12—C1A 121.8 (3)Br1—Cu1—Br1i 86.785 (17) C13—C14—C15 119.1 (4)C1B—O2B—Cu1 111.7 (2) C13—C14—H14 120.5C1B—O2B—H2B 107 (3) C15—C14—H14 120.5Cu1—O2B—H2B 110 (3) C16—C15—C14 118.2 (4)C1A—O2A—Cu1 107.5 (2) C16—C15—H15 120.9C1A—O2A—H2A 104 (3) C14—C15—H15 120.9Cu1—O2A—H2A 121 (3) C14—C13—C12 120.2 (4)H1W—O1W—H2W 103 (5) C14—C13—H13 119.9C26—N21—C22 118.9 (3) C12—C13—H13 119.9C26—N21—Cu1 126.1 (2) O2A—C1A—C12 109.8 (3)C22—N21—Cu1 115.0 (2) O2A—C1A—H1A1 109.7N21—C22—C23 120.8 (4) C12—C1A—H1A1 109.7N21—C22—C1B 116.2 (3) O2A—C1A—H1A2 109.7C23—C22—C1B 123.0 (3) C12—C1A—H1A2 109.7C24—C25—C26 118.2 (4) H1A1—C1A—H1A2 108.2C24—C25—H25 120.9 N11—C16—C15 122.7 (4)C26—C25—H25 120.9 N11—C16—H16 118.7C16—N11—C12 119.0 (3) C15—C16—H16 118.7C16—N11—Cu1 122.7 (2) C24—C23—C22 119.7 (4)C12—N11—Cu1 118.2 (2) C24—C23—H23 120.2C23—C24—C25 119.8 (4) C22—C23—H23 120.2

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O2B—H2B···O1Wii 0.71 (4) 1.86 (4) 2.573 (5) 175 (5)O2A—H2A···Br2 0.78 (5) 2.39 (5) 3.163 (3) 173 (4)O1W—H1W···Br2iii 0.75 (5) 2.60 (5) 3.319 (4) 162 (5)O1W—H2W···Br2 0.84 (6) 2.44 (6) 3.271 (3) 169 (5)

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

Comparison of unit-cell parameters of (I) with those of the related compounds (II), (III) and (IV)

(I) (II) (III) (IV)T (K) 150 150 133 90a (Å) 7.9681 (6) 7.71430 (10) 7.9154 (6) 7.9333 (3)b (Å) 9.8543 (6) 9.7359 (2) 9.5718 (6) 11.1019 (3)c (°) 11.1812 (8) 11.0072 (2) 11.1614 (8) 11.2436 (4)

supplementary materials

sup-5Acta Cryst. (2013). C69, 624-626

α (°) 74.974 (6) 74.570 (1) 72.121 (3) 102.670 (2)β (°) 72.481 (6) 72.311 (1) 70.460 (3) 102.670 (2)γ (°) 76.590 (6) 77.405 (1) 76.231 (3) 101.724 (1)V (Å3) 797.24 (10) 750.71 (2) 749.77 (9) 862.52 (5)

Comparison of the coordination environment of the metal centre in (I) with those reported for the related compounds (II),

(III) and (IV)

(I) (II) (III) (IV)M—N (Å) 1.984 (3) 1.9883 (13) 2.0988 (8) 1.97282)

1.987 (3) 1.9858 (13) 2.1004 (8) 1.971 (2)M—O (Å) 2.0384 (3) 2.0382 (12) 2.1209 (7) 2.029 (2)

2.2487 (3) 2.2466 (4) 2.1224 (8) 2.179 (2)M—X (Å) 2.4194 (2) 2.2764 (4) 2.4212 (3) 2.2581 (2)

3.2129 (6) 3.0434 (5) 2.4620 (3) 3.475 (5)