Bromidobis[3-(1H-pyrazol-1-yl-κN2)propionamide-κO]copper(II) bromide methanol monosolvate

Wagner, T.; Hrib, C.G.; Lorenz, V.; Edelmann, F.T.; Gilje, J.W.

doi:10.1107/S1600536812038111

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Pages m1253-m1254

https://doi.org/10.1107/S1600536812038111

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Bromidobis[3-(1H-pyrazol-1-yl-κN²)propionamide-κO]copper(II) bromide methanol monosolvate

Thomas Wagner,^a Cristian G. Hrib,^a Volker Lorenz,^a Frank T. Edelmann ^a ^* and John W. Gilje ^b

^aChemisches Institut, Otto-von-Guericke-Universität Magdeburg, Universitätsplatz 2, 39106 Magdeburg, Germany, and ^bDepartment of Chemistry and Biochemistry, James Madison University, Harrisonburg, VA 22807, USA
^*Correspondence e-mail: frank.edelmann@ovgu.de

(Received 2 August 2012; accepted 5 September 2012; online 8 September 2012)

The title copper(II) N-pyrazolylpropanamide (PPA) complex, [CuBr(PPA)₂]Br, was obtained in 78% yield by treatment of CuBr₂ with an excess of the ligand in methanol. Crystallization from the mother liquid afforded the title compound, i.e. the methanol solvate [CuBr(C₆H₉N₃O)₂]Br·CH₃OH or [CuBr(PPA)₂]Br·MeOH, as bright green crystals. In the solid state, the title salt comprises isolated [CuBr(PPA)₂]⁺ cations, separated bromide ions and methanol of crystallization. In the cation, the central Cu^II ion is coordinated by two N,O-chelating PPA ligands and one Br⁻ ion. The coordination geometry around the Cu^II ion is distorted trigonal–bipyramidal with the bromide ligand and the amide O atoms occupying the equatorial positions [Cu—Br = 2.4443 (4) Å; Cu—O = 2.035 (2) and 2.179 (2) Å], while the pyrazole N atoms coordinate in the axial positions [Cu—N = 1.975 (2) and 1.976 (2) Å]. In the crystal, the three constituents are linked by N—H⋯Br, O—H⋯Br, and N—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For related complexes containing multifunctional ligands with substituted pyrazole groups, see: Gracia-Anton et al. (2003 ); Mukherjee (2000 ); Pal et al. (2005 ); Shaw et al. (2004 ). For acrylamide complexes, see: Girma et al. (2005a ,b ,c , 2006 ). For related complexes containing 3-pyrazol-1-yl-propionamide, see: Girma et al. (2008 ); Wagner et al. (2012 ).

Experimental

Crystal data

[CuBr(C₆H₉N₃O)₂]Br·CH₄O
M_r = 533.73
Monoclinic, P 2₁ /n
a = 10.5075 (4) Å
b = 12.6951 (4) Å
c = 15.1551 (7) Å
β = 102.821 (3)°
V = 1971.19 (13) Å³
Z = 4
Mo Kα radiation
μ = 5.19 mm⁻¹
T = 150 K
0.40 × 0.40 × 0.30 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.046, T_max = 0.139
22729 measured reflections
5320 independent reflections
4728 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.079
S = 1.21
5320 reflections
231 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NB⋯O3ⁱ	0.88	2.07	2.926 (3)	163
N1—H1NA⋯Br2	0.88	2.56	3.434 (3)	173
N4—H4NA⋯O3ⁱⁱ	0.88	2.09	2.956 (3)	168
O3—H1O⋯Br2	0.81 (5)	2.41 (5)	3.215 (3)	175 (5)
N4—H4NB⋯Br2ⁱⁱⁱ	0.88	2.71	3.548 (3)	160
Symmetry codes: (i) -x+2, -y+1, -z; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+2, -y+2, -z.

Data collection: X-AREA (Stoe & Cie, 2002 ); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812038111/qk2039sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812038111/qk2039Isup2.hkl

checkCIF report

Comment top

Currently there is a considerable interest in the use of multifunctional ligands containing substituted pyrazole groups because of their potential applications in catalysis and their ability to form complexes that mimic structural and catalytic functions in metalloproteins (Gracia-Anton et al., 2003; Mukherjee, 2000; Pal et al., 2005; Shaw et al., 2004). As part of our continuing interest in the coordination chemistry of acrylamide (Girma et al., 2005a; Girma et al., 2005b; Girma et al., 2005c; Girma et al., 2006) and acrylamide-based ligands we have earlier synthesized and characterized an acrylamide-derived pyrazole ligand, N-pyrazolylpropanamide (= PPA) (Girma et al., 2008). This ligand is readily accessible in large quantities by base-catalyzed Michael addition of pyrazole to acrylamide. The first PPA complexes to be reported were (PPA)₂CuCl₂ and (PPA)₄Co₃Cl₆ with copper(II) and cobalt(II) chlorides, respectively. Both complexes contain the ligand in a seven-membered ring N,O-chelating fashion. Especially remarkable was the unusual zwitterionic structure of the trinuclear cobalt complex, which additionally comprises bridging N-pyrazolylpropanamide ligands (Girma et al., 2008). Most recently, the syntheses and single-crystal X-ray structures of several new first-row transition metal complexes containing the multifunctional acrylamide-derived PPA have been reported. The general synthesis involved treatment of the appropriate transition metal salts with an excess of PPA in ethanolic solution in the presence of triethylorthoformate as dehydrating agent. This way the perchlorates of iron(II) and cobalt(II) afforded the complexes [(PPA)₂M(EtOH)₂](ClO₄)₂ (M = Fe, Co) in good yields (82% resp. 85%). Light green (PPA)₂NiCl₂ has been obtained analogously from NiCl₂.6H₂O. Hydration of (PPA)₂NiCl₂ afforded the dark green cationic nickel(II) complex [(PPA)₂Ni(H₂O)₄]Cl₂. In the complexes with M = Fe, Co, and Ni the N-pyrazolylpropanamide acts as N,O-chelating ligand. In contrast, monodentate N-coordination via the pyrazolyl ring was found for the dicoordinate silver(I) complex [(PPA)₂Ag]NO₃.H₂O (Wagner et al., 2012).

In the course of these investigations we now studied the reaction of copper(II) dibromide with PPA. A reaction carried out in methanol solution using an excess over 2 equivalents of PPA afforded a green, microcrystalline solid which was shown by elemental analysis and its IR spectrum to be the bromide analogue of the previously reported (PPA)₂CuCl₂ (Girma et al., 2008), i.e. (PPA)₂CuBr₂. Comparison of the IR spectra of the free ligand PPA and (PPA)₂CuBr₂ revealed a significant decrease to lower wavenumbers in the CO absorptions (1690 cm^-1 in PPA vs. 1661 cm^-1 in (PPA)₂CuBr₂ and 1664 cm^-1 in (PPA)₂CuCl₂). This CO absorption shift is consistent with a decrease in the electron density of the amide carbonyl moiety resulting from coordination to the cationic copper(II) center. Crystallization of (PPA)₂CuBr₂ directly from the mother liquid afforded the title compound, i.e. the methanol-solvate, as bright green, X-ray quality single crystals. Surprisingly, the X-ray crystal structure determination revealed the presence of the ionic product [CuBr(PPA)₂]Br.MeOH with 5-coordinate copper. In the solid state, [CuBr(PPA)₂]Br.MeOH comprises isolated [CuBr(PPA)₂]⁺ cations, separated bromide ions and methanol of crystallization (Fig. 1). In the cation, the central Cu²⁺ ion is coordinated by two N,O-chelating PPA ligands and one Br^- ion. The coordination geometry around copper can be best described as distorted trigonal-bipyramidal with the bromo ligand and the amide O atoms occupying the equatorial positions (Cu—Br 2.4443 (4) Å; Cu—O 2.035 (2) and 2.179 (2) Å), while the pyrazolyl N-atoms coordinate in the axial positions (Cu—N 1.975 (2) and 1.976 (2) Å). This is in contrast to the neutral hexacoordinate chloro-analogue (PPA)₂CuCl₂ in which the coordination geometry around the central Cu²⁺ ion is octahedral (Girma et al., 2008). The angles at Cu in the equatorial plane of the [CuBr(PPA)₂]⁺ cation are 109.30 (8)° (O1—Cu—O2), 116.80 (6)° (O2—Cu—Br1), and 133.76 (6)° (O1—Cu—Br1), respectively. The axial angle at Cu (N3—Cu—N6) is 174.53 (9)°. The planes of the opposing pyrazole rings are inclined to each other by ~71°.

Like all previously reported transition metal PPA complexes (Wagner et al., 2012), the title compound also forms a hydrogen-bonded network in the solid state (Fig. 2). The crystal structure consists of chains of [CuBr(PPA)₂]⁺ cations linked by N—H···Br, O—H···Br, and N—H···O hydrogen bonds. The uncoordinated bromide ions are connected via O—H···Br hydrogen bonds to the methanol of crystallization and via two N—H···Br interactions with the amide NH₂ groups of different cations. N—H···O hydrogen bonds between amide NH₂ groups and the methanol of crystallization interconnect the chains.

Related literature top

For related complexes containing multifunctional ligands with substituted pyrazole groups, see: Gracia-Anton et al. (2003); Mukherjee (2000); Pal et al. (2005); Shaw et al. (2004). For acrylamide complexes, see: Girma et al. (2005a,b,c, 2006). For related complexes containing 3-pyrazol-1-yl-propionamide, see: Girma et al. (2008); Wagner et al. (2012).

Experimental top

A solution of CuBr₂ (0.6 g, 1.69 mmol) in methanol (50 ml) was combined with a solution of N-pyrazolylpropanamide (= PPA, 0.8 g, 5.5 mmol) in methanol (30 ml). After stirring for 24 h at room temperature, the reaction mixture was concentrated in vacuo to a total volume of ca 50 ml, whereupon a large quantity of the title compound precipitated in its unsolvated form [CuBr(PPA)₂]Br in the form of a green, microcrystalline solid in 78% yield (1.05 g). Bright green, X-ray quality crystals of the title compound [CuBr(PPA)₂]Br.MeOH were obtained upon standing of the mother liquid at room temperature for 14 d.

Anal. Calcd. for unsolvated C₁₂H₁₈Br₂CuN₆O₂ (M_r = 501.66): C 28.73%; H 3.62%; N 16.75%; Br 31.86%. Found: C 28.35%; H 3.46%; N 17.03%; Br 31.47%. IR (KBr): 3436m ν(N—H), 3336m ν(N—H), 3298m, 3188m, 3020w, 2964m, 2847w, 1661s ν(C=O), 1594m; ν(C=C), 1494w, 1450m, 1429m, 1418m, 1375w, 1325m, 1285m, 1262s, 1230m, 1175m, 1098vs, 1022vs, 957m, 949m, 868w, 801vs, 768m, 759m, 628m cm^-1.

Structure description top

For related complexes containing multifunctional ligands with substituted pyrazole groups, see: Gracia-Anton et al. (2003); Mukherjee (2000); Pal et al. (2005); Shaw et al. (2004). For acrylamide complexes, see: Girma et al. (2005a,b,c, 2006). For related complexes containing 3-pyrazol-1-yl-propionamide, see: Girma et al. (2008); Wagner et al. (2012).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The ion-pair of the title compound in the crystal. Thermal ellipsoids represent 50% probability levels. H-atom radii are arbitrary.
	Fig. 2. Packing diagram of the title compound. Hydrogen bonds: 1 N(1)—H(1NB)···O(3)ⁱ, 2 N(1)—H(1NA)···Br(2), 3 N(4)—H(4NA)···O(3)ⁱⁱ, 4 O(3)—H(1O)···Br(2), 5 N(4)—H(4NB)···Br(2)ⁱⁱⁱ. See Table 1 for details.

Bromidobis[3-(1H-pyrazol-1-yl-κN²)propionamide- κO]copper(II) bromide methanol monosolvate top

Crystal data top

[CuBr(C₆H₉N₃O)₂]Br·CH₄O	F(000) = 1060
M_r = 533.73	D_x = 1.798 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.5075 (4) Å	Cell parameters from 30970 reflections
b = 12.6951 (4) Å	θ = 2.0–29.6°
c = 15.1551 (7) Å	µ = 5.19 mm⁻¹
β = 102.821 (3)°	T = 150 K
V = 1971.19 (13) Å³	Prism, red
Z = 4	0.40 × 0.40 × 0.30 mm

Data collection top

Stoe IPDS 2T diffractometer	5320 independent reflections
Radiation source: fine-focus sealed tube	4728 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 6.67 pixels mm^-1	θ_max = 29.2°, θ_min = 2.1°
ω and φ scans	h = −14→14
Absorption correction: multi-scan (Blessing, 1995)	k = −16→17
T_min = 0.046, T_max = 0.139	l = −20→20
22729 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ²(F_o²) + (0.0324P)² + 1.2084P] where P = (F_o² + 2F_c²)/3
5320 reflections	(Δ/σ)_max = 0.001
231 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.70 e Å⁻³

Crystal data top

[CuBr(C₆H₉N₃O)₂]Br·CH₄O	V = 1971.19 (13) Å³
M_r = 533.73	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.5075 (4) Å	µ = 5.19 mm⁻¹
b = 12.6951 (4) Å	T = 150 K
c = 15.1551 (7) Å	0.40 × 0.40 × 0.30 mm
β = 102.821 (3)°

Data collection top

Stoe IPDS 2T diffractometer	5320 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	4728 reflections with I > 2σ(I)
T_min = 0.046, T_max = 0.139	R_int = 0.048
22729 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	Δρ_max = 0.74 e Å⁻³
5320 reflections	Δρ_min = −0.70 e Å⁻³
231 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
C1	0.8900 (3)	0.6996 (2)	−0.06693 (18)	0.0305 (5)
C2	0.7834 (3)	0.6821 (3)	−0.15080 (18)	0.0370 (6)
H2A	0.8183	0.6990	−0.2047	0.044*
H2B	0.7594	0.6065	−0.1543	0.044*
C3	0.6616 (3)	0.7466 (2)	−0.15415 (18)	0.0336 (6)
H3A	0.6871	0.8199	−0.1361	0.040*
H3B	0.6096	0.7481	−0.2172	0.040*
C4	0.4774 (3)	0.6412 (3)	−0.1195 (2)	0.0391 (7)
H4	0.4395	0.6181	−0.1792	0.047*
C5	0.4364 (3)	0.6148 (2)	−0.0431 (2)	0.0397 (7)
H5	0.3648	0.5710	−0.0386	0.048*
C6	0.5219 (3)	0.6655 (2)	0.02672 (19)	0.0319 (5)
H6	0.5181	0.6613	0.0887	0.038*
C7	0.6471 (2)	1.0403 (2)	−0.04321 (17)	0.0261 (5)
C8	0.6850 (3)	1.1169 (2)	0.03418 (19)	0.0338 (6)
H8A	0.6095	1.1633	0.0348	0.041*
H8B	0.7567	1.1619	0.0229	0.041*
C9	0.7282 (3)	1.0670 (2)	0.12653 (17)	0.0294 (5)
H9A	0.7269	1.1211	0.1734	0.035*
H9B	0.6652	1.0113	0.1333	0.035*
C10	0.9713 (3)	1.0667 (2)	0.1824 (2)	0.0355 (6)
H10	0.9809	1.1329	0.2126	0.043*
C11	1.0701 (3)	1.0012 (3)	0.1729 (2)	0.0386 (7)
H11	1.1611	1.0120	0.1948	0.046*
C12	1.0095 (3)	0.9150 (2)	0.12412 (19)	0.0330 (6)
H12	1.0537	0.8558	0.1069	0.040*
C13	0.9020 (4)	0.5691 (3)	0.1716 (3)	0.0615 (11)
H13A	0.8351	0.5250	0.1892	0.092*
H13B	0.8811	0.5784	0.1058	0.092*
H13C	0.9044	0.6380	0.2011	0.092*
N1	0.9979 (3)	0.6464 (2)	−0.06237 (19)	0.0463 (7)
H1NA	1.0636	0.6541	−0.0154	0.056*
H1NB	1.0049	0.6030	−0.1063	0.056*
N2	0.5811 (2)	0.70573 (19)	−0.09558 (15)	0.0310 (5)
N3	0.6103 (2)	0.72132 (17)	−0.00452 (14)	0.0268 (4)
N4	0.6262 (2)	1.0830 (2)	−0.12477 (15)	0.0340 (5)
H4NA	0.6005	1.0434	−0.1731	0.041*
H4NB	0.6379	1.1511	−0.1307	0.041*
N5	0.8581 (2)	1.02134 (18)	0.14175 (14)	0.0279 (4)
N6	0.8801 (2)	0.92774 (17)	0.10504 (14)	0.0269 (4)
O1	0.8780 (2)	0.76128 (17)	−0.00574 (13)	0.0347 (4)
O2	0.63174 (19)	0.94471 (15)	−0.03194 (13)	0.0311 (4)
O3	1.0247 (2)	0.51986 (18)	0.19866 (14)	0.0375 (5)
Br1	0.69094 (3)	0.80080 (2)	0.204039 (17)	0.03143 (7)
Br2	1.23867 (3)	0.66180 (2)	0.131810 (19)	0.03514 (8)
Cu1	0.74194 (3)	0.82447 (2)	0.05558 (2)	0.02424 (8)
H1O	1.078 (5)	0.559 (4)	0.184 (3)	0.065 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0342 (13)	0.0303 (13)	0.0272 (12)	0.0011 (11)	0.0074 (10)	−0.0035 (10)
C2	0.0414 (15)	0.0441 (17)	0.0247 (12)	0.0063 (13)	0.0054 (11)	−0.0076 (11)
C3	0.0390 (15)	0.0367 (15)	0.0235 (11)	0.0061 (12)	0.0033 (10)	−0.0008 (10)
C4	0.0333 (14)	0.0382 (15)	0.0401 (15)	0.0011 (12)	−0.0040 (12)	−0.0116 (12)
C5	0.0337 (14)	0.0304 (14)	0.0536 (18)	−0.0014 (12)	0.0066 (13)	−0.0055 (13)
C6	0.0340 (13)	0.0264 (13)	0.0349 (13)	0.0019 (11)	0.0066 (11)	0.0021 (10)
C7	0.0242 (11)	0.0241 (11)	0.0289 (11)	0.0065 (9)	0.0034 (9)	0.0009 (9)
C8	0.0427 (15)	0.0227 (12)	0.0331 (13)	0.0043 (11)	0.0020 (11)	−0.0025 (10)
C9	0.0324 (13)	0.0264 (12)	0.0293 (12)	0.0019 (10)	0.0064 (10)	−0.0043 (10)
C10	0.0378 (14)	0.0306 (14)	0.0350 (14)	−0.0056 (12)	0.0011 (11)	−0.0061 (11)
C11	0.0291 (14)	0.0406 (16)	0.0427 (15)	−0.0041 (12)	0.0008 (12)	−0.0059 (13)
C12	0.0283 (13)	0.0360 (14)	0.0331 (13)	0.0015 (11)	0.0038 (10)	−0.0034 (11)
C13	0.065 (2)	0.058 (2)	0.073 (3)	0.027 (2)	0.039 (2)	0.025 (2)
N1	0.0405 (14)	0.0560 (17)	0.0387 (13)	0.0153 (13)	0.0012 (11)	−0.0196 (12)
N2	0.0329 (11)	0.0318 (12)	0.0247 (10)	0.0035 (9)	−0.0010 (8)	−0.0022 (9)
N3	0.0312 (11)	0.0234 (10)	0.0237 (9)	0.0026 (8)	0.0013 (8)	−0.0005 (8)
N4	0.0432 (13)	0.0277 (11)	0.0292 (11)	0.0018 (10)	0.0040 (10)	0.0035 (9)
N5	0.0307 (11)	0.0259 (11)	0.0259 (10)	−0.0003 (9)	0.0034 (8)	−0.0050 (8)
N6	0.0276 (10)	0.0257 (10)	0.0267 (10)	0.0028 (8)	0.0045 (8)	−0.0039 (8)
O1	0.0329 (10)	0.0386 (11)	0.0322 (9)	0.0020 (9)	0.0063 (8)	−0.0129 (8)
O2	0.0359 (10)	0.0240 (9)	0.0295 (9)	0.0021 (8)	−0.0008 (7)	0.0014 (7)
O3	0.0475 (13)	0.0313 (11)	0.0350 (10)	0.0007 (9)	0.0118 (9)	0.0026 (8)
Br1	0.03704 (14)	0.03321 (14)	0.02379 (11)	0.00164 (11)	0.00622 (9)	0.00264 (9)
Br2	0.03229 (14)	0.03990 (16)	0.03307 (14)	−0.00045 (11)	0.00691 (10)	0.00324 (11)
Cu1	0.02684 (15)	0.02305 (14)	0.02175 (14)	0.00120 (12)	0.00305 (11)	−0.00200 (10)

Geometric parameters (Å, º) top

C1—O1	1.241 (3)	C9—H9B	0.9900
C1—N1	1.309 (4)	C10—N5	1.343 (3)
C1—C2	1.513 (4)	C10—C11	1.363 (5)
C2—C3	1.510 (4)	C10—H10	0.9500
C2—H2A	0.9900	C11—C12	1.393 (4)
C2—H2B	0.9900	C11—H11	0.9500
C3—N2	1.451 (4)	C12—N6	1.336 (3)
C3—H3A	0.9900	C12—H12	0.9500
C3—H3B	0.9900	C13—O3	1.410 (4)
C4—N2	1.347 (4)	C13—H13A	0.9800
C4—C5	1.365 (5)	C13—H13B	0.9800
C4—H4	0.9500	C13—H13C	0.9800
C5—C6	1.385 (4)	N1—H1NA	0.8800
C5—H5	0.9500	N1—H1NB	0.8800
C6—N3	1.336 (4)	N2—N3	1.360 (3)
C6—H6	0.9500	N3—Cu1	1.975 (2)
C7—O2	1.241 (3)	N4—H4NA	0.8800
C7—N4	1.323 (3)	N4—H4NB	0.8800
C7—C8	1.507 (4)	N5—N6	1.354 (3)
C8—C9	1.511 (4)	N6—Cu1	1.976 (2)
C8—H8A	0.9900	O1—Cu1	2.035 (2)
C8—H8B	0.9900	O2—Cu1	2.179 (2)
C9—N5	1.453 (3)	O3—H1O	0.81 (5)
C9—H9A	0.9900	Br1—Cu1	2.4443 (4)

O1—C1—N1	121.1 (3)	C10—C11—H11	127.3
O1—C1—C2	122.8 (3)	C12—C11—H11	127.3
N1—C1—C2	116.1 (2)	N6—C12—C11	110.1 (3)
C3—C2—C1	114.3 (2)	N6—C12—H12	124.9
C3—C2—H2A	108.7	C11—C12—H12	124.9
C1—C2—H2A	108.7	O3—C13—H13A	109.5
C3—C2—H2B	108.7	O3—C13—H13B	109.5
C1—C2—H2B	108.7	H13A—C13—H13B	109.5
H2A—C2—H2B	107.6	O3—C13—H13C	109.5
N2—C3—C2	113.0 (2)	H13A—C13—H13C	109.5
N2—C3—H3A	109.0	H13B—C13—H13C	109.5
C2—C3—H3A	109.0	C1—N1—H1NA	120.0
N2—C3—H3B	109.0	C1—N1—H1NB	120.0
C2—C3—H3B	109.0	H1NA—N1—H1NB	120.0
H3A—C3—H3B	107.8	C4—N2—N3	110.4 (2)
N2—C4—C5	108.1 (3)	C4—N2—C3	126.8 (2)
N2—C4—H4	126.0	N3—N2—C3	122.5 (2)
C5—C4—H4	126.0	C6—N3—N2	105.3 (2)
C4—C5—C6	105.1 (3)	C6—N3—Cu1	131.25 (19)
C4—C5—H5	127.5	N2—N3—Cu1	122.79 (18)
C6—C5—H5	127.5	C7—N4—H4NA	120.0
N3—C6—C5	111.1 (3)	C7—N4—H4NB	120.0
N3—C6—H6	124.4	H4NA—N4—H4NB	120.0
C5—C6—H6	124.4	C10—N5—N6	110.5 (2)
O2—C7—N4	122.0 (2)	C10—N5—C9	127.4 (2)
O2—C7—C8	122.9 (2)	N6—N5—C9	121.7 (2)
N4—C7—C8	115.0 (2)	C12—N6—N5	106.0 (2)
C7—C8—C9	115.0 (2)	C12—N6—Cu1	128.97 (19)
C7—C8—H8A	108.5	N5—N6—Cu1	124.08 (17)
C9—C8—H8A	108.5	C1—O1—Cu1	141.98 (19)
C7—C8—H8B	108.5	C7—O2—Cu1	134.49 (17)
C9—C8—H8B	108.5	C13—O3—H1O	107 (3)
H8A—C8—H8B	107.5	N3—Cu1—N6	174.53 (9)
N5—C9—C8	113.1 (2)	N3—Cu1—O1	91.11 (9)
N5—C9—H9A	109.0	N6—Cu1—O1	84.46 (9)
C8—C9—H9A	109.0	N3—Cu1—O2	87.74 (8)
N5—C9—H9B	109.0	N6—Cu1—O2	90.72 (8)
C8—C9—H9B	109.0	O1—Cu1—O2	109.30 (8)
H9A—C9—H9B	107.8	N3—Cu1—Br1	93.94 (7)
N5—C10—C11	107.9 (3)	N6—Cu1—Br1	91.43 (7)
N5—C10—H10	126.0	O1—Cu1—Br1	133.76 (6)
C11—C10—H10	126.0	O2—Cu1—Br1	116.80 (6)
C10—C11—C12	105.4 (3)

O1—C1—C2—C3	0.5 (4)	C9—N5—N6—C12	173.5 (2)
N1—C1—C2—C3	−178.8 (3)	C10—N5—N6—Cu1	170.06 (19)
C1—C2—C3—N2	−76.3 (3)	C9—N5—N6—Cu1	−16.9 (3)
N2—C4—C5—C6	−0.8 (3)	N1—C1—O1—Cu1	−150.9 (3)
C4—C5—C6—N3	0.6 (3)	C2—C1—O1—Cu1	29.7 (5)
O2—C7—C8—C9	11.3 (4)	N4—C7—O2—Cu1	136.7 (2)
N4—C7—C8—C9	−171.4 (3)	C8—C7—O2—Cu1	−46.1 (4)
C7—C8—C9—N5	74.4 (3)	C6—N3—Cu1—O1	137.5 (2)
N5—C10—C11—C12	0.3 (4)	N2—N3—Cu1—O1	−52.8 (2)
C10—C11—C12—N6	0.0 (4)	C6—N3—Cu1—O2	−113.2 (2)
C5—C4—N2—N3	0.7 (3)	N2—N3—Cu1—O2	56.5 (2)
C5—C4—N2—C3	175.0 (3)	C6—N3—Cu1—Br1	3.5 (2)
C2—C3—N2—C4	−95.8 (3)	N2—N3—Cu1—Br1	173.20 (19)
C2—C3—N2—N3	77.8 (3)	C12—N6—Cu1—O1	−29.6 (2)
C5—C6—N3—N2	−0.2 (3)	N5—N6—Cu1—O1	163.2 (2)
C5—C6—N3—Cu1	170.8 (2)	C12—N6—Cu1—O2	−139.0 (2)
C4—N2—N3—C6	−0.4 (3)	N5—N6—Cu1—O2	53.9 (2)
C3—N2—N3—C6	−174.9 (2)	C12—N6—Cu1—Br1	104.2 (2)
C4—N2—N3—Cu1	−172.32 (19)	N5—N6—Cu1—Br1	−62.93 (19)
C3—N2—N3—Cu1	13.2 (3)	C1—O1—Cu1—N3	12.4 (3)
C11—C10—N5—N6	−0.4 (3)	C1—O1—Cu1—N6	−164.4 (3)
C11—C10—N5—C9	−173.0 (3)	C1—O1—Cu1—O2	−75.5 (3)
C8—C9—N5—C10	94.8 (3)	C1—O1—Cu1—Br1	109.0 (3)
C8—C9—N5—N6	−77.1 (3)	C7—O2—Cu1—N3	−177.4 (3)
C11—C12—N6—N5	−0.3 (3)	C7—O2—Cu1—N6	−2.6 (3)
C11—C12—N6—Cu1	−169.2 (2)	C7—O2—Cu1—O1	−87.0 (3)
C10—N5—N6—C12	0.4 (3)	C7—O2—Cu1—Br1	89.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NB···O3ⁱ	0.88	2.07	2.926 (3)	163
N1—H1NA···Br2	0.88	2.56	3.434 (3)	173
N4—H4NA···O3ⁱⁱ	0.88	2.09	2.956 (3)	168
O3—H1O···Br2	0.81 (5)	2.41 (5)	3.215 (3)	175 (5)
N4—H4NB···Br2ⁱⁱⁱ	0.88	2.71	3.548 (3)	160

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+2, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[CuBr(C₆H₉N₃O)₂]Br·CH₄O
M_r	533.73
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	10.5075 (4), 12.6951 (4), 15.1551 (7)
β (°)	102.821 (3)
V (Å³)	1971.19 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.19
Crystal size (mm)	0.40 × 0.40 × 0.30

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.046, 0.139
No. of measured, independent and observed [I > 2σ(I)] reflections	22729, 5320, 4728
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.079, 1.21
No. of reflections	5320
No. of parameters	231
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.70

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NB···O3ⁱ	0.88	2.07	2.926 (3)	163.2
N1—H1NA···Br2	0.88	2.56	3.434 (3)	173.0
N4—H4NA···O3ⁱⁱ	0.88	2.09	2.956 (3)	167.5
O3—H1O···Br2	0.81 (5)	2.41 (5)	3.215 (3)	175 (5)
N4—H4NB···Br2ⁱⁱⁱ	0.88	2.71	3.548 (3)	160.0

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+2, −y+2, −z.

References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
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Gracia-Anton, G., Pons, J., Solans, X., Font-Bardia, M. & Ros, J. (2003). Eur. J. Inorg. Chem. pp. 2992–3000. Google Scholar
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Pal, S., Barik, A. K., Gupta, S., Hazra, A., Kar, S. K., Peng, S.-M., Lee, G.-H., Butcher, R. J., El Fallah, M. S. & Ribas, J. (2005). Inorg. Chem. 44, 3880–3889. Web of Science CSD CrossRef PubMed CAS Google Scholar
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Wagner, T., Hrib, C. G., Lorenz, V., Edelmann, F. T., Amenta, D. S., Burnside, C. J. & Gilje, J. W. (2012). Z. Anorg. Allg. Chem. 638. In the press. doi:10.1002/zaac.201200139. Google Scholar

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Volume 68| Part 10| October 2012| Pages m1253-m1254

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