Bromidobis[3-(1H-pyrazol-1-yl-κN(2))propionamide-κO]copper(II) bromide methanol monosolvate.

The title copper(II) N-pyrazolylpropanamide (PPA) complex, [CuBr(PPA)(2)]Br, was obtained in 78% yield by treatment of CuBr(2) with an excess of the ligand in methanol. Crystallization from the mother liquid afforded the title compound, i.e. the methanol solvate [CuBr(C(6)H(9)N(3)O)(2)]Br·CH(3)OH 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 = 533.73

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.079

S = 1.21

5320 reflections

231 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.74 e Å−3

Δρmin = −0.70 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812038111/qk2039sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038111/qk2039Isup2.hkl

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

[CuBr(C6H9N3O)2]Br·CH4O	F(000) = 1060
Mr = 533.73	Dx = 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

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

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(Fo2) + (0.0324P)2 + 1.2084P] where P = (Fo2 + 2Fc2)/3
5320 reflections	(Δ/σ)max = 0.001
231 parameters	Δρmax = 0.74 e Å−3
0 restraints	Δρmin = −0.70 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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

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) ; (ii) ; (iii) .