Bis[μ-3,5-bis-(2-pyrid-yl)pyrazolato]bis-(hydrogensulfato)-dicopper(II) methanol disolvate.

The title compound, [Cu(2)(C(13)H(9)N(4))(2)(HSO(4))(2)]·2CH(3)OH, consists of discrete centrosymmetric dinuclear complex mol-ecules and methanol solvent mol-ecules. The Cu(II) atom shows a square-pyramidal coordination geometry and is bonded to four N atoms of the two bis-chelating 3,5-bis-(2-pyrid-yl)pyrazol-ate ions (bpypz(-)) and one O atom of the hydrogensulfate ion. The bpypz(-) ligands in the complex mol-ecule are virtually coplanar [dihedral angle between the mean ligand planes = 0.000(1)°] with the Cu(II) atom deviating in opposite directions from their best plane by 0.2080 (12) Å. π-π stacking inter-actions between the pyridyl and pyrazole rings [centroid-centroid distance = 3.391 (3) Å] and strong O-H⋯O hydrogen bonds between the hydrogensulfate ligands and the methanol mol-ecules assemble the mol-ecules into a one-dimensional polymeric structure extending along the a axis. The methanol mol-ecule acts both as an accepter and a donor in the hydrogen bonding.

Related literature

For metal complexes of 3,5-bis­(2-pyrid­yl)n class="Chemical">pyrazole, see: Munakata et al. (1995 ▶); Nakano et al. (2004 ▶); Du et al. (2005 ▶); Yoneda, Adachi, Hayami et al. (2006 ▶); Yoneda, Adachi, Nishio et al. (2006 ▶); Ishikawa et al. (2008 ▶, 2010 ▶). For an example of a coordinated hydrogensulfate ion, see: Dragancea et al. (2008 ▶).

Experimental

Crystal data

[Cu2(C13H9N4)2(HO4S)2]·n class="Chemical">2CH4O

M = 827.82

Monoclinic,

a = 6.0909 (3) Å

b = 16.0581 (6) Å

c = 15.6579 (7) Å

β = 95.2044 (14)°

V = 1525.16 (12) Å3

Z = 2

Mo Kα radiation

μ = 1.61 mm−1

T = 200 K

0.35 × 0.04 × 0.03 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ▶) T min = 0.926, T max = 0.953

16136 measured reflections

2470 independent reflections

3262 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.068

S = 1.08

3470 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.51 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2002 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2010 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811038700/gk2397sup1.cif

Supplementary material file. DOI: 10.1107/S1600536811038700/gk2397Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038700/gk2397Isup2.hkl

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

[Cu2(C13H9N4)2(HO4S)2]·2CH4O	F(000) = 844.00
Mr = 827.82	Dx = 1.803 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 14158 reflections
a = 6.0909 (3) Å	θ = 3.4–27.5°
b = 16.0581 (6) Å	µ = 1.61 mm−1
c = 15.6579 (7) Å	T = 200 K
β = 95.2044 (14)°	Column, green
V = 1525.16 (12) Å3	0.35 × 0.04 × 0.03 mm
Z = 2

Rigaku R-AXIS RAPID diffractometer	3262 reflections with F2 > 2.0σ(F2)
Detector resolution: 10.000 pixels mm-1	Rint = 0.021
ω scans	θmax = 27.4°
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	h = −7→7
Tmin = 0.926, Tmax = 0.953	k = −20→20
16136 measured reflections	l = −20→20
2470 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0383P)2 + 0.881P] where P = (Fo2 + 2Fc2)/3
3470 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.51 e Å−3
Primary atom site location: structure-invariant direct methods

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor(wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

	x	y	z	Uiso*/Ueq
Cu1	0.28031 (3)	0.520598 (11)	0.578370 (12)	0.01532 (7)
S1	0.20037 (6)	0.55399 (2)	0.78731 (2)	0.01893 (10)
O1	0.1195 (2)	0.56027 (8)	0.69710 (8)	0.0266 (3)
O2	0.4401 (2)	0.58901 (8)	0.78864 (8)	0.0293 (3)
O3	0.2141 (3)	0.46998 (8)	0.81989 (9)	0.0292 (3)
O4	0.0797 (3)	0.60921 (9)	0.84007 (9)	0.0356 (4)
O5	0.7222 (2)	0.55846 (10)	0.91528 (9)	0.0331 (3)
N1	0.4667 (3)	0.42870 (8)	0.64544 (9)	0.0172 (3)
N2	0.0927 (2)	0.42369 (8)	0.55066 (9)	0.0175 (3)
N3	−0.1001 (2)	0.41178 (8)	0.50440 (9)	0.0172 (3)
N4	−0.4729 (3)	0.37148 (8)	0.42106 (9)	0.0180 (3)
C1	0.6627 (3)	0.43350 (10)	0.69186 (11)	0.0222 (4)
C2	0.7564 (3)	0.36790 (11)	0.73994 (11)	0.0243 (4)
C3	0.6436 (3)	0.29342 (11)	0.74028 (11)	0.0249 (4)
C4	0.4411 (3)	0.28646 (10)	0.69234 (11)	0.0221 (4)
C5	0.3577 (3)	0.35468 (10)	0.64594 (10)	0.0168 (3)
C6	0.1491 (3)	0.35246 (9)	0.59261 (10)	0.0170 (3)
C7	−0.0117 (3)	0.29197 (9)	0.57300 (10)	0.0186 (3)
C8	−0.1656 (3)	0.33282 (9)	0.51668 (10)	0.0167 (3)
C9	−0.3750 (3)	0.30969 (9)	0.47033 (10)	0.0169 (3)
C10	−0.4679 (3)	0.23107 (10)	0.47581 (11)	0.0226 (4)
C11	−0.6675 (3)	0.21423 (11)	0.42906 (12)	0.0262 (4)
C12	−0.7683 (3)	0.27685 (11)	0.37925 (12)	0.0256 (4)
C13	−0.6672 (3)	0.35401 (11)	0.37704 (11)	0.0232 (4)
C14	0.7361 (4)	0.47382 (13)	0.94479 (15)	0.0361 (5)
H1	0.7415	0.4846	0.6918	0.0267*
H2	0.8955	0.3741	0.7720	0.0292*
H3	0.7036	0.2475	0.7729	0.0299*
H4	0.3610	0.2357	0.6914	0.0266*
H5	−0.0154	0.2363	0.5932	0.0223*
H6	−0.3957	0.1894	0.5111	0.0272*
H7	−0.7334	0.1608	0.4313	0.0314*
H8	−0.9054	0.2671	0.3469	0.0308*
H9	−0.7386	0.3966	0.3428	0.0278*
H10	0.5306	0.5733	0.8344	0.0351*
H11	0.8529	0.5697	0.8873	0.0397*
H12	0.8658	0.4471	0.9240	0.0434*
H13	0.6029	0.4436	0.9229	0.0434*
H14	0.7489	0.4730	1.0076	0.0434*

	U11	U22	U33	U12	U13	U23
Cu1	0.01457 (11)	0.01325 (11)	0.01755 (11)	−0.00117 (6)	−0.00178 (7)	0.00169 (6)
S1	0.02020 (19)	0.01756 (19)	0.01917 (19)	−0.00183 (14)	0.00250 (15)	−0.00195 (14)
O1	0.0213 (6)	0.0362 (7)	0.0219 (6)	0.0049 (6)	−0.0005 (5)	−0.0002 (5)
O2	0.0235 (6)	0.0335 (7)	0.0299 (7)	−0.0093 (6)	−0.0023 (5)	0.0060 (6)
O3	0.0320 (7)	0.0207 (6)	0.0344 (8)	−0.0032 (5)	0.0007 (6)	0.0053 (5)
O4	0.0447 (8)	0.0269 (7)	0.0380 (8)	−0.0005 (6)	0.0189 (7)	−0.0097 (6)
O5	0.0244 (7)	0.0382 (8)	0.0362 (8)	−0.0030 (6)	−0.0003 (6)	0.0022 (6)
N1	0.0175 (6)	0.0153 (6)	0.0187 (7)	0.0016 (5)	0.0003 (5)	−0.0006 (5)
N2	0.0169 (6)	0.0155 (6)	0.0195 (7)	−0.0008 (5)	−0.0028 (5)	0.0018 (5)
N3	0.0171 (6)	0.0146 (6)	0.0191 (7)	−0.0022 (5)	−0.0022 (5)	0.0017 (5)
N4	0.0166 (6)	0.0173 (6)	0.0202 (7)	−0.0014 (5)	0.0014 (5)	0.0007 (5)
C1	0.0189 (8)	0.0202 (8)	0.0269 (9)	0.0003 (6)	−0.0019 (7)	−0.0028 (7)
C2	0.0204 (8)	0.0268 (9)	0.0244 (9)	0.0040 (7)	−0.0052 (7)	−0.0028 (7)
C3	0.0255 (9)	0.0247 (9)	0.0233 (9)	0.0054 (7)	−0.0043 (7)	0.0042 (7)
C4	0.0236 (8)	0.0190 (8)	0.0232 (8)	0.0006 (7)	−0.0016 (7)	0.0035 (6)
C5	0.0182 (7)	0.0164 (7)	0.0161 (7)	0.0013 (6)	0.0022 (6)	−0.0003 (6)
C6	0.0182 (7)	0.0154 (7)	0.0174 (7)	0.0015 (6)	0.0012 (6)	0.0021 (6)
C7	0.0205 (8)	0.0149 (7)	0.0203 (8)	−0.0004 (6)	0.0009 (6)	0.0022 (6)
C8	0.0183 (7)	0.0141 (7)	0.0178 (7)	−0.0015 (6)	0.0026 (6)	0.0006 (6)
C9	0.0175 (7)	0.0160 (7)	0.0173 (7)	−0.0006 (6)	0.0030 (6)	−0.0011 (6)
C10	0.0238 (8)	0.0172 (7)	0.0267 (9)	−0.0021 (7)	0.0010 (7)	0.0006 (6)
C11	0.0254 (9)	0.0208 (8)	0.0322 (10)	−0.0082 (7)	0.0020 (7)	−0.0031 (7)
C12	0.0186 (8)	0.0290 (9)	0.0286 (9)	−0.0070 (7)	−0.0020 (7)	−0.0023 (7)
C13	0.0185 (8)	0.0248 (8)	0.0254 (8)	−0.0021 (7)	−0.0027 (7)	0.0026 (7)
C14	0.0367 (11)	0.0384 (12)	0.0331 (11)	−0.0026 (9)	0.0014 (8)	0.0057 (9)

Cu1—O1	2.2696 (13)	C6—C7	1.394 (2)
Cu1—N1	2.0865 (13)	C7—C8	1.392 (2)
Cu1—N2	1.9558 (13)	C8—C9	1.457 (2)
Cu1—N3i	1.9507 (13)	C9—C10	1.389 (3)
Cu1—N4i	2.0924 (14)	C10—C11	1.387 (3)
S1—O1	1.4566 (13)	C11—C12	1.382 (3)
S1—O2	1.5630 (13)	C12—C13	1.385 (3)
S1—O3	1.4420 (14)	O2—H10	0.900
S1—O4	1.4557 (16)	O5—H11	0.960
O5—C14	1.436 (3)	C1—H1	0.950
N1—C1	1.342 (2)	C2—H2	0.950
N1—C5	1.362 (2)	C3—H3	0.950
N2—N3	1.3368 (18)	C4—H4	0.950
N2—C6	1.348 (2)	C7—H5	0.950
N3—C8	1.348 (2)	C10—H6	0.950
N4—C9	1.361 (2)	C11—H7	0.950
N4—C13	1.344 (2)	C12—H8	0.950
C1—C2	1.387 (3)	C13—H9	0.950
C2—C3	1.380 (3)	C14—H12	0.980
C3—C4	1.389 (3)	C14—H13	0.980
C4—C5	1.385 (3)	C14—H14	0.980
C5—C6	1.457 (2)
O1—Cu1—N1	92.40 (5)	N2—C6—C7	109.97 (13)
O1—Cu1—N2	96.79 (6)	C5—C6—C7	134.63 (14)
O1—Cu1—N3i	97.44 (6)	C6—C7—C8	103.33 (13)
O1—Cu1—N4i	92.72 (5)	N3—C8—C7	110.04 (13)
N1—Cu1—N2	80.16 (6)	N3—C8—C9	115.19 (13)
N1—Cu1—N3i	167.37 (6)	C7—C8—C9	134.77 (14)
N1—Cu1—N4i	107.72 (6)	N4—C9—C8	114.53 (13)
N2—Cu1—N3i	90.77 (6)	N4—C9—C10	122.53 (14)
N2—Cu1—N4i	167.42 (6)	C8—C9—C10	122.94 (14)
N3i—Cu1—N4i	79.82 (6)	C9—C10—C11	119.12 (15)
O1—S1—O2	102.78 (7)	C10—C11—C12	118.63 (16)
O1—S1—O3	114.30 (8)	C11—C12—C13	119.29 (16)
O1—S1—O4	111.38 (8)	N4—C13—C12	123.13 (16)
O2—S1—O3	107.92 (8)	N1—C1—H1	118.240
O2—S1—O4	107.00 (8)	C2—C1—H1	118.243
O3—S1—O4	112.66 (9)	C1—C2—H2	120.658
Cu1—O1—S1	129.93 (8)	C3—C2—H2	120.663
Cu1—N1—C1	130.43 (11)	C2—C3—H3	120.467
Cu1—N1—C5	112.14 (10)	C4—C3—H3	120.467
C1—N1—C5	117.20 (14)	C3—C4—H4	120.496
Cu1—N2—N3	134.51 (11)	C5—C4—H4	120.484
Cu1—N2—C6	116.71 (10)	C6—C7—H5	128.336
N3—N2—C6	108.36 (13)	C8—C7—H5	128.337
Cu1i—N3—N2	133.96 (11)	C9—C10—H6	120.442
Cu1i—N3—C8	117.54 (10)	C11—C10—H6	120.440
N2—N3—C8	108.31 (13)	C10—C11—H7	120.683
Cu1i—N4—C9	112.64 (10)	C12—C11—H7	120.692
Cu1i—N4—C13	129.97 (12)	C11—C12—H8	120.351
C9—N4—C13	117.30 (14)	C13—C12—H8	120.364
N1—C1—C2	123.52 (15)	N4—C13—H9	118.439
C1—C2—C3	118.68 (16)	C12—C13—H9	118.430
C2—C3—C4	119.07 (16)	O5—C14—H12	109.477
C3—C4—C5	119.02 (15)	O5—C14—H13	109.477
N1—C5—C4	122.52 (14)	O5—C14—H14	109.472
N1—C5—C6	114.75 (14)	H12—C14—H13	109.472
C4—C5—C6	122.73 (15)	H12—C14—H14	109.469
N2—C6—C5	115.40 (13)	H13—C14—H14	109.460
O1—Cu1—N1—C1	−85.61 (12)	Cu1—N2—C6—C5	−6.86 (18)
O1—Cu1—N1—C5	88.62 (9)	Cu1—N2—C6—C7	173.75 (9)
N1—Cu1—O1—S1	26.68 (10)	N3—N2—C6—C5	179.56 (12)
O1—Cu1—N2—N3	88.20 (13)	N3—N2—C6—C7	0.17 (17)
O1—Cu1—N2—C6	−83.23 (10)	C6—N2—N3—Cu1i	−174.97 (13)
N2—Cu1—O1—S1	107.06 (10)	C6—N2—N3—C8	−0.31 (17)
O1—Cu1—N3i—N2i	−87.66 (13)	Cu1i—N3—C8—C7	176.01 (9)
O1—Cu1—N3i—C8i	86.62 (10)	Cu1i—N3—C8—C9	−4.37 (18)
N3i—Cu1—O1—S1	−161.27 (10)	N2—N3—C8—C7	0.34 (17)
O1—Cu1—N4i—C9i	−92.61 (9)	N2—N3—C8—C9	179.96 (12)
O1—Cu1—N4i—C13i	83.70 (12)	Cu1i—N4—C9—C8	3.47 (16)
N4i—Cu1—O1—S1	−81.19 (10)	Cu1i—N4—C9—C10	−176.54 (10)
N1—Cu1—N2—N3	179.47 (14)	Cu1i—N4—C13—C12	175.54 (10)
N1—Cu1—N2—C6	8.03 (9)	C9—N4—C13—C12	−0.6 (3)
N2—Cu1—N1—C1	177.90 (13)	C13—N4—C9—C8	−179.71 (13)
N2—Cu1—N1—C5	−7.86 (9)	C13—N4—C9—C10	0.3 (3)
N1—Cu1—N4i—C9i	174.00 (8)	N1—C1—C2—C3	0.2 (3)
N1—Cu1—N4i—C13i	−9.69 (14)	C1—C2—C3—C4	0.3 (3)
N4i—Cu1—N1—C1	8.01 (14)	C2—C3—C4—C5	−0.3 (3)
N4i—Cu1—N1—C5	−177.75 (8)	C3—C4—C5—N1	−0.0 (3)
N2—Cu1—N3i—N2i	9.29 (14)	C3—C4—C5—C6	178.73 (14)
N2—Cu1—N3i—C8i	−176.42 (10)	N1—C5—C6—N2	−0.2 (2)
N3i—Cu1—N2—N3	−9.38 (14)	N1—C5—C6—C7	178.96 (15)
N3i—Cu1—N2—C6	179.19 (10)	C4—C5—C6—N2	−179.10 (14)
N3i—Cu1—N4i—C9i	4.46 (9)	C4—C5—C6—C7	0.1 (3)
N3i—Cu1—N4i—C13i	−179.23 (13)	N2—C6—C7—C8	0.03 (17)
N4i—Cu1—N3i—N2i	−179.10 (14)	C5—C6—C7—C8	−179.20 (17)
N4i—Cu1—N3i—C8i	−4.82 (9)	C6—C7—C8—N3	−0.22 (17)
O2—S1—O1—Cu1	47.83 (11)	C6—C7—C8—C9	−179.74 (16)
O3—S1—O1—Cu1	−68.82 (12)	N3—C8—C9—N4	0.3 (2)
O4—S1—O1—Cu1	162.08 (10)	N3—C8—C9—C10	−179.68 (13)
Cu1—N1—C1—C2	173.45 (10)	C7—C8—C9—N4	179.81 (17)
Cu1—N1—C5—C4	−174.59 (10)	C7—C8—C9—C10	−0.2 (3)
Cu1—N1—C5—C6	6.54 (16)	N4—C9—C10—C11	0.4 (3)
C1—N1—C5—C4	0.5 (3)	C8—C9—C10—C11	−179.63 (14)
C1—N1—C5—C6	−178.39 (13)	C9—C10—C11—C12	−0.7 (3)
C5—N1—C1—C2	−0.5 (3)	C10—C11—C12—C13	0.4 (3)
Cu1—N2—N3—Cu1i	13.1 (3)	C11—C12—C13—N4	0.3 (3)
Cu1—N2—N3—C8	−172.25 (11)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H10···O5	0.90	1.66	2.5509 (18)	170
O5—H11···O4ii	0.96	1.74	2.694 (2)	169

Table 1

Selected geometric parameters (Å, °)

Cu1—O1	2.2696 (13)
Cu1—N1	2.0865 (13)
Cu1—N2	1.9558 (13)
Cu1—N3i	1.9507 (13)
Cu1—N4i	2.0924 (14)

Symmetry code: (i) .