Hexaaqua-copper(II) bis-(tetra-fluorido-borate)-pyrazine 1,4-dioxide (1/3).

The crystal structure of the title compound, [Cu(H2O)6](BF4)2·3C4H4N2O2, comprises discrete [Cu(H2O)6](2+) cations and BF4 (-) anions along with three equivalents of pyrazine 1,4-dioxide (pzdo). The hexa-aqua-copper(II) ion and all three pzdo mol-ecules lie about crystallographic inversion centers. The lattice is supported by an extensive hydrogen-bonding network. O-H⋯O hydrogen bonding between the [Cu(H2O)6](2+) and pzdo units creates a pseudo-hexa-gonal lattice parallel to the bc plane. The BF4 (-) anions lie in the voids of that lattice, held in place by O-H⋯F hydrogen bonds, and also generate BF4 (-)-pzdo-BF4 (-)-pzdo stacks via short F⋯N contacts [2.866 (3)-3.283 (4) Å].

Related literature

For related structures see: Blake et al. (2000 ▶) [catena-(tris­(μ3-pyrazino­(2,3-f)quinoxaline)tris­ilver(I) tris­(tetra­fluorido­bor­ate) nitro­methane)]; Muesmann et al. (2011 ▶) [hexa­aqua­copper(II) 2,3,5,6-tetra­fluoro-1,4-benzene­disulfonate]; Jia et al. (2005 ▶) [hexa­kis­(tricyclo­hexyl­phosphine oxide) hexa­aqua­copper(II) bis­(tetra­fluoridoborate) sesquihydrate]; Ma et al. (2001 ▶) [hexa­aqua­copper(II) dichloride (4,4′-bipyridine-N,N′-dioxide) dihydrate]; Lu et al. (2009 ▶) [N,N′-diethyl­pyrazine­diium bis­(tetra­fluoridoborate)]; Turksoy et al. (2003 ▶) [2,5-bis­(2-meth­oxy­phen­yl)-3,6-dimethyl­pyrazinium bis­(tetra­fluorido­borate)]; Schlueter et al. (2012 ▶) [catena-[(μ2-pyrazine-N,N′-dioxide)diaqua­dichloro­copper(II)]; Shatruk et al. (2006 ▶) [Cu(II)(hat) tetra­fluoridoborate; hat = 1,4,5,8,9,12-hexa­aza­triphenyl­ene]; Verbitsky et al. (2008 ▶) [2,3-dicyano-1-ethyl-5-(4-fluoro­phen­yl)pyrazinium tetra­fluoridoborate].

Experimental

Crystal data

[Cu(H2O)6](BF4)2·3C4H4N2O2

M = 681.53

Triclinic,

a = 6.4001 (4) Å

b = 10.2719 (7) Å

c = 10.9162 (8) Å

α = 110.928 (6)°

β = 104.327 (6)°

γ = 93.937 (5)°

V = 639.59 (7) Å3

Z = 1

Cu Kα radiation

μ = 2.40 mm−1

T = 120 K

0.50 × 0.4 0× 0.35 mm

Data collection

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

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.781, T max = 1.000

3851 measured reflections

2399 independent reflections

2356 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.111

S = 1.06

2399 reflections

206 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.47 e Å−3

Δρmin = −0.85 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶) and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813007629/sj5306sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007629/sj5306Isup2.hkl

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

[Cu(H2O)6](BF4)2·3C4H4N2O2	Z = 1
Mr = 681.53	F(000) = 345
Triclinic, P1	Dx = 1.769 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 6.4001 (4) Å	Cell parameters from 3193 reflections
b = 10.2719 (7) Å	θ = 4.5–73.6°
c = 10.9162 (8) Å	µ = 2.40 mm−1
α = 110.928 (6)°	T = 120 K
β = 104.327 (6)°	Block, light blue
γ = 93.937 (5)°	0.5 × 0.4 × 0.35 mm
V = 639.59 (7) Å3

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	2399 independent reflections
Radiation source: fine-focus sealed tube	2356 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
Detector resolution: 10.6501 pixels mm-1	θmax = 70.1°, θmin = 4.5°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −8→12
Tmin = 0.781, Tmax = 1.000	l = −13→12
3851 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.111	w = 1/[σ2(Fo2) + (0.0476P)2 + 1.833P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2399 reflections	Δρmax = 1.47 e Å−3
206 parameters	Δρmin = −0.85 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0258 (19)

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
Cu1	0.5000	0.5000	0.5000	0.0101 (2)
O1	0.3542 (3)	0.3009 (2)	0.4022 (2)	0.0147 (4)
H1A	0.234 (7)	0.289 (4)	0.409 (4)	0.018*
H1B	0.340 (6)	0.266 (4)	0.326 (4)	0.018*
O2	0.2162 (3)	0.5606 (2)	0.4493 (2)	0.0226 (5)
H2A	0.178 (6)	0.631 (5)	0.493 (4)	0.027*
H2B	0.131 (7)	0.525 (4)	0.378 (5)	0.027*
O3	0.4517 (4)	0.5081 (2)	0.7053 (2)	0.0184 (4)
H3A	0.355 (7)	0.525 (4)	0.729 (4)	0.022*
H3B	0.475 (6)	0.439 (4)	0.709 (4)	0.022*
N11	−0.0418 (4)	0.4676 (2)	0.1034 (2)	0.0140 (5)
O11	−0.0811 (3)	0.4372 (2)	0.2040 (2)	0.0196 (4)
C12	−0.1425 (5)	0.5635 (3)	0.0635 (3)	0.0189 (6)
H12	−0.2414	0.6076	0.1069	0.023*
C13	0.1006 (5)	0.4040 (3)	0.0397 (3)	0.0179 (6)
H13	0.1705	0.3378	0.0661	0.022*
N21	−0.6322 (4)	0.0764 (2)	0.0681 (2)	0.0120 (5)
O21	−0.7602 (3)	0.1492 (2)	0.1319 (2)	0.0173 (4)
C22	−0.4126 (4)	0.1135 (3)	0.1184 (3)	0.0165 (6)
H22	−0.3508	0.1915	0.2000	0.020*
C23	−0.7198 (4)	−0.0376 (3)	−0.0509 (3)	0.0149 (5)
H23	−0.8710	−0.0643	−0.0866	0.018*
N31	0.0263 (4)	0.8928 (2)	0.5452 (2)	0.0136 (5)
O31	0.0475 (3)	0.7870 (2)	0.5868 (2)	0.0171 (4)
C32	−0.1066 (4)	0.9842 (3)	0.5873 (3)	0.0159 (6)
H32	−0.1798	0.9747	0.6481	0.019*
C33	0.1346 (4)	0.9090 (3)	0.4589 (3)	0.0167 (6)
H33	0.2287	0.8472	0.4306	0.020*
B1	0.4841 (5)	0.8023 (4)	0.2195 (3)	0.0183 (6)
F1	0.4718 (4)	0.9441 (2)	0.2745 (2)	0.0390 (5)
F2	0.4757 (4)	0.7527 (3)	0.0834 (2)	0.0472 (6)
F3	0.6823 (4)	0.7802 (2)	0.2911 (2)	0.0506 (7)
F4	0.3235 (4)	0.7182 (3)	0.2381 (3)	0.0523 (7)

	U11	U22	U33	U12	U13	U23
Cu1	0.0087 (3)	0.0093 (3)	0.0117 (3)	0.00147 (19)	0.0027 (2)	0.0033 (2)
O1	0.0142 (10)	0.0137 (9)	0.0148 (10)	−0.0002 (7)	0.0067 (8)	0.0028 (8)
O2	0.0159 (10)	0.0231 (11)	0.0179 (11)	0.0095 (9)	−0.0011 (8)	−0.0016 (9)
O3	0.0209 (11)	0.0207 (11)	0.0208 (10)	0.0065 (9)	0.0114 (8)	0.0122 (9)
N11	0.0117 (10)	0.0164 (11)	0.0105 (11)	0.0015 (8)	0.0007 (8)	0.0031 (9)
O11	0.0179 (10)	0.0281 (11)	0.0145 (10)	0.0035 (8)	0.0048 (8)	0.0102 (8)
C12	0.0163 (13)	0.0230 (14)	0.0188 (14)	0.0097 (11)	0.0068 (11)	0.0076 (12)
C13	0.0158 (13)	0.0182 (14)	0.0186 (14)	0.0072 (11)	0.0026 (11)	0.0064 (11)
N21	0.0109 (10)	0.0121 (10)	0.0125 (11)	0.0031 (8)	0.0041 (8)	0.0037 (9)
O21	0.0123 (9)	0.0180 (10)	0.0181 (10)	0.0059 (7)	0.0069 (7)	0.0010 (8)
C22	0.0134 (13)	0.0162 (13)	0.0141 (13)	0.0010 (10)	0.0020 (10)	0.0008 (10)
C23	0.0100 (12)	0.0163 (13)	0.0142 (13)	0.0007 (10)	0.0012 (10)	0.0028 (10)
N31	0.0110 (10)	0.0122 (10)	0.0157 (11)	−0.0003 (8)	0.0031 (9)	0.0041 (9)
O31	0.0174 (10)	0.0139 (9)	0.0222 (10)	0.0030 (7)	0.0074 (8)	0.0084 (8)
C32	0.0141 (13)	0.0147 (13)	0.0177 (13)	0.0013 (10)	0.0079 (10)	0.0030 (11)
C33	0.0148 (13)	0.0151 (13)	0.0220 (14)	0.0048 (10)	0.0107 (11)	0.0053 (11)
B1	0.0147 (15)	0.0237 (16)	0.0178 (15)	0.0024 (12)	0.0063 (12)	0.0088 (13)
F1	0.0526 (13)	0.0337 (11)	0.0487 (13)	0.0253 (10)	0.0301 (11)	0.0230 (10)
F2	0.0762 (17)	0.0527 (14)	0.0303 (11)	0.0296 (13)	0.0287 (11)	0.0243 (10)
F3	0.0430 (13)	0.0381 (12)	0.0410 (13)	0.0166 (10)	−0.0132 (10)	−0.0035 (10)
F4	0.0483 (14)	0.0424 (13)	0.0538 (15)	−0.0145 (11)	0.0319 (12)	−0.0031 (11)

Cu1—O1	1.9692 (19)	N21—O21	1.307 (3)
Cu1—O1i	1.9692 (19)	N21—C22	1.348 (4)
Cu1—O2	1.974 (2)	N21—C23	1.355 (3)
Cu1—O2i	1.974 (2)	C22—C23iii	1.363 (4)
Cu1—O3i	2.310 (2)	C22—H22	0.9300
Cu1—O3	2.310 (2)	C23—C22iii	1.363 (4)
O1—H1A	0.80 (4)	C23—H23	0.9300
O1—H1B	0.76 (4)	N31—O31	1.322 (3)
O2—H2A	0.81 (4)	N31—C32	1.346 (4)
O2—H2B	0.77 (4)	N31—C33	1.348 (4)
O3—H3A	0.74 (4)	C32—C33iv	1.366 (4)
O3—H3B	0.74 (4)	C32—H32	0.9300
N11—O11	1.318 (3)	C33—C32iv	1.366 (4)
N11—C13	1.346 (4)	C33—H33	0.9300
N11—C12	1.353 (4)	B1—F2	1.373 (4)
C12—C13ii	1.363 (4)	B1—F1	1.379 (4)
C12—H12	0.9300	B1—F3	1.395 (4)
C13—C12ii	1.363 (4)	B1—F4	1.397 (4)
C13—H13	0.9300
O1—Cu1—O1i	180.00 (14)	C13ii—C12—H12	119.7
O1—Cu1—O2	89.66 (9)	N11—C13—C12ii	120.1 (3)
O1i—Cu1—O2	90.34 (9)	N11—C13—H13	119.9
O1—Cu1—O2i	90.34 (9)	C12ii—C13—H13	119.9
O1i—Cu1—O2i	89.66 (9)	O21—N21—C22	121.0 (2)
O2—Cu1—O2i	180.00 (15)	O21—N21—C23	120.0 (2)
O1—Cu1—O3i	87.37 (8)	C22—N21—C23	119.0 (2)
O1i—Cu1—O3i	92.63 (8)	N21—C22—C23iii	120.7 (3)
O2—Cu1—O3i	88.50 (9)	N21—C22—H22	119.7
O2i—Cu1—O3i	91.50 (9)	C23iii—C22—H22	119.7
O1—Cu1—O3	92.63 (8)	N21—C23—C22iii	120.4 (2)
O1i—Cu1—O3	87.37 (8)	N21—C23—H23	119.8
O2—Cu1—O3	91.50 (9)	C22iii—C23—H23	119.8
O2i—Cu1—O3	88.50 (9)	O31—N31—C32	120.1 (2)
O3i—Cu1—O3	180.000 (1)	O31—N31—C33	120.5 (2)
Cu1—O1—H1A	112 (3)	C32—N31—C33	119.3 (2)
Cu1—O1—H1B	118 (3)	N31—C32—C33iv	120.4 (3)
H1A—O1—H1B	104 (4)	N31—C32—H32	119.8
Cu1—O2—H2A	127 (3)	C33iv—C32—H32	119.8
Cu1—O2—H2B	123 (3)	N31—C33—C32iv	120.2 (3)
H2A—O2—H2B	109 (4)	N31—C33—H33	119.9
Cu1—O3—H3A	127 (3)	C32iv—C33—H33	119.9
Cu1—O3—H3B	105 (3)	F2—B1—F1	113.8 (3)
H3A—O3—H3B	109 (4)	F2—B1—F3	107.4 (3)
O11—N11—C13	120.2 (2)	F1—B1—F3	108.8 (3)
O11—N11—C12	120.6 (2)	F2—B1—F4	109.6 (3)
C13—N11—C12	119.2 (2)	F1—B1—F4	111.9 (3)
N11—C12—C13ii	120.7 (3)	F3—B1—F4	104.7 (3)
N11—C12—H12	119.7
O11—N11—C12—C13ii	179.4 (2)	O21—N21—C23—C22iii	179.5 (2)
C13—N11—C12—C13ii	−0.2 (5)	C22—N21—C23—C22iii	0.0 (4)
O11—N11—C13—C12ii	−179.4 (2)	O31—N31—C32—C33iv	−177.9 (2)
C12—N11—C13—C12ii	0.2 (4)	C33—N31—C32—C33iv	1.1 (4)
O21—N21—C22—C23iii	−179.5 (2)	O31—N31—C33—C32iv	177.9 (2)
C23—N21—C22—C23iii	0.0 (4)	C32—N31—C33—C32iv	−1.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O31v	0.80 (4)	1.93 (4)	2.711 (3)	166 (4)
O1—H1B···O21vi	0.76 (4)	1.94 (4)	2.676 (3)	166 (4)
O2—H2A···O31	0.81 (4)	1.93 (4)	2.735 (3)	173 (4)
O2—H2B···O11	0.77 (4)	1.89 (5)	2.669 (3)	179 (4)
O3—H3A···O11v	0.74 (4)	2.07 (4)	2.806 (3)	177 (4)
O3—H3B···F4i	0.74 (4)	2.28 (4)	2.984 (4)	158 (4)
O3—H3B···F3i	0.74 (4)	2.41 (4)	3.042 (3)	145 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O31i	0.80 (4)	1.93 (4)	2.711 (3)	166 (4)
O1—H1B⋯O21ii	0.76 (4)	1.94 (4)	2.676 (3)	166 (4)
O2—H2A⋯O31	0.81 (4)	1.93 (4)	2.735 (3)	173 (4)
O2—H2B⋯O11	0.77 (4)	1.89 (5)	2.669 (3)	179 (4)
O3—H3A⋯O11i	0.74 (4)	2.07 (4)	2.806 (3)	177 (4)
O3—H3B⋯F4iii	0.74 (4)	2.28 (4)	2.984 (4)	158 (4)
O3—H3B⋯F3iii	0.74 (4)	2.41 (4)	3.042 (3)	145 (4)

Symmetry codes: (i) ; (ii) ; (iii) .