Di-methyl-ammonium tetra-aqua-(hydrogen-sulfato)-sulfato-cuprate(II).

In the title salt, [(CH3)2NH2][Cu(HSO4)(SO4)(H2O)4], one type of cation and anion is present in the asymmetric unit. The Cu(II) atom in the complex anion, [Cu(HSO4)(SO4)(H2O)4](-), has a tetra-gonal bipyramidal [4 + 2] coordination caused by a Jahn-Teller distortion, with the aqua ligands in equatorial and two O atoms of tetra-hedral HSO4 and SO4 units in apical positions. Both types of ions form sheets parallel to (010). The inter-connection within and between the sheets is reinforced by O-H⋯O and N-H⋯O hydrogen bonds, respectively, involving the water mol-ecules, the two types of sulfate anions and the ammonium groups.

Related literature

For related structures, see: Montgomery & Lingafelter (1966 ▶); Montgomery et al. (1967 ▶); Held (2003 ▶, 2014 ▶). For bond-valence parameters, see: Brown & Altermatt (1985 ▶).

Experimental

Crystal data

(C2H8N)[Cu(HSO4)(SO4)(H2O)4]

M = 374.8

Orthorhombic,

a = 7.1825 (9) Å

b = 17.9973 (15) Å

c = 19.410 (3) Å

V = 2509.0 (6) Å3

Z = 8

Mo Kα radiation

μ = 2.13 mm−1

T = 295 K

0.29 × 0.27 × 0.25 mm

Data collection

Nonius MACH3 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.960, T max = 0.999

7482 measured reflections

3801 independent reflections

2231 reflections with I > 2σ(I)

R int = 0.055

3 standard reflections every 100 reflections intensity decay: −1.4%

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.092

S = 0.97

3801 reflections

196 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.74 e Å−3

Δρmin = −0.44 e Å−3

Data collection: CAD-4 (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4; data reduction: WinGX (Farrugia, 2012 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ATOMS (Dowty, 2002 ▶) and ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814004486/wm5006sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814004486/wm5006Isup2.hkl

CCDC reference: 988936

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C2H8N)[Cu(HSO4)(SO4)(H2O)4]	F(000) = 1544
Mr = 374.8	Dx = 1.985 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 7.1825 (9) Å	θ = 21.0–26.0°
b = 17.9973 (15) Å	µ = 2.13 mm−1
c = 19.410 (3) Å	T = 295 K
V = 2509.0 (6) Å3	Parallelepiped, light blue
Z = 8	0.29 × 0.27 × 0.25 mm

Nonius MACH3 diffractometer	2231 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.055
Graphite monochromator	θmax = 30.4°, θmin = 2.3°
ω/2θ scans	h = −10→0
Absorption correction: ψ scan (North et al., 1968)	k = −25→0
Tmin = 0.960, Tmax = 0.999	l = −27→27
7482 measured reflections	3 standard reflections every 100 reflections
3801 independent reflections	intensity decay: −1.4%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.0423P)2 + 0.4413P] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max = 0.001
3801 reflections	Δρmax = 0.74 e Å−3
196 parameters	Δρmin = −0.44 e Å−3
8 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0081 (3)

Experimental. A suitable single-crystal was carefully selected under a polarizing microscope and mounted in a glass capillary.

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
Cu	0.73284 (4)	0.015242 (18)	0.126573 (17)	0.01956 (10)
O1	0.8740 (3)	0.07478 (12)	0.19257 (11)	0.0228 (4)
O2	0.5919 (3)	−0.02976 (12)	0.20235 (11)	0.0253 (5)
O3	0.8752 (3)	0.06422 (15)	0.05293 (11)	0.0293 (5)
O4	0.5959 (3)	−0.04258 (14)	0.06014 (12)	0.0312 (5)
S1	0.31024 (8)	0.11572 (4)	0.11869 (4)	0.01745 (14)
O11	0.5141 (3)	0.12213 (11)	0.11860 (11)	0.0278 (5)
O12	0.2463 (3)	0.07405 (15)	0.17900 (12)	0.0422 (6)
O13	0.2226 (3)	0.18941 (12)	0.11961 (17)	0.0566 (9)
O14	0.2441 (3)	0.07687 (16)	0.05733 (11)	0.0425 (7)
S2	1.14451 (9)	−0.12021 (4)	0.13213 (4)	0.01923 (15)
O21	1.0717 (3)	−0.20091 (11)	0.13532 (13)	0.0376 (6)
H21	1.1602	−0.2297	0.1359	0.056*
O22	0.9771 (3)	−0.07646 (12)	0.13129 (14)	0.0397 (6)
O23	1.2575 (3)	−0.11363 (13)	0.07020 (10)	0.0326 (5)
O24	1.2594 (3)	−0.10790 (13)	0.19321 (10)	0.0305 (5)
N3	−0.3234 (4)	−0.27683 (14)	0.12215 (14)	0.0310 (6)
H3A	−0.2138	−0.3010	0.1241	0.037*
H3B	−0.4141	−0.3113	0.1212	0.037*
C1	−0.3443 (6)	−0.2325 (2)	0.1854 (2)	0.0477 (10)
H1A	−0.3395	−0.2647	0.2248	0.072*
H1B	−0.4617	−0.2070	0.1845	0.072*
H1C	−0.2452	−0.1968	0.1881	0.072*
C2	−0.3304 (6)	−0.2343 (2)	0.0576 (2)	0.0465 (10)
H2A	−0.3167	−0.2676	0.0192	0.070*
H2B	−0.2312	−0.1986	0.0570	0.070*
H2C	−0.4478	−0.2091	0.0543	0.070*
H1D	0.841 (5)	0.0743 (19)	0.2340 (11)	0.044 (12)*
H1E	0.992 (3)	0.075 (2)	0.193 (2)	0.052 (14)*
H2D	0.651 (4)	−0.0538 (16)	0.2328 (13)	0.026 (9)*
H2E	0.489 (4)	−0.051 (2)	0.198 (2)	0.053 (13)*
H3D	0.827 (5)	0.077 (2)	0.0141 (13)	0.056 (13)*
H3E	0.994 (3)	0.063 (2)	0.050 (2)	0.040 (11)*
H4D	0.490 (3)	−0.062 (2)	0.062 (2)	0.058 (14)*
H4E	0.637 (6)	−0.054 (2)	0.0194 (13)	0.072 (15)*

	U11	U22	U33	U12	U13	U23
Cu	0.01968 (17)	0.02313 (17)	0.01587 (14)	−0.00449 (13)	0.00006 (14)	0.00032 (16)
O1	0.0208 (11)	0.0291 (11)	0.0184 (10)	−0.0035 (9)	−0.0013 (8)	−0.0016 (9)
O2	0.0204 (11)	0.0325 (13)	0.0230 (10)	−0.0041 (10)	−0.0013 (8)	0.0079 (9)
O3	0.0179 (11)	0.0488 (15)	0.0212 (10)	−0.0047 (11)	−0.0006 (9)	0.0110 (10)
O4	0.0244 (12)	0.0445 (14)	0.0247 (11)	−0.0111 (11)	0.0019 (9)	−0.0131 (10)
S1	0.0138 (3)	0.0171 (3)	0.0214 (3)	0.0002 (2)	−0.0004 (2)	−0.0004 (3)
O11	0.0145 (8)	0.0256 (10)	0.0433 (13)	−0.0021 (7)	−0.0001 (9)	0.0009 (10)
O12	0.0254 (12)	0.0729 (19)	0.0283 (11)	−0.0128 (13)	−0.0034 (10)	0.0189 (12)
O13	0.0242 (11)	0.0190 (10)	0.127 (3)	0.0033 (9)	−0.0063 (16)	−0.0017 (15)
O14	0.0236 (11)	0.0750 (19)	0.0288 (11)	−0.0113 (13)	0.0038 (10)	−0.0206 (12)
S2	0.0168 (3)	0.0172 (3)	0.0237 (3)	0.0008 (2)	−0.0003 (3)	−0.0003 (3)
O21	0.0240 (10)	0.0198 (10)	0.0689 (16)	−0.0024 (8)	0.0041 (11)	−0.0010 (11)
O22	0.0227 (10)	0.0305 (12)	0.0658 (16)	0.0115 (9)	−0.0030 (12)	−0.0021 (13)
O23	0.0296 (11)	0.0438 (13)	0.0244 (10)	−0.0043 (12)	0.0014 (9)	0.0018 (9)
O24	0.0281 (11)	0.0400 (12)	0.0233 (10)	−0.0026 (11)	−0.0024 (9)	−0.0032 (9)
N3	0.0294 (12)	0.0226 (11)	0.0411 (15)	0.0025 (10)	0.0030 (12)	−0.0047 (12)
C1	0.037 (2)	0.053 (2)	0.053 (2)	−0.0009 (19)	0.0071 (18)	−0.023 (2)
C2	0.046 (3)	0.039 (2)	0.055 (2)	−0.0008 (19)	−0.0074 (19)	0.0110 (19)

Cu—O4	1.927 (2)	S1—O11	1.4689 (19)
Cu—O1	1.954 (2)	S2—O22	1.438 (2)
Cu—O2	1.961 (2)	S2—O23	1.455 (2)
Cu—O3	1.966 (2)	S2—O24	1.461 (2)
Cu—O22	2.410 (2)	S2—O21	1.545 (2)
Cu—O11	2.489 (2)	O21—H21	0.8200
O1—H1D	0.838 (18)	N3—C2	1.470 (5)
O1—H1E	0.846 (18)	N3—C1	1.471 (4)
O2—H2D	0.848 (18)	N3—H3A	0.9000
O2—H2E	0.837 (19)	N3—H3B	0.9000
O3—H3D	0.857 (18)	C1—H1A	0.9600
O3—H3E	0.852 (18)	C1—H1B	0.9600
O4—H4D	0.843 (18)	C1—H1C	0.9600
O4—H4E	0.869 (19)	C2—H2A	0.9600
S1—O14	1.461 (2)	C2—H2B	0.9600
S1—O12	1.464 (2)	C2—H2C	0.9600
S1—O13	1.468 (2)
O4—Cu—O1	178.97 (10)	O14—S1—O11	111.16 (14)
O4—Cu—O2	90.88 (10)	O12—S1—O11	110.73 (14)
O1—Cu—O2	90.15 (9)	O13—S1—O11	110.88 (13)
O4—Cu—O3	91.21 (11)	S1—O11—Cu	124.65 (12)
O1—Cu—O3	87.76 (9)	O22—S2—O23	114.37 (15)
O2—Cu—O3	177.57 (10)	O22—S2—O24	113.48 (15)
O4—Cu—O22	91.55 (10)	O23—S2—O24	110.06 (12)
O1—Cu—O22	88.45 (9)	O22—S2—O21	103.44 (13)
O2—Cu—O22	93.69 (9)	O23—S2—O21	107.35 (14)
O3—Cu—O22	87.49 (10)	O24—S2—O21	107.53 (14)
O4—Cu—O11	93.07 (9)	S2—O21—H21	109.5
O1—Cu—O11	86.81 (8)	S2—O22—Cu	169.84 (15)
O2—Cu—O11	92.29 (8)	C2—N3—C1	115.2 (3)
O3—Cu—O11	86.36 (9)	C2—N3—H3A	108.5
O22—Cu—O11	172.37 (7)	C1—N3—H3A	108.5
Cu—O1—H1D	118 (3)	C2—N3—H3B	108.5
Cu—O1—H1E	122 (3)	C1—N3—H3B	108.5
H1D—O1—H1E	106 (4)	H3A—N3—H3B	107.5
Cu—O2—H2D	118 (2)	N3—C1—H1A	109.5
Cu—O2—H2E	125 (3)	N3—C1—H1B	109.5
H2D—O2—H2E	106 (4)	H1A—C1—H1B	109.5
Cu—O3—H3D	123 (3)	N3—C1—H1C	109.5
Cu—O3—H3E	123 (3)	H1A—C1—H1C	109.5
H3D—O3—H3E	111 (4)	H1B—C1—H1C	109.5
Cu—O4—H4D	132 (3)	N3—C2—H2A	109.5
Cu—O4—H4E	124 (3)	N3—C2—H2B	109.5
H4D—O4—H4E	104 (4)	H2A—C2—H2B	109.5
O14—S1—O12	107.74 (15)	N3—C2—H2C	109.5
O14—S1—O13	107.63 (17)	H2A—C2—H2C	109.5
O12—S1—O13	108.58 (17)	H2B—C2—H2C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O13i	0.90	2.22	2.932 (4)	136
N3—H3A···O11ii	0.90	2.00	2.871 (3)	164
O1—H1D···O12iii	0.84 (2)	1.82 (2)	2.656 (3)	175 (4)
O1—H1E···O12iv	0.85 (2)	1.85 (2)	2.687 (3)	171 (4)
O2—H2D···O24v	0.85 (2)	1.90 (2)	2.745 (3)	174 (3)
O2—H2E···O24vi	0.84 (2)	1.94 (2)	2.777 (3)	174 (4)
O3—H3D···O23vii	0.86 (2)	1.87 (2)	2.722 (3)	173 (4)
O3—H3E···O14iv	0.85 (2)	1.82 (2)	2.661 (3)	167 (4)
O4—H4D···O23vi	0.84 (2)	1.91 (2)	2.753 (3)	175 (4)
O4—H4E···O14viii	0.87 (2)	1.76 (2)	2.627 (3)	171 (5)
O21—H21···O13ix	0.82	1.71	2.484 (3)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O13i	0.90	2.22	2.932 (4)	136
N3—H3A⋯O11ii	0.90	2.00	2.871 (3)	164
O1—H1D⋯O12iii	0.84 (2)	1.82 (2)	2.656 (3)	175 (4)
O1—H1E⋯O12iv	0.85 (2)	1.85 (2)	2.687 (3)	171 (4)
O2—H2D⋯O24v	0.85 (2)	1.90 (2)	2.745 (3)	174 (3)
O2—H2E⋯O24vi	0.84 (2)	1.94 (2)	2.777 (3)	174 (4)
O3—H3D⋯O23vii	0.86 (2)	1.87 (2)	2.722 (3)	173 (4)
O3—H3E⋯O14iv	0.85 (2)	1.82 (2)	2.661 (3)	167 (4)
O4—H4D⋯O23vi	0.84 (2)	1.91 (2)	2.753 (3)	175 (4)
O4—H4E⋯O14viii	0.87 (2)	1.76 (2)	2.627 (3)	171 (5)
O21—H21⋯O13ix	0.82	1.71	2.484 (3)	156

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .