Di-aqua-bis-(ethyl-enedi-amine-κ(2) N,N')copper(II) bis-(sulfamerazinate).

The asymmetric unit of the title compound, [Cu(C2H8N2)2(H2O)2](C11H11N4O2S)2, contains one sulfamerazinate anion in a general position and one half-cation that is located on a center of inversion. The Cu(II) cation shows a strong Jahn-Teller distortion. It is coordinated by four N atoms of two ethyl-enedi-amine ligands in the basal plane and two O atoms at much longer distances in the axial positions in a bipyramidal coordination. In the crystal, the building blocks are connected by N-H⋯N, O-H⋯N, N-H⋯O and O-H⋯O hydrogen bonding into a two-dimensional network parallel to (001).

Related literature

For the anti­bacterial activity of sulfonamides, see: Anand (1980 ▶); Kratz et al. (2000 ▶); Grave et al. (2010 ▶). For uses of sulfamerazine, see: Murphy et al. (1943 ▶); Clark et al. (1943 ▶); Earle (1944 ▶); Forbes et al. (1946 ▶). The crystal structure of sulfamerazine was reported by Acharya et al. (1982 ▶). For a related compound in which sulfa­thia­zole acts as a deproton­ated counter-ion, see: Anacona et al. (2002 ▶).

Experimental

Crystal data

[Cu(C2H8N2)2(H2O)2](C11H11N4O2S)2

M = 746.41

Triclinic,

a = 7.5429 (4) Å

b = 8.1800 (5) Å

c = 14.8434 (8) Å

α = 75.299 (5)°

β = 82.800 (5)°

γ = 78.873 (5)°

V = 866.40 (9) Å3

Z = 1

Mo Kα radiation

μ = 0.81 mm−1

T = 293 K

0.41 × 0.36 × 0.17 mm

Data collection

Oxford Diffraction Gemini diffractometer

Absorption correction: analytical (de Meulenaer & Tompa, 1965 ▶) T min = 0.723, T max = 0.869

4738 measured reflections

4020 independent reflections

3361 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.097

S = 1.05

4020 reflections

215 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.38 e Å−3

Data collection: GEMINI (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681401068X/nc2325sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401068X/nc2325Isup2.hkl

CCDC reference: 1002145

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

[Cu(C2H8N2)2(H2O)2](C11H11N4O2S)2	Z = 1
Mr = 746.41	F(000) = 391
Triclinic, P1	Dx = 1.431 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 7.5429 (4) Å	Cell parameters from 3709 reflections
b = 8.1800 (5) Å	θ = 3–29°
c = 14.8434 (8) Å	µ = 0.81 mm−1
α = 75.299 (5)°	T = 293 K
β = 82.800 (5)°	Block, blue
γ = 78.873 (5)°	0.41 × 0.36 × 0.17 mm
V = 866.40 (9) Å3

Oxford Diffraction Gemini diffractometer	4020 independent reflections
Radiation source: fine-focus sealed tube	3361 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω/2θ scans	θmax = 29.3°, θmin = 2.9°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = −10→7
Tmin = 0.723, Tmax = 0.869	k = −9→11
4738 measured reflections	l = −20→18

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0359P)2 + 0.4528P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
4020 reflections	Δρmax = 0.33 e Å−3
215 parameters	Δρmin = −0.38 e Å−3
0 restraints

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K.Cosier, J. & Glazer, A·M., 1986. J. Appl. Cryst. 105–107.

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	0.5	0	0	0.03130 (12)
S1	0.93674 (7)	0.08503 (7)	0.18420 (3)	0.03012 (13)
O1	0.7864 (2)	−0.0053 (2)	0.18937 (11)	0.0387 (4)
O2	1.0053 (2)	0.1546 (2)	0.08903 (10)	0.0428 (4)
C20	0.8897 (3)	0.5351 (3)	0.25274 (16)	0.0355 (5)
H20	0.9615	0.6189	0.2451	0.043*
N13	0.9256 (2)	−0.0906 (2)	0.37617 (12)	0.0347 (4)
C21	0.9576 (3)	0.3893 (3)	0.22151 (15)	0.0346 (5)
H21	1.0743	0.3759	0.1924	0.041*
C16	0.8532 (3)	0.2613 (3)	0.23311 (14)	0.0291 (4)
O1W	0.4227 (2)	0.1071 (3)	0.14692 (12)	0.0552 (5)
C12	0.9149 (3)	−0.1728 (3)	0.46614 (16)	0.0435 (6)
C11	1.0858 (3)	−0.1138 (3)	0.32650 (15)	0.0310 (4)
N11	1.1063 (2)	−0.0306 (2)	0.23427 (12)	0.0325 (4)
N12	1.2372 (3)	−0.2157 (3)	0.36031 (14)	0.0469 (5)
C15	0.7356 (4)	−0.1427 (5)	0.5202 (2)	0.0659 (8)
H15A	0.6836	−0.0235	0.5029	0.099*
H15B	0.752	−0.1751	0.5858	0.099*
H15C	0.656	−0.2102	0.5066	0.099*
C13	1.0634 (4)	−0.2794 (4)	0.5060 (2)	0.0652 (9)
H13	1.0572	−0.3371	0.5686	0.078*
C14	1.2192 (4)	−0.2967 (4)	0.4501 (2)	0.0658 (9)
H14	1.3198	−0.3699	0.4761	0.079*
C17	0.6811 (3)	0.2811 (3)	0.27905 (14)	0.0323 (5)
H17	0.6123	0.1942	0.2895	0.039*
N14	0.6421 (3)	0.7043 (3)	0.32650 (17)	0.0488 (5)
C19	0.7133 (3)	0.5595 (3)	0.29608 (15)	0.0328 (5)
C18	0.6118 (3)	0.4279 (3)	0.30924 (15)	0.0343 (5)
H18	0.4955	0.44	0.3389	0.041*
N1	0.6743 (3)	−0.2106 (2)	0.05258 (13)	0.0382 (4)
H1NA	0.7839	−0.2193	0.011	0.046*
H1NB	0.7067	−0.2059	0.113	0.046*
N2	0.3086 (3)	−0.1504 (2)	0.04393 (14)	0.0394 (4)
H2NA	0.2099	−0.0953	0.0802	0.047*
H2NB	0.2601	−0.1696	−0.0093	0.047*
C1	0.5849 (4)	−0.3587 (3)	0.06228 (18)	0.0455 (6)
H1A	0.6484	−0.4586	0.1035	0.055*
H1B	0.5857	−0.384	0.0018	0.055*
C2	0.3928 (4)	−0.3160 (3)	0.10211 (18)	0.0476 (6)
H2A	0.3254	−0.4055	0.1017	0.057*
H2B	0.3916	−0.3071	0.1661	0.057*
H14A	0.5169	0.7352	0.3264	0.05*
H14B	0.7011	0.801	0.3119	0.05*
H1W	0.5101	0.0795	0.182	0.05*
H2W	0.3232	0.0599	0.182	0.05*

	U11	U22	U33	U12	U13	U23
Cu1	0.0291 (2)	0.0302 (2)	0.0334 (2)	−0.00225 (15)	−0.00634 (15)	−0.00569 (15)
S1	0.0257 (3)	0.0345 (3)	0.0295 (3)	−0.0024 (2)	−0.0030 (2)	−0.0079 (2)
O1	0.0305 (8)	0.0411 (9)	0.0488 (9)	−0.0061 (7)	−0.0087 (7)	−0.0156 (7)
O2	0.0432 (9)	0.0525 (10)	0.0277 (8)	−0.0025 (8)	0.0009 (7)	−0.0066 (7)
C20	0.0292 (11)	0.0323 (12)	0.0452 (12)	−0.0109 (9)	−0.0030 (9)	−0.0056 (10)
N13	0.0300 (9)	0.0369 (10)	0.0354 (10)	−0.0041 (8)	−0.0007 (8)	−0.0071 (8)
C21	0.0246 (10)	0.0390 (12)	0.0381 (12)	−0.0075 (9)	0.0004 (9)	−0.0051 (9)
C16	0.0275 (10)	0.0282 (10)	0.0294 (10)	−0.0025 (8)	−0.0047 (8)	−0.0035 (8)
O1W	0.0365 (9)	0.0874 (14)	0.0414 (10)	−0.0189 (9)	−0.0090 (7)	−0.0056 (9)
C12	0.0428 (13)	0.0493 (15)	0.0367 (12)	−0.0103 (11)	0.0000 (10)	−0.0068 (11)
C11	0.0270 (10)	0.0300 (11)	0.0366 (11)	−0.0028 (8)	−0.0029 (8)	−0.0099 (9)
N11	0.0231 (9)	0.0370 (10)	0.0342 (9)	−0.0004 (7)	−0.0007 (7)	−0.0066 (8)
N12	0.0329 (10)	0.0558 (13)	0.0437 (12)	0.0082 (9)	−0.0079 (9)	−0.0061 (10)
C15	0.0537 (17)	0.087 (2)	0.0487 (16)	−0.0136 (16)	0.0144 (13)	−0.0092 (15)
C13	0.0594 (18)	0.082 (2)	0.0379 (14)	0.0001 (16)	−0.0060 (13)	0.0082 (14)
C14	0.0506 (17)	0.078 (2)	0.0508 (17)	0.0136 (15)	−0.0142 (13)	0.0038 (15)
C17	0.0303 (11)	0.0299 (11)	0.0362 (11)	−0.0091 (9)	−0.0002 (9)	−0.0053 (9)
N14	0.0372 (11)	0.0357 (11)	0.0781 (15)	−0.0080 (9)	0.0029 (10)	−0.0239 (10)
C19	0.0316 (11)	0.0300 (11)	0.0357 (11)	−0.0049 (9)	−0.0051 (9)	−0.0050 (9)
C18	0.0252 (10)	0.0361 (12)	0.0397 (12)	−0.0047 (9)	0.0017 (9)	−0.0075 (9)
N1	0.0359 (10)	0.0388 (11)	0.0353 (10)	0.0005 (8)	−0.0066 (8)	−0.0037 (8)
N2	0.0352 (10)	0.0417 (11)	0.0429 (11)	−0.0046 (8)	−0.0037 (8)	−0.0141 (9)
C1	0.0549 (15)	0.0320 (12)	0.0446 (14)	−0.0010 (11)	−0.0043 (11)	−0.0047 (10)
C2	0.0555 (16)	0.0379 (14)	0.0468 (14)	−0.0136 (12)	0.0009 (12)	−0.0034 (11)

Cu1—N1	2.0016 (18)	C15—H15B	0.96
Cu1—N1i	2.0016 (18)	C15—H15C	0.96
Cu1—N2	2.0168 (19)	C13—C14	1.357 (4)
Cu1—N2i	2.0168 (19)	C13—H13	0.93
S1—O2	1.4524 (16)	C14—H14	0.93
S1—O1	1.4530 (16)	C17—C18	1.374 (3)
S1—N11	1.5806 (17)	C17—H17	0.93
S1—C16	1.752 (2)	N14—C19	1.364 (3)
C20—C21	1.373 (3)	N14—H14A	0.9300
C20—C19	1.404 (3)	N14—H14B	0.9500
C20—H20	0.93	C19—C18	1.399 (3)
N13—C12	1.334 (3)	C18—H18	0.93
N13—C11	1.341 (3)	N1—C1	1.465 (3)
C21—C16	1.393 (3)	N1—H1NA	0.97
C21—H21	0.93	N1—H1NB	0.97
C16—C17	1.389 (3)	N2—C2	1.481 (3)
O1W—H1W	0.8500	N2—H2NA	0.97
O1W—H2W	0.9500	N2—H2NB	0.97
C12—C13	1.376 (4)	C1—C2	1.505 (4)
C12—C15	1.494 (4)	C1—H1A	0.97
C11—N12	1.347 (3)	C1—H1B	0.97
C11—N11	1.370 (3)	C2—H2A	0.97
N12—C14	1.332 (3)	C2—H2B	0.97
C15—H15A	0.96
N1—Cu1—N1i	180	N12—C14—C13	124.2 (2)
N1—Cu1—N2	85.23 (8)	N12—C14—H14	117.9
N1i—Cu1—N2	94.77 (8)	C13—C14—H14	117.9
N1—Cu1—N2i	94.77 (8)	C18—C17—C16	120.5 (2)
N1i—Cu1—N2i	85.23 (8)	C18—C17—H17	119.7
N2—Cu1—N2i	180	C16—C17—H17	119.7
O2—S1—O1	113.23 (10)	C19—N14—H14A	115.00
O2—S1—N11	105.46 (9)	C19—N14—H14B	122.00
O1—S1—N11	113.64 (10)	H14A—N14—H14B	112.00
O2—S1—C16	106.20 (10)	N14—C19—C18	120.2 (2)
O1—S1—C16	106.87 (10)	N14—C19—C20	122.0 (2)
N11—S1—C16	111.27 (10)	C18—C19—C20	117.8 (2)
C21—C20—C19	121.0 (2)	C17—C18—C19	121.1 (2)
C21—C20—H20	119.5	C17—C18—H18	119.5
C19—C20—H20	119.5	C19—C18—H18	119.5
C12—N13—C11	117.89 (19)	C1—N1—Cu1	107.55 (14)
C20—C21—C16	120.5 (2)	C1—N1—H1NA	110.2
C20—C21—H21	119.7	Cu1—N1—H1NA	110.2
C16—C21—H21	119.7	C1—N1—H1NB	110.2
C17—C16—C21	119.0 (2)	Cu1—N1—H1NB	110.2
C17—C16—S1	121.54 (16)	H1NA—N1—H1NB	108.5
C21—C16—S1	119.33 (16)	C2—N2—Cu1	108.34 (14)
H1W—O1W—H2W	107.00	C2—N2—H2NA	110
N13—C12—C13	120.8 (2)	Cu1—N2—H2NA	110
N13—C12—C15	116.8 (2)	C2—N2—H2NB	110
C13—C12—C15	122.4 (2)	Cu1—N2—H2NB	110
N13—C11—N12	124.9 (2)	H2NA—N2—H2NB	108.4
N13—C11—N11	120.69 (18)	N1—C1—C2	108.2 (2)
N12—C11—N11	114.39 (19)	N1—C1—H1A	110.1
C11—N11—S1	119.66 (14)	C2—C1—H1A	110.1
C14—N12—C11	115.0 (2)	N1—C1—H1B	110.1
C12—C15—H15A	109.5	C2—C1—H1B	110.1
C12—C15—H15B	109.5	H1A—C1—H1B	108.4
H15A—C15—H15B	109.5	N2—C2—C1	108.23 (19)
C12—C15—H15C	109.5	N2—C2—H2A	110.1
H15A—C15—H15C	109.5	C1—C2—H2A	110.1
H15B—C15—H15C	109.5	N2—C2—H2B	110.1
C14—C13—C12	117.2 (2)	C1—C2—H2B	110.1
C14—C13—H13	121.4	H2A—C2—H2B	108.4
C12—C13—H13	121.4
C19—C20—C21—C16	−0.7 (3)	C16—S1—N11—C11	64.56 (19)
C20—C21—C16—C17	−1.8 (3)	N13—C11—N12—C14	0.1 (4)
C20—C21—C16—S1	174.88 (16)	N11—C11—N12—C14	179.7 (2)
O2—S1—C16—C17	129.97 (17)	N13—C12—C13—C14	0.0 (5)
O1—S1—C16—C17	8.82 (19)	C15—C12—C13—C14	−179.9 (3)
N11—S1—C16—C17	−115.76 (17)	C11—N12—C14—C13	−1.0 (5)
O2—S1—C16—C21	−46.61 (18)	C12—C13—C14—N12	1.0 (5)
O1—S1—C16—C21	−167.75 (16)	C21—C16—C17—C18	2.7 (3)
N11—S1—C16—C21	67.66 (18)	S1—C16—C17—C18	−173.90 (16)
C11—N13—C12—C13	−0.8 (4)	C21—C20—C19—N14	−179.1 (2)
C11—N13—C12—C15	179.1 (2)	C21—C20—C19—C18	2.2 (3)
C12—N13—C11—N12	0.8 (3)	C16—C17—C18—C19	−1.1 (3)
C12—N13—C11—N11	−178.8 (2)	N14—C19—C18—C17	180.0 (2)
N13—C11—N11—S1	−3.7 (3)	C20—C19—C18—C17	−1.3 (3)
N12—C11—N11—S1	176.63 (17)	Cu1—N1—C1—C2	−43.1 (2)
O2—S1—N11—C11	179.29 (17)	Cu1—N2—C2—C1	−35.0 (2)
O1—S1—N11—C11	−56.1 (2)	N1—C1—C2—N2	52.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O2ii	0.97	2.09	3.022 (3)	162
O1W—H1W···O1	0.85	2.07	2.816 (2)	145
N1—H1NB···O1	0.97	2.41	3.219 (2)	140
O1W—H2W···N11iii	0.95	1.92	2.858 (2)	171
N2—H2NA···O2iii	0.97	2.33	3.189 (3)	147
N2—H2NA···N11iii	0.97	2.47	3.319 (3)	145
N2—H2NB···O2i	0.97	2.42	3.277 (3)	147
N14—H14A···N12iv	0.93	2.09	3.003 (3)	166
N14—H14B···O1v	0.95	2.21	2.993 (3)	140
N14—H14B···N13v	0.95	2.44	3.215 (3)	139
C17—H17···O1	0.93	2.55	2.915 (3)	104

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯O2i	0.97	2.09	3.022 (3)	162
O1W—H1W⋯O1	0.85	2.07	2.816 (2)	145
N1—H1NB⋯O1	0.97	2.41	3.219 (2)	140
O1W—H2W⋯N11ii	0.95	1.92	2.858 (2)	171
N2—H2NA⋯O2ii	0.97	2.33	3.189 (3)	147
N2—H2NA⋯N11ii	0.97	2.47	3.319 (3)	145
N2—H2NB⋯O2iii	0.97	2.42	3.277 (3)	147
N14—H14A⋯N12iv	0.93	2.09	3.003 (3)	166
N14—H14B⋯O1v	0.95	2.21	2.993 (3)	140
N14—H14B⋯N13v	0.95	2.44	3.215 (3)	139

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