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The CuI atom in the title complex, [Cu(NH2SO3)2(C3H8N)(H2O)], is coordinated by the C=C bond of the allyl­ammonium cation, two N atoms of the sulfamate anions and the O atom of the H2O mol­ecule in the apical position. Thus, the central atom is in a distorted trigonal–pyramidal environment. Strong N—H...O and O—H...O contacts connect separate moieties of the complex into a three-dimensional framework. The title compound is representative of hitherto unknown copper(I)–sulfamate π-complexes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100016218/av1052sup1.cif
Contains datablocks cusa, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100016218/av1052Isup2.hkl
Contains datablock I

CCDC reference: 159979

Comment top

The complexation of allylamine (AA) with copper(I) is rather diversified because of versatile properties of AA and because of its simple structure and abundance of related allylic compounds in organic synthesis. The dual character of coordination abilities of AA as π,σ-ligand was manifested in CuX.AA (X = Cl, Br) complexes (Fayad et al., 1991). However, AA, being in the protonated form (as H+AA cation), reveals new faces of its π-coordination behaviour regarding CuI. The possibility to form strong N—H···E hydrogen bonds promotes participation of strong acids anions in the structure formation of copper(I) compounds, leading to formation of a new class of mixed-ligand cationic copper(I) π-complexes, such as [Cu2Cl2(H+AA)2](NO3)2 (Olijnyk & Myskiv, 1995), [Cu2X2(H+AA)2(H2O)]SO4 (Myskiv et al., 1994) or [Cu(OOCH)(H+AA)]CuX2 (X = Cl, Br) (Mykhalichko et al., 1994), as well as zwitterionic π-compounds, for instance, [H+AA]CuX2 (X = Cl, Br) (Myskiv et al., 1991) and [(H+AA)CuCl(NCCH2COO)] (Olijnyk et al., 1997). On the other hand, nature of the copper(I) salt anion sometimes plays a decisive role in a formation of stable solid π-complexes as it occurred in the case of [Cu2(C6H6)(CF3SO3)2] compound, in spite of the typically weak Cu(I)-(aromatic ring) interactions (Dines & Bird, 1973). Hence, copper(I) sulfamate was chosen by us as an initial salt to study its complexation abilities with allylammonium salts. \sch

The compound [(H+AA)Cu(NH2SO3)2(H2O)], (I), appears to be a zwitterionic π-complex formed by copper(I) sulfamate and allylammonium sulfamate. A sulfamic anion exhibits its coordination ability with respect to the CuI through CuI—N bonds of 2.050 (3) and 2.066 (3) Å. The third coordination place is occupied by CC group of the H+AA cation [CuI—(CC) 1.935 (3) Å]. An axial O atom from the H2O molecule [Cu—O 2.348 (3) Å] completes a copper(I) atom environment to a trigonal pyramid. A view of the asymmetric unit of (I) with our numbering scheme is in Fig. 1 and selected dimensions are in Table 1. The extent of the pyramidal distortion of the coordination sphere conforms to a certain deviation (0.203 Å) of the Cu atom from the plane of equatorial ligands (through N1, N2 and a mid-point of C1C2). The tilt of π-coordinated double bond from this plane equals 10.0°. The coordinated olefinic group C1C2 is elongated to 1.359 (5) Å. A zwitterionic nature of the complex causes monodentate function of the ligands and, in turn, mononuclear character of (I). In zwitterionic complexes, less condensed fragments occur because of rise of ionic interactions and formation of strong hydrogen bonds. Similar complex structure construction with monodentate anions one can denote in the [(C3H5)2NH2][Cu(NO3)2] zwitterionic compound (Olijnyk et al., 1995). Even the copper(I) π-compound of [(H+AA)CuCl(NCCH2COO)] composition, due to its similar zwitterionic character, does not contain any polynuclear CuCl-fragment, typical of copper(I) chloride complexes.

Since in copper(I) π-complexes donor-acceptor (ML)-σ-component is more efficient than (ML)-π-dative component, N atom with sharply pronounced donor properties suppresses markedly CuI—(CC) interaction (Myskiv & Olijnyk, 1995). Nevertheless, in the discussed complex CC bond competes successfully with the two nitrogen atoms for the coordination to CuI. This should be attributed to N—H···O bonds of 2.08–2.32 Å (Table 2), which makes the nitrogen atom more hard base with respect to soft acid Cu+. Due to such contacts the nitrogen atom of NH2SO2O- moiety partially loses the donor properties and enables the CuI—(CC) interaction. Actually, Cu+ cation is not so strongly bonded to N atoms as H+ in a zwitterionic form of sulfamic acid. This appears in much more shorter S—N distances in (I) as compared with the value of 1.772 (1) Å in the case of NH3+—SO3- (Cameron & Duncanson, 1976). Both the independent NH2SO3- ions are characterized by a slightly distorted tetrahedral geometry of S and N atoms. Other hydrogen bonds in the title structure, namely (C3H5N)H3+···O (2.10–2.12 Å) and (O)H2···O (2.02–2.10 Å) (Table 2), combine separate complex units into a three-dimensional framework (Fig. 2).

Finally, it should be noticed that the title compound is not only a new representative of copper(I) zwitterionic π-complexes with allylammonium ligand, but is one of the first copper(I) sulfamate π-complexes.

Related literature top

For related literature, see: Cameron & Duncanson (1976); Dines & Bird (1973); Fayad et al. (1991); Mykhalichko et al. (1994); Myskiv & Olijnyk (1995); Myskiv et al. (1991, 1994); Olijnyk & Myskiv (1995); Olijnyk et al. (1997); Olijnyk, Glowiak & Myskiv (1995).

Experimental top

To a water-ethanol (1:1) saturated solution of copper(I) sulfamate hydrate (3 ml) of ethanolic solution (2 ml) of allylamine (10 mmol, 0.75 ml), previously titrated by sulfamic acid to pH = 5, was added. The prepared solution was placed into a 6 ml test-tube and copper-wire electrodes in cork were inserted. Under alternating current (frequency 50 Hz) of 0.45 V colorless crystals of the complex have appeared on copper electrodes over 1 day.

Refinement top

The H atoms of H2O molecule were located in a difference electron-density map and were refined freely. The rest of H atoms were treated using a riding model (N—H 0.90; C—H 0.93–0.97 Å). For the –NH3 group, variable metric rigid group refinement (AFIX 135 instruction) was used. The residual electron-density maximum is 1.22 Å from Cu.

Computing details top

Data collection: CAD-4 Software (Enraf Nonius, 1994); cell refinement: CAD-4 Software; data reduction: Corinc (Dräger & Gattow, 1971); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The two-dimensional network assembled from hydrogen bonds.
aqua(η2-allylammonium)bis(sulfamato-N)copper(I) top
Crystal data top
[Cu(C3H8N)(NH2SO3)2(H2O)]F(000) = 680
Mr = 331.83Dx = 1.939 Mg m3
Dm = 1.92 Mg m3
Dm measured by flotation in CHCl3/CHBr3 mixture
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
a = 13.5437 (5) ÅCell parameters from 25 reflections
b = 8.8923 (1) Åθ = 32.5–37°
c = 9.7121 (4) ŵ = 6.45 mm1
β = 103.593 (2)°T = 298 K
V = 1136.91 (6) Å3Plate, colourless
Z = 40.20 × 0.17 × 0.05 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
2303 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.000
Graphite monochromatorθmax = 74.7°, θmin = 3.4°
ω/2θ scansh = 160
Absorption correction: psi scans
(Corinc; Dräger & Gattow, 1971)
k = 011
Tmin = 0.359, Tmax = 0.739l = 1112
2332 measured reflections3 standard reflections every 60 min
2332 independent reflections intensity decay: no decay, variation 0.5%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.117 w = 1/[σ2(Fo2) + (0.0575P)2 + 2.2982P]
where P = (Fo2 + 2Fc2)/3
S = 1.25(Δ/σ)max < 0.001
2332 reflectionsΔρmax = 0.74 e Å3
170 parametersΔρmin = 0.78 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0070 (5)
Crystal data top
[Cu(C3H8N)(NH2SO3)2(H2O)]V = 1136.91 (6) Å3
Mr = 331.83Z = 4
Monoclinic, P21/cCu Kα radiation
a = 13.5437 (5) ŵ = 6.45 mm1
b = 8.8923 (1) ÅT = 298 K
c = 9.7121 (4) Å0.20 × 0.17 × 0.05 mm
β = 103.593 (2)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
2303 reflections with I > 2σ(I)
Absorption correction: psi scans
(Corinc; Dräger & Gattow, 1971)
Rint = 0.000
Tmin = 0.359, Tmax = 0.7393 standard reflections every 60 min
2332 measured reflections intensity decay: no decay, variation 0.5%
2332 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 1.25Δρmax = 0.74 e Å3
2332 reflectionsΔρmin = 0.78 e Å3
170 parameters
Special details top

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.

Mean-plane data from final SHELXL refinement run:

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 1.6732 x - 3.8823 y + 8.6944 z = 1.0351

* 0.0000 M12 (mid-point of C1—C2 distance) * 0.0000 N1 * 0.0000 N2 - 0.2031 Cu

Rms deviation of fitted atoms = 0.0000

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu0.21481 (3)0.44817 (5)0.33716 (5)0.0174 (2)
S10.02568 (5)0.28010 (8)0.41619 (8)0.0173 (2)
S20.36509 (5)0.17255 (8)0.39079 (7)0.0167 (2)
O10.0771 (2)0.1461 (3)0.3855 (3)0.0280 (5)
O20.0582 (3)0.3308 (4)0.5598 (3)0.0445 (8)
O30.0830 (2)0.2706 (3)0.3647 (4)0.0443 (8)
O40.3746 (2)0.0161 (3)0.3606 (4)0.0426 (7)
O50.44758 (17)0.2618 (3)0.3620 (2)0.0232 (5)
O60.3459 (2)0.2022 (3)0.5285 (3)0.0331 (6)
O70.1960 (2)0.5313 (3)0.1029 (3)0.0244 (5)
H130.173 (4)0.483 (6)0.043 (6)0.036 (14)*
H140.167 (4)0.594 (6)0.100 (5)0.029 (13)*
N10.0622 (2)0.4155 (3)0.3166 (3)0.0226 (6)
H10.03530.50310.33650.043 (13)*
H20.03430.39450.22510.08 (2)*
N20.26068 (19)0.2417 (3)0.2771 (3)0.0156 (5)
H30.20940.17560.27030.028 (11)*
H40.27370.25050.19080.038 (12)*
N30.4089 (2)0.5527 (3)0.2168 (3)0.0244 (6)
H100.43560.47300.25830.052 (16)*
H110.45180.59750.17950.031 (11)*
H120.35660.52960.15240.042 (14)*
C10.2527 (3)0.6328 (5)0.4624 (5)0.0375 (9)
H50.22250.72010.41910.034 (12)*
H60.22400.58240.52740.066 (18)*
C20.3385 (3)0.5788 (4)0.4305 (4)0.0238 (7)
H70.36790.49140.47450.058 (16)*
C30.3873 (3)0.6568 (4)0.3260 (4)0.0265 (7)
H80.34270.73640.27950.055 (15)*
H90.45040.70290.37660.048 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0166 (3)0.0126 (3)0.0257 (3)0.00059 (16)0.01033 (19)0.00149 (16)
S10.0193 (4)0.0148 (4)0.0204 (4)0.0009 (3)0.0102 (3)0.0031 (3)
S20.0201 (4)0.0126 (4)0.0194 (4)0.0056 (3)0.0087 (3)0.0033 (3)
O10.0390 (14)0.0158 (11)0.0313 (12)0.0042 (10)0.0123 (11)0.0031 (9)
O20.071 (2)0.0427 (17)0.0188 (12)0.0113 (15)0.0085 (13)0.0027 (11)
O30.0201 (13)0.0383 (16)0.075 (2)0.0061 (11)0.0128 (13)0.0182 (15)
O40.0473 (17)0.0126 (12)0.066 (2)0.0114 (11)0.0096 (15)0.0014 (12)
O50.0185 (11)0.0274 (12)0.0254 (11)0.0019 (9)0.0081 (9)0.0040 (9)
O60.0414 (15)0.0455 (16)0.0166 (11)0.0064 (12)0.0152 (10)0.0092 (11)
O70.0262 (13)0.0169 (12)0.0289 (14)0.0043 (11)0.0040 (10)0.0023 (10)
N10.0162 (12)0.0184 (13)0.0352 (15)0.0028 (10)0.0104 (11)0.0115 (11)
N20.0155 (12)0.0138 (11)0.0185 (12)0.0013 (9)0.0060 (9)0.0004 (9)
N30.0244 (14)0.0228 (15)0.0305 (15)0.0097 (11)0.0154 (12)0.0040 (12)
C10.048 (2)0.0277 (19)0.043 (2)0.0078 (17)0.0238 (19)0.0206 (17)
C20.0305 (17)0.0189 (15)0.0231 (15)0.0068 (13)0.0083 (13)0.0084 (13)
C30.0330 (18)0.0165 (15)0.0321 (17)0.0123 (13)0.0119 (14)0.0072 (13)
Geometric parameters (Å, º) top
Cu—C12.035 (4)S1—N11.690 (3)
Cu—N12.050 (3)S2—O41.433 (3)
Cu—C22.066 (3)S2—O61.446 (2)
Cu—N22.066 (3)S2—O51.450 (2)
Cu—O72.348 (3)S2—N21.692 (3)
S1—O21.433 (3)N3—C31.488 (4)
S1—O31.442 (3)C1—C21.359 (5)
S1—O11.447 (3)C2—C31.504 (5)
C1—Cu—N1106.21 (15)O1—S1—N1104.42 (14)
C1—Cu—C238.70 (15)O4—S2—O6114.23 (19)
N1—Cu—C2144.88 (13)O4—S2—O5112.45 (17)
C1—Cu—N2146.63 (15)O6—S2—O5113.12 (16)
N1—Cu—N2102.11 (11)O4—S2—N2108.69 (16)
C2—Cu—N2110.92 (12)O6—S2—N2103.45 (14)
C1—Cu—O7106.23 (15)O5—S2—N2103.82 (13)
N1—Cu—O794.19 (11)S1—N1—Cu117.98 (15)
C2—Cu—O798.05 (12)S2—N2—Cu113.55 (13)
N2—Cu—O788.73 (10)C2—C1—Cu71.8 (2)
O2—S1—O3114.3 (2)C1—C2—C3121.7 (4)
O2—S1—O1114.02 (17)C1—C2—Cu69.5 (2)
O3—S1—O1112.47 (18)C3—C2—Cu113.7 (2)
O2—S1—N1105.59 (18)N3—C3—C2112.6 (3)
O3—S1—N1104.81 (16)
O2—S1—N1—Cu66.6 (2)N1—Cu—C1—C2178.0 (2)
O3—S1—N1—Cu172.4 (2)N2—Cu—C1—C231.0 (4)
O1—S1—N1—Cu53.9 (2)O7—Cu—C1—C282.5 (3)
C1—Cu—N1—S1101.4 (2)Cu—C1—C2—C3105.9 (3)
C2—Cu—N1—S199.3 (3)N1—Cu—C2—C13.3 (4)
N2—Cu—N1—S160.7 (2)N2—Cu—C2—C1162.3 (2)
O7—Cu—N1—S1150.31 (18)O7—Cu—C2—C1105.9 (3)
O4—S2—N2—Cu165.16 (17)C1—Cu—C2—C3116.6 (4)
O6—S2—N2—Cu43.40 (18)N1—Cu—C2—C3119.9 (3)
O5—S2—N2—Cu74.94 (16)N2—Cu—C2—C381.0 (3)
C1—Cu—N2—S215.9 (3)O7—Cu—C2—C310.7 (3)
N1—Cu—N2—S2131.80 (14)C1—C2—C3—N3129.7 (4)
C2—Cu—N2—S236.06 (18)Cu—C2—C3—N350.0 (4)
O7—Cu—N2—S2134.19 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H13···O1i0.73 (6)2.10 (6)2.818 (4)167 (5)
O7—H14···O3ii0.68 (6)2.02 (6)2.682 (4)168 (5)
N1—H1···O2iii0.902.323.180 (4)159
N2—H4···O6i0.902.082.953 (3)162
N3—H10···O50.852.122.933 (4)160
N3—H11···O5iv0.852.102.920 (4)161
N3—H12···O70.852.112.841 (4)143
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y+1/2, z+1/2; (iii) x, y+1, z+1; (iv) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu(C3H8N)(NH2SO3)2(H2O)]
Mr331.83
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)13.5437 (5), 8.8923 (1), 9.7121 (4)
β (°) 103.593 (2)
V3)1136.91 (6)
Z4
Radiation typeCu Kα
µ (mm1)6.45
Crystal size (mm)0.20 × 0.17 × 0.05
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionPsi scans
(Corinc; Dräger & Gattow, 1971)
Tmin, Tmax0.359, 0.739
No. of measured, independent and
observed [I > 2σ(I)] reflections
2332, 2332, 2303
Rint0.000
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.117, 1.25
No. of reflections2332
No. of parameters170
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.74, 0.78

Computer programs: CAD-4 Software (Enraf Nonius, 1994), CAD-4 Software, Corinc (Dräger & Gattow, 1971), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Cu—C12.035 (4)Cu—O72.348 (3)
Cu—N12.050 (3)S1—N11.690 (3)
Cu—C22.066 (3)S2—N21.692 (3)
Cu—N22.066 (3)C1—C21.359 (5)
C1—Cu—C238.70 (15)N2—Cu—O788.73 (10)
N1—Cu—N2102.11 (11)S1—N1—Cu117.98 (15)
N1—Cu—O794.19 (11)S2—N2—Cu113.55 (13)
Cu—C1—C2—C3105.9 (3)C1—C2—C3—N3129.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H13···O1i0.73 (6)2.10 (6)2.818 (4)167 (5)
O7—H14···O3ii0.68 (6)2.02 (6)2.682 (4)168 (5)
N1—H1···O2iii0.902.323.180 (4)158.9
N2—H4···O6i0.902.082.953 (3)162.1
N3—H10···O50.852.122.933 (4)159.7
N3—H11···O5iv0.852.102.920 (4)160.8
N3—H12···O70.852.112.841 (4)142.9
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y+1/2, z+1/2; (iii) x, y+1, z+1; (iv) x+1, y+1/2, z+1/2.
 

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