Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614021123/sk3562sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614021123/sk3562Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614021123/sk3562IIsup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229614021123/sk3562figS1sup4.pdf | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229614021123/sk3562figS2sup5.pdf |
CCDC references: 1025538; 1025539
Trace minerals represent a tiny proportion of the body tissue of living organisms, but they play a major role in their metabolism. The chemical form of the trace mineral has a considerable influence on its stability towards dietary ingredients like phytic acids (Vohra et al., 1965; Zhou et al., 1992) or phenolic compounds (Cook, 1990; Hurrell, 1997). Interactions can occur between them to produce insoluble components which result in a decrease in absorption of the mineral. These reactions especially concern the inorganic forms of trace minerals, for example, sulfates and oxides. Organic trace mineral forms, such as chelates, proteinates, polysaccharides and complexes, can offer protection against anti-nutritional components, depending on the stability of the chemical bonding between the metal and the ligand(s). It has been shown (Wichert et al., 2002; Spears et al., 2004; Schlegel & Windisch, 2006) that the absorption of zinc(II), for example, is superior in the complexed form rather than simply using zinc(II) sulfate. The bioavailability of copper from copper glycinate in steers fed high dietary sulfur and molybdenum has also been shown to be more effective than using copper(II) sulfate (Hansen et al., 2008). The critical part of the synthesis of such compounds lies in the manufacturing process used to obtain the correct hydrated form (Jacquier & Oguey, 2003; Meunier & Oguey, 2010). Their stability towards moisture conditions is extremely important and, for practical purposes, a free-flowing powder must be obtained in order to avoid the so called `caking phenomenon'. These crystalline organic trace mineral complexes were obtained by the reaction of metal sulfates with glycine. Two zinc(II) sulfate glycine complexes, formed under vacuum (Jacquier & Oguey, 2003), are in fact the product sold as an animal feed additive under the trade name of B-TRAXIM 2C (Pancosma SA) (Oguey et al., 2008).
Recently, the equilibrium crystallization and characterization of a series of glycine metal sulfate complexes have been reported (Tepavitcharova et al., 2012). The Gly–MSO4–H2O systems (M = MnII, FeII, CoII, ZnII and MgII) were studied by isothermal decrease of supersaturated solutions at different temperatures. They identified a number of complexes with varying water content and described the crystal structures of three ionic complexes involving magnesium(II), cobalt(II) and zinc(II), and a one-dimensional glycine cobalt(II) sulfate complex. Herein, we report the structure of a unique pentacoordinate copper(II) sulfate complex of glycine and its solid-state transformation, by heating/dehydration, from a one-dimensional to a two-dimensional coordination polymer.
In recent years there have been a number of reports of in situ single-crystal to single-crystal (SCSC) transformations (He et al., 2014; Uchida et al., 2013; Halasz, 2010; Li et al., 2009), and the subject of SCSC [2+2] photodimerizations has been reviewed by Friscic & MacGillivray (2005). Recently, reversible SCSC [2,2]-cycloaddition reactions have also been reported (Park et al., 2014). We have, for example, described the transformation of the ionic complex aquachlorido(2,2':6',2''-terpyridyl-κ3N,N',N'')copper(II) chlorido(dithionato-κO)(2,2':6',2''-terpyridyl-κ3N,N',N'') cuprate(II) dihydrate into the binuclear complex (µ-dithionato-κ2O:O')-bis[chlorido(2,2':6',2''-terpyridyl-κ3N,N',N'')copper(II)] monohydrate (Schmitt et al., 2010). On heating the crystal, the coordinated water molecule of the cation was lost and the vacant site on the CuII cation atom was occupied by an O atom of the adjacent dithionate anion.
Complex (I) was synthesized by slow evaporation of a saturated equimolar mixture of copper(II) sulfate and glycine in water under vacuum, using the technique developed by Pancosma SA (Jacquier & Oguey, 2003). A differential scanning calorimetry (DSC) measurement (Fig. S1 in the supporting information) indicated that an endothermic transformation takes place at ca 433 K. As our cryosystem did not allow us to heat the crystal on the diffractometer above 393 K, the same blue crystal used for the X-ray diffraction analysis of (I) was heated to 435 K in an oven and was found to transform into a very pale-blue crystal of (II), as shown in Fig. 1. The same transformation was also followed by variable-temperature powder X-ray diffraction (VT-PXRD), as shown in Fig. 2.
Crystal data, data collection and structure refinement details are summarized in Table 1. While (I) crystallizes in the centrosymmetric monoclinic space group P21/c, compound (II) crystallized as a non-merohedral twin in the noncentrosymmetric monoclinic space group P21. Both general twinning and inversion twinning for both components were refined with the instructions TWIN -1 0 0 0 -1 0 1 0 1 -4 and BASF 0.20 (8) 0.30 (10) 0.20 (9) (SHELXL2014; Sheldrick, 2008), implying a 180° rotation about the c* axis. These are the final refined values; the first parameter is the general twinning factor, while the second and third are the first and second component inversion twin factors, respectively. Correction for twinning reduced the R factor for the observed data [I > 2σ(I)] from 0.1237 to 0.0558. For (I), the H atoms of the water molecules and the NH3+ group were located in a difference Fourier map and freely refined. For (II), the NH3+ H atoms were included in calculated positions and treated as riding atoms, with N—H = 0.91 Å and with Uiso(H) = 1.2Ueq(N). In both (I) and (II), the methylene H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C).
The asymmetric unit of (I) consists of a CuII cation, a glycine molecule present in the zwitterion form, a sulfate anion and two water molecules (Fig. 3), and forms a one-dimensional zigzag coordination polymer (Fig. 4). Atom Cu1 is pentacoordinate and has an almost perfect square-pyramidal geometry, with a τ value of 0.06 (Addison et al., 1984; τ = 0 for a perfect square-pyramid; τ = 1 for perfect triangular-based pyramid). In the equatorial plane it is coordinated by two water molecules (atoms O1W and O2W) and two O atoms of bridging glycine carboxylate groups (atoms O1 and O2), and in the apical position by a sulfate O atom (O11). Atom Cu1 is displaced by 0.1856 (2) Å from the mean plane through atoms O1W/O2W/O1/O2 [maximum deviation 0.0337 (18) Å [For which atom?]] towards sulfate O atom O11. The Cu—O(water) bonds are slightly longer than the Cu—O(carboxylate) bonds (Table 2), while the apical Cu1—O11 bond is longer, at 2.2179 (17) Å. The intra-chain Cu···Cu distance is 4.7498 (6) Å, while the shortest inter-chain Cu···Cu distance is 5.6118 (7) Å.
In the crystal structure of (I), the one-dimensional polymers that propagate in the [001] direction are linked via N—H···O and O—H···O and bifurcated O—H,H···O and N—H···O,O hydrogen bonds, forming a three-dimensional framework (Fig. 5 and Table 3). There is also a C—H···O hydrogen bond present that consolidates the three-dimensional structure (Table 3).
After heating the same crystal of (I) to 435 K in an oven, it was remounted on the diffractometer and a full data set was measured at 173 K. It can be seen that the quality of the crystal was not as good as before (Fig. 1). When comparing typical diffraction images for the two crystals it is seen that, for (II), there are a significant number of powder diffraction lines present. However, the data were good enough to determine the crystal structure.
The asymmetric unit of (II) consists of a CuII cation, a glycine molecule present in the zwitterion form and a sulfate anion (Fig. 6). Two water molecules have been lost and the polymer chains of (I) have reorganized themselves to form a two-dimensional network (Fig. 7). The coordination sites on the CuII cation in (I) liberated by the water molecules are now occupied by sulfate O atoms.
One possible explanation for the transformation pathway is illustrated in Fig. 8. Comparing Figs. 8(a) and 8(b), it can be seen that the zigzag chains in (I) are now horizontal in (II). We propose that the coordinated sulfate O atom in (I), viz. O11, moves to coordinate the adjacent CuII cation, so forming a Cu—O—Cu bridge. This involves a twisting of the chains, resulting in a change in the intra-chain Cu1···Cu1 distance from 4.7498 (6) Å in (I) to 3.8998 (6) Å in (II). The sulfate group is then in a position where atoms O12 and O13 can coordinate and bridge two CuII cations of the adjacent chain, so forming a two-dimensional network. One problem that we have not, as yet, been able to explain is the change from a centrosymmetric arrangement in (I) to a noncentrosymmetric arrangement in (II).
In (II), atom Cu1 now has an octahedral coordination environment and exhibits a typical pseudo-Jahn–Teller distortion. In the equatorial plane it is coordinated by two O atoms of bridging carboxylate groups, O1 and O2i [symmetry code: (i) -x, 1/2 + y, 1 - z], and two sulfate O atoms, O13i and O11, with similar bond lengths (Table 4). The axial positions are occupied by a bridging sulfate O atom (O14), with Cu—O bond lengths of 2.50 (2) Å (Table 4).
In the crystal of (II), the two-dimensional networks lying parallel to (001) are linked via bifurcated N—H,H···O and N—H···O,O hydrogen bonds, forming a three-dimensional framework (Fig. 9 and Table 5). There is also a C—H···O hydrogen bond present that consolidates the three-dimensional structure (Table 5).
A search of the Cambridge Structural Database (CSD; Version 5.35, last update May 2014; Allen, 2002) for transition metal complexes of glycine gave 400 hits. However, restricting the search to glycine (NH2CH2COO; with any type of C—O bond), sulfate, MgII and first-row transition metals indicated the presence of only 14 complexes, some of which have been reported more than once. These include a number of ionic complexes, such as tetraaquabis(glycine-O)iron(II) hexaaquairon(II) bis(sulfate) (Lindqvist & Rosenstein, 1960), one-dimensional coordination polymers, for example catena-poly[[(µ2glycine)-sulfatotriaqua]zinc(II)] (Fleck & Bohatý, 2004) and catena-poly[[bis(µ2-gylcinato)-hexaaquadisulfato]dicobalt(II)] (Tepavitcharova et al., 2012), and a two-dimensional MnII coordination polymer (Weng et al., 2009). In all of these complexes the glycine molecule exists in the zwitterion form and coordinates the metal via the carboxylate group, the amine group always being protonated.
Complex (I) is the only copper(II) sulfate–glycine coordination polymer to have been synthesized to date. It is isotypic with the zinc(II) complex catena-poly[[(µ2-glycine)-diaquasulfato]zinc(II)] (Oguey et al., 2013a). These two complexes are unique, in as much as the CuII and ZnII cations have five-fold coordination environments. Complex (II) is isotypic with the two-dimensional MnII coordination polymer mentioned above that was prepared hydrothermally and which crystallized in the centrosymmetric space group P21/m.
It is interesting that, on studying single-crystal to single-crystal (SCSC) transformations of a number of these ionic complexes, different results were obtained. For example, on heating a crystal in a capillary on the diffractometer of the zinc(II) ionic complex tetraaquabis(glycine-O)zinc(II) hexaaquazinc(II) bis(sulfate) (Tepavitcharova et al., 2012), two successive SCSC transformations were observed. At ca 343 K it transformed into the one-dimensional polymer isotypic with (I), with a loss of eight water molecules (Oguey et al., 2013a). On continued heating at ca 393 K, two further water molecules were lost and the two-dimensional polymer isostructural with (II) was obtained (Oguey et al., 2014a). These two successive SCSC transformations have also been followed by cariable-temperature powder X-ray diffraction (see Fig. S2).
In contrast, for the magnesium(II) ionic complex (Elayaraja et al., 2007), heating a crystal in a capillary on the diffractometer resulted at ca 363 K in the loss of four water molecules and its SCSC transformation into the one-dimensional polymer catena-poly[[bis(µ2-gylcinato)-hexaaquadisulfato]dimagnesium(II)] (Oguey et al., 2014b). Further heating gave an amorphous powder. This last structure is isostructural with the cobalt(II) (Tepavitcharova et al., 2012), the iron(II) (Oguey et al., 2013b) and the zinc(II) (Oguey et al., 2013c) analogues.
The reversibility of the SCSC transformation of (I) into (II) was examined by immersing a powder sample of (II) into water at room temperature. A clear pale-blue solution was obtained, indicating that (II) had dissolved. The aqueous solution was allowed to evaporate in air and yielded blue crystals of (I).
For both compounds, data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2008) for (I); SHELXL2013 (Sheldrick, 2008) for (II). For both compounds, molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008). Software used to prepare material for publication: SHELXL2014/6 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010) for (I); SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010) for (II).
[Cu(SO4)(C2H5NO2)(H2O)2] | F(000) = 548 |
Mr = 270.70 | Dx = 2.286 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6347 (8) Å | Cell parameters from 6664 reflections |
b = 12.3140 (9) Å | θ = 2.4–26.1° |
c = 8.3675 (8) Å | µ = 3.06 mm−1 |
β = 90.855 (8)° | T = 173 K |
V = 786.57 (13) Å3 | Prism, blue |
Z = 4 | 0.42 × 0.30 × 0.21 mm |
Stoe IPDS 2 diffractometer | 1481 independent reflections |
Radiation source: fine-focus sealed tube | 1352 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.027 |
ϕ + ω scans | θmax = 25.6°, θmin = 2.7° |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | h = −9→9 |
Tmin = 0.850, Tmax = 1.000 | k = −14→14 |
5320 measured reflections | l = −9→10 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.0304P)2 + 0.3965P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.055 | (Δ/σ)max = 0.001 |
S = 1.13 | Δρmax = 0.76 e Å−3 |
1481 reflections | Δρmin = −0.33 e Å−3 |
147 parameters | Extinction correction: SHELXL2014/6 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0046 (8) |
[Cu(SO4)(C2H5NO2)(H2O)2] | V = 786.57 (13) Å3 |
Mr = 270.70 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.6347 (8) Å | µ = 3.06 mm−1 |
b = 12.3140 (9) Å | T = 173 K |
c = 8.3675 (8) Å | 0.42 × 0.30 × 0.21 mm |
β = 90.855 (8)° |
Stoe IPDS 2 diffractometer | 1481 independent reflections |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | 1352 reflections with I > 2σ(I) |
Tmin = 0.850, Tmax = 1.000 | Rint = 0.027 |
5320 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | Δρmax = 0.76 e Å−3 |
1481 reflections | Δρmin = −0.33 e Å−3 |
147 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.28498 (3) | 0.84131 (2) | 0.35769 (3) | 0.00946 (12) | |
O1W | 0.5449 (2) | 0.82336 (15) | 0.3700 (2) | 0.0136 (4) | |
H1WA | 0.579 (4) | 0.824 (2) | 0.456 (4) | 0.018 (8)* | |
H1WB | 0.585 (4) | 0.773 (3) | 0.321 (4) | 0.023 (8)* | |
O2W | 0.0255 (2) | 0.83224 (15) | 0.3800 (2) | 0.0130 (3) | |
H2WA | −0.022 (5) | 0.771 (3) | 0.387 (4) | 0.036 (10)* | |
H2WB | −0.007 (4) | 0.864 (3) | 0.465 (4) | 0.025 (8)* | |
O1 | 0.3000 (2) | 0.91826 (12) | 0.56027 (19) | 0.0107 (3) | |
O2 | 0.2793 (2) | 0.75656 (13) | 0.6748 (2) | 0.0121 (3) | |
N1 | 0.2361 (3) | 1.03136 (17) | 0.8164 (3) | 0.0140 (4) | |
H1A | 0.314 (4) | 1.061 (2) | 0.755 (4) | 0.012 (7)* | |
H1B | 0.138 (4) | 1.030 (3) | 0.764 (4) | 0.023 (8)* | |
H1C | 0.213 (4) | 1.064 (3) | 0.908 (4) | 0.022 (8)* | |
C1 | 0.2875 (3) | 0.85914 (19) | 0.6815 (3) | 0.0109 (5) | |
C2 | 0.2819 (3) | 0.91600 (19) | 0.8415 (3) | 0.0126 (5) | |
H2A | 0.1937 | 0.8810 | 0.9100 | 0.015* | |
H2B | 0.3976 | 0.9105 | 0.8960 | 0.015* | |
S1 | 0.21315 (7) | 1.09071 (4) | 0.24529 (7) | 0.00928 (15) | |
O11 | 0.3070 (2) | 0.98928 (13) | 0.2082 (2) | 0.0148 (4) | |
O12 | 0.1499 (2) | 1.13996 (13) | 0.0921 (2) | 0.0143 (4) | |
O13 | 0.0632 (2) | 1.06845 (14) | 0.3485 (2) | 0.0144 (4) | |
O14 | 0.3330 (2) | 1.16977 (13) | 0.3236 (2) | 0.0147 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01192 (16) | 0.00816 (17) | 0.00830 (17) | −0.00001 (10) | 0.00031 (10) | −0.00131 (11) |
O1W | 0.0151 (8) | 0.0130 (9) | 0.0127 (10) | 0.0021 (7) | −0.0006 (7) | −0.0032 (8) |
O2W | 0.0150 (8) | 0.0104 (8) | 0.0137 (9) | −0.0024 (7) | 0.0012 (7) | −0.0033 (7) |
O1 | 0.0135 (8) | 0.0097 (8) | 0.0089 (8) | 0.0000 (6) | 0.0002 (6) | 0.0017 (6) |
O2 | 0.0171 (8) | 0.0089 (8) | 0.0102 (8) | 0.0005 (6) | −0.0010 (6) | 0.0002 (6) |
N1 | 0.0193 (11) | 0.0119 (11) | 0.0109 (11) | −0.0001 (8) | 0.0023 (9) | −0.0022 (9) |
C1 | 0.0088 (10) | 0.0133 (12) | 0.0106 (12) | 0.0010 (8) | −0.0003 (8) | 0.0003 (9) |
C2 | 0.0175 (11) | 0.0117 (11) | 0.0086 (12) | 0.0007 (9) | 0.0002 (9) | −0.0003 (9) |
S1 | 0.0117 (3) | 0.0076 (3) | 0.0085 (3) | 0.0002 (2) | 0.0006 (2) | 0.0003 (2) |
O11 | 0.0203 (8) | 0.0096 (8) | 0.0147 (9) | 0.0034 (6) | 0.0053 (7) | 0.0020 (7) |
O12 | 0.0210 (9) | 0.0124 (8) | 0.0095 (8) | 0.0038 (7) | −0.0023 (7) | 0.0003 (7) |
O13 | 0.0132 (8) | 0.0157 (9) | 0.0144 (9) | −0.0021 (6) | 0.0029 (6) | −0.0013 (7) |
O14 | 0.0170 (8) | 0.0132 (8) | 0.0139 (9) | −0.0050 (6) | −0.0012 (7) | 0.0005 (7) |
Cu1—O1 | 1.9438 (17) | N1—C2 | 1.477 (3) |
Cu1—O2i | 1.9477 (17) | N1—H1A | 0.87 (3) |
Cu1—O1W | 1.9979 (17) | N1—H1B | 0.86 (4) |
Cu1—O2W | 1.9960 (17) | N1—H1C | 0.88 (4) |
Cu1—O11 | 2.2179 (17) | C1—C2 | 1.512 (3) |
O1W—H1WA | 0.76 (4) | C2—H2A | 0.9900 |
O1W—H1WB | 0.80 (4) | C2—H2B | 0.9900 |
O2—C1 | 1.266 (3) | S1—O13 | 1.4699 (17) |
O2—Cu1ii | 1.9477 (17) | S1—O11 | 1.4752 (17) |
O2W—H2WA | 0.83 (4) | S1—O14 | 1.4820 (17) |
O2W—H2WB | 0.85 (4) | S1—O12 | 1.4921 (17) |
O1—C1 | 1.253 (3) | ||
O1—Cu1—O2i | 170.76 (7) | H1A—N1—H1B | 108 (3) |
O1—Cu1—O2W | 89.52 (7) | C2—N1—H1C | 111 (2) |
O2i—Cu1—O2W | 91.61 (7) | H1A—N1—H1C | 118 (3) |
O1—Cu1—O1W | 87.88 (7) | H1B—N1—H1C | 105 (3) |
O2i—Cu1—O1W | 89.02 (8) | O1—C1—O2 | 123.2 (2) |
O2W—Cu1—O1W | 167.31 (7) | O1—C1—C2 | 116.8 (2) |
O1—Cu1—O11 | 95.01 (6) | O2—C1—C2 | 119.9 (2) |
O2i—Cu1—O11 | 93.80 (7) | N1—C2—C1 | 109.23 (19) |
O2W—Cu1—O11 | 100.51 (7) | N1—C2—H2A | 109.8 |
O1W—Cu1—O11 | 92.10 (7) | C1—C2—H2A | 109.8 |
Cu1—O1W—H1WA | 112 (2) | N1—C2—H2B | 109.8 |
Cu1—O1W—H1WB | 117 (2) | C1—C2—H2B | 109.8 |
H1WA—O1W—H1WB | 111 (3) | H2A—C2—H2B | 108.3 |
C1—O2—Cu1ii | 125.60 (15) | O13—S1—O11 | 110.52 (10) |
Cu1—O2W—H2WA | 119 (2) | O13—S1—O14 | 110.12 (10) |
Cu1—O2W—H2WB | 111 (2) | O11—S1—O14 | 110.53 (10) |
H2WA—O2W—H2WB | 103 (3) | O13—S1—O12 | 109.62 (10) |
C1—O1—Cu1 | 114.73 (14) | O11—S1—O12 | 108.38 (10) |
C2—N1—H1A | 108.9 (19) | O14—S1—O12 | 107.61 (10) |
C2—N1—H1B | 105 (2) | S1—O11—Cu1 | 122.40 (10) |
Cu1—O1—C1—O2 | 5.2 (3) | O2—C1—C2—N1 | −161.8 (2) |
Cu1—O1—C1—C2 | −174.63 (15) | O13—S1—O11—Cu1 | −20.93 (15) |
Cu1ii—O2—C1—O1 | 173.00 (16) | O14—S1—O11—Cu1 | 101.23 (12) |
Cu1ii—O2—C1—C2 | −7.1 (3) | O12—S1—O11—Cu1 | −141.07 (11) |
O1—C1—C2—N1 | 18.0 (3) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1Wiii | 0.87 (3) | 2.08 (3) | 2.917 (3) | 161 (3) |
N1—H1B···O2Wiv | 0.86 (4) | 2.42 (3) | 3.068 (3) | 133 (3) |
N1—H1B···O13iv | 0.86 (4) | 2.16 (3) | 2.923 (3) | 147 (3) |
N1—H1C···O12v | 0.88 (4) | 1.87 (4) | 2.754 (3) | 175 (3) |
O1W—H1WA···O14iii | 0.76 (4) | 1.96 (4) | 2.716 (3) | 179 (3) |
O1W—H1WB···O14vi | 0.80 (4) | 1.87 (4) | 2.667 (3) | 170 (3) |
O2W—H2WA···O12vii | 0.83 (4) | 1.90 (4) | 2.732 (2) | 174 (3) |
O2W—H2WB···O13iv | 0.85 (4) | 1.82 (4) | 2.676 (2) | 177 (3) |
C2—H2A···O12iv | 0.99 | 2.64 | 3.422 (3) | 137 |
Symmetry codes: (iii) −x+1, −y+2, −z+1; (iv) −x, −y+2, −z+1; (v) x, y, z+1; (vi) −x+1, y−1/2, −z+1/2; (vii) −x, y−1/2, −z+1/2. |
[Cu(SO4)(C2H5NO2)] | F(000) = 234 |
Mr = 234.67 | Dx = 2.754 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.8131 (8) Å | Cell parameters from 2571 reflections |
b = 7.787 (1) Å | θ = 2.6–25.9° |
c = 7.9262 (11) Å | µ = 4.21 mm−1 |
β = 107.729 (12)° | T = 173 K |
V = 282.96 (7) Å3 | Prism, very pale blue |
Z = 2 | 0.42 × 0.30 × 0.21 mm |
Stoe IPDS 2 diffractometer | 1065 independent reflections |
Radiation source: fine-focus sealed tube | 862 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.110 |
ϕ + ω scans | θmax = 25.7°, θmin = 2.6° |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | h = −5→5 |
Tmin = 0.646, Tmax = 1.000 | k = −9→9 |
3296 measured reflections | l = −9→9 |
Refinement on F2 | 1 restraint |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.067P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.043 |
1065 reflections | Δρmax = 0.82 e Å−3 |
104 parameters | Δρmin = −0.71 e Å−3 |
[Cu(SO4)(C2H5NO2)] | V = 282.96 (7) Å3 |
Mr = 234.67 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 4.8131 (8) Å | µ = 4.21 mm−1 |
b = 7.787 (1) Å | T = 173 K |
c = 7.9262 (11) Å | 0.42 × 0.30 × 0.21 mm |
β = 107.729 (12)° |
Stoe IPDS 2 diffractometer | 1065 independent reflections |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | 862 reflections with I > 2σ(I) |
Tmin = 0.646, Tmax = 1.000 | Rint = 0.110 |
3296 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 1 restraint |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.82 e Å−3 |
1065 reflections | Δρmin = −0.71 e Å−3 |
104 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 4-component inversion twin. TWIN -1 0 0 0 -1 0 1 0 1 -4 BASF 0.20187 0.30116 0.19949 (e.s.d. 0.08667 0.10598 0.08668) |
x | y | z | Uiso*/Ueq | ||
Cu1 | −0.0044 (16) | 0.7841 (9) | 0.4855 (3) | 0.0239 (6) | |
S1 | 0.3739 (11) | 0.5278 (11) | 0.3240 (6) | 0.0240 (12) | |
O1 | 0.256 (5) | 0.680 (3) | 0.699 (3) | 0.032 (5) | |
O2 | 0.274 (5) | 0.388 (3) | 0.727 (3) | 0.035 (6) | |
O11 | 0.199 (6) | 0.693 (3) | 0.329 (3) | 0.031 (5) | |
O14 | 0.660 (3) | 0.533 (3) | 0.4498 (16) | 0.028 (3) | |
O12 | 0.377 (4) | 0.516 (4) | 0.1411 (19) | 0.030 (5) | |
O13 | 0.208 (5) | 0.379 (3) | 0.358 (3) | 0.032 (5) | |
N1 | 0.779 (6) | 0.396 (2) | 0.980 (3) | 0.035 (5) | |
H1N | 0.6478 | 0.3636 | 1.0364 | 0.052* | |
H2N | 0.9566 | 0.4117 | 1.0616 | 0.052* | |
H3N | 0.7916 | 0.3123 | 0.9027 | 0.052* | |
C1 | 0.385 (4) | 0.535 (5) | 0.762 (2) | 0.023 (4) | |
C2 | 0.682 (7) | 0.557 (4) | 0.883 (3) | 0.027 (6) | |
H2A | 0.8155 | 0.5887 | 0.8149 | 0.032* | |
H2B | 0.6843 | 0.6513 | 0.9680 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0296 (14) | 0.0212 (8) | 0.0212 (11) | 0.0043 (13) | 0.008 (2) | 0.0041 (16) |
S1 | 0.033 (3) | 0.0187 (19) | 0.021 (2) | 0.001 (6) | 0.009 (2) | 0.004 (2) |
O1 | 0.027 (12) | 0.030 (12) | 0.029 (10) | 0.023 (9) | −0.008 (9) | −0.004 (9) |
O2 | 0.048 (14) | 0.023 (12) | 0.032 (11) | 0.015 (11) | 0.011 (9) | −0.003 (9) |
O11 | 0.047 (14) | 0.024 (11) | 0.025 (9) | 0.008 (11) | 0.016 (9) | 0.000 (8) |
O14 | 0.030 (6) | 0.028 (7) | 0.026 (9) | −0.008 (13) | 0.006 (6) | 0.002 (13) |
O12 | 0.050 (10) | 0.028 (12) | 0.017 (6) | −0.003 (12) | 0.019 (7) | −0.006 (8) |
O13 | 0.034 (13) | 0.027 (10) | 0.039 (11) | −0.006 (11) | 0.017 (10) | 0.004 (9) |
N1 | 0.050 (15) | 0.019 (8) | 0.035 (10) | −0.004 (12) | 0.012 (12) | −0.003 (7) |
C1 | 0.035 (11) | 0.022 (10) | 0.015 (9) | 0.016 (18) | 0.013 (8) | 0.001 (12) |
C2 | 0.033 (12) | 0.014 (16) | 0.030 (10) | 0.002 (16) | 0.006 (14) | 0.010 (10) |
Cu1—O1 | 1.95 (2) | S1—O11 | 1.55 (2) |
Cu1—O2i | 1.97 (2) | O1—C1 | 1.31 (4) |
Cu1—O11 | 1.93 (2) | O2—C1 | 1.25 (4) |
Cu1—O13i | 1.94 (2) | N1—C2 | 1.48 (3) |
Cu1—O14ii | 2.50 (2) | N1—H1N | 0.9100 |
Cu1—O14iii | 2.50 (2) | N1—H2N | 0.9100 |
O2—Cu1iv | 1.97 (2) | N1—H3N | 0.9100 |
O13—Cu1iv | 1.94 (2) | C1—C2 | 1.47 (3) |
S1—O14 | 1.432 (13) | C2—H2A | 0.9900 |
S1—O12 | 1.457 (15) | C2—H2B | 0.9900 |
S1—O13 | 1.48 (2) | ||
O11—Cu1—O13i | 179.0 (14) | C2—N1—H1N | 109.5 |
O11—Cu1—O1 | 95.1 (10) | C2—N1—H2N | 109.5 |
O13i—Cu1—O1 | 85.5 (10) | H1N—N1—H2N | 109.5 |
O11—Cu1—O2i | 86.0 (10) | C2—N1—H3N | 109.5 |
O13i—Cu1—O2i | 93.4 (10) | H1N—N1—H3N | 109.5 |
O1—Cu1—O2i | 178.7 (13) | H2N—N1—H3N | 109.5 |
O14—S1—O12 | 113.4 (9) | O2—C1—O1 | 125.4 (18) |
O14—S1—O13 | 110.6 (13) | O2—C1—C2 | 121 (3) |
O12—S1—O13 | 107.7 (14) | O1—C1—C2 | 114 (3) |
O14—S1—O11 | 112.0 (15) | N1—C2—C1 | 109 (3) |
O12—S1—O11 | 104.3 (13) | N1—C2—H2A | 109.8 |
O13—S1—O11 | 108.6 (8) | C1—C2—H2A | 109.8 |
C1—O1—Cu1 | 142.7 (17) | N1—C2—H2B | 109.8 |
C1—O2—Cu1iv | 133.7 (16) | C1—C2—H2B | 109.9 |
S1—O11—Cu1 | 134.9 (13) | H2A—C2—H2B | 108.3 |
S1—O13—Cu1iv | 145.3 (16) | ||
O14—S1—O11—Cu1 | −76 (2) | Cu1iv—O2—C1—O1 | 35 (3) |
O12—S1—O11—Cu1 | 161 (2) | Cu1iv—O2—C1—C2 | −146 (2) |
O13—S1—O11—Cu1 | 46 (2) | Cu1—O1—C1—O2 | −38 (4) |
O14—S1—O13—Cu1iv | 73 (3) | Cu1—O1—C1—C2 | 142 (3) |
O12—S1—O13—Cu1iv | −163 (2) | O2—C1—C2—N1 | −14 (3) |
O11—S1—O13—Cu1iv | −51 (3) | O1—C1—C2—N1 | 166 (2) |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+1; (iv) −x, y−1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1v | 0.91 | 2.47 | 3.10 (3) | 127 |
N1—H1N···O12vi | 0.91 | 2.11 | 2.78 (3) | 130 |
N1—H2N···O12vii | 0.91 | 2.09 | 2.92 (3) | 152 |
N1—H2N···O13vii | 0.91 | 2.31 | 3.08 (3) | 143 |
N1—H3N···O11viii | 0.91 | 2.07 | 2.94 (3) | 161 |
N1—H3N···O12viii | 0.91 | 2.44 | 3.13 (3) | 133 |
C2—H2A···O1ix | 0.99 | 2.65 | 3.62 (4) | 168 |
C2—H2A···O13iii | 0.99 | 2.63 | 3.29 (4) | 124 |
Symmetry codes: (iii) −x+1, y+1/2, −z+1; (v) −x+1, y−1/2, −z+2; (vi) x, y, z+1; (vii) x+1, y, z+1; (viii) −x+1, y−1/2, −z+1; (ix) x+1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu(SO4)(C2H5NO2)(H2O)2] | [Cu(SO4)(C2H5NO2)] |
Mr | 270.70 | 234.67 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21 |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 7.6347 (8), 12.3140 (9), 8.3675 (8) | 4.8131 (8), 7.787 (1), 7.9262 (11) |
β (°) | 90.855 (8) | 107.729 (12) |
V (Å3) | 786.57 (13) | 282.96 (7) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 3.06 | 4.21 |
Crystal size (mm) | 0.42 × 0.30 × 0.21 | 0.42 × 0.30 × 0.21 |
Data collection | ||
Diffractometer | Stoe IPDS 2 diffractometer | Stoe IPDS 2 diffractometer |
Absorption correction | Multi-scan (MULABS in PLATON; Spek, 2009) | Multi-scan (MULABS in PLATON; Spek, 2009) |
Tmin, Tmax | 0.850, 1.000 | 0.646, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5320, 1481, 1352 | 3296, 1065, 862 |
Rint | 0.027 | 0.110 |
(sin θ/λ)max (Å−1) | 0.608 | 0.609 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.055, 1.13 | 0.056, 0.132, 0.98 |
No. of reflections | 1481 | 1065 |
No. of parameters | 147 | 104 |
No. of restraints | 0 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.76, −0.33 | 0.82, −0.71 |
Computer programs: X-AREA (Stoe & Cie, 2009), X-RED32 (Stoe & Cie, 2009), SHELXS2013 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), SHELXL2014/6 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010), SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Cu1—O1 | 1.9438 (17) | Cu1—O2W | 1.9960 (17) |
Cu1—O2i | 1.9477 (17) | Cu1—O11 | 2.2179 (17) |
Cu1—O1W | 1.9979 (17) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1Wii | 0.87 (3) | 2.08 (3) | 2.917 (3) | 161 (3) |
N1—H1B···O2Wiii | 0.86 (4) | 2.42 (3) | 3.068 (3) | 133 (3) |
N1—H1B···O13iii | 0.86 (4) | 2.16 (3) | 2.923 (3) | 147 (3) |
N1—H1C···O12iv | 0.88 (4) | 1.87 (4) | 2.754 (3) | 175 (3) |
O1W—H1WA···O14ii | 0.76 (4) | 1.96 (4) | 2.716 (3) | 179 (3) |
O1W—H1WB···O14v | 0.80 (4) | 1.87 (4) | 2.667 (3) | 170 (3) |
O2W—H2WA···O12vi | 0.83 (4) | 1.90 (4) | 2.732 (2) | 174 (3) |
O2W—H2WB···O13iii | 0.85 (4) | 1.82 (4) | 2.676 (2) | 177 (3) |
C2—H2A···O12iii | 0.99 | 2.64 | 3.422 (3) | 137 |
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x, −y+2, −z+1; (iv) x, y, z+1; (v) −x+1, y−1/2, −z+1/2; (vi) −x, y−1/2, −z+1/2. |
Cu1—O1 | 1.95 (2) | Cu1—O13i | 1.94 (2) |
Cu1—O2i | 1.97 (2) | Cu1—O14ii | 2.50 (2) |
Cu1—O11 | 1.93 (2) | Cu1—O14iii | 2.50 (2) |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1iv | 0.91 | 2.47 | 3.10 (3) | 127 |
N1—H1N···O12v | 0.91 | 2.11 | 2.78 (3) | 130 |
N1—H2N···O12vi | 0.91 | 2.09 | 2.92 (3) | 152 |
N1—H2N···O13vi | 0.91 | 2.31 | 3.08 (3) | 143 |
N1—H3N···O11vii | 0.91 | 2.07 | 2.94 (3) | 161 |
N1—H3N···O12vii | 0.91 | 2.44 | 3.13 (3) | 133 |
C2—H2A···O1viii | 0.99 | 2.65 | 3.62 (4) | 168 |
C2—H2A···O13iii | 0.99 | 2.63 | 3.29 (4) | 124 |
Symmetry codes: (iii) −x+1, y+1/2, −z+1; (iv) −x+1, y−1/2, −z+2; (v) x, y, z+1; (vi) x+1, y, z+1; (vii) −x+1, y−1/2, −z+1; (viii) x+1, y, z. |