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The title compound, poly[[μ-cyano­ureato-tri-μ-hydroxido-dicopper(II)] dihydrate], {[Cu2(C2H2N3O)(OH)3]·2H2O}n, is a new layered copper(II) hydroxide salt (LHS) with cyano­ureate ions and water mol­ecules in the inter­layer space. The three distinct copper(II) ions have distorted octa­hedral geometry: one Cu (symmetry \overline{1}) is coordinated to six hydroxide groups (4OH + 2OH), whilst the other two Cu atoms (symmetries \overline{1} and 1) are coordinated to four hydroxides and two N atoms from nitrile groups of the cyano­ureate ions (4OH + 2N). The structure is held together by hydrogen-bonding inter­actions between the terminal –NH2 groups and the central cyanamide N atoms of organic anions associated with neighbouring layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109020885/em3026sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109020885/em3026Isup2.hkl
Contains datablock I

CCDC reference: 742261

Comment top

In addition to the much studied layered double hydroxides (LDH), such as hydrotalcite, Mg6Al2(OH)16(CO3).4H2O, and related transition metal substituted phases (Rives, 2001; Evans & Slade, 2006), a second class of materials with structures derived from brucite, Mg(OH)2, namely the layered metal hydroxide salts (LHS), are gaining in scientific and technological importance (Arisaga et al., 2007). This results from their potential uses as anion-exchangers, catalysts and two-dimensional magnetic materials (Laget et al., 1998, 1999; Yamanaka et al., 1992). The LHS have the general formula M2+(OH)2x(Am-)x/m.nH2O, where M is a divalent metal and A is a counteranion. Examples include M2(OH)3(A) (M = Co, Ni, Cu; A = Cl-, NO3-, CH3COO-), Cd(OH)NO3.H2O and Zn5(OH)8(NO3)2.2H2O (Arisaga et al., 2007). Most pertinent to this work are the copper hydroxide salts, Cu2(OH)3(A), where A can be a simple anion as above, or a long-chain organic anion, such as an alkylsulfonate (n-CmH2m+1OSO2-; Park & Lee, 2005) or alkylcarboxylate (n-CmH2m+1COO-; Fujita & Awaga, 1996, 1997). Adjusting the alkyl chain length in the organic anions enables the magnetic behaviour of the layered materials to be tuned by changing the relative importance of the intra- and interlayer interactions.

Full structural studies of Cu2(OH)3(A), using single-crystal and powder X-ray diffraction, have been reported in a number of cases [A = NO2- (Schmidt et al., 1993), NO3- (Effenberger, 1983; Guillou et al., 1994), Cl- (Hawthorne, 1985), Br- (Ostwald et al., 1961) and CH3COO- (Maschiocci et al., 1997)]. These results, together with EXAFS studies of compounds with A = CH3COO- and Br- (Jiménez-López et al., 1993), provide evidence for the coordination of A to Cu atoms in the copper hydroxide layers. All reported structures exhibit a Cu2(OH)3Cl botallackite-type structure, in which the Cu atoms lie in 4+2 (O + A) and 4+1+1 (O + O + A) environments.

In this work, we report the structure of the title new inorganic–organic hybrid material, Cu2(OH)3[H2NC(O)NCN].2H2O, in which cyanoureate ions and water molecules reside between the copper(II) hydroxide layers. The cyanoureate ions coordinate to Cu via the nitrile N atoms. Within the layers, there are three crystallographically distinct Cu atoms, two of which, Cu2 and Cu3, reside on special positions, 2a and 2c, respectively, while the third, Cu1, lies on a general position, 4e (Fig. 1). Each Cu atom has an elongated octahedral coordination, with four shorter Cu—O bonds (~2 Å) and two longer bonds (>2.3 Å), in accordance with the Jahn–Teller distortion of Cu in a +2 oxidation state (Table 1). In the cases of atoms Cu1 and Cu2, the longer bonds are to atom N3, and for Cu3, to atom O3. Each O atom within the layer (O1, O2 and O3) is coordinated to three Cu atoms and an H atom. All the H atoms in the structure were located in difference Fourier maps. The copper hydroxide layers lie parallel to the bc plane and stack along the a axis in an AA fashion. The CuII ions within the layers form a triangular array (Fig. 2), with the shortest Cu···Cu distances in the range 3.010 (3)–3.164 (3) Å, comparable with those found in other Cu2(OH)3A compounds known to exhibit intralayer magnetic interactions (Jiménez-López et al., 1993).

The interlayer space contains cyanoureate ions, formed by the hydrolysis of dicyanamide anions ([N(CN)2-] under basic conditions, together with water molecules. The bond lengths and angles within the cyanourea moiety are in good agreement with those observed for the anions in Ag+[H2NC(O)NCN]- (Britton, 1987) and NH4+[H2NC(O)NCN]- (Lotsch & Schnick, 2004). The cyanoureate ion is almost planar, with a cis arrangement of the N3/C2/N2 and O4 groups. This conformation enables atom O4 of the C1O4 carbonyl group to form a hydrogen bond with the O1—H1 hydroxide group of the layer, as well as with the interlayer water molecules O5H2 and O6H2 (Table 2, Fig. 3). The other hydroxide groups, O2H2 and O3H3, also form hydrogen bonds with water molecules O6H2 and O5H2, respectively, which in turn interact with each other. Hydrogen-bonding interactions between the amide N1H2 and the central atom N2 of cyanoureate anions associated with adjacent layers serve to hold the layers together.

To the best of our knowledge, Cu2(OH)3[H2NC(O)NCN].2H2O is the first example of a layered solid in which the cyanoureate ion acts a ligand coordinating to a metal centre. Compounds are known in which the cyanoureate ion links metal atoms into dimers, e.g. in [Cu2{NCNC( O)NH2}(R3Bm)](ClO4)3.4H2O (where R3Bm is an m-xylyl-linked cryptand; Escuer et al., 2004), and chains, e.g. in Ag+[H2NC(O)NCN]- (Britton, 1987). Interestingly, coordination to the Cu atoms occurs through atom N3 of the nitrile group rather than through atom N2, which formally carries the negative charge of the ion. In this respect, the behaviour of the ligand resembles that of the dicyanamide ion (Batten & Murray, 2003), particularly as observed in the two polymorphs of silver dicyanamide (Britton & Chow, 1977; Britton, 1990).

Experimental top

Single crystals of the title compound, in the form of blue–green blocks, were obtained from the hydrolysis of N(CN)2- ions under alkaline conditions. Copper(I) dicyanamide (0.10 g) (Wang et al., 1990) was dissolved in an aqueous ammonia solution (35%, 15 ml) containing 10 drops of hydrazine. This formed a deep-blue solution which, over the course of 10 min, turned through green to orange. After a few days, the solution had returned to the deep-blue colour, and after 10 months, a small number of crystals suitable for single-crystal X-ray diffraction had grown. Intense bands were observed in the IR spectrum recorded in Spectrosol over the range 4000–1300 cm-1: 3467, 3354, 3312, 3220 (ν N—H, O—H); 2174, 2137 (ν CN); 1657, 1650 (ν C—O); 1535, 1529 (δ NH2) and 1412 (ν C—N).

Refinement top

All H atoms were located in difference Fourier maps and restrained to ride on their parent atoms [O—H = N—H = 0.85 (1) Å]. For the H atoms attached to framework atoms O1 to O3, the fractional coordinates and isotropic displacement parameters were refined. For the remaining H atoms on the water molecules O5H2 and O6H2, and the amide fragment –N1H2, the fractional coordinates were refined, with Uiso(H) = 1.2Ueq(O) or 1.2Ueq(N), respectively.

Structure description top

In addition to the much studied layered double hydroxides (LDH), such as hydrotalcite, Mg6Al2(OH)16(CO3).4H2O, and related transition metal substituted phases (Rives, 2001; Evans & Slade, 2006), a second class of materials with structures derived from brucite, Mg(OH)2, namely the layered metal hydroxide salts (LHS), are gaining in scientific and technological importance (Arisaga et al., 2007). This results from their potential uses as anion-exchangers, catalysts and two-dimensional magnetic materials (Laget et al., 1998, 1999; Yamanaka et al., 1992). The LHS have the general formula M2+(OH)2x(Am-)x/m.nH2O, where M is a divalent metal and A is a counteranion. Examples include M2(OH)3(A) (M = Co, Ni, Cu; A = Cl-, NO3-, CH3COO-), Cd(OH)NO3.H2O and Zn5(OH)8(NO3)2.2H2O (Arisaga et al., 2007). Most pertinent to this work are the copper hydroxide salts, Cu2(OH)3(A), where A can be a simple anion as above, or a long-chain organic anion, such as an alkylsulfonate (n-CmH2m+1OSO2-; Park & Lee, 2005) or alkylcarboxylate (n-CmH2m+1COO-; Fujita & Awaga, 1996, 1997). Adjusting the alkyl chain length in the organic anions enables the magnetic behaviour of the layered materials to be tuned by changing the relative importance of the intra- and interlayer interactions.

Full structural studies of Cu2(OH)3(A), using single-crystal and powder X-ray diffraction, have been reported in a number of cases [A = NO2- (Schmidt et al., 1993), NO3- (Effenberger, 1983; Guillou et al., 1994), Cl- (Hawthorne, 1985), Br- (Ostwald et al., 1961) and CH3COO- (Maschiocci et al., 1997)]. These results, together with EXAFS studies of compounds with A = CH3COO- and Br- (Jiménez-López et al., 1993), provide evidence for the coordination of A to Cu atoms in the copper hydroxide layers. All reported structures exhibit a Cu2(OH)3Cl botallackite-type structure, in which the Cu atoms lie in 4+2 (O + A) and 4+1+1 (O + O + A) environments.

In this work, we report the structure of the title new inorganic–organic hybrid material, Cu2(OH)3[H2NC(O)NCN].2H2O, in which cyanoureate ions and water molecules reside between the copper(II) hydroxide layers. The cyanoureate ions coordinate to Cu via the nitrile N atoms. Within the layers, there are three crystallographically distinct Cu atoms, two of which, Cu2 and Cu3, reside on special positions, 2a and 2c, respectively, while the third, Cu1, lies on a general position, 4e (Fig. 1). Each Cu atom has an elongated octahedral coordination, with four shorter Cu—O bonds (~2 Å) and two longer bonds (>2.3 Å), in accordance with the Jahn–Teller distortion of Cu in a +2 oxidation state (Table 1). In the cases of atoms Cu1 and Cu2, the longer bonds are to atom N3, and for Cu3, to atom O3. Each O atom within the layer (O1, O2 and O3) is coordinated to three Cu atoms and an H atom. All the H atoms in the structure were located in difference Fourier maps. The copper hydroxide layers lie parallel to the bc plane and stack along the a axis in an AA fashion. The CuII ions within the layers form a triangular array (Fig. 2), with the shortest Cu···Cu distances in the range 3.010 (3)–3.164 (3) Å, comparable with those found in other Cu2(OH)3A compounds known to exhibit intralayer magnetic interactions (Jiménez-López et al., 1993).

The interlayer space contains cyanoureate ions, formed by the hydrolysis of dicyanamide anions ([N(CN)2-] under basic conditions, together with water molecules. The bond lengths and angles within the cyanourea moiety are in good agreement with those observed for the anions in Ag+[H2NC(O)NCN]- (Britton, 1987) and NH4+[H2NC(O)NCN]- (Lotsch & Schnick, 2004). The cyanoureate ion is almost planar, with a cis arrangement of the N3/C2/N2 and O4 groups. This conformation enables atom O4 of the C1O4 carbonyl group to form a hydrogen bond with the O1—H1 hydroxide group of the layer, as well as with the interlayer water molecules O5H2 and O6H2 (Table 2, Fig. 3). The other hydroxide groups, O2H2 and O3H3, also form hydrogen bonds with water molecules O6H2 and O5H2, respectively, which in turn interact with each other. Hydrogen-bonding interactions between the amide N1H2 and the central atom N2 of cyanoureate anions associated with adjacent layers serve to hold the layers together.

To the best of our knowledge, Cu2(OH)3[H2NC(O)NCN].2H2O is the first example of a layered solid in which the cyanoureate ion acts a ligand coordinating to a metal centre. Compounds are known in which the cyanoureate ion links metal atoms into dimers, e.g. in [Cu2{NCNC( O)NH2}(R3Bm)](ClO4)3.4H2O (where R3Bm is an m-xylyl-linked cryptand; Escuer et al., 2004), and chains, e.g. in Ag+[H2NC(O)NCN]- (Britton, 1987). Interestingly, coordination to the Cu atoms occurs through atom N3 of the nitrile group rather than through atom N2, which formally carries the negative charge of the ion. In this respect, the behaviour of the ligand resembles that of the dicyanamide ion (Batten & Murray, 2003), particularly as observed in the two polymorphs of silver dicyanamide (Britton & Chow, 1977; Britton, 1990).

Computing details top

Data collection: Xcalibur (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures top
[Figure 1] Fig. 1. The local coordination in the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view along the a axis of the inorganic layer, showing the triangular array of Cu1, Cu2 and Cu3 atoms within the Cu2O3 layers. Key: small white spheres, O atoms; small grey spheres, N3 atoms. The remaining atoms of the cyanoureate ions, and the hydroxide H atoms, have been omitted.
[Figure 3] Fig. 3. A view along the b axis, showing the AA stacking of the copper hydroxide layers. Hydrogen-bonding interactions between the hydroxide groups O1H, O2H and O3H, water molecules O5H2 and O6H2, and O4C1, together with those involving the N1H2 and N2 groups of adjacent cyanoureate ions, are shown as dotted lines. Key: large black spheres, Cu atoms; small light-grey spheres, O atoms; small dark-grey spheres, N atoms; small black spheres, C atoms; small white spheres, H atoms.
Poly[[µ-cyanoureato-tri-µ-hydroxido-dicopper(II)] dihydrate] top
Crystal data top
[Cu2(C2H2N3O)(OH)3]·2H2OF(000) = 592
Mr = 298.22Dx = 2.440 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6870 reflections
a = 12.4648 (5) Åθ = 5–32°
b = 6.3096 (2) ŵ = 5.25 mm1
c = 10.6032 (5) ÅT = 150 K
β = 103.269 (4)°Block, blue-green
V = 811.66 (6) Å30.20 × 0.08 × 0.06 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur area-detector
diffractometer
2688 independent reflections
Radiation source: fine-focus sealed tube1731 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω/2θ scansθmax = 32.6°, θmin = 3.4°
Absorption correction: multi-scan
DENZO/SCALEPACK (Otwinowski & Minor, 1997)
h = 1818
Tmin = 0.67, Tmax = 0.73k = 98
6870 measured reflectionsl = 1015
Refinement top
Refinement on FPrimary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.025 Method, part 1, Chebychev polynomial (Watkin, 1994; Prince, 1982), [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)],
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = robust weighting (Prince, 1982), W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 35.5 -37.7 28.1
S = 1.11(Δ/σ)max = 0.001
1731 reflectionsΔρmax = 0.96 e Å3
151 parametersΔρmin = 0.81 e Å3
9 restraints
Crystal data top
[Cu2(C2H2N3O)(OH)3]·2H2OV = 811.66 (6) Å3
Mr = 298.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.4648 (5) ŵ = 5.25 mm1
b = 6.3096 (2) ÅT = 150 K
c = 10.6032 (5) Å0.20 × 0.08 × 0.06 mm
β = 103.269 (4)°
Data collection top
Oxford Diffraction Xcalibur area-detector
diffractometer
2688 independent reflections
Absorption correction: multi-scan
DENZO/SCALEPACK (Otwinowski & Minor, 1997)
1731 reflections with I > 2σ(I)
Tmin = 0.67, Tmax = 0.73Rint = 0.028
6870 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0319 restraints
wR(F2) = 0.025H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.96 e Å3
1731 reflectionsΔρmin = 0.81 e Å3
151 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.007607 (19)0.23275 (4)0.25437 (2)0.0061
Cu20.00000.50000.50000.0056
Cu30.00000.00000.50000.0053
O10.08154 (11)0.2938 (2)0.61558 (15)0.0058
O20.06983 (14)0.0258 (2)0.34803 (17)0.0066
O30.06870 (12)0.2500 (2)0.39781 (15)0.0056
O40.30960 (11)0.2882 (3)0.66427 (16)0.0155
O50.29541 (14)0.8486 (3)0.64881 (18)0.0185
O60.29652 (13)0.9384 (3)0.37316 (18)0.0199
N10.48208 (16)0.3833 (4)0.6566 (2)0.0253
N20.34458 (14)0.4518 (4)0.4811 (2)0.0154
N30.14777 (17)0.4720 (3)0.3721 (2)0.0126
C10.37405 (16)0.3694 (3)0.6025 (2)0.0133
C20.23926 (17)0.4572 (4)0.4272 (2)0.0107
H10.1498 (9)0.317 (5)0.637 (3)0.011 (6)*
H20.1390 (9)0.039 (5)0.361 (3)0.014 (7)*
H30.1375 (9)0.235 (5)0.375 (3)0.021 (8)*
H40.504 (2)0.311 (5)0.725 (2)0.0300*
H50.526 (2)0.433 (6)0.614 (3)0.0300*
H60.307 (2)0.829 (5)0.5742 (15)0.0240*
H70.296 (3)0.9814 (17)0.659 (4)0.0240*
H80.315 (3)1.053 (3)0.342 (3)0.0240*
H90.310 (3)0.845 (4)0.321 (3)0.0240*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.00884 (10)0.00598 (9)0.00393 (11)0.00157 (11)0.00209 (8)0.00160 (11)
Cu20.0077 (2)0.0046 (2)0.0039 (2)0.00026 (8)0.00002 (15)0.00009 (9)
Cu30.0080 (2)0.0048 (2)0.0034 (2)0.00099 (8)0.00181 (15)0.00063 (10)
O10.0069 (5)0.0056 (6)0.0052 (6)0.0005 (5)0.0020 (4)0.0000 (5)
O20.0081 (7)0.0078 (5)0.0042 (7)0.0007 (5)0.0021 (5)0.0002 (5)
O30.0081 (5)0.0056 (6)0.0037 (6)0.0014 (5)0.0022 (4)0.0012 (5)
O40.0124 (6)0.0200 (7)0.0145 (7)0.0008 (6)0.0040 (5)0.0035 (7)
O50.0213 (8)0.0159 (7)0.0177 (9)0.0013 (6)0.0034 (6)0.0020 (7)
O60.0191 (7)0.0188 (8)0.0227 (9)0.0017 (7)0.0064 (7)0.0032 (8)
N10.0103 (8)0.0479 (13)0.0159 (10)0.0009 (8)0.0005 (7)0.0125 (9)
N20.0090 (8)0.0242 (8)0.0131 (10)0.0039 (8)0.0028 (6)0.0023 (9)
N30.0136 (9)0.0138 (7)0.0102 (9)0.0005 (7)0.0028 (7)0.0009 (7)
C10.0109 (8)0.0161 (8)0.0127 (10)0.0001 (6)0.0027 (7)0.0032 (7)
C20.0136 (9)0.0136 (7)0.0058 (9)0.0025 (8)0.0040 (7)0.0008 (8)
Geometric parameters (Å, º) top
Cu1—O1i1.9145 (17)Cu3—O31.9923 (15)
Cu1—O21.9736 (16)Cu3—O3v1.9923 (15)
Cu1—O2ii1.9877 (16)O1—H10.841 (9)
Cu1—O31.9733 (17)O2—H20.846 (9)
Cu1—N32.426 (2)O3—H30.841 (9)
Cu1—N3iii2.658 (2)O4—C11.256 (3)
Cu2—O11.9119 (14)O5—H60.845 (10)
Cu2—O1iv1.9119 (14)O5—H70.844 (9)
Cu2—O31.9925 (14)O6—H80.850 (10)
Cu2—O3iv1.9925 (14)O6—H90.85 (3)
Cu2—N32.532 (2)N1—C11.340 (3)
Cu2—N3iv2.532 (2)N1—H40.846 (10)
Cu3—O12.3238 (15)N1—H50.85 (3)
Cu3—O1v2.3238 (15)N2—C11.359 (3)
Cu3—O22.0061 (18)N2—C21.307 (3)
Cu3—O2v2.0061 (18)N3—C21.159 (3)
N3iii—Cu1—O2ii89.58 (6)O1v—Cu3—O3105.27 (6)
N3iii—Cu1—O1i88.94 (6)O2v—Cu3—O399.27 (6)
O2ii—Cu1—O1i84.62 (7)O3v—Cu3—O3180
N3iii—Cu1—O284.20 (6)O1—Cu3—O374.73 (6)
O2ii—Cu1—O2173.67 (5)O2—Cu3—O380.73 (6)
O1i—Cu1—O296.40 (7)Cu3—O1—Cu1vi96.09 (6)
N3iii—Cu1—O389.92 (6)Cu3—O1—Cu295.80 (6)
O2ii—Cu1—O396.85 (7)Cu1vi—O1—Cu2105.87 (7)
O1i—Cu1—O3178.14 (6)Cu3—O1—H1125 (2)
O2—Cu1—O382.01 (7)Cu1vi—O1—H1116 (2)
N3iii—Cu1—N3179.15 (2)Cu2—O1—H1114 (2)
O2ii—Cu1—N390.36 (7)Cu3—O2—Cu1iii104.78 (8)
O1i—Cu1—N391.90 (7)Cu3—O2—Cu198.30 (7)
O2—Cu1—N395.84 (7)Cu1iii—O2—Cu1105.85 (8)
O3—Cu1—N389.24 (7)Cu3—O2—H2120 (2)
N3iv—Cu2—O3iv85.88 (7)Cu1iii—O2—H2111 (2)
N3iv—Cu2—O1iv87.18 (7)Cu1—O2—H2116 (2)
O3iv—Cu2—O1iv84.76 (6)Cu2—O3—Cu3104.69 (6)
N3iv—Cu2—O192.82 (7)Cu2—O3—Cu1103.87 (7)
O3iv—Cu2—O195.24 (6)Cu3—O3—Cu198.77 (7)
O1iv—Cu2—O1180Cu2—O3—H3122 (2)
N3iv—Cu2—O394.12 (7)Cu3—O3—H3111 (2)
O3iv—Cu2—O3180Cu1—O3—H3114 (2)
O1iv—Cu2—O395.24 (6)H6—O5—H7106 (3)
O1—Cu2—O384.76 (6)H8—O6—H9103 (3)
N3iv—Cu2—N3180C1—N1—H4115 (2)
O3iv—Cu2—N394.12 (7)C1—N1—H5120 (2)
O1iv—Cu2—N392.82 (7)H4—N1—H5122 (3)
O1—Cu2—N387.18 (7)C1—N2—C2116.8 (2)
O3—Cu2—N385.88 (7)Cu1—N3—Cu278.03 (6)
O1v—Cu3—O2v105.69 (6)Cu1—N3—Cu1ii76.72 (6)
O1v—Cu3—O3v74.73 (6)Cu2—N3—Cu1ii72.03 (6)
O2v—Cu3—O3v80.73 (6)Cu1—N3—C2135.90 (18)
O1v—Cu3—O1180Cu2—N3—C2119.21 (19)
O2v—Cu3—O174.31 (6)Cu1ii—N3—C2145.31 (18)
O3v—Cu3—O1105.27 (6)N2—C1—N1114.0 (2)
O1v—Cu3—O274.31 (6)N2—C1—O4125.73 (18)
O2v—Cu3—O2180N1—C1—O4120.3 (2)
O3v—Cu3—O299.27 (6)N2—C2—N3174.7 (3)
O1—Cu3—O2105.69 (6)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y+1/2, z+1/2; (iii) x, y1/2, z+1/2; (iv) x, y+1, z+1; (v) x, y, z+1; (vi) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O40.84 (1)1.95 (1)2.770 (2)163 (3)
O2—H2···O6vii0.85 (1)1.94 (1)2.786 (2)175
O3—H3···O5iv0.84 (1)2.00 (2)2.824 (2)167
N1—H5···N2viii0.85 (3)2.21 (3)3.055 (3)174
O5—H6···O60.85 (1)2.22 (2)2.980 (3)150 (3)
O5—H7···O4ix0.84 (1)1.94 (1)2.782 (3)172
O6—H8···O4x0.85 (1)2.12 (3)2.842 (3)142
O6—H9···O5x0.85 (3)2.17 (3)2.987 (3)161
Symmetry codes: (iv) x, y+1, z+1; (vii) x, y1, z; (viii) x+1, y+1, z+1; (ix) x, y+1, z; (x) x, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formula[Cu2(C2H2N3O)(OH)3]·2H2O
Mr298.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)12.4648 (5), 6.3096 (2), 10.6032 (5)
β (°) 103.269 (4)
V3)811.66 (6)
Z4
Radiation typeMo Kα
µ (mm1)5.25
Crystal size (mm)0.20 × 0.08 × 0.06
Data collection
DiffractometerOxford Diffraction Xcalibur area-detector
Absorption correctionMulti-scan
DENZO/SCALEPACK (Otwinowski & Minor, 1997)
Tmin, Tmax0.67, 0.73
No. of measured, independent and
observed [I > 2σ(I)] reflections
6870, 2688, 1731
Rint0.028
(sin θ/λ)max1)0.757
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.025, 1.11
No. of reflections1731
No. of parameters151
No. of restraints9
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.96, 0.81

Computer programs: Xcalibur (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).

Selected geometric parameters (Å, º) top
Cu1—O1i1.9145 (17)Cu3—O12.3238 (15)
Cu1—O21.9736 (16)Cu3—O22.0061 (18)
Cu1—O2ii1.9877 (16)Cu3—O31.9923 (15)
Cu1—O31.9733 (17)O4—C11.256 (3)
Cu1—N32.426 (2)N1—C11.340 (3)
Cu1—N3iii2.658 (2)N2—C11.359 (3)
Cu2—O11.9119 (14)N2—C21.307 (3)
Cu2—O31.9925 (14)N3—C21.159 (3)
Cu2—N32.532 (2)
N3iii—Cu1—O2ii89.58 (6)O2v—Cu3—O174.31 (6)
N3iii—Cu1—O1i88.94 (6)O3v—Cu3—O1105.27 (6)
O2ii—Cu1—O1i84.62 (7)O2v—Cu3—O2180
N3iii—Cu1—O284.20 (6)O3v—Cu3—O299.27 (6)
O2ii—Cu1—O2173.67 (5)O1—Cu3—O2105.69 (6)
O1i—Cu1—O296.40 (7)O3v—Cu3—O3180
N3iii—Cu1—O389.92 (6)O1—Cu3—O374.73 (6)
O2ii—Cu1—O396.85 (7)O2—Cu3—O380.73 (6)
O1i—Cu1—O3178.14 (6)Cu3—O1—Cu1vi96.09 (6)
O2—Cu1—O382.01 (7)Cu3—O1—Cu295.80 (6)
N3iii—Cu1—N3179.15 (2)Cu1vi—O1—Cu2105.87 (7)
O2ii—Cu1—N390.36 (7)Cu3—O2—Cu1iii104.78 (8)
O1i—Cu1—N391.90 (7)Cu3—O2—Cu198.30 (7)
O2—Cu1—N395.84 (7)Cu1iii—O2—Cu1105.85 (8)
O3—Cu1—N389.24 (7)Cu2—O3—Cu3104.69 (6)
N3iv—Cu2—O192.82 (7)Cu2—O3—Cu1103.87 (7)
O3iv—Cu2—O195.24 (6)Cu3—O3—Cu198.77 (7)
O1iv—Cu2—O1180C1—N2—C2116.8 (2)
N3iv—Cu2—O394.12 (7)Cu1—N3—C2135.90 (18)
O3iv—Cu2—O3180Cu2—N3—C2119.21 (19)
O1—Cu2—O384.76 (6)Cu1ii—N3—C2145.31 (18)
N3iv—Cu2—N3180N2—C1—N1114.0 (2)
O1—Cu2—N387.18 (7)N2—C1—O4125.73 (18)
O3—Cu2—N385.88 (7)N1—C1—O4120.3 (2)
O1v—Cu3—O1180N2—C2—N3174.7 (3)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y+1/2, z+1/2; (iii) x, y1/2, z+1/2; (iv) x, y+1, z+1; (v) x, y, z+1; (vi) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O40.841 (9)1.954 (14)2.770 (2)163 (3)
O2—H2···O6vii0.846 (9)1.943 (14)2.786 (2)175
O3—H3···O5iv0.841 (9)1.997 (16)2.824 (2)167
N1—H5···N2viii0.85 (3)2.21 (3)3.055 (3)174
O5—H6···O60.845 (10)2.216 (18)2.980 (3)150 (3)
O5—H7···O4ix0.844 (9)1.943 (11)2.782 (3)172
O6—H8···O4x0.849 (10)2.12 (3)2.842 (3)142
O6—H9···O5x0.850 (30)2.17 (3)2.987 (3)161
Symmetry codes: (iv) x, y+1, z+1; (vii) x, y1, z; (viii) x+1, y+1, z+1; (ix) x, y+1, z; (x) x, y+3/2, z1/2.
 

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