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When {2,2′-[(2-methyl-2-nitro­propane-1,3-di­yl)diimino]­di­ace­tato}­copper(II), [Cu(C8H13N3O6)], (I), was crystallized from a binary mixture of methanol and water, a monoclinic two-dimensional water- and methanol-solvated metal–organic framework (MOF) structure, distinctly different from the known ortho­rhom­bic one-dimensional coordination polymer of (I), was isolated, namely catena-poly[[copper(II)-μ3-2,2′-[(2-methyl-2-nitro­propane-1,3-di­yl)diimino]diacetato] methanol 0.45-solvate 0.55-hydrate], {[Cu(C8H13N3O6)]·0.45CH3OH·0.55H2O}n, (II). The monoclinic structure of (II) comprises centrosymmetric dimers stabilized by a dative covalent Cu2O2 core and intra­molecular N—H...O hydrogen bonds. Each dimer is linked to four neighbouring dimers via symmetry-related (opposing) pairs of bridging carboxyl­ate O atoms to generate a `diamondoid' net or two-dimensional coordination network. Tight voids of 166 Å3 are located between these two-dimensional MOF sheets and contain a mixture of water and methanol with fractional occupancies of 0.55 and 0.45, respectively. The two-dimensional MOF sheets have nanometre-scale spacings (11.2 Å) in the crystal structure. Hydrogen-bonding between the methanol/water hydroxy groups and a Cu-bound bridging carboxyl­ate O atom apparently negates thermal desolvation of the structure below 358 K in an uncrushed crystal of (II).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010903128X/fg3106sup1.cif
Contains datablocks II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010903128X/fg3106IIsup2.hkl
Contains datablock II

CCDC reference: 749688

Comment top

The reaction of CuII ions in methanol with two molar equivalents of an amino acid such as glycine (HL) in the presence of a base affords the nominally square-planar chelate CuL2. The geometric isomer with cis amino groups is pre-organized for N,N-chelate ring formation (i.e. ring closure) in the presence of excess formaldehyde, one molar equivalent of a diprotic carbon nucleophile such as nitroethane, and excess base. This elegant template reaction, which links the cis metal-bound NH2 groups with a three-carbon bridge, was developed by Comba and co-workers 23 years ago (Comba et al., 1986) and then extended sometime later to include compound (I) and its derivatives (Comba et al., 1991). More recent synthetic efforts by others with the same type of system have employed diethylmalonate as the carbon diacid for ring closure (Supriya et al., 2007). The reduced ligand (in which the nitro group is converted into an amino group) has also been condensed with aldehydes to form Schiff base analogues of (I) with pendant non-coordinating base groups (Villanueva et al., 1998).

The structure of (I) crystallized from water has an unsolvated crystal structure (orthorhombic, P212121) and has been reported previously (Comba et al., 1991). In (I), the CuII ion is weakly bound to the carboxylate O atom of an adjacent molecule to form an infinite one-dimensional coordination polymer in which the five-coordinate mononuclear repeat units are linked by long axial Cu—O bonds (2.60 Å). Although nominally five-coordinate, the coordination geometry at the CuII ion is closer to being square-planar than square-pyramidal, due to the in-plane location of the metal ion relative to the ligand donor atoms (Comba et al., 1991). In the present study, we report the structure of compound (II), the monoclinic water/methanol solvate of (I). In (II), the copper chelate forms a novel MOF extended structure based upon a half-solvated two-dimensional rhombus net of Ci-symmetry dimeric repeats. The markedly different extended structure of the material described here leads to significant structural differences for the metal centre that clearly reflect supramolecular control of the molecular geometry of the copper chelate.

The molecular structure of (II), i.e. the symmetry-unique monomer unit of the Ci-symmetry coordination dimer, is shown in Fig. 1. The CuII ion exhibits the expected four-coordinate geometry within the tetradentate chelate. The equatorial Cu—O and Cu—N distances average 1.955 (14) and 1.996 (4) Å, respectively. The mean Cu—O distance is within the normal range expected for terminal carboxylates bound to CuII [1.96 (2) Å; Orpen et al., 1989]. It is, however, noteworthy that the Cu1—O1 distance is significantly shorter than the Cu1—O3 distance (Table 1), presumably because atom O1 is involved in bridging the two CuII ions of the dimeric structure (see below). Although the average equatorial Cu—O distance is normal, the mean Cu—N distance is compressed by the chelate ring and is thus shorter than that of a standard secondary amine bound to CuII [2.03 (3) Å; Orpen et al., 1989]. The four ligand donor atoms lie exactly on the best-fit (least-squares) mean plane, with the CuII ion displaced by 0.179 (1) Å out of this plane in the direction opposite to that of the two N—H group bond vectors. Consequently, and in contrast with the orthorhombic structure of (I) reported earlier (Comba et al., 1991), the coordination geometry of the CuII ion in (II) is closest to being square-pyramidal if one considers all dative covalent bonds < 2.5 Å in length to the CuII ion (see below).

That said, consideration of all metal–ligand interactions (first coordination sphere) less than the sum of the van der Waals radii of the pairwise interacting atoms (O···Cu 2.92 Å, O···N 2.95 Å; Bondi, 1964) suggests that the coordination geometry of each CuII centre is best described as a distorted octahedron with a significant axial displacement of the metal ion away from the Cu2O2 dimer core towards the closest axially coordinated (bridging) carboxylate O atom. The axial Cu—O distances of (II) are therefore markedly different, with the intra-dimer distance [Cu1—O1i = 2.7247 (15) Å] significantly longer than the inter-dimer distance [Cu—O4iv = 2.3410 (15)Å], and both are considerably longer than the equatorial Cu—O bonds [symmetry codes: (i) 1 - x, 1 - y, -z; (iv) 3/2 - x, -1/2 + y, 1/2 - z]. Interestingly, the equatorial Cu—O and Cu—N distances of the present monoclinic structure, (II), are some 0.03 and 0.01 Å longer, respectively, than those of the orthorhombic crystalline form, (I) (Comba et al., 1991). This clearly reflects the bond elongation required to support the out-of-plane displacement of the CuII ion in (II) and, ultimately, the markedly different extended structures of the two materials.

One intriguing hallmark of the molecular conformation of (I) [(II)?] is the approximate chair conformation of the six-membered chelate ring, in which the nitro group and amino group H atoms are positioned on the same side of the ring. (The ring-closing reaction could produce the alternative configurational isomer at C4 with the C8 methyl group axial, but does not.) Several noteworthy intramolecular hydrogen bonds appear to result from this particular chelate ring conformation (Table 2). More specifically, the nitro group O atoms (O5 and O6) are neatly hydrogen-bonded and thus `tethered' to the closest amino group H atoms (H101 and H102). This may have some impact on transition-state geometries during the ring-closing reaction and certainly has some directional influence on thermal libration of the nitro group, as evidenced by the similar principal axes of displacement for the two O atoms. (The O-atom displacements are predominantly towards the amino group H atoms, as opposed to a more isotropic electron-density distribution which might be expected if rotational motion about the C4—N3 axis were favoured to a greater extent.) Perhaps more significant from the standpoint of conformational stability is the fact that the amino group H atoms of one chelate ring within the Ci-symmetry dimer are hydrogen-bonded to the closest carboxylate group O atoms of the second chelate. These hydrogen bonds clearly complement the structural stability associated with the Cu2O2 core of the dimer. On the whole, the six-membered chelate ring is somewhat flattened in the region of the CuII ion, such that the chelate-ring geometry tends towards being partly half-chair-like in conformation. This ring-flattening effect is highlighted by the fact that the CuII ion and the opposite C atom, C4, are displaced from the six-atom chelate ring mean plane (defined by atoms Cu1/N1/C3–C5/N2) by 0.127 (2) and 0.264 (2) Å, respectively.

The unit-cell packing shown in Fig. 3(a) clearly reveals the infinite two-dimensional network structure (or MOF architecture) of compound (II). As evidenced by the distinct arrangement of the Ci-symmetry Cu2O2 dimer units in the structure, chains of interconnected dimers run parallel to, and include, the [110] plane. Furthermore, these chains are linked obliquely to adjacent chains via bridging Cu—O bonds, giving rise to a second series of parallel chains of interconnected dimers running parallel to, and including, the [110] plane. In effect, the two-dimensional coordination framework creates a `diamondoid' or rhombus-like two-dimensional net. This net lies in the [202] plane and, together with its translational repeats, generates parallel stacks of rather unusual metal–organic sheets in the crystal structure. The distance between parallel metal–organic sheets, e.g. that between the [202] and [202] planes, is 11.18 (1) Å.

The interesting layered crystal structure of (I) [(II)?], with a reasonably large nanometre-scale interlayer separation, creates solvent-accessible voids of 166 Å3 in the crystal structure. Upon closer inspection (PLATON; Spek, 2009), these voids comprise two 83 Å3 voids centred at (1/2, 0.0, 1/2) and (0.0, 1/2, 1.0). The cavities are just large enough to accommodate methanol molecules (molecular volume ~71 Å3) or water molecules (molecular volume ~ 30 Å3), and compound (I) was, not surprisingly, isolated as the mixed water/methanol solvate, (II), with a fractional composition ratio (from electron-density maxima) of 0.55/0.45 (Fig. 3b). The methanol and water O atoms are located at the same coordinates in the structure and the hydroxyl groups of both solvents are clearly hydrogen-bonded to the bridging carboxylate group atoms O4 (Table 2). Although the unit-occupancy solvent atom H1S was cleanly located in a difference Fourier map, the remaining water H atom and the H atoms belonging to the methyl group of the methanol solvate molecule were not located and were omitted from the structural model during refinement. A full unit-occupancy methanol molecule can not be accommodated, as the methanol methyl C atom is too close [2.343 (3) Å] to the inversion-related methyl C atom at (2 - x, 1 - y, -z).

Finally, other somewhat more simple CuII coordination compounds based on 4,4'-bipyridine linking ligands have been described with two-dimensional MOF sheet-like structures that form clathrates with small molecules such as CO2 (Kondo et al., 2006). This particular material exhibited reversible sorption/desorption of the guest molecules with varying CO2 partial pressure. Given the increasing likelihood that MOFs may become the materials of choice for gas-storage applications (Czaja et al., 2009), we attempted to desolvate the crystal of (II), i.e. (I).0.55H2O.0.45CH3OH, used for X-ray data collection. This crystal was neatly glued to the glass microfibre through only a very small area of the largest crystal face, thereby exposing >90% of the crystal surface to the atmosphere. Furthermore, the crystal faces were clean and uncovered by inert mounting oil. The glass-mounted crystal was warmed and maintained at 358 K in a thermal convection oven for 3 d. However, complete desolvation was not observed under the conditions tested (as judged from a post-warming X-ray data set), possibly due to the tight solvent-binding cavities, and to hydrogen-bonding between the solvent guests and the rigid host MOF.

Experimental top

Compound (I) was synthesized by the literature method (Comba et al., 1991). X-ray quality crystals of (II) were grown by slow diffusion of methanol into a solution of (I) in distilled water at room temperature over a period of 3 d.

Refinement top

All H atoms of the metal complex of (II) were clearly visible in difference maps and then allowed for as riding atoms, with N—H = 0.93, methylene C—H = 0.99 and methyl C—H = 0.98 Å, and with Uiso(H) = 1.2Ueq(N or C) for methylene C, or 1.5Ueq(C) for methyl C. The water/methanol hydroxy H atom was included at the position found in the difference map.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of equal though arbitrary radii. The O atoms of the fractionally occupied methanol and water solvate molecules share the same site (O1S) and are hydrogen-bonded to atom O4 via atom H1S (shared site). The partially occupied methanol atom C1S is shown with an open bond to atom O1S. The methyl-group H atoms were not located in the difference Fourier map.
[Figure 2] Fig. 2. Ball and cylinder representation of the Ci-symmetry dimer that forms the repeat unit of the two-dimensional coordination polymer, or MOF structure, in the water/methanol solvate, (II). Bonds to atoms that lead to extension of the two-dimensional array are shown as dotted lines. H atoms (except those attached to N atoms) and solvent molecules have been omitted for clarity. [Symmetry codes: (i) 1 - x, 1 - y, -z; (ii) 3/2 - x, 1/2 + y, 1/2 - z; (iii) -1/2 + x, 1/2 - y, -1/2 + z; (iv) 3/2 - x, -1/2 + y, 1/2 - z; (v) -1/2 + x, 3/2 - y, -1/2 + z.
[Figure 3] Fig. 3. Views of part of the unit-cell contents of (II). (a) Projection approximately down the c axis. Methanol solvent molecules and H atoms have been omitted for clarity. (b) Projection approximately down the b axis, highlighting the location of the solvent-containing sites between the two-dimensional MOF layers. Intermolecular hydrogen bonds are indicated by dashed lines. CuII ions and solvent atoms are represented by spheres; all other atoms and bonds are represented as cylinders, or as end-capped cylinders in the case of terminal atoms. H atoms not involved in hydrogen-bonding have been omitted for clarity.
catena-poly[{µ3-2,2'-[(2-methyl-2-nitropropane-1,3- diyl)diimino]diacetato}copper(II)–methanol–water (1/0.45/0.55) top
Crystal data top
[Cu(C8H13N3O6)]·0.45CH4O·0.55H2OF(000) = 684
Mr = 335.08Dx = 1.750 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4693 reflections
a = 13.0407 (16) Åθ = 3.9–28.5°
b = 8.0578 (15) ŵ = 1.76 mm1
c = 13.383 (2) ÅT = 200 K
β = 115.726 (16)°Rectangular, blue-purple
V = 1266.9 (3) Å30.55 × 0.45 × 0.38 mm
Z = 4
Data collection top
Oxford Xcalibur2
diffractometer
2974 independent reflections
Radiation source: fine-focus sealed tube2401 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 8.4190 pixels mm-1θmax = 28.7°, θmin = 3.9°
ω scansh = 1617
Absorption correction: multi-scan
[CrysAlis RED (Oxford Diffraction, 2006); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
k = 1010
Tmin = 0.387, Tmax = 0.511l = 1717
13298 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.0483P)2 + 0.234P]
where P = (Fo2 + 2Fc2)/3
2974 reflections(Δ/σ)max = 0.001
186 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
[Cu(C8H13N3O6)]·0.45CH4O·0.55H2OV = 1266.9 (3) Å3
Mr = 335.08Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.0407 (16) ŵ = 1.76 mm1
b = 8.0578 (15) ÅT = 200 K
c = 13.383 (2) Å0.55 × 0.45 × 0.38 mm
β = 115.726 (16)°
Data collection top
Oxford Xcalibur2
diffractometer
2974 independent reflections
Absorption correction: multi-scan
[CrysAlis RED (Oxford Diffraction, 2006); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
2401 reflections with I > 2σ(I)
Tmin = 0.387, Tmax = 0.511Rint = 0.023
13298 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.085H-atom parameters constrained
S = 1.15Δρmax = 0.44 e Å3
2974 reflectionsΔρmin = 0.37 e Å3
186 parameters
Special details top

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. 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.

Final difference Fourier synthesis cycles located both a methanol and a water solvate molecule clearly hydrogen-bonded to carboxylate oxygen O4. Various models were tested to effect stable refinement of the solvent molecules. The most suitable treatment had the fractionally occupied methanol and water atoms O1S and H1S located at the same lattice sites summing up to unit occupancy. The methyl group of the methanol solvent molecule, in contrast, had an occupancy factor of 0.45, in effect requiring (I) to be a mixed water/methanol solvate of 0.55/0.45 fractional composition. No restraints were necessary to achieve refinement convergence with this approach.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.572812 (19)0.43953 (3)0.135407 (19)0.01577 (10)
O10.54400 (12)0.30903 (18)0.00358 (11)0.0181 (3)
O20.42778 (12)0.11413 (19)0.10515 (12)0.0212 (3)
O30.71071 (12)0.54406 (17)0.13960 (11)0.0171 (3)
O40.84447 (12)0.72833 (19)0.23393 (11)0.0201 (3)
O50.26376 (19)0.6346 (3)0.1131 (2)0.0643 (7)
O60.38471 (18)0.8069 (3)0.2256 (2)0.0604 (6)
N10.41743 (15)0.3628 (2)0.10928 (14)0.0184 (4)
H1010.36550.43300.05620.022*
N20.59049 (14)0.6078 (2)0.25097 (14)0.0171 (4)
H1020.55390.70340.21360.020*
N30.34979 (17)0.6656 (3)0.19686 (19)0.0363 (5)
C10.46187 (17)0.2030 (2)0.02231 (16)0.0171 (4)
C20.40542 (18)0.1970 (3)0.05647 (17)0.0206 (4)
H2A0.32390.16840.01490.025*
H2B0.44230.11130.11400.025*
C30.38875 (19)0.3608 (3)0.20433 (19)0.0245 (5)
H3A0.43090.26880.25440.029*
H3B0.30650.33700.17660.029*
C40.4155 (2)0.5213 (3)0.2714 (2)0.0266 (5)
C50.54229 (19)0.5677 (3)0.32878 (18)0.0221 (5)
H5A0.55200.66460.37760.027*
H5B0.58540.47400.37620.027*
C60.71369 (17)0.6473 (3)0.30783 (17)0.0185 (4)
H6A0.75360.56530.36730.022*
H6B0.72500.75900.34180.022*
C70.76104 (17)0.6420 (3)0.22209 (16)0.0158 (4)
C80.3708 (2)0.5061 (4)0.3597 (2)0.0414 (7)
H8A0.40870.41320.40930.062*
H8B0.28850.48630.32350.062*
H8C0.38650.60910.40280.062*
O1S0.8891 (2)0.6816 (3)0.04747 (19)0.0572 (6)
C1S0.9499 (6)0.5456 (8)0.0491 (7)0.057 (2)0.45
H1S0.867 (4)0.657 (5)0.105 (3)0.098 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01401 (14)0.01581 (16)0.01615 (15)0.00174 (9)0.00529 (10)0.00397 (10)
O10.0184 (7)0.0165 (8)0.0167 (7)0.0011 (6)0.0052 (6)0.0022 (6)
O20.0248 (8)0.0147 (7)0.0182 (7)0.0001 (6)0.0038 (6)0.0036 (6)
O30.0173 (7)0.0160 (8)0.0177 (7)0.0013 (5)0.0074 (6)0.0026 (6)
O40.0177 (7)0.0207 (8)0.0215 (7)0.0047 (6)0.0083 (6)0.0027 (6)
O50.0446 (13)0.0572 (15)0.0644 (15)0.0176 (11)0.0013 (11)0.0135 (12)
O60.0419 (12)0.0342 (12)0.0938 (17)0.0070 (9)0.0189 (12)0.0060 (12)
N10.0179 (9)0.0172 (9)0.0179 (9)0.0001 (7)0.0057 (7)0.0032 (7)
N20.0153 (8)0.0168 (9)0.0182 (9)0.0003 (7)0.0064 (7)0.0011 (7)
N30.0236 (11)0.0364 (14)0.0494 (14)0.0046 (9)0.0164 (10)0.0110 (11)
C10.0173 (9)0.0115 (10)0.0171 (10)0.0062 (7)0.0024 (8)0.0021 (8)
C20.0207 (10)0.0170 (11)0.0217 (10)0.0030 (8)0.0070 (9)0.0034 (9)
C30.0212 (11)0.0283 (13)0.0263 (12)0.0066 (9)0.0125 (9)0.0056 (10)
C40.0231 (11)0.0288 (13)0.0319 (13)0.0030 (9)0.0158 (10)0.0075 (10)
C50.0226 (11)0.0248 (12)0.0216 (11)0.0040 (9)0.0121 (9)0.0066 (9)
C60.0170 (10)0.0193 (12)0.0163 (10)0.0033 (8)0.0047 (8)0.0033 (8)
C70.0157 (10)0.0136 (10)0.0158 (10)0.0038 (8)0.0047 (8)0.0017 (8)
C80.0372 (15)0.0543 (17)0.0455 (16)0.0201 (13)0.0299 (13)0.0218 (14)
O1S0.0716 (16)0.0622 (15)0.0548 (13)0.0033 (12)0.0432 (13)0.0057 (12)
C1S0.043 (4)0.039 (4)0.078 (5)0.009 (3)0.018 (4)0.018 (4)
Geometric parameters (Å, º) top
Cu1—O11.9453 (14)N3—C41.529 (3)
Cu1—O1i2.7247 (15)C1—C21.526 (3)
Cu1—O31.9644 (14)C2—H2A0.9900
Cu1—N21.9934 (18)C2—H2B0.9900
Cu1—N11.9988 (18)C3—C41.526 (3)
Cu1—O4ii2.3410 (15)C3—H3A0.9900
O1—C11.294 (2)C3—H3B0.9900
O2—C11.229 (2)C4—C81.534 (3)
O3—C71.282 (2)C4—C51.536 (3)
O4—C71.242 (2)C5—H5A0.9900
O4—Cu1iii2.3410 (15)C5—H5B0.9900
O5—N31.219 (3)C6—C71.521 (3)
O6—N31.225 (3)C6—H6A0.9900
N1—C31.474 (3)C6—H6B0.9900
N1—C21.487 (3)C8—H8A0.9800
N1—H1010.9300C8—H8B0.9800
N2—C51.467 (3)C8—H8C0.9800
N2—C61.483 (3)O1S—C1S1.347 (7)
N2—H1020.9300O1S—H1S0.95 (5)
O1—Cu1—O394.11 (6)H2A—C2—H2B108.4
O1—Cu1—N2169.44 (7)N1—C3—C4114.78 (18)
O1—Cu1—N183.80 (7)N1—C3—H3A108.6
O1—Cu1—O4ii97.44 (6)C4—C3—H3A108.6
O3—Cu1—N1169.60 (7)N1—C3—H3B108.6
O3—Cu1—N283.69 (6)C4—C3—H3B108.6
O3—Cu1—O4ii99.85 (6)H3A—C3—H3B107.5
N1—Cu1—O4ii90.53 (6)C3—C4—N3109.92 (19)
N2—Cu1—N196.50 (7)C3—C4—C8108.6 (2)
N2—Cu1—O4ii93.11 (7)N3—C4—C8105.7 (2)
C1—O1—Cu1114.29 (13)C3—C4—C5114.99 (19)
C7—O3—Cu1114.13 (13)N3—C4—C5108.54 (19)
C7—O4—Cu1iii126.62 (13)C8—C4—C5108.71 (19)
C3—N1—C2112.73 (17)N2—C5—C4113.46 (18)
C3—N1—Cu1118.05 (13)N2—C5—H5A108.9
C2—N1—Cu1104.51 (13)C4—C5—H5A108.9
C3—N1—H101107.0N2—C5—H5B108.9
C2—N1—H101107.0C4—C5—H5B108.9
Cu1—N1—H101107.0H5A—C5—H5B107.7
C5—N2—C6112.67 (16)N2—C6—C7108.10 (16)
C5—N2—Cu1117.40 (13)N2—C6—H6A110.1
C6—N2—Cu1106.19 (12)C7—C6—H6A110.1
C5—N2—H102106.7N2—C6—H6B110.1
C6—N2—H102106.7C7—C6—H6B110.1
Cu1—N2—H102106.7H6A—C6—H6B108.4
O5—N3—O6123.2 (2)O4—C7—O3123.19 (19)
O5—N3—C4118.4 (2)O4—C7—C6120.51 (18)
O6—N3—C4118.4 (2)O3—C7—C6116.30 (17)
O2—C1—O1124.0 (2)C4—C8—H8A109.5
O2—C1—C2120.71 (19)C4—C8—H8B109.5
O1—C1—C2115.28 (17)H8A—C8—H8B109.5
N1—C2—C1108.49 (17)C4—C8—H8C109.5
N1—C2—H2A110.0H8A—C8—H8C109.5
C1—C2—H2A110.0H8B—C8—H8C109.5
N1—C2—H2B110.0C1S—O1S—H1S102 (3)
C1—C2—H2B110.0
O3—Cu1—O1—C1172.87 (13)Cu1—N1—C2—C137.89 (18)
N2—Cu1—O1—C1109.6 (3)O2—C1—C2—N1150.80 (18)
N1—Cu1—O1—C117.36 (13)O1—C1—C2—N127.6 (2)
O4ii—Cu1—O1—C172.36 (13)C2—N1—C3—C4171.79 (18)
O1—Cu1—O3—C7177.83 (13)Cu1—N1—C3—C449.7 (2)
N2—Cu1—O3—C712.54 (14)N1—C3—C4—N359.5 (2)
N1—Cu1—O3—C7104.2 (4)N1—C3—C4—C8174.6 (2)
O4ii—Cu1—O3—C779.54 (14)N1—C3—C4—C563.4 (3)
O1—Cu1—N1—C3156.77 (16)O5—N3—C4—C323.1 (3)
O3—Cu1—N1—C3124.3 (3)O6—N3—C4—C3158.6 (2)
N2—Cu1—N1—C333.85 (16)O5—N3—C4—C893.9 (3)
O4ii—Cu1—N1—C359.35 (16)O6—N3—C4—C884.5 (3)
O1—Cu1—N1—C230.60 (12)O5—N3—C4—C5149.7 (2)
O3—Cu1—N1—C2109.5 (4)O6—N3—C4—C532.0 (3)
N2—Cu1—N1—C2160.02 (13)C6—N2—C5—C4178.27 (18)
O4ii—Cu1—N1—C266.82 (12)Cu1—N2—C5—C454.4 (2)
O1—Cu1—N2—C5127.4 (3)C3—C4—C5—N265.9 (3)
O3—Cu1—N2—C5154.09 (16)N3—C4—C5—N257.7 (2)
N1—Cu1—N2—C536.38 (16)C8—C4—C5—N2172.2 (2)
O4ii—Cu1—N2—C554.51 (15)C5—N2—C6—C7165.38 (17)
O1—Cu1—N2—C6105.5 (3)Cu1—N2—C6—C735.54 (18)
O3—Cu1—N2—C627.03 (13)Cu1iii—O4—C7—O3170.26 (13)
N1—Cu1—N2—C6163.44 (13)Cu1iii—O4—C7—C610.3 (3)
O4ii—Cu1—N2—C672.55 (13)Cu1—O3—C7—O4174.49 (15)
Cu1—O1—C1—O2176.88 (15)Cu1—O3—C7—C66.0 (2)
Cu1—O1—C1—C21.5 (2)N2—C6—C7—O4151.78 (19)
C3—N1—C2—C1167.32 (16)N2—C6—C7—O328.7 (2)
Symmetry codes: (i) x+1, y+1, z; (ii) x+3/2, y1/2, z+1/2; (iii) x+3/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1S—H1S···O40.951.962.823 (3)163
N1—H101···O50.932.422.984 (3)119
N1—H101···O3i0.932.373.101 (3)135
N2—H102···O60.932.433.017 (3)121
N2—H102···O2i0.932.152.912 (3)138
Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu(C8H13N3O6)]·0.45CH4O·0.55H2O
Mr335.08
Crystal system, space groupMonoclinic, P21/n
Temperature (K)200
a, b, c (Å)13.0407 (16), 8.0578 (15), 13.383 (2)
β (°) 115.726 (16)
V3)1266.9 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.76
Crystal size (mm)0.55 × 0.45 × 0.38
Data collection
DiffractometerOxford Xcalibur2
diffractometer
Absorption correctionMulti-scan
[CrysAlis RED (Oxford Diffraction, 2006); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
Tmin, Tmax0.387, 0.511
No. of measured, independent and
observed [I > 2σ(I)] reflections
13298, 2974, 2401
Rint0.023
(sin θ/λ)max1)0.675
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.085, 1.15
No. of reflections2974
No. of parameters186
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.44, 0.37

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and WinGX (Farrugia, 1999), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Cu1—O11.9453 (14)Cu1—N21.9934 (18)
Cu1—O1i2.7247 (15)Cu1—N11.9988 (18)
Cu1—O31.9644 (14)Cu1—O4ii2.3410 (15)
O1—Cu1—O394.11 (6)O3—Cu1—N283.69 (6)
O1—Cu1—N2169.44 (7)O3—Cu1—O4ii99.85 (6)
O1—Cu1—N183.80 (7)N1—Cu1—O4ii90.53 (6)
O1—Cu1—O4ii97.44 (6)N2—Cu1—N196.50 (7)
O3—Cu1—N1169.60 (7)N2—Cu1—O4ii93.11 (7)
Symmetry codes: (i) x+1, y+1, z; (ii) x+3/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1S—H1S···O40.951.962.823 (3)163
N1—H101···O50.932.422.984 (3)119
N1—H101···O3i0.932.373.101 (3)135
N2—H102···O60.932.433.017 (3)121
N2—H102···O2i0.932.152.912 (3)138
Symmetry code: (i) x+1, y+1, z.
 

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