Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614022190/wq3076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614022190/wq3076Isup2.hkl |
CCDC reference: 833136
In recent decades, metal complexes with an azide (N3-) anion acting as a bridging ligand have been studied extensively (Ribas et al., 1999), since N3- is a versatile ligand and can efficiently mediate magnetic coupling between paramagnetic metal ions. Due to this and its various possible binding modes, the azide anion has been extensively employed in the construction of coordination complexes with structures ranging from discrete complexes (Murugesu et al., 2004; Scott et al., 2005; Ako et al., 2006) to one-dimensional (Mukherjee et al., 2001; Liu et al., 2003; Gao et al., 2005), two-dimensional (Escuer et al., 2005; Zhai et al., 2006; Cheng et al., 2007) or three-dimensional networks (Zeng et al., 2006). Among the reported azide-based complexes, EO (µ2-1,1-) and EE (µ2-1,3-) coordination modes are two typical bridging modes, but the azide ligand can bridge more than two metals in a combination of EO and EE modes (see Scheme 1) (Zhang et al., 2006; Escuer et al., 2010; Yu et al., 2010; Mukherjee et al., 2011). To our knowledge, the azide anion usually co-operates with the organic co-ligand to construct coordination complexes. The topology structures of these complexes are strongly affected by the nature of the organic co-ligands, for example, shape, size, coordination ability etc. Thus, detailed research into the effect of organic co-ligands on the structural features of azide compounds is very important. Indeed, until now the major emphasis in the field has been the search for suitable organic co-ligands. Some bridging or chelating organics ligands, such as ethylenediamine (Mondal & Mukherjee, 2008), 2,2'-bipyridyl (Yang et al., 2008) and some pyridine derivatives (Ray et al., 2008), have been used as co-ligands to construct polynuclear or high-dimensional metal–azide compounds. While some weakly coordinating organic ligands can also affect the structural features of metal–azide compounds, these have been only rarely studied (Liu et al., 2008; Wu et al., 2011; Mautner et al., 1999). Here, a novel CuII–azide compound modified by a simple weak coordinating N-donor organic ligand, namely poly[piperazine-1,4-dium [tetra-µ3-azido-κ12N1:N1:N1-hexa-µ2-azido-κ12N1:N1-di-µ2-azido-κ4N1:N3-pentacopper(II)] tetrahydrate], (I), is reported. In (I), azide ligands link CuII cations to form two-dimensional condensed layers. The piperazine molecules are diprotonated and act as counter-cations.
Crystals of (I) were obtained by slow diffusion in an H-shaped tube. In one side of the H-tube was placed an aqueous solution containing Cu(OAc)2.H2O (0.25 g, 1.25 mmol). NaN3 (0.18 g, 2.5 mmol) and piperazine (0.24 g, 2.5 mmol) were dissolved in ethanol (5 ml; pH = 4, adjusted by HCl), which was placed in the other side of the H-tube. Ethanol was then carefully added until the solutions on both sides reached the bridge. Slow diffusion between the two solutions afforded black block-shaped crystals of (I) after one week (yield 65%, based on Cu). Analysis, calculated for C4H20Cu5N38O4: C 4.89, N 54.16, H 2.04%; found: C 4.93, N 54.82, H 1.99%. IR (KBr, ν, cm-1): 3436 (br, s), 2063 (s), 2037 (s), 1631 (m), 1384 (m), 1128 (w), 884 (w), 619 (w).
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and treated as riding on their parent atoms, with N—H = 0.90 Å, alkyl C—H = 0.97 Å and water O—H = 0.85 Å, and with Uiso(H) = 1.2Ueq(N,C,O). Atoms N6 and O1 were resolved into two positions using SHELXL97 (Sheldrick, 2008) PART instructions.
X-ray single-crystal diffraction studies of (I) (Fig. 1) reveal that the crystallographically unique unit is composed of two and a half CuII cations, six azide anions, half of a diprotonated piperazine molecule and two solvent water molecules. Among the six crystallographically unique azide anions, two [N1–N3 bridging atoms Cu1, Cu2i and Cu3iv, and N7—N9 bridging Cu1v, Cu2 and Cu3; symmetry code: (i) -x, -y+2, -z+1, (iv) -x, -y+1, z+1; (v) x, y-1, z] adopt the µ3-1,1,1-N3- coordination mode, three (N4–N6, N10–N12 and N13–N15) adopt the EO coordination mode, while N16/N18 adopts an EE coordination mode. Among the three crystallographically unique CuII cations, Cu1 sits on a centre of inversion and adopts an octahedral geometry, the equatorial (eq) plane is surrounded by two µ3-1,1,1-N3- (N1–N3 and N1i–N3i) and two EO azide anions [N1/N3 and N4/N6, and their symmetry-related counterparts N1i/N3i and N4i/N6i, bridging Cu1 and Cu2, and Cu1 and Cu2i, respectively; symmetry code: (i) ???? [Please complete]]. The Cu1—N distances are 1.984 (3) and 1.998 (3) Å, respectively. The axial (ax) positions are occupied by another two µ3-1,1,1-N3- anions [N7ii–N9ii and N7iv–N9iv; symmetry code: (ii) x, y+1, z]. The Cu—Nax distance 2.747 (3) Å is apparently longer than that of Cu—Neq, which may be explained by the Jahn–Teller effect. Atom Cu2 is located in a square-pyramidal environment coordinated by two µ3-1,1,1-N3- (N1i–N3i and N7–N9) and three EO azide anions (N4/N6, N10/N12 and N13ii/N15ii), of which four N atoms (N1A, N4, N7 and N10 bridging Cu1 and Cu2, Cu2 and Cu3, respectively) occupy the equatorial plane with an average Cu2—Neq distance of 2.001 (3) Å. The axial position of the square pyramid is occupied by a fifth N atom (N13ii), which bridges to atom Cu3ii. The Cu2—Nax distance is 2.309 (3) Å. Atom Cu3 also adopts a square-pyramidal geometry coordinated by three EO azide (N7/N9, N10/N12 and N13/N15) and two EE azide anions [N16/N18 and N16iv/N18iv; symmetry code: (iv) ???? [Please complete]]. The three EO azide N atoms (N7, N10 and N13) and one EE azide N atom (N18iv, bridging to Cu3iv) occupy the equatorial plane, with an average Cu3—Neq distance of 2.002 (3) Å. The axial position of the square pyramid of Cu3 is occupied by the other EE azide N atom [N16, bridging to Cu3iii; symmetry code: (iii) ???? [Please complete]], with a Cu3—Nax distance of 2.358 (3) Å. The square pyramids of Cu2 and Cu3 are both slightly distorted, with τ values of 0.050 and 0.075, respectively (Addison et al., 1984). Thus, two unique CuII cations (Cu2 and Cu3), their centrosymmetrically equivalent CuII cations (Cu2i and Cu3i) and the central Cu1 atom are linearly arranged and all doubly bridged by EO azide anions in an equatorial–equatorial disposition to generate a linear pentanuclear unit. The Cu—N(EO—N3)—Cu angles are similar, with an average value of 100.99 (15)°.
As shown in Fig. 2, each pentanuclear unit is connected to two adjacent units via four single EO azide bridges at the Cu2 and Cu3 sites in an equatorial–axial disposition to form a one-dimensional tape extending along the b axis, with a Cu—N(EO—N3)—Cu angle of 109.72 (13)°. The tapes are further linked through EE azide anions at the Cu3 sites in an equatorial–axial disposition to form a two-dimensional condensed layer parallel to the [101] plane, with a Cu—N(EE—N3)—Cu dihedral angle of 25.5 (3)°. As far as we know, many Cu–azide compounds have been studied, in which the N-donor organic co-ligands cooperate with the azide anions to link the Cu centres to form one-, two- or three-dimensional structures. Only a few Cu–azide condensed layers have been reported, for example [Cu6(N3)14]n (Liu et al., 2008) and [Cu7(N3)16]n (Wu et al., 2011) layers, which are constructed by Cu6 rings and Cu7 linear chains, respectively. Thus, (I) is a novel example containing pentanuclear linear units. The [Cu5(N3)12]n layer is anionic, which is charge-balanced by a layer of diprotonated piperazine molecules hydrogen-bonded to water molecules, similar to the reported Cu–azide condensed compounds, in which N,N'-dimethylethylenediammonium, N,N,N'-trimethylethylenediammonium and 1-(pyridin-2-yl)-2-(2-hydroxyethyl)imidazo[1,5-a]pyridinium were selected as counter-cations.
As shown in Fig. 3(a), the O2 water molecule acts as a hydrogen-bond donor to the adjacent disordered O1/O1' water molecule, forming an O—H···O hydrogen bond. Simutaneously, O2 acts as a hydrogen-bond acceptor from the protonated piperazine atom H1B to form an N—H···O hydrogen bond. Thus, the symmetric piperazine-1,4-dium (H2pip) cation hydrogen-bonds with two O2 water molecules through its two equivalent >NH2+ groups. Thus, one H2pip cation and four solvent water molecules hydrogen-bond with each other to form a water–piperazinediium supramolecular subunit. In this supramolecular subunit, atoms O1/O1' are both involved in one O—H···O hydrogen bond as hydrogen-bond acceptors, while O2 acts as a hydrogen-bond donor and acceptor, bonding with O1/O1' and N19, respectively, and is involved in one O—H···O and one N—H···O hydrogen bond.
In the supramolecular subunit, there are six types of H atom which are not involved in O—H···O or N—H···O hydrogen bonds, namely four attached to the disordered water molecule O1/O1', one attached to O2 and one from the –NH2 group. These H atoms all form hydrogen bonds with azide N atoms from adjacent [Cu5(N3)12]n coordination layers. As shown in Fig. 3(b), the two >NH2+ groups of the H2pip cation hydrogen-bond with two N18 atoms from two adjacent coordination layers through atoms H1A. The solvent water molecules O1/O1' and O2 provide their remaining H atoms to form hydrogen bonds with N6/N6', and N9 and N15, respectively, from the coordination layers. Thus, the water–piperazinediium supramolecular subunits act as a `glue' and link the [Cu5(N3)12]n coordination layers through hydrogen bonds to form a three-dimensional supramolecular network. The parameters of selected coordination bonds and all hydrogen bonds are listed in Tables 2 and 3, respectively.
In summary, the simple N-donor organic molecule piperazine has been used to tune the structure of the Cu–azide system, resulting in a novel compound, {(H2pip)[Cu5(N3)12].4H2O}n. In this compound, five CuII centres are arranged in a linear manner through eight EO azide anions, which are further connected with each other to form two-dimensional condensed Cu–azide anion layers by another eight azide anions adopting EO or EE coordination modes. The protonated piperazine cations and solvent water molecules are located between the Cu–azide layers and hydrogen-bond with the azide N atoms. Thus, the Cu–azide coordination layers are linked to form a three-dimensional supramolecular network.
Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
(C4H12N2)[Cu5(N3)12]·4H2O | F(000) = 974 |
Mr = 982.28 | Dx = 2.066 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 16.343 (3) Å | Cell parameters from 2772 reflections |
b = 5.7477 (11) Å | θ = 1.7–25.0° |
c = 16.812 (3) Å | µ = 3.40 mm−1 |
β = 91.10 (3)° | T = 293 K |
V = 1579.0 (5) Å3 | Block, black |
Z = 2 | 0.22 × 0.21 × 0.19 mm |
Bruker SMART CCD area-detector diffractometer | 2772 independent reflections |
Radiation source: fine-focus sealed tube | 2080 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −19→19 |
Tmin = 0.522, Tmax = 0.564 | k = −6→6 |
7506 measured reflections | l = −15→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0265P)2] where P = (Fo2 + 2Fc2)/3 |
2772 reflections | (Δ/σ)max = 0.001 |
252 parameters | Δρmax = 0.45 e Å−3 |
522 restraints | Δρmin = −0.50 e Å−3 |
(C4H12N2)[Cu5(N3)12]·4H2O | V = 1579.0 (5) Å3 |
Mr = 982.28 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.343 (3) Å | µ = 3.40 mm−1 |
b = 5.7477 (11) Å | T = 293 K |
c = 16.812 (3) Å | 0.22 × 0.21 × 0.19 mm |
β = 91.10 (3)° |
Bruker SMART CCD area-detector diffractometer | 2772 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2080 reflections with I > 2σ(I) |
Tmin = 0.522, Tmax = 0.564 | Rint = 0.053 |
7506 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 522 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.45 e Å−3 |
2772 reflections | Δρmin = −0.50 e Å−3 |
252 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.0000 | 1.0000 | 0.5000 | 0.02402 (17) | |
Cu2 | 0.07589 (2) | 0.57208 (8) | 0.58419 (2) | 0.02086 (13) | |
Cu3 | 0.13723 (2) | 0.11424 (7) | 0.66215 (2) | 0.02121 (14) | |
N1 | 0.00263 (17) | 1.1650 (5) | 0.39549 (16) | 0.0245 (7) | |
N2 | 0.04243 (19) | 1.1250 (6) | 0.33707 (19) | 0.0325 (8) | |
N3 | 0.0785 (2) | 1.0904 (8) | 0.2810 (2) | 0.0705 (14) | |
N4 | 0.06828 (18) | 0.7236 (5) | 0.47703 (16) | 0.0265 (7) | |
N7 | 0.12900 (17) | 0.2692 (5) | 0.55257 (16) | 0.0226 (7) | |
N8 | 0.1836 (2) | 0.2482 (6) | 0.50541 (19) | 0.0333 (8) | |
N9 | 0.2340 (3) | 0.2218 (8) | 0.4603 (2) | 0.0767 (14) | |
N10 | 0.06509 (18) | 0.3886 (5) | 0.68196 (17) | 0.0273 (7) | |
N11 | 0.04725 (18) | 0.4540 (5) | 0.74812 (19) | 0.0272 (7) | |
N12 | 0.0300 (2) | 0.5116 (7) | 0.8105 (2) | 0.0518 (11) | |
N13 | 0.18198 (18) | −0.1853 (5) | 0.62292 (17) | 0.0276 (7) | |
N14 | 0.2487 (2) | −0.1951 (5) | 0.59446 (17) | 0.0280 (7) | |
N15 | 0.3128 (2) | −0.2094 (7) | 0.5675 (2) | 0.0534 (11) | |
N16 | 0.2715 (2) | 0.2613 (6) | 0.6757 (2) | 0.0471 (10) | |
N17 | 0.32242 (18) | 0.3779 (5) | 0.70271 (17) | 0.0273 (7) | |
N18 | 0.37683 (18) | 0.4982 (5) | 0.72859 (17) | 0.0303 (8) | |
N19 | 0.00763 (19) | −0.0287 (6) | 0.91541 (17) | 0.0382 (9) | |
H1A | 0.0341 | 0.0032 | 0.8702 | 0.046* | |
H1B | −0.0347 | −0.1230 | 0.9032 | 0.046* | |
C1 | −0.0234 (2) | 0.1897 (7) | 0.9499 (2) | 0.0402 (11) | |
H19A | −0.0624 | 0.2602 | 0.9130 | 0.048* | |
H19B | 0.0217 | 0.2975 | 0.9577 | 0.048* | |
C2 | 0.0641 (2) | −0.1485 (7) | 0.9720 (2) | 0.0347 (10) | |
H2A | 0.1127 | −0.0543 | 0.9805 | 0.042* | |
H2B | 0.0808 | −0.2962 | 0.9496 | 0.042* | |
O2 | 0.87024 (18) | 0.7007 (6) | 0.90155 (18) | 0.0768 (11) | |
H2E | 0.8479 | 0.6958 | 0.9468 | 0.092* | |
H2F | 0.8362 | 0.6508 | 0.8667 | 0.092* | |
O1 | 0.7768 (5) | 0.545 (2) | 0.7752 (5) | 0.108 (4) | 0.589 (11) |
H1E | 0.7343 | 0.6188 | 0.7886 | 0.130* | 0.589 (11) |
H1F | 0.7714 | 0.5025 | 0.7269 | 0.130* | 0.589 (11) |
O1' | 0.8184 (9) | 0.363 (3) | 0.8038 (7) | 0.126 (5) | 0.411 (11) |
H1'A | 0.7716 | 0.3014 | 0.8092 | 0.152* | 0.411 (11) |
H1'B | 0.8272 | 0.3799 | 0.7544 | 0.152* | 0.411 (11) |
N5 | 0.1105 (2) | 0.6869 (6) | 0.4225 (2) | 0.0365 (8) | |
N6 | 0.1731 (14) | 0.702 (4) | 0.3866 (15) | 0.044 (4) | 0.29 (3) |
N6' | 0.1405 (10) | 0.626 (2) | 0.3625 (6) | 0.061 (3) | 0.71 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0314 (4) | 0.0213 (4) | 0.0195 (3) | 0.0118 (3) | 0.0045 (3) | 0.0049 (3) |
Cu2 | 0.0275 (3) | 0.0176 (3) | 0.0176 (2) | 0.00720 (19) | 0.00326 (18) | 0.00312 (18) |
Cu3 | 0.0262 (3) | 0.0163 (3) | 0.0212 (2) | 0.0047 (2) | 0.00177 (18) | 0.00195 (19) |
N1 | 0.0338 (18) | 0.0217 (18) | 0.0184 (16) | 0.0126 (14) | 0.0052 (14) | 0.0049 (14) |
N2 | 0.0362 (19) | 0.031 (2) | 0.0306 (19) | 0.0112 (16) | 0.0042 (16) | 0.0096 (16) |
N3 | 0.078 (3) | 0.088 (4) | 0.047 (2) | 0.044 (3) | 0.037 (2) | 0.022 (2) |
N4 | 0.0393 (19) | 0.0245 (19) | 0.0159 (16) | 0.0150 (15) | 0.0075 (14) | 0.0050 (13) |
N7 | 0.0289 (17) | 0.0178 (17) | 0.0213 (16) | 0.0085 (13) | 0.0047 (13) | 0.0018 (13) |
N8 | 0.039 (2) | 0.031 (2) | 0.0305 (19) | 0.0128 (16) | 0.0020 (16) | 0.0055 (15) |
N9 | 0.082 (3) | 0.086 (4) | 0.064 (3) | 0.040 (3) | 0.046 (2) | 0.022 (3) |
N10 | 0.0396 (19) | 0.0204 (19) | 0.0223 (17) | 0.0126 (15) | 0.0071 (14) | 0.0042 (14) |
N11 | 0.0335 (18) | 0.0186 (19) | 0.0295 (19) | 0.0083 (14) | 0.0033 (15) | 0.0079 (15) |
N12 | 0.079 (3) | 0.048 (3) | 0.028 (2) | 0.014 (2) | 0.0190 (19) | 0.0017 (18) |
N13 | 0.0292 (18) | 0.0176 (17) | 0.0360 (19) | 0.0018 (14) | 0.0025 (15) | −0.0029 (14) |
N14 | 0.036 (2) | 0.0185 (19) | 0.0297 (18) | 0.0056 (15) | −0.0015 (16) | −0.0013 (14) |
N15 | 0.043 (2) | 0.051 (3) | 0.068 (3) | 0.012 (2) | 0.027 (2) | 0.000 (2) |
N16 | 0.037 (2) | 0.048 (2) | 0.055 (2) | −0.0148 (18) | −0.0058 (17) | −0.0198 (18) |
N17 | 0.0284 (18) | 0.029 (2) | 0.0248 (17) | 0.0013 (16) | 0.0049 (14) | −0.0046 (15) |
N18 | 0.0322 (19) | 0.030 (2) | 0.0285 (18) | −0.0122 (15) | 0.0009 (14) | −0.0126 (15) |
N19 | 0.042 (2) | 0.042 (2) | 0.0314 (19) | −0.0028 (17) | 0.0172 (15) | 0.0021 (17) |
C1 | 0.045 (3) | 0.033 (3) | 0.043 (3) | 0.005 (2) | 0.012 (2) | 0.009 (2) |
C2 | 0.035 (2) | 0.027 (3) | 0.042 (2) | 0.0035 (19) | 0.0145 (19) | 0.001 (2) |
O2 | 0.057 (2) | 0.112 (3) | 0.063 (2) | −0.028 (2) | 0.0219 (17) | −0.029 (2) |
O1 | 0.084 (6) | 0.145 (8) | 0.097 (6) | −0.016 (5) | 0.037 (4) | −0.067 (6) |
O1' | 0.128 (9) | 0.161 (11) | 0.092 (7) | −0.024 (8) | 0.036 (6) | −0.058 (8) |
N5 | 0.046 (2) | 0.028 (2) | 0.036 (2) | 0.0148 (17) | 0.0069 (17) | 0.0152 (17) |
N6 | 0.042 (7) | 0.051 (7) | 0.038 (7) | 0.007 (6) | 0.018 (6) | 0.002 (6) |
N6' | 0.077 (7) | 0.066 (6) | 0.040 (4) | 0.021 (5) | 0.029 (4) | 0.002 (4) |
Cu1—N4 | 1.984 (3) | N2—N3 | 1.139 (4) |
Cu1—N4i | 1.984 (3) | N4—N5 | 1.176 (4) |
Cu1—N1 | 1.998 (3) | N7—N8 | 1.211 (4) |
Cu1—N1i | 1.998 (3) | N8—N9 | 1.141 (5) |
Cu1—N7ii | 2.747 (3) | N10—N11 | 1.215 (4) |
Cu2—N10 | 1.964 (3) | N11—N12 | 1.141 (4) |
Cu2—N4 | 2.003 (3) | N13—N14 | 1.201 (4) |
Cu2—N1i | 2.016 (3) | N13—Cu2v | 2.309 (3) |
Cu2—N7 | 2.021 (3) | N14—N15 | 1.152 (4) |
Cu2—N13ii | 2.309 (3) | N16—N17 | 1.155 (4) |
Cu3—N18iii | 1.972 (3) | N17—N18 | 1.201 (4) |
Cu3—N13 | 1.988 (3) | N18—Cu3vi | 1.972 (3) |
Cu3—N10 | 2.001 (3) | N19—C1 | 1.477 (5) |
Cu3—N7 | 2.048 (3) | N19—C2 | 1.482 (4) |
Cu3—N16 | 2.358 (3) | C1—C2vii | 1.502 (5) |
Cu3—N1iv | 2.942 (3) | C2—C1vii | 1.502 (5) |
N1—N2 | 1.210 (4) | N5—N6' | 1.182 (11) |
N1—Cu2i | 2.016 (3) | ||
N4—Cu1—N4i | 180.000 (1) | N13—Cu3—N1iv | 72.94 (10) |
N4—Cu1—N1 | 100.79 (11) | N10—Cu3—N1iv | 91.62 (10) |
N4i—Cu1—N1 | 79.21 (11) | N18iii—Cu3—N1iv | 91.07 (10) |
N4—Cu1—N1i | 79.21 (11) | N16—Cu3—N1iv | 160.58 (10) |
N4i—Cu1—N1i | 100.79 (11) | N2—N1—Cu1 | 130.1 (2) |
N1—Cu1—N1i | 180.000 (1) | N2—N1—Cu2i | 129.3 (2) |
N1—Cu1—N7ii | 89.22 (10) | Cu1—N1—Cu2i | 100.51 (13) |
N4—Cu1—N7ii | 94.74 (10) | N3—N2—N1 | 178.3 (4) |
N1i—Cu1—N7ii | 90.79 (10) | N5—N4—Cu1 | 129.5 (3) |
N4i—Cu1—N7ii | 85.26 (10) | N5—N4—Cu2 | 126.6 (2) |
N10—Cu2—N4 | 168.95 (13) | Cu1—N4—Cu2 | 101.45 (13) |
N10—Cu2—N1i | 101.13 (12) | N8—N7—Cu2 | 125.7 (3) |
N4—Cu2—N1i | 78.33 (11) | N8—N7—Cu3 | 120.6 (2) |
N10—Cu2—N7 | 78.67 (12) | Cu2—N7—Cu3 | 99.15 (12) |
N4—Cu2—N7 | 99.06 (11) | N9—N8—N7 | 177.8 (5) |
N1i—Cu2—N7 | 165.54 (12) | N11—N10—Cu2 | 128.9 (2) |
N10—Cu2—N13ii | 99.63 (12) | N11—N10—Cu3 | 123.3 (2) |
N4—Cu2—N13ii | 91.40 (12) | Cu2—N10—Cu3 | 102.78 (13) |
N1i—Cu2—N13ii | 88.66 (12) | N12—N11—N10 | 178.8 (4) |
N7—Cu2—N13ii | 105.68 (11) | N14—N13—Cu3 | 121.0 (3) |
N18iii—Cu3—N13 | 93.81 (13) | N14—N13—Cu2v | 122.8 (2) |
N18iii—Cu3—N10 | 91.83 (12) | Cu3—N13—Cu2v | 109.72 (13) |
N13—Cu3—N10 | 163.64 (12) | N15—N14—N13 | 178.6 (4) |
N18iii—Cu3—N7 | 167.98 (12) | N17—N16—Cu3 | 155.3 (3) |
N13—Cu3—N7 | 95.54 (12) | N16—N17—N18 | 177.9 (4) |
N10—Cu3—N7 | 77.18 (11) | N17—N18—Cu3vi | 115.7 (3) |
N18iii—Cu3—N16 | 98.96 (13) | C1—N19—C2 | 110.9 (3) |
N13—Cu3—N16 | 89.72 (12) | N19—C1—C2vii | 111.7 (3) |
N10—Cu3—N16 | 104.56 (13) | N19—C2—C1vii | 110.7 (3) |
N7—Cu3—N16 | 88.64 (12) | N4—N5—N6' | 167.6 (11) |
N7—Cu3—N1iv | 85.48 (10) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y+1, z; (iii) −x+1/2, y−1/2, −z+3/2; (iv) −x, −y+1, −z+1; (v) x, y−1, z; (vi) −x+1/2, y+1/2, −z+3/2; (vii) −x, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N19—H1A···N18iii | 0.90 | 2.23 | 3.103 (4) | 163 |
N19—H1B···O2viii | 0.90 | 1.85 | 2.738 (4) | 167 |
O2—H2E···N15ix | 0.85 | 2.12 | 2.961 (5) | 170 |
O2—H2F···O1 | 0.85 | 1.90 | 2.744 (8) | 169 |
O2—H2F···O1′ | 0.85 | 1.98 | 2.672 (12) | 138 |
O1—H1E···N6x | 0.85 | 2.20 | 2.94 (2) | 145 |
O1—H1F···N6xi | 0.85 | 2.43 | 3.19 (3) | 149 |
O1′—H1′A···N9ix | 0.85 | 2.63 | 3.034 (12) | 111 |
O1′—H1′B···N6′xi | 0.85 | 2.05 | 2.888 (14) | 171 |
Symmetry codes: (iii) −x+1/2, y−1/2, −z+3/2; (viii) x−1, y−1, z; (ix) x+1/2, −y+1/2, z+1/2; (x) x+1/2, −y+3/2, z+1/2; (xi) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C4H12N2)[Cu5(N3)12]·4H2O |
Mr | 982.28 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 16.343 (3), 5.7477 (11), 16.812 (3) |
β (°) | 91.10 (3) |
V (Å3) | 1579.0 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.40 |
Crystal size (mm) | 0.22 × 0.21 × 0.19 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.522, 0.564 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7506, 2772, 2080 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.072, 1.02 |
No. of reflections | 2772 |
No. of parameters | 252 |
No. of restraints | 522 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.50 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Cu1—N4 | 1.984 (3) | Cu2—N13i | 2.309 (3) |
Cu1—N1 | 1.998 (3) | Cu3—N18iii | 1.972 (3) |
Cu1—N7i | 2.747 (3) | Cu3—N13 | 1.988 (3) |
Cu2—N10 | 1.964 (3) | Cu3—N10 | 2.001 (3) |
Cu2—N4 | 2.003 (3) | Cu3—N7 | 2.048 (3) |
Cu2—N1ii | 2.016 (3) | Cu3—N16 | 2.358 (3) |
Cu2—N7 | 2.021 (3) | Cu3—N1iv | 2.942 (3) |
N4—Cu1—N4ii | 180.000 (1) | N7—Cu2—N13i | 105.68 (11) |
N4—Cu1—N1 | 100.79 (11) | N18iii—Cu3—N13 | 93.81 (13) |
N4ii—Cu1—N1 | 79.21 (11) | N18iii—Cu3—N10 | 91.83 (12) |
N1—Cu1—N7i | 89.22 (10) | N13—Cu3—N10 | 163.64 (12) |
N4—Cu1—N7i | 94.74 (10) | N18iii—Cu3—N7 | 167.98 (12) |
N1ii—Cu1—N7i | 90.79 (10) | N13—Cu3—N7 | 95.54 (12) |
N4ii—Cu1—N7i | 85.26 (10) | N10—Cu3—N7 | 77.18 (11) |
N10—Cu2—N4 | 168.95 (13) | N18iii—Cu3—N16 | 98.96 (13) |
N10—Cu2—N1ii | 101.13 (12) | N13—Cu3—N16 | 89.72 (12) |
N4—Cu2—N1ii | 78.33 (11) | N10—Cu3—N16 | 104.56 (13) |
N10—Cu2—N7 | 78.67 (12) | N7—Cu3—N16 | 88.64 (12) |
N4—Cu2—N7 | 99.06 (11) | N7—Cu3—N1iv | 85.48 (10) |
N1ii—Cu2—N7 | 165.54 (12) | N13—Cu3—N1iv | 72.94 (10) |
N10—Cu2—N13i | 99.63 (12) | N10—Cu3—N1iv | 91.62 (10) |
N4—Cu2—N13i | 91.40 (12) | N18iii—Cu3—N1iv | 91.07 (10) |
N1ii—Cu2—N13i | 88.66 (12) | N16—Cu3—N1iv | 160.58 (10) |
Symmetry codes: (i) x, y+1, z; (ii) −x, −y+2, −z+1; (iii) −x+1/2, y−1/2, −z+3/2; (iv) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N19—H1A···N18iii | 0.90 | 2.23 | 3.103 (4) | 163.2 |
N19—H1B···O2v | 0.90 | 1.85 | 2.738 (4) | 166.7 |
O2—H2E···N15vi | 0.85 | 2.12 | 2.961 (5) | 169.5 |
O2—H2F···O1 | 0.85 | 1.90 | 2.744 (8) | 169.2 |
O2—H2F···O1' | 0.85 | 1.98 | 2.672 (12) | 137.5 |
O1—H1E···N6vii | 0.85 | 2.20 | 2.94 (2) | 145.1 |
O1—H1F···N6viii | 0.85 | 2.43 | 3.19 (3) | 148.6 |
O1'—H1'A···N9vi | 0.85 | 2.63 | 3.034 (12) | 110.7 |
O1'—H1'B···N6'viii | 0.85 | 2.05 | 2.888 (14) | 170.8 |
Symmetry codes: (iii) −x+1/2, y−1/2, −z+3/2; (v) x−1, y−1, z; (vi) x+1/2, −y+1/2, z+1/2; (vii) x+1/2, −y+3/2, z+1/2; (viii) −x+1, −y+1, −z+1. |