Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S205322961400504X/sk3539sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S205322961400504X/sk3539Isup2.hkl |
CCDC reference: 990184
Polynitrile ligands are of great interest as they can lead to a rich variety of supramolecular architectures (Setifi et al., 2009, 2014; Benmansour et al., 2010, 2012). One such ligand is the dicyanamide anion, [N(CN)2]- (dca), which can coordinate to metal centres in a wide variety of ways, using either the central N atom as a ligating atom or one or both of the terminal N atoms, or various combinations of these N atoms. In addition, each terminal N atom can coordinate to either one metal centre or two. Overall, eight different modes of coordination have been identified and the number of different metal centres to which a single dca ligand can coordinate ranges from one to five, leading to the formation of coordination polymers which may be one-, two- or three-dimensional (Batten & Murray, 2003). We have therefore found it of interest to explore the effect of chelating co-ligands on the architectures of CuII complexes containing dca ligands, and here we report the synthesis and structure of catena-poly[[[4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole-κ2N1,N5](dicyanamido-κN)copper(II)]-µ2-dicyanamido-κ2N:N'], (I) (Fig. 1).
Copper(II) nitrate dihydrate (0.25 mmol, 60 mg) and 4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole (0.25 mmol, 59 mg) were dissolved in water (10 ml), producing a blue solution. A solution of sodium dicyanamide (0.5 mmol, 44 mg) in water (5 ml) was then added with stirring. The resulting solution was filtered and the filtrate set aside to crystallize at ambient temperature and in the presence of air. After 10 d, the resulting blue crystals of (I) were collected by filtration, washed with water and dried in air (yield 85%).
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and then treated as riding. C-bound H atoms were treated as riding in geometrically idealized positions, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). The H atoms bonded to atom N41 were permitted to ride at the positions located in a difference map, with Uiso(H) = 1.2Ueq(N), giving the N—H distances shown in Table 3. Reflection 001, which had been attenuated by the beam stop, was omitted from the final refinements.
In the title compound, (I), the 4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole ligand coordinates to the CuII centre via triazole and pyridine atoms N1 and N51 (Fig. 1), and the two independent dicyanamide (dca) ligands are coordinated via atoms N13 and N23. In addition, atom N15 at (x, y, z) coordinates to the CuII centre at (x - 1, y, z), so completing the square-pyramidal coordination at the CuII centre (Fig. 2) and generating a one-dimensional coordination polymer running parallel to the [100] direction (Fig. 3), along which the Cu···Cu distance is 7.5946 (5) Å. The behaviour of the two dca ligands thus differs, in that the anion containing atom N11 acts as a bridging ligand between a pair of CuII centres related by translation, whereas the anion containing atom N21 exhibits no bridging action. Of the five independent Cu—N distances (Table 2), the apical distance Cu1—N15i [symmetry code: (i) x + 1, y, z] is longer than the remainder, and it is significantly longer than the two basal Cu—N distances (Cu1—N13 and Cu1—N23) which involve the dca ligands.
Addison et al. (1984) have introduced a simple parameter, denoted τ, which can be used to assess the geometry of five-coordinate geometries which are intermediate between the idealized trigonal bipyramidal and square-pyramidal forms. For trigonal bipyamidal geometry, where the bond angles conform exactly to D3h (6m2) symmetry, the value of τ is 1.00, and for square-pyramidal geometry, where the bond angles conform exactly to C4v (4mm) symmetry, the value of τ is 0.00. In compound (I), the value of τ is 0.249, indicating a coordination geometry which approximates much more closely to square-pyramidal than trigonal bipyramidal (Fig. 2). For mutually cis pairs of ligand atoms, the bond angles at the CuII centre (Table 2, and Figs. 1 and 2) range from 78.77 (7) to 94.20 (8)° within the basal ligand group (atoms N1, N51, N13 and N23), and from 95.15 (7) to 105.20 (8)° for the angles between apical atom N15i and the basal atoms.
Within the triazole ring, the four independent N—C distances (Table 2) span a rather small range, ca 0.06 Å, despite the fact that the N1—C5 and N2—C3 bonds are formally double bonds, whereas the N4—C3 and N4—C5 bonds are formally single bonds; these observations point to a considerable degree of aromatic delocalization within this ring. Amine atom N4 is markedly pyramidal, with a sum of bond angles of 317.8°, but despite this atom N41 does not act as a hydrogen-bond acceptor. The non-H atoms of the bis(pyridyl)triazole ligand are fairly close to being coplanar; the dihedral angles between the triazole ring and the pyridine rings containing atoms N31 and N51 are 9.72 (11) and 6.38 (11)°, respectively, while the dihedral angle between the two pyridine rings is only 3.53 (11)°.
In the bridging dca ligand, the N11—C12 and N11—C14 distances are identical within experimental uncertainty (Table 2), but in the terminal ligand the corresponding distances are significantly different. This indicates that, for the terminal ligand, in addition to any contribution from the symmetrical form (A), there are unequal contributions from the two canonical forms (B) and (C) (see Scheme 1), such that the anionic terminus is bonded to the CuII centre, but forms (B) and (C) contribute equally to the electronic structure of the bridging ligand. [Scheme does not show these forms. Also, final sentence contradicts itself - the contributions must be either equal or unequal, they can't be both.]
There is a short intramolecular N—H···N interaction (Table 3) which may be associated with the near coplanarity of the rings containing atoms N1 and N31. The coordination polymer chains are linked into bilayers by a combination of N—H···N and C—H···N hydrogen bonds, and it is convenient to consider first the C—H···N hydrogen bond, although this is probably the weaker of the two. The C—H···N hydrogen bond, which has atom N21 as the acceptor, links the coordination polymer chains related by translation along the [011] direction via a C(12) (Bernstein et al., 1995) motif to form a sheet lying parallel to (011) and built from a single type of 36-membered ring (Fig. 3). Inversion-related pairs of these sheets are linked into bilayers by the intermolecular N—H···N hydrogen bond in an R22(22) motif (Fig. 4). It may be worth noting that, in both of these hydrogen bonds, the acceptor N atom lies in the terminal dca ligand. There is a second short intermolecular C—H···N contact present, this time involving triazole atom N2, but the C—H···N angle is only 126° (Table 3), so this contact cannot be regarded as structurally significant (Wood et al., 2009).
The hydrogen-bonded bilayer is reinforced by two π–π stacking interactions, both of which involve pairs of rings, one in each component sheet of the bilayer. The N31/C32–C36 pyridine rings at (x, y, z) and (-x + 1, -y + 1, -z + 2) are strictly parallel, with an interplanar separation of 3.278 (2) Å; the ring-centroid separation is 3.533 (2) Å, corresponding to a ring-centroid offset of 1.318 (2) Å. The planes of the triazole ring at (x, y, z) and the N31/C32–C36 pyridine ring at (-x + 2, -y + 1, -z + 2) make a dihedral angle of 9.7 (2)°, and shortest perpendicular distance from the centroid of one ring to the plane of the other is ca 3.17 Å. The ring-centroid separation is 3.613 (2) Å, corresponding to ring-centroid offset of ca 1.73 Å, indicative of only a rather weak interaction.
It is of interest briefly to compare the structure of (I) reported here with those of some related CuII compounds also containing dca ligands, where fairly minor changes in the constitution of the nonbridging heteroaromatic co-ligands lead to quite wide variations in the nature of the supramolecular assembly. Thus in [Cu(dca)2(Hambi)], (II), where Hambi represents 2-(aminomethyl)benzimidazole, the CuII cation lies on a centre of inversion in space group P1 (He et al., 2003). The bidentate Hambi ligands occupy the equatorial sites in an axially elongated (4+2) coordination polyhedron, and the apical sites are occupied by dca ligands coordinated via the central N atoms, as opposed to the terminal N atoms which are involved in (I). There is no further coordination to CuII, so the aggregation can be regarded as finite or zero-dimensional. Finite zero-dimensional aggregation is also observed in [Cu(bpca)(dca)(H2O)], (III), where bpca represents bis(pyridin-2-ylcarbonyl)amidate (Vangdal et al., 2002). Here, inversion-related pairs of CuII centres are linked by inversion-related pairs of bidentate dca ligands coordinated via the central N atom and one of the terminal atoms, so forming a dimeric unit containing an eight-membered ring structure.
In the complex [Cu(dca)2(2,2'-bipyridyl)], (IV) (Potočňák et al., 2002; Vangdal et al., 2002), the two dca ligands adopt different coordination modes, one acting as a bidentate bridging ligand while the other is monodentate. Only the terminal N atoms of the dca ligands are involved in metal coordination, as found in (I), but this differs from the bridging action found in (III). A one-dimensional coordination polymer thus results in (IV), analogous to that in (I), but whereas the CuII centres along the polymer chain in (I) are related by translation, those in (IV) are related by a glide plane: the Cu···Cu distances along the chain in (IV) were reported as 8.212 (1) (Potočňák et al., 2002) and 8.1999 (8) Å (Vangdal et al., 2002), slightly longer than the corresponding distance of 7.5946 (5) Å in (I). Chains similar to those in (I) are observed in [Cu(dca)2(5,5'-dimethyl-2,2'-bipyridyl)], (V) (Kooijman et al., 2002), with a Cu···Cu distance between Cu centres related by translation along the chain of 7.5297 (10) Å, and in [Cu(dca)2(dpa)], (VI) (dpa is 2,2-dipridylamine; Carranza et al., 2002), with an intrachain Cu···Cu distance of 7.689 (2) Å.
A more complex one-dimensional coordination polymer is present in [Cu(dca)2(2,2'-bipyrimidyl)], (VII) (Vangdal et al., 2002), the composition of which differs from that of (IV) only in the number of N atoms in the heteroaromatic rings. In (VII), the 2,2'-bipyrimidyl ligand, which lies across a centre of inversion in space group P21/c, acts as a bis-bidentate ligand towards two inversion-related CuII centres; as in compounds (I) and (IV)–(VI), the dca ligands coordinate only via the terminal N atoms, where one is monodentate and the other bidentate. The bidentate dca ligand links two CuII centres related by translation, and the combination of translation and inversion generates a molecular ladder structure in the form of a chain of centrosymmetric edge-fused 20-membered rings. The shortest Cu···Cu distance along the ladder is 7.555 (2) Å, while the distance between two CuII centres sharing a common 2,2'-bipyrimidyl ligand is 5.5673 (4) Å. In [Cu(dca)2(2-aminopyridine)2], (VIII) (van Albada et al., 2000), both dca ligands are bidentate, coordinating via the terminal N atoms and producing a chain of spiro-fused 12-membered rings with an intrachain Cu···Cu distance of 7.570 Å (no s.u. value was given).
The constitution of [Cu(dca)2(1,10-phen)], (IX) (1,10-phen is 1,10-phenanthroline; Wang et al., 2000; Luo, Hong, Weng et al., 2002), differs from that of (IV) only in the presence of an additional ring in the heteroaromatic ligand. However, the resulting coordination polymer is now two-dimensional, forming a sheet containing equal numbers of 12- and 36-membered rings, in which both dca ligands are bidentate, again using only the terminal N atoms. The six-coordination of the CuII centre is very distorted, with axial Cu—N distances of 2.287 (4) and 2.821 (4) Å. The two shortest Cu···Cu distances within the sheet are 7.3002 (7) and 7.7079 (4) Å (Wang et al., 2000). It may be noted here that the structure of the cadmium analogue of (IX), [Cd(dca)2(1,10-phen)], has also been reported (Luo, Hong, Cao et al., 2002), and this compound appears to be isostructural with the Cu analogue, with axially elongated (4+2) coordination at the Cd atom. This striking and rather unexpected similarity was not noted in the almost simultaneous reports (Luo, Hong, Weng et al., 2002; Luo, Hong, Cao et al., 2002) on these structures.
The dca ligand contains only five atoms but, despite this simplicity, four distinct modes of coordination to CuII can be identified in compounds (I)–(IX): (a) monodentate coordination via the central N atom (µ3-coordination; Batten & Murray, 2003); (b) monodentate coordination via one of the terminal N atoms (µ1-coordination); (c) bidentate coordination via the central N atom and one of the terminal N atoms (µ1,3-coordination); and (d) bidentate coordination via the two terminal N atoms (µ1,5-coordination). Mode (a) is the sole form observed in the mononuclear compound (II), and mode (c) is the sole form observed in the binuclear compound (III) and in the chain polymer (VII): modes (b) and (d) occur together in compounds (I) and (IV)–(VIII), each of which forms a one-dimensional coordination polymer, while mode (d) is the sole form observed in (IX), where the coordination polymer is two-dimensional. Accordingly, dca appears to be a versatile ligand, as indicated by both the various coordination modes available, either singly or in combination, and the wide variety of coordination architectures which can result [van Albada compound was originally a duplicate (VII). It is now (VIII) and the phen compound is (IX). Please check carefully to make sure this has not introduced further errors].
Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
[Cu(C2N3)2(C12H10N6)] | Z = 2 |
Mr = 433.91 | F(000) = 438 |
Triclinic, P1 | Dx = 1.691 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5946 (5) Å | Cell parameters from 6098 reflections |
b = 8.4284 (5) Å | θ = 2.5–32.5° |
c = 14.1106 (8) Å | µ = 1.32 mm−1 |
α = 96.668 (4)° | T = 150 K |
β = 101.019 (5)° | Block, blue |
γ = 102.962 (4)° | 0.25 × 0.22 × 0.22 mm |
V = 851.96 (9) Å3 |
Agilent Xcalibur diffractometer | 4835 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 32.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −11→11 |
Tmin = 0.694, Tmax = 0.749 | k = −12→12 |
13231 measured reflections | l = −21→20 |
6097 independent reflections |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0355P)2] where P = (Fo2 + 2Fc2)/3 |
6097 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
[Cu(C2N3)2(C12H10N6)] | γ = 102.962 (4)° |
Mr = 433.91 | V = 851.96 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5946 (5) Å | Mo Kα radiation |
b = 8.4284 (5) Å | µ = 1.32 mm−1 |
c = 14.1106 (8) Å | T = 150 K |
α = 96.668 (4)° | 0.25 × 0.22 × 0.22 mm |
β = 101.019 (5)° |
Agilent Xcalibur diffractometer | 6097 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4835 reflections with I > 2σ(I) |
Tmin = 0.694, Tmax = 0.749 | Rint = 0.048 |
13231 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.44 e Å−3 |
6097 reflections | Δρmin = −0.59 e Å−3 |
262 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.75026 (3) | 0.22702 (3) | 0.601776 (17) | 0.01768 (8) | |
N1 | 0.7736 (2) | 0.2875 (2) | 0.74376 (12) | 0.0170 (3) | |
N2 | 0.7463 (2) | 0.4178 (2) | 0.80088 (12) | 0.0183 (3) | |
C3 | 0.7618 (3) | 0.3802 (2) | 0.88962 (14) | 0.0172 (4) | |
N4 | 0.7979 (2) | 0.2274 (2) | 0.89006 (11) | 0.0167 (3) | |
C5 | 0.8072 (3) | 0.1757 (2) | 0.79761 (14) | 0.0163 (4) | |
N11 | 0.3537 (3) | 0.5046 (2) | 0.63214 (14) | 0.0287 (4) | |
C12 | 0.4691 (3) | 0.4291 (3) | 0.60224 (15) | 0.0206 (4) | |
N13 | 0.5809 (2) | 0.3718 (2) | 0.57711 (12) | 0.0239 (4) | |
C14 | 0.1779 (3) | 0.4303 (3) | 0.61239 (14) | 0.0208 (4) | |
N15 | 0.0202 (3) | 0.3759 (2) | 0.60091 (13) | 0.0267 (4) | |
N21 | 0.6398 (3) | −0.0063 (2) | 0.29552 (14) | 0.0325 (5) | |
C22 | 0.6667 (3) | 0.0704 (3) | 0.38353 (15) | 0.0216 (4) | |
N23 | 0.6942 (3) | 0.1209 (2) | 0.46577 (13) | 0.0287 (4) | |
C24 | 0.5993 (3) | 0.0588 (3) | 0.21636 (16) | 0.0249 (5) | |
N25 | 0.5623 (3) | 0.0958 (3) | 0.14076 (14) | 0.0345 (5) | |
N31 | 0.8001 (2) | 0.4446 (2) | 1.06232 (12) | 0.0219 (4) | |
C32 | 0.7492 (3) | 0.4897 (2) | 0.97524 (14) | 0.0177 (4) | |
C33 | 0.6868 (3) | 0.6302 (3) | 0.96337 (15) | 0.0215 (4) | |
H33 | 0.6522 | 0.6576 | 0.9002 | 0.026* | |
C34 | 0.6767 (3) | 0.7294 (3) | 1.04667 (16) | 0.0257 (5) | |
H34 | 0.6362 | 0.8275 | 1.0418 | 0.031* | |
C35 | 0.7263 (3) | 0.6835 (3) | 1.13709 (16) | 0.0260 (5) | |
H35 | 0.7199 | 0.7490 | 1.1953 | 0.031* | |
C36 | 0.7850 (3) | 0.5410 (3) | 1.14086 (15) | 0.0251 (5) | |
H36 | 0.8168 | 0.5093 | 1.2030 | 0.030* | |
N41 | 0.8140 (3) | 0.1338 (2) | 0.96739 (12) | 0.0232 (4) | |
H41A | 0.7058 | 0.0592 | 0.9580 | 0.028* | |
H41B | 0.8217 | 0.2051 | 1.0224 | 0.028* | |
N51 | 0.8200 (2) | 0.0212 (2) | 0.65314 (12) | 0.0190 (3) | |
C52 | 0.8430 (3) | 0.0252 (2) | 0.75076 (14) | 0.0177 (4) | |
C53 | 0.8977 (3) | −0.0954 (3) | 0.79808 (16) | 0.0232 (4) | |
H53 | 0.9144 | −0.0875 | 0.8671 | 0.028* | |
C54 | 0.9277 (3) | −0.2290 (3) | 0.74188 (18) | 0.0274 (5) | |
H54 | 0.9657 | −0.3147 | 0.7720 | 0.033* | |
C55 | 0.9019 (3) | −0.2361 (3) | 0.64206 (17) | 0.0277 (5) | |
H55 | 0.9201 | −0.3274 | 0.6024 | 0.033* | |
C56 | 0.8493 (3) | −0.1087 (3) | 0.60037 (16) | 0.0239 (4) | |
H56 | 0.8332 | −0.1137 | 0.5316 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01992 (13) | 0.02354 (14) | 0.01221 (12) | 0.01002 (10) | 0.00448 (9) | 0.00316 (9) |
N1 | 0.0205 (8) | 0.0179 (8) | 0.0148 (8) | 0.0081 (7) | 0.0053 (6) | 0.0031 (6) |
N2 | 0.0236 (9) | 0.0183 (8) | 0.0153 (8) | 0.0077 (7) | 0.0068 (7) | 0.0027 (7) |
C3 | 0.0161 (9) | 0.0194 (9) | 0.0171 (9) | 0.0050 (7) | 0.0046 (7) | 0.0042 (8) |
N4 | 0.0203 (8) | 0.0176 (8) | 0.0139 (7) | 0.0061 (7) | 0.0047 (6) | 0.0051 (6) |
C5 | 0.0163 (9) | 0.0186 (9) | 0.0147 (9) | 0.0046 (7) | 0.0044 (7) | 0.0034 (7) |
N31 | 0.0218 (9) | 0.0280 (9) | 0.0156 (8) | 0.0081 (7) | 0.0028 (7) | 0.0013 (7) |
C32 | 0.0162 (9) | 0.0208 (10) | 0.0153 (9) | 0.0029 (8) | 0.0051 (7) | 0.0015 (8) |
C33 | 0.0240 (10) | 0.0213 (10) | 0.0209 (10) | 0.0055 (8) | 0.0089 (8) | 0.0037 (8) |
C34 | 0.0284 (11) | 0.0204 (10) | 0.0290 (11) | 0.0047 (9) | 0.0121 (9) | 0.0002 (9) |
C35 | 0.0257 (11) | 0.0283 (11) | 0.0224 (10) | 0.0054 (9) | 0.0082 (9) | −0.0046 (9) |
C36 | 0.0247 (11) | 0.0352 (12) | 0.0149 (9) | 0.0089 (9) | 0.0031 (8) | 0.0015 (9) |
N41 | 0.0317 (10) | 0.0251 (9) | 0.0157 (8) | 0.0097 (8) | 0.0062 (7) | 0.0093 (7) |
N51 | 0.0201 (8) | 0.0201 (8) | 0.0177 (8) | 0.0073 (7) | 0.0049 (7) | 0.0016 (7) |
C52 | 0.0161 (9) | 0.0186 (9) | 0.0196 (9) | 0.0048 (7) | 0.0058 (7) | 0.0038 (8) |
C53 | 0.0251 (11) | 0.0238 (10) | 0.0247 (11) | 0.0083 (9) | 0.0085 (9) | 0.0105 (9) |
C54 | 0.0305 (12) | 0.0190 (10) | 0.0376 (13) | 0.0100 (9) | 0.0123 (10) | 0.0099 (9) |
C55 | 0.0297 (12) | 0.0196 (10) | 0.0344 (12) | 0.0084 (9) | 0.0090 (10) | −0.0008 (9) |
C56 | 0.0268 (11) | 0.0228 (10) | 0.0223 (10) | 0.0085 (9) | 0.0062 (9) | −0.0011 (9) |
N11 | 0.0234 (10) | 0.0299 (10) | 0.0340 (11) | 0.0084 (8) | 0.0121 (8) | −0.0026 (9) |
C12 | 0.0198 (10) | 0.0250 (10) | 0.0174 (9) | 0.0052 (8) | 0.0044 (8) | 0.0058 (8) |
N13 | 0.0243 (9) | 0.0339 (10) | 0.0176 (8) | 0.0143 (8) | 0.0042 (7) | 0.0074 (8) |
C14 | 0.0284 (11) | 0.0257 (11) | 0.0139 (9) | 0.0140 (9) | 0.0092 (8) | 0.0044 (8) |
N15 | 0.0240 (10) | 0.0350 (11) | 0.0248 (9) | 0.0108 (8) | 0.0098 (8) | 0.0059 (8) |
N21 | 0.0501 (13) | 0.0296 (11) | 0.0158 (9) | 0.0115 (10) | 0.0033 (8) | −0.0008 (8) |
C22 | 0.0221 (10) | 0.0218 (10) | 0.0213 (10) | 0.0069 (8) | 0.0042 (8) | 0.0039 (8) |
N23 | 0.0382 (11) | 0.0317 (10) | 0.0190 (9) | 0.0146 (9) | 0.0058 (8) | 0.0046 (8) |
C24 | 0.0242 (11) | 0.0238 (11) | 0.0219 (11) | 0.0016 (9) | 0.0051 (9) | −0.0057 (9) |
N25 | 0.0428 (12) | 0.0361 (12) | 0.0212 (10) | 0.0064 (10) | 0.0044 (9) | 0.0026 (9) |
Cu1—N1 | 1.9727 (16) | C36—H36 | 0.9500 |
Cu1—N13 | 1.9737 (18) | N41—H41A | 0.8918 |
Cu1—N23 | 1.9447 (18) | N41—H41B | 0.9089 |
Cu1—N51 | 2.0912 (17) | N51—C56 | 1.336 (3) |
Cu1—N15i | 2.1534 (19) | N51—C52 | 1.350 (2) |
N1—N2 | 1.364 (2) | C52—C53 | 1.376 (3) |
N2—C3 | 1.317 (2) | C53—C54 | 1.388 (3) |
C3—N4 | 1.377 (3) | C53—H53 | 0.9500 |
N4—C5 | 1.347 (2) | C54—C55 | 1.377 (3) |
C5—N1 | 1.316 (2) | C54—H54 | 0.9500 |
N4—N41 | 1.421 (2) | C55—C56 | 1.381 (3) |
C3—C32 | 1.464 (3) | C55—H55 | 0.9500 |
C5—C52 | 1.465 (3) | C56—H56 | 0.9500 |
N31—C36 | 1.335 (3) | N11—C12 | 1.297 (3) |
N31—C32 | 1.340 (3) | C12—N13 | 1.157 (3) |
C32—C33 | 1.386 (3) | N11—C14 | 1.301 (3) |
C33—C34 | 1.386 (3) | C14—N15 | 1.155 (3) |
C33—H33 | 0.9500 | N15—Cu1ii | 2.1534 (19) |
C34—C35 | 1.384 (3) | N21—C22 | 1.288 (3) |
C34—H34 | 0.9500 | C22—N23 | 1.151 (3) |
C35—C36 | 1.374 (3) | N21—C24 | 1.315 (3) |
C35—H35 | 0.9500 | C24—N25 | 1.147 (3) |
N1—Cu1—N51 | 78.77 (7) | C34—C35—H35 | 120.7 |
N1—Cu1—N13 | 89.47 (7) | N31—C36—C35 | 123.9 (2) |
N13—Cu1—N23 | 94.20 (8) | N31—C36—H36 | 118.0 |
N23—Cu1—N51 | 92.58 (7) | C35—C36—H36 | 118.0 |
N1—Cu1—N23 | 167.27 (8) | N4—N41—H41A | 106.8 |
N13—Cu1—N51 | 152.33 (7) | N4—N41—H41B | 105.2 |
N1—Cu1—N15i | 95.15 (7) | H41A—N41—H41B | 105.8 |
N13—Cu1—N15i | 105.20 (8) | C56—N51—C52 | 117.69 (18) |
N23—Cu1—N15i | 95.64 (8) | C56—N51—Cu1 | 126.98 (14) |
N51—Cu1—N15i | 100.77 (7) | C52—N51—Cu1 | 115.29 (13) |
C5—N1—N2 | 109.55 (16) | N51—C52—C53 | 123.38 (19) |
C5—N1—Cu1 | 116.22 (13) | N51—C52—C5 | 110.82 (17) |
N2—N1—Cu1 | 133.94 (13) | C53—C52—C5 | 125.77 (19) |
C3—N2—N1 | 105.99 (16) | C52—C53—C54 | 117.9 (2) |
N2—C3—N4 | 110.10 (17) | C52—C53—H53 | 121.0 |
N2—C3—C32 | 124.22 (18) | C54—C53—H53 | 121.0 |
N4—C3—C32 | 125.63 (18) | C55—C54—C53 | 119.3 (2) |
C5—N4—C3 | 105.43 (16) | C55—C54—H54 | 120.3 |
C5—N4—N41 | 124.93 (16) | C53—C54—H54 | 120.3 |
C3—N4—N41 | 129.57 (16) | C54—C55—C56 | 119.2 (2) |
N1—C5—N4 | 108.89 (17) | C54—C55—H55 | 120.4 |
N1—C5—C52 | 118.64 (17) | C56—C55—H55 | 120.4 |
N4—C5—C52 | 132.45 (18) | N51—C56—C55 | 122.5 (2) |
C36—N31—C32 | 116.81 (19) | N51—C56—H56 | 118.7 |
N31—C32—C33 | 123.82 (18) | C55—C56—H56 | 118.7 |
N31—C32—C3 | 116.13 (18) | C12—N11—C14 | 119.6 (2) |
C33—C32—C3 | 120.04 (18) | N11—C12—N13 | 175.4 (3) |
C34—C33—C32 | 117.8 (2) | N11—C14—N15 | 173.7 (2) |
C34—C33—H33 | 121.1 | C22—N21—C24 | 124.3 (2) |
C32—C33—H33 | 121.1 | N21—C22—N23 | 171.4 (2) |
C35—C34—C33 | 119.1 (2) | N21—C24—N25 | 171.1 (3) |
C35—C34—H34 | 120.4 | C12—N13—Cu1 | 147.64 (17) |
C33—C34—H34 | 120.4 | C14—N15—Cu1ii | 164.63 (18) |
C36—C35—C34 | 118.5 (2) | C22—N23—Cu1 | 174.51 (19) |
C36—C35—H35 | 120.7 | ||
N23—Cu1—N1—C5 | 44.0 (4) | C32—C33—C34—C35 | −0.8 (3) |
N13—Cu1—N1—C5 | 150.98 (15) | C33—C34—C35—C36 | 0.4 (3) |
N51—Cu1—N1—C5 | −3.82 (14) | C32—N31—C36—C35 | −1.9 (3) |
N15i—Cu1—N1—C5 | −103.81 (15) | C34—C35—C36—N31 | 1.1 (3) |
N23—Cu1—N1—N2 | −128.9 (3) | N23—Cu1—N51—C56 | 12.70 (19) |
N13—Cu1—N1—N2 | −21.96 (18) | N1—Cu1—N51—C56 | −176.71 (19) |
N51—Cu1—N1—N2 | −176.76 (19) | N13—Cu1—N51—C56 | 116.8 (2) |
N15i—Cu1—N1—N2 | 83.25 (18) | N15i—Cu1—N51—C56 | −83.54 (18) |
C5—N1—N2—C3 | −0.9 (2) | N23—Cu1—N51—C52 | −169.56 (15) |
Cu1—N1—N2—C3 | 172.42 (15) | N1—Cu1—N51—C52 | 1.02 (14) |
N1—N2—C3—N4 | −0.2 (2) | N13—Cu1—N51—C52 | −65.5 (2) |
N1—N2—C3—C32 | 177.54 (17) | N15i—Cu1—N51—C52 | 94.20 (15) |
N2—C3—N4—C5 | 1.2 (2) | C56—N51—C52—C53 | 1.2 (3) |
C32—C3—N4—C5 | −176.55 (18) | Cu1—N51—C52—C53 | −176.76 (16) |
N2—C3—N4—N41 | −175.82 (18) | C56—N51—C52—C5 | 179.54 (18) |
C32—C3—N4—N41 | 6.5 (3) | Cu1—N51—C52—C5 | 1.6 (2) |
N2—N1—C5—N4 | 1.6 (2) | N1—C5—C52—N51 | −5.0 (3) |
Cu1—N1—C5—N4 | −172.98 (12) | N4—C5—C52—N51 | 173.8 (2) |
N2—N1—C5—C52 | −179.29 (16) | N1—C5—C52—C53 | 173.32 (19) |
Cu1—N1—C5—C52 | 6.1 (2) | N4—C5—C52—C53 | −7.9 (4) |
C3—N4—C5—N1 | −1.7 (2) | N51—C52—C53—C54 | −1.1 (3) |
N41—N4—C5—N1 | 175.48 (17) | C5—C52—C53—C54 | −179.15 (19) |
C3—N4—C5—C52 | 179.4 (2) | C52—C53—C54—C55 | 0.0 (3) |
N41—N4—C5—C52 | −3.4 (3) | C53—C54—C55—C56 | 0.9 (3) |
C36—N31—C32—C33 | 1.4 (3) | C52—N51—C56—C55 | −0.2 (3) |
C36—N31—C32—C3 | −178.40 (18) | Cu1—N51—C56—C55 | 177.45 (16) |
N2—C3—C32—N31 | −168.69 (18) | C54—C55—C56—N51 | −0.8 (3) |
N4—C3—C32—N31 | 8.7 (3) | N23—Cu1—N13—C12 | 136.6 (3) |
N2—C3—C32—C33 | 11.5 (3) | N1—Cu1—N13—C12 | −31.2 (3) |
N4—C3—C32—C33 | −171.04 (19) | N51—Cu1—N13—C12 | 32.9 (4) |
N31—C32—C33—C34 | 0.0 (3) | N15i—Cu1—N13—C12 | −126.4 (3) |
C3—C32—C33—C34 | 179.72 (18) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N41—H41A···N25iii | 0.89 | 2.26 | 3.067 (3) | 151 |
N41—H41B···N31 | 0.91 | 2.08 | 2.834 (2) | 139 |
C35—H35···N21iv | 0.95 | 2.61 | 3.499 (3) | 155 |
C54—H54···N2v | 0.95 | 2.61 | 3.260 (3) | 126 |
Symmetry codes: (iii) −x+1, −y, −z+1; (iv) x, y+1, z+1; (v) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2N3)2(C12H10N6)] |
Mr | 433.91 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 7.5946 (5), 8.4284 (5), 14.1106 (8) |
α, β, γ (°) | 96.668 (4), 101.019 (5), 102.962 (4) |
V (Å3) | 851.96 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.25 × 0.22 × 0.22 |
Data collection | |
Diffractometer | Agilent Xcalibur diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.694, 0.749 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13231, 6097, 4835 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.756 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.101, 1.06 |
No. of reflections | 6097 |
No. of parameters | 262 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.59 |
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Cu1—N1 | 1.9727 (16) | N4—N41 | 1.421 (2) |
Cu1—N13 | 1.9737 (18) | N11—C12 | 1.297 (3) |
Cu1—N23 | 1.9447 (18) | C12—N13 | 1.157 (3) |
Cu1—N51 | 2.0912 (17) | N11—C14 | 1.301 (3) |
Cu1—N15i | 2.1534 (19) | C14—N15 | 1.155 (3) |
N1—N2 | 1.364 (2) | N21—C22 | 1.288 (3) |
N2—C3 | 1.317 (2) | C22—N23 | 1.151 (3) |
C3—N4 | 1.377 (3) | N21—C24 | 1.315 (3) |
N4—C5 | 1.347 (2) | C24—N25 | 1.147 (3) |
C5—N1 | 1.316 (2) | ||
N1—Cu1—N51 | 78.77 (7) | C12—N11—C14 | 119.6 (2) |
N1—Cu1—N13 | 89.47 (7) | N11—C12—N13 | 175.4 (3) |
N13—Cu1—N23 | 94.20 (8) | N11—C14—N15 | 173.7 (2) |
N23—Cu1—N51 | 92.58 (7) | C22—N21—C24 | 124.3 (2) |
N1—Cu1—N23 | 167.27 (8) | N21—C22—N23 | 171.4 (2) |
N13—Cu1—N51 | 152.33 (7) | N21—C24—N25 | 171.1 (3) |
N1—Cu1—N15i | 95.15 (7) | C12—N13—Cu1 | 147.64 (17) |
N13—Cu1—N15i | 105.20 (8) | C14—N15—Cu1ii | 164.63 (18) |
N23—Cu1—N15i | 95.64 (8) | C22—N23—Cu1 | 174.51 (19) |
N51—Cu1—N15i | 100.77 (7) | ||
N2—C3—C32—N31 | −168.69 (18) | N1—C5—C52—N51 | −5.0 (3) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N41—H41A···N25iii | 0.89 | 2.26 | 3.067 (3) | 151 |
N41—H41B···N31 | 0.91 | 2.08 | 2.834 (2) | 139 |
C35—H35···N21iv | 0.95 | 2.61 | 3.499 (3) | 155 |
C54—H54···N2v | 0.95 | 2.61 | 3.260 (3) | 126 |
Symmetry codes: (iii) −x+1, −y, −z+1; (iv) x, y+1, z+1; (v) x, y−1, z. |