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5-[4-(1,2,4-Triazol-4-yl)phen­yl]-1H-tetra­zole, C9H7N7, (I), an asymmetric heterobifunctional organic ligand containing triazole (tr) and tetra­zole (tz) termini linked directly through a 1,4-phenyl­ene spacer, crystallizes in the polar space group Pc. The heterocyclic functions, serving as single hydrogen-bond donor (tz) or acceptor (tr) units, afford hydrogen-bonded zigzag chains with no crystallographic centre of inversion. In the structure of catena-poly[[di­aqua­cad­mium(II)]bis{μ2-5-[4-(1,2,4-triazol-4-yl)phenyl]tetra­zol-1-ido-κ2N1:N1′}], [Cd(C9H6N7)2(H2O)2]n, (II), the CdII dication resides on a centre of in­version in an octa­hedral {N4O2} environment. In the equatorial plane, the CdII polyhedron is built up from four N atoms of two kinds, namely of trans-coordinating tr and tz fragments [Cd—N = 2.2926 (17) and 2.3603 (18) Å], and the coordinating aqua ligands occupy the two apical sites. The metal centres are separated at a distance of 11.1006 (7) Å by means of the double-bridging tetra­zolate anion, L, forming a chain structure. The water ligands and tz fragments inter­act with one another, like a double hydrogen-bond donor–acceptor synthon, leading to a hydrogen-bonded three-dimensional array.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112038498/fg3264sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112038498/fg3264Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112038498/fg3264IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112038498/fg3264Isup4.cml
Supplementary material

CCDC references: 906564; 906565

Comment top

The ligand-design approach has proved to be a crucial starting point and attractive design tool for the rapid development of metal–organic frameworks (MOFs), as well as for modulating their properties (Elsevier et al., 2003). An interesting perspective may be focused on the screening of heterobitopic ligands consisting of parent azole heterocycles [e.g. 1,2,4-triazole/tetrazole (Aromí et al., 2011) or their close 1,2,4-triazole/pyrazole analogues etc.], each of which represents a widely known class of organic bridges. The introduction of asymmetry into the bridging-ligand topology may be considered as an interesting supramolecular design tool for engineering acentric and chiral coordination solids (Zhang et al., 2008). On the other hand, the presence of neutral and acidic heterofunctional donors can also provide specificity towards the preferential coordination of metal ions via the formation of M–[N—N]–M linkages. As mentioned earlier by Colombo et al. (2011), the strength of the resulting M—N bonds correlates well with the pKa values for the deprotonation of the N—H bond in the azole heterocycle. This may be one of the reasons why tetrazolide-based MOFs demonstrate relatively low thermal stability and water sensitivity, which significantly limits their application in hydrogen storage (Dinca et al., 2006) and Lewis acid catalysis (Horike et al., 2008). Thus, azolide–MOF stability can be optimized and increased through the introduction of heterobifunctional N-donor groups. Recently, Bondar et al. (2008) described a 1,2,4-triazole/tetrazole ligand linked by a p-phenylene spacer, which shows promise for the production of microporous coordination polymers prepared in aqueous media under hydrothermal conditions. Another interesting example, demonstrating the heterobitopic ligand concept in the construction of porous heterometallic Cd/{Cu6(OH)6} frameworks, was provided by Govor et al. (2011). 4-(3,5-Dimethylpyrazol-4-yl)-1,2,4-triazole was utilized in the self-assembly of halide-incorporating nanocluster {Cu6(OH)6} container molecules for halogenated hydrocarbone sorption applications, and their rational integration into polymeric solids was realised using a `step-by-step' approach. These findings have stimulated our interest in heterobitopic ligands. In this paper, we report the crystal structures of the title heterobifunctional ligand, HL, (I), which contains both 1,2,4-triazole and tetrazole functions, and its cadmium complex, [CdL2(H2O)2], (II).

The organic ligand (I), crystallizing in the polar space group Pc, is a dipolar molecule in which two different functions (tr and tz) are separated by a 1,4-phenylene (ph) spacer. Its asymmetric unit contains a whole molecule of 5-[4-(1,2,4-triazol-4-yl)phenyl]-1H-tetrazole (Fig. 1). Similar to simple 5-phenyl-1H-tetrazole (Krygowski & Cyranski, 1996), in (I) the C1—N4 [1.325 (4) Å] and especially the N2—N3 [1.291 (5) Å] bonds of the tetrazole ring are shorter than the other three, suggesting that the compound exists as the 1H-tautomer. It is known that, in solution and in the gas phase, 5-substituted tetrazoles appear in two tautomeric forms, 1H and 2H, while in the solid state 1H-tetrazole is preferred (Kiselev et al., 2011). This could be the reason for the angular directed intermolecular (tz)NH—N(tr) bonding vectors, leading preferentially to zigzag orientated chains of (I), in which the molecular dipoles interact accurately in the donor–acceptor sequence [N1—H1···N5i; Fig. 2 and Table 2]. Additionally, the packing motifs are supported by weaker C—H···N contacts (C3—H3···N4ii and C8—H8···N4iii, Table 2), affording a three-dimensional hydrogen-bonding net (Desiraju & Steiner, 1999). These interactions cause the tz–benzene pair to be even more coplanar than the opposite side of (I) [the C3—N7—C7—C8 and N4—C1—C4—C5 torsion angles are 24.8 (6) and 10.1 (6)°, respectively]. Also, this packing mode eliminates the presence of a crystallographic centre of inversion and the individual molecular dipoles are not cancelled out in the crystal structure.

In the cadmium complex, (II), the asymmetric unit consists of a deprotonated organic ligand, a water molecule and a CdII cation. This last lies on an inversion centre and adopts a slightly distorted octahedral {N4O2} environment involving four N atoms of singly coordinated tetrazolide [Cd—N(tz) = 2.3603 (18) Å] and triazole [Cd—N(tr) = 2.2926 (17) Å] donor groups in a 1:1 ratio, and two O atoms of the coordinated water molecules [Cd1—O1 = 2.3960 (15) Å] (Fig. 3). These three donors occupy trans dispositions in the coordination environment of the CdII centres. The significant differences observed for the Cd—N distances may indicate a more ionic character of the Cd—N(tz) bond than the Cd—N(tr) bond. The organic ligands, utilizing one N1(tr) [No N1 in triazole] and one N1(tz) atom, act as a bidentate double-bridge between adjacent CdII cations [related by symmetry code (1 + x, 1 + y, 1 + z)], connecting them at a distance of 11.1006 (7) Å into a linear chain running almost perpendicular to the [112] plane.

The partially coordinated tetrazolide can be considered as a scaffold with multiple H-acceptor sites (through peripheral atoms N3 and N4), whereas the bound water molecule is a double H donor. Two water molecules and two tz fragments interact with one another, leading to a ten-membered {H—O—H—[N—N]—}2 synthon in the ab plane [O1···N4ii = 2.900 (3) and O1···N3iii = 2.920 (2) Å, Fig. 4]. In terms of graph-set analysis, these cyclic rings can be identified as R44(10) (Etter et al., 1990). Indeed, the {H—O—H—[N—N]—}2 motifs are very characteristic and essential to controlling the organisation of the extended structures of molecular diaqua-bis[5-(2-pyridyl)tetrazolato]copper(II) (Mukhopadhyay et al., 2009) and the related diaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato-k2O,O']cobalt(II), cadmium(II) and copper(II) analogues (Lukashuk et al., 2007).

Thus, the [Cd(C9H6N7)2(H2O)2] chains of (I) are tightly packed in a three-dimensional hydrogen-bonded network, which is additionally stabilized by means of numerous weak (tr)C—H—N(tz) interactions (Table 4).

In complex (II), it is interesting to note that the Ntr,Ntz coordinating ligand possesses an arc-shaped configuration that may be a consequence of the close interligand disposition in the polymeric chain (Fig. 5). A similar deformation effect for a tetradentate ligand was previously observed in the three-dimensional framework structure of [Cu24-L)3]Cl.12H2O (Bondar et al., 2008).

Summarizing, we have shown that 5-[4-(1,2,4-triazol-4-yl)phenyl]-1H-tetrazole is a prospective heterobifunctional asymmetric ligand for the controlled construction of acentric solids and coordination polymers utilizing triazole and tetrazolide donor moieties. The singly coordinated tetrazolide group tends to be involved in the formation of a cyclic hydrogen-bonded {H—O—H—[N—N]—}2 synthon, which may be an important component for the organization of the crystal structures of coordination polymers.

Related literature top

For related literature, see: Aromí et al. (2011); Bondar et al. (2008); Colombo et al. (2011); Desiraju & Steiner (1999); Dinca et al. (2006); Elsevier et al. (2003); Etter et al. (1990); Govor et al. (2011); Horike et al. (2008); Kiselev et al. (2011); Krygowski & Cyranski (1996); Lukashuk et al. (2007); Mukhopadhyay et al. (2009); Zhang et al. (2008).

Experimental top

All materials were of reagent grade and used as received. The organic ligand, 5-[4-(1,2,4-triazol-4-yl)phenyl]-1H-tetrazole (HL), (I), was prepared according to a previously described procedure (Bondar et al., 2008). Colourless prismatic monocrystals of HL suitable for X-ray analysis were grown by recrystallization from a hot aqueous solution.

For the synthesis of [CdL2(H2O)2], (II), HL (10.6 mg, 49.7 µmol) was placed in a 50 ml test tube and dissolved in hot water (25 ml). To this solution was added Cd(NO3)2.4H2O (0.0308 mg, 99.8 µmol) in water (5 ml). The test-tube was closed, placed into a 2 l Dewar flask filled with hot water and allowed to cool slowly to ambient temperature over period of 48 h. The yellowish [Colourless in CIF tables - please clarify] prisms of (II) which formed were collected and dried at room temperature (yield 8.1 mg, 56%).

Refinement top

All H atoms were located in difference maps and then refined as riding, with O—H = 0.85, N—H = 0.88 or C—H = 0.95 Å, and with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(N,O).

Computing details top

For both compounds, data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-NT (Bruker, 1999); data reduction: SAINT-NT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecule of HL, (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The hydrogen-bonding motif of (I), showing the zigzag packing of the HL molecules. The ligand dipoles are aligned in a parallel mode, forming layers. [Symmetry codes: (i) x - 1, -y + 1, z + 1/2; (ii) x + 1, y + 1, z; (iii) x, y + 1, z.]
[Figure 3] Fig. 3. A fragment of the structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) x - 1, y - 1, z - 1; (iii) -x, -y, -z; (iv) x +1, y + 1, z + 1.]
[Figure 4] Fig. 4. Projections of the structure of (II), showing the formation of (a) the cyclic hydrogen-bonded {H—O—H—[N—N]—}2 synthon and (b) the hydrogen-bonded network. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (ii) -x + 1, -y, -z; (iii) x, y + 1, z; (iv) -x + 1, -y, -z + 1.]
[Figure 5] Fig. 5. The packing of (II), showing the O—H···N(tz) interchain interactions that lead to the three-dimensional hydrogen-bonded framework. Hydrogen bonds are represented as dashed lines. [Symmetry code: (ii) -x + 1, -y, -z.]
(I) 5-[4-(1,2,4-Triazol-4-yl)phenyl]-1H-tetrazole top
Crystal data top
C9H7N7F(000) = 220
Mr = 213.22Dx = 1.562 Mg m3
Monoclinic, PcMo Kα radiation, λ = 0.71073 Å
a = 3.7413 (7) ÅCell parameters from 2647 reflections
b = 7.8684 (9) Åθ = 2.6–26.2°
c = 15.4092 (13) ŵ = 0.11 mm1
β = 91.54 (3)°T = 153 K
V = 453.39 (11) Å3Prism, colourless
Z = 20.28 × 0.25 × 0.25 mm
Data collection top
Bruker APEXII area-detector
diffractometer
1317 independent reflections
Radiation source: fine-focus sealed tube956 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ω scansθmax = 26.2°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 43
Tmin = 0.970, Tmax = 0.974k = 98
2647 measured reflectionsl = 1918
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0469P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
1317 reflectionsΔρmax = 0.20 e Å3
146 parametersΔρmin = 0.19 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.029 (7)
Crystal data top
C9H7N7V = 453.39 (11) Å3
Mr = 213.22Z = 2
Monoclinic, PcMo Kα radiation
a = 3.7413 (7) ŵ = 0.11 mm1
b = 7.8684 (9) ÅT = 153 K
c = 15.4092 (13) Å0.28 × 0.25 × 0.25 mm
β = 91.54 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer
1317 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
956 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.974Rint = 0.052
2647 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0492 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 0.99Δρmax = 0.20 e Å3
1317 reflectionsΔρmin = 0.19 e Å3
146 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.2057 (10)0.0201 (4)0.4166 (2)0.0397 (10)
H10.15680.11720.44210.059*
N20.1482 (10)0.1347 (5)0.4501 (2)0.0491 (12)
N30.2613 (11)0.2436 (4)0.3944 (3)0.0491 (10)
N40.3861 (9)0.1614 (4)0.3234 (2)0.0415 (10)
N50.9698 (11)0.6829 (5)0.0076 (3)0.0527 (11)
N61.0454 (11)0.7764 (4)0.0823 (3)0.0536 (11)
N70.8134 (8)0.5311 (4)0.1196 (2)0.0331 (9)
C10.3488 (10)0.0032 (5)0.3388 (3)0.0303 (10)
C20.8341 (13)0.5384 (6)0.0331 (3)0.0464 (12)
H20.75950.44970.00500.056*
C30.9542 (13)0.6819 (5)0.1474 (3)0.0462 (11)
H30.98210.71390.20670.055*
C40.4573 (10)0.1405 (4)0.2812 (3)0.0276 (10)
C50.5620 (11)0.1047 (5)0.1973 (3)0.0361 (11)
H50.55440.00920.17680.043*
C60.6765 (10)0.2322 (5)0.1436 (3)0.0344 (11)
H60.74620.20720.08620.041*
C70.6888 (11)0.3960 (5)0.1742 (3)0.0302 (10)
C80.5793 (11)0.4361 (5)0.2564 (3)0.0399 (12)
H80.58320.55060.27600.048*
C90.4645 (11)0.3083 (5)0.3097 (3)0.0351 (10)
H90.38930.33480.36650.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.050 (2)0.032 (2)0.038 (2)0.0069 (18)0.0162 (19)0.0039 (17)
N20.066 (3)0.042 (2)0.040 (3)0.012 (2)0.009 (2)0.005 (2)
N30.067 (3)0.037 (2)0.043 (2)0.003 (2)0.015 (2)0.0077 (19)
N40.061 (3)0.029 (2)0.035 (2)0.0046 (18)0.0164 (19)0.0033 (16)
N50.057 (2)0.048 (2)0.054 (3)0.005 (2)0.023 (2)0.008 (2)
N60.061 (3)0.048 (2)0.053 (3)0.004 (2)0.007 (2)0.007 (2)
N70.040 (2)0.0288 (19)0.031 (2)0.0005 (17)0.0030 (17)0.0005 (17)
C10.030 (2)0.031 (2)0.030 (3)0.0002 (19)0.010 (2)0.0021 (18)
C20.059 (3)0.047 (3)0.035 (3)0.001 (2)0.014 (2)0.002 (2)
C30.056 (3)0.043 (3)0.040 (3)0.015 (2)0.001 (2)0.002 (2)
C40.031 (2)0.024 (2)0.028 (2)0.0046 (17)0.0031 (18)0.0002 (17)
C50.048 (3)0.026 (2)0.035 (3)0.004 (2)0.006 (2)0.0054 (19)
C60.043 (2)0.036 (2)0.025 (3)0.003 (2)0.011 (2)0.0020 (18)
C70.032 (2)0.032 (2)0.027 (2)0.0010 (18)0.0045 (19)0.0056 (19)
C80.051 (3)0.034 (3)0.035 (3)0.005 (2)0.013 (2)0.004 (2)
C90.046 (2)0.037 (2)0.023 (3)0.002 (2)0.008 (2)0.0026 (19)
Geometric parameters (Å, º) top
N1—C11.333 (5)C2—H20.9500
N1—N21.342 (4)C3—H30.9500
N1—H10.8800C4—C51.390 (5)
N2—N31.291 (5)C4—C91.391 (5)
N3—N41.364 (5)C5—C61.376 (5)
N4—C11.325 (4)C5—H50.9500
N5—C21.310 (5)C6—C71.373 (5)
N5—N61.389 (6)C6—H60.9500
N6—C31.303 (5)C7—C81.379 (6)
N7—C21.337 (5)C8—C91.374 (5)
N7—C31.363 (5)C8—H80.9500
N7—C71.442 (5)C9—H90.9500
C1—C41.463 (5)
C1—N1—N2109.1 (4)N7—C3—H3124.4
C1—N1—H1125.4C5—C4—C9118.8 (3)
N2—N1—H1125.4C5—C4—C1120.3 (3)
N3—N2—N1106.7 (4)C9—C4—C1120.9 (4)
N2—N3—N4110.1 (3)C6—C5—C4120.8 (3)
C1—N4—N3106.2 (3)C6—C5—H5119.6
C2—N5—N6106.4 (4)C4—C5—H5119.6
C3—N6—N5106.5 (4)C7—C6—C5119.1 (4)
C2—N7—C3104.2 (3)C7—C6—H6120.5
C2—N7—C7129.9 (4)C5—C6—H6120.5
C3—N7—C7125.9 (4)C6—C7—C8121.5 (4)
N4—C1—N1107.8 (4)C6—C7—N7120.0 (4)
N4—C1—C4125.5 (4)C8—C7—N7118.5 (4)
N1—C1—C4126.7 (4)C9—C8—C7119.1 (4)
N5—C2—N7111.7 (4)C9—C8—H8120.5
N5—C2—H2124.1C7—C8—H8120.5
N7—C2—H2124.1C8—C9—C4120.7 (4)
N6—C3—N7111.2 (4)C8—C9—H9119.7
N6—C3—H3124.4C4—C9—H9119.7
C1—N1—N2—N31.3 (5)N4—C1—C4—C9168.7 (4)
N1—N2—N3—N41.4 (6)N1—C1—C4—C99.2 (6)
N2—N3—N4—C10.9 (6)C9—C4—C5—C61.1 (6)
C2—N5—N6—C30.6 (5)C1—C4—C5—C6177.7 (4)
N3—N4—C1—N10.1 (5)C4—C5—C6—C70.5 (6)
N3—N4—C1—C4178.2 (4)C5—C6—C7—C81.9 (6)
N2—N1—C1—N40.8 (5)C5—C6—C7—N7179.0 (4)
N2—N1—C1—C4179.0 (4)C2—N7—C7—C620.9 (7)
N6—N5—C2—N70.4 (6)C3—N7—C7—C6156.1 (4)
C3—N7—C2—N51.2 (5)C2—N7—C7—C8158.2 (5)
C7—N7—C2—N5178.7 (4)C3—N7—C7—C824.8 (6)
N5—N6—C3—N71.4 (5)C6—C7—C8—C91.8 (7)
C2—N7—C3—N61.6 (5)N7—C7—C8—C9179.1 (4)
C7—N7—C3—N6179.3 (4)C7—C8—C9—C40.2 (7)
N4—C1—C4—C510.1 (6)C5—C4—C9—C81.2 (6)
N1—C1—C4—C5172.0 (4)C1—C4—C9—C8177.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N5i0.882.012.875 (6)170
C3—H3···N4ii0.952.523.353 (6)147
C8—H8···N4iii0.952.503.414 (5)162
Symmetry codes: (i) x1, y+1, z+1/2; (ii) x+1, y+1, z; (iii) x, y+1, z.
(II) catena-poly[[diaquacadmium(II)]bis{µ2-5-[4-(1,2,4-triazol-4- yl)phenyl]tetrazol-1-ato-κ2N1:N1'}] top
Crystal data top
[Cd(C9H6N7)2(H2O)2]Z = 1
Mr = 572.85F(000) = 286
Triclinic, P1Dx = 1.897 Mg m3
a = 7.6554 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.8589 (7) ÅCell parameters from 5552 reflections
c = 9.0762 (8) Åθ = 2.3–26.4°
α = 98.926 (2)°µ = 1.14 mm1
β = 98.066 (3)°T = 296 K
γ = 108.354 (2)°Prism, pale yellow
V = 501.47 (7) Å30.24 × 0.23 × 0.20 mm
Data collection top
Bruker APEXII area-detector
diffractometer
2037 independent reflections
Radiation source: fine-focus sealed tube1968 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ω scansθmax = 26.4°, θmin = 2.3°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.771, Tmax = 0.804k = 99
5552 measured reflectionsl = 1111
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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.050H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0209P)2 + 0.1279P]
where P = (Fo2 + 2Fc2)/3
2037 reflections(Δ/σ)max < 0.001
160 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
[Cd(C9H6N7)2(H2O)2]γ = 108.354 (2)°
Mr = 572.85V = 501.47 (7) Å3
Triclinic, P1Z = 1
a = 7.6554 (5) ÅMo Kα radiation
b = 7.8589 (7) ŵ = 1.14 mm1
c = 9.0762 (8) ÅT = 296 K
α = 98.926 (2)°0.24 × 0.23 × 0.20 mm
β = 98.066 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer
2037 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1968 reflections with I > 2σ(I)
Tmin = 0.771, Tmax = 0.804Rint = 0.026
5552 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.050H-atom parameters constrained
S = 1.10Δρmax = 0.32 e Å3
2037 reflectionsΔρmin = 0.35 e Å3
160 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.00000.00000.00000.02171 (8)
O10.1967 (2)0.2477 (2)0.09102 (18)0.0302 (4)
H1W0.29440.23820.12060.045*
H2W0.21690.36050.05640.045*
N10.2390 (3)0.1184 (2)0.0725 (2)0.0253 (4)
N20.1788 (3)0.2991 (2)0.0089 (2)0.0279 (4)
N30.3029 (3)0.3682 (2)0.0608 (2)0.0279 (4)
N40.4485 (3)0.2359 (2)0.1607 (2)0.0266 (4)
N50.9402 (3)0.8268 (2)0.7588 (2)0.0255 (4)
N60.9261 (3)0.9092 (2)0.6358 (2)0.0302 (5)
N70.8147 (2)0.6093 (2)0.55559 (19)0.0219 (4)
C10.4042 (3)0.0840 (3)0.1654 (2)0.0210 (5)
C20.8748 (3)0.6495 (3)0.7085 (2)0.0248 (5)
H20.87010.56340.76880.030*
C30.8520 (3)0.7760 (3)0.5173 (3)0.0273 (5)
H30.82730.79240.41820.033*
C40.5182 (3)0.0953 (3)0.2636 (2)0.0213 (5)
C50.6397 (3)0.1085 (3)0.3974 (3)0.0256 (5)
H50.65430.00270.42220.031*
C60.7391 (3)0.2763 (3)0.4940 (3)0.0256 (5)
H60.81960.28340.58340.031*
C70.7180 (3)0.4335 (3)0.4565 (2)0.0206 (5)
C80.5989 (3)0.4239 (3)0.3232 (2)0.0255 (5)
H80.58480.52990.29840.031*
C90.5018 (3)0.2556 (3)0.2279 (2)0.0243 (5)
H90.42340.24930.13750.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02407 (13)0.01785 (12)0.02010 (13)0.00692 (9)0.00001 (9)0.00038 (9)
O10.0299 (9)0.0188 (8)0.0405 (10)0.0069 (7)0.0087 (7)0.0040 (7)
N10.0239 (10)0.0175 (9)0.0301 (11)0.0060 (8)0.0004 (8)0.0000 (8)
N20.0294 (11)0.0176 (9)0.0317 (11)0.0055 (8)0.0019 (9)0.0003 (8)
N30.0311 (11)0.0196 (9)0.0309 (11)0.0081 (8)0.0051 (9)0.0019 (8)
N40.0271 (10)0.0221 (9)0.0283 (10)0.0083 (8)0.0022 (8)0.0021 (8)
N50.0301 (11)0.0236 (10)0.0201 (10)0.0079 (8)0.0024 (8)0.0024 (8)
N60.0405 (12)0.0220 (10)0.0247 (10)0.0085 (9)0.0013 (9)0.0043 (8)
N70.0240 (10)0.0183 (9)0.0194 (9)0.0048 (8)0.0004 (8)0.0015 (7)
C10.0225 (11)0.0193 (10)0.0215 (11)0.0075 (9)0.0044 (9)0.0042 (8)
C20.0304 (12)0.0213 (11)0.0201 (11)0.0064 (9)0.0021 (10)0.0046 (9)
C30.0363 (13)0.0196 (11)0.0235 (12)0.0077 (10)0.0005 (10)0.0060 (9)
C40.0193 (11)0.0198 (10)0.0226 (11)0.0049 (9)0.0042 (9)0.0023 (9)
C50.0289 (12)0.0190 (11)0.0306 (13)0.0118 (9)0.0034 (10)0.0054 (9)
C60.0256 (12)0.0254 (11)0.0237 (12)0.0097 (10)0.0018 (10)0.0031 (9)
C70.0196 (11)0.0191 (10)0.0200 (11)0.0045 (8)0.0032 (9)0.0007 (8)
C80.0295 (12)0.0205 (11)0.0250 (12)0.0076 (9)0.0018 (10)0.0061 (9)
C90.0244 (12)0.0244 (11)0.0200 (11)0.0071 (9)0.0029 (9)0.0028 (9)
Geometric parameters (Å, º) top
Cd1—N5i2.2926 (17)N7—C21.353 (3)
Cd1—N5ii2.2926 (17)N7—C31.361 (3)
Cd1—N12.3603 (18)N7—C71.432 (3)
Cd1—N1iii2.3603 (18)C1—C41.470 (3)
Cd1—O12.3960 (15)C2—H20.9300
Cd1—O1iii2.3960 (15)C3—H30.9300
O1—H1W0.8500C4—C91.387 (3)
O1—H2W0.8500C4—C51.390 (3)
N1—C11.341 (3)C5—C61.381 (3)
N1—N21.349 (2)C5—H50.9300
N2—N31.303 (3)C6—C71.382 (3)
N3—N41.356 (2)C6—H60.9300
N4—C11.336 (3)C7—C81.385 (3)
N5—C21.304 (3)C8—C91.377 (3)
N5—N61.382 (3)C8—H80.9300
N5—Cd1iv2.2926 (17)C9—H90.9300
N6—C31.296 (3)
N5i—Cd1—N5ii180C2—N7—C7128.60 (18)
N5i—Cd1—N190.69 (6)C3—N7—C7126.93 (18)
N5ii—Cd1—N189.31 (6)N4—C1—N1111.01 (18)
N5i—Cd1—N1iii89.31 (6)N4—C1—C4124.4 (2)
N5ii—Cd1—N1iii90.69 (6)N1—C1—C4124.56 (19)
N1—Cd1—N1iii180N5—C2—N7110.04 (19)
N5i—Cd1—O193.04 (6)N5—C2—H2125.0
N5ii—Cd1—O186.96 (6)N7—C2—H2125.0
N1—Cd1—O195.31 (6)N6—C3—N7111.7 (2)
N1iii—Cd1—O184.69 (6)N6—C3—H3124.1
N5i—Cd1—O1iii86.96 (6)N7—C3—H3124.1
N5ii—Cd1—O1iii93.04 (6)C9—C4—C5118.26 (19)
N1—Cd1—O1iii84.69 (6)C9—C4—C1120.6 (2)
N1iii—Cd1—O1iii95.31 (6)C5—C4—C1121.10 (19)
O1—Cd1—O1iii180C6—C5—C4121.1 (2)
Cd1—O1—H1W119.3C6—C5—H5119.4
Cd1—O1—H2W124.5C4—C5—H5119.4
H1W—O1—H2W108.3C5—C6—C7119.4 (2)
C1—N1—N2105.42 (17)C5—C6—H6120.3
C1—N1—Cd1145.03 (14)C7—C6—H6120.3
N2—N1—Cd1108.93 (13)C6—C7—C8120.6 (2)
N3—N2—N1108.92 (17)C6—C7—N7121.01 (19)
N2—N3—N4110.09 (17)C8—C7—N7118.39 (19)
C1—N4—N3104.55 (18)C9—C8—C7119.3 (2)
C2—N5—N6108.23 (17)C9—C8—H8120.4
C2—N5—Cd1iv130.92 (15)C7—C8—H8120.4
N6—N5—Cd1iv119.03 (13)C8—C9—C4121.4 (2)
C3—N6—N5105.74 (17)C8—C9—H9119.3
C2—N7—C3104.24 (18)C4—C9—H9119.3
N5i—Cd1—N1—C129.8 (3)C7—N7—C2—N5173.7 (2)
N5ii—Cd1—N1—C1150.2 (3)N5—N6—C3—N70.5 (3)
O1—Cd1—N1—C163.3 (3)C2—N7—C3—N60.9 (3)
O1iii—Cd1—N1—C1116.7 (3)C7—N7—C3—N6173.9 (2)
N5i—Cd1—N1—N2139.03 (14)N4—C1—C4—C9157.8 (2)
N5ii—Cd1—N1—N240.97 (14)N1—C1—C4—C924.6 (3)
O1—Cd1—N1—N2127.84 (13)N4—C1—C4—C524.6 (3)
O1iii—Cd1—N1—N252.16 (13)N1—C1—C4—C5153.0 (2)
C1—N1—N2—N30.4 (2)C9—C4—C5—C61.2 (3)
Cd1—N1—N2—N3173.80 (14)C1—C4—C5—C6176.4 (2)
N1—N2—N3—N40.3 (2)C4—C5—C6—C70.3 (3)
N2—N3—N4—C10.0 (2)C5—C6—C7—C80.2 (3)
C2—N5—N6—C30.2 (3)C5—C6—C7—N7178.35 (19)
Cd1iv—N5—N6—C3166.14 (16)C2—N7—C7—C627.1 (3)
N3—N4—C1—N10.2 (2)C3—N7—C7—C6159.4 (2)
N3—N4—C1—C4177.64 (19)C2—N7—C7—C8151.6 (2)
N2—N1—C1—N40.4 (2)C3—N7—C7—C822.0 (3)
Cd1—N1—C1—N4169.44 (18)C6—C7—C8—C90.1 (3)
N2—N1—C1—C4177.47 (19)N7—C7—C8—C9178.74 (19)
Cd1—N1—C1—C48.4 (4)C7—C8—C9—C41.1 (3)
N6—N5—C2—N70.8 (3)C5—C4—C9—C81.6 (3)
Cd1iv—N5—C2—N7163.34 (15)C1—C4—C9—C8176.0 (2)
C3—N7—C2—N51.0 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y1, z1; (iii) x, y, z; (iv) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···N4v0.852.062.900 (3)172
O1—H2W···N3vi0.852.082.920 (2)169
C2—H2···N3vii0.932.563.386 (3)149
Symmetry codes: (v) x+1, y, z; (vi) x, y+1, z; (vii) x+1, y, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC9H7N7[Cd(C9H6N7)2(H2O)2]
Mr213.22572.85
Crystal system, space groupMonoclinic, PcTriclinic, P1
Temperature (K)153296
a, b, c (Å)3.7413 (7), 7.8684 (9), 15.4092 (13)7.6554 (5), 7.8589 (7), 9.0762 (8)
α, β, γ (°)90, 91.54 (3), 9098.926 (2), 98.066 (3), 108.354 (2)
V3)453.39 (11)501.47 (7)
Z21
Radiation typeMo KαMo Kα
µ (mm1)0.111.14
Crystal size (mm)0.28 × 0.25 × 0.250.24 × 0.23 × 0.20
Data collection
DiffractometerBruker APEXII area-detector
diffractometer
Bruker APEXII area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.970, 0.9740.771, 0.804
No. of measured, independent and
observed [I > 2σ(I)] reflections
2647, 1317, 956 5552, 2037, 1968
Rint0.0520.026
(sin θ/λ)max1)0.6210.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.104, 0.99 0.024, 0.050, 1.10
No. of reflections13172037
No. of parameters146160
No. of restraints20
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.190.32, 0.35

Computer programs: SMART-NT (Bruker, 1998), SAINT-NT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999).

Selected bond lengths (Å) for (I) top
N1—C11.333 (5)N5—C21.310 (5)
N1—N21.342 (4)N5—N61.389 (6)
N2—N31.291 (5)N6—C31.303 (5)
N3—N41.364 (5)N7—C21.337 (5)
N4—C11.325 (4)N7—C31.363 (5)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N5i0.882.012.875 (6)170
C3—H3···N4ii0.952.523.353 (6)147
C8—H8···N4iii0.952.503.414 (5)162
Symmetry codes: (i) x1, y+1, z+1/2; (ii) x+1, y+1, z; (iii) x, y+1, z.
Selected bond lengths (Å) for (II) top
Cd1—N5i2.2926 (17)N3—N41.356 (2)
Cd1—N12.3603 (18)N4—C11.336 (3)
Cd1—O12.3960 (15)N5—C21.304 (3)
N1—C11.341 (3)N6—C31.296 (3)
N1—N21.349 (2)N7—C21.353 (3)
N2—N31.303 (3)N7—C31.361 (3)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···N4ii0.852.062.900 (3)172
O1—H2W···N3iii0.852.082.920 (2)169
C2—H2···N3iv0.932.563.386 (3)149
Symmetry codes: (ii) x+1, y, z; (iii) x, y+1, z; (iv) x+1, y, z+1.
 

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