Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017356/yf3039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017356/yf3039Isup2.hkl |
CCDC reference: 958903
Considerable attention has been drawn recently to the derivatives of 2,2':6',2''-terpyridine which have been synthesized with the aim of giving new supramolecular properties to the ligand and its metal complexes (Constable, 2007; Wild et al., 2011). A diverse range of easy synthetic methods have allowed the introduction of a large selection of substituents at different positions (Wild et al., 2011; Heller & Schubert, 2003). The 4'-position of terpyridine has usually been the preferred one to introduce N-donor substituents like pyridyl-based groups, which has enabled the diversification of the types of noncovalent interaction present, such as hydrogen bonding, π–π stacking etc. In this regard, the insertion of the heteroaromatic pyrimidine group has led to the formation of the π-conjugated terpyridine 4'-(pyrimidin-5-yl)-2,2':6',2''- terpyridine (L2), which was reacted with iron(II) and ruthenium(II) to give the cationic homoleptic species [M(L2)]2+ (M = Fe, Ru; Beves et al., 2008). Only the X-ray crystal structure of the ruthenium(II) complex was reported, showing that L2 is bonded in a tridentate manner using its terpyridine fragment and that the expected noncovalent π–π interactions are weak compared with those in related systems (Beves et al., 2008). As an extension of the supramolecular study of this class of ligand with pyrimidine–terpyridine arrays, we have decided to modify the structure of L2 by introducing a benzene ring between the pyrimidine and terpyridine portions. Under this premise, the ligand 4'-[4-(pyrimidin-5-yl)phenyl]-2,2':6',2''-terpyridine (L1) was synthesized and characterized spectroscopically. The coordinating properties of L1 were tested by reacting it with cadmium(II) nitrate to form the title neutral complex, (I), the supramolecular motif of which is dominated by a significant number of π–π interactions involving all the aromatic rings.
4'-[4-(Pyrimidin-5-yl)phenyl]-2,2':6',2''-terpyridine (L1) was prepared according to the method of Wang & Hanan (2005). 2-Acetylpyridine (0.61 g, 5.0 mmol) and KOH (039 g, 5.0 mmol) were added to a solution of 4-(pyrimidin-5-yl)benzaldehyde (0.46 g, 2.5 mmol) in ethanol (22 ml). The mixture was stirred over a period of 12 h, then an excess of aqueous NH3 (8.6 ml, 25%, 115 mmol) was added and the stirring was continued for a further 24 h. The solid was filtered off, and washed with water (5 × 10 ml) and ethanol (3 × 10 ml). The product was disolved in CHCl3 (20 ml) and the addition of methanol (60 ml) afforded a crystalline solid, which was washed with methanol (3 × 10 ml). The crude product was purified by column chromatography over alumina (EtOAc–CH3OH 10%) to give needle-like crystals (yield 0.42 g, 43%; m.p. 502–504 K). Analysis, calculated for C25H17N5: C 77.50, H 4.42, N 18.08%; found: C77.25, H 4.40, N 18.36%.
For the preparation of complex (I), an excess of Cd(NO3)2 (140.0 mg, 0.454 mmol) was added to a hot solution (using an oil bath at 331–335 K) of L1 (4.7 mg, 0.012 mmol) in MeOH (2.5 ml) contained in a closed volumetric flask (10 ml). The resultant solution was heated in the oil bath for 2 h. Prismatic light-yellow crystals of (I) were obtained after the removal of the hot solvent, and were washed with MeOH (2 × 4 ml) and dried in air (yield 3.5 mg, 43%).
The two solvent water molecules appeared disordered over three sites. Their site-occupancy factors were refined in the initial stages, but showed a small oscilatory behaviour (amplitude < 0.05) which precluded convergence of the refinement process. Thus, water O-atom occupancies were kept fixed at the mean values obtained during cycling. H atoms pertaining to the water molecules could not be reliably determined from a difference map and were not included in the model. All remaining H atoms on undisordered parents were found in a difference Fourier map but were treated differently in the refinement. Those attached to C atoms were further idealized and refined as riding, with aromatic C—H = 0.93 Å. Those attached to atom O1W were refined with O—H and H···H distances restrained to 0.85 (1) and 1.35 (1) Å. respectively. In all cases, Uiso(H) = 1.2Ueq(host).
The monomeric structure of (I) (Fig. 1) consists of a seven-coordinated CdII centre (Table 2), which is bound to a tridentate chelating L1 ligand, one water O atom and two nitrate groups. One of the nitrate groups acts in a bidentate chelating fashion and the other as just a monodentate ligand (see below for a discussion of its coordination character). The environment of atom Cd1 is a slightly deformed pentagonal bipyramid, with the two chelating ligands defining the CdN3O2 base [Cd—N = 2.327 (4)-=2.379 (4)Å and Cd—O = 2.400 (5)–2.540 (5) Å]. The two chelates bind in a slightly noncoplanar fashion [dihedral angle between the CdN3 and CdO2 coordination planes = 12.8 (2)°], leading to a maximum deviation from the least-squares plane of 0.192 (2)Å for atom O22. The monocoordinated ligands occupy the apical positions, with the Cd1—O1W [2.324 (4) Å] and Cd1—O23 [2.354 (5)Å] bonds forming an angle of 160.0 (2)° with each other, and angles of 3.4 (2) and 17.5 (2)°, respectively, with the normal to the plane. The bond-valence sum (BVS) for Cd1, with standard parameters taken from Brown (2009), led to a BVS of 1.994 valence units (v.u.) (expected value = 2.000 v.u.).
An interesting situation is posed by the nitrate anions Nit2 (atoms N12/O12/O22/O32) and Nit3 (atoms N13/O13/O23/O33). Even if at first glance only Nit2 appears as definitely bidentate, the relative orientation of Nit3 towards the cation suggests the possible existence of a weak Cd—O33 interaction in Nit3, in spite of the rather large Cd1···O33 distance [3.008 (4) Å].
When the internal geometries of both nitrate anions are compared, many small deviations from an ideal threefold symmetry appear which may support this hypothesis, viz. the O—N—O angle facing atom Cd1 is much smaller than the remaining two in the anion, a usual characteristic of chelation [115.6 (6) versus 120.7 (6)–123.7 (6)° in Nit2, and 116.3 (7) versus 121.2 (8)–122.4 (7)° in Nit3], complemented by a `hint' of shortening of the third N—O bond [1.218 (7) versus 1.222 (7)–1.237 (7) Å in Nit2, and 1.205 (7) versus 1.213 (7)–1.216 (7) Å in Nit3]. Admittedly this is a weak argument, since these differences are barely significant on a statistical level and, in the case of Nit3, could be partially caused by libration effects.
The BVS for such a hypothetical Cd—O bond would be very much on the borderline of significance (~0.05 v.u.), so the situation could be described, at most, as a `semicoordination'.
The L1 ligand presents an essentially planar substructure made up of the four N-containing groups. The four heterocycles (Cg1–Cg4 in Fig. 1) adopt a collective flattened disposition, with a mean deviation from the least-squares plane of 0.05 Å and a maximum distance of 0.173 (2) Å for atom C91. However, the central phenyl ring (Cg5) protrudes significantly from this planar geometry through a rotation of 31.4 (2)° around the C161···C221 axis, forced by packing requirements, as we shall discuss below.
Noncovalent interactions in (I) are of various types and strengths, and are presented in Table 3 (hydrogen bonding) and Table 4 (π–π interactions). For the sake of simplicity, in what follows we shall use a shorthand notation, viz. `[Tn(m)]' to denote `Table n (mth entry)'.
In addition to the contacts presented in Table 3, there are a few O···O short contacts involving disordered water molecules (to which no H atoms could be assigned, as explained in the Refinement section) and which are obviously due to hydrogen-bonding interactions. The most significant ones are O2W···O3W = 2.706 (15) Å and O2W···O22(-x + 1, -y + 1, -z + 1) = 2.789 (10) Å.
The most noticeable packing motif that the noncovalent interactions give rise to in (I) is a dimeric unit (shown between square brackets in Fig. 2), built up around an inversion centre (A in Fig. 2) by one strong hydrogen bond [T3(1)] and two π–π interactions [T4(1,2)], together with their symmetry-related counterparts. These dimers interact with their symmetric equivalents by the inversion centre B in Fig. 2, via two further π–π bonds [T4(3,4)] and a weak C—H···O hydrogen bond [T3(2)], to form columnar arrays parallel to [100] (Fig. 2). Inspection of Fig. 2 and Table 4 shows that benzene ring 5 is involved in both types of interaction, and in order to comply with this double role the group needs to rotate out of plane of the other four heterocycles of the L1 ligand.
It is perhaps worth noting that the only symmetry elements involved in the formation of these columns are inversion centres (types A or B, as defined in Fig. 2). The remaining ones (c-glide planes and a twofold screw axis) serve to generate symmetry-related columns. A detailed view of the way in which the resulting [100] columns are arranged in space is shown in Fig. 3. In particular, the cross interactions are provided by a π–π interaction [T4(5)]. [T3(3-7)] present interactions involving the disordered water molecules, shown in the central part of Fig. 3.
Even though a comparison of the noncovalent interactions and packing geometries in the present CdL1 complex, (I), with those of related structures would be highly desirable, any attempt to do so with its closest relative, the above referenced Ru-L2 complex, (II), would be inappropriate, due to intrinsic differences between the two monomeric complexes. While (I) is electrically neutral and the linkage between molecules is thus mainly provided by hydrogen-bonding and π–π interactions, structure (II) is ionic, the molecular assembly being a 2+ cation balanced by hexafluorophosphate anions in 1:2 ratio. In this latter complex, direct interactions between molecules not mediated by the anions are rather weak or non-existent, so a comparison must be postponed until further work on the subject is available.
For related literature, see: Beves et al. (2008); Brown (2009); Constable (2007); Heller & Schubert (2003); Wang & Hanan (2005); Wild et al. (2011).
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
[Cd(NO3)2(C25H17N5)(H2O)]·2H2O | Z = 4 |
Mr = 677.90 | F(000) = 1368 |
Monoclinic, P21/c | Dx = 1.657 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9422 (4) Å | µ = 0.87 mm−1 |
b = 22.0793 (11) Å | T = 294 K |
c = 15.5923 (7) Å | Prism, light yellow |
β = 96.281 (4)° | 0.36 × 0.12 × 0.10 mm |
V = 2717.8 (2) Å3 |
Oxford Gemini S Ultra CCD area-detector diffractometer | 6278 independent reflections |
Radiation source: fine-focus sealed tube | 3447 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
ω scans, thick slices | θmax = 28.7°, θmin = 3.5° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −10→10 |
Tmin = 0.88, Tmax = 0.92 | k = −25→28 |
14498 measured reflections | l = −20→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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0478P)2] where P = (Fo2 + 2Fc2)/3 |
6278 reflections | (Δ/σ)max = 0.001 |
394 parameters | Δρmax = 0.56 e Å−3 |
14 restraints | Δρmin = −0.56 e Å−3 |
[Cd(NO3)2(C25H17N5)(H2O)]·2H2O | V = 2717.8 (2) Å3 |
Mr = 677.90 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.9422 (4) Å | µ = 0.87 mm−1 |
b = 22.0793 (11) Å | T = 294 K |
c = 15.5923 (7) Å | 0.36 × 0.12 × 0.10 mm |
β = 96.281 (4)° |
Oxford Gemini S Ultra CCD area-detector diffractometer | 6278 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 3447 reflections with I > 2σ(I) |
Tmin = 0.88, Tmax = 0.92 | Rint = 0.061 |
14498 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 14 restraints |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.56 e Å−3 |
6278 reflections | Δρmin = −0.56 e Å−3 |
394 parameters |
Experimental. IR (KBr, ν, cm-1): 1586, 1412, 1383, 831, 789. 1H NMR (300 MHz, CDCl3, 298 K, δ, p.p.m.): 9.25 (s, 1H), 9.04 (s, 2H), 8.80 (s, 2H), 8.75 (ddd, 2H, J = 4.8, 1.7 and 0.6 Hz), 8.7 (dt, 2H, J = 7.9 and 1.1 Hz), 8.08 (d, 2H, J = 8.4 Hz), 7.91 (td, 2H, J = 7.9 and 1.7 Hz), 7.75 (d, 2H, J = 8.4 Hz), 7.38 (ddd, 2H, J = 7.9, 4.8 and 1.1 Hz). 13C-PND and 13C-DEPT NMR (75 MHz, CDCl3, 298 K, δ, p.p.m.): 157.7 (1 CH), 156.1 (3 Cquat), 156.0 (2 Cquat), 154.9 (2 CH), 149.1 (2 CH), 139.2 (1 Cquat), 136.9 (2 CH), 134.8 (1 Cquat), 133.7 (1 Cquat), 128.4 (2 CH), 127.4 (2 CH), 123.9 (2 CH), 121.4 (2 CH), 118.7 (2 CH). MS (EI+, 70eV) for C25H17N5 ([M+]) 387 (100%). |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cd1 | 0.45706 (5) | 0.332305 (18) | 0.34623 (3) | 0.04502 (16) | |
N11 | 0.5691 (5) | 0.2572 (2) | 0.2589 (3) | 0.0419 (11) | |
N21 | 0.4013 (5) | 0.23553 (19) | 0.3951 (3) | 0.0373 (10) | |
N31 | 0.3283 (6) | 0.3378 (2) | 0.4749 (3) | 0.0500 (12) | |
N41 | 0.1268 (5) | −0.2189 (2) | 0.5714 (3) | 0.0478 (12) | |
N51 | 0.0042 (6) | −0.1683 (2) | 0.6832 (3) | 0.0526 (12) | |
C11 | 0.6514 (7) | 0.2706 (3) | 0.1915 (4) | 0.0495 (14) | |
H11 | 0.6755 | 0.3111 | 0.1813 | 0.059* | |
C21 | 0.7024 (8) | 0.2277 (3) | 0.1365 (4) | 0.0553 (16) | |
H21 | 0.7631 | 0.2385 | 0.0911 | 0.066* | |
C31 | 0.6622 (7) | 0.1690 (3) | 0.1497 (4) | 0.0514 (15) | |
H31 | 0.6926 | 0.1390 | 0.1124 | 0.062* | |
C41 | 0.5760 (7) | 0.1538 (3) | 0.2190 (3) | 0.0450 (14) | |
H41 | 0.5477 | 0.1138 | 0.2290 | 0.054* | |
C51 | 0.5323 (6) | 0.1997 (2) | 0.2733 (3) | 0.0347 (12) | |
C61 | 0.4454 (6) | 0.1870 (2) | 0.3506 (3) | 0.0339 (11) | |
C71 | 0.4155 (6) | 0.1289 (2) | 0.3807 (3) | 0.0375 (12) | |
H71 | 0.4453 | 0.0953 | 0.3497 | 0.045* | |
C81 | 0.3415 (6) | 0.1208 (2) | 0.4566 (3) | 0.0345 (12) | |
C91 | 0.3005 (6) | 0.1727 (2) | 0.5011 (3) | 0.0390 (12) | |
H91 | 0.2527 | 0.1693 | 0.5528 | 0.047* | |
C101 | 0.3313 (6) | 0.2291 (2) | 0.4679 (3) | 0.0353 (12) | |
C111 | 0.2811 (6) | 0.2861 (2) | 0.5106 (3) | 0.0383 (12) | |
C121 | 0.1982 (7) | 0.2866 (3) | 0.5823 (4) | 0.0531 (15) | |
H121 | 0.1682 | 0.2502 | 0.6065 | 0.064* | |
C131 | 0.1584 (8) | 0.3405 (3) | 0.6195 (4) | 0.0607 (17) | |
H131 | 0.1007 | 0.3412 | 0.6683 | 0.073* | |
C141 | 0.2055 (9) | 0.3924 (3) | 0.5828 (4) | 0.0696 (19) | |
H141 | 0.1799 | 0.4297 | 0.6058 | 0.084* | |
C151 | 0.2908 (9) | 0.3895 (3) | 0.5120 (4) | 0.0661 (18) | |
H151 | 0.3245 | 0.4256 | 0.4882 | 0.079* | |
C161 | 0.3035 (6) | 0.0601 (2) | 0.4894 (3) | 0.0339 (12) | |
C171 | 0.2946 (6) | 0.0496 (2) | 0.5762 (4) | 0.0436 (13) | |
H171 | 0.3232 | 0.0806 | 0.6155 | 0.052* | |
C181 | 0.2447 (6) | −0.0052 (3) | 0.6060 (3) | 0.0433 (13) | |
H181 | 0.2408 | −0.0108 | 0.6649 | 0.052* | |
C191 | 0.1995 (6) | −0.0528 (2) | 0.5489 (3) | 0.0346 (12) | |
C201 | 0.2112 (7) | −0.0430 (2) | 0.4611 (3) | 0.0428 (13) | |
H201 | 0.1827 | −0.0739 | 0.4217 | 0.051* | |
C211 | 0.2649 (6) | 0.0120 (3) | 0.4329 (3) | 0.0434 (13) | |
H211 | 0.2757 | 0.0173 | 0.3746 | 0.052* | |
C221 | 0.1416 (6) | −0.1113 (2) | 0.5808 (3) | 0.0342 (12) | |
C231 | 0.1740 (6) | −0.1655 (3) | 0.5426 (3) | 0.0419 (13) | |
H231 | 0.2320 | −0.1649 | 0.4939 | 0.050* | |
C241 | 0.0435 (7) | −0.2170 (3) | 0.6405 (4) | 0.0513 (16) | |
H241 | 0.0090 | −0.2540 | 0.6612 | 0.062* | |
C251 | 0.0540 (6) | −0.1161 (3) | 0.6518 (3) | 0.0444 (13) | |
H251 | 0.0280 | −0.0806 | 0.6796 | 0.053* | |
O12 | 0.6046 (7) | 0.4094 (2) | 0.2593 (3) | 0.0863 (14) | |
O22 | 0.4395 (7) | 0.4408 (2) | 0.3442 (4) | 0.1045 (18) | |
N12 | 0.5409 (7) | 0.4529 (3) | 0.2918 (4) | 0.0640 (15) | |
O32 | 0.5704 (6) | 0.5053 (2) | 0.2741 (3) | 0.0795 (14) | |
O23 | 0.2574 (7) | 0.3285 (3) | 0.2231 (3) | 0.0920 (17) | |
O33 | 0.0883 (9) | 0.3624 (3) | 0.3024 (5) | 0.134 (2) | |
N13 | 0.1169 (9) | 0.3481 (3) | 0.2301 (4) | 0.0697 (16) | |
O13 | 0.0075 (6) | 0.3499 (3) | 0.1702 (4) | 0.110 (2) | |
O1W | 0.7171 (6) | 0.3363 (2) | 0.4303 (4) | 0.0774 (14) | |
H1WA | 0.791 (3) | 0.3615 (19) | 0.418 (4) | 0.093* | |
H1WB | 0.770 (4) | 0.3037 (9) | 0.443 (4) | 0.093* | |
O2W | 0.8116 (13) | 0.4759 (4) | 0.6262 (7) | 0.125 (4) | 0.60 |
O3W | 0.8423 (11) | 0.4462 (3) | 0.4602 (6) | 0.138 (3) | 0.75 |
O4W | 1.0571 (12) | 0.5145 (4) | 0.7217 (7) | 0.131 (4) | 0.65 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0645 (3) | 0.0310 (2) | 0.0411 (2) | 0.0020 (2) | 0.01241 (18) | 0.00396 (19) |
N11 | 0.052 (3) | 0.037 (3) | 0.038 (3) | −0.001 (2) | 0.010 (2) | 0.003 (2) |
N21 | 0.044 (2) | 0.033 (3) | 0.036 (2) | 0.004 (2) | 0.004 (2) | 0.001 (2) |
N31 | 0.077 (3) | 0.033 (3) | 0.042 (3) | 0.012 (2) | 0.014 (2) | −0.002 (2) |
N41 | 0.056 (3) | 0.031 (3) | 0.056 (3) | −0.004 (2) | 0.006 (2) | 0.005 (2) |
N51 | 0.052 (3) | 0.054 (4) | 0.054 (3) | −0.007 (3) | 0.014 (2) | 0.015 (3) |
C11 | 0.067 (4) | 0.037 (4) | 0.047 (4) | −0.003 (3) | 0.019 (3) | 0.004 (3) |
C21 | 0.076 (4) | 0.055 (4) | 0.039 (3) | 0.007 (3) | 0.024 (3) | 0.009 (3) |
C31 | 0.071 (4) | 0.044 (4) | 0.042 (3) | 0.006 (3) | 0.020 (3) | −0.001 (3) |
C41 | 0.058 (3) | 0.036 (3) | 0.042 (3) | 0.000 (3) | 0.010 (3) | −0.001 (2) |
C51 | 0.038 (3) | 0.038 (3) | 0.029 (3) | −0.003 (2) | 0.005 (2) | 0.005 (2) |
C61 | 0.033 (2) | 0.031 (3) | 0.038 (3) | 0.002 (2) | 0.004 (2) | 0.001 (2) |
C71 | 0.039 (3) | 0.033 (3) | 0.042 (3) | 0.002 (2) | 0.009 (2) | −0.002 (2) |
C81 | 0.038 (3) | 0.031 (3) | 0.035 (3) | 0.004 (2) | 0.003 (2) | 0.002 (2) |
C91 | 0.049 (3) | 0.037 (3) | 0.032 (3) | 0.000 (3) | 0.010 (2) | 0.002 (2) |
C101 | 0.040 (3) | 0.031 (3) | 0.035 (3) | 0.002 (2) | 0.004 (2) | −0.002 (2) |
C111 | 0.044 (3) | 0.036 (3) | 0.036 (3) | 0.008 (2) | 0.007 (2) | 0.000 (2) |
C121 | 0.069 (4) | 0.043 (4) | 0.051 (4) | −0.002 (3) | 0.022 (3) | 0.001 (3) |
C131 | 0.075 (4) | 0.055 (5) | 0.057 (4) | 0.007 (3) | 0.027 (3) | −0.005 (3) |
C141 | 0.099 (5) | 0.050 (5) | 0.062 (5) | 0.017 (4) | 0.022 (4) | −0.012 (4) |
C151 | 0.104 (5) | 0.034 (4) | 0.064 (4) | 0.012 (4) | 0.030 (4) | 0.007 (3) |
C161 | 0.038 (3) | 0.027 (3) | 0.037 (3) | −0.001 (2) | 0.007 (2) | 0.001 (2) |
C171 | 0.055 (3) | 0.031 (3) | 0.045 (3) | −0.005 (3) | 0.006 (3) | −0.002 (3) |
C181 | 0.058 (3) | 0.041 (3) | 0.031 (3) | −0.004 (3) | 0.005 (2) | 0.006 (3) |
C191 | 0.036 (3) | 0.029 (3) | 0.040 (3) | 0.000 (2) | 0.007 (2) | 0.006 (2) |
C201 | 0.060 (3) | 0.031 (3) | 0.038 (3) | −0.005 (3) | 0.009 (3) | 0.000 (2) |
C211 | 0.060 (3) | 0.041 (4) | 0.031 (3) | 0.001 (3) | 0.014 (3) | 0.001 (2) |
C221 | 0.037 (3) | 0.032 (3) | 0.033 (3) | −0.001 (2) | 0.000 (2) | 0.005 (2) |
C231 | 0.047 (3) | 0.038 (3) | 0.042 (3) | −0.002 (3) | 0.008 (2) | 0.003 (3) |
C241 | 0.054 (3) | 0.044 (4) | 0.053 (4) | −0.011 (3) | −0.004 (3) | 0.014 (3) |
C251 | 0.047 (3) | 0.045 (4) | 0.042 (3) | 0.000 (3) | 0.010 (3) | 0.006 (3) |
O12 | 0.123 (4) | 0.045 (3) | 0.093 (4) | 0.009 (3) | 0.022 (3) | 0.008 (3) |
O22 | 0.142 (5) | 0.056 (3) | 0.126 (5) | 0.003 (3) | 0.062 (4) | 0.027 (3) |
N12 | 0.083 (4) | 0.046 (4) | 0.063 (4) | −0.003 (3) | 0.010 (3) | 0.011 (3) |
O32 | 0.116 (4) | 0.034 (3) | 0.089 (3) | −0.012 (3) | 0.015 (3) | 0.015 (3) |
O23 | 0.084 (3) | 0.110 (5) | 0.077 (4) | 0.037 (3) | −0.011 (3) | −0.008 (3) |
O33 | 0.179 (7) | 0.134 (6) | 0.094 (5) | 0.009 (5) | 0.033 (5) | −0.019 (4) |
N13 | 0.097 (5) | 0.060 (4) | 0.054 (4) | 0.004 (3) | 0.014 (4) | 0.012 (3) |
O13 | 0.072 (3) | 0.145 (6) | 0.106 (5) | 0.007 (3) | −0.019 (3) | 0.034 (4) |
O1W | 0.090 (3) | 0.054 (3) | 0.084 (3) | 0.004 (2) | −0.008 (3) | −0.004 (3) |
O2W | 0.163 (9) | 0.082 (7) | 0.138 (9) | 0.053 (6) | 0.059 (7) | 0.022 (6) |
O3W | 0.161 (7) | 0.066 (6) | 0.173 (9) | −0.025 (5) | −0.042 (7) | 0.013 (6) |
O4W | 0.128 (7) | 0.098 (8) | 0.181 (10) | 0.016 (6) | 0.084 (7) | 0.007 (7) |
Cd1—O1W | 2.324 (4) | C101—C111 | 1.497 (7) |
Cd1—N21 | 2.327 (4) | C111—C121 | 1.358 (7) |
Cd1—N31 | 2.352 (5) | C121—C131 | 1.374 (8) |
Cd1—O23 | 2.354 (5) | C121—H121 | 0.9300 |
Cd1—N11 | 2.379 (4) | C131—C141 | 1.352 (9) |
Cd1—O22 | 2.400 (5) | C131—H131 | 0.9300 |
Cd1—O12 | 2.540 (5) | C141—C151 | 1.358 (9) |
N11—C51 | 1.328 (6) | C141—H141 | 0.9300 |
N11—C11 | 1.330 (7) | C151—H151 | 0.9300 |
N21—C101 | 1.325 (6) | C161—C171 | 1.382 (7) |
N21—C61 | 1.343 (6) | C161—C211 | 1.392 (7) |
N31—C151 | 1.328 (7) | C171—C181 | 1.371 (7) |
N31—C111 | 1.343 (7) | C171—H171 | 0.9300 |
N41—C241 | 1.325 (7) | C181—C191 | 1.398 (7) |
N41—C231 | 1.329 (6) | C181—H181 | 0.9300 |
N51—C241 | 1.318 (7) | C191—C201 | 1.398 (7) |
N51—C251 | 1.331 (7) | C191—C221 | 1.475 (7) |
C11—C21 | 1.370 (8) | C201—C211 | 1.376 (7) |
C11—H11 | 0.9300 | C201—H201 | 0.9300 |
C21—C31 | 1.356 (8) | C211—H211 | 0.9300 |
C21—H21 | 0.9300 | C221—C231 | 1.375 (7) |
C31—C41 | 1.382 (7) | C221—C251 | 1.375 (7) |
C31—H31 | 0.9300 | C231—H231 | 0.9300 |
C41—C51 | 1.388 (7) | C241—H241 | 0.9300 |
C41—H41 | 0.9300 | C251—H251 | 0.9300 |
C51—C61 | 1.481 (7) | O12—N12 | 1.222 (7) |
C61—C71 | 1.395 (7) | O22—N12 | 1.237 (7) |
C71—C81 | 1.389 (7) | O32—N12 | 1.218 (7) |
C71—H71 | 0.9300 | O23—N13 | 1.213 (7) |
C81—C91 | 1.397 (7) | O33—N13 | 1.216 (7) |
C81—C161 | 1.478 (7) | O13—N13 | 1.205 (7) |
C91—C101 | 1.381 (7) | O1W—H1WA | 0.846 (10) |
C91—H91 | 0.9300 | O1W—H1WB | 0.847 (10) |
Cd1···O33 | 3.008 (4) | ||
O1W—Cd1—N21 | 92.25 (15) | N21—C101—C111 | 116.6 (5) |
O1W—Cd1—N31 | 87.67 (18) | C91—C101—C111 | 121.6 (5) |
N21—Cd1—N31 | 69.67 (15) | N31—C111—C121 | 121.1 (5) |
O1W—Cd1—O23 | 160.0 (2) | N31—C111—C101 | 115.5 (5) |
N21—Cd1—O23 | 95.66 (17) | C121—C111—C101 | 123.4 (5) |
N31—Cd1—O23 | 112.35 (18) | C111—C121—C131 | 120.6 (6) |
O1W—Cd1—N11 | 89.08 (17) | C111—C121—H121 | 119.7 |
N21—Cd1—N11 | 69.15 (15) | C131—C121—H121 | 119.7 |
N31—Cd1—N11 | 138.52 (16) | C141—C131—C121 | 117.9 (6) |
O23—Cd1—N11 | 76.66 (17) | C141—C131—H131 | 121.1 |
O1W—Cd1—O22 | 90.95 (18) | C121—C131—H131 | 121.1 |
N21—Cd1—O22 | 155.24 (18) | C131—C141—C151 | 119.4 (6) |
N31—Cd1—O22 | 85.95 (18) | C131—C141—H141 | 120.3 |
O23—Cd1—O22 | 89.5 (2) | C151—C141—H141 | 120.3 |
N11—Cd1—O22 | 135.46 (18) | N31—C151—C141 | 123.3 (6) |
O1W—Cd1—O12 | 80.93 (18) | N31—C151—H151 | 118.4 |
N21—Cd1—O12 | 154.84 (17) | C141—C151—H151 | 118.4 |
N31—Cd1—O12 | 133.55 (17) | C171—C161—C211 | 117.4 (5) |
O23—Cd1—O12 | 84.14 (19) | C171—C161—C81 | 121.7 (5) |
N11—Cd1—O12 | 86.45 (17) | C211—C161—C81 | 120.7 (5) |
O22—Cd1—O12 | 49.73 (17) | C181—C171—C161 | 121.8 (5) |
C51—N11—C11 | 118.8 (5) | C181—C171—H171 | 119.1 |
C51—N11—Cd1 | 117.8 (3) | C161—C171—H171 | 119.1 |
C11—N11—Cd1 | 123.0 (4) | C171—C181—C191 | 120.7 (5) |
C101—N21—C61 | 120.9 (5) | C171—C181—H181 | 119.6 |
C101—N21—Cd1 | 119.4 (3) | C191—C181—H181 | 119.6 |
C61—N21—Cd1 | 119.6 (3) | C201—C191—C181 | 117.9 (5) |
C151—N31—C111 | 117.7 (5) | C201—C191—C221 | 121.4 (5) |
C151—N31—Cd1 | 123.7 (4) | C181—C191—C221 | 120.7 (5) |
C111—N31—Cd1 | 118.5 (4) | C211—C201—C191 | 120.4 (5) |
C241—N41—C231 | 115.6 (5) | C211—C201—H201 | 119.8 |
C241—N51—C251 | 115.1 (5) | C191—C201—H201 | 119.8 |
N11—C11—C21 | 123.1 (6) | C201—C211—C161 | 121.7 (5) |
N11—C11—H11 | 118.5 | C201—C211—H211 | 119.2 |
C21—C11—H11 | 118.5 | C161—C211—H211 | 119.2 |
C31—C21—C11 | 118.4 (6) | C231—C221—C251 | 114.6 (5) |
C31—C21—H21 | 120.8 | C231—C221—C191 | 122.5 (5) |
C11—C21—H21 | 120.8 | C251—C221—C191 | 122.9 (5) |
C21—C31—C41 | 119.7 (5) | N41—C231—C221 | 123.6 (5) |
C21—C31—H31 | 120.1 | N41—C231—H231 | 118.2 |
C41—C31—H31 | 120.1 | C221—C231—H231 | 118.2 |
C31—C41—C51 | 118.6 (5) | N51—C241—N41 | 127.1 (6) |
C31—C41—H41 | 120.7 | N51—C241—H241 | 116.5 |
C51—C41—H41 | 120.7 | N41—C241—H241 | 116.5 |
N11—C51—C41 | 121.4 (5) | N51—C251—C221 | 124.1 (5) |
N11—C51—C61 | 116.7 (5) | N51—C251—H251 | 118.0 |
C41—C51—C61 | 121.9 (5) | C221—C251—H251 | 118.0 |
N21—C61—C71 | 119.8 (5) | N12—O12—Cd1 | 94.0 (4) |
N21—C61—C51 | 116.2 (5) | N12—O22—Cd1 | 100.6 (4) |
C71—C61—C51 | 124.0 (5) | O32—N12—O12 | 123.7 (6) |
C81—C71—C61 | 120.5 (5) | O32—N12—O22 | 120.7 (6) |
C81—C71—H71 | 119.7 | O12—N12—O22 | 115.6 (6) |
C61—C71—H71 | 119.7 | N13—O23—Cd1 | 117.3 (5) |
C71—C81—C91 | 117.5 (5) | O13—N13—O23 | 122.4 (7) |
C71—C81—C161 | 122.3 (5) | O13—N13—O33 | 121.2 (8) |
C91—C81—C161 | 120.3 (5) | O23—N13—O33 | 116.3 (7) |
C101—C91—C81 | 119.5 (5) | Cd1—O1W—H1WA | 119 (3) |
C101—C91—H91 | 120.2 | Cd1—O1W—H1WB | 119 (3) |
C81—C91—H91 | 120.2 | H1WA—O1W—H1WB | 105.9 (17) |
N21—C101—C91 | 121.7 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···N41i | 0.85 (3) | 2.07 (2) | 2.875 (6) | 160 (6) |
C241—H241···O33ii | 0.93 | 2.60 | 3.521 (9) | 172 |
O1W—H1WA···O3W | 0.85 (4) | 2.01 (4) | 2.644 (8) | 131 (4) |
C41—H41···O32iii | 0.93 | 2.57 | 3.484 (8) | 168 |
C121—H121···O23iv | 0.93 | 2.56 | 3.358 (9) | 144 |
C131—H131···N51v | 0.93 | 2.55 | 3.470 (8) | 168 |
C201—H201···O13vi | 0.93 | 2.59 | 3.467 (8) | 158 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z+1; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+1/2, z+1/2; (v) −x, y+1/2, −z+3/2; (vi) −x, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(NO3)2(C25H17N5)(H2O)]·2H2O |
Mr | 677.90 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 7.9422 (4), 22.0793 (11), 15.5923 (7) |
β (°) | 96.281 (4) |
V (Å3) | 2717.8 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.87 |
Crystal size (mm) | 0.36 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Oxford Gemini S Ultra CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.88, 0.92 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14498, 6278, 3447 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.677 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.142, 1.00 |
No. of reflections | 6278 |
No. of parameters | 394 |
No. of restraints | 14 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.56, −0.56 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Cd1—O1W | 2.324 (4) | Cd1—N11 | 2.379 (4) |
Cd1—N21 | 2.327 (4) | Cd1—O22 | 2.400 (5) |
Cd1—N31 | 2.352 (5) | Cd1—O12 | 2.540 (5) |
Cd1—O23 | 2.354 (5) | ||
Cd1···O33 | 3.008 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···N41i | 0.85 (3) | 2.07 (2) | 2.875 (6) | 160 (6) |
C241—H241···O33ii | 0.93 | 2.60 | 3.521 (9) | 172 |
O1W—H1WA···O3W | 0.85 (4) | 2.01 (4) | 2.644 (8) | 131 (4) |
C41—H41···O32iii | 0.93 | 2.57 | 3.484 (8) | 168 |
C121—H121···O23iv | 0.93 | 2.56 | 3.358 (9) | 144 |
C131—H131···N51v | 0.93 | 2.55 | 3.470 (8) | 168 |
C201—H201···O13vi | 0.93 | 2.59 | 3.467 (8) | 158 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z+1; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+1/2, z+1/2; (v) −x, y+1/2, −z+3/2; (vi) −x, y−1/2, −z+1/2. |
Group 1···Group 2 | ccd (Å) | da (°) | sa (°) | ipd (Å) |
Cg1···Cg4i | 3.638 (3) | 2.5 (3) | 21.8 (4) | 3.377 (7) |
Cg5···Cg5i | 4.034 (3) | 0 | 21.93 (1) | 3.742 (2) |
Cg2···Cg4ii | 3.673 (3) | 6.3 (2) | 25.(3) | 3.31 (8) |
Cg5···Cg5ii | 4.001 (3) | 0 | 20.39 (1) | 3.751 (2) |
Cg1···Cg3vii | 3.807 (3) | 7.9 (3) | 21.(4) | 3.54 (9) |
Symmetry codes: (i) -x + 1, -y, -z + 1; (ii) -x, -y, -z + 1;
(vii) x, -y + 1/2, z - 1/2. Cg1 is the centroid of the N11/C11–C51 ring, Cg2 that of the N21/C61–C101 ring, Cg3 that of the N31/C111–C151 ring, Cg4 that of the N41/N51/C231–C251 ring and Cg5 that of the C161–C211 ring. Notes: ccd is the centre-to-centre distance, da is the dihedral angle between rings, ipd is the interplanar distance or (mean) distance from one plane to the neighbouring centroid, and sa is the slippage angle or (mean) angle subtended by the intercentroid vector to the plane normals. For details, see Janiak (2000). |
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