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1-[6-(1H-Pyrrolo[2,3-b]pyridin-1-yl)pyridin-2-yl]-1H-pyrrolo[2,3-b]pyridin-7-ium tetra­chloridoferrate(III), (C19H14N5)[FeCl4], (II), and [2,6-bis­(1H-pyrrolo[2,3-b]pyridin-1-yl-κN7)pyridine-κN]bis­(nitrato-κO)copper(II), [Cu(NO3)2(C19H13N5)], (III), were prepared by self-assembly from FeCl3·6H2O or Cu(NO3)2·3H2O and 2,6-bis­(1H-pyrrolo[2,3-b]pyridin-1-yl)­pyridine [commonly called 2,6-bis­(aza­indole)­pyridine, bap], C19H13N5, (I). Compound (I) crystallizes with Z′ = 2 in the P\overline{1} space group, with both independent molecules adopting a transtrans conformation. Compound (II) is a salt complex with weak C—H...Cl inter­actions giving rise to a zigzag network with π-stacking down the a axis. Complex (III) lies across a twofold rotation axis in the C2/c space group. The CuII center in (III) has an N3O2 trigonal–bipyramidal environment. The nitrate ligand coordinates in a monodentate fashion, while the bap ligand adopts a twisted tridentate binding mode. C—H...O inter­actions give rise to a ribbon motif.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107039686/gd3124sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107039686/gd3124Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107039686/gd3124IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107039686/gd3124IIIsup4.hkl
Contains datablock III

CCDC references: 665482; 665483; 665484

Comment top

Organometallic supramolecular structures and materials remain a popular area of interest because of their spectral and electrochemical properties, and are thus potentially useful as molecular devices, sensors and catalysts (James, 2003; Braga, 2003; Blake et al., 1999; Balzani & Juris, 2001). A plethora of geometric frameworks, dependent on the coordination preferences of the metal ion and the nature of the bridging ligand, have been reported (Moulton & Zaworotko, 2001). We were further inspired by the inorganic crystal engineering work reported by Mukherjee and coworkers (Mukherjee et al., 2003; Balamurugan et al., 2004), where C—H···Cl hydrogen bonding interactions proved a useful tool in forming supramolecular networks composed of [(L3)MnCl2(EtOH)] and [(L6)FeCl3] [L3 is 2-[3-(2'-pyridyl)pyrazol-1-ylmethyl]pyridine; L6 is methyl[2-(2-pyridyl)ethyl](2-pyridylmethyl)amine].

Our continuing research effort focuses on cyclometallating aryldiamine and polypyridyl ligands (i) as a mechanism to tune the electronic structure of square-planar platinum(II) and palladium(II) (Jude et al., 2005; Tastan et al., 2006), and (ii) as potential bridges to form more elaborate molecular architectures, such as triangles or larger polygons (Schweiger et al., 2001, 2002). Thus, an ongoing effort is to synthesize a library of appropriate ligands. The synthesis and structural characterization of 2,6-bis(azaindole)pyridine, (I) (bap), is described here. Furthermore, in addition to complexes with PtII and PdII, we would like to expand our studies to include other transition metals. In this report, we present our findings when FeIII and CuII salts are reacted with (I).

Compound (I) (Fig. 1) crystallizes with two independent molecules in the asymmetric unit. Both molecules adopt a trans,trans conformation (see Table 1). Similar torsion angles are observed for the monoclinic (Bowes et al., 2005) and orthorhombic forms (Bessel et al., 1992) of 2,2':6',2"-terpyridine (tpy) and 2,6-bis(5,6,7,8-tetrahydroquinol-2-yl)pyridine (the torsion angles about the Cquinolyl—Cpyridine bond are −168.5 and 165.7°; Sasaki et al., 1998). On the other hand, 1,3-bis(7-azaindolyl)benzene (bab; Wu et al., 2001) and 1-bromo-3,5-bis(7-azaindolyl)benzene (babBr; Song et al., 2001) crystallize with noncoplanar azaindolyl rings, giving rise to a curved conformation (the torsion angles about the Nazaindolyl—Cbenzene bonds are in the 20–45° range).

Self-assembly of FeCl3·6H2O with (I) forms the salt (bapH)FeCl4, (II) (Fig. 2). The bapH+ cation is protonated at atom N1. A typical intramolecular N—H···N hydrogen bond occurs between atoms N1 and N5 [N1···N5 = 2.873 (3) Å]. The through-space separations N1···N3 and N5···N3 are 2.722 (3) and 2.832 (2) Å, respectively. The presence of the intramolecular hydrogen bond causes a conformational change in the molecule, giving rise to a cis,cis conformation [the torsion angles about the Nazaindolyl—Cpyridine bonds are 3.8 (3) and 0.03 (3)°] with the azaindolyl rings essentially coplanar [the dihedral angles between the azaindolyl and pyridine rings are 3.32 (1) and 1.29 (1)°]. The Cl—Fe—Cl angles (Table 2) are consistent with tetrahedral geometry about the FeIII center. The Fe—Cl distances are comparable to those in related complexes containing the FeCl4 anion (for example, Zora et al., 1990; Chan & Baird, 2004; Lewis et al., 2002).

Weak C—H···Cl interactions (Aullón et al., 1998, Brammer et al., 2001), forming a zigzag network, are observed between the bapH+ cation and the FeCl4 anion (see Table 3). π-Stacked interactions between neighboring cations run down the a axis; the interleaved layers are separated by ~3.4 Å [every second layer is in register [please clarify what is meant by this] with a separation of 6.6695 (1) Å (the a axis cell length)]. Typical ππ interactions in organic compounds are less than 3.8 Å (Janiak, 2000).

Focused on forming square-planar complexes where (I) adopts a tridentate binding motif, we turned our attention to RuIII and CuII salts. Attempts to react (I) with RuCl3.nH2O failed to yield a product. However, reaction of Cu(NO3)2·3H2O with (I) resulted in the formation of (bap)Cu(NO3)2, (III) (Fig. 3a). The molecule crystallizes such that molecular and crystallographic twofold rotation symmetry coincide. The geometry about the CuII center is trigonal–bipyramidal, with an N3O2 environment. Both NO3 ions coordinate in a monodentate fashion through an O atom [Cu—O2 = 2.1746 (14) Å and Cu···O1 = 2.636 (2) Å]. Bond lengths and angles (see Table 4) are typical and comparable to those in [(phtpy)Cu(OH)(NO3)][(phtpy)Cu(NO3)2] (Kumar or Padhi & Manivannan, 2006) and (tpyBr2)Cu(NO3)2 (Lam et al., 2006). C—H···O interactions (see Table 5) give rise to a ribbon motif.

The bap ligand in (III) adopts a twisted, tridentate binding mode [C8—N3—Cu—N1 = 23.0 (1)°; Fig. 3b]. Perusal of the literature shows that the related structures [(tpyOH)Cu(OH2](ClO4)2 (Jeitler & Turnbull, 2005), [(phtpy)Cu(OH)(NO3)][(phtpy)Cu(NO3)2] (Kumar or Padhi & Manivannan, 2006) and (tpyBr2)Cu(NO3)2 (Lam et al., 2006) sport a tridentate-bound tpy ligand; however, the tpy rings are nearly planar (the C—N—M—N torsion angles are less than 6°). The chelate distortion from planarity in bap is echoed by the closely related bab and babR ligands in (bab)MCl and (babBr)MCl (M = Pd and Pt) (with twisted geometry, having C—N—M—N torsion angles in the range 20–34°; Song et al., 2001). For (babR)Re(CO)3 (R = H, F, CF3 and MeO) complexes, the chelate takes on a folded, butterfly geometry (Tani et al., 2004). Characteristic of these structures is the increased nonplanarity of the tridentate ligand (twist or butterfly conformations) as the progression tpy, tpyOH, tpyO, phtpy ~ tpyBr2 < bap, bab, bapR is made, consistent with a direct relationship between increased steric effects near the metal coordination plane and the degree of nonplanarity.

Related literature top

For related literature, see: Aullón et al. (1998); Balamurugan et al. (2004); Balzani & Juris (2001); Bessel et al. (1992); Blake et al. (1999); Bowes et al. (2005); Braga (2003); Brammer et al. (2001); Chan & Baird (2004); James (2003); Janiak (2000); Jeitler & Turnbull (2005); Jude et al. (2005); Lam et al. (2006); Lewis et al. (2002); Moulton & Zaworotko (2001); Mukherjee et al. (2003); Parsons & Gould (2001); Sasaki et al. (1998); Schweiger et al. (2001, 2002); Song et al. (2001); Tani et al. (2004); Tastan et al. (2006); Watkin et al. (2001); Wu et al. (2001); Zora et al. (1990).

Experimental top

Compound (I) was prepared by a modified procedure based on the synthesis of bab (Wu et al., 2001). 2,6-Dibromopyridine (8.6 mmol, 2.0407 g), 7-azaindole (18 mmol, 2.1415 g), potassium carbonate (14.8 mmol, 2.0526 g) and cupric sulfate (1.75 mmol, 0.2792 g) were added to a flask under an argon atmosphere. The mixture was heated with stirring for 4 h at 483 K. After cooling to room temperature, the resulting mixture was extracted with methylene chloride and water. The organic layer was separated, dried with MgSO4 and filtered, and the solvent volume was reduced. Hexanes were added to precipitate (I) as a white crystalline solid (2.1 mmol, 0.6700 g, 25% yield). Colorless crystals suitable for X-ray analysis were grown by slow evaporation of a methanol–methylene chloride solution.

FeCl3·6H2O in methanol was layered over a solution of (I) in methylene chloride (1:1 molar ratio of reactants, 5 ml of each solvent) in a test tube. The test tube was covered with Parafilm. Crystallite formation occurred within a few hours at room temperature. Yellow, X-ray quality crystals of (II) were harvested after 1–2 weeks.

In an analogous fashion, equimolar amounts of Cu(NO3)2·3H2O and (I) in methanol and methylene chloride, respectively, were allowed to react. Light-green, X-ray quality crystals of (III) were obtained after 1–2 weeks.

Refinement top

Initial refinement of (I) in P1 yielded a structure solution with R1 19%. Subsequent refinements included the twin law (1 0 0, 0 1 0, 0 1 1) obtained from ROTAX (Parsons & Gould, 2001) as implemented in CRYSTALS (Betteridge et al., 2003). The twin fraction ratio is 42:58. The N-bound H atom in (II) was located directly; the position and isotropic displacement parameters were refined. All remaining H atoms were either located or calculated and treated as riding (C—H = 0.95 Å); the isotropic displacement parameters were defined as 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2003) for (I), (II); APEX2 (Bruker, 2005) for (III). Cell refinement: SAINT (Bruker, 2003) for (I), (II); SAINT (Bruker, 2005) for (III). Data reduction: SAINT (Bruker, 2003) for (I), (II); SAINT (Bruker, 2005) for (III). For all compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2003); program(s) used to refine structure: SHELXTL. Molecular graphics: SHELXTL for (I); SHELXTL and DIAMOND (Brandenburg, 2007) for (II), (III). For all compounds, software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic labelling scheme and 50% probability displacement ellipsoids. Both independent molecules show similar conformations, therefore only molecule A is shown.
[Figure 2] Fig. 2. The structure of (II), showing the atomic labelling scheme and 50% probability displacement ellipsoids.
[Figure 3] Fig. 3. (a) The structure of (III), showing the atomic labelling scheme [symmetry code: (i) −x + 1, y, −z + 1/2] and 50% probability displacement ellipsoids. (b) A view down the Cu—N3—C10 axis, showing the ligand twist.
(I) 2,6-bis(1H-pyrrolo[2,3-b]pyridin-1-yl)pyridine top
Crystal data top
C19H13N5Z = 4
Mr = 311.34F(000) = 648
Triclinic, P1Dx = 1.444 Mg m3
Hall symbol: -P 1Cu Kα radiation, λ = 1.54178 Å
a = 6.6377 (2) ÅCell parameters from 6337 reflections
b = 10.1397 (3) Åθ = 4.2–67.4°
c = 21.9214 (6) ŵ = 0.72 mm1
α = 76.609 (1)°T = 150 K
β = 86.563 (10)°Blade, colorless
γ = 90.004 (1)°0.35 × 0.10 × 0.05 mm
V = 1432.56 (7) Å3
Data collection top
Bruker SMART 6000 CCD
diffractometer
4847 independent reflections
Radiation source: fine-focus sealed tube4215 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 0.8 pixels mm-1θmax = 67.4°, θmin = 2.1°
ω scansh = 77
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1111
Tmin = 0.787, Tmax = 0.965l = 2624
11609 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0853P)2 + 0.017P]
where P = (Fo2 + 2Fc2)/3
4847 reflections(Δ/σ)max < 0.001
434 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C19H13N5γ = 90.004 (1)°
Mr = 311.34V = 1432.56 (7) Å3
Triclinic, P1Z = 4
a = 6.6377 (2) ÅCu Kα radiation
b = 10.1397 (3) ŵ = 0.72 mm1
c = 21.9214 (6) ÅT = 150 K
α = 76.609 (1)°0.35 × 0.10 × 0.05 mm
β = 86.563 (10)°
Data collection top
Bruker SMART 6000 CCD
diffractometer
4847 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
4215 reflections with I > 2σ(I)
Tmin = 0.787, Tmax = 0.965Rint = 0.026
11609 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.122H-atom parameters constrained
S = 1.06Δρmax = 0.32 e Å3
4847 reflectionsΔρmin = 0.24 e Å3
434 parameters
Special details top

Experimental. A suitable crystal was mounted on the tip of a glass fiber with paratone-N and immediately transferred to the goniostat bathed in a cold stream.

The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I).

Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely on absorption effects and crystal size.

1H NMR (CHCl3): 8.870(d), 8.492(d), 8.472(dd), 8.099(t), 7.230(dd), 6.710(d).

Elemental Analysis for C19H13N5: calc. C, 73.30; H, 4.21; N, 22.49. found. C, 70.99; H, 4.12, N, 21.82.

MS: 312.149(M+) m/z

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.

The twin law (obtained from ROTAX (Parsons & Gould, 2001) as implemented in CRYSTALS (Watkin, et al., 2001) was applied in the refinement: −1 0 0 0 1 0 0 1 − 1 The twin fraction ratio is 42:58.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A1.2093 (3)0.0078 (2)0.38200 (11)0.0331 (6)
N2A0.9641 (3)0.1468 (2)0.42534 (10)0.0276 (5)
N3A0.9622 (3)0.2678 (2)0.50197 (10)0.0280 (5)
N4A0.9163 (3)0.3937 (2)0.57642 (10)0.0263 (5)
N5A1.1214 (3)0.4534 (3)0.65468 (11)0.0315 (5)
C1A1.2334 (4)0.0635 (3)0.33766 (14)0.0360 (7)
H1A1.35690.10970.33490.043*
C2A1.0901 (5)0.0744 (3)0.29556 (14)0.0409 (8)
H2A1.11880.12520.26480.049*
C3A0.9052 (4)0.0118 (3)0.29807 (13)0.0347 (7)
H3A0.80550.01860.26960.042*
C4A0.8716 (4)0.0615 (3)0.34393 (13)0.0285 (6)
C5A1.0295 (4)0.0671 (3)0.38304 (13)0.0269 (6)
C6A0.7058 (4)0.1356 (3)0.36362 (13)0.0334 (6)
H6A0.57760.14770.34620.040*
C7A0.7672 (4)0.1850 (3)0.41186 (12)0.0302 (6)
H7A0.68640.23880.43370.036*
C8A1.0671 (4)0.1855 (3)0.47358 (12)0.0266 (6)
C9A1.2584 (4)0.1395 (3)0.48988 (12)0.0282 (6)
H9A1.33010.08060.46860.034*
C10A1.3389 (4)0.1836 (3)0.53843 (12)0.0304 (6)
H10A1.46950.15480.55090.036*
C11A1.2331 (4)0.2688 (3)0.56931 (13)0.0306 (6)
H11A1.28740.29860.60300.037*
C12A1.0438 (4)0.3087 (3)0.54876 (12)0.0254 (6)
C13A0.7206 (4)0.4250 (3)0.55896 (13)0.0314 (6)
H13A0.65840.39480.52660.038*
C14A0.6310 (4)0.5040 (3)0.59412 (13)0.0325 (6)
H14A0.49770.53800.59120.039*
C15A0.9525 (4)0.4568 (3)0.62463 (12)0.0263 (6)
C16A0.7742 (4)0.5268 (3)0.63644 (13)0.0300 (6)
C17A0.7763 (4)0.6000 (3)0.68338 (13)0.0330 (7)
H17A0.66220.64960.69320.040*
C18A0.9506 (4)0.5973 (3)0.71476 (13)0.0331 (6)
H18A0.95780.64530.74700.040*
C19A1.1155 (4)0.5247 (3)0.69956 (13)0.0334 (7)
H19A1.23260.52530.72240.040*
N1B0.3449 (3)1.0995 (3)0.15837 (11)0.0324 (6)
N2B0.5512 (3)0.9733 (2)0.07774 (10)0.0275 (5)
N3B0.5174 (3)0.7710 (2)0.00275 (10)0.0260 (5)
N4B0.5224 (3)0.5744 (2)0.07439 (10)0.0275 (5)
N5B0.2898 (3)0.3844 (2)0.11605 (11)0.0323 (6)
C1B0.3484 (4)1.2103 (3)0.20667 (13)0.0363 (7)
H1B0.23101.22890.22970.044*
C2B0.5125 (4)1.2986 (3)0.22478 (14)0.0399 (7)
H2B0.50541.37430.25940.048*
C3B0.6847 (4)1.2765 (3)0.19261 (14)0.0367 (7)
H3B0.79761.33660.20420.044*
C4B0.6898 (4)1.1636 (3)0.14249 (13)0.0303 (6)
C5B0.5137 (4)1.0800 (3)0.12846 (12)0.0270 (6)
C6B0.8350 (4)1.1042 (3)0.09937 (13)0.0346 (7)
H6B0.96751.13790.09750.041*
C7B0.7488 (4)0.9907 (3)0.06147 (13)0.0317 (6)
H7B0.81340.93150.02850.038*
C8B0.4288 (4)0.8593 (3)0.04827 (12)0.0271 (6)
C9B0.2371 (4)0.8393 (3)0.06649 (12)0.0285 (6)
H9B0.17830.90310.09920.034*
C10B0.1350 (4)0.7217 (3)0.03476 (12)0.0305 (6)
H10B0.00330.70410.04600.037*
C11B0.2217 (4)0.6292 (3)0.01308 (12)0.0290 (6)
H11B0.15240.54880.03520.035*
C12B0.4156 (4)0.6605 (3)0.02702 (12)0.0263 (6)
C13B0.7177 (4)0.6047 (3)0.08766 (12)0.0299 (6)
H13B0.79240.68410.06720.036*
C14B0.7863 (4)0.5044 (3)0.13412 (13)0.0328 (6)
H14B0.91480.50140.15120.039*
C15B0.4644 (4)0.4492 (3)0.11488 (12)0.0271 (6)
C16B0.6286 (4)0.4047 (3)0.15235 (12)0.0275 (6)
C17B0.6045 (4)0.2802 (3)0.19563 (13)0.0349 (7)
H17B0.70820.24490.22260.042*
C18B0.4243 (4)0.2099 (3)0.19793 (13)0.0361 (7)
H18B0.40330.12430.22650.043*
C19B0.2738 (4)0.2648 (3)0.15838 (13)0.0349 (7)
H19B0.15150.21430.16150.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0353 (12)0.0293 (13)0.0341 (14)0.0027 (10)0.0065 (10)0.0084 (11)
N2A0.0305 (11)0.0257 (13)0.0265 (12)0.0015 (9)0.0025 (9)0.0070 (10)
N3A0.0336 (12)0.0246 (12)0.0250 (12)0.0028 (10)0.0024 (9)0.0052 (10)
N4A0.0301 (11)0.0257 (12)0.0240 (12)0.0013 (9)0.0018 (9)0.0088 (9)
N5A0.0304 (11)0.0337 (14)0.0329 (13)0.0024 (10)0.0017 (10)0.0125 (11)
C1A0.0390 (15)0.0312 (16)0.0383 (18)0.0027 (13)0.0118 (13)0.0126 (13)
C2A0.0548 (19)0.0341 (16)0.0362 (17)0.0039 (14)0.0122 (14)0.0166 (14)
C3A0.0452 (16)0.0303 (16)0.0302 (15)0.0029 (13)0.0002 (12)0.0110 (13)
C4A0.0354 (14)0.0250 (15)0.0246 (14)0.0044 (12)0.0027 (11)0.0061 (12)
C5A0.0343 (14)0.0201 (14)0.0248 (14)0.0038 (11)0.0077 (11)0.0043 (11)
C6A0.0362 (14)0.0291 (15)0.0336 (15)0.0025 (12)0.0014 (12)0.0048 (12)
C7A0.0282 (13)0.0274 (15)0.0338 (16)0.0042 (11)0.0025 (11)0.0060 (12)
C8A0.0306 (13)0.0212 (13)0.0268 (14)0.0022 (11)0.0054 (11)0.0052 (11)
C9A0.0305 (13)0.0257 (14)0.0278 (14)0.0004 (11)0.0040 (11)0.0064 (11)
C10A0.0287 (13)0.0282 (15)0.0325 (15)0.0026 (11)0.0021 (11)0.0044 (12)
C11A0.0321 (14)0.0303 (15)0.0281 (14)0.0009 (12)0.0000 (11)0.0044 (12)
C12A0.0284 (13)0.0208 (13)0.0247 (14)0.0021 (10)0.0060 (10)0.0022 (11)
C13A0.0299 (13)0.0310 (15)0.0345 (16)0.0010 (11)0.0006 (11)0.0105 (12)
C14A0.0284 (13)0.0323 (15)0.0363 (16)0.0035 (12)0.0021 (11)0.0077 (12)
C15A0.0302 (13)0.0226 (14)0.0239 (14)0.0055 (11)0.0057 (10)0.0026 (11)
C16A0.0320 (14)0.0220 (15)0.0319 (16)0.0004 (11)0.0067 (12)0.0000 (12)
C17A0.0396 (15)0.0253 (14)0.0304 (15)0.0001 (12)0.0094 (12)0.0017 (12)
C18A0.0430 (16)0.0298 (15)0.0269 (14)0.0044 (12)0.0073 (12)0.0099 (12)
C19A0.0399 (15)0.0329 (16)0.0289 (15)0.0024 (13)0.0006 (12)0.0108 (13)
N1B0.0387 (13)0.0241 (13)0.0336 (13)0.0013 (10)0.0003 (10)0.0058 (11)
N2B0.0288 (11)0.0254 (12)0.0287 (12)0.0011 (9)0.0039 (9)0.0085 (10)
N3B0.0300 (11)0.0245 (12)0.0250 (12)0.0022 (9)0.0029 (9)0.0098 (10)
N4B0.0296 (11)0.0264 (13)0.0257 (12)0.0023 (10)0.0018 (9)0.0052 (10)
N5B0.0352 (12)0.0283 (13)0.0323 (13)0.0020 (10)0.0071 (10)0.0075 (11)
C1B0.0446 (16)0.0304 (16)0.0322 (16)0.0041 (13)0.0012 (13)0.0046 (12)
C2B0.0509 (17)0.0270 (15)0.0382 (17)0.0061 (14)0.0110 (14)0.0038 (13)
C3B0.0438 (16)0.0209 (14)0.0415 (17)0.0038 (13)0.0171 (13)0.0044 (13)
C4B0.0325 (14)0.0260 (16)0.0346 (16)0.0030 (11)0.0083 (12)0.0140 (12)
C5B0.0305 (13)0.0227 (14)0.0278 (15)0.0012 (11)0.0055 (11)0.0080 (11)
C6B0.0325 (14)0.0293 (15)0.0404 (17)0.0037 (12)0.0074 (12)0.0074 (12)
C7B0.0321 (14)0.0300 (15)0.0344 (15)0.0014 (12)0.0001 (12)0.0109 (12)
C8B0.0312 (13)0.0248 (14)0.0270 (15)0.0008 (11)0.0045 (11)0.0109 (11)
C9B0.0310 (13)0.0274 (15)0.0277 (14)0.0029 (11)0.0040 (11)0.0072 (12)
C10B0.0273 (13)0.0311 (15)0.0336 (15)0.0030 (12)0.0001 (11)0.0092 (12)
C11B0.0327 (13)0.0251 (14)0.0287 (14)0.0037 (11)0.0034 (11)0.0066 (11)
C12B0.0319 (13)0.0250 (14)0.0245 (14)0.0037 (11)0.0027 (10)0.0117 (11)
C13B0.0288 (13)0.0340 (16)0.0291 (15)0.0025 (12)0.0015 (11)0.0124 (12)
C14B0.0350 (14)0.0322 (15)0.0309 (15)0.0010 (12)0.0034 (12)0.0065 (12)
C15B0.0314 (13)0.0260 (15)0.0260 (15)0.0011 (12)0.0060 (11)0.0120 (12)
C16B0.0339 (13)0.0268 (15)0.0225 (14)0.0049 (12)0.0024 (11)0.0084 (12)
C17B0.0423 (16)0.0325 (17)0.0288 (15)0.0046 (14)0.0014 (12)0.0059 (13)
C18B0.0504 (17)0.0268 (15)0.0283 (15)0.0005 (13)0.0092 (13)0.0035 (12)
C19B0.0385 (15)0.0347 (18)0.0336 (17)0.0051 (13)0.0073 (12)0.0145 (14)
Geometric parameters (Å, º) top
N1A—C5A1.337 (3)N1B—C5B1.324 (3)
N1A—C1A1.342 (4)N1B—C1B1.353 (4)
N2A—C7A1.392 (3)N2B—C5B1.395 (3)
N2A—C5A1.415 (3)N2B—C7B1.402 (3)
N2A—C8A1.421 (3)N2B—C8B1.416 (3)
N3A—C8A1.326 (3)N3B—C12B1.322 (3)
N3A—C12A1.334 (3)N3B—C8B1.341 (4)
N4A—C15A1.388 (4)N4B—C13B1.395 (3)
N4A—C13A1.392 (3)N4B—C15B1.408 (4)
N4A—C12A1.417 (3)N4B—C12B1.418 (3)
N5A—C15A1.331 (3)N5B—C15B1.328 (4)
N5A—C19A1.348 (4)N5B—C19B1.345 (4)
C1A—C2A1.386 (4)C1B—C2B1.389 (4)
C1A—H1A0.9500C1B—H1B0.9500
C2A—C3A1.386 (4)C2B—C3B1.370 (4)
C2A—H2A0.9500C2B—H2B0.9500
C3A—C4A1.390 (4)C3B—C4B1.393 (4)
C3A—H3A0.9500C3B—H3B0.9500
C4A—C5A1.403 (4)C4B—C5B1.420 (4)
C4A—C6A1.434 (4)C4B—C6B1.425 (4)
C6A—C7A1.354 (4)C6B—C7B1.357 (4)
C6A—H6A0.9500C6B—H6B0.9500
C7A—H7A0.9500C7B—H7B0.9500
C8A—C9A1.390 (4)C8B—C9B1.385 (4)
C9A—C10A1.381 (4)C9B—C10B1.387 (4)
C9A—H9A0.9500C9B—H9B0.9500
C10A—C11A1.382 (4)C10B—C11B1.388 (4)
C10A—H10A0.9500C10B—H10B0.9500
C11A—C12A1.389 (4)C11B—C12B1.393 (4)
C11A—H11A0.9500C11B—H11B0.9500
C13A—C14A1.349 (4)C13B—C14B1.361 (4)
C13A—H13A0.9500C13B—H13B0.9500
C14A—C16A1.422 (4)C14B—C16B1.428 (4)
C14A—H14A0.9500C14B—H14B0.9500
C15A—C16A1.421 (4)C15B—C16B1.415 (4)
C16A—C17A1.402 (4)C16B—C17B1.395 (4)
C17A—C18A1.378 (4)C17B—C18B1.385 (4)
C17A—H17A0.9500C17B—H17B0.9500
C18A—C19A1.385 (4)C18B—C19B1.393 (4)
C18A—H18A0.9500C18B—H18B0.9500
C19A—H19A0.9500C19B—H19B0.9500
C5A—N1A—C1A113.5 (3)C5B—N1B—C1B114.5 (3)
C7A—N2A—C5A106.8 (2)C5B—N2B—C7B107.3 (2)
C7A—N2A—C8A123.1 (2)C5B—N2B—C8B129.7 (2)
C5A—N2A—C8A130.0 (2)C7B—N2B—C8B122.8 (2)
C8A—N3A—C12A118.5 (2)C12B—N3B—C8B118.5 (2)
C15A—N4A—C13A107.5 (2)C13B—N4B—C15B107.5 (2)
C15A—N4A—C12A129.3 (2)C13B—N4B—C12B122.4 (2)
C13A—N4A—C12A123.2 (2)C15B—N4B—C12B130.0 (2)
C15A—N5A—C19A114.6 (2)C15B—N5B—C19B114.1 (3)
N1A—C1A—C2A124.4 (3)N1B—C1B—C2B124.3 (3)
N1A—C1A—H1A117.8N1B—C1B—H1B117.8
C2A—C1A—H1A117.8C2B—C1B—H1B117.8
C3A—C2A—C1A120.4 (3)C3B—C2B—C1B119.9 (3)
C3A—C2A—H2A119.8C3B—C2B—H2B120.0
C1A—C2A—H2A119.8C1B—C2B—H2B120.0
C2A—C3A—C4A117.3 (3)C2B—C3B—C4B118.2 (3)
C2A—C3A—H3A121.3C2B—C3B—H3B120.9
C4A—C3A—H3A121.3C4B—C3B—H3B120.9
C3A—C4A—C5A116.9 (3)C3B—C4B—C5B116.9 (3)
C3A—C4A—C6A135.3 (3)C3B—C4B—C6B135.8 (3)
C5A—C4A—C6A107.8 (2)C5B—C4B—C6B107.3 (3)
N1A—C5A—C4A127.3 (3)N1B—C5B—N2B126.2 (2)
N1A—C5A—N2A125.3 (3)N1B—C5B—C4B126.2 (3)
C4A—C5A—N2A107.4 (2)N2B—C5B—C4B107.6 (2)
C7A—C6A—C4A106.8 (2)C7B—C6B—C4B107.3 (3)
C7A—C6A—H6A126.6C7B—C6B—H6B126.4
C4A—C6A—H6A126.6C4B—C6B—H6B126.4
C6A—C7A—N2A111.1 (2)C6B—C7B—N2B110.5 (3)
C6A—C7A—H7A124.4C6B—C7B—H7B124.8
N2A—C7A—H7A124.4N2B—C7B—H7B124.8
N3A—C8A—C9A123.5 (3)N3B—C8B—C9B123.3 (3)
N3A—C8A—N2A113.5 (2)N3B—C8B—N2B114.1 (2)
C9A—C8A—N2A123.0 (2)C9B—C8B—N2B122.6 (2)
C10A—C9A—C8A116.8 (2)C8B—C9B—C10B116.8 (3)
C10A—C9A—H9A121.6C8B—C9B—H9B121.6
C8A—C9A—H9A121.6C10B—C9B—H9B121.6
C9A—C10A—C11A121.3 (2)C9B—C10B—C11B121.2 (2)
C9A—C10A—H10A119.4C9B—C10B—H10B119.4
C11A—C10A—H10A119.4C11B—C10B—H10B119.4
C10A—C11A—C12A116.9 (3)C10B—C11B—C12B116.6 (3)
C10A—C11A—H11A121.6C10B—C11B—H11B121.7
C12A—C11A—H11A121.6C12B—C11B—H11B121.7
N3A—C12A—C11A123.1 (3)N3B—C12B—C11B123.6 (2)
N3A—C12A—N4A113.4 (2)N3B—C12B—N4B114.0 (2)
C11A—C12A—N4A123.4 (2)C11B—C12B—N4B122.5 (3)
C14A—C13A—N4A110.9 (2)C14B—C13B—N4B110.5 (3)
C14A—C13A—H13A124.5C14B—C13B—H13B124.7
N4A—C13A—H13A124.5N4B—C13B—H13B124.7
C13A—C14A—C16A107.0 (2)C13B—C14B—C16B107.1 (2)
C13A—C14A—H14A126.5C13B—C14B—H14B126.4
C16A—C14A—H14A126.5C16B—C14B—H14B126.4
N5A—C15A—N4A127.1 (2)N5B—C15B—N4B126.0 (3)
N5A—C15A—C16A125.7 (3)N5B—C15B—C16B126.9 (3)
N4A—C15A—C16A107.2 (2)N4B—C15B—C16B107.1 (2)
C17A—C16A—C15A117.4 (3)C17B—C16B—C15B116.8 (3)
C17A—C16A—C14A135.1 (3)C17B—C16B—C14B135.5 (3)
C15A—C16A—C14A107.4 (2)C15B—C16B—C14B107.7 (2)
C18A—C17A—C16A117.3 (3)C18B—C17B—C16B117.7 (3)
C18A—C17A—H17A121.3C18B—C17B—H17B121.1
C16A—C17A—H17A121.3C16B—C17B—H17B121.1
C17A—C18A—C19A120.3 (3)C17B—C18B—C19B120.0 (3)
C17A—C18A—H18A119.8C17B—C18B—H18B120.0
C19A—C18A—H18A119.8C19B—C18B—H18B120.0
N5A—C19A—C18A124.6 (3)N5B—C19B—C18B124.5 (3)
N5A—C19A—H19A117.7N5B—C19B—H19B117.8
C18A—C19A—H19A117.7C18B—C19B—H19B117.8
C5A—N1A—C1A—C2A1.2 (4)C5B—N1B—C1B—C2B0.0 (4)
N1A—C1A—C2A—C3A1.4 (5)N1B—C1B—C2B—C3B0.5 (5)
C1A—C2A—C3A—C4A0.2 (4)C1B—C2B—C3B—C4B0.7 (4)
C2A—C3A—C4A—C5A1.0 (4)C2B—C3B—C4B—C5B0.3 (4)
C2A—C3A—C4A—C6A177.7 (3)C2B—C3B—C4B—C6B178.3 (3)
C1A—N1A—C5A—C4A0.1 (4)C1B—N1B—C5B—N2B179.2 (2)
C1A—N1A—C5A—N2A179.3 (2)C1B—N1B—C5B—C4B0.4 (4)
C3A—C4A—C5A—N1A1.2 (4)C7B—N2B—C5B—N1B179.0 (3)
C6A—C4A—C5A—N1A177.8 (3)C8B—N2B—C5B—N1B3.5 (4)
C3A—C4A—C5A—N2A179.5 (2)C7B—N2B—C5B—C4B0.6 (3)
C6A—C4A—C5A—N2A1.5 (3)C8B—N2B—C5B—C4B176.2 (2)
C7A—N2A—C5A—N1A178.1 (3)C3B—C4B—C5B—N1B0.2 (4)
C8A—N2A—C5A—N1A1.8 (4)C6B—C4B—C5B—N1B179.2 (3)
C7A—N2A—C5A—C4A1.3 (3)C3B—C4B—C5B—N2B179.4 (2)
C8A—N2A—C5A—C4A178.9 (3)C6B—C4B—C5B—N2B0.4 (3)
C3A—C4A—C6A—C7A179.9 (3)C3B—C4B—C6B—C7B178.7 (3)
C5A—C4A—C6A—C7A1.2 (3)C5B—C4B—C6B—C7B0.0 (3)
C4A—C6A—C7A—N2A0.4 (3)C4B—C6B—C7B—N2B0.4 (3)
C5A—N2A—C7A—C6A0.6 (3)C5B—N2B—C7B—C6B0.6 (3)
C8A—N2A—C7A—C6A179.6 (2)C8B—N2B—C7B—C6B176.5 (2)
C12A—N3A—C8A—C9A0.2 (4)C12B—N3B—C8B—C9B1.2 (4)
C12A—N3A—C8A—N2A179.0 (2)C12B—N3B—C8B—N2B179.2 (2)
C7A—N2A—C8A—N3A3.8 (4)C5B—N2B—C8B—N3B176.1 (2)
C5A—N2A—C8A—N3A176.4 (2)C7B—N2B—C8B—N3B1.1 (3)
C7A—N2A—C8A—C9A175.4 (2)C5B—N2B—C8B—C9B2.0 (4)
C5A—N2A—C8A—C9A4.5 (4)C7B—N2B—C8B—C9B176.9 (2)
N3A—C8A—C9A—C10A0.1 (4)N3B—C8B—C9B—C10B0.6 (4)
N2A—C8A—C9A—C10A178.9 (2)N2B—C8B—C9B—C10B178.4 (2)
C8A—C9A—C10A—C11A0.3 (4)C8B—C9B—C10B—C11B0.2 (4)
C9A—C10A—C11A—C12A0.6 (4)C9B—C10B—C11B—C12B0.4 (4)
C8A—N3A—C12A—C11A0.2 (4)C8B—N3B—C12B—C11B1.0 (4)
C8A—N3A—C12A—N4A178.6 (2)C8B—N3B—C12B—N4B179.7 (2)
C10A—C11A—C12A—N3A0.6 (4)C10B—C11B—C12B—N3B0.2 (4)
C10A—C11A—C12A—N4A178.9 (2)C10B—C11B—C12B—N4B179.4 (2)
C15A—N4A—C12A—N3A178.4 (2)C13B—N4B—C12B—N3B0.3 (3)
C13A—N4A—C12A—N3A3.6 (4)C15B—N4B—C12B—N3B179.4 (2)
C15A—N4A—C12A—C11A3.2 (4)C13B—N4B—C12B—C11B179.0 (2)
C13A—N4A—C12A—C11A174.9 (2)C15B—N4B—C12B—C11B0.2 (4)
C15A—N4A—C13A—C14A0.4 (3)C15B—N4B—C13B—C14B0.5 (3)
C12A—N4A—C13A—C14A178.0 (2)C12B—N4B—C13B—C14B178.8 (2)
N4A—C13A—C14A—C16A0.4 (3)N4B—C13B—C14B—C16B0.4 (3)
C19A—N5A—C15A—N4A179.7 (2)C19B—N5B—C15B—N4B178.6 (2)
C19A—N5A—C15A—C16A0.3 (4)C19B—N5B—C15B—C16B0.5 (4)
C13A—N4A—C15A—N5A179.7 (3)C13B—N4B—C15B—N5B178.7 (2)
C12A—N4A—C15A—N5A2.0 (5)C12B—N4B—C15B—N5B0.6 (4)
C13A—N4A—C15A—C16A0.3 (3)C13B—N4B—C15B—C16B0.3 (3)
C12A—N4A—C15A—C16A178.0 (2)C12B—N4B—C15B—C16B178.9 (2)
N5A—C15A—C16A—C17A0.7 (4)N5B—C15B—C16B—C17B0.7 (4)
N4A—C15A—C16A—C17A179.3 (2)N4B—C15B—C16B—C17B179.0 (2)
N5A—C15A—C16A—C14A179.9 (3)N5B—C15B—C16B—C14B178.4 (3)
N4A—C15A—C16A—C14A0.0 (3)N4B—C15B—C16B—C14B0.1 (3)
C13A—C14A—C16A—C17A178.9 (3)C13B—C14B—C16B—C17B179.1 (3)
C13A—C14A—C16A—C15A0.2 (3)C13B—C14B—C16B—C15B0.2 (3)
C15A—C16A—C17A—C18A0.6 (4)C15B—C16B—C17B—C18B0.8 (4)
C14A—C16A—C17A—C18A179.6 (3)C14B—C16B—C17B—C18B178.1 (3)
C16A—C17A—C18A—C19A0.2 (4)C16B—C17B—C18B—C19B0.8 (4)
C15A—N5A—C19A—C18A0.1 (4)C15B—N5B—C19B—C18B0.5 (4)
C17A—C18A—C19A—N5A0.1 (5)C17B—C18B—C19B—N5B0.7 (4)
(II) 1-[6-(1H-Pyrrolo[2,3-b]pyridin-1-yl)pyridin-2-yl]-1H-pyrrolo[2,3-b]pyridin-7-ium tetrachloridoferrate(III) top
Crystal data top
(C19H14N5)[FeCl4]F(000) = 1028
Mr = 510.00Dx = 1.656 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ynCell parameters from 7864 reflections
a = 6.6695 (1) Åθ = 3.8–67.9°
b = 23.2657 (4) ŵ = 10.86 mm1
c = 13.3959 (2) ÅT = 150 K
β = 100.312 (1)°Rod, yellow
V = 2045.07 (6) Å30.19 × 0.04 × 0.02 mm
Z = 4
Data collection top
Bruker SMART 6000 CCD
diffractometer
3653 independent reflections
Radiation source: fine-focus sealed tube3210 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
Detector resolution: 0.8 pixels mm-1θmax = 68.0°, θmin = 3.8°
ω scansh = 77
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2727
Tmin = 0.232, Tmax = 0.812l = 1515
17199 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0412P)2 + 0.4538P]
where P = (Fo2 + 2Fc2)/3
3653 reflections(Δ/σ)max = 0.001
266 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
(C19H14N5)[FeCl4]V = 2045.07 (6) Å3
Mr = 510.00Z = 4
Monoclinic, P21/nCu Kα radiation
a = 6.6695 (1) ŵ = 10.86 mm1
b = 23.2657 (4) ÅT = 150 K
c = 13.3959 (2) Å0.19 × 0.04 × 0.02 mm
β = 100.312 (1)°
Data collection top
Bruker SMART 6000 CCD
diffractometer
3653 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3210 reflections with I > 2σ(I)
Tmin = 0.232, Tmax = 0.812Rint = 0.041
17199 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.34 e Å3
3653 reflectionsΔρmin = 0.25 e Å3
266 parameters
Special details top

Experimental. A suitable crystal was mounted on the tip of a glass fiber with paratone-N and immediately transferred to the goniostat bathed in a cold stream.

The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I).

Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely on absorption effects and crystal size.

Spectroscopic characterization: UV-vis (λmax, methanol, room temp): 317 nm

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
Fe0.24826 (5)0.656709 (14)1.04461 (2)0.02627 (11)
Cl10.04490 (9)0.63538 (3)1.08877 (5)0.04501 (17)
Cl20.19512 (9)0.72098 (2)0.92257 (4)0.03491 (14)
Cl30.45343 (9)0.69060 (2)1.17814 (4)0.03408 (14)
Cl40.38472 (11)0.57906 (3)0.99304 (4)0.04551 (17)
N10.2212 (3)0.61000 (8)0.44891 (13)0.0231 (4)
H200.223 (4)0.5728 (12)0.4349 (19)0.035 (7)*
N20.2900 (3)0.60012 (8)0.63369 (12)0.0243 (4)
N30.2688 (2)0.51067 (8)0.55802 (12)0.0231 (4)
N40.2442 (3)0.42441 (7)0.46941 (13)0.0251 (4)
N50.2089 (3)0.50207 (8)0.34382 (13)0.0251 (4)
C10.1861 (4)0.64788 (10)0.37103 (17)0.0313 (5)
H10.16150.63380.30330.038*
C20.1853 (4)0.70629 (10)0.38758 (18)0.0351 (5)
H20.15930.73190.33150.042*
C30.2222 (3)0.72811 (10)0.48580 (18)0.0322 (5)
H30.22230.76840.49760.039*
C40.2588 (3)0.68972 (10)0.56600 (17)0.0275 (5)
C50.2551 (3)0.63021 (9)0.54446 (15)0.0234 (4)
C60.2985 (3)0.69449 (10)0.67409 (17)0.0321 (5)
H60.31060.72920.71200.039*
C70.3155 (3)0.64099 (10)0.71230 (17)0.0310 (5)
H70.34110.63200.78260.037*
C80.2927 (3)0.53972 (9)0.64524 (15)0.0239 (4)
C90.3176 (3)0.51435 (10)0.74024 (16)0.0305 (5)
H90.33140.53670.80040.037*
C100.3214 (3)0.45496 (11)0.74326 (17)0.0342 (5)
H100.33940.43570.80670.041*
C110.2991 (3)0.42353 (10)0.65449 (17)0.0315 (5)
H110.30210.38270.65560.038*
C120.2718 (3)0.45380 (9)0.56286 (16)0.0234 (4)
C130.2399 (3)0.36419 (10)0.46016 (18)0.0312 (5)
H130.25670.33820.51570.037*
C140.2089 (3)0.34837 (9)0.36190 (19)0.0334 (5)
H140.19940.31010.33670.040*
C150.2143 (3)0.44682 (9)0.37025 (16)0.0231 (4)
C160.1931 (3)0.39961 (10)0.30255 (18)0.0293 (5)
C170.1642 (3)0.41114 (11)0.19900 (18)0.0352 (5)
H170.14890.38100.15040.042*
C180.1588 (4)0.46809 (11)0.16961 (18)0.0359 (5)
H180.14010.47790.09970.043*
C190.1807 (3)0.51077 (10)0.24289 (16)0.0305 (5)
H190.17540.54950.22000.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe0.0317 (2)0.02549 (19)0.02148 (18)0.00005 (14)0.00449 (14)0.00114 (13)
Cl10.0327 (3)0.0534 (4)0.0491 (4)0.0008 (3)0.0075 (3)0.0239 (3)
Cl20.0489 (3)0.0316 (3)0.0250 (3)0.0015 (2)0.0087 (2)0.0052 (2)
Cl30.0432 (3)0.0321 (3)0.0252 (3)0.0036 (2)0.0014 (2)0.0025 (2)
Cl40.0652 (4)0.0380 (3)0.0296 (3)0.0163 (3)0.0014 (3)0.0083 (2)
N10.0253 (9)0.0226 (9)0.0223 (9)0.0014 (7)0.0064 (7)0.0019 (7)
N20.0231 (9)0.0301 (9)0.0201 (8)0.0013 (7)0.0045 (7)0.0040 (7)
N30.0209 (9)0.0261 (9)0.0228 (8)0.0003 (7)0.0048 (7)0.0009 (7)
N40.0247 (9)0.0221 (9)0.0288 (9)0.0011 (7)0.0056 (7)0.0010 (7)
N50.0248 (9)0.0262 (9)0.0237 (9)0.0005 (7)0.0029 (7)0.0021 (7)
C10.0394 (13)0.0307 (12)0.0251 (11)0.0007 (10)0.0092 (10)0.0010 (9)
C20.0448 (14)0.0275 (12)0.0353 (12)0.0001 (10)0.0129 (11)0.0050 (10)
C30.0316 (12)0.0242 (11)0.0431 (13)0.0024 (9)0.0129 (10)0.0027 (10)
C40.0214 (11)0.0279 (11)0.0346 (12)0.0011 (8)0.0088 (9)0.0073 (9)
C50.0163 (10)0.0271 (11)0.0268 (10)0.0003 (8)0.0041 (8)0.0035 (9)
C60.0277 (12)0.0336 (12)0.0350 (12)0.0003 (9)0.0053 (10)0.0131 (10)
C70.0284 (12)0.0399 (13)0.0243 (11)0.0021 (10)0.0036 (9)0.0113 (10)
C80.0175 (10)0.0306 (11)0.0238 (10)0.0001 (8)0.0042 (8)0.0001 (9)
C90.0276 (11)0.0419 (13)0.0216 (10)0.0018 (10)0.0032 (9)0.0000 (10)
C100.0304 (12)0.0442 (14)0.0271 (11)0.0017 (10)0.0025 (9)0.0120 (10)
C110.0280 (12)0.0316 (12)0.0336 (12)0.0015 (9)0.0021 (9)0.0069 (10)
C120.0167 (10)0.0255 (11)0.0283 (11)0.0001 (8)0.0047 (8)0.0027 (9)
C130.0288 (12)0.0215 (11)0.0442 (13)0.0003 (9)0.0091 (10)0.0056 (10)
C140.0299 (12)0.0231 (11)0.0489 (14)0.0014 (9)0.0112 (11)0.0093 (10)
C150.0162 (10)0.0266 (10)0.0266 (10)0.0013 (8)0.0039 (8)0.0024 (9)
C160.0191 (11)0.0311 (12)0.0380 (12)0.0033 (9)0.0061 (9)0.0094 (10)
C170.0300 (12)0.0397 (14)0.0356 (12)0.0043 (10)0.0050 (10)0.0156 (11)
C180.0344 (13)0.0461 (14)0.0262 (11)0.0004 (10)0.0024 (9)0.0063 (11)
C190.0308 (12)0.0343 (12)0.0256 (11)0.0023 (10)0.0033 (9)0.0006 (10)
Geometric parameters (Å, º) top
Fe—Cl42.1895 (7)C4—C51.414 (3)
Fe—Cl32.1949 (6)C4—C61.429 (3)
Fe—Cl22.1970 (6)C6—C71.343 (3)
Fe—Cl12.1985 (7)C6—H60.9500
N1—C51.344 (3)C7—H70.9500
N1—C11.354 (3)C8—C91.386 (3)
N1—H200.89 (3)C9—C101.382 (3)
N2—C51.369 (3)C9—H90.9500
N2—C71.406 (3)C10—C111.381 (3)
N2—C81.414 (3)C10—H100.9500
N3—C121.325 (3)C11—C121.398 (3)
N3—C81.335 (3)C11—H110.9500
N4—C131.406 (3)C13—C141.347 (3)
N4—C151.408 (3)C13—H130.9500
N4—C121.409 (3)C14—C161.426 (3)
N5—C151.332 (3)C14—H140.9500
N5—C191.347 (3)C15—C161.415 (3)
C1—C21.377 (3)C16—C171.392 (3)
C1—H10.9500C17—C181.381 (4)
C2—C31.391 (3)C17—H170.9500
C2—H20.9500C18—C191.385 (3)
C3—C41.385 (3)C18—H180.9500
C3—H30.9500C19—H190.9500
Cl4—Fe—Cl3108.65 (3)N2—C7—H7124.7
Cl4—Fe—Cl2110.34 (3)N3—C8—C9124.3 (2)
Cl3—Fe—Cl2110.85 (3)N3—C8—N2114.24 (17)
Cl4—Fe—Cl1109.79 (3)C9—C8—N2121.41 (19)
Cl3—Fe—Cl1108.45 (3)C10—C9—C8116.8 (2)
Cl2—Fe—Cl1108.73 (3)C10—C9—H9121.6
C5—N1—C1118.84 (19)C8—C9—H9121.6
C5—N1—H20122.5 (16)C11—C10—C9120.4 (2)
C1—N1—H20118.7 (16)C11—C10—H10119.8
C5—N2—C7106.68 (18)C9—C10—H10119.8
C5—N2—C8126.93 (17)C10—C11—C12117.8 (2)
C7—N2—C8126.35 (18)C10—C11—H11121.1
C12—N3—C8117.69 (18)C12—C11—H11121.1
C13—N4—C15106.78 (18)N3—C12—C11123.0 (2)
C13—N4—C12123.99 (18)N3—C12—N4116.28 (18)
C15—N4—C12129.23 (18)C11—C12—N4120.7 (2)
C15—N5—C19113.84 (19)C14—C13—N4110.8 (2)
N1—C1—C2121.6 (2)C14—C13—H13124.6
N1—C1—H1119.2N4—C13—H13124.6
C2—C1—H1119.2C13—C14—C16107.4 (2)
C1—C2—C3120.5 (2)C13—C14—H14126.3
C1—C2—H2119.8C16—C14—H14126.3
C3—C2—H2119.8N5—C15—N4126.92 (19)
C4—C3—C2118.4 (2)N5—C15—C16125.7 (2)
C4—C3—H3120.8N4—C15—C16107.36 (19)
C2—C3—H3120.8C17—C16—C15118.0 (2)
C3—C4—C5118.6 (2)C17—C16—C14134.4 (2)
C3—C4—C6135.3 (2)C15—C16—C14107.6 (2)
C5—C4—C6106.0 (2)C18—C17—C16117.4 (2)
N1—C5—N2128.8 (2)C18—C17—H17121.3
N1—C5—C4122.1 (2)C16—C17—H17121.3
N2—C5—C4109.18 (18)C17—C18—C19119.4 (2)
C7—C6—C4107.6 (2)C17—C18—H18120.3
C7—C6—H6126.2C19—C18—H18120.3
C4—C6—H6126.2N5—C19—C18125.6 (2)
C6—C7—N2110.5 (2)N5—C19—H19117.2
C6—C7—H7124.7C18—C19—H19117.2
C5—N1—C1—C20.3 (3)C9—C10—C11—C120.3 (3)
N1—C1—C2—C30.4 (4)C8—N3—C12—C110.1 (3)
C1—C2—C3—C40.3 (3)C8—N3—C12—N4179.43 (16)
C2—C3—C4—C50.6 (3)C10—C11—C12—N30.7 (3)
C2—C3—C4—C6178.8 (2)C10—C11—C12—N4178.78 (19)
C1—N1—C5—N2178.7 (2)C13—N4—C12—N3178.96 (18)
C1—N1—C5—C41.2 (3)C15—N4—C12—N30.3 (3)
C7—N2—C5—N1179.8 (2)C13—N4—C12—C110.6 (3)
C8—N2—C5—N11.9 (3)C15—N4—C12—C11179.8 (2)
C7—N2—C5—C40.1 (2)C15—N4—C13—C140.1 (2)
C8—N2—C5—C4178.05 (18)C12—N4—C13—C14179.27 (19)
C3—C4—C5—N11.3 (3)N4—C13—C14—C160.4 (3)
C6—C4—C5—N1179.98 (18)C19—N5—C15—N4179.06 (19)
C3—C4—C5—N2178.61 (18)C19—N5—C15—C160.1 (3)
C6—C4—C5—N20.1 (2)C13—N4—C15—N5179.5 (2)
C3—C4—C6—C7178.1 (2)C12—N4—C15—N51.2 (3)
C5—C4—C6—C70.3 (2)C13—N4—C15—C160.2 (2)
C4—C6—C7—N20.4 (3)C12—N4—C15—C16179.56 (18)
C5—N2—C7—C60.3 (2)N5—C15—C16—C170.1 (3)
C8—N2—C7—C6178.27 (19)N4—C15—C16—C17179.19 (18)
C12—N3—C8—C91.0 (3)N5—C15—C16—C14179.7 (2)
C12—N3—C8—N2179.31 (17)N4—C15—C16—C140.4 (2)
C5—N2—C8—N33.8 (3)C13—C14—C16—C17179.0 (2)
C7—N2—C8—N3178.71 (18)C13—C14—C16—C150.5 (2)
C5—N2—C8—C9176.0 (2)C15—C16—C17—C180.1 (3)
C7—N2—C8—C91.6 (3)C14—C16—C17—C18179.4 (2)
N3—C8—C9—C101.3 (3)C16—C17—C18—C190.3 (3)
N2—C8—C9—C10178.99 (19)C15—N5—C19—C180.2 (3)
C8—C9—C10—C110.6 (3)C17—C18—C19—N50.4 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H20···N50.89 (3)2.04 (3)2.873 (3)156 (2)
C3—H3···Cl1i0.952.873.692 (2)146
C19—H19···Cl1ii0.952.883.718 (2)147
C13—H13···Cl2iii0.952.853.676 (2)146
C9—H9···Cl40.952.733.660 (2)168
Symmetry codes: (i) x+1/2, y+3/2, z1/2; (ii) x, y, z1; (iii) x+1/2, y1/2, z+3/2.
(III) [2,6-bis(1H-pyrrolo[2,3-b]pyridin-1-yl-κN7)pyridine-κN]bis(nitrato-κO)copper(II) top
Crystal data top
[Cu(NO3)2(C19H13N5)]F(000) = 1012
Mr = 498.90Dx = 1.774 Mg m3
Monoclinic, C2/cSynchrotron radiation, λ = 0.77490 Å
Hall symbol: -C 2ycCell parameters from 6914 reflections
a = 17.3858 (12) Åθ = 3.5–31.1°
b = 12.8324 (8) ŵ = 1.55 mm1
c = 8.4011 (6) ÅT = 193 K
β = 94.726 (2)°Block, light green
V = 1867.9 (2) Å30.06 × 0.04 × 0.04 mm
Z = 4
Data collection top
Bruker Platinum 200
diffractometer
2319 independent reflections
Radiation source: synchrotron2155 reflections with I > 2σ(I)
Si-<111> channel cut crystal monochromatorRint = 0.105
ω scansθmax = 31.2°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 2323
Tmin = 0.913, Tmax = 0.941k = 1717
10400 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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0999P)2]
where P = (Fo2 + 2Fc2)/3
2319 reflections(Δ/σ)max < 0.001
151 parametersΔρmax = 0.65 e Å3
0 restraintsΔρmin = 0.59 e Å3
Crystal data top
[Cu(NO3)2(C19H13N5)]V = 1867.9 (2) Å3
Mr = 498.90Z = 4
Monoclinic, C2/cSynchrotron radiation, λ = 0.77490 Å
a = 17.3858 (12) ŵ = 1.55 mm1
b = 12.8324 (8) ÅT = 193 K
c = 8.4011 (6) Å0.06 × 0.04 × 0.04 mm
β = 94.726 (2)°
Data collection top
Bruker Platinum 200
diffractometer
2319 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2155 reflections with I > 2σ(I)
Tmin = 0.913, Tmax = 0.941Rint = 0.105
10400 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 1.01Δρmax = 0.65 e Å3
2319 reflectionsΔρmin = 0.59 e Å3
151 parameters
Special details top

Experimental. A suitable crystal was mounted on a loop using paratone-N and immediately transferred to the goniostat bathed in a cold stream.

The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I).

Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely on absorption effects and crystal size.

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
Cu0.50000.24229 (2)0.25000.01959 (16)
O10.62850 (14)0.26401 (13)0.1072 (3)0.0408 (5)
O20.57340 (8)0.11953 (12)0.16803 (18)0.0331 (4)
O30.67996 (10)0.11592 (16)0.0500 (2)0.0450 (5)
N10.43589 (11)0.23703 (11)0.0466 (2)0.0230 (4)
N20.38335 (9)0.40958 (12)0.08054 (19)0.0230 (3)
N30.50000.40723 (16)0.25000.0191 (4)
N40.62831 (9)0.16708 (14)0.1063 (2)0.0267 (4)
C10.42788 (12)0.14922 (15)0.0438 (3)0.0279 (4)
H10.46300.09340.02090.033*
C20.37129 (13)0.13744 (16)0.1671 (3)0.0323 (4)
H20.36980.07560.22950.039*
C30.31621 (12)0.21463 (19)0.2019 (3)0.0305 (4)
H30.27620.20630.28500.037*
C40.32248 (11)0.30497 (16)0.1089 (2)0.0258 (4)
C50.38480 (10)0.31237 (14)0.0091 (2)0.0214 (4)
C60.28003 (12)0.40102 (18)0.1029 (3)0.0320 (5)
H60.23420.41850.16670.038*
C70.31711 (11)0.46146 (17)0.0095 (2)0.0299 (4)
H70.30120.52940.03740.036*
C80.44387 (10)0.46267 (14)0.1666 (2)0.0207 (4)
C90.44355 (12)0.57160 (14)0.1590 (2)0.0265 (4)
H90.40540.60770.09290.032*
C100.50000.6251 (2)0.25000.0288 (6)
H100.50000.69920.25000.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0197 (2)0.0155 (2)0.0231 (2)0.0000.00104 (15)0.000
O10.0446 (11)0.0331 (9)0.0441 (12)0.0063 (7)0.0005 (9)0.0064 (7)
O20.0312 (7)0.0336 (8)0.0350 (9)0.0039 (6)0.0052 (7)0.0004 (6)
O30.0387 (9)0.0606 (12)0.0367 (9)0.0283 (8)0.0095 (7)0.0039 (8)
N10.0237 (9)0.0192 (7)0.0259 (9)0.0014 (6)0.0008 (7)0.0017 (6)
N20.0221 (7)0.0225 (7)0.0239 (8)0.0056 (6)0.0012 (6)0.0009 (6)
N30.0197 (9)0.0164 (9)0.0213 (10)0.0000.0033 (8)0.000
N40.0242 (8)0.0342 (9)0.0212 (8)0.0105 (6)0.0015 (6)0.0019 (6)
C10.0305 (9)0.0203 (8)0.0322 (10)0.0008 (7)0.0023 (8)0.0031 (8)
C20.0388 (11)0.0268 (10)0.0306 (10)0.0040 (8)0.0017 (9)0.0075 (8)
C30.0285 (9)0.0355 (11)0.0264 (10)0.0041 (9)0.0047 (8)0.0010 (9)
C40.0219 (8)0.0298 (9)0.0252 (9)0.0008 (7)0.0002 (7)0.0015 (8)
C50.0204 (8)0.0218 (8)0.0221 (9)0.0009 (6)0.0024 (7)0.0002 (6)
C60.0248 (9)0.0393 (11)0.0310 (11)0.0077 (8)0.0023 (8)0.0011 (9)
C70.0263 (9)0.0330 (10)0.0300 (10)0.0110 (8)0.0001 (7)0.0009 (8)
C80.0231 (8)0.0205 (8)0.0188 (8)0.0026 (6)0.0039 (6)0.0004 (6)
C90.0340 (10)0.0200 (9)0.0260 (10)0.0065 (7)0.0056 (8)0.0023 (7)
C100.0418 (15)0.0149 (11)0.0313 (14)0.0000.0130 (12)0.000
Geometric parameters (Å, º) top
Cu—N11.963 (2)C1—H10.9500
Cu—N1i1.963 (2)C2—C31.392 (3)
Cu—N32.117 (2)C2—H20.9500
Cu—O2i2.1746 (14)C3—C41.397 (3)
Cu—O22.1746 (14)C3—H30.9500
O1—N41.244 (2)C4—C51.410 (3)
O2—N41.278 (2)C4—C61.439 (3)
O3—N41.237 (2)C6—C71.345 (3)
N1—C51.333 (2)C6—H60.9500
N1—C11.360 (2)C7—H70.9500
N2—C51.386 (2)C8—C91.399 (3)
N2—C81.403 (2)C9—C101.377 (2)
N2—C71.419 (2)C9—H90.9500
N3—C81.355 (2)C10—C9i1.377 (2)
N3—C8i1.355 (2)C10—H100.9500
C1—C21.377 (3)
N1—Cu—N1i176.05 (8)C1—C2—H2119.5
N1—Cu—N391.97 (4)C3—C2—H2119.5
N1i—Cu—N391.97 (4)C2—C3—C4116.91 (19)
N1—Cu—O2i86.84 (6)C2—C3—H3121.5
N1i—Cu—O2i90.30 (6)C4—C3—H3121.5
N3—Cu—O2i136.42 (4)C3—C4—C5117.96 (17)
N1—Cu—O290.30 (6)C3—C4—C6135.5 (2)
N1i—Cu—O286.84 (6)C5—C4—C6106.52 (18)
N3—Cu—O2136.42 (4)N1—C5—N2125.88 (18)
O2i—Cu—O287.16 (8)N1—C5—C4125.16 (18)
N4—O2—Cu105.07 (12)N2—C5—C4108.95 (15)
C5—N1—C1115.69 (19)C7—C6—C4107.50 (18)
C5—N1—Cu120.02 (14)C7—C6—H6126.2
C1—N1—Cu122.65 (14)C4—C6—H6126.2
C5—N2—C8128.38 (15)C6—C7—N2110.51 (18)
C5—N2—C7106.46 (16)C6—C7—H7124.7
C8—N2—C7122.50 (16)N2—C7—H7124.7
C8—N3—C8i116.7 (2)N3—C8—C9123.23 (18)
C8—N3—Cu121.67 (11)N3—C8—N2119.28 (16)
C8i—N3—Cu121.67 (11)C9—C8—N2117.48 (17)
O3—N4—O1122.1 (2)C10—C9—C8118.24 (19)
O3—N4—O2119.44 (19)C10—C9—H9120.9
O1—N4—O2118.47 (18)C8—C9—H9120.9
N1—C1—C2123.04 (19)C9—C10—C9i120.1 (2)
N1—C1—H1118.5C9—C10—H10119.9
C2—C1—H1118.5C9i—C10—H10119.9
C1—C2—C3121.08 (19)
N1—Cu—O2—N493.05 (13)Cu—N1—C5—N216.6 (2)
N1i—Cu—O2—N489.67 (13)C1—N1—C5—C43.5 (3)
N3—Cu—O2—N40.13 (15)Cu—N1—C5—C4162.30 (15)
O2i—Cu—O2—N4179.87 (15)C8—N2—C5—N121.6 (3)
N3—Cu—N1—C530.90 (15)C7—N2—C5—N1176.81 (19)
O2i—Cu—N1—C5105.49 (15)C8—N2—C5—C4159.28 (17)
O2—Cu—N1—C5167.37 (15)C7—N2—C5—C42.26 (19)
N3—Cu—N1—C1164.33 (16)C3—C4—C5—N14.6 (3)
O2i—Cu—N1—C159.28 (17)C6—C4—C5—N1176.72 (18)
O2—Cu—N1—C127.86 (17)C3—C4—C5—N2176.34 (16)
N1—Cu—N3—C823.00 (10)C6—C4—C5—N22.4 (2)
N1i—Cu—N3—C8157.00 (10)C3—C4—C6—C7176.8 (2)
O2i—Cu—N3—C864.49 (10)C5—C4—C6—C71.5 (2)
O2—Cu—N3—C8115.51 (10)C4—C6—C7—N20.1 (2)
N1—Cu—N3—C8i157.00 (10)C5—N2—C7—C61.3 (2)
N1i—Cu—N3—C8i23.00 (10)C8—N2—C7—C6161.57 (17)
O2i—Cu—N3—C8i115.51 (10)C8i—N3—C8—C92.47 (12)
O2—Cu—N3—C8i64.49 (10)Cu—N3—C8—C9177.53 (12)
Cu—O2—N4—O3179.42 (15)C8i—N3—C8—N2178.74 (16)
Cu—O2—N4—O10.5 (2)Cu—N3—C8—N21.25 (16)
C5—N1—C1—C20.3 (3)C5—N2—C8—N330.3 (2)
Cu—N1—C1—C2165.64 (16)C7—N2—C8—N3170.78 (14)
N1—C1—C2—C32.8 (3)C5—N2—C8—C9148.54 (17)
C1—C2—C3—C41.6 (3)C7—N2—C8—C910.4 (2)
C2—C3—C4—C51.8 (3)N3—C8—C9—C104.9 (2)
C2—C3—C4—C6180.0 (2)N2—C8—C9—C10176.34 (13)
C1—N1—C5—N2177.58 (17)C8—C9—C10—C9i2.27 (11)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O1ii0.952.393.249 (3)150
C6—H6···O3iii0.952.533.277 (3)136
C7—H7···O3iv0.952.393.141 (2)135
Symmetry codes: (ii) x+1, y+1, z; (iii) x1/2, y+1/2, z1/2; (iv) x1/2, y+1/2, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC19H13N5(C19H14N5)[FeCl4][Cu(NO3)2(C19H13N5)]
Mr311.34510.00498.90
Crystal system, space groupTriclinic, P1Monoclinic, P21/nMonoclinic, C2/c
Temperature (K)150150193
a, b, c (Å)6.6377 (2), 10.1397 (3), 21.9214 (6)6.6695 (1), 23.2657 (4), 13.3959 (2)17.3858 (12), 12.8324 (8), 8.4011 (6)
α, β, γ (°)76.609 (1), 86.563 (10), 90.004 (1)90, 100.312 (1), 9090, 94.726 (2), 90
V3)1432.56 (7)2045.07 (6)1867.9 (2)
Z444
Radiation typeCu KαCu KαSynchrotron, λ = 0.77490 Å
µ (mm1)0.7210.861.55
Crystal size (mm)0.35 × 0.10 × 0.050.19 × 0.04 × 0.020.06 × 0.04 × 0.04
Data collection
DiffractometerBruker SMART 6000 CCD
diffractometer
Bruker SMART 6000 CCD
diffractometer
Bruker Platinum 200
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.787, 0.9650.232, 0.8120.913, 0.941
No. of measured, independent and
observed [I > 2σ(I)] reflections
11609, 4847, 4215 17199, 3653, 3210 10400, 2319, 2155
Rint0.0260.0410.105
(sin θ/λ)max1)0.5990.6010.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.122, 1.06 0.029, 0.075, 1.04 0.052, 0.134, 1.01
No. of reflections484736532319
No. of parameters434266151
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.240.34, 0.250.65, 0.59

Computer programs: SMART (Bruker, 2003), APEX2 (Bruker, 2005), SAINT (Bruker, 2003), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2003), SHELXTL and DIAMOND (Brandenburg, 2007).

Selected torsion angles (º) for (I) top
C5A—N2A—C8A—N3A176.4 (2)C5B—N2B—C8B—N3B176.1 (2)
C15A—N4A—C12A—N3A178.4 (2)C15B—N4B—C12B—N3B179.4 (2)
Selected geometric parameters (Å, º) for (II) top
Fe—Cl42.1895 (7)Fe—Cl22.1970 (6)
Fe—Cl32.1949 (6)Fe—Cl12.1985 (7)
Cl4—Fe—Cl3108.65 (3)Cl4—Fe—Cl1109.79 (3)
Cl4—Fe—Cl2110.34 (3)Cl3—Fe—Cl1108.45 (3)
Cl3—Fe—Cl2110.85 (3)Cl2—Fe—Cl1108.73 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H20···N50.89 (3)2.04 (3)2.873 (3)156 (2)
C3—H3···Cl1i0.952.873.692 (2)146
C19—H19···Cl1ii0.952.883.718 (2)147
C13—H13···Cl2iii0.952.853.676 (2)146
C9—H9···Cl40.952.733.660 (2)168
Symmetry codes: (i) x+1/2, y+3/2, z1/2; (ii) x, y, z1; (iii) x+1/2, y1/2, z+3/2.
Selected geometric parameters (Å, º) for (III) top
Cu—N11.963 (2)Cu—O22.1746 (14)
Cu—N32.117 (2)
N1—Cu—N1i176.05 (8)N1i—Cu—O286.84 (6)
N1—Cu—N391.97 (4)N3—Cu—O2136.42 (4)
N1—Cu—O290.30 (6)O2i—Cu—O287.16 (8)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O1ii0.952.393.249 (3)150
C6—H6···O3iii0.952.533.277 (3)136
C7—H7···O3iv0.952.393.141 (2)135
Symmetry codes: (ii) x+1, y+1, z; (iii) x1/2, y+1/2, z1/2; (iv) x1/2, y+1/2, z.
 

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