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In N,N,N′,N′-tetra­kis(2-pyridyl­methyl)­propane-1,3-diamine, C27H30N6, (I), and N,N,N′,N′-tetra­kis(2-pyridyl­methyl)­butane-1,4-diamine, C28H32N6, (II), the twofold rotational symmetry of (I) favours the formation of a one-dimensional hydrogen-bonded polymer with two columns of C—H...N hydrogen bonds, while the inversion symmetry of (II) allows the formation of a one-dimensional hydrogen-bonded polymer stabilized by four columns of C—H...N hydrogen bonds. The possible role played by the chain length of the linking alkanediamine in determining the type of supra­molecular architecture in this series of compounds is discussed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107049293/hj3054sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107049293/hj3054Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107049293/hj3054IIsup3.hkl
Contains datablock II

CCDC references: 669200; 669201

Comment top

The tetra(pyridyl) compounds formed by the reaction of four molar equivalents of 2-picolylchloride with an α,ω-alkyldiamine are versatile bis(tridentate) ligands for the synthesis of binuclear transition metal complexes. Coordination compounds based on this ligand system were first reported by Anderegg & Wenk (1967) and later by Toftlund & Yde-Andersen (1981). More recently, the p-phenylenediamine derivative was used to synthesize various copper complexes (Buchen et al., 1997), while the m-phenylenediamine derivatives have been used to synthesize a range of copper(II), iron(II) and nickel(II) complexes (Schindler et al., 1992; Foxon et al., 2007).

Following the improved synthesis of N,N,N',N'-tetrakis(2-pyridylmethyl)-α,ω-alkyldiamines described by Sato et al. (1992), various binuclear metal complexes have been prepared. Thus, platinum(II) complexes of these ligands with varied bridging alkyl chain lengths have been used in mechanistic studies (Hoffmann & van Eldik, 2003). We have used several of these ligands for the coordination of platinum group metals in our laboratory and have obtained crystals suitable for X-ray diffraction analysis of two new metal-free derivatives, namely N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-propanediamine, (I), and N,N,N',N'-tetrakis(2-pyridylmethyl)-1,4-butanediamine, (II). The crystal structure of the 1,2-ethanediamine analogue (n = 0) was reported only quite recently by Fujihara et al. (2004).

The structure of (I) has C2 molecular point group symmetry by virtue of the location of the central C atom of the propyl chain (C1) on a twofold rotation axis (Fig. 1). The methylene groups of the structure all adopt the expected staggered (lowest energy) conformation (Munro & Camp, 2003). The C—Nsp2 and C—Nsp3 bonds in the structure (Table 1) compare favourably with those reported for the related C2 symmetry 1,2-ethanediamine analogue of (I) (Fujihara et al., 2004), but have been determined to a higher precision in the present structure. The pyridyl ring containing atom N2 is oriented at 14 (1)° relative to the mean plane of the bridging propyl group, while that containing atom N3 is in a near-orthogonal orientation [81 (1)°].

The underlying reason for the different relative orientations of the pyridyl rings is not immediately apparent from the crystal packing (Fig. 2), which reflects a rather loose interlocked arrangement of layers of (I) in which the propyl chains are all oriented in approximately the same direction as the diagonal plane perpendicular to the (101) direction. A plot of the unit-cell contents using the van der Waals radii of the atoms (not shown) clearly reflects the loose packing in this system [there are no short van der Waals contacts < Σ(van der Waals radii)]. Weak (possibly stabilizing) ππ intermolecular interactions do, however, occur in (I). Specifically, if Cg1 defines the centre of gravity of the pyridyl ring containing atom N2, then the closest symmetry-related neighbouring ring centroid is located < 6 Å away [Cg1···Cg1i = 5.057 (2) Å; symmetry code: (i) −x, 1 − y, −z]. The interplanar separation is 3.395 (2) Å with a lateral offset (or slippage) of 3.747 (2) Å. The metrics of this interaction reflect weak edge-to-edge ππ overlap (at best) for the C4—C5 π bonds in the inversion pair.

The rather intriguing relative orientations of the pyridyl rings in (I), particularly the fact that the ring containing atom N2 points in the same direction as the b axis of the unit cell, reflect the formation of pairs of C—H···N hydrogen bonds [H···N = 2.56 (2) Å and C—H···N = 145 (1)°] that run collinear with the b axis (Table 2). These unconventional hydrogen bonds lead to the formation of one-dimensional hydrogen-bonded molecular stacks in the crystal structure (Fig. 3). Similar C—H···N hydrogen bonds are observed in the 1,2-ethanediamine analogue of (I) (Fujihara et al., 2004), for which n = 0 in the scheme [mean H···N distance = 2.63 (5) Å and mean C—H···N angle = 163 (7)°]. However, as discussed below, the number of linker CH2 groups that make up the diamine core of the molecule appears to dictate rather precisely the number of hydrogen-bonded columns (i.e. the supramolecular architecture) formed in this type of system. An additional noteworthy comment for (I) is that some stabilization of the interlocked packing evident in Fig. 2, due to the formation of weak C—H···π bonds [averaging 2.91 (4) Å; Table 2] roughly orthogonal to the stacking axis of each C—H···N hydrogen-bonded column, is likely. In effect, the hydrogen-bonded columns of (I) are tethered laterally by these significant, though often overlooked, interactions (Nishio, 2004).

Compound (II) has crystallographically required inversion symmetry, with the centroid of the central CH2—CH2 bond located on the inversion centre (Fig. 4). As a result, the symmetry-unique pyridyl rings are oriented such that the pyridyl N atoms point in the same general direction (two up, two down), in marked contrast to the C2 symmetry structure of (I). The pyridyl ring containing atom N2 is oriented at 53 (1)° relative to the mean plane of the bridging butyl group, and that containing atom N3 is similarly oriented [55 (1)°]. The congruent pyridyl ring orientations for (II) directly reflect the supramolecular architecture within the system (see below), which differs significantly from that of (I). The C—N distances listed in Table 3 are, as expected, in agreement with those of the propyl-bridged analogue, (I), and the ethyl-bridged analogue reported by Fujihara et al. (2004). Interestingly, the latter structure also crystallizes in the space group P1 on a special position (Ci point group symmetry). As discussed below, the significance of the molecular symmetry is that it most likely determines the type of supramolecular structure formed in this class of compounds.

The crystal packing of the unit-cell contents for (II) is similar in principle to that observed for (I). Specifically, the molecules interlock neatly within the (011) plane and are stacked in columns perpendicular to this plane, i.e. along the a axis (Fig. 5). The crystal packing is somewhat looser for (II), however, and two inversion-related voids at general positions measuring 5.7 Å3 (probe radius = 1.0 Å) are located in the unit cell and are surrounded by pyridyl groups. (These voids are too small to accomodate a solvent but do illustrate the low-density crystal packing in this system.) A possible reason for the low-density packing within the (011) layers is the formation of hydrogen-bonded stacks along the a-axis direction (Fig. 6). It is quite probable that optimization of hydrogen bonding in the crystal structure is energetically favoured over optimization of weaker van der Waals interactions. In the case of (II), the inversion symmetry clearly facilitates the formation of one-dimensional hydrogen-bonded polymers through two pairs of inversion-related C—H···N hydrogen bonds (Table 4). The hydrogen-bonded molecular stacks are thus held together by four columns of C—H···N hydrogen bonds with interaction vectors approximately along the a-axis direction. As noted above, the C—H···N hydrogen bonds in the 1,2-diaminoethane analogue of (II) have a mean H···N distance of 2.63 (5) Å and mean C—H···N angle of 163 (7)° (Fujihara et al., 2004). The hydrogen bonding in (II) [mean H···N distance of 2.5 (1) Å and mean C—H···N angle of 166 (15)°] is therefore slightly tighter than in the 1,2-diaminoethane derivative, despite very similar angular interactions between the pyridyl rings within the hydrogen-bonded stacks. Interestingly, the C—H···N angle for (I) of 145 (1)° is significantly more acute than that for (II) and reflects a somewhat less ideal hydrogen-bonding interaction.

As with (I), there are several C—H···π intermolecular interactions in (II) which are formed between molecules within adjacent hydrogen-bonded columns (Table 4) and which average 2.79 (7) Å. These slightly weaker interactions roughly perpendicular to the direction of the C—H···N hydrogen bonds evidently further stabilize the interlocked supramolecular stacks. A significant additional packing stabilization, namely ππ interactions between the pyridyl ring containing atom N2 and the inversion-related pyridine ring of the closest neighbour, is also evident in this system. Specifically, if Cg1 defines the centre of gravity of this pyridyl ring in the asymmetric unit, then the Cg1···Cg1i interaction is 3.848 (2) Å [symmetry code: (i) −x, 2 − y, 1 − z]. The mean plane separation of the coplanar rings is 3.336 (2) Å (i.e. very similar to the graphite layer separation; Bacon, 1951) and the lateral shift or slippage is 1.917 (2) Å. In effect, two pyridyl rings overlap by exact superposition of the C5—C6 bond of one molecule with the C6—C5 bond of the second through a centre of inversion mid-way between the planes passing through each bond.

Finally, it is intriguing to note that exactly the same supramolecular architecture observed for (II) (i.e. four C—H···N hydrogen-bonded columns) occurs in the Ci symmetry 1,2-ethanediamine analogue (Fujihara et al., 2004), while the C2 symmetry propyl-bridged derivative, (I), exhibits one-dimensional stacks based on only two columns of hydrogen bonds. Clearly, the number of methylene groups of the linking diamine core in these compounds affects the type of hydrogen-bonded stack that may be formed. Although based on relatively few data at present, a possible trend is that an even number of linking CH2 groups favours hydrogen-bonded stacks with four columns of hydrogen bonds due to the Ci symmetry of the constituent monomers.

Experimental top

Compounds (I) and (II) were synthesized following the literature method of Sato et al. (1992). Colourless crystals (X-ray quality) were obtained from solutions in ethanol by slow evaporation of the solvent over several days.

Spectroscopic data for (I): 1H NMR (500 MHz, D2O spiked with DCl, δ, p.p.m.): 8.60 (d, 4H), 8.38 (t, 4H), 7.94 (d, 4H), 7.82 (t, 4H), 4.20 (s, 8H), 2.50 (t, 4H), 1.71 (m, 2H); 13C NMR (125 MHz, D2O spiked with DCl, δ, p.p.m.): 23.0, 52.5, 55.0, 127.1, 128.0, 128.0, 145.0, 148.0, 154.0; CHN analysis, calculated for C27H30N6: C 73.94, H 6.89, N 19.17%; found: C 74.08, H 6.96, N 19.17%; MS–ES+ m/e: 439.2453 (M + 1)+, 461.2428 (M + Na)+.

Spectroscopic data for (II): 1H NMR (500 MHz, CD3OD, δ, p.p.m.): 8.41 (d, 4H), 7.77 (td, 4H), 7.58 (d, 4H), 7.26 (tt, 4H), 3.31 (m, 8H), 2.45 (s, br, 4H), 1.49 (m, 4H); CHN analysis, calculated for C28H32N6: C 74.30, H 7.13, N 18.57%; found: C 74.30, H 7.13, N 18.53%; MS–ES+ m/e: 453.2199 (M + 1)+, 475.2120 (M + Na)+.

Refinement top

All H atoms were located in a final difference Fourier map and refined isotropically without restraints.

Computing details top

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A plot of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 60% probability level. H atoms are shown only as the intersections and endpoints of bonds represented as cylinders. Unlabelled atoms are related to labelled atoms by the symmetry operator (−x, y, −z + 1/2). [Please check added text]
[Figure 2] Fig. 2. The unit-cell contents for (I), viewed approximately down the b axis. H atoms have been omitted for clarity; all other atoms are shown only as the intersections and endpoints of bonds represented as cylinders.
[Figure 3] Fig. 3. A view of (I), illustrating a single one-dimensional hydrogen-bonded stack of molecules running collinear with the b axis of the unit cell. The symmetry-unique hydrogen-bond distance (in Å) is shown. [Symmetry code: (i) x, 1 + y, z.]
[Figure 4] Fig. 4. A plot of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 60% probability level. H atoms are shown only as the intersections and endpoints of bonds represented as cylinders. Unlabelled atoms are related to labelled atoms by the symmetry operator (2 − x, −y, −z). [Please check added text]
[Figure 5] Fig. 5. The unit-cell contents for (II), viewed approximately down the a axis. H atoms have been omitted for clarity; all other atoms are shown only as the intersections and endpoints of bonds represented as cylinders.
[Figure 6] Fig. 6. A view of (II), illustrating a single one-dimensional hydrogen-bonded stack of molecules running collinear with the a axis of the unit cell. The symmetry-unique hydrogen-bond distances (in Å) are shown. [Symmetry code: (i) −1 + x, y, z.]
(I) N,N,N',N'-tetrakis(2-pyridylmethyl)propane-1,3-diamine top
Crystal data top
C27H30N6F(000) = 936
Mr = 438.57Dx = 1.202 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4212 reflections
a = 24.615 (3) Åθ = 3.8–31.9°
b = 6.0114 (11) ŵ = 0.07 mm1
c = 17.1066 (19) ÅT = 293 K
β = 106.702 (10)°Rhomb, colourless
V = 2424.4 (6) Å30.6 × 0.4 × 0.3 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur2 CCD
diffractometer
2270 reflections with I > 2σ(I)
ω/2θ' scansRint = 0.020
Absorption correction: multi-scan
empirical (using intensity measurements) absorption correction using spherical harmonics (CrysAlis RED; Oxford Diffraction, 2006)
θmax = 31.8°, θmin = 3.8°
Tmin = 0.945, Tmax = 0.973h = 3634
11733 measured reflectionsk = 87
3834 independent reflectionsl = 2424
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.041 w = 1/[σ2(Fo2) + (0.0612P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.111(Δ/σ)max < 0.001
S = 0.99Δρmax = 0.21 e Å3
3834 reflectionsΔρmin = 0.17 e Å3
210 parameters
Crystal data top
C27H30N6V = 2424.4 (6) Å3
Mr = 438.57Z = 4
Monoclinic, C2/cMo Kα radiation
a = 24.615 (3) ŵ = 0.07 mm1
b = 6.0114 (11) ÅT = 293 K
c = 17.1066 (19) Å0.6 × 0.4 × 0.3 mm
β = 106.702 (10)°
Data collection top
Oxford Diffraction Xcalibur2 CCD
diffractometer
3834 independent reflections
Absorption correction: multi-scan
empirical (using intensity measurements) absorption correction using spherical harmonics (CrysAlis RED; Oxford Diffraction, 2006)
2270 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.973Rint = 0.020
11733 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.111All H-atom parameters refined
S = 0.99Δρmax = 0.21 e Å3
3834 reflectionsΔρmin = 0.17 e Å3
210 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C100.1036 (3)0.250.0551 (4)
C20.03464 (4)0.03968 (18)0.20777 (6)0.0390 (2)
C30.03637 (4)0.22770 (19)0.10117 (6)0.0416 (2)
C40.06879 (4)0.31329 (16)0.04474 (5)0.0356 (2)
C50.08145 (4)0.53778 (18)0.04144 (7)0.0449 (3)
C60.11086 (5)0.6086 (2)0.01185 (8)0.0549 (3)
C70.12658 (5)0.4560 (2)0.06086 (7)0.0531 (3)
C80.11214 (5)0.2371 (2)0.05432 (7)0.0514 (3)
C90.11736 (4)0.20198 (18)0.22258 (6)0.0386 (2)
C100.16314 (4)0.05196 (16)0.27434 (6)0.0358 (2)
C110.17418 (4)0.15789 (18)0.24891 (7)0.0464 (3)
C120.21837 (5)0.2823 (2)0.29844 (9)0.0581 (3)
C130.25048 (5)0.1912 (2)0.37108 (9)0.0655 (4)
C140.23698 (5)0.0180 (3)0.39186 (8)0.0661 (4)
N10.07053 (3)0.08069 (13)0.16600 (5)0.0362 (2)
N20.08379 (4)0.16204 (14)0.00322 (5)0.0454 (2)
N30.19398 (4)0.14097 (16)0.34567 (5)0.0510 (2)
H1A0.0270 (6)0.203 (3)0.2936 (9)0.094 (5)*
H2A0.0600 (5)0.1444 (18)0.2496 (7)0.050 (3)*
H2B0.0089 (5)0.1360 (18)0.1658 (7)0.045 (3)*
H3A0.0032 (5)0.1409 (18)0.0691 (7)0.051 (3)*
H3B0.0214 (5)0.3650 (18)0.1256 (7)0.052 (3)*
H50.0700 (5)0.642 (2)0.0763 (8)0.058 (3)*
H60.1192 (6)0.766 (3)0.0141 (8)0.071 (4)*
H70.1467 (5)0.498 (2)0.0980 (8)0.068 (4)*
H80.1210 (5)0.121 (2)0.0893 (8)0.068 (4)*
H9A0.1357 (4)0.2966 (18)0.1899 (7)0.047 (3)*
H9B0.1041 (4)0.3047 (18)0.2614 (7)0.045 (3)*
H110.1508 (5)0.2103 (19)0.1972 (8)0.053 (3)*
H120.2244 (6)0.428 (2)0.2791 (8)0.075 (4)*
H130.2821 (6)0.274 (3)0.4083 (9)0.091 (5)*
H140.2595 (7)0.089 (2)0.4459 (10)0.086 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0604 (10)0.0573 (10)0.0631 (10)00.0427 (9)0
C20.0348 (5)0.0474 (6)0.0384 (5)0.0027 (4)0.0162 (4)0.0009 (5)
C30.0329 (5)0.0561 (6)0.0367 (5)0.0058 (5)0.0116 (4)0.0040 (5)
C40.0321 (5)0.0414 (5)0.0312 (4)0.0043 (4)0.0058 (3)0.0004 (4)
C50.0456 (6)0.0391 (6)0.0478 (6)0.0082 (4)0.0098 (5)0.0014 (5)
C60.0523 (7)0.0408 (6)0.0680 (8)0.0003 (5)0.0115 (6)0.0165 (6)
C70.0494 (6)0.0649 (8)0.0479 (6)0.0017 (6)0.0186 (5)0.0175 (6)
C80.0613 (7)0.0566 (7)0.0433 (6)0.0012 (5)0.0260 (5)0.0033 (5)
C90.0341 (5)0.0426 (5)0.0386 (5)0.0001 (4)0.0095 (4)0.0003 (4)
C100.0285 (4)0.0442 (5)0.0367 (5)0.0023 (4)0.0126 (4)0.0014 (4)
C110.0362 (5)0.0487 (6)0.0541 (6)0.0013 (4)0.0126 (5)0.0057 (5)
C120.0430 (6)0.0484 (7)0.0857 (9)0.0067 (5)0.0230 (6)0.0056 (6)
C130.0436 (7)0.0773 (9)0.0694 (8)0.0137 (6)0.0062 (6)0.0200 (7)
C140.0505 (7)0.0891 (10)0.0486 (7)0.0087 (7)0.0017 (6)0.0009 (7)
N10.0285 (4)0.0478 (5)0.0333 (4)0.0002 (3)0.0107 (3)0.0024 (3)
N20.0553 (5)0.0421 (5)0.0440 (5)0.0038 (4)0.0224 (4)0.0045 (4)
N30.0426 (5)0.0639 (6)0.0424 (5)0.0042 (4)0.0056 (4)0.0059 (4)
Geometric parameters (Å, º) top
C1—C2i1.5314 (14)C7—H70.945 (13)
C1—C21.5314 (14)C8—N21.3436 (13)
C1—H1A1.034 (15)C8—H80.984 (14)
C2—N11.4757 (12)C9—N11.4682 (12)
C2—H2A1.020 (12)C9—C101.5144 (13)
C2—H2B0.995 (11)C9—H9A0.992 (11)
C3—N11.4772 (13)C9—H9B1.027 (11)
C3—C41.5086 (13)C10—N31.3488 (13)
C3—H3A0.992 (12)C10—C111.3865 (15)
C3—H3B1.039 (12)C11—C121.3896 (16)
C4—N21.3455 (12)C11—H110.959 (13)
C4—C51.3899 (15)C12—C131.3801 (19)
C5—C61.3840 (16)C12—H120.960 (14)
C5—H50.960 (13)C13—C141.373 (2)
C6—C71.3718 (18)C13—H130.986 (16)
C6—H60.972 (15)C14—N31.3454 (15)
C7—C81.3756 (17)C14—H141.025 (16)
C2i—C1—C2111.53 (14)N2—C8—H8113.9 (8)
C2i—C1—H1A108.3 (8)C7—C8—H8121.4 (8)
C2—C1—H1A109.6 (8)N1—C9—C10113.64 (8)
N1—C2—C1116.40 (10)N1—C9—H9A108.2 (6)
N1—C2—H2A108.2 (6)C10—C9—H9A106.8 (6)
C1—C2—H2A109.1 (6)N1—C9—H9B112.9 (6)
N1—C2—H2B106.4 (6)C10—C9—H9B107.6 (6)
C1—C2—H2B110.0 (6)H9A—C9—H9B107.5 (9)
H2A—C2—H2B106.3 (9)N3—C10—C11122.32 (9)
N1—C3—C4113.12 (7)N3—C10—C9115.06 (8)
N1—C3—H3A107.5 (6)C11—C10—C9122.57 (9)
C4—C3—H3A109.2 (7)C10—C11—C12119.22 (11)
N1—C3—H3B111.4 (6)C10—C11—H11117.9 (7)
C4—C3—H3B107.5 (6)C12—C11—H11122.9 (7)
H3A—C3—H3B107.9 (9)C13—C12—C11118.72 (12)
N2—C4—C5121.82 (9)C13—C12—H12124.4 (8)
N2—C4—C3116.62 (9)C11—C12—H12116.8 (8)
C5—C4—C3121.55 (9)C14—C13—C12118.56 (11)
C6—C5—C4119.44 (10)C14—C13—H13119.9 (10)
C6—C5—H5120.6 (7)C12—C13—H13121.6 (10)
C4—C5—H5119.9 (7)N3—C14—C13124.00 (12)
C7—C6—C5119.30 (11)N3—C14—H14115.5 (8)
C7—C6—H6121.8 (8)C13—C14—H14120.5 (8)
C5—C6—H6118.9 (8)C9—N1—C2112.96 (8)
C6—C7—C8117.73 (11)C9—N1—C3111.56 (8)
C6—C7—H7121.8 (8)C2—N1—C3111.47 (7)
C8—C7—H7120.5 (8)C8—N2—C4117.03 (9)
N2—C8—C7124.67 (11)C14—N3—C10117.17 (10)
C2i—C1—C2—N1179.05 (10)C12—C13—C14—N30.2 (2)
N1—C3—C4—N267.15 (11)C10—C9—N1—C270.39 (10)
N1—C3—C4—C5114.10 (11)C10—C9—N1—C3163.12 (8)
N2—C4—C5—C60.74 (15)C1—C2—N1—C966.74 (10)
C3—C4—C5—C6179.42 (9)C1—C2—N1—C359.81 (10)
C4—C5—C6—C70.48 (16)C4—C3—N1—C965.75 (11)
C5—C6—C7—C80.07 (17)C4—C3—N1—C2166.94 (8)
C6—C7—C8—N20.11 (18)C7—C8—N2—C40.12 (17)
N1—C9—C10—N3155.42 (8)C5—C4—N2—C80.55 (14)
N1—C9—C10—C1127.15 (13)C3—C4—N2—C8179.30 (9)
N3—C10—C11—C120.24 (16)C13—C14—N3—C100.86 (19)
C9—C10—C11—C12177.48 (10)C11—C10—N3—C140.64 (15)
C10—C11—C12—C130.94 (17)C9—C10—N3—C14176.79 (10)
C11—C12—C13—C140.74 (19)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N2ii0.97 (2)2.56 (2)3.404 (2)145 (1)
C8—H8···Cg2iii0.98 (1)2.94 (1)3.700 (2)135 (1)
C12—H12···Cg2iv0.96 (1)2.88 (1)3.586 (2)131 (1)
Symmetry codes: (ii) x, y+1, z; (iii) x, y, z1/2; (iv) x+1/2, y1/2, z+1/2.
(II) N,N,N',N'-tetrakis(2-pyridylmethyl)butane-1,4-diamine top
Crystal data top
C28H32N6Z = 1
Mr = 452.6F(000) = 242
Triclinic, P1Dx = 1.218 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.1942 (3) ÅCell parameters from 6130 reflections
b = 9.2425 (3) Åθ = 3.5–33.9°
c = 11.6798 (5) ŵ = 0.07 mm1
α = 101.756 (3)°T = 100 K
β = 96.953 (4)°Thick plate, colourless
γ = 106.289 (4)°0.5 × 0.4 × 0.2 mm
V = 616.96 (5) Å3
Data collection top
Oxford Diffraction Xcalibur2 CCD
diffractometer
3241 reflections with I > 2σ(I)
ω/2θ scansRint = 0.020
Absorption correction: multi-scan
empirical (using intensity measurements) absorption correction using spherical harmonics (CrysAlis RED; Oxford Diffraction, 2006)
θmax = 34.0°, θmin = 3.6°
Tmin = 0.945, Tmax = 0.983h = 89
9960 measured reflectionsk = 1413
4227 independent reflectionsl = 1718
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.045 w = 1/[σ2(Fo2) + (0.1013P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.139(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.51 e Å3
4227 reflectionsΔρmin = 0.27 e Å3
218 parameters
Crystal data top
C28H32N6γ = 106.289 (4)°
Mr = 452.6V = 616.96 (5) Å3
Triclinic, P1Z = 1
a = 6.1942 (3) ÅMo Kα radiation
b = 9.2425 (3) ŵ = 0.07 mm1
c = 11.6798 (5) ÅT = 100 K
α = 101.756 (3)°0.5 × 0.4 × 0.2 mm
β = 96.953 (4)°
Data collection top
Oxford Diffraction Xcalibur2 CCD
diffractometer
4227 independent reflections
Absorption correction: multi-scan
empirical (using intensity measurements) absorption correction using spherical harmonics (CrysAlis RED; Oxford Diffraction, 2006)
3241 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.983Rint = 0.020
9960 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.139All H-atom parameters refined
S = 1.02Δρmax = 0.51 e Å3
4227 reflectionsΔρmin = 0.27 e Å3
218 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.87861 (15)0.00048 (10)0.00591 (8)0.01689 (18)
C20.73069 (15)0.01230 (10)0.11180 (8)0.01632 (17)
C30.70889 (15)0.06927 (10)0.29429 (8)0.01621 (17)
C40.77234 (14)0.05903 (10)0.37091 (7)0.01496 (17)
C51.00079 (15)0.05395 (10)0.36452 (8)0.01618 (17)
C61.05392 (16)0.16940 (11)0.44113 (8)0.01828 (18)
C70.87743 (17)0.28621 (12)0.52090 (9)0.0230 (2)
C80.65573 (18)0.28353 (13)0.52117 (10)0.0278 (2)
C90.81079 (16)0.26152 (10)0.10755 (8)0.01667 (17)
C100.95777 (15)0.39319 (9)0.14940 (7)0.01498 (17)
C111.19356 (16)0.42026 (11)0.13810 (8)0.01878 (18)
C121.32435 (16)0.54041 (11)0.17909 (8)0.02066 (19)
C131.21481 (16)0.63050 (10)0.23023 (8)0.01931 (19)
C140.98061 (16)0.59657 (10)0.23707 (8)0.01879 (18)
N10.82702 (12)0.11135 (8)0.17002 (6)0.01422 (15)
N20.60084 (14)0.17227 (10)0.44725 (7)0.02344 (19)
N30.85111 (13)0.48060 (9)0.19789 (7)0.01747 (17)
H1A0.798 (2)0.0940 (15)0.0365 (11)0.024 (3)*
H1B0.884 (2)0.0915 (15)0.0655 (11)0.022 (3)*
H2A0.7176 (19)0.1124 (13)0.1645 (10)0.015 (3)*
H2B0.570 (2)0.0168 (15)0.0987 (11)0.024 (3)*
H3A0.7539 (19)0.1644 (14)0.3292 (10)0.021 (3)*
H3B0.535 (2)0.0357 (14)0.3021 (11)0.023 (3)*
H51.119 (2)0.0295 (16)0.3118 (12)0.028 (3)*
H61.214 (2)0.1659 (14)0.4404 (11)0.022 (3)*
H70.906 (2)0.3698 (16)0.5767 (12)0.029 (3)*
H80.526 (2)0.3655 (17)0.5761 (12)0.031 (3)*
H9A0.871 (2)0.2793 (15)0.0191 (12)0.024 (3)*
H9B0.647 (2)0.2652 (14)0.1204 (10)0.018 (3)*
H111.270 (2)0.3527 (14)0.1017 (12)0.023 (3)*
H121.490 (2)0.5575 (16)0.1701 (12)0.032 (3)*
H131.301 (2)0.7165 (15)0.2597 (11)0.026 (3)*
H140.899 (2)0.6610 (15)0.2710 (11)0.026 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0190 (4)0.0163 (4)0.0167 (4)0.0053 (3)0.0056 (3)0.0061 (3)
C20.0160 (4)0.0132 (4)0.0189 (4)0.0022 (3)0.0044 (3)0.0049 (3)
C30.0161 (4)0.0164 (4)0.0155 (4)0.0063 (3)0.0012 (3)0.0020 (3)
C40.0151 (4)0.0143 (4)0.0150 (4)0.0042 (3)0.0027 (3)0.0032 (3)
C50.0148 (4)0.0156 (4)0.0165 (4)0.0035 (3)0.0014 (3)0.0032 (3)
C60.0183 (4)0.0210 (4)0.0186 (4)0.0088 (3)0.0060 (3)0.0066 (3)
C70.0254 (5)0.0216 (4)0.0211 (4)0.0094 (4)0.0055 (4)0.0004 (3)
C80.0209 (5)0.0239 (5)0.0282 (5)0.0043 (4)0.0002 (4)0.0094 (4)
C90.0198 (4)0.0129 (4)0.0175 (4)0.0054 (3)0.0059 (3)0.0025 (3)
C100.0166 (4)0.0115 (3)0.0154 (4)0.0039 (3)0.0031 (3)0.0010 (3)
C110.0173 (4)0.0166 (4)0.0222 (4)0.0061 (3)0.0021 (3)0.0044 (3)
C120.0157 (4)0.0190 (4)0.0238 (4)0.0025 (3)0.0028 (3)0.0023 (3)
C130.0203 (4)0.0135 (4)0.0205 (4)0.0008 (3)0.0039 (3)0.0025 (3)
C140.0215 (4)0.0141 (4)0.0203 (4)0.0052 (3)0.0027 (3)0.0046 (3)
N10.0171 (3)0.0109 (3)0.0137 (3)0.0035 (3)0.0027 (3)0.0022 (2)
N20.0158 (4)0.0221 (4)0.0253 (4)0.0034 (3)0.0011 (3)0.0044 (3)
N30.0180 (3)0.0146 (3)0.0199 (4)0.0053 (3)0.0032 (3)0.0045 (3)
Geometric parameters (Å, º) top
C1—C21.5229 (12)C7—H70.977 (14)
C1—C1i1.5244 (17)C8—N21.3506 (13)
C1—H1A1.026 (13)C8—H80.984 (15)
C1—H1B0.972 (13)C9—N11.4671 (11)
C2—N11.4687 (10)C9—C101.5091 (11)
C2—H2A0.977 (12)C9—H9A1.018 (13)
C2—H2B1.015 (12)C9—H9B1.019 (12)
C3—N11.4651 (11)C10—N31.3435 (11)
C3—C41.5085 (12)C10—C111.3957 (12)
C3—H3A1.026 (12)C11—C121.3872 (13)
C3—H3B1.018 (12)C11—H111.009 (12)
C4—N21.3363 (12)C12—C131.3899 (13)
C4—C51.3950 (12)C12—H120.983 (13)
C5—C61.3881 (12)C13—C141.3841 (13)
C5—H50.945 (14)C13—H130.976 (13)
C6—C71.3821 (14)C14—N31.3447 (11)
C6—H60.984 (12)C14—H140.992 (13)
C7—C81.3801 (15)
C2—C1—C1i112.98 (9)N2—C8—C7123.47 (9)
C2—C1—H1A106.9 (7)N2—C8—H8115.6 (8)
C1i—C1—H1A110.2 (7)C7—C8—H8121.0 (8)
C2—C1—H1B110.7 (7)N1—C9—C10110.95 (7)
C1i—C1—H1B109.7 (8)N1—C9—H9A108.2 (7)
H1A—C1—H1B106.0 (10)C10—C9—H9A107.7 (7)
N1—C2—C1113.85 (7)N1—C9—H9B112.1 (7)
N1—C2—H2A108.4 (7)C10—C9—H9B108.0 (7)
C1—C2—H2A106.7 (6)H9A—C9—H9B109.8 (10)
N1—C2—H2B111.8 (7)N3—C10—C11122.38 (8)
C1—C2—H2B109.1 (7)N3—C10—C9117.05 (8)
H2A—C2—H2B106.6 (10)C11—C10—C9120.57 (7)
N1—C3—C4112.34 (7)C12—C11—C10119.46 (8)
N1—C3—H3A109.3 (6)C12—C11—H11119.6 (7)
C4—C3—H3A107.3 (7)C10—C11—H11121.0 (7)
N1—C3—H3B112.2 (7)C11—C12—C13118.45 (9)
C4—C3—H3B108.5 (7)C11—C12—H12118.1 (8)
H3A—C3—H3B107.0 (9)C13—C12—H12123.5 (8)
N2—C4—C5122.54 (8)C14—C13—C12118.36 (8)
N2—C4—C3116.67 (8)C14—C13—H13120.8 (7)
C5—C4—C3120.74 (8)C12—C13—H13120.9 (7)
C6—C5—C4119.15 (8)N3—C14—C13124.01 (8)
C6—C5—H5119.9 (8)N3—C14—H14116.0 (7)
C4—C5—H5120.8 (8)C13—C14—H14120.0 (7)
C7—C6—C5118.58 (8)C3—N1—C9110.03 (7)
C7—C6—H6120.9 (7)C3—N1—C2109.96 (7)
C5—C6—H6120.5 (7)C9—N1—C2111.55 (7)
C8—C7—C6118.77 (9)C4—N2—C8117.49 (8)
C8—C7—H7119.6 (8)C10—N3—C14117.33 (8)
C6—C7—H7121.6 (8)
C1i—C1—C2—N156.58 (12)C12—C13—C14—N30.48 (14)
N1—C3—C4—N2136.20 (8)C4—C3—N1—C9164.47 (7)
N1—C3—C4—C546.42 (10)C4—C3—N1—C272.29 (9)
N2—C4—C5—C60.85 (13)C10—C9—N1—C371.12 (9)
C3—C4—C5—C6176.36 (8)C10—C9—N1—C2166.57 (7)
C4—C5—C6—C70.34 (12)C1—C2—N1—C3165.15 (7)
C5—C6—C7—C80.06 (14)C1—C2—N1—C972.50 (9)
C6—C7—C8—N20.00 (17)C5—C4—N2—C80.90 (14)
N1—C9—C10—N3120.23 (8)C3—C4—N2—C8176.42 (8)
N1—C9—C10—C1159.36 (10)C7—C8—N2—C40.48 (16)
N3—C10—C11—C120.65 (13)C11—C10—N3—C140.60 (13)
C9—C10—C11—C12178.91 (8)C9—C10—N3—C14178.97 (7)
C10—C11—C12—C130.11 (14)C13—C14—N3—C100.04 (13)
C11—C12—C13—C140.42 (13)
Symmetry code: (i) x+2, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N2ii0.98 (1)2.42 (1)3.405 (1)177 (1)
C12—H12···N3ii0.98 (1)2.57 (2)3.484 (1)155 (1)
C7—H7···Cg2iii0.98 (1)2.79 (2)3.663 (1)149 (1)
C9—H9A···Cg2iv1.02 (1)2.72 (2)3.545 (1)139 (1)
C14—H14···Cg1v0.99 (1)2.86 (2)3.756 (1)151 (1)
Symmetry codes: (ii) x+1, y, z; (iii) x, y+2, z+1; (iv) x, y+1, z; (v) x, y1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC27H30N6C28H32N6
Mr438.57452.6
Crystal system, space groupMonoclinic, C2/cTriclinic, P1
Temperature (K)293100
a, b, c (Å)24.615 (3), 6.0114 (11), 17.1066 (19)6.1942 (3), 9.2425 (3), 11.6798 (5)
α, β, γ (°)90, 106.702 (10), 90101.756 (3), 96.953 (4), 106.289 (4)
V3)2424.4 (6)616.96 (5)
Z41
Radiation typeMo KαMo Kα
µ (mm1)0.070.07
Crystal size (mm)0.6 × 0.4 × 0.30.5 × 0.4 × 0.2
Data collection
DiffractometerOxford Diffraction Xcalibur2 CCD
diffractometer
Oxford Diffraction Xcalibur2 CCD
diffractometer
Absorption correctionMulti-scan
empirical (using intensity measurements) absorption correction using spherical harmonics (CrysAlis RED; Oxford Diffraction, 2006)
Multi-scan
empirical (using intensity measurements) absorption correction using spherical harmonics (CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.945, 0.9730.945, 0.983
No. of measured, independent and
observed [I > 2σ(I)] reflections
11733, 3834, 2270 9960, 4227, 3241
Rint0.0200.020
(sin θ/λ)max1)0.7410.787
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.111, 0.99 0.045, 0.139, 1.02
No. of reflections38344227
No. of parameters210218
H-atom treatmentAll H-atom parameters refinedAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.21, 0.170.51, 0.27

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) for (I) top
C2—N11.4757 (12)C9—N11.4682 (12)
C3—N11.4772 (13)C10—N31.3488 (13)
C4—N21.3455 (12)C14—N31.3454 (15)
C8—N21.3436 (13)
C9—N1—C2112.96 (8)C8—N2—C4117.03 (9)
C9—N1—C3111.56 (8)C14—N3—C10117.17 (10)
C2—N1—C3111.47 (7)
N1—C3—C4—N267.15 (11)N1—C9—C10—N3155.42 (8)
N1—C3—C4—C5114.10 (11)N1—C9—C10—C1127.15 (13)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N2i0.97 (2)2.56 (2)3.404 (2)145 (1)
C8—H8···Cg2ii0.98 (1)2.94 (1)3.700 (2)135 (1)
C12—H12···Cg2iii0.96 (1)2.88 (1)3.586 (2)131 (1)
Symmetry codes: (i) x, y+1, z; (ii) x, y, z1/2; (iii) x+1/2, y1/2, z+1/2.
Selected geometric parameters (Å, º) for (II) top
C2—N11.4687 (10)C9—N11.4671 (11)
C3—N11.4651 (11)C10—N31.3435 (11)
C4—N21.3363 (12)C14—N31.3447 (11)
C8—N21.3506 (13)
C3—N1—C9110.03 (7)C4—N2—C8117.49 (8)
C3—N1—C2109.96 (7)C10—N3—C14117.33 (8)
C9—N1—C2111.55 (7)
C1i—C1—C2—N156.58 (12)N1—C9—C10—N3120.23 (8)
N1—C3—C4—N2136.20 (8)N1—C9—C10—C1159.36 (10)
N1—C3—C4—C546.42 (10)
Symmetry code: (i) x+2, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N2ii0.98 (1)2.42 (1)3.405 (1)177 (1)
C12—H12···N3ii0.98 (1)2.57 (2)3.484 (1)155 (1)
C7—H7···Cg2iii0.98 (1)2.79 (2)3.663 (1)149 (1)
C9—H9A···Cg2iv1.02 (1)2.72 (2)3.545 (1)139 (1)
C14—H14···Cg1v0.99 (1)2.86 (2)3.756 (1)151 (1)
Symmetry codes: (ii) x+1, y, z; (iii) x, y+2, z+1; (iv) x, y+1, z; (v) x, y1, z.
 

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