Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027857/lh2420sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027857/lh2420Isup2.hkl |
CCDC reference: 654940
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.042
- wR factor = 0.132
- Data-to-parameter ratio = 11.0
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............ 23.26 Deg.
Author Response: The low theta value is because the crystals did not diffract to higher resolution than that. Originally, the data were processed to 0.85\%A resolution (24.71\% in \q) but the signal to noise ratio (I/s) between 0.90-0.85\%A was very low. So the data was cut to 0.90\%A resolution (23.26 in \q) |
Alert level B THETM01_ALERT_3_B The value of sine(theta_max)/wavelength is less than 0.575 Calculated sin(theta_max)/wavelength = 0.5556 PLAT023_ALERT_3_B Resolution (too) Low [sin(th)/Lambda < 0.6]..... 23.26 Deg.
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N37 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C42 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C39 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT355_ALERT_3_C Long O-H Bond (0.82A) O2W - H2W2 ... 1.02 Ang. PLAT481_ALERT_4_C Long D...A H-Bond Reported C1 .. CG2 .. 4.11 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C25 H28 N4 O2 Atom count from _chemical_formula_moiety:C25 H30 N4 O2 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
1 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For a detailed account of the synthetic methodology of the anhydrous form, L2, of the title compound, L2.2H2O, see Keegan et al. (2001), and for its metal complexes, see: Yoshida & Ichikawa (1997); Hannon et al. (1997); He et al. (2000); Keegan et al. (2002).
For related literature, see: Bernstein et al. (1995); Desiraju (1989); Desiraju & Steiner (1999); Etter (1990); Jodry & Lacour (2000); Kruger et al. (2001).
The anhydrous analogue of the title compound, L2, was prepared by reported methods (Keegan et al., 2001). An attempted synthesis of a Pt(II) complex of L2 resulted in the title compound, L2.2H2O, whose details are given below. Potassium tetrachloroplatinate(II) (0.5 g, 1.2 mmol) dissolved in 6 ml of deionized water by gentle heating was added dropwise to 10 ml solution of L2 (0.23 g, 0.6 mmol) in THF dropwise under a N2 atmosphere. The orange-red suspension formed was stirred under a N2 atmosphere and then filtered. The filtrate was allowed to evaporate slowly at room temperature to yield yellow crystals of the title compound.
The methylene and phenyl H atoms were included in calculated positions with C—H distances at 0.97 & 0.93 Å, respectively, and refined by a riding model. The hydrogen atoms of two water molecules were located from the difference map and refined. The thermal parameters of all H-atoms were obtained as 1.2Ueq of the respective carrier atoms.
The self assembly of highly ordered molecular structures from small components is of much current interest with applications in areas such as fabrication of nanoscale devices and molecular machinery. An example of such self assembly is the formation of double- or triple-helical architectures (Jodry & Lacour, 2000) from multidentate organic ligands and their metal complexes (Yoshida & Ichikawa, 1997, Hannon et al., 1997, He et al., 2000, Keegan et al., 2002). The design of these structures usually involves suitably compartmentalized ligands, which are capable of forming weak π···π interactions between their aromatic rings (Kruger et al., 2001). This paper reports the molecular and supramolecular architecture of the title compound which displays several of these and other interactions.
The molecular structure of the title compound, L2.2H2O, is shown in Fig. 1 and selected geometric parameters are given in Table 1. The N17—C18 & N37—C38 distances are consistent with C—N single bonds whereas the C14—N17 & C34—N37 bond distances are shorter than those expected for C—N single bonds. However, the C14—N17—C18 & C34—N37—C38 bond angles are considerably larger than expected for sp3 hybridized nitrogen atoms, which may suggest a possible interaction between the lone pair on nitrogen and the aromatic cloud of the attached phenyl ring, thereby suggesting considerable sp2 character for these nitrogen atoms. This is further confirmed by the sum of the bond angles around the two aliphatic nitrogen atoms, N17 & N37 [359.5 (2)].
Any two adjacent pairs of rings are non-coplanar as confirmed by their interplanar angles, cg1 & cg3, 80.55 (8)°, cg3 & cg4, 78.54 (7)° and cg2 & cg4, 83.44 (9)°. The two pyridyl rings are also relatively non-coplanar as shown by their interplanar angle (cg1 & cg2, 80.6 (1)°). The interplanar angles between cg1 & cg4 is 3.2 (1)° and cg2 & cg3 is 31.7 (8)°. The pyridyl and phenyl rings (cg1 & cg3 and cg2 & cg4) show significant deviation from coplanarity due to a twist in the molecule as reflected in the torsion angles, C14—N17—C18—C19 and C34—N37—C38—C39. cg1, cg2, cg3 and cg4 refer to C19/N20/C21/C22/C23/C24, C39/N40/C41/C42/C43/C44, C11—C16 and C31—C36 rings, respectively.
The crystal structure of L2.2H2O is stabilized by the interplay of O—H···O, N—H···O, O—H···N, C—H···π (Table 2), π···π and van der Waals interactions. The hydrogen bond distances are similar to those reported in the literature (Desiraju & Steiner, 1999; Desiraju, 1989). The N—H···O interactions generate a motif of graph set R22(7) (Bernstein et al., 1995 & Etter, 1990) and form infinite one-dimensional chains along [010] (Fig. 2). Directed 4-membered cooperative O—H···O quadrilaterals of graph set R22(8) contribute to the supramolecular aggregation of the title compound. The N—H···O, O—H···N and O—H···O interactions together generate an infinite two-dimensional network along the base vectors [010] & [101] and through the plane (10–1). There are three significant intermolecular C—H···π interactions (Table 2) in the title compound. The C—H···π interactions in the title compound can best be classified as face-to-face interactions in contrast to the presence of edge-to-face C—H···π and N—H···π interactions in L2 (Keegan et al., 2001). There is a significant face-to-face π···π interaction between cg1 and cg4 (-x, 2 - y, -z) at 3.904 Å. Within and between asymmetric units, there are two significant vdW interactions, O1W & O2W, 2.763 Å and O2W & O1W (0.5 - x, -0.5 + y, 0.5 - z), 2.751 Å, respectively.
The overall structure of L2.2H2O is maze-like consisting of interleaved molecules stabilized by π···π interactions and by a H-bonding network involving water molecules, amino groups and pyridyl nitrogen atoms.
For a detailed account of the synthetic methodology of the anhydrous form, L2, of the title compound, L2.2H2O, see Keegan et al. (2001), and for its metal complexes, see: Yoshida & Ichikawa (1997); Hannon et al. (1997); He et al. (2000); Keegan et al. (2002).
For related literature, see: Bernstein et al. (1995); Desiraju (1989); Desiraju & Steiner (1999); Etter (1990); Jodry & Lacour (2000); Kruger et al. (2001).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C25H26N4·2H2O | F(000) = 888 |
Mr = 416.51 | Dx = 1.209 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3590 reflections |
a = 13.8250 (13) Å | θ = 1.6–23.3° |
b = 6.5843 (6) Å | µ = 0.08 mm−1 |
c = 25.291 (2) Å | T = 293 K |
β = 96.461 (2)° | Prism, yellow |
V = 2287.6 (4) Å3 | 0.45 × 0.41 × 0.27 mm |
Z = 4 |
Bruker SMART 1000 diffractometer | 3292 independent reflections |
Radiation source: fine-focus sealed tube | 2173 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 23.3°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | h = −15→15 |
Tmin = 0.966, Tmax = 0.979 | k = −7→7 |
15266 measured reflections | l = −29→29 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0471P)2 + 0.9837P] where P = (Fo2 + 2Fc2)/3 |
3292 reflections | (Δ/σ)max < 0.001 |
298 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.12 e Å−3 |
C25H26N4·2H2O | V = 2287.6 (4) Å3 |
Mr = 416.51 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.8250 (13) Å | µ = 0.08 mm−1 |
b = 6.5843 (6) Å | T = 293 K |
c = 25.291 (2) Å | 0.45 × 0.41 × 0.27 mm |
β = 96.461 (2)° |
Bruker SMART 1000 diffractometer | 3292 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 2173 reflections with I > 2σ(I) |
Tmin = 0.966, Tmax = 0.979 | Rint = 0.030 |
15266 measured reflections | θmax = 23.3° |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.38 e Å−3 |
3292 reflections | Δρmin = −0.12 e Å−3 |
298 parameters |
Experimental. Elemental analysis for C25H28N4O2 (%) calculated (found) C 72.1 (72.6), H 6.7 (6.6), N 13.5 (13.7). Mass spectrometry (HL2+) 381 1H NMR (CDCl3, p.p.m.): 8.60 (s, 2H), 7.70 (td, 2H), 7.39 (d, 2H), 7.24 (t, 2H), 7.00 (d, 4H), 6.61 (d, 4H), 4.49 (s, 4H), 3.77 (s, 2H) |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.87779 (18) | 0.5628 (5) | 0.42784 (10) | 0.0827 (8) | |
H1A | 0.9162 | 0.4405 | 0.4254 | 0.099* | |
H1B | 0.9076 | 0.6702 | 0.4090 | 0.099* | |
C11 | 0.77551 (18) | 0.5258 (4) | 0.40167 (10) | 0.0677 (7) | |
C12 | 0.7160 (2) | 0.6854 (4) | 0.38258 (10) | 0.0748 (7) | |
H12 | 0.7415 | 0.8162 | 0.3838 | 0.090* | |
C13 | 0.62098 (19) | 0.6572 (4) | 0.36204 (10) | 0.0718 (7) | |
H13 | 0.5838 | 0.7682 | 0.3493 | 0.086* | |
C14 | 0.57952 (18) | 0.4653 (4) | 0.36000 (9) | 0.0635 (6) | |
C15 | 0.63801 (19) | 0.3049 (4) | 0.37885 (10) | 0.0727 (7) | |
H15 | 0.6125 | 0.1742 | 0.3781 | 0.087* | |
C16 | 0.73429 (19) | 0.3368 (4) | 0.39883 (10) | 0.0734 (7) | |
H16 | 0.7722 | 0.2258 | 0.4107 | 0.088* | |
N17 | 0.48350 (17) | 0.4426 (4) | 0.34013 (10) | 0.0833 (7) | |
H17 | 0.449 (2) | 0.547 (4) | 0.3274 (11) | 0.100* | |
C18 | 0.43134 (19) | 0.2539 (4) | 0.34144 (10) | 0.0774 (8) | |
H18A | 0.4692 | 0.1480 | 0.3268 | 0.093* | |
H18B | 0.3704 | 0.2661 | 0.3186 | 0.093* | |
C19 | 0.40925 (17) | 0.1884 (5) | 0.39610 (10) | 0.0714 (7) | |
N20 | 0.38042 (16) | −0.0038 (4) | 0.39905 (9) | 0.0821 (7) | |
C21 | 0.3573 (2) | −0.0687 (6) | 0.44635 (15) | 0.1067 (11) | |
H21 | 0.3371 | −0.2026 | 0.4492 | 0.128* | |
C22 | 0.3620 (2) | 0.0530 (9) | 0.49074 (14) | 0.1204 (14) | |
H22 | 0.3457 | 0.0021 | 0.5229 | 0.144* | |
C23 | 0.3909 (3) | 0.2485 (8) | 0.48680 (15) | 0.1195 (13) | |
H23 | 0.3941 | 0.3344 | 0.5161 | 0.143* | |
C24 | 0.4152 (2) | 0.3174 (5) | 0.43919 (13) | 0.0948 (9) | |
H24 | 0.4358 | 0.4508 | 0.4359 | 0.114* | |
C31 | 0.87835 (16) | 0.6217 (4) | 0.48559 (10) | 0.0678 (7) | |
C32 | 0.85431 (18) | 0.4802 (4) | 0.52260 (11) | 0.0748 (7) | |
H32 | 0.8413 | 0.3472 | 0.5117 | 0.090* | |
C33 | 0.84924 (19) | 0.5308 (4) | 0.57473 (11) | 0.0726 (7) | |
H33 | 0.8331 | 0.4317 | 0.5984 | 0.087* | |
C34 | 0.86786 (18) | 0.7282 (4) | 0.59285 (10) | 0.0661 (7) | |
C35 | 0.89461 (18) | 0.8687 (4) | 0.55661 (11) | 0.0735 (7) | |
H35 | 0.9099 | 1.0008 | 0.5676 | 0.088* | |
C36 | 0.89886 (17) | 0.8149 (4) | 0.50424 (11) | 0.0731 (7) | |
H36 | 0.9163 | 0.9131 | 0.4806 | 0.088* | |
N37 | 0.8591 (2) | 0.7726 (4) | 0.64518 (10) | 0.0911 (8) | |
H37 | 0.842 (2) | 0.674 (5) | 0.6653 (12) | 0.109* | |
C38 | 0.8702 (2) | 0.9706 (4) | 0.66792 (11) | 0.0796 (8) | |
H38A | 0.8344 | 0.9760 | 0.6988 | 0.096* | |
H38B | 0.8407 | 1.0681 | 0.6422 | 0.096* | |
C39 | 0.9734 (2) | 1.0348 (4) | 0.68468 (10) | 0.0721 (7) | |
N40 | 0.98277 (19) | 1.2202 (4) | 0.70503 (9) | 0.0897 (7) | |
C41 | 1.0730 (3) | 1.2855 (7) | 0.72215 (14) | 0.1294 (15) | |
H41 | 1.0806 | 1.4148 | 0.7368 | 0.155* | |
C42 | 1.1531 (3) | 1.1699 (11) | 0.71890 (16) | 0.158 (2) | |
H42 | 1.2143 | 1.2200 | 0.7314 | 0.190* | |
C43 | 1.1442 (3) | 0.9828 (10) | 0.69761 (15) | 0.1420 (18) | |
H43 | 1.1988 | 0.9030 | 0.6948 | 0.170* | |
C44 | 1.0528 (3) | 0.9122 (6) | 0.68019 (12) | 0.1015 (10) | |
H44 | 1.0445 | 0.7830 | 0.6655 | 0.122* | |
O1W | 0.65233 (15) | 0.2278 (3) | 0.69672 (8) | 0.0831 (6) | |
H1W1 | 0.651 (2) | 0.140 (4) | 0.7242 (11) | 0.100* | |
H1W2 | 0.646 (2) | 0.153 (4) | 0.6664 (11) | 0.100* | |
O2W | 0.81936 (17) | 0.4559 (3) | 0.72040 (7) | 0.0841 (6) | |
H2W1 | 0.764 (2) | 0.386 (4) | 0.7116 (11) | 0.101* | |
H2W2 | 0.879 (2) | 0.370 (5) | 0.7162 (11) | 0.101* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0612 (17) | 0.108 (2) | 0.0804 (18) | −0.0081 (15) | 0.0146 (13) | −0.0091 (16) |
C11 | 0.0611 (15) | 0.0806 (19) | 0.0626 (15) | −0.0043 (14) | 0.0131 (12) | −0.0071 (14) |
C12 | 0.0813 (19) | 0.0669 (17) | 0.0761 (17) | −0.0181 (15) | 0.0092 (14) | −0.0013 (14) |
C13 | 0.0803 (19) | 0.0594 (16) | 0.0734 (17) | −0.0030 (14) | −0.0016 (14) | 0.0038 (13) |
C14 | 0.0663 (16) | 0.0631 (16) | 0.0595 (14) | −0.0014 (13) | 0.0007 (12) | −0.0008 (12) |
C15 | 0.0754 (18) | 0.0564 (16) | 0.0839 (18) | −0.0034 (14) | −0.0015 (14) | −0.0021 (14) |
C16 | 0.0690 (17) | 0.0724 (18) | 0.0774 (17) | 0.0098 (14) | 0.0015 (13) | −0.0031 (14) |
N17 | 0.0748 (16) | 0.0674 (15) | 0.1012 (18) | −0.0049 (12) | −0.0184 (13) | 0.0072 (13) |
C18 | 0.0681 (17) | 0.0843 (19) | 0.0767 (18) | −0.0089 (14) | −0.0052 (13) | 0.0045 (15) |
C19 | 0.0516 (14) | 0.089 (2) | 0.0717 (17) | −0.0012 (14) | −0.0025 (12) | −0.0064 (16) |
N20 | 0.0722 (15) | 0.0931 (18) | 0.0804 (16) | −0.0068 (13) | 0.0053 (12) | 0.0068 (14) |
C21 | 0.087 (2) | 0.125 (3) | 0.108 (3) | −0.011 (2) | 0.012 (2) | 0.025 (2) |
C22 | 0.082 (2) | 0.203 (5) | 0.078 (2) | −0.010 (3) | 0.0149 (18) | 0.009 (3) |
C23 | 0.084 (2) | 0.187 (4) | 0.088 (3) | −0.010 (3) | 0.0137 (19) | −0.033 (3) |
C24 | 0.084 (2) | 0.117 (3) | 0.083 (2) | −0.0076 (18) | 0.0075 (16) | −0.024 (2) |
C31 | 0.0490 (14) | 0.0813 (19) | 0.0725 (17) | −0.0074 (13) | 0.0041 (12) | −0.0014 (15) |
C32 | 0.0761 (18) | 0.0635 (16) | 0.0830 (19) | −0.0072 (14) | 0.0013 (14) | −0.0039 (15) |
C33 | 0.0828 (18) | 0.0609 (16) | 0.0734 (18) | −0.0088 (14) | 0.0054 (14) | 0.0060 (14) |
C34 | 0.0690 (16) | 0.0594 (15) | 0.0692 (17) | −0.0057 (13) | 0.0044 (12) | 0.0047 (13) |
C35 | 0.0797 (18) | 0.0607 (16) | 0.0790 (18) | −0.0120 (13) | 0.0043 (14) | 0.0031 (14) |
C36 | 0.0627 (16) | 0.0785 (19) | 0.0773 (18) | −0.0138 (14) | 0.0040 (13) | 0.0133 (15) |
N37 | 0.136 (2) | 0.0649 (16) | 0.0749 (17) | −0.0216 (15) | 0.0226 (15) | −0.0046 (12) |
C38 | 0.090 (2) | 0.0688 (18) | 0.0803 (18) | −0.0060 (15) | 0.0122 (15) | −0.0059 (15) |
C39 | 0.0812 (19) | 0.0817 (19) | 0.0538 (15) | 0.0013 (16) | 0.0098 (13) | 0.0048 (14) |
N40 | 0.0999 (19) | 0.0971 (19) | 0.0734 (15) | −0.0213 (15) | 0.0159 (13) | −0.0147 (14) |
C41 | 0.126 (3) | 0.171 (4) | 0.094 (3) | −0.056 (3) | 0.026 (2) | −0.041 (3) |
C42 | 0.101 (3) | 0.290 (7) | 0.083 (3) | −0.039 (4) | 0.012 (2) | −0.046 (4) |
C43 | 0.089 (3) | 0.258 (6) | 0.077 (2) | 0.040 (3) | −0.001 (2) | −0.005 (3) |
C44 | 0.096 (2) | 0.129 (3) | 0.078 (2) | 0.027 (2) | 0.0021 (18) | 0.0007 (19) |
O1W | 0.0961 (14) | 0.0633 (12) | 0.0872 (14) | −0.0003 (10) | −0.0018 (12) | 0.0047 (10) |
O2W | 0.1074 (16) | 0.0667 (12) | 0.0776 (12) | −0.0125 (11) | 0.0077 (11) | −0.0065 (10) |
C1—C31 | 1.510 (3) | C31—C36 | 1.375 (3) |
C1—C11 | 1.512 (3) | C31—C32 | 1.387 (3) |
C1—H1A | 0.9700 | C32—C33 | 1.369 (3) |
C1—H1B | 0.9700 | C32—H32 | 0.9300 |
C11—C16 | 1.367 (3) | C33—C34 | 1.392 (3) |
C11—C12 | 1.387 (4) | C33—H33 | 0.9300 |
C12—C13 | 1.369 (3) | C34—N37 | 1.374 (3) |
C12—H12 | 0.9300 | C34—C35 | 1.382 (3) |
C13—C14 | 1.386 (3) | C35—C36 | 1.379 (3) |
C13—H13 | 0.9300 | C35—H35 | 0.9300 |
C14—N17 | 1.374 (3) | C36—H36 | 0.9300 |
C14—C15 | 1.382 (3) | N37—C38 | 1.426 (3) |
C15—C16 | 1.386 (3) | N37—H37 | 0.87 (3) |
C15—H15 | 0.9300 | C38—C39 | 1.502 (4) |
C16—H16 | 0.9300 | C38—H38A | 0.9700 |
N17—C18 | 1.439 (3) | C38—H38B | 0.9700 |
N17—H17 | 0.88 (3) | C39—N40 | 1.326 (3) |
C18—C19 | 1.512 (4) | C39—C44 | 1.377 (4) |
C18—H18A | 0.9700 | N40—C41 | 1.344 (4) |
C18—H18B | 0.9700 | C41—C42 | 1.354 (6) |
C19—N20 | 1.332 (3) | C41—H41 | 0.9300 |
C19—C24 | 1.377 (4) | C42—C43 | 1.345 (6) |
N20—C21 | 1.342 (4) | C42—H42 | 0.9300 |
C21—C22 | 1.375 (5) | C43—C44 | 1.372 (5) |
C21—H21 | 0.9300 | C43—H43 | 0.9300 |
C22—C23 | 1.355 (5) | C44—H44 | 0.9300 |
C22—H22 | 0.9300 | O1W—H1W1 | 0.91 (3) |
C23—C24 | 1.364 (5) | O1W—H1W2 | 0.91 (3) |
C23—H23 | 0.9300 | O2W—H2W1 | 0.90 (3) |
C24—H24 | 0.9300 | O2W—H2W2 | 1.02 (3) |
C31—C1—C11 | 111.6 (2) | C23—C24—H24 | 120.2 |
C31—C1—H1A | 109.3 | C19—C24—H24 | 120.2 |
C11—C1—H1A | 109.3 | C36—C31—C32 | 116.5 (2) |
C31—C1—H1B | 109.3 | C36—C31—C1 | 123.2 (3) |
C11—C1—H1B | 109.3 | C32—C31—C1 | 120.3 (3) |
H1A—C1—H1B | 108.0 | C33—C32—C31 | 121.9 (2) |
C16—C11—C12 | 116.3 (2) | C33—C32—H32 | 119.1 |
C16—C11—C1 | 122.2 (3) | C31—C32—H32 | 119.1 |
C12—C11—C1 | 121.3 (3) | C32—C33—C34 | 121.1 (2) |
C13—C12—C11 | 122.4 (2) | C32—C33—H33 | 119.5 |
C13—C12—H12 | 118.8 | C34—C33—H33 | 119.5 |
C11—C12—H12 | 118.8 | N37—C34—C35 | 123.7 (2) |
C12—C13—C14 | 120.8 (2) | N37—C34—C33 | 118.9 (2) |
C12—C13—H13 | 119.6 | C35—C34—C33 | 117.4 (2) |
C14—C13—H13 | 119.6 | C36—C35—C34 | 120.6 (2) |
N17—C14—C15 | 123.2 (2) | C36—C35—H35 | 119.7 |
N17—C14—C13 | 119.4 (2) | C34—C35—H35 | 119.7 |
C15—C14—C13 | 117.4 (2) | C31—C36—C35 | 122.5 (2) |
C14—C15—C16 | 120.7 (2) | C31—C36—H36 | 118.7 |
C14—C15—H15 | 119.6 | C35—C36—H36 | 118.7 |
C16—C15—H15 | 119.6 | C34—N37—C38 | 124.5 (2) |
C11—C16—C15 | 122.3 (2) | C34—N37—H37 | 117 (2) |
C11—C16—H16 | 118.8 | C38—N37—H37 | 118 (2) |
C15—C16—H16 | 118.8 | N37—C38—C39 | 115.2 (2) |
C14—N17—C18 | 123.5 (2) | N37—C38—H38A | 108.5 |
C14—N17—H17 | 120 (2) | C39—C38—H38A | 108.5 |
C18—N17—H17 | 115.9 (19) | N37—C38—H38B | 108.5 |
N17—C18—C19 | 114.9 (2) | C39—C38—H38B | 108.5 |
N17—C18—H18A | 108.6 | H38A—C38—H38B | 107.5 |
C19—C18—H18A | 108.5 | N40—C39—C44 | 121.8 (3) |
N17—C18—H18B | 108.6 | N40—C39—C38 | 114.6 (3) |
C19—C18—H18B | 108.5 | C44—C39—C38 | 123.5 (3) |
H18A—C18—H18B | 107.5 | C39—N40—C41 | 117.8 (3) |
N20—C19—C24 | 122.3 (3) | N40—C41—C42 | 122.5 (4) |
N20—C19—C18 | 114.5 (2) | N40—C41—H41 | 118.8 |
C24—C19—C18 | 123.2 (3) | C42—C41—H41 | 118.8 |
C19—N20—C21 | 117.1 (3) | C43—C42—C41 | 120.0 (4) |
N20—C21—C22 | 123.2 (4) | C43—C42—H42 | 120.0 |
N20—C21—H21 | 118.4 | C41—C42—H42 | 120.0 |
C22—C21—H21 | 118.4 | C42—C43—C44 | 118.6 (4) |
C23—C22—C21 | 118.8 (4) | C42—C43—H43 | 120.7 |
C23—C22—H22 | 120.6 | C44—C43—H43 | 120.7 |
C21—C22—H22 | 120.6 | C43—C44—C39 | 119.2 (4) |
C22—C23—C24 | 119.0 (4) | C43—C44—H44 | 120.4 |
C22—C23—H23 | 120.5 | C39—C44—H44 | 120.4 |
C24—C23—H23 | 120.5 | H1W1—O1W—H1W2 | 107 (3) |
C23—C24—C19 | 119.7 (3) | H2W1—O2W—H2W2 | 112 (3) |
C31—C1—C11—C16 | −93.3 (3) | C11—C1—C31—C36 | −108.3 (3) |
C31—C1—C11—C12 | 82.0 (3) | C11—C1—C31—C32 | 69.5 (3) |
C16—C11—C12—C13 | 0.1 (4) | C36—C31—C32—C33 | 1.3 (4) |
C1—C11—C12—C13 | −175.4 (2) | C1—C31—C32—C33 | −176.6 (2) |
C11—C12—C13—C14 | 0.7 (4) | C31—C32—C33—C34 | 0.2 (4) |
C12—C13—C14—N17 | 178.7 (2) | C32—C33—C34—N37 | 178.2 (2) |
C12—C13—C14—C15 | −0.7 (4) | C32—C33—C34—C35 | −2.0 (4) |
N17—C14—C15—C16 | −179.5 (2) | N37—C34—C35—C36 | −177.9 (3) |
C13—C14—C15—C16 | −0.1 (4) | C33—C34—C35—C36 | 2.3 (4) |
C12—C11—C16—C15 | −1.0 (4) | C32—C31—C36—C35 | −1.0 (4) |
C1—C11—C16—C15 | 174.5 (2) | C1—C31—C36—C35 | 176.9 (2) |
C14—C15—C16—C11 | 1.0 (4) | C34—C35—C36—C31 | −0.8 (4) |
C15—C14—N17—C18 | 6.1 (4) | C35—C34—N37—C38 | 4.3 (4) |
C13—C14—N17—C18 | −173.3 (2) | C33—C34—N37—C38 | −175.9 (3) |
C14—N17—C18—C19 | 70.8 (3) | C34—N37—C38—C39 | −82.8 (3) |
N17—C18—C19—N20 | −166.2 (2) | N37—C38—C39—N40 | 179.0 (2) |
N17—C18—C19—C24 | 15.8 (4) | N37—C38—C39—C44 | −1.7 (4) |
C24—C19—N20—C21 | −0.2 (4) | C44—C39—N40—C41 | −1.0 (4) |
C18—C19—N20—C21 | −178.3 (2) | C38—C39—N40—C41 | 178.3 (3) |
C19—N20—C21—C22 | 0.1 (5) | C39—N40—C41—C42 | 0.5 (5) |
N20—C21—C22—C23 | 0.3 (6) | N40—C41—C42—C43 | 0.4 (7) |
C21—C22—C23—C24 | −0.7 (6) | C41—C42—C43—C44 | −0.9 (7) |
C22—C23—C24—C19 | 0.6 (5) | C42—C43—C44—C39 | 0.4 (6) |
N20—C19—C24—C23 | −0.1 (4) | N40—C39—C44—C43 | 0.5 (4) |
C18—C19—C24—C23 | 177.8 (3) | C38—C39—C44—C43 | −178.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N17—H17···O1Wi | 0.88 (3) | 2.08 (3) | 2.951 (3) | 170 (3) |
N37—H37···O2W | 0.87 (3) | 2.05 (3) | 2.916 (3) | 171 (3) |
O1W—H1W1···O2Wii | 0.91 (3) | 1.86 (3) | 2.751 (3) | 166 (3) |
O1W—H1W2···N20iii | 0.91 (3) | 1.92 (3) | 2.829 (3) | 174 (3) |
O2W—H2W1···O1W | 0.90 (3) | 1.87 (3) | 2.763 (3) | 176 (3) |
O2W—H2W2···N40iv | 1.02 (3) | 1.79 (3) | 2.804 (3) | 177 (2) |
C1—H1A···Cg4v | 0.97 | 3.03 | 3.777 | 135 |
C1—H1B···Cg2vi | 0.97 | 3.24 | 4.106 | 150 |
C23—H23···Cg3vii | 0.93 | 3.10 | 3.959 | 154 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+1, −y, −z+1; (iv) x, y−1, z; (v) −x+1, −y+2, −z; (vi) −x+1, −y+1, −z; (vii) −x, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | C25H26N4·2H2O |
Mr | 416.51 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 13.8250 (13), 6.5843 (6), 25.291 (2) |
β (°) | 96.461 (2) |
V (Å3) | 2287.6 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.45 × 0.41 × 0.27 |
Data collection | |
Diffractometer | Bruker SMART 1000 |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.966, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15266, 3292, 2173 |
Rint | 0.030 |
θmax (°) | 23.3 |
(sin θ/λ)max (Å−1) | 0.556 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.132, 1.02 |
No. of reflections | 3292 |
No. of parameters | 298 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.12 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N17—H17···O1Wi | 0.88 (3) | 2.08 (3) | 2.951 (3) | 170 (3) |
N37—H37···O2W | 0.87 (3) | 2.05 (3) | 2.916 (3) | 171 (3) |
O1W—H1W1···O2Wii | 0.91 (3) | 1.86 (3) | 2.751 (3) | 166 (3) |
O1W—H1W2···N20iii | 0.91 (3) | 1.92 (3) | 2.829 (3) | 174 (3) |
O2W—H2W1···O1W | 0.90 (3) | 1.87 (3) | 2.763 (3) | 176 (3) |
O2W—H2W2···N40iv | 1.02 (3) | 1.79 (3) | 2.804 (3) | 177 (2) |
C1—H1A···Cg4v | 0.97 | 3.033 | 3.777 | 134.5 |
C1—H1B···Cg2vi | 0.97 | 3.239 | 4.106 | 149.7 |
C23—H23···Cg3vii | 0.93 | 3.101 | 3.959 | 154.1 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+1, −y, −z+1; (iv) x, y−1, z; (v) −x+1, −y+2, −z; (vi) −x+1, −y+1, −z; (vii) −x, −y+2, −z. |
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The self assembly of highly ordered molecular structures from small components is of much current interest with applications in areas such as fabrication of nanoscale devices and molecular machinery. An example of such self assembly is the formation of double- or triple-helical architectures (Jodry & Lacour, 2000) from multidentate organic ligands and their metal complexes (Yoshida & Ichikawa, 1997, Hannon et al., 1997, He et al., 2000, Keegan et al., 2002). The design of these structures usually involves suitably compartmentalized ligands, which are capable of forming weak π···π interactions between their aromatic rings (Kruger et al., 2001). This paper reports the molecular and supramolecular architecture of the title compound which displays several of these and other interactions.
The molecular structure of the title compound, L2.2H2O, is shown in Fig. 1 and selected geometric parameters are given in Table 1. The N17—C18 & N37—C38 distances are consistent with C—N single bonds whereas the C14—N17 & C34—N37 bond distances are shorter than those expected for C—N single bonds. However, the C14—N17—C18 & C34—N37—C38 bond angles are considerably larger than expected for sp3 hybridized nitrogen atoms, which may suggest a possible interaction between the lone pair on nitrogen and the aromatic cloud of the attached phenyl ring, thereby suggesting considerable sp2 character for these nitrogen atoms. This is further confirmed by the sum of the bond angles around the two aliphatic nitrogen atoms, N17 & N37 [359.5 (2)].
Any two adjacent pairs of rings are non-coplanar as confirmed by their interplanar angles, cg1 & cg3, 80.55 (8)°, cg3 & cg4, 78.54 (7)° and cg2 & cg4, 83.44 (9)°. The two pyridyl rings are also relatively non-coplanar as shown by their interplanar angle (cg1 & cg2, 80.6 (1)°). The interplanar angles between cg1 & cg4 is 3.2 (1)° and cg2 & cg3 is 31.7 (8)°. The pyridyl and phenyl rings (cg1 & cg3 and cg2 & cg4) show significant deviation from coplanarity due to a twist in the molecule as reflected in the torsion angles, C14—N17—C18—C19 and C34—N37—C38—C39. cg1, cg2, cg3 and cg4 refer to C19/N20/C21/C22/C23/C24, C39/N40/C41/C42/C43/C44, C11—C16 and C31—C36 rings, respectively.
The crystal structure of L2.2H2O is stabilized by the interplay of O—H···O, N—H···O, O—H···N, C—H···π (Table 2), π···π and van der Waals interactions. The hydrogen bond distances are similar to those reported in the literature (Desiraju & Steiner, 1999; Desiraju, 1989). The N—H···O interactions generate a motif of graph set R22(7) (Bernstein et al., 1995 & Etter, 1990) and form infinite one-dimensional chains along [010] (Fig. 2). Directed 4-membered cooperative O—H···O quadrilaterals of graph set R22(8) contribute to the supramolecular aggregation of the title compound. The N—H···O, O—H···N and O—H···O interactions together generate an infinite two-dimensional network along the base vectors [010] & [101] and through the plane (10–1). There are three significant intermolecular C—H···π interactions (Table 2) in the title compound. The C—H···π interactions in the title compound can best be classified as face-to-face interactions in contrast to the presence of edge-to-face C—H···π and N—H···π interactions in L2 (Keegan et al., 2001). There is a significant face-to-face π···π interaction between cg1 and cg4 (-x, 2 - y, -z) at 3.904 Å. Within and between asymmetric units, there are two significant vdW interactions, O1W & O2W, 2.763 Å and O2W & O1W (0.5 - x, -0.5 + y, 0.5 - z), 2.751 Å, respectively.
The overall structure of L2.2H2O is maze-like consisting of interleaved molecules stabilized by π···π interactions and by a H-bonding network involving water molecules, amino groups and pyridyl nitrogen atoms.