Bis[4-(2-pyridylmethyl­amino)phenyl]­methane dihydrate

Maneiro, M.; Llamas-Saiz, A.L.; Vembu, N.; Nolan, K.B.

doi:10.1107/S1600536807027857

Bis[4-(2-pyridylmethylamino)phenyl]methane dihydrate

M. Maneiro, A. L. Llamas-Saiz, N. Vembu and K. B. Nolan

The pyridyl and benzene rings in the title compound, C₂₅H₂₆N₄·2H₂O, show significant deviation from coplanarity due to a twist in the molecule, and this is reflected in the C—N(H)—C—C torsion angles of −82.8 (3) and 70.8 (3)°. The supramolecular architecture is effected by O—H

O quadrilaterals, one-dimensional N—H

O chains, two-dimensional networks of O—H

O, N—H

O and O—H

N interactions, face-to-face C—H

π and π–π interactions [with a ring-centroid separation of 3.904 (2) Å] and intra- and intermolecular van der Waals interactions. The overall structure of the title compound is maze-like, consisting of interleaved molecules stabilized by π–π interactions and by a hydrogen-bonding network involving water molecules, amino groups and pyridyl N atoms.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027857/lh2420sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027857/lh2420Isup2.hkl Contains datablock I

CCDC reference: 654940

checkCIF report

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

Comment top

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.

Related literature top

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).

Experimental top

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.

Structure description top

For related literature, see: Bernstein et al. (1995); Desiraju (1989); Desiraju & Steiner (1999); Etter (1990); Jodry & Lacour (2000); Kruger et al. (2001).

Computing details top

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.

Figures top

	Fig. 1. The asymmetric unit of L2.2H₂O, with atom labels and 50% probability displacement ellipsoids for non-H atoms. H-atoms are depicted as spheres of arbitrary radius.
	Fig. 2. View along y-axis showing O—H···O quadrilaterals and N—H···O networks. Hydrogen bonds are shown as dashed lines.

Bis[4-(2-pyridylmethylamino)phenyl]methane dihydrate top

Crystal data top

C₂₅H₂₆N₄·2H₂O	F(000) = 888
M_r = 416.51	D_x = 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

Data collection top

Bruker SMART 1000 diffractometer	3292 independent reflections
Radiation source: fine-focus sealed tube	2173 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 23.3°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −15→15
T_min = 0.966, T_max = 0.979	k = −7→7
15266 measured reflections	l = −29→29

Refinement top

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(F_o²) + (0.0471P)² + 0.9837P] where P = (F_o² + 2F_c²)/3
3292 reflections	(Δ/σ)_max < 0.001
298 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₂₅H₂₆N₄·2H₂O	V = 2287.6 (4) Å³
M_r = 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)°

Data collection top

Bruker SMART 1000 diffractometer	3292 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	2173 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.979	R_int = 0.030
15266 measured reflections	θ_max = 23.3°

Refinement top

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	Δρ_max = 0.38 e Å⁻³
3292 reflections	Δρ_min = −0.12 e Å⁻³
298 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···N40^iv	1.02 (3)	1.79 (3)	2.804 (3)	177 (2)
C1—H1A···Cg4^v	0.97	3.03	3.777	135
C1—H1B···Cg2^vi	0.97	3.24	4.106	150
C23—H23···Cg3^vii	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
M_r	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)
T_min, T_max	0.966, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	15266, 3292, 2173
R_int	0.030
θ_max (°)	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
Δρ_max, Δρ_min (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.