2-[(E)-(1,10-Phenanthrolin-5-yl)imino­meth­yl]phenol methanol monosolvate

Öztürk Yíldírím, S.; Demirhan, N.; Elmalí, F.; Butcher, R.J.

doi:10.1107/S1600536812011890

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages o1173-o1174

doi:10.1107/S1600536812011890

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2-[(E)-(1,10-Phenanthrolin-5-yl)iminomethyl]phenol methanol monosolvate

Sema Öztürk Yíldírím,^a,^b Nebahat Demirhan,^c Fikriye Elmalí ^c and Ray J. Butcher ^d ^*

^aInorganic Chemistry Department, Howard University, Washington, DC 20059, USA, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^cYíldíz Technical University, Faculty of Arts and Sciences, Chemistry Department, 34210 Esenler, Istanbul, Turkey, and ^dDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 12 March 2012; accepted 19 March 2012; online 24 March 2012)

In the title multi-donor Schiff base compound, C₁₉H₁₃N₃O·CH₃OH, the dihedral angle between the mean planes of the phenanthroline and phenol rings is 59.3 (1)°. The Schiff base molecule is linked to the solvent molecule by an O—H⋯O hydrogen bond. In the crystal, the components are linked by O—H⋯N hydrogen bonds, weak O—H⋯N interactions and π–π stacking interactions [centroid–centroid distances = 3.701 (1) and 3.656 (1) Å].

Related literature

For the role played by 1,10-phenanthroline and its derivatives as molecular scaffolds for supramolecular assemblies, see: Balzani et al. (1996 ). For the metal-chelating properties of the 1,10-phenanthroline ligand, see: Sammes & Yahioglu (1994 ). For the photochemical and redox properties of phenanthroline rings, see: Camren et al. (1996 ); Bolger et al. (1996 ); Msood & Hodgson (1993 ). For Schiff bases as oxygen-carriers and as photochromic or thermochromic materials, see: Hobday & Smith (1973 ); Gul et al. (1986 ); Can & Bekaroglu (1988 ); Avciata et al. (1995 , 1998 ); Demirhan et al. (2002 ). For the synthesis of 5-amino-1,10-phenanthroline, see: Gillard & Hill (1974 ). For related structures, see: Wu et al. (2011 ); Fun et al. (2010 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₉H₁₃N₃O·CH₄O
M_r = 331.37
Monoclinic, P c
a = 11.9398 (12) Å
b = 4.6680 (5) Å
c = 14.7818 (18) Å
β = 101.961 (11)°
V = 805.98 (16) Å³
Z = 2
Cu Kα radiation
μ = 0.73 mm⁻¹
T = 123 K
1.15 × 0.84 × 0.06 mm

Data collection

Oxford Diffraction Gemini-R diffractometer
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), using a multi-faceted crystal model (Clark & Reid, 1995 )] T_min = 0.505, T_max = 0.954
3176 measured reflections
1960 independent reflections
1885 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.110
S = 1.04
1960 reflections
229 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1S	0.84	1.81	2.640 (3)	172
O1S—H1S⋯N1ⁱ	0.84	2.01	2.829 (3)	163
O1S—H1S⋯N2ⁱ	0.84	2.68	3.242 (3)	126
Symmetry code: (i) x+1, y+1, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812011890/jj2127sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011890/jj2127Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812011890/jj2127Isup3.cml

checkCIF report

Comment top

1,10-Phenanthroline and its derivatives play important roles as molecular scaffolding for supramolecular assemblies (Balzani et al., 1996). These have played a major role in the development of polypyridyl metal complexes. The metal chelating property of the 1,10-phenanthroline ligand and its derivatives have been utilized in a range of analytical reagents as well as for the development of bioinorganic probes (Sammes & Yahioglu, 1994). The photochemical and redox properties of complexes can be varied systematically through appropriate substitution on the phenanthroline rings (Camren et al., 1996: Bolger et al., 1996: Msood & Hodgson, 1993).

The coordination chemistry of Schiff bases derived from salicylaldehyde has been the subject of many studies because of their interesting properties; e.g. as oxygen-carriers to mimic some complicated biological systems, as photochromic or thermochromic materials (Hobday & Smith, 1973: Gul et al., 1986: Can & Bekaroglu, 1988: Avciata et al. 1995; Avciata et al. 1998; Demirhan et al. 2002).

We report here the synthesis and characterization a new multidonor Schiff base derivative, (I), carrying N₃O donor atoms and prepared from the condensation reaction of 5-amino-1,10-phenanthroline with salicylaldehyde.

The title molecule C₁₉H₁₃N₃O.CH₃OH, crystallized as a methanol monosolvate (Fig. 1). All bond lengths are as expected (Allen et al., 1987) and are comparable to those observed in related structures (Wu et al., 2011; Fun et al., 2010). The molecule is not planar, forming a dihedral angle of 59.3 (1)° between the mean planes of the phenanthroline (N1/N2/C1—C12) and phenol (C14—C19) rings.

In the crystal, O—H···N hydrogen bonds and weak O—H···N intermolecular interactions are observed (Table 1) as well as weak π-π stacking interactions [Cg1···Cg2 (x, 1+y, z) = 3.701 (1) Å and Cg1···Cg3 (x, 1+y,z) = 3.656 (1) Å, where Cg1(N1/C1—C4/C12), Cg2(N2/C7—C11) and Cg3(C4—C7/C11—C12) are the centroids of the phenonthroline ring], (Fig. 2).

Related literature top

For the role played by 1,10-phenanthroline and its derivatives as molecular scaffolds for supramolecular assemblies, see: Balzani et al. (1996). For the metal-chelating properties of the 1,10-phenanthroline ligand, see: Sammes & Yahioglu (1994). For the photochemical and redox properties of phenanthroline rings, see: Camren et al. (1996); Bolger et al. (1996); Msood & Hodgson (1993). For Schiff bases as oxygen-carriers and as photochromic or thermochromic materials, see: Hobday & Smith (1973); Gul et al. (1986); Can & Bekaroglu (1988); Avciata et al. (1995, 1998); Demirhan et al. (2002). For the synthesis of 5-amino-1,10-phenanthroline, see: Gillard & Hill (1974). For related structures, see: Wu et al. (2011); Fun et al. (2010). For standard bond lengths, see: Allen et al. (1987).

Experimental top

5-Amino-1,10-phenanthroline (Gillard & Hill, 1974) (1.5 g, 7.69 mmol) in 50 ml absolute methanol was added to salicylaldehyde (0.93 g, 7.69 mmol) dissolved in 20 ml diethylether and 100 ml absolute ethanol. After refluxing this mixture for 4.5 h, the precipitate was filtered off and then washed with water and ether. The product was obtained as a yellow precipitate (70° yield). It was soluble in methanol, ethanol and chloroform. Yield 1.79 g (78%). m.p. 451–453 K; Anal. Calcd. for C₁₉H₁₃N₃O.CH₃OH (299.32 g/mol) C, 74.24; H, 4.38; N, 14.04. Found: C, 74.86; H, 4.12; N, 14.66.

Structure description top

For the role played by 1,10-phenanthroline and its derivatives as molecular scaffolds for supramolecular assemblies, see: Balzani et al. (1996). For the metal-chelating properties of the 1,10-phenanthroline ligand, see: Sammes & Yahioglu (1994). For the photochemical and redox properties of phenanthroline rings, see: Camren et al. (1996); Bolger et al. (1996); Msood & Hodgson (1993). For Schiff bases as oxygen-carriers and as photochromic or thermochromic materials, see: Hobday & Smith (1973); Gul et al. (1986); Can & Bekaroglu (1988); Avciata et al. (1995, 1998); Demirhan et al. (2002). For the synthesis of 5-amino-1,10-phenanthroline, see: Gillard & Hill (1974). For related structures, see: Wu et al. (2011); Fun et al. (2010). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level for non-hydrogen atoms. Hydrogen bonds are drawn as dashed lines.
	Fig. 2. The molecular packing of the title compound. Hydrogen bonds are drawn as dashed lines.

2-[(E)-(1,10-Phenanthrolin-5-yl)iminomethyl]phenol methanol monosolvate top

Crystal data top

C₁₉H₁₃N₃O·CH₄O	F(000) = 348
M_r = 331.37	D_x = 1.365 Mg m⁻³
Monoclinic, Pc	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P -2yc	Cell parameters from 1347 reflections
a = 11.9398 (12) Å	θ = 3.1–75.2°
b = 4.6680 (5) Å	µ = 0.73 mm⁻¹
c = 14.7818 (18) Å	T = 123 K
β = 101.961 (11)°	Triangular plate, yellow
V = 805.98 (16) Å³	1.15 × 0.84 × 0.06 mm
Z = 2

Data collection top

Oxford Diffraction Gemini-R diffractometer	1960 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1885 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 10.5081 pixels mm^-1	θ_max = 75.2°, θ_min = 3.1°
ω scans	h = −13→14
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2007), using a multi-faceted crystal model (Clark & Reid, 1995)]	k = −5→5
T_min = 0.505, T_max = 0.954	l = −18→12
3176 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0747P)² + 0.0897P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1960 reflections	Δρ_max = 0.24 e Å⁻³
229 parameters	Δρ_min = −0.17 e Å⁻³
2 restraints	Absolute structure: Flack, H. D. (1983). Acta Cryst. A39, 876–881, 303 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −1.5 (18)

Crystal data top

C₁₉H₁₃N₃O·CH₄O	V = 805.98 (16) Å³
M_r = 331.37	Z = 2
Monoclinic, Pc	Cu Kα radiation
a = 11.9398 (12) Å	µ = 0.73 mm⁻¹
b = 4.6680 (5) Å	T = 123 K
c = 14.7818 (18) Å	1.15 × 0.84 × 0.06 mm
β = 101.961 (11)°

Data collection top

Oxford Diffraction Gemini-R diffractometer	1960 independent reflections
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2007), using a multi-faceted crystal model (Clark & Reid, 1995)]	1885 reflections with I > 2σ(I)
T_min = 0.505, T_max = 0.954	R_int = 0.030
3176 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.110	Δρ_max = 0.24 e Å⁻³
S = 1.04	Δρ_min = −0.17 e Å⁻³
1960 reflections	Absolute structure: Flack, H. D. (1983). Acta Cryst. A39, 876–881, 303 Friedel pairs
229 parameters	Absolute structure parameter: −1.5 (18)
2 restraints

Special details top

Experimental. The crystal was very fragile. On cutting the crystal shattered so an incident collimator of 1.0 mm was used.

IR (KBr): 3435(Ar—OH), 3020(Ar), 1616 (C=N—C). ¹³ C NMR, 167 (C—OH), 165 (C=C—N), 150,152 and 148 (C=N) p.p.m.. LC—MS, m/z (%): 298 (M-1). In the electronic spectrum two band appears at 281 and 340 nm which can be assigned to the π -π * and n-π * transition of C=C and C=N group.

The FTIR spectra were obtained on a Perkin Elmer Spectrum One Bv 5.0 spectrophotometer. ¹H NMR and ¹³C NMR spectra were recorded on a Varian UNITY INOVA 500 MHz s pectrometer. Mass spectra were measured on a FinniganTM LCQTM Advantage MAX spectrometer. Electronic spectra were obtained on a Agilent 8453 UV-Vis. Spectroscopy System. Elemental analyses were obtained on a Thermo Finnigan Flash EA 112. All other chemicals employed were of the highest grade available.

Absorption correction: CrysAlis RED, (Oxford Diffraction, 2007) Analytical numeric absorption correction using a multifaceted crystal model (Clark & Reid, 1995).

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
O1	0.98484 (16)	1.4695 (5)	0.63127 (14)	0.0337 (4)
H1	1.0514	1.5260	0.6545	0.051*
O1S	1.18635 (15)	1.6610 (4)	0.71862 (14)	0.0307 (4)
H1S	1.2497	1.6321	0.7038	0.046*
N1	0.41348 (18)	0.5215 (5)	0.70687 (15)	0.0254 (4)
N2	0.32594 (18)	0.8980 (5)	0.56783 (15)	0.0268 (4)
N3	0.70428 (17)	1.0456 (5)	0.50248 (15)	0.0256 (4)
C1	0.4567 (2)	0.3337 (6)	0.77219 (17)	0.0275 (5)
H1A	0.4061	0.2468	0.8058	0.033*
C2	0.5729 (2)	0.2556 (6)	0.79469 (18)	0.0291 (5)
H2A	0.5997	0.1206	0.8424	0.035*
C3	0.6463 (2)	0.3780 (5)	0.74647 (18)	0.0265 (5)
H3A	0.7252	0.3282	0.7600	0.032*
C4	0.60430 (19)	0.5796 (5)	0.67619 (16)	0.0233 (5)
C5	0.6784 (2)	0.7166 (5)	0.62454 (17)	0.0237 (5)
H5A	0.7577	0.6711	0.6372	0.028*
C6	0.63612 (19)	0.9123 (5)	0.55719 (16)	0.0234 (5)
C7	0.5151 (2)	0.9788 (5)	0.53588 (16)	0.0227 (5)
C8	0.4682 (2)	1.1790 (6)	0.46665 (17)	0.0258 (5)
H8A	0.5159	1.2761	0.4326	0.031*
C9	0.3527 (2)	1.2309 (6)	0.44944 (19)	0.0299 (5)
H9A	0.3191	1.3639	0.4030	0.036*
C10	0.2852 (2)	1.0854 (6)	0.50113 (19)	0.0297 (5)
H10A	0.2052	1.1223	0.4879	0.036*
C11	0.4404 (2)	0.8465 (5)	0.58528 (16)	0.0233 (5)
C12	0.48604 (19)	0.6424 (5)	0.65842 (16)	0.0221 (5)
C13	0.8014 (2)	1.1466 (6)	0.54239 (17)	0.0252 (5)
H13A	0.8229	1.1375	0.6079	0.030*
C14	0.8805 (2)	1.2756 (5)	0.49080 (18)	0.0258 (5)
C15	0.9738 (2)	1.4372 (5)	0.53890 (18)	0.0268 (5)
C16	1.0503 (2)	1.5581 (6)	0.4904 (2)	0.0311 (5)
H16A	1.1138	1.6655	0.5226	0.037*
C17	1.0351 (2)	1.5235 (6)	0.3963 (2)	0.0358 (6)
H17A	1.0878	1.6080	0.3641	0.043*
C18	0.9425 (2)	1.3650 (8)	0.3476 (2)	0.0382 (6)
H18A	0.9323	1.3405	0.2826	0.046*
C19	0.8661 (2)	1.2446 (6)	0.39525 (18)	0.0305 (5)
H19A	0.8027	1.1387	0.3623	0.037*
C1S	1.1695 (2)	1.9603 (6)	0.7274 (2)	0.0368 (6)
H1S1	1.2045	2.0217	0.7903	0.055*
H1S2	1.0873	2.0020	0.7150	0.055*
H1S3	1.2051	2.0636	0.6829	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0270 (8)	0.0449 (11)	0.0295 (9)	−0.0100 (8)	0.0067 (7)	−0.0060 (8)
O1S	0.0226 (8)	0.0333 (9)	0.0364 (10)	−0.0025 (7)	0.0064 (7)	−0.0027 (8)
N1	0.0220 (9)	0.0255 (10)	0.0282 (10)	−0.0003 (8)	0.0040 (8)	−0.0010 (9)
N2	0.0228 (9)	0.0262 (10)	0.0310 (11)	0.0006 (8)	0.0047 (8)	0.0015 (8)
N3	0.0223 (10)	0.0280 (10)	0.0269 (10)	−0.0002 (8)	0.0061 (8)	−0.0011 (8)
C1	0.0298 (12)	0.0264 (12)	0.0271 (12)	−0.0032 (10)	0.0081 (10)	0.0005 (10)
C2	0.0306 (12)	0.0284 (12)	0.0262 (12)	−0.0009 (10)	0.0011 (9)	0.0011 (9)
C3	0.0243 (11)	0.0253 (11)	0.0277 (12)	0.0021 (9)	0.0002 (9)	−0.0014 (10)
C4	0.0227 (12)	0.0209 (10)	0.0255 (12)	−0.0011 (9)	0.0029 (9)	−0.0024 (9)
C5	0.0203 (10)	0.0243 (11)	0.0260 (11)	0.0004 (9)	0.0035 (8)	−0.0032 (9)
C6	0.0236 (11)	0.0220 (10)	0.0244 (11)	−0.0013 (9)	0.0044 (9)	−0.0041 (9)
C7	0.0227 (10)	0.0212 (10)	0.0233 (11)	−0.0013 (8)	0.0025 (9)	−0.0029 (9)
C8	0.0286 (12)	0.0246 (11)	0.0242 (11)	−0.0008 (9)	0.0053 (9)	−0.0010 (9)
C9	0.0309 (13)	0.0298 (11)	0.0272 (11)	0.0032 (10)	0.0022 (10)	0.0041 (10)
C10	0.0225 (12)	0.0290 (12)	0.0363 (13)	0.0035 (9)	0.0032 (10)	0.0019 (11)
C11	0.0221 (11)	0.0217 (10)	0.0250 (11)	−0.0013 (8)	0.0024 (9)	−0.0033 (9)
C12	0.0206 (10)	0.0206 (11)	0.0246 (11)	−0.0011 (8)	0.0034 (9)	−0.0023 (9)
C13	0.0241 (11)	0.0259 (11)	0.0257 (11)	0.0017 (9)	0.0057 (8)	0.0000 (9)
C14	0.0214 (10)	0.0268 (11)	0.0294 (12)	0.0020 (9)	0.0056 (9)	0.0022 (10)
C15	0.0222 (10)	0.0275 (11)	0.0308 (12)	0.0021 (9)	0.0056 (9)	0.0002 (10)
C16	0.0215 (11)	0.0326 (13)	0.0397 (14)	−0.0031 (10)	0.0072 (10)	0.0021 (11)
C17	0.0248 (11)	0.0432 (14)	0.0417 (15)	0.0030 (11)	0.0123 (10)	0.0150 (12)
C18	0.0313 (13)	0.0560 (18)	0.0273 (12)	0.0040 (12)	0.0061 (10)	0.0063 (12)
C19	0.0228 (11)	0.0403 (14)	0.0279 (12)	−0.0011 (10)	0.0039 (9)	0.0007 (11)
C1S	0.0318 (13)	0.0350 (14)	0.0451 (16)	−0.0016 (11)	0.0115 (11)	−0.0054 (12)

Geometric parameters (Å, º) top

O1—C15	1.353 (3)	C7—C8	1.413 (3)
O1—H1	0.8400	C8—C9	1.371 (4)
O1S—C1S	1.421 (3)	C8—H8A	0.9500
O1S—H1S	0.8400	C9—C10	1.396 (4)
N1—C1	1.327 (3)	C9—H9A	0.9500
N1—C12	1.356 (3)	C10—H10A	0.9500
N2—C10	1.333 (3)	C11—C12	1.459 (3)
N2—C11	1.359 (3)	C13—C14	1.462 (3)
N3—C13	1.277 (3)	C13—H13A	0.9500
N3—C6	1.406 (3)	C14—C19	1.395 (4)
C1—C2	1.406 (4)	C14—C15	1.410 (3)
C1—H1A	0.9500	C15—C16	1.393 (3)
C2—C3	1.365 (4)	C16—C17	1.374 (4)
C2—H2A	0.9500	C16—H16A	0.9500
C3—C4	1.414 (4)	C17—C18	1.399 (4)
C3—H3A	0.9500	C17—H17A	0.9500
C4—C12	1.412 (3)	C18—C19	1.382 (4)
C4—C5	1.434 (3)	C18—H18A	0.9500
C5—C6	1.368 (3)	C19—H19A	0.9500
C5—H5A	0.9500	C1S—H1S1	0.9800
C6—C7	1.447 (3)	C1S—H1S2	0.9800
C7—C11	1.407 (3)	C1S—H1S3	0.9800

C15—O1—H1	109.5	C9—C10—H10A	118.0
C1S—O1S—H1S	109.5	N2—C11—C7	123.0 (2)
C1—N1—C12	117.7 (2)	N2—C11—C12	117.5 (2)
C10—N2—C11	117.1 (2)	C7—C11—C12	119.5 (2)
C13—N3—C6	118.4 (2)	N1—C12—C4	122.6 (2)
N1—C1—C2	124.0 (2)	N1—C12—C11	118.80 (19)
N1—C1—H1A	118.0	C4—C12—C11	118.6 (2)
C2—C1—H1A	118.0	N3—C13—C14	122.3 (2)
C3—C2—C1	118.5 (2)	N3—C13—H13A	118.9
C3—C2—H2A	120.8	C14—C13—H13A	118.9
C1—C2—H2A	120.8	C19—C14—C15	119.0 (2)
C2—C3—C4	119.6 (2)	C19—C14—C13	121.9 (2)
C2—C3—H3A	120.2	C15—C14—C13	119.1 (2)
C4—C3—H3A	120.2	O1—C15—C16	122.5 (2)
C12—C4—C3	117.6 (2)	O1—C15—C14	118.0 (2)
C12—C4—C5	120.8 (2)	C16—C15—C14	119.4 (2)
C3—C4—C5	121.6 (2)	C17—C16—C15	120.7 (2)
C6—C5—C4	120.6 (2)	C17—C16—H16A	119.7
C6—C5—H5A	119.7	C15—C16—H16A	119.7
C4—C5—H5A	119.7	C16—C17—C18	120.5 (3)
C5—C6—N3	122.9 (2)	C16—C17—H17A	119.7
C5—C6—C7	120.2 (2)	C18—C17—H17A	119.7
N3—C6—C7	116.8 (2)	C19—C18—C17	119.2 (3)
C11—C7—C8	117.9 (2)	C19—C18—H18A	120.4
C11—C7—C6	120.3 (2)	C17—C18—H18A	120.4
C8—C7—C6	121.8 (2)	C18—C19—C14	121.2 (2)
C9—C8—C7	118.9 (2)	C18—C19—H19A	119.4
C9—C8—H8A	120.5	C14—C19—H19A	119.4
C7—C8—H8A	120.5	O1S—C1S—H1S1	109.5
C8—C9—C10	119.0 (2)	O1S—C1S—H1S2	109.5
C8—C9—H9A	120.5	H1S1—C1S—H1S2	109.5
C10—C9—H9A	120.5	O1S—C1S—H1S3	109.5
N2—C10—C9	124.1 (2)	H1S1—C1S—H1S3	109.5
N2—C10—H10A	118.0	H1S2—C1S—H1S3	109.5

C12—N1—C1—C2	0.7 (4)	C6—C7—C11—C12	0.2 (3)
N1—C1—C2—C3	−0.4 (4)	C1—N1—C12—C4	−1.2 (3)
C1—C2—C3—C4	0.4 (4)	C1—N1—C12—C11	179.1 (2)
C2—C3—C4—C12	−0.8 (3)	C3—C4—C12—N1	1.2 (3)
C2—C3—C4—C5	179.2 (2)	C5—C4—C12—N1	−178.7 (2)
C12—C4—C5—C6	0.3 (3)	C3—C4—C12—C11	−179.1 (2)
C3—C4—C5—C6	−179.6 (2)	C5—C4—C12—C11	1.0 (3)
C4—C5—C6—N3	−177.8 (2)	N2—C11—C12—N1	−2.0 (3)
C4—C5—C6—C7	−1.3 (3)	C7—C11—C12—N1	178.5 (2)
C13—N3—C6—C5	−46.2 (3)	N2—C11—C12—C4	178.3 (2)
C13—N3—C6—C7	137.3 (2)	C7—C11—C12—C4	−1.2 (3)
C5—C6—C7—C11	1.1 (3)	C6—N3—C13—C14	176.8 (2)
N3—C6—C7—C11	177.8 (2)	N3—C13—C14—C19	−13.4 (4)
C5—C6—C7—C8	−179.8 (2)	N3—C13—C14—C15	166.3 (2)
N3—C6—C7—C8	−3.1 (3)	C19—C14—C15—O1	178.7 (2)
C11—C7—C8—C9	−1.3 (3)	C13—C14—C15—O1	−1.0 (3)
C6—C7—C8—C9	179.6 (2)	C19—C14—C15—C16	−1.0 (3)
C7—C8—C9—C10	0.3 (4)	C13—C14—C15—C16	179.3 (2)
C11—N2—C10—C9	−0.4 (4)	O1—C15—C16—C17	−179.1 (2)
C8—C9—C10—N2	0.6 (4)	C14—C15—C16—C17	0.7 (4)
C10—N2—C11—C7	−0.7 (3)	C15—C16—C17—C18	−0.3 (4)
C10—N2—C11—C12	179.8 (2)	C16—C17—C18—C19	0.3 (4)
C8—C7—C11—N2	1.6 (3)	C17—C18—C19—C14	−0.7 (4)
C6—C7—C11—N2	−179.3 (2)	C15—C14—C19—C18	1.1 (4)
C8—C7—C11—C12	−178.9 (2)	C13—C14—C19—C18	−179.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1S	0.84	1.81	2.640 (3)	172
O1S—H1S···N1ⁱ	0.84	2.01	2.829 (3)	163
O1S—H1S···N2ⁱ	0.84	2.68	3.242 (3)	126

Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₃N₃O·CH₄O
M_r	331.37
Crystal system, space group	Monoclinic, Pc
Temperature (K)	123
a, b, c (Å)	11.9398 (12), 4.6680 (5), 14.7818 (18)
β (°)	101.961 (11)
V (Å³)	805.98 (16)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	1.15 × 0.84 × 0.06

Data collection
Diffractometer	Oxford Diffraction Gemini-R
Absorption correction	Analytical [CrysAlis RED (Oxford Diffraction, 2007), using a multi-faceted crystal model (Clark & Reid, 1995)]
T_min, T_max	0.505, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	3176, 1960, 1885
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.110, 1.04
No. of reflections	1960
No. of parameters	229
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.17
Absolute structure	Flack, H. D. (1983). Acta Cryst. A39, 876–881, 303 Friedel pairs
Absolute structure parameter	−1.5 (18)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1S	0.84	1.81	2.640 (3)	171.8
O1S—H1S···N1ⁱ	0.84	2.01	2.829 (3)	163.2
O1S—H1S···N2ⁱ	0.84	2.68	3.242 (3)	125.8

Symmetry code: (i) x+1, y+1, z.

Acknowledgements

RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the diffractometer.

References

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