3-(1-Methyl­pyrrolidin-2-yl­idene)-3H-indole sesquihydrate

Helliwell, M.; Aghazadeh, M.; Baradarani, M.M.; Joule, J.A.

doi:10.1107/S1600536809047606

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3114

doi:10.1107/S1600536809047606

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3-(1-Methylpyrrolidin-2-ylidene)-3H-indole sesquihydrate

Madeleine Helliwell,^a Masomeh Aghazadeh,^b Mehdi M. Baradarani ^b and John A. Joule ^a ^*

^aThe School of Chemistry, The University of Manchester, Manchester M13 9PL, England, and ^bDepartment of Chemistry, Faculty of Science, University of Urmia, Urmia 57135, Iran
^*Correspondence e-mail: mmbaradarani@yahoo.com

(Received 28 October 2009; accepted 10 November 2009; online 18 November 2009)

The asymmetric unit of the title compound, C₁₃H₁₄N₂·1.5H₂O, contains two similar molecules of 3-(1-methylpyrrolidin-2-ylidene)-3H-indole, (I), and three water molecules. (I) is the product of reacting indole with 1-methylpyrrolidin-2-one in the presence of phosphorus oxychloride. Both organic molecules are almost completely planar; the maximum distances above and below the least-squares plane through all the atoms of molecule 1 are 0.050 (8) and −0.045 (8) Å, respectively, and the deviations for molecule 2 are 0.096 (8) and −0.059 (8) Å, respectively. In the crystal, the two crystallographically different molecules alternate in π-stacked columns [centroid–centroid distances = 3.729 (5) and 3.858 (5) Å], which are linked by O—H⋯N hydrogen bonds to a network of hydrogen-bonded water molecules. O—H⋯O interactions are also present.

Related literature

For the original synthesis of 3-(1-methylpyrrolidin-2-ylidene)-3H-indole, see: Youngdale et al. (1964 ). For a study of its extraordinarily high basicity, see: Harris & Joule (1978 ) and for examples of its synthetic applications, see: Bishop et al. (1981 , 1982 ); Al-Khawaja et al. (1984 ).

Experimental

Crystal data

C₁₃H₁₄N₂·1.5H₂O
M_r = 225.29
Triclinic, $[P \overline 1]$
a = 7.139 (5) Å
b = 10.805 (8) Å
c = 15.737 (11) Å
α = 88.460 (13)°
β = 88.163 (14)°
γ = 71.506 (13)°
V = 1150.4 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.60 × 0.06 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
4171 measured reflections
1814 independent reflections
1183 reflections with I > 2σ(I)
R_int = 0.114
θ_max = 18.8°

Refinement

R[F² > 2σ(F²)] = 0.078
wR(F²) = 0.154
S = 1.10
1814 reflections
318 parameters
304 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2S—H4S⋯N1	0.91 (3)	1.88 (3)	2.781 (7)	170 (7)
O3S—H6S⋯N3ⁱ	0.92 (3)	1.87 (4)	2.733 (7)	156 (6)
O3S—H5S⋯O2S	0.91 (3)	1.86 (3)	2.757 (7)	168 (6)
O2S—H3S⋯O1Sⁱⁱ	0.90 (3)	1.94 (3)	2.807 (7)	160 (6)
O1S—H2S⋯O3Sⁱⁱⁱ	0.91 (3)	1.95 (4)	2.840 (7)	166 (7)
O1S—H1S⋯O3S^iv	0.91 (3)	1.90 (4)	2.782 (6)	162 (6)
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z+1; (iii) x, y-1, z; (iv) -x+2, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; 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/S1600536809047606/sj2666sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809047606/sj2666Isup2.hkl

checkCIF report

Comment top

Vilsmeier reactions of indole using a tertiary amide in combination with phosphorus oxychloride give rise to 3-acylindoles corresponding to the acyl residue of the amide. However, when 1-methylpyrrolidin-2-one is used as the amide component, 3-(1-methylpyrrolidin-2-ylidene)- 3H-indole (1) is the product (Youngdale et al., 1964). We have discussed this structure and studied its strong basicity (Harris & Joule, 1978) and other reactions (Bishop et al., 1981. Bishop et al., 1982. Al-Khawaja et al., 1984). In order to further understand the chemical reactivity of (1) we felt it was important to crystallographically establish the planar structure, predicted by resonance contributor (2), Fig 3, and also to verify the geometry of the exocyclic double bond.

The asymmetric unit of (1) contains two similar molecules of (1), together with three water molecules. The two molecules are essentially planar; the maximum distances above and below the least squares plane through all the atoms of molecule 1 are 0.050 (8) and -0.045 (8) Å for atoms C12 and C11, respectively; the maximum distances above and below the least squares plane through all the atoms of molecule 2 are 0.096 (8) and -0.059 (8) Å, for atoms C24 and C18, respectively. The two ring systems linked by a double bond in each molecule of (1), are essentially coplanar, with dihedral angles of 0.7 (2) between the atoms C1-C8/N1 and C9-C12/N2 and 2.7 (2)° between the atoms C14-C21/N3 and C22-C25/N4. The conjugation between the two nitrogen atoms, as illustrated by (2) is reflected in the bond lengths: in particular, the C8—N1 double bond at 1.311 (8) Å is long for a double bond between carbon and nitrogen, and the C9—N2 single bond at 1.316 (8) Å is correspondingly short, and almost identical in length to that of the nitrogen-carbon double bond; for molecule 2, the respective corresponding distances are 1.320 (8) and 1.322 (8) Å, for C21—N3 and C22—N4. One intriguing aspect of the crystal packing is shown in Figure 2. The two crystallographically different molecules lie one above the other and are parallel to one another, with a dihedral angle between the molecules of 0.6 (1) °. The molecules stack in such a way as to locate the positively charged end of the resonating system (cf. (2)) over the negatively charged end of the system in the second molecule. Each molecule forms π-stacking interactions with the crystallographically different molecule above and below it, to form columns along a (Figure 2); the perpendicular distance between the ring N2/C9—C12 in molecule 1 to the ring C14—C19 in molecule 2 is 3.404 Å, with a centroid to centroid distance of 3.729 (5) Å (symmetry equivalent x, y, z), whilst the perpendicular distance of the N2/C9—C12 ring in molecule 1 to the C14—C19 in molecule 2 on the other side of molecule 1 is 3.461 Å, with a centroid to centroid distance of 3.858 (5) Å (symmetry equivalent 1 + x, y, z). Between the π-stack columns of molecules 1 and 2 is a network of H-bonded water molecules, which link the columns together via hydrogen bonds between O2S and O3S, and N1 and N3, respectively (see Table 1).

Related literature top

For the original synthesis of 3-(1-methylpyrrolidin-2-ylidene)-3H-indole, see: Youngdale et al. (1964). For a study of its extraordinarily high basicity, see: Harris & Joule (1978) and for examples of its synthetic applications, see: Bishop et al. (1981, 1982); Al-Khawaja et al. (1984). [The scheme should show the hydrate molecules]

Experimental top

To 1-methyl-2-pyrrolidinone (4 mL, 0.04 mol) cooled in an ice bath was added phosphorous oxychloride (4.08 g, 0.026 mol) with stirring during 30 min. The temperature did not exceed 288 K. The mixture was stirred for an additional 10 min, and then a solution of indole (2.80 g, 0.024 mol) in 1-methyl-2-pyrrolidinone (4 mL) was added slowly during 1 h. The temperature rose to 318 K and a solid separated. The mixture was heated at 353 K for 3 h, and then mixed with water (100 mL). The clear solution was made basic by the addition of sodium hydroxide (6 g) in water (30 mL) causing a solid to separate. The solid was filtered off and washed with water. Recrystallization from ethanol-water afforded 3-(1-methylpyrrolidin-2-ylidene)-3H-indole (4.21 g, 90 percent), m.p. 491-492 K.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. Plot showing the two crystallographically independent molecules of (1), with 50% probability ellipsoids.
	Fig. 2. Packing diagram of (1) viewed approximately down b, showing the columns of π-stacked molecules linked by a network of hydrogen bonded water molecules. Only H atoms bonded to water have been included
	Fig. 3. The synthesis of 3-(1-methylpyrrolidin-2-ylidene)-3H-indole

3-(1-Methylpyrrolidin-2-ylidene)-3H-indole sesquihydrate top

Crystal data top

C₁₃H₁₄N₂·1.5H₂O	Z = 4
M_r = 225.29	F(000) = 484
Triclinic, P1	D_x = 1.301 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.139 (5) Å	Cell parameters from 443 reflections
b = 10.805 (8) Å	θ = 2.4–24.5°
c = 15.737 (11) Å	µ = 0.09 mm⁻¹
α = 88.460 (13)°	T = 100 K
β = 88.163 (14)°	Needle, colourless
γ = 71.506 (13)°	0.60 × 0.06 × 0.06 mm
V = 1150.4 (15) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1183 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.114
Graphite monochromator	θ_max = 18.8°, θ_min = 1.3°
ϕ and ω scans	h = −6→6
4171 measured reflections	k = −9→9
1814 independent reflections	l = −14→14

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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0362P)²] where P = (F_o² + 2F_c²)/3
1814 reflections	(Δ/σ)_max = 0.001
318 parameters	Δρ_max = 0.22 e Å⁻³
304 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₁₄N₂·1.5H₂O	γ = 71.506 (13)°
M_r = 225.29	V = 1150.4 (15) Å³
Triclinic, P1	Z = 4
a = 7.139 (5) Å	Mo Kα radiation
b = 10.805 (8) Å	µ = 0.09 mm⁻¹
c = 15.737 (11) Å	T = 100 K
α = 88.460 (13)°	0.60 × 0.06 × 0.06 mm
β = 88.163 (14)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1183 reflections with I > 2σ(I)
4171 measured reflections	R_int = 0.114
1814 independent reflections	θ_max = 18.8°

Refinement top

R[F² > 2σ(F²)] = 0.078	304 restraints
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.22 e Å⁻³
1814 reflections	Δρ_min = −0.21 e Å⁻³
318 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.

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
N1	0.7963 (8)	0.5559 (6)	0.3397 (3)	0.0218 (13)
N2	1.1666 (8)	0.1553 (5)	0.2862 (4)	0.0197 (12)
C1	0.7801 (10)	0.5929 (7)	0.2549 (5)	0.0210 (13)
C2	0.6760 (10)	0.7167 (7)	0.2242 (4)	0.0232 (15)
H2	0.6089	0.7853	0.2614	0.028*
C3	0.6748 (10)	0.7354 (7)	0.1365 (4)	0.0246 (15)
H3	0.6085	0.8192	0.1131	0.030*
C4	0.7688 (10)	0.6334 (7)	0.0826 (5)	0.0237 (15)
H4	0.7643	0.6481	0.0228	0.028*
C5	0.8696 (10)	0.5100 (7)	0.1151 (4)	0.0218 (15)
H5	0.9336	0.4409	0.0777	0.026*
C6	0.8759 (10)	0.4885 (7)	0.2022 (4)	0.0214 (13)
C7	0.9652 (10)	0.3799 (7)	0.2581 (4)	0.0182 (13)
C8	0.9041 (10)	0.4325 (7)	0.3407 (5)	0.0218 (14)
H8	0.9387	0.3824	0.3917	0.026*
C9	1.0810 (10)	0.2546 (7)	0.2355 (4)	0.0208 (14)
C10	1.1279 (10)	0.2148 (6)	0.1464 (4)	0.0238 (15)
H10A	1.1960	0.2709	0.1167	0.029*
H10B	1.0057	0.2217	0.1160	0.029*
C11	1.2626 (10)	0.0733 (7)	0.1498 (4)	0.0257 (15)
H11A	1.2081	0.0170	0.1163	0.031*
H11B	1.3965	0.0662	0.1271	0.031*
C12	1.2691 (10)	0.0343 (7)	0.2431 (4)	0.0247 (15)
H12A	1.2010	−0.0315	0.2542	0.030*
H12B	1.4072	−0.0018	0.2619	0.030*
C13	1.1556 (11)	0.1523 (7)	0.3784 (4)	0.0285 (19)
H13A	1.1991	0.2225	0.4004	0.043*
H13B	1.2413	0.0679	0.3996	0.043*
H13C	1.0190	0.1646	0.3975	0.043*
N3	0.6780 (8)	0.1334 (5)	0.3039 (3)	0.0217 (13)
N4	0.3174 (8)	0.5470 (5)	0.3151 (3)	0.0203 (13)
C14	0.6954 (10)	0.1348 (7)	0.2164 (4)	0.0194 (13)
C15	0.7912 (10)	0.0279 (7)	0.1667 (5)	0.0233 (15)
H15	0.8549	−0.0551	0.1918	0.028*
C16	0.7910 (10)	0.0458 (7)	0.0809 (4)	0.0205 (15)
H16	0.8565	−0.0254	0.0453	0.025*
C17	0.6952 (10)	0.1682 (7)	0.0447 (5)	0.0210 (15)
H17	0.6958	0.1783	−0.0154	0.025*
C18	0.5994 (9)	0.2753 (7)	0.0939 (4)	0.0179 (14)
H18	0.5394	0.3586	0.0683	0.022*
C19	0.5934 (10)	0.2576 (7)	0.1811 (4)	0.0182 (13)
C20	0.5096 (10)	0.3380 (7)	0.2535 (4)	0.0172 (13)
C21	0.5704 (10)	0.2530 (7)	0.3247 (4)	0.0188 (14)
H21	0.5370	0.2794	0.3817	0.023*
C22	0.3950 (10)	0.4706 (7)	0.2503 (4)	0.0178 (13)
C23	0.3398 (10)	0.5486 (6)	0.1704 (4)	0.0218 (15)
H23A	0.2712	0.5061	0.1326	0.026*
H23B	0.4594	0.5561	0.1400	0.026*
C24	0.2046 (10)	0.6821 (7)	0.1952 (4)	0.0251 (15)
H24A	0.0690	0.6961	0.1754	0.030*
H24B	0.2536	0.7514	0.1703	0.030*
C25	0.2075 (11)	0.6824 (7)	0.2915 (4)	0.0261 (15)
H25A	0.2751	0.7431	0.3112	0.031*
H25B	0.0716	0.7082	0.3163	0.031*
C26	0.3396 (11)	0.5135 (7)	0.4050 (4)	0.0300 (19)
H26A	0.2749	0.4479	0.4195	0.045*
H26B	0.2785	0.5918	0.4386	0.045*
H26C	0.4803	0.4782	0.4177	0.045*
O1S	0.7757 (7)	0.1501 (5)	0.5280 (3)	0.0306 (14)
H1S	0.902 (5)	0.140 (6)	0.543 (4)	0.046*
H2S	0.779 (9)	0.078 (5)	0.498 (4)	0.046*
O2S	0.6375 (7)	0.7582 (5)	0.4528 (3)	0.0291 (14)
H3S	0.508 (5)	0.768 (6)	0.459 (4)	0.044*
H4S	0.695 (8)	0.686 (5)	0.421 (4)	0.044*
O3S	0.8359 (7)	0.9358 (5)	0.4183 (3)	0.0286 (14)
H5S	0.762 (9)	0.881 (6)	0.423 (4)	0.043*
H6S	0.798 (9)	0.984 (6)	0.369 (3)	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.016 (3)	0.023 (3)	0.027 (2)	−0.007 (2)	−0.006 (2)	−0.002 (2)
N2	0.012 (3)	0.020 (3)	0.028 (2)	−0.006 (2)	−0.004 (2)	0.001 (2)
C1	0.012 (3)	0.024 (3)	0.029 (2)	−0.008 (2)	−0.009 (3)	0.000 (2)
C2	0.010 (3)	0.027 (3)	0.033 (3)	−0.005 (3)	−0.009 (3)	0.000 (3)
C3	0.010 (3)	0.029 (3)	0.035 (3)	−0.007 (3)	−0.006 (3)	0.003 (3)
C4	0.010 (3)	0.032 (3)	0.032 (3)	−0.009 (3)	−0.007 (3)	0.003 (2)
C5	0.012 (3)	0.026 (3)	0.028 (3)	−0.007 (3)	−0.008 (3)	0.001 (2)
C6	0.012 (3)	0.025 (2)	0.027 (2)	−0.005 (2)	−0.011 (3)	0.001 (2)
C7	0.010 (3)	0.022 (2)	0.024 (3)	−0.007 (2)	−0.009 (2)	0.001 (2)
C8	0.014 (3)	0.025 (3)	0.026 (3)	−0.005 (3)	−0.010 (3)	0.001 (2)
C9	0.013 (3)	0.022 (3)	0.027 (3)	−0.006 (2)	−0.005 (2)	0.003 (2)
C10	0.016 (3)	0.025 (3)	0.029 (3)	−0.005 (3)	−0.003 (3)	0.001 (2)
C11	0.018 (3)	0.026 (3)	0.032 (3)	−0.004 (3)	−0.007 (3)	−0.003 (3)
C12	0.015 (3)	0.024 (3)	0.034 (3)	−0.003 (3)	−0.010 (3)	−0.003 (2)
C13	0.026 (4)	0.023 (4)	0.029 (3)	0.001 (4)	−0.002 (4)	0.010 (3)
N3	0.020 (3)	0.023 (3)	0.022 (2)	−0.007 (2)	−0.010 (3)	0.005 (2)
N4	0.015 (3)	0.023 (3)	0.022 (2)	−0.004 (2)	−0.007 (2)	0.001 (2)
C14	0.015 (3)	0.021 (3)	0.023 (2)	−0.007 (2)	−0.006 (3)	0.003 (2)
C15	0.020 (3)	0.021 (3)	0.029 (3)	−0.007 (3)	−0.005 (3)	0.002 (2)
C16	0.014 (3)	0.022 (3)	0.030 (3)	−0.010 (3)	−0.005 (3)	−0.003 (3)
C17	0.013 (3)	0.026 (3)	0.028 (3)	−0.010 (3)	−0.011 (3)	−0.002 (2)
C18	0.012 (3)	0.021 (3)	0.024 (3)	−0.008 (3)	−0.009 (3)	0.003 (2)
C19	0.011 (3)	0.021 (3)	0.022 (2)	−0.005 (2)	−0.008 (3)	0.004 (2)
C20	0.013 (3)	0.020 (2)	0.021 (2)	−0.009 (2)	−0.007 (2)	0.003 (2)
C21	0.017 (3)	0.023 (3)	0.019 (3)	−0.010 (3)	−0.008 (3)	0.002 (2)
C22	0.014 (3)	0.022 (2)	0.020 (2)	−0.008 (2)	−0.007 (2)	0.000 (2)
C23	0.019 (3)	0.021 (3)	0.026 (3)	−0.005 (3)	−0.012 (3)	0.003 (2)
C24	0.020 (3)	0.023 (3)	0.031 (3)	−0.004 (3)	−0.008 (3)	0.005 (3)
C25	0.021 (3)	0.024 (3)	0.030 (3)	−0.002 (3)	−0.007 (3)	0.002 (2)
C26	0.035 (5)	0.029 (4)	0.019 (3)	0.001 (4)	0.000 (4)	0.000 (3)
O1S	0.014 (3)	0.036 (4)	0.041 (4)	−0.006 (3)	−0.009 (3)	−0.008 (3)
O2S	0.020 (3)	0.034 (4)	0.035 (4)	−0.009 (3)	−0.005 (3)	−0.004 (3)
O3S	0.021 (3)	0.032 (4)	0.034 (3)	−0.009 (3)	−0.015 (3)	0.011 (3)

Geometric parameters (Å, º) top

N1—C8	1.311 (8)	N4—C26	1.453 (8)
N1—C1	1.381 (8)	N4—C25	1.468 (8)
N2—C9	1.316 (8)	C14—C15	1.388 (9)
N2—C13	1.450 (8)	C14—C19	1.405 (9)
N2—C12	1.454 (8)	C15—C16	1.358 (9)
C1—C2	1.390 (9)	C15—H15	0.9500
C1—C6	1.397 (9)	C16—C17	1.397 (9)
C2—C3	1.389 (9)	C16—H16	0.9500
C2—H2	0.9500	C17—C18	1.384 (9)
C3—C4	1.389 (9)	C17—H17	0.9500
C3—H3	0.9500	C18—C19	1.382 (9)
C4—C5	1.391 (9)	C18—H18	0.9500
C4—H4	0.9500	C19—C20	1.446 (9)
C5—C6	1.384 (9)	C20—C22	1.407 (9)
C5—H5	0.9500	C20—C21	1.418 (9)
C6—C7	1.436 (9)	C21—H21	0.9500
C7—C9	1.393 (9)	C22—C23	1.486 (9)
C7—C8	1.431 (9)	C23—C24	1.512 (9)
C8—H8	0.9500	C23—H23A	0.9900
C9—C10	1.475 (9)	C23—H23B	0.9900
C10—C11	1.527 (9)	C24—C25	1.518 (9)
C10—H10A	0.9900	C24—H24A	0.9900
C10—H10B	0.9900	C24—H24B	0.9900
C11—C12	1.514 (9)	C25—H25A	0.9900
C11—H11A	0.9900	C25—H25B	0.9900
C11—H11B	0.9900	C26—H26A	0.9800
C12—H12A	0.9900	C26—H26B	0.9800
C12—H12B	0.9900	C26—H26C	0.9800
C13—H13A	0.9800	O1S—H1S	0.91 (3)
C13—H13B	0.9800	O1S—H2S	0.91 (3)
C13—H13C	0.9800	O2S—H3S	0.90 (3)
N3—C21	1.320 (8)	O2S—H4S	0.91 (3)
N3—C14	1.379 (8)	O3S—H5S	0.91 (3)
N4—C22	1.322 (8)	O3S—H6S	0.92 (3)

C8—N1—C1	105.4 (6)	C22—N4—C25	114.9 (5)
C9—N2—C13	127.0 (6)	C26—N4—C25	117.8 (5)
C9—N2—C12	114.8 (6)	N3—C14—C15	125.5 (7)
C13—N2—C12	118.0 (6)	N3—C14—C19	111.9 (6)
N1—C1—C2	125.1 (7)	C15—C14—C19	122.4 (7)
N1—C1—C6	111.6 (6)	C16—C15—C14	117.9 (7)
C2—C1—C6	123.3 (7)	C16—C15—H15	121.0
C3—C2—C1	116.9 (7)	C14—C15—H15	121.0
C3—C2—H2	121.6	C15—C16—C17	120.4 (7)
C1—C2—H2	121.6	C15—C16—H16	119.8
C2—C3—C4	121.1 (7)	C17—C16—H16	119.8
C2—C3—H3	119.5	C18—C17—C16	122.0 (7)
C4—C3—H3	119.5	C18—C17—H17	119.0
C3—C4—C5	120.8 (7)	C16—C17—H17	119.0
C3—C4—H4	119.6	C19—C18—C17	118.2 (7)
C5—C4—H4	119.6	C19—C18—H18	120.9
C6—C5—C4	119.6 (7)	C17—C18—H18	120.9
C6—C5—H5	120.2	C18—C19—C14	118.9 (6)
C4—C5—H5	120.2	C18—C19—C20	136.4 (7)
C5—C6—C1	118.3 (7)	C14—C19—C20	104.7 (6)
C5—C6—C7	135.7 (7)	C22—C20—C21	129.8 (6)
C1—C6—C7	105.9 (6)	C22—C20—C19	125.9 (6)
C9—C7—C8	129.5 (6)	C21—C20—C19	104.3 (6)
C9—C7—C6	127.5 (6)	N3—C21—C20	113.4 (6)
C8—C7—C6	103.0 (6)	N3—C21—H21	123.3
N1—C8—C7	114.1 (6)	C20—C21—H21	123.3
N1—C8—H8	123.0	N4—C22—C20	127.5 (6)
C7—C8—H8	123.0	N4—C22—C23	108.2 (6)
N2—C9—C7	127.9 (6)	C20—C22—C23	124.3 (6)
N2—C9—C10	109.2 (6)	C22—C23—C24	107.1 (6)
C7—C9—C10	122.9 (6)	C22—C23—H23A	110.3
C9—C10—C11	106.1 (5)	C24—C23—H23A	110.3
C9—C10—H10A	110.5	C22—C23—H23B	110.3
C11—C10—H10A	110.5	C24—C23—H23B	110.3
C9—C10—H10B	110.5	H23A—C23—H23B	108.5
C11—C10—H10B	110.5	C23—C24—C25	105.0 (5)
H10A—C10—H10B	108.7	C23—C24—H24A	110.7
C12—C11—C10	105.0 (6)	C25—C24—H24A	110.7
C12—C11—H11A	110.7	C23—C24—H24B	110.7
C10—C11—H11A	110.7	C25—C24—H24B	110.7
C12—C11—H11B	110.7	H24A—C24—H24B	108.8
C10—C11—H11B	110.7	N4—C25—C24	104.1 (5)
H11A—C11—H11B	108.8	N4—C25—H25A	110.9
N2—C12—C11	104.2 (6)	C24—C25—H25A	110.9
N2—C12—H12A	110.9	N4—C25—H25B	110.9
C11—C12—H12A	110.9	C24—C25—H25B	110.9
N2—C12—H12B	110.9	H25A—C25—H25B	109.0
C11—C12—H12B	110.9	N4—C26—H26A	109.5
H12A—C12—H12B	108.9	N4—C26—H26B	109.5
N2—C13—H13A	109.5	H26A—C26—H26B	109.5
N2—C13—H13B	109.5	N4—C26—H26C	109.5
H13A—C13—H13B	109.5	H26A—C26—H26C	109.5
N2—C13—H13C	109.5	H26B—C26—H26C	109.5
H13A—C13—H13C	109.5	H1S—O1S—H2S	107 (4)
H13B—C13—H13C	109.5	H3S—O2S—H4S	108 (4)
C21—N3—C14	105.7 (6)	H5S—O3S—H6S	106 (4)
C22—N4—C26	127.3 (6)

C8—N1—C1—C2	179.4 (7)	C21—N3—C14—C15	−177.6 (7)
C8—N1—C1—C6	1.7 (8)	C21—N3—C14—C19	−1.0 (8)
N1—C1—C2—C3	−179.4 (7)	N3—C14—C15—C16	178.7 (6)
C6—C1—C2—C3	−1.9 (11)	C19—C14—C15—C16	2.5 (11)
C1—C2—C3—C4	1.8 (10)	C14—C15—C16—C17	−0.6 (10)
C2—C3—C4—C5	−0.9 (11)	C15—C16—C17—C18	0.7 (11)
C3—C4—C5—C6	0.1 (11)	C16—C17—C18—C19	−2.5 (11)
C4—C5—C6—C1	−0.1 (10)	C17—C18—C19—C14	4.2 (10)
C4—C5—C6—C7	−178.3 (8)	C17—C18—C19—C20	−178.5 (7)
N1—C1—C6—C5	178.9 (6)	N3—C14—C19—C18	179.0 (6)
C2—C1—C6—C5	1.1 (11)	C15—C14—C19—C18	−4.4 (11)
N1—C1—C6—C7	−2.5 (8)	N3—C14—C19—C20	0.9 (8)
C2—C1—C6—C7	179.8 (6)	C15—C14—C19—C20	177.6 (6)
C5—C6—C7—C9	0.0 (14)	C18—C19—C20—C22	1.9 (13)
C1—C6—C7—C9	−178.3 (7)	C14—C19—C20—C22	179.5 (6)
C5—C6—C7—C8	−179.5 (8)	C18—C19—C20—C21	−178.0 (8)
C1—C6—C7—C8	2.1 (7)	C14—C19—C20—C21	−0.4 (7)
C1—N1—C8—C7	−0.2 (8)	C14—N3—C21—C20	0.7 (8)
C9—C7—C8—N1	179.3 (7)	C22—C20—C21—N3	179.9 (7)
C6—C7—C8—N1	−1.2 (8)	C19—C20—C21—N3	−0.2 (8)
C13—N2—C9—C7	1.9 (11)	C26—N4—C22—C20	2.9 (12)
C12—N2—C9—C7	176.7 (7)	C25—N4—C22—C20	178.9 (6)
C13—N2—C9—C10	−178.9 (6)	C26—N4—C22—C23	−177.4 (6)
C12—N2—C9—C10	−4.1 (8)	C25—N4—C22—C23	−1.4 (8)
C8—C7—C9—N2	−2.1 (12)	C21—C20—C22—N4	0.3 (12)
C6—C7—C9—N2	178.5 (7)	C19—C20—C22—N4	−179.5 (7)
C8—C7—C9—C10	178.8 (7)	C21—C20—C22—C23	−179.3 (7)
C6—C7—C9—C10	−0.6 (11)	C19—C20—C22—C23	0.8 (11)
N2—C9—C10—C11	−1.2 (8)	N4—C22—C23—C24	−3.9 (8)
C7—C9—C10—C11	178.0 (7)	C20—C22—C23—C24	175.8 (6)
C9—C10—C11—C12	5.7 (7)	C22—C23—C24—C25	7.3 (8)
C9—N2—C12—C11	7.7 (8)	C22—N4—C25—C24	6.0 (8)
C13—N2—C12—C11	−177.0 (6)	C26—N4—C25—C24	−177.6 (6)
C10—C11—C12—N2	−7.6 (7)	C23—C24—C25—N4	−7.8 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2S—H4S···N1	0.91 (3)	1.88 (3)	2.781 (7)	170 (7)
O3S—H6S···N3ⁱ	0.92 (3)	1.87 (4)	2.733 (7)	156 (6)
O3S—H5S···O2S	0.91 (3)	1.86 (3)	2.757 (7)	168 (6)
O2S—H3S···O1Sⁱⁱ	0.90 (3)	1.94 (3)	2.807 (7)	160 (6)
O1S—H2S···O3Sⁱⁱⁱ	0.91 (3)	1.95 (4)	2.840 (7)	166 (7)
O1S—H1S···O3S^iv	0.91 (3)	1.90 (4)	2.782 (6)	162 (6)

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂·1.5H₂O
M_r	225.29
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.139 (5), 10.805 (8), 15.737 (11)
α, β, γ (°)	88.460 (13), 88.163 (14), 71.506 (13)
V (Å³)	1150.4 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.60 × 0.06 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4171, 1814, 1183
R_int	0.114
θ_max (°)	18.8
(sin θ/λ)_max (Å⁻¹)	0.454

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.154, 1.10
No. of reflections	1814
No. of parameters	318
No. of restraints	304
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.21

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), 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
O2S—H4S···N1	0.91 (3)	1.88 (3)	2.781 (7)	170 (7)
O3S—H6S···N3ⁱ	0.92 (3)	1.87 (4)	2.733 (7)	156 (6)
O3S—H5S···O2S	0.91 (3)	1.86 (3)	2.757 (7)	168 (6)
O2S—H3S···O1Sⁱⁱ	0.90 (3)	1.94 (3)	2.807 (7)	160 (6)
O1S—H2S···O3Sⁱⁱⁱ	0.91 (3)	1.95 (4)	2.840 (7)	166 (7)
O1S—H1S···O3S^iv	0.91 (3)	1.90 (4)	2.782 (6)	162 (6)

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+2, −y+1, −z+1.

Acknowledgements

The authors are grateful to the University of Urmia for financial suport of the preparative aspects of this work.

References

Al-Khawaja, I. K., Beddoes, R. L., Bishop, D. I., Cernik, R. J., Joule, J. A. & Mills, O. S. (1984). J. Chem. Res. (S.), pp. 2738–2767. Google Scholar
Bishop, D. I., Al-Khawaja, I. K., Heatley, F. & Joule, J. A. (1982). J. Chem. Res. (S.), pp. 1766–1776. Google Scholar
Bishop, D. I., Al-Khawaja, I. K. & Joule, J. A. (1981). J. Chem. Res. (S.), pp. 4279–4290. Google Scholar
Bruker (2001). SMART Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2002). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Harris, M. & Joule, J. A. (1978). J. Chem. Res. (S.), pp. 470–483. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Youngdale, G. A., Anger, D. G., Anthony, W. C., Da Vanzo, J. P., Greig, M. E., Heinzelman, R. V., Keasling, H. H. & Szmuszkovicz, J. (1964). J. Med. Chem. 7, 415–427. CrossRef PubMed CAS Web of Science Google Scholar