5,11-Diisopropyl-2,8-dimethyl-1H,7H-diimidazo[c,h][1,6]diazecine dihydrate

Mendoza-Díaz, G.; Betancourt-Mendiola, M. de L.; Bernès, S.

doi:10.1107/S1600536810025808

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages o1958-o1959

https://doi.org/10.1107/S1600536810025808

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5,11-Diisopropyl-2,8-dimethyl-1H,7H-diimidazo[c,h][1,6]diazecine dihydrate

Guillermo Mendoza-Díaz,^a ^* María de Lourdes Betancourt-Mendiola ^b and Sylvain Bernès ^c

^aUniversidad de Guanajuato, División de Ciencias e Ingeniería, Departamento de Ingeniería Física, Lomas del Bosque No. 103, Col. Lomas del Campestre, 37150 Leon, Gto., Mexico, ^bUniversidad de Guanajuato, División de Ciencias Naturales y Exactas, Departamento de Química, Noria Alta s/n, 36050 Guanajuato, Gto., Mexico, and ^cDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, N.L., Mexico
^*Correspondence e-mail: mendozag@quijote.ugto.mx

(Received 8 June 2010; accepted 30 June 2010; online 10 July 2010)

Crystals of the title compound, C₁₈H₃₀N₆·2H₂O, are composed of units of diimidazo[c,h][1,6]diazecine and two water molecules. The asymmetric unit contains one half-molecule of diazecine and one uncoordinated water molecule in a general position. The complete ten-membered heterocycle is generated by an inversion center.The organic residue and water molecules form a two-dimensional hydrogen-bonded network. The 1,6-diazecine ring shows a chair conformation, with angles and distances in normal ranges.

Related literature

For background to imidazoles, see: Bouwman et al. (1990 ). For the Mannich reaction, see: Stocker et al. (1970 ). The reaction of formaldehyde, or other aldehydes, with different substrates and conditions has been widely used in organic synthesis, see: Teo et al. (1993 ); Berndt (1970 ); Geue et al. (1994 ); Karunakaran & Kandaswamy (1994 ); Baumann et al. (1984 ); Stocker et al. (1970); Mendoza-Díaz et al. (1996 ). For a similar structure, see: Mendoza-Díaz et al. (2002 ). For the structures of copper complexes with different diazecine derivatives, see: Gasque, Mijangos & Ortiz-Frade (2005 ); Gasque, Olguín & Bernès (2005 ); Luna-Ramírez et al. (2008 ).

Experimental

Crystal data

C₁₈H₃₀N₆·2H₂O
M_r = 366.51
Orthorhombic, P b c n
a = 12.571 (3) Å
b = 14.665 (3) Å
c = 10.877 (4) Å
V = 2005.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 300 K
0.6 × 0.2 × 0.2 mm

Data collection

Siemens P4 diffractometer
2495 measured reflections
1768 independent reflections
1126 reflections with I > 2σ(I)
R_int = 0.022
3 standard reflections every 97 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.157
S = 1.72
1768 reflections
131 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱⁱ	0.92 (2)	1.94 (2)	2.815 (3)	159 (2)
O1—H11⋯N3ⁱⁱⁱ	0.99 (3)	1.91 (3)	2.890 (3)	169 (3)
O1—H12⋯N7^iv	0.94 (3)	2.07 (3)	2.943 (2)	155 (3)
Symmetry codes: (ii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: XSCANS (Siemens, 1996 ); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ), PLUTON (Spek, 1992 , 1993 ) and PLATON (Spek, 2009 ); ; software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810025808/pb2033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810025808/pb2033Isup2.hkl

checkCIF report

Comment top

Imidazole chemistry is of great interest because their wide occurrences in biological systems like a component in the aminoacid histidine or other metabolites as histamine. Also, synthetic imidazole derivatives have found useful in medicine as antihistaminic, antielmitic, antifungiic or amebicide drugs, some of these compounds are 4-disubstituted aminomethyl imidazoles and has been prepared for different multistep process.

The development of new imidazole containing compounds, that could help in the understanding of their properties and the role that imidazole plays in different enzymes, it has been of great interests since many years (Bouwman et al., 1990). Therefore, the continuous develop for easy synthetic processes to obtain new imidazole derivatives is a matter of permanent research.

Mannich reaction is one of those powerful and easy reactions. This reaction is a one-step method to attach aminomethyl groups to the imidazole ring (Stocker et al., 1970). The reaction of formaldehyde, or other aldehydes, with different substrates and conditions has been widely used in organic synthesis. Some of these reactions involve coordinated amino acids (Teo et al., 1993; Berndt, 1970), coordinate amines (Geue et al., 1994), aromatic rings and secondary amines (Karunakaran & Kandaswamy, 1994), 2,4(5)disubtituted imidazoles and secondary amines (Baumann et al., 1984; Stocker et al., 1970). Previously, we have used this reaction under basic conditions to condense propylamine, formaldehyde and 2-methylimidazole (Mendoza-Díaz, Driessen & Reedijk, 1996). The product obtained by the double addition of the formaldehyde on the imidazole ring at the 4 and 5 positions was the heterocyclic 10 member ring: 1,6-diazecine with the imidazole rings fused through the bond between the carbons 4 and 5. In the crystal structure of that compound, an interesting hydrogen bond network was observed, where a cluster of six water molecules in a flat-hexagonal arrangement is in between the diazecine molecules, making a three dimensional network. Also, crystal structure of a similar compound, where instead of propyl substituent an ethanoic acid residue is present has been reported, (Mendoza-Díaz, Driessen, Reedijk, Gorter, Gasque & Thomson, 2002). In this case the water molecules conform an ice-type ring that binds the organic residue in a two dimensional network. Several crystal structures of copper complexes with different diazecine derivatives has been reported (Gasque, Mijangos & Ortiz-Frade, 2005), (Gasque, Olguín & Bernès, 2005), (Luna-Ramírez, Bernès & Gasque, 2008). In all cases the chair conformation of the diazecine ring has been observed.

In this paper, we report the crystal and molecular structure of the title compound, (hereafter referred as isopromeim).

The ORTEP plot showing the molecular structure of isopromeim is shown in figure 1 and bond lengths and angles are in the table of selected geometrical data. The 2-methyl group and the methylene carbons attached directly to the imidazole ring are essentially in the same least squere plane of the imidazole. A slight twist of the C(6) and C(8a) is observed due to their participation in the 1,6-diazecine ring. These deviations from the least squares plane of the imidazole are 0.068 (2) and 0.046 (2) Å, respectively; whereas for the 2-methyl group is -0.009 (3) Å out of plane. These values indicate that there is a slight difference with the n-propyl derivative previously reported. The angle formed between the bond C(5)—C(6) and the least squares plane of the imidazole is 2.71 (15)° and for the bond C(4)—C(8a) and the same plane is only of 1.77 (15)°, whereas for the bond between the methyl group and the imidazole ring (the bond C(2)—C(6)) is 0.49 (18)°.

The 10-member ring of the 1,6-diazecine has a chair -type conformation, linking the two imidazole rings. The angles at the nitrogen bridge in the 1,6-diazecine sum 334.6° indicating a pyramidal conformation.

Isopromeim crystals consist of units of the title compound and two water molecules. These water molecules form a two dimensional network along the crystallographic planes (010) and (100). Particularly, these water molecules link the molecules of isopromeim in a two dimensional structure, as it is illustrated in figure 2. In this hydrogen-bond-bridge are involved the corresponding waters molecules and the nitrogen atoms of the organic residue. Water molecule is acting as a proton-donor and also as a proton-acceptor.

The differences between crystal packing of the propyl and isopropyl derivative indicates that even the diazecine ring is essentially the same in these compounds. Residues attached will drive and control the way that water crystallize. This finding could help in the understanding of how in some imidazole-enzymes may activate water for hydrolysis processes.

Related literature top

For related literature, see: Baumann et al. (1984); Berndt (1970); Bouwman et al. (1990); Gasque, Mijangos & Ortiz-Frade (2005); Gasque, Olguín & Bernès (2005); Geue et al. (1994); Karunakaran & Kandaswamy (1994); Luna-Ramírez, Bernès & Gasque (2008); Mendoza-Díaz, Driessen & Reedijk (1996); Stocker et al. (1970); Teo et al. (1993). Mendoza-Díaz, Driessen, Reedijk, Gorter, Gasque & Thomson (2002).

Experimental top

4.10 g (0.05 mol) of 2-methyl-imidazole and 3.01 g (0.05 mol) of iso-propylamine were added into 20 ml of distilled water. Into this mixture, a solution of 3.13 g of para-formaldehyde, (0.1 mol)previously dissolved in 20 ml of water was slowly added with stirring. The pH was adjusted between 11–12 and then it was allowed 8 days under stirring. A first microcrystalline white precipitated was filtered off and washed with cold water. Yield 3.56 g (14%). The remain solution was allowed to slow evaporation, after two weeks a second crop of a crystalline product was isolated, washed with cold water and dried in air, yielding another 7.35 g (total yield 51%). The two crops were dissolved together into 25 ml of hot methanol and then a small amount of water (about 1 ml) was added. The final solution was cooled in the refrigerator. After three weeks colorless crystals with needle shape and well formed were filtered off. Single crystals were selected for X-ray data collection.

Structure description top

In this paper, we report the crystal and molecular structure of the title compound, (hereafter referred as isopromeim).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006), PLUTON (Spek, 1992, 1993) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP plot (Spek, 2009) of isopromeim, showing the atomic numbering scheme. Observe that the diazecine ring is in a chair conformation.
	Fig. 2. PLUTON98 (Spek, 1992, 1993) plot showing a partial view of the hydrogen bond network in the isopromeim crystal.

5,11-Diisopropyl-2,8-dimethyl-1H,7H- diimidazo[c,h][1,6]diazecine dihydrate top

Crystal data top

C₁₈H₃₀N₆·2H₂O	F(000) = 800
M_r = 366.51	D_x = 1.214 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 100 reflections
a = 12.571 (3) Å	θ = 5.0–12.2°
b = 14.665 (3) Å	µ = 0.08 mm⁻¹
c = 10.877 (4) Å	T = 300 K
V = 2005.3 (9) Å³	Needle, colourless
Z = 4	0.6 × 0.2 × 0.2 mm

Data collection top

Siemens P4 diffractometer	R_int = 0.022
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.1°
Graphite monochromator	h = −2→14
ω scans	k = −17→1
2495 measured reflections	l = −1→12
1768 independent reflections	3 standard reflections every 97 reflections
1126 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.157	w = 1/[σ²(F_o²) + (0.05P)²] where P = (F_o² + 2F_c²)/3
S = 1.72	(Δ/σ)_max < 0.001
1768 reflections	Δρ_max = 0.19 e Å⁻³
131 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.027 (3)

Crystal data top

C₁₈H₃₀N₆·2H₂O	V = 2005.3 (9) Å³
M_r = 366.51	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 12.571 (3) Å	µ = 0.08 mm⁻¹
b = 14.665 (3) Å	T = 300 K
c = 10.877 (4) Å	0.6 × 0.2 × 0.2 mm

Data collection top

Siemens P4 diffractometer	R_int = 0.022
2495 measured reflections	3 standard reflections every 97 reflections
1768 independent reflections	intensity decay: 1%
1126 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.72	Δρ_max = 0.19 e Å⁻³
1768 reflections	Δρ_min = −0.24 e Å⁻³
131 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.78914 (15)	0.45225 (13)	−0.09908 (19)	0.0590 (6)
H1	0.774 (2)	0.3945 (16)	−0.128 (2)	0.071*
C2	0.7545 (2)	0.53228 (16)	−0.1446 (2)	0.0593 (7)
N3	0.80031 (14)	0.60155 (12)	−0.08879 (17)	0.0572 (6)
C4	0.86930 (18)	0.56315 (14)	−0.0031 (2)	0.0522 (6)
C5	0.86320 (18)	0.47026 (14)	−0.0089 (2)	0.0539 (6)
C6	0.91226 (18)	0.39548 (14)	0.0627 (2)	0.0569 (6)
H6A	0.9597	0.4214	0.1237	0.068*
H6B	0.8568	0.3625	0.1060	0.068*
N7	0.97232 (14)	0.33121 (11)	−0.01421 (16)	0.0529 (5)
C8	1.06008 (17)	0.38073 (15)	−0.0766 (2)	0.0570 (6)
H8A	1.0291	0.4204	−0.1384	0.068*
H8B	1.1038	0.3364	−0.1193	0.068*
C9	0.6734 (2)	0.53789 (17)	−0.2431 (3)	0.0764 (8)
H9A	0.6610	0.6007	−0.2637	0.115*
H9B	0.6083	0.5107	−0.2151	0.115*
H9C	0.6984	0.5059	−0.3145	0.115*
C10	1.00890 (19)	0.25037 (14)	0.0567 (2)	0.0611 (7)
H10A	1.0537	0.2714	0.1248	0.073*
C11	1.0735 (2)	0.18781 (17)	−0.0234 (3)	0.0848 (9)
H11A	1.1404	0.2161	−0.0423	0.127*
H11B	1.0355	0.1760	−0.0983	0.127*
H11C	1.0859	0.1314	0.0191	0.127*
C12	0.9152 (2)	0.19821 (17)	0.1096 (3)	0.0739 (8)
H12A	0.8770	0.2366	0.1658	0.111*
H12B	0.9405	0.1452	0.1522	0.111*
H12C	0.8687	0.1798	0.0441	0.111*
O1	0.70233 (15)	0.23151 (12)	0.32676 (16)	0.0700 (6)
H11	0.742 (2)	0.284 (2)	0.362 (3)	0.105*
H12	0.639 (2)	0.2290 (19)	0.372 (3)	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0540 (12)	0.0480 (12)	0.0750 (14)	−0.0032 (10)	−0.0048 (11)	0.0004 (10)
C2	0.0537 (14)	0.0502 (14)	0.0739 (15)	0.0007 (12)	−0.0024 (12)	−0.0009 (12)
N3	0.0513 (11)	0.0508 (12)	0.0694 (13)	0.0023 (9)	−0.0020 (10)	0.0001 (10)
C4	0.0485 (12)	0.0487 (12)	0.0594 (13)	0.0030 (11)	0.0034 (12)	0.0008 (11)
C5	0.0471 (12)	0.0533 (14)	0.0614 (13)	−0.0013 (11)	0.0040 (12)	0.0021 (12)
C6	0.0577 (13)	0.0527 (13)	0.0601 (13)	0.0022 (11)	0.0065 (12)	0.0038 (11)
N7	0.0569 (10)	0.0459 (10)	0.0560 (10)	0.0003 (9)	−0.0004 (9)	0.0033 (9)
C8	0.0585 (14)	0.0544 (13)	0.0580 (13)	−0.0003 (11)	0.0030 (12)	−0.0022 (11)
C9	0.0684 (16)	0.0679 (16)	0.0928 (18)	−0.0031 (13)	−0.0230 (15)	0.0016 (15)
C10	0.0640 (14)	0.0486 (13)	0.0705 (16)	−0.0009 (12)	−0.0115 (13)	0.0066 (11)
C11	0.0915 (19)	0.0565 (15)	0.107 (2)	0.0182 (15)	0.0023 (18)	0.0028 (16)
C12	0.0824 (17)	0.0592 (15)	0.0801 (17)	−0.0076 (14)	−0.0075 (15)	0.0177 (14)
O1	0.0766 (13)	0.0569 (11)	0.0765 (12)	−0.0053 (9)	0.0098 (10)	−0.0044 (9)

Geometric parameters (Å, º) top

N1—C2	1.346 (3)	C8—H8B	0.9700
N1—C5	1.378 (3)	C9—H9A	0.9600
N1—H1	0.92 (2)	C9—H9B	0.9600
C2—N3	1.316 (3)	C9—H9C	0.9600
C2—C9	1.481 (4)	C10—C11	1.504 (3)
N3—C4	1.392 (3)	C10—C12	1.518 (3)
C4—C5	1.366 (3)	C10—H10A	0.9800
C4—C8ⁱ	1.489 (3)	C11—H11A	0.9600
C5—C6	1.480 (3)	C11—H11B	0.9600
C6—N7	1.469 (3)	C11—H11C	0.9600
C6—H6A	0.9700	C12—H12A	0.9600
C6—H6B	0.9700	C12—H12B	0.9600
N7—C8	1.485 (3)	C12—H12C	0.9600
N7—C10	1.487 (3)	O1—H11	0.99 (3)
C8—C4ⁱ	1.489 (3)	O1—H12	0.94 (3)
C8—H8A	0.9700

C2—N1—C5	108.25 (19)	H8A—C8—H8B	107.3
C2—N1—H1	127.6 (16)	C2—C9—H9A	109.5
C5—N1—H1	123.7 (16)	C2—C9—H9B	109.5
N3—C2—N1	111.2 (2)	H9A—C9—H9B	109.5
N3—C2—C9	126.3 (2)	C2—C9—H9C	109.5
N1—C2—C9	122.5 (2)	H9A—C9—H9C	109.5
C2—N3—C4	105.62 (19)	H9B—C9—H9C	109.5
C5—C4—N3	109.7 (2)	N7—C10—C11	110.64 (19)
C5—C4—C8ⁱ	127.7 (2)	N7—C10—C12	110.98 (19)
N3—C4—C8ⁱ	122.53 (19)	C11—C10—C12	109.4 (2)
C4—C5—N1	105.2 (2)	N7—C10—H10A	108.6
C4—C5—C6	133.7 (2)	C11—C10—H10A	108.6
N1—C5—C6	120.95 (19)	C12—C10—H10A	108.6
N7—C6—C5	112.94 (18)	C10—C11—H11A	109.5
N7—C6—H6A	109.0	C10—C11—H11B	109.5
C5—C6—H6A	109.0	H11A—C11—H11B	109.5
N7—C6—H6B	109.0	C10—C11—H11C	109.5
C5—C6—H6B	109.0	H11A—C11—H11C	109.5
H6A—C6—H6B	107.8	H11B—C11—H11C	109.5
C6—N7—C8	109.17 (15)	C10—C12—H12A	109.5
C6—N7—C10	112.00 (16)	C10—C12—H12B	109.5
C8—N7—C10	113.41 (18)	H12A—C12—H12B	109.5
N7—C8—C4ⁱ	116.58 (19)	C10—C12—H12C	109.5
N7—C8—H8A	108.1	H12A—C12—H12C	109.5
C4ⁱ—C8—H8A	108.1	H12B—C12—H12C	109.5
N7—C8—H8B	108.1	H11—O1—H12	105 (2)
C4ⁱ—C8—H8B	108.1

C5—N1—C2—N3	−0.7 (3)	C2—N1—C5—C6	177.1 (2)
C5—N1—C2—C9	−179.6 (2)	C4—C5—C6—N7	−123.6 (3)
N1—C2—N3—C4	0.6 (3)	N1—C5—C6—N7	61.1 (3)
C9—C2—N3—C4	179.4 (2)	C5—C6—N7—C8	61.0 (2)
C2—N3—C4—C5	−0.2 (3)	C5—C6—N7—C10	−172.52 (18)
C2—N3—C4—C8ⁱ	177.6 (2)	C6—N7—C8—C4ⁱ	51.4 (2)
N3—C4—C5—N1	−0.2 (3)	C10—N7—C8—C4ⁱ	−74.2 (2)
C8ⁱ—C4—C5—N1	−177.9 (2)	C6—N7—C10—C11	−177.84 (18)
N3—C4—C5—C6	−176.1 (2)	C8—N7—C10—C11	−53.7 (2)
C8ⁱ—C4—C5—C6	6.2 (4)	C6—N7—C10—C12	60.6 (2)
C2—N1—C5—C4	0.6 (3)	C8—N7—C10—C12	−175.3 (2)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.92 (2)	1.94 (2)	2.815 (3)	159 (2)
O1—H11···N3ⁱⁱⁱ	0.99 (3)	1.91 (3)	2.890 (3)	169 (3)
O1—H12···N7^iv	0.94 (3)	2.07 (3)	2.943 (2)	155 (3)

Symmetry codes: (ii) −x+3/2, −y+1/2, z−1/2; (iii) x, −y+1, z+1/2; (iv) −x+3/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₃₀N₆·2H₂O
M_r	366.51
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	300
a, b, c (Å)	12.571 (3), 14.665 (3), 10.877 (4)
V (Å³)	2005.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.6 × 0.2 × 0.2

Data collection
Diffractometer	Siemens P4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2495, 1768, 1126
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.157, 1.72
No. of reflections	1768
No. of parameters	131
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.24

Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), PLUTON (Spek, 1992, 1993) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

N1—C2	1.346 (3)	C5—C6	1.480 (3)
N1—C5	1.378 (3)	C6—N7	1.469 (3)
N1—H1	0.92 (2)	N7—C8	1.485 (3)
C2—N3	1.316 (3)	N7—C10	1.487 (3)
C2—C9	1.481 (4)	C8—C4ⁱ	1.489 (3)
N3—C4	1.392 (3)	C10—C11	1.504 (3)
C4—C5	1.366 (3)	C10—C12	1.518 (3)
C4—C8ⁱ	1.489 (3)

C2—N1—C5	108.25 (19)	C4—C5—N1	105.2 (2)
C2—N1—H1	127.6 (16)	C4—C5—C6	133.7 (2)
C5—N1—H1	123.7 (16)	N1—C5—C6	120.95 (19)
N3—C2—N1	111.2 (2)	N7—C6—C5	112.94 (18)
N3—C2—C9	126.3 (2)	C6—N7—C10	112.00 (16)
N1—C2—C9	122.5 (2)	C8—N7—C10	113.41 (18)
C2—N3—C4	105.62 (19)	N7—C8—C4ⁱ	116.58 (19)
C5—C4—N3	109.7 (2)	N7—C10—C11	110.64 (19)
C5—C4—C8ⁱ	127.7 (2)	N7—C10—C12	110.98 (19)
N3—C4—C8ⁱ	122.53 (19)	C11—C10—C12	109.4 (2)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.92 (2)	1.94 (2)	2.815 (3)	159 (2)
O1—H11···N3ⁱⁱⁱ	0.99 (3)	1.91 (3)	2.890 (3)	169 (3)
O1—H12···N7^iv	0.94 (3)	2.07 (3)	2.943 (2)	155 (3)

Symmetry codes: (ii) −x+3/2, −y+1/2, z−1/2; (iii) x, −y+1, z+1/2; (iv) −x+3/2, −y+1/2, z+1/2.

Acknowledgements

The authors are grateful to Dirección de Investigación y Posgrado de la Universidad de Guanajuato for financial support.

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