Acta Crystallographica Section E: Crystallographic Communications

Acta Crystallogr E Crystallogr Commun. 72(Pt 11): 1651-1653

Mechanochemical synthesis and crystal structure of a 1:2 co-crystal of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) and 4-chloro-3,5-dimethylphenol

Augusto Riveraa*, Jicli José Rojasa, John Sadat-Bernala, Jaime Ríos-Mottaa, Michael Bolteb

a. Universidad Nacional de Colombia, Sede Bogotá, Facultad de Ciencias, Departamento de Química, Cra 30 No. 45-03, Bogotá, Código Postal 110911, Colombia

b. Institut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von Laue-Str. 7, 60438 Frankfurt/Main, Germany

Correspondence e-mail: ariverau@unal.edu.co

© Rivera et al. 2016

DOI: 10.1107/S2056989016016650

Published online: 25 October 2016

Abstract

In the crystal, the 1:2 co-crystalline adducts are linked by π–π stacking interactions.

Abstract

Solvent-free treatment of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecano (TATU) with 4-chloro-3,5-dimethylphenol led to the formation of the title co-crystal, C₇H₁₄N₄·2C₈H₉ClO. The asymmetric unit contains one aminal cage molecule and two phenol molecules linked via two O—H⋯N hydrogen bonds. In the aminal cage, the N–CH₂–CH₂–N unit is slightly distorted from a syn periplanar geometry. Aromatic π–π stacking between the benzene rings from two different neighbouring phenol molecules [centroid–centroid distance = 4.0570 (11) Å] consolidates the crystal packing.

Chemical context  

Phenols and cyclic aminals are known to form a variety of supramolecular aggregates via O—H⋯N hydrogen bonds, and complexes of phenols with various nitrogen bases are model systems often applied in the study of the nature of the hydrogen bond (Majerz et al. 2007 ▸). Previously, hydrogen bonding between the hydroxyl group of acidic groups such as phenols and heterocyclic nitrogen atoms has proved to be a useful and powerful organizing force for the formation of supramolecules (Jin et al., 2014 ▸). In a continuation of our previously published work in this area (Rivera et al., 2007 ▸, 2015 ▸) and as a part of our research on compounds in which a cyclic aminal acts as a central host and organizes guest molecules around it via hydrogen bonding, we report herein the synthesis and crystal structure of title compound. This was assembled through hydrogen-bonding interactions between the cyclic aminal 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) and 4-chloro-3,5-dimethylphenol.

In recent years, we have become interested in this cage aminal, which contains two pairs of non-equivalent nitrogen atoms. Another intriguing feature of TATU is that, in contrast with the related aminal 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane (TATD) for example (Riddell & Murray-Rust, 1970 ▸), TATU did not react with phenols when the reaction was attempted under standard conditions in various organic solvents. Instead, the reaction only took place when the mixture was at heated in an oil-bath at 393 K for 15 min under solvent-free conditions, affording symmetrical 1,3-bis(2-hydroxybenzyl)imidazolidines (BISBIAs) in good yields (Hernández, 2007 ▸). We also discovered that, under mechanochemical conditions, grinding the reagents in a mortar and pestle, the reaction of TATU with phenols affords phenol–aminal aggregates in excellent yields. Furthermore, no side products form in the reaction mixture. Usually, washing the homogeneous mixture with an appropriate solvent and filtration of the solid gives the pure adduct. In this article, we report the crystal structure of the title compound, an adduct obtained on milling a 1:2 stoichiometric mixture of TATU and 4-chloro-3,5-dimethylphenol in an agate mortar. This mechanochemical process provides a convenient and efficient method to produce these adducts, and is also environmentally friendly.

Structural commentary  

The title compound crystallizes in space group P2₁/n with one aminal cage molecule and two 4-chloro-3,5-dimethylphenol molecules in the asymmetric unit (Fig. 1 ▸) linked by two hydrogen bonds (Table 1 ▸). Nitrogen atoms with the higher sp ³ character act as acceptors in this case, with Σα(C–N–C) = 328.18 and 327.77° for N3 and N4, respectively, as seen with a previous reported TATU hydroquinone adduct (Rivera et al., 2007 ▸). The geometry of the N–C–C–N group of the adamanzane cage in the title compound is slightly distorted from a syn periplanar geometry, as evidenced by the N1—C1—C2—N2 dihedral angle [2.7 (3)°].

Supramolecular features  

In addition to the O—H⋯N contacts that form the 1:2 co-crystals, weak offset π–π stacking interactions link adjacent O1 and O2 phenol rings with a rather long separation between the centroids [Cg8⋯Cg9i = 4.0570 (11); symmetry code: (i)  + x,  − y,  + z; Cg8 and Cg9 are the centroids of the C11–16 and C21–C26 rings, respectively] and the benzene ring planes are inclined to one another by 0.58 (9)°. These additional contacts link the three-membered co-crystal units into chains approximately parallel to (03), Fig. 2 ▸.

Database survey  

Only three comparable structures were found in the Cambridge Structural Database (Groom et al. 2016 ▸), namely 1,3,6,8-tetra-azatricyclo(4.3.1.13,8)undecane hydroquinone (HICTOD; Rivera et al., 2007 ▸), 3,6,8-triaza-1-azoniatricyclo[4.3.1.13,8]undecane pentachlorophenolate monohydrate (OMODEA; Rivera et al., 2011 ▸), and 4-nitrophenol 1,3,6,8-tetra-azatricyclo[4.3.1.13,8]undecane (VUXMEI; Rivera et al., 2015 ▸).

Synthesis and crystallization  

A mixture of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecano (TATU) (154 mg, 1 mmol) and 4-chloro-3,5-dimethylphenol (313 mg, 2 mmol) was ground using a mortar and pestle at room temperature for 15 min. Completion of the reaction was monitored by TLC. The mixture was recrystallized from n-hexane solution to obtain colourless crystals suitable for X-ray analysis, m.p. = 375–376 K. (yield: 63%).

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were located in a difference electron-density map. C-bound H atoms were fixed geometrically (C—H = 0.95 or 0.99Å) and refined using a riding-model approximation, with U iso(H) set to 1.2U eq of the parent atom. The hydroxyl H atoms were refined freely.

Figure 1View larger versionFigure 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.

Figure 2View larger versionFigure 2. Packing diagram for title compound, viewed along the b axis.

See full table Table 1. Hydrogen-bond geometry (Å, °)

See full table Table 2. Experimental details

Supplementary Material

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Acknowledgments

We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia for financial support of this work (research project No. 28427). JJR is also grateful to COLCIENCIAS for his doctoral scholarship

supplementary crystallographic information

Crystal data

See full table

Data collection

See full table

Refinement

See full table

Special details

See full table

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

See full table

Atomic displacement parameters (Å²)

See full table

Geometric parameters (Å, º)

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Hydrogen-bond geometry (Å, º)

See full table

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References

Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179.

Hernández, M. C. (2007). M. Sc. Thesis, Facultad de Ciencias, Universidad Nacional de Colombia, Bogotá D. C., Colombia.

Jin, S., Liu, H., Gao, X. J., Lin, Z., Chen, G. & Wang, D. (2014). J. Mol. Struct. 1075, 124–138.

Majerz, I., Kwiatkowska, E. & Koll, A. (2007). J. Mol. Struct. 831, 106–113.

Riddell, F. G. & Murray-Rust, P. (1970). J. Chem. Soc. D, Chem. Commun. pp. 1074–1075.

Rivera, A., González-Salas, D., Ríos-Motta, J., Hernández-Barragán, A. & Joseph-Nathan, P. (2007). J. Mol. Struct. 837, 142–146.

Rivera, A., Osorio, H. J., Uribe, J. M., Ríos-Motta, J. & Bolte, M. (2015). Acta Cryst. E71, 1356–1360.

Rivera, A., Sadat-Bernal, J., Ríos-Motta, J., Dušek, M. & Fejfarová, K. (2011). J. Chem. Crystallogr. 41, 591–595.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.

Stoe & Cie (2001). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.

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C₇H₁₄N₄·2C₈H₉ClO | F(000) = 992
Mr = 467.42 | Dx = 1.293 Mg m⁻³
Monoclinic, P2₁/n | Mo Kα radiation, λ = 0.71073 Å
a = 14.5170 (8) Å | Cell parameters from 23030 reflections
b = 7.6178 (4) Å | θ = 3.3–25.9°
c = 22.1756 (11) Å | µ = 0.30 mm⁻¹
β = 101.824 (4)° | T = 173 K
V = 2400.3 (2) Å³ | Block, colourless
Z = 4 | 0.28 × 0.24 × 0.24 mm

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STOE IPDS II two-circle diffractometer | 3584 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.032
ω scans | θmax = 25.7°, θmin = 3.3°
Absorption correction: multi-scan (X-Area; Stoe & Cie, 2001) | h = −17→17
Tmin = 0.609, Tmax = 1.000 | k = −9→9
23030 measured reflections | l = −26→26
4501 independent reflections |

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Refinement on F² | 0 restraints
Least-squares matrix: full | Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.100 | w = 1/[σ²(Fo²) + (0.0488P)² + 0.6672P] where P = (Fo² + 2Fc²)/3
S = 1.03 | (Δ/σ)max = 0.001
4501 reflections | Δρmax = 0.28 e Å⁻³
292 parameters | Δρmin = −0.30 e Å⁻³

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Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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| x | y | z | Uiso*/Ueq |
N1 | 0.32321 (11) | 1.00388 (19) | 0.72849 (7) | 0.0303 (3) |
N2 | 0.48631 (12) | 0.9345 (2) | 0.67795 (8) | 0.0386 (4) |
N3 | 0.43541 (11) | 0.75773 (19) | 0.75911 (7) | 0.0287 (3) |
N4 | 0.33805 (11) | 0.76332 (19) | 0.65546 (7) | 0.0291 (3) |
C1 | 0.37625 (16) | 1.1541 (3) | 0.71281 (10) | 0.0417 (5) |
H1A | 0.3950 | 1.2268 | 0.7503 | 0.050* |
H1B | 0.3331 | 1.2259 | 0.6821 | 0.050* |
C2 | 0.46513 (17) | 1.1172 (3) | 0.68706 (11) | 0.0488 (5) |
H2A | 0.4585 | 1.1784 | 0.6470 | 0.059* |
H2B | 0.5197 | 1.1697 | 0.7155 | 0.059* |
C3 | 0.37388 (13) | 0.8935 (2) | 0.77837 (8) | 0.0305 (4) |
H3A | 0.3274 | 0.8343 | 0.7984 | 0.037* |
H3B | 0.4130 | 0.9700 | 0.8096 | 0.037* |
C4 | 0.41772 (15) | 0.8403 (3) | 0.63247 (9) | 0.0373 (5) |
H4A | 0.4506 | 0.7448 | 0.6152 | 0.045* |
H4B | 0.3922 | 0.9219 | 0.5984 | 0.045* |
C5 | 0.27736 (14) | 0.8983 (2) | 0.67616 (8) | 0.0310 (4) |
H5A | 0.2533 | 0.9778 | 0.6412 | 0.037* |
H5B | 0.2224 | 0.8387 | 0.6871 | 0.037* |
C6 | 0.51400 (14) | 0.8331 (3) | 0.73454 (9) | 0.0368 (4) |
H6A | 0.5514 | 0.9097 | 0.7665 | 0.044* |
H6B | 0.5555 | 0.7361 | 0.7268 | 0.044* |
C7 | 0.37716 (14) | 0.6537 (2) | 0.70954 (8) | 0.0307 (4) |
H7A | 0.3249 | 0.5985 | 0.7252 | 0.037* |
H7B | 0.4159 | 0.5588 | 0.6970 | 0.037* |
Cl1 | 0.76106 (5) | −0.00986 (9) | 0.86534 (3) | 0.0680 (2) |
O1 | 0.45719 (10) | 0.5078 (2) | 0.85145 (7) | 0.0395 (3) |
H1 | 0.461 (2) | 0.582 (4) | 0.8252 (13) | 0.066 (9)* |
C11 | 0.52937 (13) | 0.3920 (2) | 0.85398 (8) | 0.0299 (4) |
C12 | 0.60769 (14) | 0.4285 (3) | 0.82904 (8) | 0.0340 (4) |
H12 | 0.6118 | 0.5383 | 0.8094 | 0.041* |
C13 | 0.68020 (15) | 0.3070 (3) | 0.83229 (9) | 0.0394 (5) |
C14 | 0.67140 (15) | 0.1475 (3) | 0.86136 (9) | 0.0391 (5) |
C15 | 0.59503 (15) | 0.1077 (2) | 0.88797 (8) | 0.0369 (5) |
C16 | 0.52400 (14) | 0.2321 (2) | 0.88326 (8) | 0.0328 (4) |
H16 | 0.4706 | 0.2073 | 0.9004 | 0.039* |
C17 | 0.76413 (18) | 0.3517 (4) | 0.80495 (12) | 0.0633 (7) |
H17A | 0.7570 | 0.4708 | 0.7879 | 0.095* |
H17B | 0.7685 | 0.2680 | 0.7721 | 0.095* |
H17C | 0.8215 | 0.3453 | 0.8371 | 0.095* |
C18 | 0.58762 (19) | −0.0650 (3) | 0.92064 (11) | 0.0518 (6) |
H18A | 0.5329 | −0.0619 | 0.9401 | 0.078* |
H18B | 0.6448 | −0.0835 | 0.9522 | 0.078* |
H18C | 0.5804 | −0.1612 | 0.8907 | 0.078* |
Cl2 | 0.31094 (4) | −0.07547 (7) | 0.46192 (3) | 0.05106 (17) |
O2 | 0.20265 (11) | 0.53522 (18) | 0.59453 (7) | 0.0378 (3) |
H2 | 0.252 (2) | 0.606 (4) | 0.6060 (12) | 0.057 (7)* |
C21 | 0.23133 (14) | 0.3965 (2) | 0.56384 (8) | 0.0295 (4) |
C22 | 0.17280 (14) | 0.2507 (2) | 0.55338 (8) | 0.0297 (4) |
H22 | 0.1157 | 0.2507 | 0.5681 | 0.036* |
C23 | 0.19606 (13) | 0.1043 (2) | 0.52177 (8) | 0.0298 (4) |
C24 | 0.28058 (15) | 0.1093 (2) | 0.50121 (8) | 0.0343 (4) |
C25 | 0.34103 (15) | 0.2525 (3) | 0.51093 (10) | 0.0406 (5) |
C26 | 0.31481 (15) | 0.3973 (3) | 0.54264 (9) | 0.0365 (4) |
H26 | 0.3547 | 0.4972 | 0.5497 | 0.044* |
C27 | 0.13190 (16) | −0.0528 (3) | 0.51162 (9) | 0.0389 (5) |
H27A | 0.1059 | −0.0664 | 0.4675 | 0.058* |
H27B | 0.0804 | −0.0360 | 0.5336 | 0.058* |
H27C | 0.1676 | −0.1583 | 0.5272 | 0.058* |
C28 | 0.4326 (2) | 0.2544 (4) | 0.48876 (15) | 0.0711 (8) |
H28A | 0.4759 | 0.1682 | 0.5121 | 0.107* |
H28B | 0.4608 | 0.3716 | 0.4949 | 0.107* |
H28C | 0.4207 | 0.2245 | 0.4449 | 0.107* |

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| U ¹¹ | U ²² | U ³³ | U ¹² | U ¹³ | U ²³
N1 | 0.0329 (9) | 0.0276 (8) | 0.0293 (8) | 0.0056 (7) | 0.0039 (7) | −0.0013 (6)
N2 | 0.0354 (9) | 0.0409 (9) | 0.0402 (9) | −0.0042 (8) | 0.0095 (8) | 0.0104 (7)
N3 | 0.0250 (8) | 0.0308 (8) | 0.0310 (8) | 0.0028 (6) | 0.0070 (6) | 0.0059 (6)
N4 | 0.0319 (9) | 0.0288 (8) | 0.0276 (7) | −0.0004 (7) | 0.0082 (7) | −0.0025 (6)
C1 | 0.0506 (13) | 0.0288 (10) | 0.0423 (11) | −0.0006 (9) | 0.0015 (10) | 0.0027 (8)
C2 | 0.0509 (14) | 0.0415 (12) | 0.0519 (13) | −0.0107 (10) | 0.0053 (11) | 0.0087 (10)
C3 | 0.0334 (10) | 0.0332 (9) | 0.0246 (8) | 0.0036 (8) | 0.0053 (8) | −0.0007 (7)
C4 | 0.0407 (12) | 0.0431 (11) | 0.0309 (10) | 0.0008 (9) | 0.0138 (9) | 0.0035 (8)
C5 | 0.0296 (10) | 0.0330 (9) | 0.0285 (9) | 0.0039 (8) | 0.0014 (7) | −0.0018 (8)
C6 | 0.0267 (10) | 0.0452 (11) | 0.0386 (10) | −0.0007 (9) | 0.0068 (8) | 0.0098 (9)
C7 | 0.0340 (10) | 0.0249 (8) | 0.0354 (10) | 0.0029 (8) | 0.0118 (8) | 0.0021 (7)
Cl1 | 0.0767 (5) | 0.0679 (4) | 0.0573 (4) | 0.0424 (4) | 0.0085 (3) | −0.0006 (3)
O1 | 0.0345 (8) | 0.0433 (8) | 0.0426 (8) | 0.0090 (6) | 0.0122 (6) | 0.0165 (7)
C11 | 0.0282 (10) | 0.0333 (9) | 0.0262 (8) | 0.0007 (8) | 0.0011 (7) | 0.0004 (7)
C12 | 0.0347 (11) | 0.0367 (10) | 0.0299 (9) | 0.0003 (8) | 0.0049 (8) | 0.0060 (8)
C13 | 0.0359 (11) | 0.0503 (12) | 0.0315 (10) | 0.0066 (9) | 0.0056 (9) | 0.0006 (9)
C14 | 0.0438 (12) | 0.0394 (11) | 0.0306 (10) | 0.0132 (9) | −0.0010 (9) | −0.0045 (8)
C15 | 0.0481 (12) | 0.0283 (10) | 0.0275 (9) | −0.0005 (9) | −0.0080 (9) | −0.0018 (7)
C16 | 0.0339 (11) | 0.0343 (10) | 0.0278 (9) | −0.0065 (8) | 0.0004 (8) | 0.0022 (8)
C17 | 0.0464 (15) | 0.0883 (19) | 0.0611 (15) | 0.0167 (14) | 0.0248 (13) | 0.0160 (14)
C18 | 0.0695 (17) | 0.0326 (11) | 0.0457 (12) | −0.0027 (11) | −0.0063 (11) | 0.0054 (9)
Cl2 | 0.0568 (4) | 0.0446 (3) | 0.0520 (3) | 0.0121 (3) | 0.0117 (3) | −0.0150 (2)
O2 | 0.0397 (8) | 0.0314 (7) | 0.0422 (8) | −0.0010 (6) | 0.0079 (6) | −0.0103 (6)
C21 | 0.0357 (10) | 0.0258 (9) | 0.0254 (8) | 0.0051 (8) | 0.0021 (8) | 0.0006 (7)
C22 | 0.0297 (10) | 0.0326 (9) | 0.0258 (9) | 0.0019 (8) | 0.0033 (7) | 0.0006 (7)
C23 | 0.0343 (10) | 0.0297 (9) | 0.0225 (8) | 0.0027 (8) | −0.0009 (7) | 0.0019 (7)
C24 | 0.0402 (11) | 0.0313 (10) | 0.0303 (9) | 0.0075 (8) | 0.0048 (8) | −0.0029 (8)
C25 | 0.0386 (12) | 0.0407 (11) | 0.0447 (11) | 0.0030 (9) | 0.0139 (9) | −0.0002 (9)
C26 | 0.0362 (11) | 0.0319 (10) | 0.0418 (11) | −0.0041 (8) | 0.0091 (9) | −0.0004 (8)
C27 | 0.0461 (12) | 0.0317 (10) | 0.0360 (10) | −0.0050 (9) | 0.0017 (9) | −0.0023 (8)
C28 | 0.0551 (17) | 0.0679 (17) | 0.102 (2) | −0.0075 (14) | 0.0432 (16) | −0.0208 (16)

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N1—C5 | 1.456 (2) | C12—H12 | 0.9500
N1—C1 | 1.460 (3) | C13—C14 | 1.393 (3)
N1—C3 | 1.462 (2) | C13—C17 | 1.507 (3)
N2—C2 | 1.448 (3) | C14—C15 | 1.392 (3)
N2—C4 | 1.453 (3) | C15—C16 | 1.388 (3)
N2—C6 | 1.458 (2) | C15—C18 | 1.516 (3)
N3—C7 | 1.473 (2) | C16—H16 | 0.9500
N3—C6 | 1.477 (2) | C17—H17A | 0.9800
N3—C3 | 1.485 (2) | C17—H17B | 0.9800
N4—C7 | 1.476 (2) | C17—H17C | 0.9800
N4—C4 | 1.478 (2) | C18—H18A | 0.9800
N4—C5 | 1.487 (2) | C18—H18B | 0.9800
C1—C2 | 1.540 (3) | C18—H18C | 0.9800
C1—H1A | 0.9900 | Cl2—C24 | 1.7585 (19)
C1—H1B | 0.9900 | O2—C21 | 1.367 (2)
C2—H2A | 0.9900 | O2—H2 | 0.89 (3)
C2—H2B | 0.9900 | C21—C26 | 1.387 (3)
C3—H3A | 0.9900 | C21—C22 | 1.389 (3)
C3—H3B | 0.9900 | C22—C23 | 1.395 (3)
C4—H4A | 0.9900 | C22—H22 | 0.9500
C4—H4B | 0.9900 | C23—C24 | 1.394 (3)
C5—H5A | 0.9900 | C23—C27 | 1.505 (3)
C5—H5B | 0.9900 | C24—C25 | 1.389 (3)
C6—H6A | 0.9900 | C25—C26 | 1.402 (3)
C6—H6B | 0.9900 | C25—C28 | 1.509 (3)
C7—H7A | 0.9900 | C26—H26 | 0.9500
C7—H7B | 0.9900 | C27—H27A | 0.9800
Cl1—C14 | 1.759 (2) | C27—H27B | 0.9800
O1—C11 | 1.362 (2) | C27—H27C | 0.9800
O1—H1 | 0.82 (3) | C28—H28A | 0.9800
C11—C16 | 1.390 (3) | C28—H28B | 0.9800
C11—C12 | 1.390 (3) | C28—H28C | 0.9800
C12—C13 | 1.392 (3) |  |
C5—N1—C1 | 114.85 (15) | C11—C12—C13 | 121.18 (18)
C5—N1—C3 | 111.23 (14) | C11—C12—H12 | 119.4
C1—N1—C3 | 115.00 (16) | C13—C12—H12 | 119.4
C2—N2—C4 | 115.88 (18) | C12—C13—C14 | 117.61 (18)
C2—N2—C6 | 114.72 (17) | C12—C13—C17 | 119.6 (2)
C4—N2—C6 | 111.36 (16) | C14—C13—C17 | 122.8 (2)
C7—N3—C6 | 107.59 (14) | C15—C14—C13 | 122.87 (18)
C7—N3—C3 | 107.58 (14) | C15—C14—Cl1 | 118.40 (16)
C6—N3—C3 | 113.01 (15) | C13—C14—Cl1 | 118.73 (16)
C7—N4—C4 | 107.88 (15) | C16—C15—C14 | 117.60 (18)
C7—N4—C5 | 107.10 (13) | C16—C15—C18 | 120.2 (2)
C4—N4—C5 | 112.79 (15) | C14—C15—C18 | 122.2 (2)
N1—C1—C2 | 117.90 (16) | C15—C16—C11 | 121.41 (18)
N1—C1—H1A | 107.8 | C15—C16—H16 | 119.3
C2—C1—H1A | 107.8 | C11—C16—H16 | 119.3
N1—C1—H1B | 107.8 | C13—C17—H17A | 109.5
C2—C1—H1B | 107.8 | C13—C17—H17B | 109.5
H1A—C1—H1B | 107.2 | H17A—C17—H17B | 109.5
N2—C2—C1 | 116.43 (17) | C13—C17—H17C | 109.5
N2—C2—H2A | 108.2 | H17A—C17—H17C | 109.5
C1—C2—H2A | 108.2 | H17B—C17—H17C | 109.5
N2—C2—H2B | 108.2 | C15—C18—H18A | 109.5
C1—C2—H2B | 108.2 | C15—C18—H18B | 109.5
H2A—C2—H2B | 107.3 | H18A—C18—H18B | 109.5
N1—C3—N3 | 114.96 (14) | C15—C18—H18C | 109.5
N1—C3—H3A | 108.5 | H18A—C18—H18C | 109.5
N3—C3—H3A | 108.5 | H18B—C18—H18C | 109.5
N1—C3—H3B | 108.5 | C21—O2—H2 | 107.7 (17)
N3—C3—H3B | 108.5 | O2—C21—C26 | 122.80 (17)
H3A—C3—H3B | 107.5 | O2—C21—C22 | 117.58 (17)
N2—C4—N4 | 115.46 (15) | C26—C21—C22 | 119.62 (16)
N2—C4—H4A | 108.4 | C21—C22—C23 | 121.36 (17)
N4—C4—H4A | 108.4 | C21—C22—H22 | 119.3
N2—C4—H4B | 108.4 | C23—C22—H22 | 119.3
N4—C4—H4B | 108.4 | C24—C23—C22 | 117.53 (17)
H4A—C4—H4B | 107.5 | C24—C23—C27 | 122.14 (17)
N1—C5—N4 | 115.16 (15) | C22—C23—C27 | 120.33 (17)
N1—C5—H5A | 108.5 | C25—C24—C23 | 122.76 (17)
N4—C5—H5A | 108.5 | C25—C24—Cl2 | 119.41 (15)
N1—C5—H5B | 108.5 | C23—C24—Cl2 | 117.82 (15)
N4—C5—H5B | 108.5 | C24—C25—C26 | 117.89 (18)
H5A—C5—H5B | 107.5 | C24—C25—C28 | 121.85 (19)
N2—C6—N3 | 115.20 (16) | C26—C25—C28 | 120.3 (2)
N2—C6—H6A | 108.5 | C21—C26—C25 | 120.83 (18)
N3—C6—H6A | 108.5 | C21—C26—H26 | 119.6
N2—C6—H6B | 108.5 | C25—C26—H26 | 119.6
N3—C6—H6B | 108.5 | C23—C27—H27A | 109.5
H6A—C6—H6B | 107.5 | C23—C27—H27B | 109.5
N3—C7—N4 | 111.60 (14) | H27A—C27—H27B | 109.5
N3—C7—H7A | 109.3 | C23—C27—H27C | 109.5
N4—C7—H7A | 109.3 | H27A—C27—H27C | 109.5
N3—C7—H7B | 109.3 | H27B—C27—H27C | 109.5
N4—C7—H7B | 109.3 | C25—C28—H28A | 109.5
H7A—C7—H7B | 108.0 | C25—C28—H28B | 109.5
C11—O1—H1 | 109 (2) | H28A—C28—H28B | 109.5
O1—C11—C16 | 118.06 (17) | C25—C28—H28C | 109.5
O1—C11—C12 | 122.63 (17) | H28A—C28—H28C | 109.5
C16—C11—C12 | 119.31 (18) | H28B—C28—H28C | 109.5
C5—N1—C1—C2 | −67.1 (2) | C12—C13—C14—C15 | −1.4 (3)
C3—N1—C1—C2 | 63.9 (2) | C17—C13—C14—C15 | 178.4 (2)
C4—N2—C2—C1 | 64.0 (2) | C12—C13—C14—Cl1 | 179.18 (15)
C6—N2—C2—C1 | −68.0 (3) | C17—C13—C14—Cl1 | −1.0 (3)
N1—C1—C2—N2 | 2.7 (3) | C13—C14—C15—C16 | 1.9 (3)
C5—N1—C3—N3 | 48.2 (2) | Cl1—C14—C15—C16 | −178.69 (14)
C1—N1—C3—N3 | −84.51 (19) | C13—C14—C15—C18 | −178.64 (19)
C7—N3—C3—N1 | −54.22 (19) | Cl1—C14—C15—C18 | 0.7 (3)
C6—N3—C3—N1 | 64.4 (2) | C14—C15—C16—C11 | −1.1 (3)
C2—N2—C4—N4 | −85.9 (2) | C18—C15—C16—C11 | 179.49 (18)
C6—N2—C4—N4 | 47.6 (2) | O1—C11—C16—C15 | −179.65 (17)
C7—N4—C4—N2 | −53.5 (2) | C12—C11—C16—C15 | −0.2 (3)
C5—N4—C4—N2 | 64.6 (2) | O2—C21—C22—C23 | 179.19 (16)
C1—N1—C5—N4 | 84.1 (2) | C26—C21—C22—C23 | −0.1 (3)
C3—N1—C5—N4 | −48.8 (2) | C21—C22—C23—C24 | 0.2 (3)
C7—N4—C5—N1 | 54.95 (19) | C21—C22—C23—C27 | 179.35 (17)
C4—N4—C5—N1 | −63.6 (2) | C22—C23—C24—C25 | −0.1 (3)
C2—N2—C6—N3 | 85.9 (2) | C27—C23—C24—C25 | −179.16 (19)
C4—N2—C6—N3 | −48.2 (2) | C22—C23—C24—Cl2 | 179.44 (13)
C7—N3—C6—N2 | 54.5 (2) | C27—C23—C24—Cl2 | 0.4 (2)
C3—N3—C6—N2 | −64.1 (2) | C23—C24—C25—C26 | −0.2 (3)
C6—N3—C7—N4 | −60.74 (18) | Cl2—C24—C25—C26 | −179.73 (15)
C3—N3—C7—N4 | 61.31 (17) | C23—C24—C25—C28 | 179.4 (2)
C4—N4—C7—N3 | 60.23 (18) | Cl2—C24—C25—C28 | −0.1 (3)
C5—N4—C7—N3 | −61.44 (18) | O2—C21—C26—C25 | −179.47 (18)
O1—C11—C12—C13 | −179.85 (18) | C22—C21—C26—C25 | −0.2 (3)
C16—C11—C12—C13 | 0.7 (3) | C24—C25—C26—C21 | 0.4 (3)
C11—C12—C13—C14 | 0.1 (3) | C28—C25—C26—C21 | −179.3 (2)
C11—C12—C13—C17 | −179.7 (2) |  |

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D—H···A | D—H | H···A | D···A | D—H···A
O1—H1···N3 | 0.82 (3) | 1.96 (3) | 2.766 (2) | 166 (3)
O2—H2···N4 | 0.89 (3) | 1.90 (3) | 2.760 (2) | 160 (2)

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Figure 1.

The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.

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Figure 2.

Packing diagram for title compound, viewed along the b axis.

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Table 1. Hydrogen-bond geometry (Å, °)

D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A
O1—H1⋯N3 | 0.82 (3) | 1.96 (3) | 2.766 (2) | 166 (3)
O2—H2⋯N4 | 0.89 (3) | 1.90 (3) | 2.760 (2) | 160 (2)

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Table 2. Experimental details

Crystal data
Chemical formula | C₇H₁₄N₄·2C₈H₉ClO
M r | 467.42
Crystal system, space group | Monoclinic, P2₁/n
Temperature (K) | 173
a, b, c (Å) | 14.5170 (8), 7.6178 (4), 22.1756 (11)
β (°) | 101.824 (4)
V (Å³) | 2400.3 (2)
Z | 4
Radiation type | Mo Kα
μ (mm⁻¹) | 0.30
Crystal size (mm) | 0.28 × 0.24 × 0.24
Data collection
Diffractometer | STOE IPDS II two-circle
Absorption correction | Multi-scan (X-AREA; Stoe & Cie, 2001 ▸)
T min, T max | 0.609, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections | 23030, 4501, 3584
R int | 0.032
(sin θ/λ)max (Å⁻¹) | 0.611
Refinement
R[F ² > 2σ(F ²)], wR(F ²), S | 0.042, 0.100, 1.03
No. of reflections | 4501
No. of parameters | 292
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å⁻³) | 0.28, −0.30

Computer programs: X-AREA (Stoe & Cie, 2001 ▸), SHELXS (Sheldrick, 2008 ▸), SHELXL2014/7 (Sheldrick, 2015 ▸) and XP in SHELXTL-Plus (Sheldrick, 2008 ▸).

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