Acta Crystallographica Section E: Crystallographic Communications

Acta Crystallogr E Crystallogr Commun. 72(Pt 11): 1648-1650

Crystal structure of the 1:2 co-crystal of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) and 4-chlorophenol (1/2)

Augusto Riveraa*, Jicli José Rojasa, Héctor Jairo Osoriob, Jaime Ríos-Mottaa, Michael Boltec

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

b. Universidad Nacional de Colombia, Sede Manizales, Manizales, Colombia

c. 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/S2056989016016546

Published online: 25 October 2016

Abstract

The components of the ternary co-crystalline adduct are linked by intermolecular O–H⋯N hydrogen bonds.

Abstract

In the title compound, C₇H₁₄N₄·2C₆H₅ClO, which crystallized with two crystallographically independent 4-chlorophenol molecules and one 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) molecule in the asymmetric unit, the independent components are linked by two O—H⋯N hydrogen bonds. The hydrogen-bond acceptor sites are two non-equivalent N atoms from the aminal cage structure, and the tricyclic system distorts by changing the C—N bond lengths. In the crystal, these hydrogen-bonded aggregates are linked into chains along the c axis by C—H⋯N hydrogen bonds. The crystal structure also features C—H⋯π contacts.

Chemical context  

Following our previous work on phenol–amine adducts based on cyclic aminal cages with phenol derivatives (Rivera et al., 2015a ▸,b ▸,c ▸), we report herein the synthesis and crystal structure of the title 1:2 complex assembled through hydrogen-bonding interactions between the aminal cage, 1,3,6,8-tetraazatricyclo [4.3.1.13,8]undecane (TATU), with 4-chlorophenol under solvent-free conditions at low temperature.

TATU, a small tricyclic aminal cage, is an interesting option for studying hydrogen-bonding situations as it has four nitrogen atoms as potential hydrogen-bond acceptors. These N atoms have two different environments, N1 and N2 from the ethylene fragment (NCH₂CH₂N) and N3 and N4 from the 1,1-gem-diaminic units. These present two discrete options for hydrogen bonding to the aminal cage. With different types of phenols, the preference for a particular hydrogen-bond-interaction site depends strongly upon the lone-pair orbital hybridization of the nitrogen atom (Rivera et al., 2007 ▸). Studies on phenol complexes with tertiary amines in the solid state show that the proton transfer depends not only on the ΔpKa (pKa amine − pKa acid) value but also on steric and packing effects (Majerz & Sawka-Dobrowolska, 1996 ▸). In the structure found for the three-component aggregates observed here, both types of nitrogen atom mentioned above are involved in hydrogen bonding with N1 and N3 acting as hydrogen-bond acceptors. The reaction to produce the co-crystal occurs efficiently in the solid state by grinding a mixture of finely powdered TATU and 4-chlorophenol at room temperature; there are no by-products, and the work-up procedure is easy.

Structural commentary  

The molecular structure of the title compound is illustrated in Fig. 1 ▸. The asymmetric unit comprises two crystallographically independent 4-chlorophenol molecules and one 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) molecule. The phenols are linked to the aminal cage by two O—H⋯N hydrogen bonds (Table 1 ▸), forming 2:1 hydrogen-bonded aggregates. This is similar to the situation observed in the structure of the 2:1 co-crystal of 4-nitrophenol and TATU (Rivera et al., 2015a ▸) which also crystallizes in the P2₁/c space group and has two different types of N atom acting as the hydrogen-bond acceptors. The measured dimensions of the aminal cage structure in the present adduct are similar to the corresponding values in this related structure. The observed N—CH₂ bond lengths are longer than those found in a co-crystal formed between TATU and hydoquinone (Rivera et al., 2007 ▸). This is presumably related to the formation of strong hydrogen bonds by the N1 and N3 hydrogen atoms.

A comparison of the O—H⋯N hydrogen bonds in the title compound with those found for the nitrophenyl analogue (Rivera, et al., 2015a ▸) reveal that both N⋯O distances are significantly longer in the current structure, suggesting that the hydrogen bonds may be somewhat weaker.

Supramolecular features  

In the crystal of title compound, O1—H1⋯N1 and C15—H15⋯N2 hydrogen bonds form columns of TATU molecules and O1 chlorophenol molecules along the c axis, Fig. 2 ▸. The columns are linked by O2—H2⋯N3 hydrogen bonds on one side and C2—H2A⋯Cg8 contacts on the other (Cg8 is the centroid of the C11–C16 ring).

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., 2015a ▸). These structures have already been discussed above.

Synthesis and crystallization  

A mixture of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) (154 mg, 1 mmol) and 4-chlorophenol (257 mg, 2 mmol) was mixed thoroughly in a mortar and then ground at room temperature for 15 min. Progress of the reaction was monitored by TLC. Crystals suitable for X-ray diffraction were obtained from a methanol solution upon slow evaporation of the solvent at room temperature (72% yield, m.p. = 334–336 K)

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were located in difference electron-density maps. The hydroxyl H atoms were refined freely, while C-bound H atoms were fixed geometrically (C—H = 0.95, 0.98 or 0.99 Å) and refined using a riding model, with U iso(H) values set at 1.2U eq of the parent atom (1.5 for methyl groups).

Figure 1View larger versionFigure 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms bonded to C atoms are omitted for clarity. Hydrogen bonds are drawn as dashed lines.

Figure 2View larger versionFigure 2. The crystal packing of the title compound, showing the chain that extends along the c-axis direction. C—H⋯N and O—H⋯N hydrogen bonds are drawn as dashed lines

See full tableTable 1. Hydrogen-bond geometry (Å, °) Cg8 is the centroid of the C11–C16 ring.

See full table Table 2. Experimental details

Supplementary Material

Open In Web Browser

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)

See full table

Hydrogen-bond geometry (Å, º)

Cg8 is the centroid of the C11–C16 ring.

See full table

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

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References

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

Majerz, I. & Sawka-Dobrowolska, W. (1996). J. Chem. Crystallogr. 26, 147–152.

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. (2015a). Acta Cryst. E71, 1356–1360.

Rivera, A., Rojas, J. J., Ríos-Motta, J. & Bolte, M. (2015b). Acta Cryst. E71, 737–740.

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

Rivera, A., Uribe, J. M., Rojas, J. J., Ríos-Motta, J. & Bolte, M. (2015c). Acta Cryst. E71, 463–465.

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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C₇H₁₄N₄·2C₆H₅ClO | F(000) = 864
Mr = 411.32 | Dx = 1.390 Mg m⁻³
Monoclinic, P2₁/c | Mo Kα radiation, λ = 0.71073 Å
a = 5.9495 (3) Å | Cell parameters from 37763 reflections
b = 27.6927 (8) Å | θ = 1.7–27.6°
c = 11.9402 (5) Å | µ = 0.35 mm⁻¹
β = 92.585 (3)° | T = 173 K
V = 1965.24 (14) Å³ | Block, colourless
Z = 4 | 0.26 × 0.25 × 0.24 mm

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STOE IPDS II two-circle diffractometer | 4105 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.045
ω scans | θmax = 27.1°, θmin = 1.9°
Absorption correction: multi-scan (X-Area; Stoe & Cie, 2001) | h = −7→7
Tmin = 0.604, Tmax = 1.000 | k = −35→35
37763 measured reflections | l = −15→15
4251 independent reflections |

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Refinement on F² | Hydrogen site location: mixed
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.040 | w = 1/[σ²(Fo²) + (0.0575P)² + 0.6451P] where P = (Fo² + 2Fc²)/3
wR(F²) = 0.109 | (Δ/σ)max = 0.002
S = 1.09 | Δρmax = 0.40 e Å⁻³
4251 reflections | Δρmin = −0.26 e Å⁻³
253 parameters | Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc*=kFc[1+0.001xFc²λ³/sin(2θ)]-1/4
0 restraints | Extinction coefficient: 0.062 (7)

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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 |
Cl1 | −0.04590 (7) | 0.26962 (2) | −0.10224 (3) | 0.04449 (15) |
O1 | 0.5641 (2) | 0.35658 (5) | 0.24199 (10) | 0.0479 (3) |
H1 | 0.510 (4) | 0.3572 (9) | 0.310 (2) | 0.073 (7)* |
C11 | 0.4191 (3) | 0.33578 (5) | 0.16530 (12) | 0.0356 (3) |
C12 | 0.2099 (3) | 0.31750 (6) | 0.19246 (12) | 0.0387 (3) |
H12 | 0.1644 | 0.3193 | 0.2676 | 0.046* |
C13 | 0.0679 (2) | 0.29680 (5) | 0.11068 (12) | 0.0367 (3) |
H13 | −0.0747 | 0.2845 | 0.1293 | 0.044* |
C14 | 0.1366 (2) | 0.29428 (5) | 0.00163 (12) | 0.0339 (3) |
C15 | 0.3445 (2) | 0.31185 (5) | −0.02693 (12) | 0.0348 (3) |
H15 | 0.3898 | 0.3097 | −0.1020 | 0.042* |
C16 | 0.4855 (2) | 0.33256 (5) | 0.05517 (12) | 0.0350 (3) |
H16 | 0.6283 | 0.3447 | 0.0362 | 0.042* |
Cl2 | 1.00806 (8) | 0.58275 (2) | 1.06573 (4) | 0.05235 (16) |
O2 | 0.7563 (2) | 0.49889 (4) | 0.62512 (9) | 0.0406 (3) |
H2 | 0.655 (4) | 0.4764 (8) | 0.6299 (19) | 0.059 (6)* |
C21 | 0.8062 (2) | 0.51843 (5) | 0.72828 (12) | 0.0328 (3) |
C22 | 1.0146 (2) | 0.54078 (5) | 0.74570 (13) | 0.0376 (3) |
H22 | 1.1157 | 0.5421 | 0.6864 | 0.045* |
C23 | 1.0755 (2) | 0.56101 (5) | 0.84860 (14) | 0.0391 (3) |
H23 | 1.2175 | 0.5763 | 0.8601 | 0.047* |
C24 | 0.9276 (3) | 0.55872 (5) | 0.93448 (13) | 0.0367 (3) |
C25 | 0.7182 (3) | 0.53749 (5) | 0.91821 (14) | 0.0406 (3) |
H25 | 0.6167 | 0.5367 | 0.9774 | 0.049* |
C26 | 0.6576 (2) | 0.51743 (5) | 0.81477 (14) | 0.0382 (3) |
H26 | 0.5137 | 0.5029 | 0.8030 | 0.046* |
N1 | 0.43277 (18) | 0.36094 (4) | 0.46248 (10) | 0.0308 (3) |
N2 | 0.44381 (19) | 0.33973 (4) | 0.69815 (10) | 0.0324 (3) |
N3 | 0.47481 (19) | 0.42152 (4) | 0.61627 (10) | 0.0310 (3) |
N4 | 0.12298 (18) | 0.37751 (4) | 0.59049 (9) | 0.0310 (3) |
C1 | 0.5461 (3) | 0.31658 (5) | 0.49947 (13) | 0.0385 (3) |
H1A | 0.7030 | 0.3179 | 0.4754 | 0.046* |
H1B | 0.4717 | 0.2892 | 0.4595 | 0.046* |
C2 | 0.5526 (3) | 0.30537 (6) | 0.62630 (14) | 0.0393 (3) |
H2A | 0.4821 | 0.2734 | 0.6366 | 0.047* |
H2B | 0.7122 | 0.3026 | 0.6527 | 0.047* |
C3 | 0.5404 (2) | 0.40561 (5) | 0.50412 (11) | 0.0307 (3) |
H3A | 0.5042 | 0.4318 | 0.4498 | 0.037* |
H3B | 0.7055 | 0.4009 | 0.5064 | 0.037* |
C4 | 0.1997 (2) | 0.34370 (5) | 0.67956 (11) | 0.0330 (3) |
H4A | 0.1345 | 0.3539 | 0.7506 | 0.040* |
H4B | 0.1389 | 0.3113 | 0.6609 | 0.040* |
C5 | 0.1885 (2) | 0.36212 (5) | 0.47928 (11) | 0.0329 (3) |
H5A | 0.1172 | 0.3841 | 0.4228 | 0.039* |
H5B | 0.1268 | 0.3294 | 0.4646 | 0.039* |
C6 | 0.5478 (2) | 0.38714 (5) | 0.70586 (11) | 0.0338 (3) |
H6A | 0.7129 | 0.3831 | 0.7043 | 0.041* |
H6B | 0.5145 | 0.4015 | 0.7792 | 0.041* |
C7 | 0.2262 (2) | 0.42473 (5) | 0.61453 (12) | 0.0339 (3) |
H7A | 0.1786 | 0.4365 | 0.6881 | 0.041* |
H7B | 0.1737 | 0.4482 | 0.5566 | 0.041* |

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| U ¹¹ | U ²² | U ³³ | U ¹² | U ¹³ | U ²³
Cl1 | 0.0475 (2) | 0.0507 (2) | 0.0351 (2) | −0.00710 (16) | 0.00008 (15) | −0.00103 (15)
O1 | 0.0452 (6) | 0.0666 (8) | 0.0328 (6) | −0.0153 (5) | 0.0091 (5) | −0.0071 (5)
C11 | 0.0382 (7) | 0.0384 (7) | 0.0307 (7) | −0.0009 (6) | 0.0052 (5) | −0.0002 (5)
C12 | 0.0437 (8) | 0.0445 (8) | 0.0288 (7) | −0.0034 (6) | 0.0106 (6) | −0.0010 (6)
C13 | 0.0364 (7) | 0.0390 (7) | 0.0353 (7) | −0.0010 (6) | 0.0087 (6) | 0.0023 (6)
C14 | 0.0385 (7) | 0.0332 (7) | 0.0301 (7) | 0.0036 (5) | 0.0016 (5) | 0.0031 (5)
C15 | 0.0396 (7) | 0.0375 (7) | 0.0278 (6) | 0.0049 (6) | 0.0070 (5) | 0.0053 (5)
C16 | 0.0365 (7) | 0.0377 (7) | 0.0314 (7) | 0.0014 (6) | 0.0084 (5) | 0.0040 (5)
Cl2 | 0.0697 (3) | 0.0430 (2) | 0.0434 (2) | 0.00721 (18) | −0.00754 (19) | −0.00895 (16)
O2 | 0.0466 (6) | 0.0377 (5) | 0.0373 (6) | −0.0086 (5) | 0.0001 (4) | 0.0005 (4)
C21 | 0.0355 (7) | 0.0269 (6) | 0.0360 (7) | 0.0002 (5) | 0.0003 (5) | 0.0035 (5)
C22 | 0.0357 (7) | 0.0348 (7) | 0.0428 (8) | −0.0045 (6) | 0.0079 (6) | 0.0012 (6)
C23 | 0.0342 (7) | 0.0344 (7) | 0.0486 (8) | −0.0033 (5) | −0.0004 (6) | −0.0018 (6)
C24 | 0.0437 (8) | 0.0279 (6) | 0.0381 (7) | 0.0051 (5) | −0.0018 (6) | −0.0006 (5)
C25 | 0.0431 (8) | 0.0358 (7) | 0.0437 (8) | −0.0002 (6) | 0.0104 (6) | 0.0003 (6)
C26 | 0.0317 (7) | 0.0348 (7) | 0.0485 (8) | −0.0032 (5) | 0.0051 (6) | −0.0005 (6)
N1 | 0.0275 (5) | 0.0360 (6) | 0.0291 (5) | −0.0013 (4) | 0.0036 (4) | −0.0042 (4)
N2 | 0.0306 (6) | 0.0366 (6) | 0.0300 (6) | 0.0007 (4) | 0.0005 (4) | 0.0031 (5)
N3 | 0.0308 (6) | 0.0320 (6) | 0.0301 (6) | −0.0003 (4) | 0.0017 (4) | −0.0026 (4)
N4 | 0.0257 (5) | 0.0392 (6) | 0.0282 (6) | 0.0020 (4) | 0.0030 (4) | −0.0008 (5)
C1 | 0.0364 (7) | 0.0358 (7) | 0.0438 (8) | 0.0028 (6) | 0.0076 (6) | −0.0058 (6)
C2 | 0.0353 (7) | 0.0367 (7) | 0.0459 (8) | 0.0047 (6) | 0.0016 (6) | 0.0015 (6)
C3 | 0.0291 (6) | 0.0340 (7) | 0.0294 (6) | −0.0022 (5) | 0.0041 (5) | 0.0003 (5)
C4 | 0.0294 (6) | 0.0400 (7) | 0.0298 (6) | −0.0017 (5) | 0.0051 (5) | 0.0032 (5)
C5 | 0.0259 (6) | 0.0457 (8) | 0.0270 (6) | −0.0020 (5) | 0.0005 (5) | −0.0027 (5)
C6 | 0.0328 (7) | 0.0403 (7) | 0.0280 (6) | −0.0016 (5) | −0.0030 (5) | −0.0024 (5)
C7 | 0.0318 (7) | 0.0347 (7) | 0.0354 (7) | 0.0057 (5) | 0.0038 (5) | −0.0025 (5)

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Cl1—C14 | 1.7497 (15) | N1—C3 | 1.4692 (17)
O1—C11 | 1.3579 (19) | N1—C5 | 1.4766 (17)
O1—H1 | 0.88 (3) | N2—C6 | 1.4524 (18)
C11—C16 | 1.3929 (19) | N2—C2 | 1.4529 (19)
C11—C12 | 1.395 (2) | N2—C4 | 1.4635 (17)
C12—C13 | 1.386 (2) | N3—C3 | 1.4789 (17)
C12—H12 | 0.9500 | N3—C7 | 1.4808 (17)
C13—C14 | 1.384 (2) | N3—C6 | 1.4824 (18)
C13—H13 | 0.9500 | N4—C5 | 1.4639 (17)
C14—C15 | 1.386 (2) | N4—C7 | 1.4675 (18)
C15—C16 | 1.386 (2) | N4—C4 | 1.4739 (17)
C15—H15 | 0.9500 | C1—C2 | 1.545 (2)
C16—H16 | 0.9500 | C1—H1A | 0.9900
Cl2—C24 | 1.7494 (15) | C1—H1B | 0.9900
O2—C21 | 1.3657 (18) | C2—H2A | 0.9900
O2—H2 | 0.87 (2) | C2—H2B | 0.9900
C21—C26 | 1.390 (2) | C3—H3A | 0.9900
C21—C22 | 1.393 (2) | C3—H3B | 0.9900
C22—C23 | 1.384 (2) | C4—H4A | 0.9900
C22—H22 | 0.9500 | C4—H4B | 0.9900
C23—C24 | 1.382 (2) | C5—H5A | 0.9900
C23—H23 | 0.9500 | C5—H5B | 0.9900
C24—C25 | 1.384 (2) | C6—H6A | 0.9900
C25—C26 | 1.387 (2) | C6—H6B | 0.9900
C25—H25 | 0.9500 | C7—H7A | 0.9900
C26—H26 | 0.9500 | C7—H7B | 0.9900
N1—C1 | 1.4601 (19) |  |
C11—O1—H1 | 112.3 (16) | C7—N3—C6 | 107.96 (11)
O1—C11—C16 | 117.72 (13) | C5—N4—C7 | 108.10 (11)
O1—C11—C12 | 122.92 (13) | C5—N4—C4 | 112.53 (11)
C16—C11—C12 | 119.36 (14) | C7—N4—C4 | 108.15 (11)
C13—C12—C11 | 120.54 (13) | N1—C1—C2 | 117.17 (12)
C13—C12—H12 | 119.7 | N1—C1—H1A | 108.0
C11—C12—H12 | 119.7 | C2—C1—H1A | 108.0
C14—C13—C12 | 119.15 (13) | N1—C1—H1B | 108.0
C14—C13—H13 | 120.4 | C2—C1—H1B | 108.0
C12—C13—H13 | 120.4 | H1A—C1—H1B | 107.2
C13—C14—C15 | 121.22 (14) | N2—C2—C1 | 117.06 (12)
C13—C14—Cl1 | 119.11 (12) | N2—C2—H2A | 108.0
C15—C14—Cl1 | 119.65 (11) | C1—C2—H2A | 108.0
C16—C15—C14 | 119.34 (13) | N2—C2—H2B | 108.0
C16—C15—H15 | 120.3 | C1—C2—H2B | 108.0
C14—C15—H15 | 120.3 | H2A—C2—H2B | 107.3
C15—C16—C11 | 120.39 (13) | N1—C3—N3 | 115.37 (11)
C15—C16—H16 | 119.8 | N1—C3—H3A | 108.4
C11—C16—H16 | 119.8 | N3—C3—H3A | 108.4
C21—O2—H2 | 110.4 (15) | N1—C3—H3B | 108.4
O2—C21—C26 | 122.85 (13) | N3—C3—H3B | 108.4
O2—C21—C22 | 117.81 (13) | H3A—C3—H3B | 107.5
C26—C21—C22 | 119.33 (14) | N2—C4—N4 | 115.47 (11)
C23—C22—C21 | 120.55 (14) | N2—C4—H4A | 108.4
C23—C22—H22 | 119.7 | N4—C4—H4A | 108.4
C21—C22—H22 | 119.7 | N2—C4—H4B | 108.4
C24—C23—C22 | 119.35 (14) | N4—C4—H4B | 108.4
C24—C23—H23 | 120.3 | H4A—C4—H4B | 107.5
C22—C23—H23 | 120.3 | N4—C5—N1 | 115.69 (11)
C23—C24—C25 | 120.97 (14) | N4—C5—H5A | 108.4
C23—C24—Cl2 | 119.32 (12) | N1—C5—H5A | 108.4
C25—C24—Cl2 | 119.71 (12) | N4—C5—H5B | 108.4
C24—C25—C26 | 119.44 (14) | N1—C5—H5B | 108.4
C24—C25—H25 | 120.3 | H5A—C5—H5B | 107.4
C26—C25—H25 | 120.3 | N2—C6—N3 | 115.14 (11)
C25—C26—C21 | 120.33 (14) | N2—C6—H6A | 108.5
C25—C26—H26 | 119.8 | N3—C6—H6A | 108.5
C21—C26—H26 | 119.8 | N2—C6—H6B | 108.5
C1—N1—C3 | 114.69 (11) | N3—C6—H6B | 108.5
C1—N1—C5 | 114.92 (11) | H6A—C6—H6B | 107.5
C3—N1—C5 | 110.62 (11) | N4—C7—N3 | 111.00 (11)
C6—N2—C2 | 115.45 (12) | N4—C7—H7A | 109.4
C6—N2—C4 | 111.01 (11) | N3—C7—H7A | 109.4
C2—N2—C4 | 115.17 (12) | N4—C7—H7B | 109.4
C3—N3—C7 | 108.03 (10) | N3—C7—H7B | 109.4
C3—N3—C6 | 112.41 (11) | H7A—C7—H7B | 108.0
O1—C11—C12—C13 | 179.72 (15) | C4—N2—C2—C1 | 65.17 (17)
C16—C11—C12—C13 | −0.7 (2) | N1—C1—C2—N2 | 0.5 (2)
C11—C12—C13—C14 | 0.3 (2) | C1—N1—C3—N3 | −85.46 (14)
C12—C13—C14—C15 | 0.3 (2) | C5—N1—C3—N3 | 46.49 (15)
C12—C13—C14—Cl1 | −178.29 (12) | C7—N3—C3—N1 | −53.85 (15)
C13—C14—C15—C16 | −0.4 (2) | C6—N3—C3—N1 | 65.16 (15)
Cl1—C14—C15—C16 | 178.18 (11) | C6—N2—C4—N4 | 47.85 (15)
C14—C15—C16—C11 | −0.1 (2) | C2—N2—C4—N4 | −85.71 (15)
O1—C11—C16—C15 | −179.79 (14) | C5—N4—C4—N2 | 65.04 (15)
C12—C11—C16—C15 | 0.6 (2) | C7—N4—C4—N2 | −54.30 (15)
O2—C21—C22—C23 | −179.63 (13) | C7—N4—C5—N1 | 54.75 (15)
C26—C21—C22—C23 | 1.2 (2) | C4—N4—C5—N1 | −64.62 (16)
C21—C22—C23—C24 | 0.2 (2) | C1—N1—C5—N4 | 84.81 (15)
C22—C23—C24—C25 | −1.5 (2) | C3—N1—C5—N4 | −47.03 (16)
C22—C23—C24—Cl2 | 178.15 (12) | C2—N2—C6—N3 | 85.50 (15)
C23—C24—C25—C26 | 1.2 (2) | C4—N2—C6—N3 | −47.92 (15)
Cl2—C24—C25—C26 | −178.40 (12) | C3—N3—C6—N2 | −64.54 (15)
C24—C25—C26—C21 | 0.3 (2) | C7—N3—C6—N2 | 54.51 (15)
O2—C21—C26—C25 | 179.42 (14) | C5—N4—C7—N3 | −61.56 (14)
C22—C21—C26—C25 | −1.5 (2) | C4—N4—C7—N3 | 60.53 (14)
C3—N1—C1—C2 | 64.76 (16) | C3—N3—C7—N4 | 61.15 (14)
C5—N1—C1—C2 | −65.11 (16) | C6—N3—C7—N4 | −60.65 (14)
C6—N2—C2—C1 | −66.31 (17) |  |

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D—H···A | D—H | H···A | D···A | D—H···A
O1—H1···N1 | 0.88 (3) | 1.91 (3) | 2.7824 (16) | 172 (2)
O2—H2···N3 | 0.87 (2) | 1.86 (2) | 2.7186 (16) | 167 (2)
C15—H15···N2i | 0.95 | 2.56 | 3.4491 (18) | 156
C2—H2A···Cg8ii | 0.99 | 2.79 | 3.7348 (18) | 160

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Figure 1.

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms bonded to C atoms are omitted for clarity. Hydrogen bonds are drawn as dashed lines.

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Figure 2.

The crystal packing of the title compound, showing the chain that extends along the c-axis direction. C—H⋯N and O—H⋯N hydrogen bonds are drawn as dashed lines

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

Cg8 is the centroid of the C11–C16 ring.

D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A
O1—H1⋯N1 | 0.88 (3) | 1.91 (3) | 2.7824 (16) | 172 (2)
O2—H2⋯N3 | 0.87 (2) | 1.86 (2) | 2.7186 (16) | 167 (2)
C15—H15⋯N2i | 0.95 | 2.56 | 3.4491 (18) | 156
C2—H2A⋯Cg8ii | 0.99 | 2.79 | 3.7348 (18) | 160

Symmetry codes: (i) ; (ii) .

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Table 2. Experimental details

Crystal data
Chemical formula | C₇H₁₄N₄·2C₆H₅ClO
M r | 411.32
Crystal system, space group | Monoclinic, P2₁/c
Temperature (K) | 173
a, b, c (Å) | 5.9495 (3), 27.6927 (8), 11.9402 (5)
β (°) | 92.585 (3)
V (Å³) | 1965.24 (14)
Z | 4
Radiation type | Mo Kα
μ (mm⁻¹) | 0.35
Crystal size (mm) | 0.26 × 0.25 × 0.24
Data collection
Diffractometer | STOE IPDS II two-circle
Absorption correction | Multi-scan (X-AREA; Stoe & Cie, 2001 ▸)
T min, T max | 0.604, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections | 37763, 4251, 4105
R int | 0.045
(sin θ/λ)max (Å⁻¹) | 0.640
Refinement
R[F ² > 2σ(F ²)], wR(F ²), S | 0.040, 0.109, 1.09
No. of reflections | 4251
No. of parameters | 253
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å⁻³) | 0.40, −0.26

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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