Resorcinol–triethyl­enediamine (1/1)

Gao, Y.-H.

doi:10.1107/S1600536811029308

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2158

doi:10.1107/S1600536811029308

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Resorcinol–triethylenediamine (1/1)

Yi-Hong Gao ^a ^*

^aCollege of Chemistry & Chemical Engineering, Xianyang Nomal University, Xianyang 712000, People's Republic of China
^*Correspondence e-mail: shanxiab@163.com

(Received 8 July 2011; accepted 20 July 2011; online 30 July 2011)

The title co-crystal, C₆H₁₂N₂·C₆H₆O₂, is composed of neutral resorcinol and triethylenediamine molecules in which the resorcinol molecules came from the in situ decarboxylation of 2,4-dihydroxybenzoic acid. In the crystal, the components are connected by O—H⋯N hydrogen bonds, forming a chain in the b-axis direction.

Related literature

For background to alkali metal bis(salicylato)borates, see: Barthel et al. (2000 ) and to organic base bis(salicylato)borates, see: Han et al. (2007 ); Li & Liu (2006 ).

Experimental

Crystal data

C₆H₁₂N₂·C₆H₆O₂
M_r = 222.29
Monoclinic, P 2₁ /c
a = 9.4882 (5) Å
b = 23.7390 (11) Å
c = 11.2532 (6) Å
β = 113.335 (6)°
V = 2327.3 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.45 × 0.43 × 0.02 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.789, T_max = 1.000
8717 measured reflections
4091 independent reflections
3270 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.121
S = 1.03
4091 reflections
290 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.98	2.7577 (18)	158
O2—H2⋯N2ⁱ	0.82	1.93	2.7279 (17)	164
O3—H3⋯N4ⁱⁱ	0.82	1.89	2.6816 (19)	162
O4—H4⋯N3	0.82	1.88	2.6525 (19)	156
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811029308/vm2111sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811029308/vm2111Isup2.hkl

checkCIF report

Comment top

Alkali metal bis(salicylato)borates have received much attention, since lithium organoborates have been considered as the lithium battery electrolytes (Barthel et al., 2000). In contrast, studies of organic base bis(salicylato)borates have been less extensive (Li and Liu, 2006; Han et al., 2007). In the process of the synthesis of such compounds, a new crystal with supramolecular structure of [(C₆H₆O₂)₂ (C₆H₁₂N₂)₂] has been obtained.

Single crystal diffraction has revealed that the title compound crystallizes in the monoclinic space group P2₁/c. It is composed of neutral resorcinol and triethylenediamine molecules (Fig.1), in which the resorcinol molecules came from the in situ decarboxylation of 2, 4-dihydroxy benzoic acid. These two kinds of molecules are connected by O—H···N hydrogen bonds to form one-dimensional supramolecular structure (Fig.2), with O···N distances in the range 2.6525 (19) – 2.7577 (18) Å and O—H···N angles in the range 156–164° (Table 1).

In order to evaluate the thermal stability of the synthesized compounds, TG experiments were employed under N₂ atmosphere (Fig. 3). The crystal is stable before 150 °C, and quickly completes the decomposition process from 150 °C to 250 °C. The total weight loss of 99.02% corresponds to the self-decomposition of all organic matter (calculated value of 100%). The luminescent properties of this compound in the solid state at room temperature were investigated. As shown in Fig. 4, upon excitation of the solid sample at 300 nm, it exhibited strong fluorescent emission bands at 420 nm.

Related literature top

For background to alkali metal bis(salicylato)borates , see: Barthel et al. (2000) and to organic base bis(salicylato)borates, see: Han et al. (2007); Li & Liu (2006).

Experimental top

All reagents used in the synthesis were analytic grade and were used without further purification. A solution of boric acid (0.1684 g) in 2.5 ml distilled water was added to a stirred solution of 2, 4-dihydroxybenzoic acid (0.7706 g) in 10 ml of a mixed ethanol/water (1:1) solvent. The reaction mixture was stirred at 80 °C for 20 minutes, then 0.5507 g of triethylenediamine hexahydrate was added slowly. After 4 h continued heating and stirring, the obtained clear solution was then allowed to stand in an open beaker for several days at room temperature. The resulting colorless crystals were collected and dried in air at ambient temperature. IR (KBr pellets, cm^-1): 458, 541, 686, 778, 837, 956, 1058, 1147, 1347, 1450, 1609, 1789, 2354, 2875, 2945 and 3054.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Asymmetric unit structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level
	Fig. 2. One-dimensional chain formation of the title compound constructed by hydrogen bonding (dashed lines).
	Fig. 3. TG curve of the thermal decomposition of the title compound.
	Fig. 4. Solid state fluorescent excitation (a) and emission (b) of the title compound at room temperature.

Resorcinol–triethylenediamine (1/1) top

Crystal data top

C₆H₁₂N₂·C₆H₆O₂	F(000) = 960
M_r = 222.29	D_x = 1.269 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.4882 (5) Å	Cell parameters from 4982 reflections
b = 23.7390 (11) Å	θ = 2.5–28.7°
c = 11.2532 (6) Å	µ = 0.09 mm⁻¹
β = 113.335 (6)°	T = 293 K
V = 2327.3 (2) Å³	Block, colorless
Z = 8	0.45 × 0.43 × 0.02 mm

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	4091 independent reflections
Radiation source: fine-focus sealed tube	3270 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 16.0356 pixels mm^-1	θ_max = 25.0°, θ_min = 2.5°
ϕ and ω scans	h = −11→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −25→28
T_min = 0.789, T_max = 1.000	l = −13→13
8717 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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0581P)² + 0.6593P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4091 reflections	Δρ_max = 0.19 e Å⁻³
290 parameters	Δρ_min = −0.16 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: 0.0037 (5)

Crystal data top

C₆H₁₂N₂·C₆H₆O₂	V = 2327.3 (2) Å³
M_r = 222.29	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.4882 (5) Å	µ = 0.09 mm⁻¹
b = 23.7390 (11) Å	T = 293 K
c = 11.2532 (6) Å	0.45 × 0.43 × 0.02 mm
β = 113.335 (6)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	4091 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	3270 reflections with I > 2σ(I)
T_min = 0.789, T_max = 1.000	R_int = 0.017
8717 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.03	Δρ_max = 0.19 e Å⁻³
4091 reflections	Δρ_min = −0.16 e Å⁻³
290 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	0.57689 (16)	0.11324 (6)	0.29731 (13)	0.0351 (3)
N2	0.50838 (16)	0.01065 (5)	0.22286 (13)	0.0339 (3)
N3	0.08210 (16)	0.23305 (6)	0.76867 (13)	0.0370 (3)
N4	0.01256 (16)	0.12882 (6)	0.72564 (13)	0.0382 (4)
O1	0.66383 (16)	0.21624 (5)	0.41752 (11)	0.0498 (4)
H1	0.6499	0.1888	0.3698	0.075*
O2	0.57485 (17)	0.41139 (5)	0.40869 (12)	0.0513 (4)
H2	0.5375	0.4376	0.3585	0.077*
O3	0.10750 (18)	0.52913 (5)	0.87710 (13)	0.0639 (5)
H3	0.0696	0.5564	0.8308	0.096*
O4	0.16822 (17)	0.33461 (5)	0.86965 (13)	0.0623 (4)
H4	0.1466	0.3072	0.8214	0.093*
C1	0.60465 (18)	0.26301 (7)	0.34498 (15)	0.0329 (4)
C2	0.61811 (19)	0.31376 (7)	0.40953 (15)	0.0351 (4)
H2A	0.6659	0.3149	0.4994	0.042*
C3	0.56053 (19)	0.36304 (7)	0.34055 (15)	0.0334 (4)
C4	0.4897 (2)	0.36123 (7)	0.20618 (16)	0.0383 (4)
H4A	0.4502	0.3939	0.1593	0.046*
C5	0.4784 (2)	0.31060 (7)	0.14309 (16)	0.0429 (4)
H5	0.4320	0.3095	0.0532	0.051*
C6	0.5348 (2)	0.26146 (7)	0.21091 (16)	0.0406 (4)
H6	0.5261	0.2276	0.1670	0.049*
C7	0.10691 (19)	0.38158 (7)	0.80009 (17)	0.0381 (4)
C8	0.13280 (19)	0.43163 (7)	0.86713 (17)	0.0389 (4)
H8	0.1890	0.4317	0.9562	0.047*
C9	0.07617 (19)	0.48179 (7)	0.80370 (17)	0.0378 (4)
C10	−0.0087 (2)	0.48160 (7)	0.67068 (17)	0.0412 (4)
H10	−0.0467	0.5151	0.6268	0.049*
C11	−0.0358 (2)	0.43120 (8)	0.60472 (17)	0.0449 (5)
H11	−0.0936	0.4310	0.5159	0.054*
C12	0.0208 (2)	0.38112 (8)	0.66717 (17)	0.0429 (4)
H12	0.0017	0.3475	0.6212	0.051*
C13	0.5384 (2)	0.08133 (7)	0.39281 (16)	0.0415 (4)
H13A	0.4484	0.0977	0.4000	0.050*
H13B	0.6229	0.0837	0.4769	0.050*
C14	0.5066 (2)	0.01928 (7)	0.35205 (17)	0.0422 (4)
H14A	0.5841	−0.0043	0.4147	0.051*
H14B	0.4073	0.0084	0.3504	0.051*
C15	0.4430 (2)	0.11111 (7)	0.17216 (17)	0.0445 (5)
H15A	0.4681	0.1296	0.1061	0.053*
H15B	0.3575	0.1311	0.1794	0.053*
C16	0.3966 (2)	0.04980 (7)	0.13256 (17)	0.0444 (5)
H16A	0.2957	0.0427	0.1321	0.053*
H16B	0.3913	0.0435	0.0457	0.053*
C17	0.7064 (2)	0.08497 (8)	0.2814 (2)	0.0471 (5)
H17A	0.7935	0.0835	0.3642	0.056*
H17B	0.7365	0.1063	0.2218	0.056*
C18	0.6620 (2)	0.02515 (8)	0.2297 (2)	0.0458 (5)
H18A	0.6632	0.0223	0.1441	0.055*
H18B	0.7364	−0.0013	0.2859	0.055*
C19	0.0785 (3)	0.21639 (8)	0.64220 (19)	0.0555 (5)
H19A	0.1771	0.2244	0.6387	0.067*
H19B	0.0009	0.2381	0.5748	0.067*
C20	0.0428 (3)	0.15370 (8)	0.61859 (19)	0.0543 (5)
H20A	−0.0462	0.1486	0.5382	0.065*
H20B	0.1291	0.1346	0.6106	0.065*
C21	−0.0700 (2)	0.22206 (8)	0.7684 (2)	0.0494 (5)
H21A	−0.1456	0.2454	0.7035	0.059*
H21B	−0.0699	0.2319	0.8521	0.059*
C22	−0.1134 (2)	0.16008 (8)	0.7396 (2)	0.0514 (5)
H22A	−0.1356	0.1440	0.8095	0.062*
H22B	−0.2050	0.1570	0.6605	0.062*
C23	0.1955 (2)	0.19796 (8)	0.86864 (19)	0.0491 (5)
H23A	0.2009	0.2091	0.9533	0.059*
H23B	0.2960	0.2036	0.8670	0.059*
C24	0.1510 (2)	0.13541 (8)	0.84538 (19)	0.0491 (5)
H24A	0.2349	0.1142	0.8386	0.059*
H24B	0.1319	0.1207	0.9180	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0378 (8)	0.0284 (7)	0.0371 (7)	−0.0008 (6)	0.0126 (6)	−0.0023 (6)
N2	0.0394 (8)	0.0272 (7)	0.0350 (7)	−0.0009 (6)	0.0148 (6)	−0.0003 (6)
N3	0.0382 (8)	0.0283 (7)	0.0412 (8)	0.0004 (6)	0.0124 (6)	−0.0014 (6)
N4	0.0408 (8)	0.0281 (7)	0.0431 (8)	−0.0031 (6)	0.0138 (6)	−0.0005 (6)
O1	0.0681 (9)	0.0267 (6)	0.0416 (7)	0.0065 (6)	0.0080 (6)	0.0021 (5)
O2	0.0786 (10)	0.0290 (7)	0.0418 (7)	0.0095 (6)	0.0192 (7)	−0.0008 (5)
O3	0.0823 (11)	0.0259 (7)	0.0576 (9)	0.0054 (7)	0.0000 (7)	−0.0026 (6)
O4	0.0767 (10)	0.0246 (7)	0.0555 (8)	0.0021 (6)	−0.0060 (7)	0.0006 (6)
C1	0.0328 (9)	0.0274 (8)	0.0368 (9)	0.0013 (7)	0.0121 (7)	0.0033 (7)
C2	0.0390 (9)	0.0338 (9)	0.0303 (8)	0.0019 (7)	0.0113 (7)	0.0023 (7)
C3	0.0353 (9)	0.0282 (8)	0.0385 (9)	0.0001 (7)	0.0164 (7)	−0.0002 (7)
C4	0.0398 (10)	0.0328 (9)	0.0388 (9)	0.0035 (8)	0.0118 (7)	0.0084 (7)
C5	0.0495 (11)	0.0419 (10)	0.0300 (9)	−0.0025 (8)	0.0081 (7)	0.0003 (7)
C6	0.0460 (10)	0.0330 (9)	0.0378 (9)	−0.0034 (8)	0.0115 (8)	−0.0049 (7)
C7	0.0325 (9)	0.0282 (9)	0.0466 (10)	−0.0003 (7)	0.0082 (7)	0.0034 (7)
C8	0.0371 (9)	0.0299 (9)	0.0394 (9)	−0.0019 (7)	0.0043 (7)	0.0022 (7)
C9	0.0343 (9)	0.0275 (9)	0.0474 (10)	−0.0009 (7)	0.0119 (7)	0.0007 (7)
C10	0.0426 (10)	0.0352 (10)	0.0456 (10)	0.0087 (8)	0.0171 (8)	0.0102 (8)
C11	0.0466 (11)	0.0503 (11)	0.0350 (9)	0.0052 (9)	0.0131 (8)	0.0034 (8)
C12	0.0445 (10)	0.0359 (10)	0.0460 (10)	−0.0003 (8)	0.0156 (8)	−0.0063 (8)
C13	0.0528 (11)	0.0383 (10)	0.0364 (9)	0.0007 (8)	0.0208 (8)	−0.0038 (7)
C14	0.0551 (11)	0.0350 (10)	0.0411 (10)	−0.0009 (8)	0.0241 (8)	0.0031 (7)
C15	0.0492 (11)	0.0317 (9)	0.0422 (10)	0.0027 (8)	0.0071 (8)	0.0033 (8)
C16	0.0444 (10)	0.0371 (10)	0.0388 (10)	−0.0023 (8)	0.0029 (8)	0.0010 (8)
C17	0.0399 (10)	0.0425 (11)	0.0629 (12)	−0.0079 (8)	0.0246 (9)	−0.0122 (9)
C18	0.0452 (11)	0.0411 (11)	0.0574 (11)	0.0012 (9)	0.0271 (9)	−0.0091 (9)
C19	0.0784 (15)	0.0443 (11)	0.0535 (12)	−0.0100 (11)	0.0365 (11)	0.0010 (9)
C20	0.0795 (15)	0.0443 (11)	0.0462 (11)	−0.0066 (10)	0.0326 (10)	−0.0112 (9)
C21	0.0422 (10)	0.0457 (11)	0.0599 (12)	0.0057 (9)	0.0198 (9)	−0.0080 (9)
C22	0.0396 (10)	0.0475 (11)	0.0700 (13)	−0.0047 (9)	0.0247 (10)	−0.0018 (10)
C23	0.0402 (10)	0.0382 (10)	0.0533 (11)	0.0008 (8)	0.0020 (8)	−0.0026 (8)
C24	0.0467 (11)	0.0348 (10)	0.0535 (11)	0.0047 (8)	0.0067 (9)	0.0050 (8)

Geometric parameters (Å, º) top

N1—C17	1.472 (2)	C10—C11	1.377 (3)
N1—C13	1.474 (2)	C10—H10	0.9300
N1—C15	1.478 (2)	C11—C12	1.377 (2)
N2—C18	1.469 (2)	C11—H11	0.9300
N2—C16	1.472 (2)	C12—H12	0.9300
N2—C14	1.475 (2)	C13—C14	1.537 (2)
N3—C21	1.465 (2)	C13—H13A	0.9700
N3—C19	1.464 (2)	C13—H13B	0.9700
N3—C23	1.469 (2)	C14—H14A	0.9700
N4—C24	1.471 (2)	C14—H14B	0.9700
N4—C22	1.467 (2)	C15—C16	1.535 (2)
N4—C20	1.468 (2)	C15—H15A	0.9700
O1—C1	1.3605 (19)	C15—H15B	0.9700
O1—H1	0.8200	C16—H16A	0.9700
O2—C3	1.3569 (19)	C16—H16B	0.9700
O2—H2	0.8200	C17—C18	1.529 (2)
O3—C9	1.356 (2)	C17—H17A	0.9700
O3—H3	0.8200	C17—H17B	0.9700
O4—C7	1.354 (2)	C18—H18A	0.9700
O4—H4	0.8200	C18—H18B	0.9700
C1—C6	1.387 (2)	C19—C20	1.526 (3)
C1—C2	1.386 (2)	C19—H19A	0.9700
C2—C3	1.391 (2)	C19—H19B	0.9700
C2—H2A	0.9300	C20—H20A	0.9700
C3—C4	1.391 (2)	C20—H20B	0.9700
C4—C5	1.378 (2)	C21—C22	1.528 (3)
C4—H4A	0.9300	C21—H21A	0.9700
C5—C6	1.381 (2)	C21—H21B	0.9700
C5—H5	0.9300	C22—H22A	0.9700
C6—H6	0.9300	C22—H22B	0.9700
C7—C8	1.376 (2)	C23—C24	1.538 (2)
C7—C12	1.392 (2)	C23—H23A	0.9700
C8—C9	1.383 (2)	C23—H23B	0.9700
C8—H8	0.9300	C24—H24A	0.9700
C9—C10	1.391 (2)	C24—H24B	0.9700

C17—N1—C13	108.30 (14)	C13—C14—H14B	109.6
C17—N1—C15	108.24 (14)	H14A—C14—H14B	108.1
C13—N1—C15	108.02 (14)	N1—C15—C16	110.39 (13)
C18—N2—C16	108.44 (14)	N1—C15—H15A	109.6
C18—N2—C14	108.32 (14)	C16—C15—H15A	109.6
C16—N2—C14	107.85 (14)	N1—C15—H15B	109.6
C21—N3—C19	107.84 (15)	C16—C15—H15B	109.6
C21—N3—C23	108.82 (15)	H15A—C15—H15B	108.1
C19—N3—C23	108.61 (15)	N2—C16—C15	110.69 (13)
C24—N4—C22	108.51 (15)	N2—C16—H16A	109.5
C24—N4—C20	108.35 (15)	C15—C16—H16A	109.5
C22—N4—C20	108.48 (15)	N2—C16—H16B	109.5
C1—O1—H1	109.5	C15—C16—H16B	109.5
C3—O2—H2	109.5	H16A—C16—H16B	108.1
C9—O3—H3	109.5	N1—C17—C18	110.62 (14)
C7—O4—H4	109.5	N1—C17—H17A	109.5
O1—C1—C6	122.46 (15)	C18—C17—H17A	109.5
O1—C1—C2	117.66 (14)	N1—C17—H17B	109.5
C6—C1—C2	119.87 (15)	C18—C17—H17B	109.5
C1—C2—C3	120.29 (14)	H17A—C17—H17B	108.1
C1—C2—H2A	119.9	N2—C18—C17	110.82 (14)
C3—C2—H2A	119.9	N2—C18—H18A	109.5
O2—C3—C2	117.83 (14)	C17—C18—H18A	109.5
O2—C3—C4	122.52 (15)	N2—C18—H18B	109.5
C2—C3—C4	119.64 (15)	C17—C18—H18B	109.5
C5—C4—C3	119.50 (15)	H18A—C18—H18B	108.1
C5—C4—H4A	120.2	N3—C19—C20	110.52 (15)
C3—C4—H4A	120.2	N3—C19—H19A	109.5
C6—C5—C4	121.20 (15)	C20—C19—H19A	109.5
C6—C5—H5	119.4	N3—C19—H19B	109.5
C4—C5—H5	119.4	C20—C19—H19B	109.5
C5—C6—C1	119.50 (16)	H19A—C19—H19B	108.1
C5—C6—H6	120.3	N4—C20—C19	110.57 (14)
C1—C6—H6	120.3	N4—C20—H20A	109.5
O4—C7—C8	116.83 (15)	C19—C20—H20A	109.5
O4—C7—C12	123.35 (15)	N4—C20—H20B	109.5
C8—C7—C12	119.82 (15)	C19—C20—H20B	109.5
C7—C8—C9	120.79 (15)	H20A—C20—H20B	108.1
C7—C8—H8	119.6	N3—C21—C22	110.75 (15)
C9—C8—H8	119.6	N3—C21—H21A	109.5
O3—C9—C8	116.91 (15)	C22—C21—H21A	109.5
O3—C9—C10	123.51 (15)	N3—C21—H21B	109.5
C8—C9—C10	119.58 (16)	C22—C21—H21B	109.5
C11—C10—C9	119.20 (16)	H21A—C21—H21B	108.1
C11—C10—H10	120.4	N4—C22—C21	110.34 (15)
C9—C10—H10	120.4	N4—C22—H22A	109.6
C10—C11—C12	121.54 (16)	C21—C22—H22A	109.6
C10—C11—H11	119.2	N4—C22—H22B	109.6
C12—C11—H11	119.2	C21—C22—H22B	109.6
C11—C12—C7	119.07 (16)	H22A—C22—H22B	108.1
C11—C12—H12	120.5	N3—C23—C24	110.40 (14)
C7—C12—H12	120.5	N3—C23—H23A	109.6
N1—C13—C14	110.55 (13)	C24—C23—H23A	109.6
N1—C13—H13A	109.5	N3—C23—H23B	109.6
C14—C13—H13A	109.5	C24—C23—H23B	109.6
N1—C13—H13B	109.5	H23A—C23—H23B	108.1
C14—C13—H13B	109.5	N4—C24—C23	110.13 (14)
H13A—C13—H13B	108.1	N4—C24—H24A	109.6
N2—C14—C13	110.48 (14)	C23—C24—H24A	109.6
N2—C14—H14A	109.6	N4—C24—H24B	109.6
C13—C14—H14A	109.6	C23—C24—H24B	109.6
N2—C14—H14B	109.6	H24A—C24—H24B	108.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.98	2.7577 (18)	158
O2—H2···N2ⁱ	0.82	1.93	2.7279 (17)	164
O3—H3···N4ⁱⁱ	0.82	1.89	2.6816 (19)	162
O4—H4···N3	0.82	1.88	2.6525 (19)	156

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

Experimental details

Crystal data
Chemical formula	C₆H₁₂N₂·C₆H₆O₂
M_r	222.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.4882 (5), 23.7390 (11), 11.2532 (6)
β (°)	113.335 (6)
V (Å³)	2327.3 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.45 × 0.43 × 0.02

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.789, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8717, 4091, 3270
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.121, 1.03
No. of reflections	4091
No. of parameters	290
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.98	2.7577 (18)	158
O2—H2···N2ⁱ	0.82	1.93	2.7279 (17)	164
O3—H3···N4ⁱⁱ	0.82	1.89	2.6816 (19)	162
O4—H4···N3	0.82	1.88	2.6525 (19)	156

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

Acknowledgements

The author thanks Xiangyang Normal University for supporting this study.

References

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