Benzene-1,3-diol–1,4-diaza­bicyclo­[2.2.2]octane (1/1)

Arman, H.D.; Tiekink, E.R.T.

doi:10.1107/S1600536810030199

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2188

https://doi.org/10.1107/S1600536810030199

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Benzene-1,3-diol–1,4-diazabicyclo[2.2.2]octane (1/1)

Hadi D. Arman ^a ‡ and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 29 July 2010; accepted 29 July 2010; online 31 July 2010)

There are two independent but virtually identical molecules of each component in the asymmetric unit of the title 1:1 adduct, C₆H₁₂N₂·C₆H₆O₂. In the crystal, the constituents are connected into a supramolecular chain along the b axis by O—H⋯N hydrogen bonds. Weak C—H⋯O bonds cross-link the chains.

Related literature

For related studies on co-crystal/adduct formation, see: Broker & Tiekink (2007 ); Broker et al. (2008 ); Arman et al. (2010 ).

Experimental

Crystal data

C₆H₁₂N₂·C₆H₆O₂
M_r = 222.28
Monoclinic, P 2₁ /c
a = 9.3620 (19) Å
b = 23.645 (5) Å
c = 11.072 (2) Å
β = 112.64 (3)°
V = 2262.1 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 98 K
0.40 × 0.25 × 0.07 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.423, T_max = 1.000
11918 measured reflections
3973 independent reflections
3355 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.157
S = 1.00
3973 reflections
301 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 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
O1—H1O⋯N1ⁱ	0.85 (2)	1.81 (2)	2.639 (3)	167 (3)
O2—H2O⋯N2	0.85 (3)	1.84 (2)	2.670 (3)	169 (3)
O3—H3O⋯N3ⁱⁱ	0.85 (2)	1.88 (2)	2.718 (3)	171 (2)
O4—H4O⋯N4	0.85 (2)	1.93 (2)	2.763 (3)	169 (3)
C23—H23⋯O1ⁱⁱⁱ	0.95	2.55	3.330 (3)	139
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810030199/hb5588sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030199/hb5588Isup2.hkl

checkCIF report

Comment top

As a part of on-going studies into co-crystallization experiments with N-containing molecules (Broker & Tiekink, 2007; Broker et al., 2008; Arman et al. 2010), the co-crystallization of benzene-1,3-diol and 1,4-diazabicyclo[2.2.2]octane (dabco) was investigated, leading to the isolation of the 1:1 co-crystal, (I).

The crystallographic asymmetric unit of (I) comprises two independent benzene-1,3-diol molecules, Figs 1 and 2, and two independent dabco molecules, Figs 3 and 4. The molecules associate via O–H···N hydrogen bonds with each benzene-1,3-diol molecule bridging two independent dabco molecules. This results in the formation of a supramolecular chain along the b axis, Fig. 5 and Table 1. Chains are consolidated in the crystal structure by C–H···O contacts, Fig. 6 and Table 1.

Related literature top

For related studies on co-crystal/adduct formation, see: Broker & Tiekink (2007); Broker et al. (2008); Arman et al. (2010).

Experimental top

Colourless prisms of (I) were isolated from the 1/1 co-crystallization of 1,4-diazabicyclo[2.2.2]octane (Sigma-Aldrich, 0.18 mmol) and benzene-1,3-diol (ACROS, 0.18 mmol) in acetone/ethanol solution, m. pt. 513–517 K

Structure description top

For related studies on co-crystal/adduct formation, see: Broker & Tiekink (2007); Broker et al. (2008); Arman et al. (2010).

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the first independent benzene-1,3-diol molecule in (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Molecular structure of the second independent benzene-1,3-diol molecule in (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 3. Molecular structure of the first independent 1,4-diazabicyclo[2.2.2]octane molecule in (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 4. Molecular structure of the second independent 1,4-diazabicyclo[2.2.2]octane molecule in (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 5. Supramolecular chain along the b axis in (I) mediated by O–H···N hydrogen bonding (orange dashed lines).
	Fig. 6. View in projection down the a axis of the unit-cell contents of (I). The O–H···N hydrogen bonding and C–H···O contacts are shown as orange and blue dashed lines, respectively.

Benzene-1,3-diol–1,4-diazabicyclo[2.2.2]octane (1/1) top

Crystal data top

C₆H₁₂N₂·C₆H₆O₂	F(000) = 960
M_r = 222.28	D_x = 1.305 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10564 reflections
a = 9.3620 (19) Å	θ = 2.0–40.2°
b = 23.645 (5) Å	µ = 0.09 mm⁻¹
c = 11.072 (2) Å	T = 98 K
β = 112.64 (3)°	Prism, colourless
V = 2262.1 (8) Å³	0.40 × 0.25 × 0.07 mm
Z = 8

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	3973 independent reflections
Radiation source: fine-focus sealed tube	3355 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 28.5714 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω scans	h = −8→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −25→28
T_min = 0.423, T_max = 1.000	l = −13→13
11918 measured reflections

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0661P)² + 2.685P] where P = (F_o² + 2F_c²)/3
3973 reflections	(Δ/σ)_max < 0.001
301 parameters	Δρ_max = 0.27 e Å⁻³
4 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₆H₁₂N₂·C₆H₆O₂	V = 2262.1 (8) Å³
M_r = 222.28	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3620 (19) Å	µ = 0.09 mm⁻¹
b = 23.645 (5) Å	T = 98 K
c = 11.072 (2) Å	0.40 × 0.25 × 0.07 mm
β = 112.64 (3)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	3973 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3355 reflections with I > 2σ(I)
T_min = 0.423, T_max = 1.000	R_int = 0.049
11918 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	4 restraints
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.27 e Å⁻³
3973 reflections	Δρ_min = −0.24 e Å⁻³
301 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
O1	0.6822 (2)	1.16554 (7)	0.36932 (18)	0.0301 (5)
H1O	0.648 (4)	1.1955 (8)	0.326 (3)	0.045*
O2	0.6063 (2)	0.97031 (7)	0.37749 (18)	0.0314 (5)
H2O	0.562 (4)	0.9413 (9)	0.335 (3)	0.047*
O3	0.0808 (2)	0.41271 (7)	0.41406 (17)	0.0263 (4)
H3O	0.051 (4)	0.4413 (9)	0.364 (2)	0.039*
O4	0.1800 (2)	0.21654 (7)	0.42386 (17)	0.0266 (4)
H4O	0.149 (4)	0.1873 (8)	0.377 (3)	0.040*
N1	0.4071 (3)	0.76680 (8)	0.2317 (2)	0.0228 (5)
N2	0.4791 (3)	0.87151 (8)	0.2746 (2)	0.0219 (5)
N3	0.0069 (3)	0.01097 (8)	0.22198 (19)	0.0205 (5)
N4	0.0848 (3)	0.11358 (8)	0.30117 (19)	0.0202 (5)
C1	0.2920 (3)	0.80228 (10)	0.1308 (3)	0.0269 (6)
H1A	0.1892	0.7976	0.1356	0.032*
H1B	0.2838	0.7901	0.0428	0.032*
C2	0.3406 (3)	0.86513 (10)	0.1519 (2)	0.0245 (6)
H2A	0.3639	0.8789	0.0770	0.029*
H2B	0.2546	0.8881	0.1568	0.029*
C3	0.5626 (3)	0.77703 (10)	0.2309 (3)	0.0262 (6)
H3A	0.5622	0.7678	0.1435	0.031*
H3B	0.6391	0.7522	0.2961	0.031*
C4	0.6094 (3)	0.83966 (10)	0.2637 (3)	0.0269 (6)
H4A	0.7005	0.8420	0.3473	0.032*
H4B	0.6378	0.8564	0.1941	0.032*
C5	0.4101 (4)	0.78343 (10)	0.3614 (3)	0.0275 (6)
H5A	0.4911	0.7617	0.4307	0.033*
H5B	0.3090	0.7747	0.3663	0.033*
C6	0.4438 (4)	0.84720 (10)	0.3833 (2)	0.0274 (6)
H6A	0.3528	0.8667	0.3887	0.033*
H6B	0.5329	0.8532	0.4671	0.033*
C7	−0.1050 (3)	0.05173 (10)	0.1344 (2)	0.0240 (6)
H7A	−0.2073	0.0464	0.1396	0.029*
H7B	−0.1166	0.0448	0.0429	0.029*
C8	−0.0488 (3)	0.11313 (10)	0.1737 (2)	0.0240 (6)
H8A	−0.0181	0.1303	0.1057	0.029*
H8B	−0.1342	0.1360	0.1803	0.029*
C9	0.1632 (3)	0.02439 (10)	0.2251 (3)	0.0241 (6)
H9A	0.1609	0.0237	0.1350	0.029*
H9B	0.2378	−0.0046	0.2770	0.029*
C10	0.2163 (3)	0.08326 (10)	0.2863 (3)	0.0249 (6)
H10A	0.3018	0.0790	0.3729	0.030*
H10B	0.2552	0.1055	0.2296	0.030*
C11	0.0090 (3)	0.01896 (10)	0.3555 (2)	0.0239 (6)
H11A	0.0908	−0.0050	0.4182	0.029*
H11B	−0.0917	0.0072	0.3572	0.029*
C12	0.0401 (3)	0.08194 (10)	0.3972 (2)	0.0227 (6)
H12A	−0.0543	0.0989	0.4019	0.027*
H12B	0.1241	0.0844	0.4850	0.027*
C13	0.6158 (3)	1.11889 (10)	0.2989 (3)	0.0227 (6)
C14	0.6381 (3)	1.06812 (10)	0.3673 (2)	0.0237 (6)
H14	0.6957	1.0678	0.4591	0.028*
C15	0.5772 (3)	1.01792 (10)	0.3030 (2)	0.0221 (5)
C16	0.4901 (3)	1.01835 (10)	0.1682 (2)	0.0234 (6)
H16	0.4480	0.9843	0.1231	0.028*
C17	0.4663 (3)	1.06950 (10)	0.1012 (2)	0.0245 (6)
H17	0.4067	1.0700	0.0097	0.029*
C18	0.5274 (3)	1.11975 (10)	0.1644 (2)	0.0238 (6)
H18	0.5095	1.1543	0.1171	0.029*
C19	0.0690 (3)	0.36384 (10)	0.3458 (2)	0.0207 (5)
C20	0.1297 (3)	0.31467 (10)	0.4162 (2)	0.0219 (5)
H20	0.1791	0.3161	0.5089	0.026*
C21	0.1181 (3)	0.26331 (10)	0.3511 (2)	0.0205 (5)
C22	0.0461 (3)	0.26154 (10)	0.2147 (2)	0.0234 (6)
H22	0.0377	0.2267	0.1696	0.028*
C23	−0.0129 (3)	0.31076 (10)	0.1454 (2)	0.0246 (6)
H23	−0.0601	0.3094	0.0526	0.030*
C24	−0.0042 (3)	0.36198 (10)	0.2093 (2)	0.0235 (6)
H24	−0.0473	0.3953	0.1611	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0397 (12)	0.0137 (9)	0.0289 (10)	−0.0014 (8)	0.0046 (9)	−0.0009 (7)
O2	0.0439 (13)	0.0143 (9)	0.0301 (10)	−0.0031 (8)	0.0077 (10)	0.0008 (7)
O3	0.0398 (12)	0.0156 (8)	0.0241 (9)	0.0037 (8)	0.0132 (9)	0.0001 (7)
O4	0.0385 (12)	0.0141 (8)	0.0251 (9)	0.0026 (8)	0.0098 (9)	0.0011 (7)
N1	0.0286 (13)	0.0180 (10)	0.0238 (11)	0.0002 (9)	0.0124 (10)	−0.0012 (8)
N2	0.0272 (13)	0.0181 (10)	0.0226 (11)	−0.0002 (9)	0.0121 (10)	0.0000 (8)
N3	0.0256 (12)	0.0182 (10)	0.0204 (10)	0.0006 (8)	0.0118 (9)	−0.0003 (8)
N4	0.0245 (12)	0.0172 (10)	0.0211 (10)	0.0004 (8)	0.0114 (9)	0.0006 (8)
C1	0.0279 (15)	0.0211 (13)	0.0276 (13)	0.0016 (11)	0.0062 (12)	−0.0009 (10)
C2	0.0265 (15)	0.0200 (12)	0.0261 (13)	0.0020 (10)	0.0092 (12)	0.0016 (10)
C3	0.0283 (15)	0.0238 (13)	0.0289 (13)	0.0026 (11)	0.0137 (12)	−0.0024 (10)
C4	0.0273 (15)	0.0246 (13)	0.0326 (14)	−0.0010 (11)	0.0158 (12)	−0.0009 (11)
C5	0.0372 (17)	0.0230 (13)	0.0262 (13)	−0.0039 (11)	0.0164 (13)	0.0014 (10)
C6	0.0378 (17)	0.0245 (13)	0.0239 (13)	−0.0037 (11)	0.0162 (13)	−0.0026 (10)
C7	0.0278 (15)	0.0211 (12)	0.0225 (12)	−0.0004 (10)	0.0090 (12)	0.0010 (10)
C8	0.0309 (16)	0.0184 (12)	0.0218 (12)	0.0016 (11)	0.0091 (12)	0.0018 (10)
C9	0.0290 (15)	0.0199 (12)	0.0274 (13)	0.0017 (11)	0.0152 (12)	−0.0017 (10)
C10	0.0248 (15)	0.0229 (12)	0.0304 (13)	−0.0024 (11)	0.0145 (12)	−0.0044 (10)
C11	0.0333 (16)	0.0190 (12)	0.0225 (12)	0.0013 (11)	0.0142 (12)	0.0026 (10)
C12	0.0281 (15)	0.0237 (12)	0.0205 (12)	0.0008 (10)	0.0138 (12)	−0.0004 (10)
C13	0.0221 (14)	0.0177 (12)	0.0302 (13)	0.0000 (10)	0.0121 (12)	−0.0013 (10)
C14	0.0249 (14)	0.0218 (12)	0.0223 (12)	0.0035 (10)	0.0069 (11)	0.0006 (10)
C15	0.0231 (14)	0.0174 (12)	0.0288 (13)	0.0009 (10)	0.0134 (12)	0.0005 (10)
C16	0.0263 (15)	0.0199 (12)	0.0262 (13)	−0.0015 (10)	0.0126 (12)	−0.0040 (10)
C17	0.0246 (15)	0.0294 (13)	0.0221 (12)	0.0010 (11)	0.0120 (11)	−0.0021 (10)
C18	0.0286 (15)	0.0193 (12)	0.0258 (13)	0.0026 (10)	0.0127 (12)	0.0037 (10)
C19	0.0199 (14)	0.0183 (12)	0.0265 (13)	−0.0023 (10)	0.0118 (11)	−0.0011 (10)
C20	0.0249 (14)	0.0228 (12)	0.0205 (12)	−0.0013 (10)	0.0116 (11)	−0.0001 (10)
C21	0.0231 (14)	0.0183 (12)	0.0239 (12)	−0.0002 (10)	0.0132 (11)	0.0016 (9)
C22	0.0285 (15)	0.0167 (12)	0.0265 (13)	−0.0028 (10)	0.0123 (12)	−0.0037 (10)
C23	0.0287 (15)	0.0252 (13)	0.0217 (12)	−0.0024 (11)	0.0117 (11)	−0.0003 (10)
C24	0.0253 (15)	0.0210 (12)	0.0253 (13)	0.0015 (10)	0.0110 (12)	0.0032 (10)

Geometric parameters (Å, º) top

O1—C13	1.356 (3)	C7—C8	1.548 (3)
O1—H1O	0.85 (2)	C7—H7A	0.9900
O2—C15	1.360 (3)	C7—H7B	0.9900
O2—H2O	0.85 (3)	C8—H8A	0.9900
O3—C19	1.362 (3)	C8—H8B	0.9900
O3—H3O	0.85 (2)	C9—C10	1.544 (3)
O4—C21	1.360 (3)	C9—H9A	0.9900
O4—H4O	0.85 (2)	C9—H9B	0.9900
N1—C1	1.479 (3)	C10—H10A	0.9900
N1—C3	1.479 (4)	C10—H10B	0.9900
N1—C5	1.479 (3)	C11—C12	1.553 (3)
N2—C4	1.477 (3)	C11—H11A	0.9900
N2—C6	1.482 (3)	C11—H11B	0.9900
N2—C2	1.481 (3)	C12—H12A	0.9900
N3—C7	1.478 (3)	C12—H12B	0.9900
N3—C11	1.483 (3)	C13—C14	1.392 (3)
N3—C9	1.484 (3)	C13—C18	1.397 (4)
N4—C8	1.482 (3)	C14—C15	1.389 (3)
N4—C12	1.486 (3)	C14—H14	0.9500
N4—C10	1.488 (3)	C15—C16	1.398 (4)
C1—C2	1.545 (3)	C16—C17	1.391 (3)
C1—H1A	0.9900	C16—H16	0.9500
C1—H1B	0.9900	C17—C18	1.386 (3)
C2—H2A	0.9900	C17—H17	0.9500
C2—H2B	0.9900	C18—H18	0.9500
C3—C4	1.547 (3)	C19—C20	1.393 (3)
C3—H3A	0.9900	C19—C24	1.399 (3)
C3—H3B	0.9900	C20—C21	1.395 (3)
C4—H4A	0.9900	C20—H20	0.9500
C4—H4B	0.9900	C21—C22	1.397 (3)
C5—C6	1.541 (3)	C22—C23	1.387 (3)
C5—H5A	0.9900	C22—H22	0.9500
C5—H5B	0.9900	C23—C24	1.389 (3)
C6—H6A	0.9900	C23—H23	0.9500
C6—H6B	0.9900	C24—H24	0.9500

C13—O1—H1O	111 (2)	C7—C8—H8B	109.6
C15—O2—H2O	113 (2)	H8A—C8—H8B	108.1
C19—O3—H3O	112 (2)	N3—C9—C10	110.6 (2)
C21—O4—H4O	110 (2)	N3—C9—H9A	109.5
C1—N1—C3	109.6 (2)	C10—C9—H9A	109.5
C1—N1—C5	108.6 (2)	N3—C9—H9B	109.5
C3—N1—C5	108.2 (2)	C10—C9—H9B	109.5
C4—N2—C6	108.5 (2)	H9A—C9—H9B	108.1
C4—N2—C2	109.38 (19)	N4—C10—C9	110.0 (2)
C6—N2—C2	108.4 (2)	N4—C10—H10A	109.7
C7—N3—C11	107.77 (19)	C9—C10—H10A	109.7
C7—N3—C9	108.61 (19)	N4—C10—H10B	109.7
C11—N3—C9	108.3 (2)	C9—C10—H10B	109.7
C8—N4—C12	108.1 (2)	H10A—C10—H10B	108.2
C8—N4—C10	108.79 (19)	N3—C11—C12	110.32 (19)
C12—N4—C10	108.05 (19)	N3—C11—H11A	109.6
N1—C1—C2	110.2 (2)	C12—C11—H11A	109.6
N1—C1—H1A	109.6	N3—C11—H11B	109.6
C2—C1—H1A	109.6	C12—C11—H11B	109.6
N1—C1—H1B	109.6	H11A—C11—H11B	108.1
C2—C1—H1B	109.6	N4—C12—C11	110.03 (19)
H1A—C1—H1B	108.1	N4—C12—H12A	109.7
N2—C2—C1	109.9 (2)	C11—C12—H12A	109.7
N2—C2—H2A	109.7	N4—C12—H12B	109.7
C1—C2—H2A	109.7	C11—C12—H12B	109.7
N2—C2—H2B	109.7	H12A—C12—H12B	108.2
C1—C2—H2B	109.7	O1—C13—C14	116.7 (2)
H2A—C2—H2B	108.2	O1—C13—C18	123.6 (2)
N1—C3—C4	110.2 (2)	C14—C13—C18	119.7 (2)
N1—C3—H3A	109.6	C13—C14—C15	120.8 (2)
C4—C3—H3A	109.6	C13—C14—H14	119.6
N1—C3—H3B	109.6	C15—C14—H14	119.6
C4—C3—H3B	109.6	O2—C15—C14	116.7 (2)
H3A—C3—H3B	108.1	O2—C15—C16	123.5 (2)
N2—C4—C3	109.8 (2)	C14—C15—C16	119.8 (2)
N2—C4—H4A	109.7	C17—C16—C15	118.9 (2)
C3—C4—H4A	109.7	C17—C16—H16	120.5
N2—C4—H4B	109.7	C15—C16—H16	120.5
C3—C4—H4B	109.7	C18—C17—C16	121.7 (2)
H4A—C4—H4B	108.2	C18—C17—H17	119.2
N1—C5—C6	109.8 (2)	C16—C17—H17	119.1
N1—C5—H5A	109.7	C17—C18—C13	119.1 (2)
C6—C5—H5A	109.7	C17—C18—H18	120.5
N1—C5—H5B	109.7	C13—C18—H18	120.5
C6—C5—H5B	109.7	O3—C19—C20	118.0 (2)
H5A—C5—H5B	108.2	O3—C19—C24	121.8 (2)
N2—C6—C5	110.4 (2)	C20—C19—C24	120.2 (2)
N2—C6—H6A	109.6	C21—C20—C19	120.2 (2)
C5—C6—H6A	109.6	C21—C20—H20	119.9
N2—C6—H6B	109.6	C19—C20—H20	119.9
C5—C6—H6B	109.6	O4—C21—C20	118.1 (2)
H6A—C6—H6B	108.1	O4—C21—C22	122.3 (2)
N3—C7—C8	110.4 (2)	C20—C21—C22	119.6 (2)
N3—C7—H7A	109.6	C23—C22—C21	119.8 (2)
C8—C7—H7A	109.6	C23—C22—H22	120.1
N3—C7—H7B	109.6	C21—C22—H22	120.1
C8—C7—H7B	109.6	C22—C23—C24	121.1 (2)
H7A—C7—H7B	108.1	C22—C23—H23	119.4
N4—C8—C7	110.20 (19)	C24—C23—H23	119.4
N4—C8—H8A	109.6	C23—C24—C19	119.1 (2)
C7—C8—H8A	109.6	C23—C24—H24	120.5
N4—C8—H8B	109.6	C19—C24—H24	120.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1ⁱ	0.85 (2)	1.81 (2)	2.639 (3)	167 (3)
O2—H2O···N2	0.85 (3)	1.84 (2)	2.670 (3)	169 (3)
O3—H3O···N3ⁱⁱ	0.85 (2)	1.88 (2)	2.718 (3)	171 (2)
O4—H4O···N4	0.85 (2)	1.93 (2)	2.763 (3)	169 (3)
C23—H23···O1ⁱⁱⁱ	0.95	2.55	3.330 (3)	139

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

Experimental details

Crystal data
Chemical formula	C₆H₁₂N₂·C₆H₆O₂
M_r	222.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	98
a, b, c (Å)	9.3620 (19), 23.645 (5), 11.072 (2)
β (°)	112.64 (3)
V (Å³)	2262.1 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.25 × 0.07

Data collection
Diffractometer	Rigaku AFC12K/SATURN724
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.423, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11918, 3973, 3355
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.157, 1.00
No. of reflections	3973
No. of parameters	301
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.24

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1ⁱ	0.85 (2)	1.81 (2)	2.639 (3)	167 (3)
O2—H2O···N2	0.85 (3)	1.84 (2)	2.670 (3)	169 (3)
O3—H3O···N3ⁱⁱ	0.85 (2)	1.88 (2)	2.718 (3)	171 (2)
O4—H4O···N4	0.85 (2)	1.93 (2)	2.763 (3)	169 (3)
C23—H23···O1ⁱⁱⁱ	0.95	2.55	3.330 (3)	139

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

Footnotes

‡Additional correspondence author, e-mail: xcosmo3@gmail.com.

References

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