Benzene-1,3-diol-1,4-diaza-bicyclo-[2.2.2]octane (1/1).

There are two independent but virtually identical mol-ecules of each component in the asymmetric unit of the title 1:1 adduct, C(6)H(12)N(2)·C(6)H(6)O(2). In the crystal, the constituents are connected into a supra-molecular 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 = 222.28

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.064

wR(F 2) = 0.157

S = 1.00

3973 reflections

301 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.24 e Å−3

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 ▶).

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030199/hb5588Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H12N2·C6H6O2	F(000) = 960
Mr = 222.28	Dx = 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

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

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(Fo2) + (0.0661P)2 + 2.685P] where P = (Fo2 + 2Fc2)/3
3973 reflections	(Δ/σ)max < 0.001
301 parameters	Δρmax = 0.27 e Å−3
4 restraints	Δρmin = −0.24 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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

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) ; (ii) ; (iii) .