The 1:1 adduct of 5-methylbenzene-1,3-diol (orcin) and 1,4-di­aza­bicyclo­[2.2.2]­octane

In the title adduct, C₆H₁₂N₂·C₇H₈O₂, the orcin and 1,4-di­aza­bi­cyclo­[2.2.2]­octane moieties are held together by O—H...N hydrogen bonds. One-dimensional chiral hydrogen-bonded chains are formed along the b axis. Neighbouring chains are held together principally by van der Waals interactions and are interrelated by translation, resulting in a chiral layer.

S1. Comment

Chiral crystals can be formed through self-assembly even from achiral molecules (Jacques et al., 1981). It is possible to synthesize substances asymmetrically from such crystals by solid state reactions (Elgavi et al., 1973; Green et al., 1979; Sakamoto, 1997). Furthermore, chiral crystallization is relevant to the origin of chiral compounds in nature (Addadi & Lahav, 1979). The design of chiral crystalline complexes from different achiral molecules (Koshima et al., 1996, 1997, 1998, 1999; Koshima & Honke 1999) is an active field. It has been reported previously that a resorcinol-urea adduct crystallizes in a chiral space group, P2₁2₁2₁ (Pickering & Small, 1982). In our case, the chiral crystal of the title adduct, (I), was synthesized from two achiral compounds, 5-methylresorcinol (orcin) and 1,4-diazabicyclo[2.2.2]octane (DABCO). Here, the structure and the chirality of (I) are discussed. \sch

There are two crystallographically independent molecules each of DABCO and orcin in the unit cell of (I) (Fig. 1). In the structure of (I), the orcin and DABCO moieties are linked by O1—H1···N1, O2—H2···N3, O3—H3···N4ⁱ and O4—H4···N2ⁱⁱ hydrogen bonds (Fig. 2 and Table 2; symmetry codes as in Table 2).

The resorcinol hydroxy group may be arranged in one of the ways depicted in Scheme 2. In (I), the orcin hydroxy groups assume the first motif, which is in contrast with the third motif observed in the resorcinol-urea (1/1) adduct (Pickering & Small, 1982) and the second motif observed in the resorcinol-isonicotinamide (1/2) adduct (Vishweshwar et al., 2003). The orcin molecules are pseudo-C₂ symmetrically related.

As shown in Fig. 2, one-dimensional chiral hydrogen-bonded chains are formed along the b axis, with the screw-pitch equal to the length of the b axis. The chain can be described in graph-set notation (Etter, 1990; Grell et al., 2000) as C₄⁴(22). Neighbouring chains in the (001) plane are associated with each other principally by van der Waals interactions and are interrelated by translation, thus resulting in a chiral layer. There are four kinds of chiral layer in the crystal of (I). C—H···O hydrogen bonds (Table 2) play an important role in stabilizing the chiral structure. Neighbouring chiral layers are related to each other via C5—H5B···O2ⁱⁱⁱ, C6—H6A···O3ⁱⁱⁱ and C10—H10A···O1^iv hydrogen bonds (symmetry codes as in Table 2?).

There are four C—H···π interactions in the crystal, namely C8—H8Aⁱⁱⁱ···π(C13/C15/C17) (3.30 Å), C7—H7Bⁱⁱⁱ···π(C13/C15/C17) (3.36 Å), C1—H1B(x + 1/2, 3/2 − y, 2 − z)···π(C20/C22/C24) (3.37 Å) and C2—H2A(x + 1/2, 3/2 − y, 2 − z)···π(C20/C22/C24) (3.30 Å), where the values in parentheses indicate the distances between the H atom and the centroid of the phenyl ring. As a result of the balance of C—H···O and C—H···π interactions, the two orcin molecules that are bridged by a DABCO molecule are fixed in a dihedral angle of 30.8 (3)°.

DABCO may assume one of four conformations, namely ordered and non-distorted, ordered and distorted, disordered and non-distorted, or disordered and distorted (Nimmo & Lucas, 1976). The disordered conformations are frequently observed, such as in DABCO-biphenol (1/1) (Ferguson et al., 1998), DABCO-perchloric acid (1/1) (Katrusiak, 2000) and DABCO-maleic acid (1/2) (Sun & Jin, 2002). In (I), both of the DABCO molecules are ordered, and they are almost non-distorted, as indicated by N—C—C—N torsion angles with mean values of 1.2 (4) and 0.9 (4)°, respectively, for N1/N2 and N3/N4.

S2. Experimental

Equimolar quantites of DABCO and orcin were mixed and dissolved in sufficient water by heating to a temperature where a clear solution resulted. Single crystals of (I) were formed by standing the resulting solution overnight at 293 K.

S3. Refinement

All H atoms were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.82–0.97 Å, with isotropic displacement parameters 1.2–1.5 times U_eq of the parent atoms. Because of the lack of atoms heavier than O and the short measuring wavelength of Mo radiation, no useful absolute structure parameter can be refined.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The orcin and DABCO moieties of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. Part of the crystal structure of (I), showing the infinite chiral chains along the b axis. Hydrogen bonds are shown as dashed lines.

5-methyl-1,3-benzenediol (orcin) 1,4-diazabicyclo[2.2.2]octane (1/1)

Crystal data

C6H12N2·C7H8O2	F(000) = 1024.0
Mr = 236.31	Dx = 1.206 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 346 reflections
a = 12.2569 (6) Å	θ = 2.4–23.0°
b = 12.5985 (6) Å	µ = 0.08 mm^−1
c = 16.8506 (9) Å	T = 293 K
V = 2602.0 (2) Å^3	Prism, colourless
Z = 8	0.46 × 0.42 × 0.38 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2129 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.2°, θmin = 2.0°
ϕ and ω scans	h = −11→14
13862 measured reflections	k = −15→14
2645 independent reflections	l = −20→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1095P)^2 + 0.08P] where P = (Fo^2 + 2Fc^2)/3
2645 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.35392 (19)	0.96077 (19)	0.89770 (15)	0.0491 (6)
N2	0.15548 (18)	1.02328 (19)	0.90321 (15)	0.0505 (6)
C1	0.3493 (2)	1.0765 (2)	0.8976 (2)	0.0600 (8)
H1A	0.3846	1.1036	0.8502	0.072*
H1B	0.3880	1.1039	0.9434	0.072*
C2	0.2297 (2)	1.1140 (2)	0.8999 (2)	0.0576 (8)
H2A	0.2185	1.1587	0.9460	0.069*
H2B	0.2142	1.1559	0.8529	0.069*
C3	0.3012 (2)	0.9225 (2)	0.97123 (17)	0.0570 (8)
H3A	0.3403	0.9496	1.0170	0.068*
H3B	0.3040	0.8456	0.9729	0.068*
C4	0.1823 (2)	0.9594 (2)	0.97427 (19)	0.0573 (8)
H4A	0.1345	0.8982	0.9769	0.069*
H4B	0.1706	1.0017	1.0216	0.069*
C5	0.2942 (2)	0.9217 (2)	0.82898 (19)	0.0577 (8)
H5A	0.2979	0.8448	0.8275	0.069*
H5B	0.3275	0.9488	0.7809	0.069*
C6	0.1739 (2)	0.9569 (2)	0.8325 (2)	0.0608 (8)
H6A	0.1558	0.9969	0.7851	0.073*
H6B	0.1270	0.8950	0.8346	0.073*
N3	0.35698 (19)	0.54541 (18)	0.84590 (16)	0.0494 (6)
N4	0.15835 (19)	0.48274 (19)	0.85339 (14)	0.0495 (6)
C7	0.3516 (2)	0.4295 (2)	0.8488 (2)	0.0621 (8)
H7A	0.3914	0.4040	0.8947	0.075*
H7B	0.3857	0.4002	0.8017	0.075*
C8	0.2329 (2)	0.3924 (2)	0.8535 (2)	0.0611 (9)
H8A	0.2169	0.3469	0.8085	0.073*
H8B	0.2224	0.3514	0.9015	0.073*
C9	0.3046 (2)	0.5863 (3)	0.91765 (19)	0.0620 (8)
H9A	0.3085	0.6632	0.9179	0.074*
H9B	0.3431	0.5603	0.9640	0.074*
C10	0.1844 (2)	0.5511 (3)	0.92158 (19)	0.0610 (8)
H10A	0.1715	0.5126	0.9705	0.073*
H10B	0.1374	0.6130	0.9212	0.073*
C11	0.2956 (2)	0.5814 (2)	0.77530 (18)	0.0563 (8)
H11A	0.3293	0.5532	0.7277	0.068*
H11B	0.2976	0.6583	0.7722	0.068*
C12	0.1769 (2)	0.5438 (2)	0.78034 (19)	0.0574 (8)
H12A	0.1286	0.6048	0.7794	0.069*
H12B	0.1602	0.4999	0.7347	0.069*
O1	0.57360 (16)	0.94161 (16)	0.89557 (16)	0.0635 (7)
H1	0.5072	0.9335	0.8943	0.095*
O2	0.57432 (16)	0.56999 (15)	0.82461 (16)	0.0681 (7)
H2	0.5080	0.5773	0.8276	0.102*
C13	0.6235 (2)	0.8483 (2)	0.87842 (16)	0.0429 (7)
C14	0.5672 (2)	0.7558 (2)	0.85998 (17)	0.0453 (7)
H14	0.4913	0.7554	0.8601	0.054*
C15	0.6241 (2)	0.6642 (2)	0.84145 (17)	0.0450 (7)
C16	0.7375 (2)	0.6648 (2)	0.84002 (18)	0.0477 (7)
H16	0.7755	0.6035	0.8265	0.057*
C17	0.7937 (2)	0.7569 (2)	0.85878 (17)	0.0452 (7)
C18	0.7373 (2)	0.8482 (2)	0.87774 (18)	0.0467 (7)
H18	0.7753	0.9099	0.8901	0.056*
C19	0.9172 (3)	0.7574 (2)	0.8584 (2)	0.0721 (12)
H19A	0.9431	0.8266	0.8730	0.108*
H19B	0.9431	0.7399	0.8063	0.108*
H19C	0.9438	0.7060	0.8958	0.108*
O3	0.94242 (16)	0.44160 (16)	0.85138 (16)	0.0685 (7)
H3	1.0089	0.4345	0.8523	0.103*
O4	0.94221 (17)	0.06990 (16)	0.92750 (16)	0.0719 (7)
H4	1.0087	0.0764	0.9250	0.108*
C20	0.8941 (2)	0.3474 (2)	0.86996 (16)	0.0432 (6)
C21	0.7802 (2)	0.3470 (2)	0.87098 (17)	0.0453 (7)
H21	0.7421	0.4085	0.8582	0.054*
C22	0.7241 (2)	0.2566 (2)	0.89075 (17)	0.0448 (7)
C23	0.7804 (2)	0.1653 (2)	0.91022 (18)	0.0482 (7)
H23	0.7424	0.1043	0.9244	0.058*
C24	0.8937 (2)	0.1643 (2)	0.90865 (18)	0.0466 (7)
C25	0.9511 (2)	0.2553 (2)	0.88899 (17)	0.0453 (7)
H25	1.0270	0.2549	0.8885	0.054*
C26	0.6006 (3)	0.2572 (3)	0.8901 (2)	0.0664 (10)
H26A	0.5749	0.3265	0.8757	0.100*
H26B	0.5739	0.2393	0.9420	0.100*
H26C	0.5746	0.2061	0.8523	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0362 (12)	0.0518 (13)	0.0591 (15)	0.0082 (10)	−0.0013 (11)	−0.0028 (11)
N2	0.0365 (12)	0.0533 (13)	0.0615 (14)	0.0050 (11)	0.0012 (11)	0.0055 (12)
C1	0.0456 (17)	0.0526 (16)	0.082 (2)	−0.0102 (14)	0.0029 (16)	−0.0071 (17)
C2	0.0573 (18)	0.0402 (15)	0.075 (2)	0.0086 (13)	0.0062 (16)	0.0042 (15)
C3	0.0573 (18)	0.0576 (17)	0.0561 (17)	0.0127 (15)	−0.0036 (14)	0.0041 (15)
C4	0.0470 (16)	0.0638 (18)	0.0611 (18)	0.0024 (15)	0.0064 (14)	0.0107 (15)
C5	0.0533 (17)	0.0558 (16)	0.0638 (19)	0.0006 (15)	0.0013 (15)	−0.0100 (16)
C6	0.0485 (17)	0.0697 (18)	0.0642 (19)	−0.0071 (15)	−0.0099 (15)	−0.0034 (16)
N3	0.0369 (12)	0.0495 (13)	0.0619 (15)	−0.0079 (10)	0.0008 (11)	−0.0025 (11)
N4	0.0376 (12)	0.0534 (13)	0.0575 (14)	−0.0095 (11)	0.0002 (11)	0.0031 (12)
C7	0.0483 (17)	0.0528 (17)	0.085 (2)	0.0099 (14)	−0.0013 (17)	−0.0016 (17)
C8	0.0576 (19)	0.0468 (16)	0.079 (2)	−0.0078 (14)	−0.0040 (17)	0.0079 (16)
C9	0.0566 (19)	0.0627 (18)	0.067 (2)	−0.0086 (16)	−0.0027 (16)	−0.0097 (17)
C10	0.0558 (19)	0.0679 (19)	0.0593 (19)	−0.0003 (16)	0.0107 (15)	−0.0039 (15)
C11	0.0562 (18)	0.0573 (17)	0.0555 (17)	−0.0083 (15)	0.0027 (14)	0.0104 (15)
C12	0.0457 (15)	0.0659 (18)	0.0605 (18)	0.0022 (15)	−0.0032 (14)	0.0085 (14)
O1	0.0355 (10)	0.0504 (12)	0.1047 (19)	0.0060 (9)	−0.0029 (11)	−0.0166 (12)
O2	0.0389 (11)	0.0505 (12)	0.115 (2)	−0.0082 (9)	0.0092 (12)	−0.0198 (13)
C13	0.0291 (13)	0.0475 (15)	0.0521 (16)	0.0043 (11)	−0.0021 (11)	−0.0009 (13)
C14	0.0240 (12)	0.0520 (16)	0.060 (2)	−0.0012 (11)	0.0016 (12)	−0.0015 (14)
C15	0.0299 (13)	0.0468 (15)	0.0581 (17)	−0.0047 (11)	0.0050 (12)	−0.0009 (14)
C16	0.0362 (14)	0.0420 (14)	0.0649 (18)	0.0039 (11)	0.0074 (13)	0.0006 (14)
C17	0.0289 (13)	0.0521 (15)	0.0544 (18)	−0.0009 (11)	0.0029 (12)	0.0084 (14)
C18	0.0344 (14)	0.0458 (15)	0.0600 (17)	−0.0054 (12)	−0.0014 (12)	−0.0002 (13)
C19	0.0284 (14)	0.071 (2)	0.117 (3)	0.0004 (14)	0.0065 (17)	0.004 (2)
O3	0.0337 (11)	0.0549 (12)	0.117 (2)	−0.0070 (10)	−0.0063 (12)	0.0267 (13)
O4	0.0380 (11)	0.0519 (12)	0.126 (2)	0.0077 (10)	0.0113 (12)	0.0248 (14)
C20	0.0312 (13)	0.0477 (15)	0.0506 (16)	−0.0053 (11)	−0.0018 (11)	0.0021 (12)
C21	0.0311 (13)	0.0466 (14)	0.0582 (17)	0.0037 (12)	−0.0030 (12)	0.0001 (13)
C22	0.0302 (14)	0.0496 (15)	0.0544 (18)	0.0001 (11)	−0.0001 (12)	−0.0113 (14)
C23	0.0350 (14)	0.0430 (14)	0.0665 (19)	−0.0032 (12)	0.0077 (13)	−0.0027 (14)
C24	0.0333 (14)	0.0439 (14)	0.0627 (18)	0.0038 (11)	0.0042 (12)	0.0023 (14)
C25	0.0208 (12)	0.0533 (16)	0.0619 (19)	0.0002 (11)	−0.0011 (11)	0.0046 (14)
C26	0.0295 (15)	0.072 (2)	0.097 (3)	0.0004 (14)	0.0050 (16)	−0.004 (2)

Geometric parameters (Å, º)

N1—C5	1.456 (4)	C11—H11A	0.9700
N1—C1	1.459 (4)	C11—H11B	0.9700
N1—C3	1.478 (4)	C12—H12A	0.9700
N2—C2	1.462 (4)	C12—H12B	0.9700
N2—C6	1.473 (4)	O1—C13	1.357 (3)
N2—C4	1.479 (4)	O1—H1	0.8200
C1—C2	1.540 (4)	O2—C15	1.364 (3)
C1—H1A	0.9700	O2—H2	0.8200
C1—H1B	0.9700	C13—C14	1.390 (4)
C2—H2A	0.9700	C13—C18	1.396 (3)
C2—H2B	0.9700	C14—C15	1.384 (4)
C3—C4	1.531 (4)	C14—H14	0.9300
C3—H3A	0.9700	C15—C16	1.390 (3)
C3—H3B	0.9700	C16—C17	1.386 (4)
C4—H4A	0.9700	C16—H16	0.9300
C4—H4B	0.9700	C17—C18	1.379 (4)
C5—C6	1.540 (4)	C17—C19	1.515 (4)
C5—H5A	0.9700	C18—H18	0.9300
C5—H5B	0.9700	C19—H19A	0.9600
C6—H6A	0.9700	C19—H19B	0.9600
C6—H6B	0.9700	C19—H19C	0.9600
N3—C7	1.462 (4)	O3—C20	1.363 (3)
N3—C9	1.463 (4)	O3—H3	0.8200
N3—C11	1.479 (4)	O4—C24	1.367 (3)
N4—C8	1.459 (4)	O4—H4	0.8200
N4—C12	1.469 (4)	C20—C25	1.392 (4)
N4—C10	1.471 (4)	C20—C21	1.396 (3)
C7—C8	1.530 (4)	C21—C22	1.371 (4)
C7—H7A	0.9700	C21—H21	0.9300
C7—H7B	0.9700	C22—C23	1.382 (4)
C8—H8A	0.9700	C22—C26	1.514 (4)
C8—H8B	0.9700	C23—C24	1.388 (4)
C9—C10	1.540 (4)	C23—H23	0.9300
C9—H9A	0.9700	C24—C25	1.386 (4)
C9—H9B	0.9700	C25—H25	0.9300
C10—H10A	0.9700	C26—H26A	0.9600
C10—H10B	0.9700	C26—H26B	0.9600
C11—C12	1.532 (4)	C26—H26C	0.9600
C5—N1—C1	108.5 (3)	C9—C10—H10A	109.7
C5—N1—C3	109.7 (2)	N4—C10—H10B	109.7
C1—N1—C3	108.1 (3)	C9—C10—H10B	109.7
C2—N2—C6	108.5 (2)	H10A—C10—H10B	108.2
C2—N2—C4	108.5 (2)	N3—C11—C12	110.1 (2)
C6—N2—C4	108.2 (2)	N3—C11—H11A	109.6
N1—C1—C2	110.1 (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	108.2
C2—C1—H1B	109.6	N4—C12—C11	110.8 (2)
H1A—C1—H1B	108.2	N4—C12—H12A	109.5
N2—C2—C1	110.7 (2)	C11—C12—H12A	109.5
N2—C2—H2A	109.5	N4—C12—H12B	109.5
C1—C2—H2A	109.5	C11—C12—H12B	109.5
N2—C2—H2B	109.5	H12A—C12—H12B	108.1
C1—C2—H2B	109.5	C13—O1—H1	109.5
H2A—C2—H2B	108.1	C15—O2—H2	109.5
N1—C3—C4	110.2 (2)	O1—C13—C14	123.4 (2)
N1—C3—H3A	109.6	O1—C13—C18	117.0 (2)
C4—C3—H3A	109.6	C14—C13—C18	119.6 (3)
N1—C3—H3B	109.6	C15—C14—C13	119.9 (2)
C4—C3—H3B	109.6	C15—C14—H14	120.0
H3A—C3—H3B	108.1	C13—C14—H14	120.0
N2—C4—C3	110.5 (2)	O2—C15—C14	123.1 (2)
N2—C4—H4A	109.6	O2—C15—C16	116.6 (2)
C3—C4—H4A	109.6	C14—C15—C16	120.2 (3)
N2—C4—H4B	109.6	C17—C16—C15	119.9 (3)
C3—C4—H4B	109.6	C17—C16—H16	120.1
H4A—C4—H4B	108.1	C15—C16—H16	120.1
N1—C5—C6	110.7 (2)	C18—C17—C16	120.1 (2)
N1—C5—H5A	109.5	C18—C17—C19	119.9 (3)
C6—C5—H5A	109.5	C16—C17—C19	120.0 (3)
N1—C5—H5B	109.5	C17—C18—C13	120.2 (3)
C6—C5—H5B	109.5	C17—C18—H18	119.9
H5A—C5—H5B	108.1	C13—C18—H18	119.9
N2—C6—C5	110.0 (2)	C17—C19—H19A	109.5
N2—C6—H6A	109.7	C17—C19—H19B	109.5
C5—C6—H6A	109.7	H19A—C19—H19B	109.5
N2—C6—H6B	109.7	C17—C19—H19C	109.5
C5—C6—H6B	109.7	H19A—C19—H19C	109.5
H6A—C6—H6B	108.2	H19B—C19—H19C	109.5
C7—N3—C9	107.7 (3)	C20—O3—H3	109.5
C7—N3—C11	108.1 (3)	C24—O4—H4	109.5
C9—N3—C11	109.5 (2)	O3—C20—C25	124.1 (2)
C8—N4—C12	108.2 (2)	O3—C20—C21	116.1 (3)
C8—N4—C10	108.7 (2)	C25—C20—C21	119.8 (3)
C12—N4—C10	108.3 (2)	C22—C21—C20	120.5 (3)
N3—C7—C8	110.5 (2)	C22—C21—H21	119.8
N3—C7—H7A	109.6	C20—C21—H21	119.8
C8—C7—H7A	109.6	C21—C22—C23	119.9 (3)
N3—C7—H7B	109.6	C21—C22—C26	119.7 (3)
C8—C7—H7B	109.6	C23—C22—C26	120.4 (3)
H7A—C7—H7B	108.1	C22—C23—C24	120.2 (3)
N4—C8—C7	110.9 (2)	C22—C23—H23	119.9
N4—C8—H8A	109.5	C24—C23—H23	119.9
C7—C8—H8A	109.5	O4—C24—C25	123.6 (2)
N4—C8—H8B	109.5	O4—C24—C23	116.0 (3)
C7—C8—H8B	109.5	C25—C24—C23	120.3 (3)
H8A—C8—H8B	108.0	C24—C25—C20	119.3 (2)
N3—C9—C10	110.7 (2)	C24—C25—H25	120.4
N3—C9—H9A	109.5	C20—C25—H25	120.4
C10—C9—H9A	109.5	C22—C26—H26A	109.5
N3—C9—H9B	109.5	C22—C26—H26B	109.5
C10—C9—H9B	109.5	H26A—C26—H26B	109.5
H9A—C9—H9B	108.1	C22—C26—H26C	109.5
N4—C10—C9	110.0 (2)	H26A—C26—H26C	109.5
N4—C10—H10A	109.7	H26B—C26—H26C	109.5
C5—N1—C1—C2	58.6 (3)	C8—N4—C12—C11	−58.5 (3)
C3—N1—C1—C2	−60.3 (3)	C10—N4—C12—C11	59.1 (3)
C6—N2—C2—C1	−59.3 (3)	N3—C11—C12—N4	−0.2 (4)
C4—N2—C2—C1	58.0 (3)	O1—C13—C14—C15	178.6 (3)
N1—C1—C2—N2	1.2 (4)	C18—C13—C14—C15	0.3 (4)
C5—N1—C3—C4	−58.2 (3)	C13—C14—C15—O2	178.4 (3)
C1—N1—C3—C4	59.9 (3)	C13—C14—C15—C16	−1.0 (4)
C2—N2—C4—C3	−58.3 (3)	O2—C15—C16—C17	−178.1 (3)
C6—N2—C4—C3	59.3 (3)	C14—C15—C16—C17	1.3 (5)
N1—C3—C4—N2	−0.5 (4)	C15—C16—C17—C18	−0.9 (5)
C1—N1—C5—C6	−60.5 (3)	C15—C16—C17—C19	179.1 (3)
C3—N1—C5—C6	57.3 (3)	C16—C17—C18—C13	0.2 (4)
C2—N2—C6—C5	57.4 (3)	C19—C17—C18—C13	−179.8 (3)
C4—N2—C6—C5	−60.1 (3)	O1—C13—C18—C17	−178.3 (3)
N1—C5—C6—N2	2.0 (4)	C14—C13—C18—C17	0.1 (5)
C9—N3—C7—C8	59.1 (4)	O3—C20—C21—C22	−178.5 (3)
C11—N3—C7—C8	−59.2 (4)	C25—C20—C21—C22	0.1 (4)
C12—N4—C8—C7	58.6 (3)	C20—C21—C22—C23	0.3 (4)
C10—N4—C8—C7	−58.8 (3)	C20—C21—C22—C26	−178.9 (3)
N3—C7—C8—N4	0.3 (4)	C21—C22—C23—C24	−1.0 (5)
C7—N3—C9—C10	−60.4 (3)	C26—C22—C23—C24	178.3 (3)
C11—N3—C9—C10	56.9 (3)	C22—C23—C24—O4	−178.9 (3)
C8—N4—C10—C9	57.0 (3)	C22—C23—C24—C25	1.2 (5)
C12—N4—C10—C9	−60.2 (3)	O4—C24—C25—C20	179.4 (3)
N3—C9—C10—N4	2.3 (4)	C23—C24—C25—C20	−0.7 (4)
C7—N3—C11—C12	59.0 (3)	O3—C20—C25—C24	178.6 (3)
C9—N3—C11—C12	−58.1 (3)	C21—C20—C25—C24	0.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.91	2.704 (3)	162
O2—H2···N3	0.82	1.92	2.706 (3)	161
O3—H3···N4^i	0.82	1.93	2.697 (3)	155
O4—H4···N2^ii	0.82	1.95	2.710 (3)	153
C5—H5B···O2^iii	0.97	2.63	3.576 (4)	164
C6—H6A···O3^iii	0.97	2.69	3.417 (4)	132
C10—H10A···O1^iv	0.97	2.62	3.369 (4)	134

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