Supramolecular hydrogen-bonding patterns of co-crystals containing the active pharmaceutical ingredient (API) phloroglucinol and N-heterocycles

The active pharmaceutical ingredient phloroglucinol (PHL) has been taken as an illustrative molecule to explore the intermolecular interactions which can be established with other molecular entities to build PHL pharmaceutical co-crystals. The crystal structures of five newly synthesized co-crystals are reported, where PHL is crystallized with N-heterocycles, namely 2-hydroxy-6-methylpyridine (1), 2,4-dimethyl-6-hydroxypyrimidine (2), 4-phenylpyridine (3), 2-hydroxypyridine (4) and 2,3,5,6-tetramethylpyrazine (5). The structural characteristics of these co-crystals, as far as the hydrogen-bonding networks and the crystalline architectures are concerned, are strongly dependent on the chemical features of the coformer molecules, as well as on their size and shape. A detailed analysis of the intermolecular interactions established in all the PHL co-crystals of known structures has allowed the recognition of some regularities in the packing modes that can be useful in the design of new supramolecular adducts forming predictable structural motifs.

Computing details

For all compounds, data collection: Kappa CCD server software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al.,1999); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014); molecular graphics: ORTEPIII (Burnett & Johnson, 1996). Software used to prepare material for publication: 'SHELXL2014/7 (Sheldrick, 2014; WinGX (Farrugia, 1999) for shelx; SHELXL2014/7 (Sheldrick, 2014); WinGX (Farrugia, 1999) for comp2, comp4, comp5; 'SHELXL2014/7 (Sheldrick, 2014); WinGX (Farrugia, 1999)' for comp3.

(shelx) tris(2-hydroxy-6-methyl-pyridine) phloroglucinol hydrate

Crystal data

C6H6O3·3(C6H7NO)·H2O	F(000) = 1000
Mr = 471.50	Dx = 1.278 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.2625 (5) Å	Cell parameters from 8382 reflections
b = 14.1634 (7) Å	θ = 2–25°
c = 15.4250 (9) Å	µ = 0.10 mm^−1
β = 113.8431 (16)°	T = 295 K
V = 2450.4 (2) Å^3	Prismatic, colourless
Z = 4	0.28 × 0.14 × 0.10 mm

Data collection

Nonius Kappa CCD diffractometer	Rint = 0.126
Graphite monochromator	θmax = 25.0°, θmin = 2.9°
φ scans and ω scans	h = −14→14
8382 measured reflections	k = −16→16
4321 independent reflections	l = −18→18
1632 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.096	w = 1/[σ^2(Fo^2) + (0.1446P)^2 + 1.0433P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.325	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.69 e Å^−3
4321 reflections	Δρmin = −0.29 e Å^−3
316 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.006 (2)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	−0.0806 (5)	0.0794 (4)	0.5958 (4)	0.0536 (14)
H1N	−0.1382	0.1054	0.5493	0.064*
N2	−0.6243 (5)	−0.0187 (4)	0.3820 (4)	0.0574 (15)
H2N	−0.5950	0.0230	0.4260	0.069*
N3	−0.3218 (5)	−0.9785 (4)	0.3637 (4)	0.0571 (15)
H3N	−0.2608	−1.0043	0.4074	0.069*
O1	−0.1676 (4)	−0.5472 (3)	0.5116 (4)	0.0666 (14)
H1A	−0.2195	−0.5791	0.5183	0.100*
O2	−0.4223 (4)	−0.2988 (3)	0.5253 (3)	0.0658 (14)
H2A	−0.4266	−0.2410	0.5236	0.099*
O3	−0.0603 (5)	−0.2337 (4)	0.4890 (4)	0.0810 (17)
H3A	−0.0833	−0.1794	0.4894	0.122*
O4	−0.1189 (4)	−0.0542 (3)	0.5084 (4)	0.0632 (14)
O5	−0.4794 (6)	−0.1184 (4)	0.4816 (5)	0.099 (2)
O6	−0.2843 (4)	−0.8452 (4)	0.4538 (4)	0.0749 (15)
O1W	−0.3425 (6)	−0.6670 (4)	0.4895 (6)	0.106 (2)
C1	−0.1961 (6)	−0.4532 (5)	0.5094 (5)	0.0519 (17)
C2	−0.2986 (5)	−0.4231 (4)	0.5177 (4)	0.0486 (16)
H2	−0.3521	−0.4665	0.5237	0.058*
C3	−0.3202 (5)	−0.3265 (4)	0.5169 (4)	0.0476 (16)
C4	−0.2425 (6)	−0.2622 (5)	0.5070 (5)	0.0547 (18)
H4	−0.2579	−0.1979	0.5061	0.066*
C5	−0.1395 (6)	−0.2945 (5)	0.4981 (5)	0.0532 (17)
C6	−0.1174 (6)	−0.3886 (5)	0.4990 (5)	0.0518 (17)
H6	−0.0493	−0.4096	0.4925	0.062*
C7	−0.0553 (6)	−0.0121 (5)	0.5850 (5)	0.0563 (18)
C8	0.0388 (7)	−0.0530 (6)	0.6627 (6)	0.075 (2)
H8	0.0603	−0.1155	0.6598	0.090*
C9	0.0979 (8)	−0.0011 (8)	0.7417 (6)	0.089 (3)
H9	0.1605	−0.0283	0.7925	0.107*
C10	0.0663 (7)	0.0921 (7)	0.7477 (6)	0.080 (2)
H10	0.1068	0.1262	0.8029	0.095*
C11	−0.0227 (6)	0.1336 (5)	0.6739 (5)	0.0587 (19)
C12	−0.0590 (7)	0.2319 (6)	0.6713 (6)	0.081 (3)
H121	−0.0076	0.2712	0.6536	0.097*
H122	−0.0537	0.2503	0.7328	0.097*
H123	−0.1398	0.2390	0.6257	0.097*
C13	−0.5767 (9)	−0.1049 (7)	0.3973 (8)	0.089 (3)
C14	−0.6290 (8)	−0.1744 (6)	0.3237 (6)	0.074 (2)
H14	−0.6000	−0.2359	0.3315	0.088*
C15	−0.7178 (11)	−0.1491 (9)	0.2462 (8)	0.113 (4)
H15	−0.7508	−0.1933	0.1980	0.136*
C16	−0.7672 (8)	−0.0548 (7)	0.2318 (7)	0.083 (3)
H16	−0.8319	−0.0392	0.1761	0.100*
C17	−0.7197 (9)	0.0076 (8)	0.2979 (7)	0.094 (3)
C18	−0.7619 (8)	0.1052 (7)	0.2945 (7)	0.104 (3)
H181	−0.6969	0.1481	0.3056	0.125*
H182	−0.7921	0.1140	0.3424	0.125*
H183	−0.8241	0.1175	0.2333	0.125*
C19	−0.3488 (6)	−0.8883 (5)	0.3786 (5)	0.0589 (19)
C20	−0.4538 (7)	−0.8511 (6)	0.3058 (6)	0.068 (2)
H20	−0.4795	−0.7909	0.3126	0.081*
C21	−0.5166 (7)	−0.9012 (6)	0.2272 (5)	0.072 (2)
H21	−0.5831	−0.8741	0.1799	0.087*
C22	−0.4842 (7)	−0.9926 (6)	0.2151 (5)	0.070 (2)
H22	−0.5293	−1.0269	0.1611	0.084*
C23	−0.3840 (6)	−1.0314 (5)	0.2846 (5)	0.0570 (18)
C24	−0.3403 (7)	−1.1281 (6)	0.2834 (6)	0.079 (2)
H241	−0.2580	−1.1258	0.2927	0.095*
H242	−0.3865	−1.1570	0.2234	0.095*
H433	−0.3478	−1.1643	0.3333	0.095*
H1W	−0.320 (6)	−0.727 (3)	0.481 (5)	0.08 (2)*
H2W	−0.421 (4)	−0.670 (10)	0.473 (9)	0.18 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.053 (3)	0.050 (4)	0.051 (4)	−0.005 (3)	0.013 (3)	0.001 (3)
N2	0.050 (3)	0.060 (4)	0.054 (4)	0.011 (3)	0.014 (3)	0.005 (3)
N3	0.053 (3)	0.048 (4)	0.057 (4)	0.002 (3)	0.008 (3)	0.005 (3)
O1	0.073 (3)	0.034 (3)	0.096 (4)	0.006 (2)	0.037 (3)	−0.003 (2)
O2	0.063 (3)	0.051 (3)	0.092 (4)	0.008 (2)	0.040 (3)	0.006 (3)
O3	0.084 (3)	0.052 (3)	0.132 (5)	−0.005 (3)	0.069 (4)	0.003 (3)
O4	0.060 (3)	0.041 (3)	0.075 (4)	−0.002 (2)	0.013 (3)	−0.001 (3)
O5	0.127 (5)	0.057 (4)	0.146 (6)	0.027 (4)	0.088 (5)	0.017 (4)
O6	0.065 (3)	0.053 (3)	0.084 (4)	0.005 (3)	0.007 (3)	−0.018 (3)
O1W	0.088 (5)	0.046 (4)	0.201 (8)	−0.009 (3)	0.078 (5)	−0.017 (4)
C1	0.054 (4)	0.042 (4)	0.053 (4)	0.008 (3)	0.014 (4)	0.001 (3)
C2	0.048 (4)	0.041 (4)	0.050 (4)	0.000 (3)	0.012 (3)	0.004 (3)
C3	0.048 (4)	0.042 (4)	0.050 (4)	0.005 (3)	0.017 (3)	0.004 (3)
C4	0.067 (4)	0.038 (4)	0.062 (5)	0.000 (3)	0.029 (4)	−0.001 (3)
C5	0.068 (4)	0.041 (4)	0.060 (5)	−0.006 (3)	0.035 (4)	−0.005 (3)
C6	0.049 (4)	0.046 (4)	0.059 (4)	0.003 (3)	0.021 (3)	−0.005 (3)
C7	0.057 (4)	0.043 (4)	0.064 (5)	−0.008 (4)	0.020 (4)	0.003 (4)
C8	0.080 (6)	0.063 (5)	0.067 (6)	0.003 (4)	0.015 (5)	0.015 (5)
C9	0.086 (6)	0.104 (8)	0.061 (6)	−0.003 (6)	0.012 (5)	0.010 (6)
C10	0.075 (6)	0.098 (7)	0.056 (5)	−0.021 (5)	0.017 (5)	−0.013 (5)
C11	0.059 (4)	0.063 (5)	0.046 (4)	−0.009 (4)	0.012 (4)	−0.014 (4)
C12	0.090 (6)	0.069 (6)	0.099 (7)	−0.021 (5)	0.054 (5)	−0.036 (5)
C13	0.081 (6)	0.081 (7)	0.110 (8)	0.018 (6)	0.042 (6)	0.025 (6)
C14	0.093 (6)	0.053 (5)	0.072 (6)	−0.002 (5)	0.030 (5)	−0.011 (5)
C15	0.128 (9)	0.127 (11)	0.091 (8)	−0.020 (8)	0.051 (8)	−0.016 (7)
C16	0.087 (6)	0.083 (7)	0.079 (7)	−0.013 (5)	0.032 (5)	−0.010 (5)
C17	0.093 (7)	0.107 (8)	0.096 (8)	−0.011 (6)	0.053 (6)	−0.002 (7)
C18	0.090 (6)	0.107 (8)	0.141 (8)	0.059 (6)	0.072 (6)	0.056 (7)
C19	0.056 (4)	0.049 (4)	0.069 (5)	−0.002 (4)	0.021 (4)	0.009 (4)
C20	0.070 (5)	0.060 (5)	0.067 (5)	0.006 (4)	0.021 (4)	0.010 (4)
C21	0.069 (5)	0.077 (6)	0.054 (5)	0.003 (4)	0.007 (4)	0.009 (4)
C22	0.067 (5)	0.084 (6)	0.042 (4)	−0.016 (5)	0.006 (4)	0.002 (4)
C23	0.054 (4)	0.061 (5)	0.050 (4)	−0.010 (4)	0.015 (4)	−0.001 (4)
C24	0.082 (6)	0.065 (5)	0.087 (6)	−0.015 (4)	0.031 (5)	−0.018 (5)

Geometric parameters (Å, º)

N1—C7	1.359 (8)	C8—H8	0.9300
N1—C11	1.361 (8)	C9—C10	1.390 (12)
N1—H1N	0.8600	C9—H9	0.9300
N2—C13	1.334 (10)	C10—C11	1.352 (11)
N2—C17	1.401 (11)	C10—H10	0.9300
N2—H2N	0.8600	C11—C12	1.457 (10)
N3—C19	1.362 (9)	C12—H121	0.9600
N3—C23	1.371 (8)	C12—H122	0.9600
N3—H3N	0.8600	C12—H123	0.9600
O1—C1	1.373 (7)	C13—C14	1.443 (12)
O1—H1A	0.8200	C14—C15	1.301 (12)
O2—C3	1.367 (7)	C14—H14	0.9300
O2—H2A	0.8200	C15—C16	1.446 (14)
O3—C5	1.348 (7)	C15—H15	0.9300
O3—H3A	0.8200	C16—C17	1.296 (12)
O4—C7	1.271 (8)	C16—H16	0.9300
O5—C13	1.377 (11)	C17—C18	1.470 (13)
O6—C19	1.266 (8)	C18—H181	0.9600
O1W—H1W	0.91 (4)	C18—H182	0.9600
O1W—H2W	0.89 (4)	C18—H183	0.9600
C1—C2	1.382 (9)	C19—C20	1.424 (10)
C1—C6	1.385 (9)	C20—C21	1.346 (10)
C2—C3	1.393 (8)	C20—H20	0.9300
C2—H2	0.9300	C21—C22	1.388 (11)
C3—C4	1.371 (8)	C21—H21	0.9300
C4—C5	1.400 (8)	C22—C23	1.377 (10)
C4—H4	0.9300	C22—H22	0.9300
C5—C6	1.358 (9)	C23—C24	1.473 (10)
C6—H6	0.9300	C24—H241	0.9600
C7—C8	1.409 (10)	C24—H242	0.9600
C8—C9	1.354 (11)	C24—H433	0.9600
C7—N1—C11	125.7 (6)	C11—C12—H122	109.5
C7—N1—H1N	117.2	H121—C12—H122	109.5
C11—N1—H1N	117.2	C11—C12—H123	109.5
C13—N2—C17	123.3 (8)	H121—C12—H123	109.5
C13—N2—H2N	118.3	H122—C12—H123	109.5
C17—N2—H2N	118.3	N2—C13—O5	116.4 (9)
C19—N3—C23	125.3 (6)	N2—C13—C14	117.5 (9)
C19—N3—H3N	117.4	O5—C13—C14	126.1 (8)
C23—N3—H3N	117.4	C15—C14—C13	118.4 (9)
C1—O1—H1A	109.5	C15—C14—H14	120.8
C3—O2—H2A	109.5	C13—C14—H14	120.8
C5—O3—H3A	109.5	C14—C15—C16	122.6 (10)
H1W—O1W—H2W	105 (10)	C14—C15—H15	118.7
O1—C1—C2	121.9 (6)	C16—C15—H15	118.7
O1—C1—C6	117.5 (6)	C17—C16—C15	118.8 (10)
C2—C1—C6	120.6 (6)	C17—C16—H16	120.6
C1—C2—C3	118.6 (6)	C15—C16—H16	120.6
C1—C2—H2	120.7	C16—C17—N2	119.3 (10)
C3—C2—H2	120.7	C16—C17—C18	125.0 (11)
O2—C3—C4	121.6 (6)	N2—C17—C18	115.7 (9)
O2—C3—C2	117.4 (5)	C17—C18—H181	109.5
C4—C3—C2	121.0 (6)	C17—C18—H182	109.5
C3—C4—C5	119.3 (6)	H181—C18—H182	109.5
C3—C4—H4	120.4	C17—C18—H183	109.5
C5—C4—H4	120.4	H181—C18—H183	109.5
O3—C5—C6	118.6 (6)	H182—C18—H183	109.5
O3—C5—C4	121.2 (6)	O6—C19—N3	120.2 (6)
C6—C5—C4	120.2 (6)	O6—C19—C20	125.1 (7)
C5—C6—C1	120.3 (6)	N3—C19—C20	114.7 (7)
C5—C6—H6	119.9	C21—C20—C19	121.4 (8)
C1—C6—H6	119.9	C21—C20—H20	119.3
O4—C7—N1	118.5 (6)	C19—C20—H20	119.3
O4—C7—C8	125.6 (7)	C20—C21—C22	121.5 (7)
N1—C7—C8	115.9 (7)	C20—C21—H21	119.3
C9—C8—C7	119.9 (8)	C22—C21—H21	119.3
C9—C8—H8	120.1	C23—C22—C21	118.8 (7)
C7—C8—H8	120.1	C23—C22—H22	120.6
C8—C9—C10	120.9 (8)	C21—C22—H22	120.6
C8—C9—H9	119.6	N3—C23—C22	118.3 (7)
C10—C9—H9	119.6	N3—C23—C24	116.4 (7)
C11—C10—C9	120.6 (8)	C22—C23—C24	125.2 (7)
C11—C10—H10	119.7	C23—C24—H241	109.5
C9—C10—H10	119.7	C23—C24—H242	109.5
C10—C11—N1	117.0 (7)	H241—C24—H242	109.5
C10—C11—C12	125.0 (8)	C23—C24—H433	109.5
N1—C11—C12	118.0 (7)	H241—C24—H433	109.5
C11—C12—H121	109.5	H242—C24—H433	109.5

(comp2) Phloroglucinol tris(2,4-dimethyl-6-hydroxy-pyrimidine)

Crystal data

C6H6O3·3(C6H8N2O)	Z = 2
Mr = 498.54	F(000) = 528
Triclinic, P1	Dx = 1.322 Mg m^−3
a = 7.7212 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.4488 (2) Å	Cell parameters from 9568 reflections
c = 14.2673 (3) Å	θ = 3.0–28.0°
α = 112.6081 (11)°	µ = 0.10 mm^−1
β = 95.5610 (9)°	T = 295 K
γ = 93.5410 (9)°	Plate, colourless
V = 1252.65 (5) Å^3	0.35 × 0.17 × 0.11 mm

Data collection

Nonius Kappa CCD diffractometer	4293 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 28.0°, θmin = 5.3°
φ scans and ω scans	h = −10→8
9568 measured reflections	k = −16→16
5979 independent reflections	l = −18→18

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.222	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.1393P)^2 + 0.3023P] where P = (Fo^2 + 2Fc^2)/3
5979 reflections	(Δ/σ)max < 0.001
373 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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.

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 > 2sigma(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
O1	0.3756 (3)	0.58303 (16)	0.13070 (14)	0.0659 (5)
O2	0.2271 (3)	0.44957 (16)	0.39002 (13)	0.0633 (5)
O3	0.4759 (3)	0.20061 (14)	0.11112 (15)	0.0657 (5)
O5	−0.31766 (19)	0.85627 (13)	0.61130 (11)	0.0516 (4)
O4	−0.1973 (2)	0.94382 (14)	0.41276 (12)	0.0591 (4)
O6	1.05781 (19)	−0.03254 (15)	−0.20524 (12)	0.0614 (5)
N1	0.1452 (2)	0.75058 (14)	0.23877 (13)	0.0471 (4)
N2	0.0785 (2)	0.89774 (14)	0.38674 (13)	0.0439 (4)
N3	0.0287 (2)	0.64036 (14)	0.46303 (12)	0.0435 (4)
N4	−0.0429 (2)	0.80137 (14)	0.59886 (12)	0.0424 (4)
N5	0.7041 (2)	0.14725 (14)	−0.03188 (12)	0.0452 (4)
N6	0.7788 (2)	0.00704 (13)	−0.18109 (12)	0.0401 (4)
C1	0.3678 (3)	0.49968 (18)	0.17148 (15)	0.0441 (4)
C2	0.2999 (3)	0.52093 (17)	0.26300 (14)	0.0434 (4)
C3	0.2947 (3)	0.43446 (17)	0.30176 (14)	0.0427 (4)
C4	0.3587 (3)	0.32860 (18)	0.25095 (15)	0.0457 (4)
C5	0.4239 (2)	0.30866 (17)	0.15904 (15)	0.0438 (4)
C6	0.4309 (3)	0.39410 (18)	0.11860 (15)	0.0448 (4)
C7	−0.0317 (3)	0.72478 (18)	0.20485 (15)	0.0486 (5)
C8	−0.1532 (3)	0.78579 (19)	0.25974 (16)	0.0515 (5)
C9	−0.1001 (3)	0.88044 (17)	0.35615 (16)	0.0450 (4)
C10	0.1936 (3)	0.83405 (17)	0.32857 (15)	0.0432 (4)
C11	−0.0821 (4)	0.6227 (2)	0.10418 (19)	0.0712 (7)
H111	−0.0300	0.5556	0.1065	0.085*
H112	−0.0415	0.6417	0.0503	0.085*
H113	−0.2072	0.6056	0.0914	0.085*
C12	0.3820 (3)	0.8645 (2)	0.3735 (2)	0.0615 (6)
H121	0.4183	0.8069	0.3985	0.074*
H122	0.3969	0.9401	0.4291	0.074*
H123	0.4519	0.8662	0.3219	0.074*
C13	−0.1436 (3)	0.62262 (16)	0.41987 (14)	0.0426 (4)
C14	−0.2646 (3)	0.69276 (18)	0.46437 (15)	0.0455 (4)
C15	−0.2182 (2)	0.78834 (16)	0.56096 (14)	0.0403 (4)
C16	0.0728 (2)	0.72874 (16)	0.55078 (14)	0.0420 (4)
C17	−0.1876 (4)	0.5183 (2)	0.32066 (17)	0.0628 (6)
H171	−0.0962	0.5142	0.2787	0.075*
H172	−0.2962	0.5254	0.2856	0.075*
H173	−0.1988	0.4485	0.3341	0.075*
C18	0.2571 (3)	0.7547 (2)	0.60246 (19)	0.0648 (7)
H181	0.3327	0.7729	0.5598	0.078*
H182	0.2921	0.6877	0.6140	0.078*
H183	0.2649	0.8204	0.6669	0.078*
C19	0.9564 (2)	0.02541 (17)	−0.14786 (15)	0.0441 (4)
C20	0.6599 (2)	0.06603 (16)	−0.12357 (14)	0.0412 (4)
C21	0.8792 (3)	0.17125 (18)	0.00618 (15)	0.0489 (5)
C22	1.0040 (3)	0.1136 (2)	−0.04741 (16)	0.0528 (5)
C23	0.9210 (4)	0.2666 (3)	0.11063 (19)	0.0732 (8)
H231	0.8321	0.3192	0.1219	0.088*
H232	1.0324	0.3087	0.1160	0.088*
H233	0.9252	0.2331	0.1611	0.088*
C24	0.4717 (3)	0.0345 (2)	−0.16750 (19)	0.0588 (6)
H241	0.4049	0.0954	−0.1296	0.071*
H242	0.4299	−0.0376	−0.1634	0.071*
H243	0.4590	0.0253	−0.2379	0.071*
H1	0.481 (3)	0.375 (2)	0.056 (2)	0.057 (7)*
H2	0.356 (4)	0.269 (3)	0.278 (2)	0.077 (8)*
H3	0.257 (3)	0.593 (3)	0.297 (2)	0.062 (7)*
H4	−0.272 (4)	0.768 (3)	0.237 (2)	0.068 (8)*
H5	−0.382 (4)	0.681 (2)	0.433 (2)	0.067 (8)*
H6	1.124 (4)	0.129 (2)	−0.021 (2)	0.069 (8)*
H1O	0.534 (4)	0.198 (3)	0.066 (3)	0.080 (10)*
H2O	0.185 (4)	0.509 (3)	0.411 (2)	0.072 (9)*
H3O	0.325 (4)	0.638 (3)	0.165 (2)	0.073 (9)*
H1N	0.121 (4)	0.955 (3)	0.460 (2)	0.064 (7)*
H2N	0.740 (3)	−0.048 (2)	−0.250 (2)	0.058 (7)*
H3N	−0.012 (3)	0.857 (3)	0.662 (2)	0.061 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0904 (13)	0.0608 (10)	0.0659 (10)	0.0381 (9)	0.0425 (10)	0.0341 (9)
O2	0.0927 (13)	0.0593 (10)	0.0500 (9)	0.0382 (9)	0.0377 (8)	0.0238 (8)
O3	0.0809 (12)	0.0445 (8)	0.0735 (11)	0.0280 (8)	0.0457 (10)	0.0138 (8)
O5	0.0461 (8)	0.0515 (8)	0.0454 (8)	0.0169 (6)	0.0131 (6)	0.0028 (6)
O4	0.0444 (8)	0.0574 (9)	0.0559 (9)	0.0142 (7)	0.0135 (7)	−0.0021 (7)
O6	0.0392 (8)	0.0650 (10)	0.0512 (8)	0.0093 (7)	0.0135 (6)	−0.0109 (7)
N1	0.0607 (10)	0.0380 (8)	0.0437 (9)	0.0204 (7)	0.0197 (8)	0.0118 (7)
N2	0.0435 (9)	0.0377 (8)	0.0418 (8)	0.0100 (6)	0.0117 (7)	0.0040 (7)
N3	0.0438 (9)	0.0402 (8)	0.0367 (8)	0.0093 (6)	0.0130 (6)	0.0019 (6)
N4	0.0408 (8)	0.0373 (8)	0.0359 (8)	0.0052 (6)	0.0117 (6)	−0.0019 (6)
N5	0.0440 (9)	0.0402 (8)	0.0399 (8)	0.0097 (6)	0.0137 (7)	0.0004 (7)
N6	0.0373 (8)	0.0335 (7)	0.0369 (8)	0.0056 (6)	0.0099 (6)	−0.0012 (6)
C1	0.0435 (10)	0.0466 (10)	0.0419 (10)	0.0140 (8)	0.0118 (8)	0.0142 (8)
C2	0.0488 (10)	0.0387 (9)	0.0381 (9)	0.0182 (8)	0.0131 (8)	0.0063 (7)
C3	0.0456 (10)	0.0446 (10)	0.0344 (8)	0.0154 (8)	0.0112 (7)	0.0086 (7)
C4	0.0490 (11)	0.0418 (10)	0.0453 (10)	0.0167 (8)	0.0145 (8)	0.0125 (8)
C5	0.0402 (9)	0.0396 (9)	0.0440 (10)	0.0131 (7)	0.0123 (7)	0.0053 (8)
C6	0.0441 (10)	0.0484 (11)	0.0367 (9)	0.0158 (8)	0.0143 (8)	0.0074 (8)
C7	0.0647 (13)	0.0387 (10)	0.0371 (9)	0.0137 (9)	0.0069 (9)	0.0079 (8)
C8	0.0520 (12)	0.0466 (11)	0.0440 (11)	0.0104 (9)	0.0026 (9)	0.0050 (9)
C9	0.0445 (10)	0.0399 (9)	0.0445 (10)	0.0097 (8)	0.0119 (8)	0.0078 (8)
C10	0.0480 (10)	0.0372 (9)	0.0451 (10)	0.0146 (8)	0.0157 (8)	0.0131 (8)
C11	0.098 (2)	0.0546 (14)	0.0437 (12)	0.0178 (13)	0.0032 (12)	0.0001 (10)
C12	0.0455 (12)	0.0583 (13)	0.0727 (15)	0.0160 (10)	0.0175 (10)	0.0130 (12)
C13	0.0491 (10)	0.0376 (9)	0.0325 (8)	0.0041 (7)	0.0084 (7)	0.0036 (7)
C14	0.0447 (10)	0.0447 (10)	0.0374 (9)	0.0087 (8)	0.0048 (8)	0.0052 (8)
C15	0.0417 (9)	0.0382 (9)	0.0365 (9)	0.0092 (7)	0.0121 (7)	0.0073 (7)
C16	0.0392 (9)	0.0400 (9)	0.0377 (9)	0.0060 (7)	0.0126 (7)	0.0032 (7)
C17	0.0672 (15)	0.0515 (12)	0.0443 (11)	0.0060 (11)	0.0030 (10)	−0.0078 (10)
C18	0.0392 (11)	0.0731 (16)	0.0558 (13)	0.0081 (10)	0.0064 (9)	−0.0036 (11)
C19	0.0375 (9)	0.0401 (9)	0.0413 (9)	0.0049 (7)	0.0111 (7)	−0.0002 (8)
C20	0.0403 (9)	0.0368 (9)	0.0396 (9)	0.0085 (7)	0.0109 (7)	0.0054 (7)
C21	0.0468 (11)	0.0445 (10)	0.0387 (9)	0.0031 (8)	0.0079 (8)	−0.0022 (8)
C22	0.0389 (10)	0.0561 (12)	0.0422 (10)	0.0034 (9)	0.0064 (8)	−0.0037 (9)
C23	0.0616 (14)	0.0729 (16)	0.0469 (12)	0.0034 (12)	0.0073 (10)	−0.0175 (11)
C24	0.0399 (11)	0.0633 (14)	0.0564 (12)	0.0116 (9)	0.0071 (9)	0.0042 (11)

Geometric parameters (Å, º)

O1—C1	1.372 (2)	C7—C8	1.358 (3)
O1—H3O	0.82 (3)	C7—C11	1.502 (3)
O2—C3	1.360 (2)	C8—C9	1.426 (3)
O2—H2O	0.79 (3)	C8—H4	0.92 (3)
O3—C5	1.360 (2)	C10—C12	1.495 (3)
O3—H1O	0.81 (3)	C11—H111	0.9600
O5—C15	1.241 (2)	C11—H112	0.9600
O4—C9	1.241 (2)	C11—H113	0.9600
O6—C19	1.243 (2)	C12—H121	0.9600
N1—C10	1.303 (3)	C12—H122	0.9600
N1—C7	1.379 (3)	C12—H123	0.9600
N2—C10	1.353 (2)	C13—C14	1.352 (3)
N2—C9	1.383 (3)	C13—C17	1.498 (3)
N2—H1N	1.01 (3)	C14—C15	1.426 (3)
N3—C16	1.306 (2)	C14—H5	0.95 (3)
N3—C13	1.378 (3)	C16—C18	1.493 (3)
N4—C16	1.352 (2)	C17—H171	0.9600
N4—C15	1.384 (2)	C17—H172	0.9600
N4—H3N	0.89 (3)	C17—H173	0.9600
N5—C20	1.305 (2)	C18—H181	0.9600
N5—C21	1.377 (3)	C18—H182	0.9600
N6—C20	1.350 (2)	C18—H183	0.9600
N6—C19	1.381 (2)	C19—C22	1.426 (3)
N6—H2N	0.96 (3)	C20—C24	1.491 (3)
C1—C6	1.387 (3)	C21—C22	1.354 (3)
C1—C2	1.391 (3)	C21—C23	1.494 (3)
C2—C3	1.387 (3)	C22—H6	0.95 (3)
C2—H3	0.94 (3)	C23—H231	0.9600
C3—C4	1.386 (3)	C23—H232	0.9600
C4—C5	1.389 (3)	C23—H233	0.9600
C4—H2	0.95 (3)	C24—H241	0.9600
C5—C6	1.392 (3)	C24—H242	0.9600
C6—H1	0.96 (3)	C24—H243	0.9600
C1—O1—H3O	108 (2)	H121—C12—H122	109.5
C3—O2—H2O	112 (2)	C10—C12—H123	109.5
C5—O3—H1O	112 (2)	H121—C12—H123	109.5
C10—N1—C7	117.54 (17)	H122—C12—H123	109.5
C10—N2—C9	123.14 (17)	C14—C13—N3	122.65 (17)
C10—N2—H1N	119.5 (16)	C14—C13—C17	122.44 (19)
C9—N2—H1N	117.0 (16)	N3—C13—C17	114.90 (18)
C16—N3—C13	117.22 (16)	C13—C14—C15	120.47 (19)
C16—N4—C15	123.48 (16)	C13—C14—H5	122.1 (17)
C16—N4—H3N	121.0 (18)	C15—C14—H5	117.4 (17)
C15—N4—H3N	115.2 (18)	O5—C15—N4	119.73 (17)
C20—N5—C21	117.60 (16)	O5—C15—C14	126.75 (18)
C20—N6—C19	123.30 (16)	N4—C15—C14	113.52 (16)
C20—N6—H2N	119.2 (16)	N3—C16—N4	122.62 (18)
C19—N6—H2N	117.4 (15)	N3—C16—C18	120.69 (17)
O1—C1—C6	117.65 (17)	N4—C16—C18	116.69 (17)
O1—C1—C2	121.02 (18)	C13—C17—H171	109.5
C6—C1—C2	121.32 (18)	C13—C17—H172	109.5
C3—C2—C1	119.21 (17)	H171—C17—H172	109.5
C3—C2—H3	121.5 (16)	C13—C17—H173	109.5
C1—C2—H3	119.3 (16)	H171—C17—H173	109.5
O2—C3—C4	117.59 (18)	H172—C17—H173	109.5
O2—C3—C2	121.80 (17)	C16—C18—H181	109.5
C4—C3—C2	120.61 (17)	C16—C18—H182	109.5
C3—C4—C5	119.23 (19)	H181—C18—H182	109.5
C3—C4—H2	120.7 (18)	C16—C18—H183	109.5
C5—C4—H2	120.1 (18)	H181—C18—H183	109.5
O3—C5—C4	115.78 (19)	H182—C18—H183	109.5
O3—C5—C6	122.94 (18)	O6—C19—N6	119.56 (17)
C4—C5—C6	121.27 (18)	O6—C19—C22	126.37 (18)
C1—C6—C5	118.33 (17)	N6—C19—C22	114.07 (17)
C1—C6—H1	125.2 (15)	N5—C20—N6	122.45 (17)
C5—C6—H1	116.5 (15)	N5—C20—C24	119.83 (17)
C8—C7—N1	122.36 (19)	N6—C20—C24	117.71 (17)
C8—C7—C11	121.9 (2)	C22—C21—N5	122.52 (18)
N1—C7—C11	115.7 (2)	C22—C21—C23	122.7 (2)
C7—C8—C9	120.2 (2)	N5—C21—C23	114.81 (19)
C7—C8—H4	122.3 (18)	C21—C22—C19	120.05 (19)
C9—C8—H4	117.5 (18)	C21—C22—H6	122.6 (18)
O4—C9—N2	119.53 (18)	C19—C22—H6	117.4 (18)
O4—C9—C8	126.5 (2)	C21—C23—H231	109.5
N2—C9—C8	113.98 (18)	C21—C23—H232	109.5
N1—C10—N2	122.70 (19)	H231—C23—H232	109.5
N1—C10—C12	121.25 (18)	C21—C23—H233	109.5
N2—C10—C12	116.05 (18)	H231—C23—H233	109.5
C7—C11—H111	109.5	H232—C23—H233	109.5
C7—C11—H112	109.5	C20—C24—H241	109.5
H111—C11—H112	109.5	C20—C24—H242	109.5
C7—C11—H113	109.5	H241—C24—H242	109.5
H111—C11—H113	109.5	C20—C24—H243	109.5
H112—C11—H113	109.5	H241—C24—H243	109.5
C10—C12—H121	109.5	H242—C24—H243	109.5
C10—C12—H122	109.5

(comp3) bis(4-phenyl-pyridine) phloroglucinol

Crystal data

C6H6O3·2(C11H9N)	F(000) = 920
Mr = 436.49	Dx = 1.249 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.4503 (4) Å	Cell parameters from 10162 reflections
b = 7.3939 (2) Å	θ = 2–28°
c = 18.7699 (5) Å	µ = 0.08 mm^−1
β = 114.9241 (13)°	T = 295 K
V = 2322.11 (10) Å^3	Needle, colourless
Z = 4	0.35 × 0.26 × 0.09 mm

Data collection

Nonius Kappa CCD diffractometer	2961 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.049
Graphite monochromator	θmax = 28.0°, θmin = 3.4°
φ scans and ω scans	h = −24→24
10162 measured reflections	k = −9→9
5582 independent reflections	l = −24→24

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.195	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.1157P)^2] where P = (Fo^2 + 2Fc^2)/3
5582 reflections	(Δ/σ)max < 0.001
394 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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.

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 > 2sigma(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
O1	0.69892 (10)	0.41480 (17)	0.14851 (10)	0.0609 (4)
O2	0.68594 (10)	−0.2224 (2)	0.12354 (10)	0.0659 (5)
O3	0.81314 (10)	0.0459 (2)	0.37662 (9)	0.0642 (4)
C1	0.71552 (11)	0.2464 (2)	0.18146 (11)	0.0444 (4)
C2	0.69261 (12)	0.0922 (2)	0.13554 (12)	0.0478 (5)
C3	0.71049 (12)	−0.0751 (2)	0.17216 (12)	0.0469 (5)
C4	0.75069 (12)	−0.0905 (3)	0.25263 (13)	0.0487 (5)
C5	0.77378 (11)	0.0659 (3)	0.29783 (11)	0.0465 (5)
C6	0.75558 (11)	0.2350 (3)	0.26243 (12)	0.0471 (5)
N1	0.62979 (15)	0.4111 (3)	−0.00806 (11)	0.0676 (6)
C7	0.5535 (2)	0.3645 (4)	−0.03844 (15)	0.0717 (7)
C8	0.50385 (16)	0.3629 (3)	−0.11804 (14)	0.0633 (6)
C9	0.53440 (12)	0.4143 (2)	−0.17069 (12)	0.0483 (5)
C10	0.61486 (14)	0.4623 (3)	−0.13857 (14)	0.0586 (6)
C11	0.65937 (16)	0.4598 (3)	−0.05863 (15)	0.0669 (6)
C12	0.48437 (13)	0.4172 (3)	−0.25629 (13)	0.0524 (5)
C13	0.40231 (16)	0.4466 (3)	−0.28507 (16)	0.0694 (6)
C14	0.3544 (2)	0.4453 (4)	−0.36389 (19)	0.0916 (9)
C15	0.3863 (3)	0.4159 (4)	−0.41599 (19)	0.0939 (11)
C16	0.4671 (3)	0.3904 (4)	−0.39000 (17)	0.0864 (10)
C17	0.51704 (18)	0.3901 (3)	−0.30984 (15)	0.0654 (6)
N2	0.85754 (14)	0.3671 (3)	0.45711 (12)	0.0757 (6)
C18	0.84399 (19)	0.3846 (4)	0.52100 (16)	0.0832 (8)
C19	0.86288 (17)	0.5347 (4)	0.56755 (15)	0.0740 (7)
C20	0.89806 (12)	0.6832 (3)	0.54922 (12)	0.0546 (5)
C21	0.91185 (16)	0.6664 (4)	0.48227 (14)	0.0680 (6)
C22	0.89108 (17)	0.5102 (4)	0.43879 (15)	0.0737 (7)
C23	0.92161 (12)	0.8450 (3)	0.59935 (12)	0.0542 (5)
C24	0.87485 (15)	0.9116 (4)	0.63537 (15)	0.0669 (6)
C25	0.89933 (17)	1.0596 (4)	0.68472 (16)	0.0774 (8)
C26	0.97062 (18)	1.1443 (4)	0.69939 (16)	0.0766 (7)
C27	1.01751 (18)	1.0814 (4)	0.66412 (17)	0.0763 (7)
C28	0.99283 (15)	0.9341 (3)	0.61399 (15)	0.0640 (6)
H2O	0.7036 (18)	−0.327 (5)	0.1517 (19)	0.108 (11)*
H1	0.7687 (13)	0.351 (4)	0.2928 (14)	0.064 (6)*
H2	0.7623 (11)	−0.208 (3)	0.2765 (12)	0.052 (5)*
H3	0.6643 (14)	0.101 (3)	0.0777 (15)	0.062 (6)*
H4	1.0673 (17)	1.143 (4)	0.6727 (16)	0.087 (8)*
H5	0.5738 (16)	0.359 (3)	−0.2902 (15)	0.073 (7)*
H6	0.9332 (14)	0.762 (4)	0.4646 (14)	0.073 (7)*
H7	0.8637 (18)	1.114 (4)	0.7051 (17)	0.090 (8)*
H8	0.8256 (17)	0.849 (4)	0.6249 (15)	0.079 (7)*
H9	1.0269 (14)	0.889 (3)	0.5894 (14)	0.066 (6)*
H10	0.6385 (13)	0.502 (3)	−0.1694 (12)	0.053 (6)*
H11	0.9028 (17)	0.499 (4)	0.3894 (19)	0.097 (9)*
H12	0.3774 (18)	0.478 (4)	−0.2498 (18)	0.094 (9)*
H13	0.4933 (19)	0.381 (4)	−0.419 (2)	0.098 (10)*
H14	0.9876 (19)	1.251 (5)	0.735 (2)	0.113 (11)*
H15	0.8462 (18)	0.543 (4)	0.6084 (19)	0.097 (9)*
H1O	0.676 (2)	0.408 (4)	0.096 (2)	0.102 (10)*
H3O	0.8266 (18)	0.157 (5)	0.400 (2)	0.097 (10)*
H16	0.5311 (14)	0.334 (3)	−0.0048 (15)	0.068 (7)*
H17	0.4488 (18)	0.327 (4)	−0.1367 (16)	0.084 (8)*
H18	0.294 (3)	0.465 (5)	−0.384 (3)	0.140 (13)*
H19	0.351 (2)	0.418 (5)	−0.467 (2)	0.125 (13)*
H20	0.7214 (18)	0.497 (4)	−0.0346 (16)	0.087 (8)*
H21	0.8245 (17)	0.276 (4)	0.5347 (17)	0.098 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0938 (12)	0.0263 (7)	0.0507 (9)	0.0036 (7)	0.0190 (8)	0.0026 (6)
O2	0.0961 (12)	0.0295 (8)	0.0633 (10)	−0.0001 (8)	0.0250 (9)	−0.0063 (7)
O3	0.0777 (10)	0.0549 (10)	0.0486 (9)	0.0036 (8)	0.0155 (8)	0.0067 (7)
C1	0.0541 (11)	0.0300 (9)	0.0490 (11)	0.0030 (8)	0.0216 (9)	0.0027 (8)
C2	0.0620 (12)	0.0331 (10)	0.0472 (11)	0.0027 (8)	0.0220 (10)	−0.0004 (8)
C3	0.0554 (11)	0.0317 (10)	0.0561 (12)	−0.0020 (8)	0.0261 (10)	−0.0040 (8)
C4	0.0553 (12)	0.0343 (10)	0.0590 (12)	0.0042 (8)	0.0264 (10)	0.0066 (9)
C5	0.0480 (10)	0.0435 (11)	0.0482 (11)	0.0023 (8)	0.0204 (9)	0.0044 (8)
C6	0.0570 (11)	0.0341 (10)	0.0499 (11)	−0.0002 (8)	0.0222 (10)	−0.0030 (8)
N1	0.0934 (16)	0.0448 (11)	0.0550 (11)	0.0081 (10)	0.0219 (11)	0.0056 (8)
C7	0.104 (2)	0.0615 (15)	0.0634 (15)	0.0117 (14)	0.0485 (16)	0.0176 (12)
C8	0.0702 (15)	0.0605 (14)	0.0643 (14)	0.0058 (12)	0.0334 (13)	0.0113 (11)
C9	0.0591 (12)	0.0366 (10)	0.0529 (11)	0.0080 (8)	0.0272 (10)	0.0038 (8)
C10	0.0628 (14)	0.0553 (13)	0.0618 (13)	0.0048 (10)	0.0304 (12)	0.0071 (11)
C11	0.0720 (16)	0.0540 (14)	0.0619 (14)	0.0022 (11)	0.0158 (13)	0.0032 (11)
C12	0.0650 (13)	0.0380 (10)	0.0535 (12)	0.0046 (9)	0.0244 (11)	0.0016 (9)
C13	0.0672 (15)	0.0676 (16)	0.0642 (15)	0.0096 (12)	0.0187 (13)	0.0082 (12)
C14	0.092 (2)	0.088 (2)	0.0672 (18)	0.0051 (17)	0.0072 (17)	0.0104 (15)
C15	0.130 (3)	0.0609 (17)	0.0534 (17)	−0.0106 (17)	0.0023 (19)	0.0122 (13)
C16	0.143 (3)	0.0641 (17)	0.0646 (17)	−0.0039 (17)	0.055 (2)	−0.0003 (13)
C17	0.0899 (18)	0.0546 (13)	0.0587 (14)	0.0058 (12)	0.0382 (14)	0.0024 (11)
N2	0.0865 (14)	0.0634 (13)	0.0527 (12)	0.0009 (11)	0.0053 (10)	−0.0033 (10)
C18	0.105 (2)	0.0662 (17)	0.0575 (15)	−0.0241 (15)	0.0144 (15)	0.0009 (13)
C19	0.0905 (18)	0.0729 (17)	0.0548 (14)	−0.0201 (14)	0.0270 (14)	−0.0028 (12)
C20	0.0528 (11)	0.0544 (12)	0.0491 (11)	0.0024 (10)	0.0143 (10)	0.0035 (10)
C21	0.0795 (16)	0.0649 (16)	0.0598 (14)	−0.0059 (13)	0.0295 (13)	−0.0004 (12)
C22	0.0857 (18)	0.0707 (17)	0.0572 (14)	−0.0006 (14)	0.0226 (13)	−0.0076 (13)
C23	0.0533 (11)	0.0560 (13)	0.0501 (11)	0.0002 (10)	0.0186 (10)	0.0017 (10)
C24	0.0553 (14)	0.0774 (17)	0.0665 (15)	−0.0004 (12)	0.0244 (12)	−0.0069 (12)
C25	0.0735 (17)	0.0881 (19)	0.0697 (16)	0.0142 (15)	0.0292 (14)	−0.0138 (14)
C26	0.0840 (19)	0.0684 (17)	0.0652 (15)	0.0014 (14)	0.0195 (14)	−0.0130 (14)
C27	0.0731 (16)	0.0715 (17)	0.0795 (18)	−0.0170 (14)	0.0277 (15)	−0.0108 (13)
C28	0.0631 (14)	0.0645 (15)	0.0678 (15)	−0.0064 (11)	0.0309 (13)	−0.0062 (11)

Geometric parameters (Å, º)

O1—C1	1.367 (2)	C14—C15	1.355 (5)
O1—H1O	0.90 (4)	C14—H18	1.03 (4)
O2—C3	1.369 (2)	C15—C16	1.372 (5)
O2—H2O	0.91 (4)	C15—H19	0.91 (4)
O3—C5	1.353 (2)	C16—C17	1.394 (4)
O3—H3O	0.92 (4)	C16—H13	0.87 (3)
C1—C2	1.383 (3)	C17—H5	0.98 (3)
C1—C6	1.384 (3)	N2—C18	1.331 (4)
C2—C3	1.386 (3)	N2—C22	1.342 (4)
C2—H3	0.99 (2)	C18—C19	1.363 (4)
C3—C4	1.378 (3)	C18—H21	0.96 (3)
C4—C5	1.391 (3)	C19—C20	1.390 (3)
C4—H2	0.96 (2)	C19—H15	0.94 (3)
C5—C6	1.389 (3)	C20—C21	1.389 (3)
C6—H1	1.00 (3)	C20—C23	1.470 (3)
N1—C7	1.322 (4)	C21—C22	1.372 (4)
N1—C11	1.329 (3)	C21—H6	0.93 (3)
C7—C8	1.385 (4)	C22—H11	1.04 (3)
C7—H16	0.92 (2)	C23—C28	1.390 (3)
C8—C9	1.382 (3)	C23—C24	1.391 (3)
C8—H17	0.96 (3)	C24—C25	1.381 (4)
C9—C10	1.392 (3)	C24—H8	0.96 (3)
C9—C12	1.478 (3)	C25—C26	1.376 (4)
C10—C11	1.374 (3)	C25—H7	0.98 (3)
C10—H10	0.91 (2)	C26—C27	1.373 (4)
C11—H20	1.07 (3)	C26—H14	0.99 (4)
C12—C17	1.387 (3)	C27—C28	1.385 (4)
C12—C13	1.394 (3)	C27—H4	0.98 (3)
C13—C14	1.367 (4)	C28—H9	0.98 (2)
C13—H12	0.98 (3)
C1—O1—H1O	111 (2)	C13—C14—H18	121 (2)
C3—O2—H2O	110 (2)	C14—C15—C16	120.2 (3)
C5—O3—H3O	110 (2)	C14—C15—H19	115 (2)
O1—C1—C2	121.15 (17)	C16—C15—H19	125 (2)
O1—C1—C6	117.79 (17)	C15—C16—C17	120.6 (3)
C2—C1—C6	121.05 (17)	C15—C16—H13	127 (2)
C1—C2—C3	118.69 (19)	C17—C16—H13	113 (2)
C1—C2—H3	120.9 (13)	C12—C17—C16	119.4 (3)
C3—C2—H3	120.5 (13)	C12—C17—H5	118.9 (15)
O2—C3—C4	122.60 (18)	C16—C17—H5	121.4 (15)
O2—C3—C2	115.87 (18)	C18—N2—C22	115.9 (2)
C4—C3—C2	121.53 (17)	N2—C18—C19	124.2 (3)
C3—C4—C5	118.99 (18)	N2—C18—H21	113.1 (18)
C3—C4—H2	119.8 (12)	C19—C18—H21	122.3 (18)
C5—C4—H2	121.2 (12)	C18—C19—C20	120.3 (3)
O3—C5—C6	122.09 (18)	C18—C19—H15	119 (2)
O3—C5—C4	117.46 (17)	C20—C19—H15	120 (2)
C6—C5—C4	120.44 (18)	C21—C20—C19	115.9 (2)
C1—C6—C5	119.29 (18)	C21—C20—C23	122.3 (2)
C1—C6—H1	117.6 (14)	C19—C20—C23	121.8 (2)
C5—C6—H1	123.1 (14)	C22—C21—C20	120.1 (2)
C7—N1—C11	116.4 (2)	C22—C21—H6	118.5 (15)
N1—C7—C8	124.6 (2)	C20—C21—H6	121.3 (16)
N1—C7—H16	118.3 (15)	N2—C22—C21	123.7 (3)
C8—C7—H16	117.0 (15)	N2—C22—H11	117.1 (17)
C9—C8—C7	119.0 (2)	C21—C22—H11	119.2 (17)
C9—C8—H17	120.2 (16)	C28—C23—C24	117.7 (2)
C7—C8—H17	120.8 (16)	C28—C23—C20	120.80 (19)
C8—C9—C10	116.3 (2)	C24—C23—C20	121.5 (2)
C8—C9—C12	121.7 (2)	C25—C24—C23	120.8 (2)
C10—C9—C12	122.04 (19)	C25—C24—H8	122.2 (15)
C11—C10—C9	120.5 (2)	C23—C24—H8	117.0 (16)
C11—C10—H10	118.3 (14)	C26—C25—C24	120.6 (3)
C9—C10—H10	121.2 (13)	C26—C25—H7	118.8 (17)
N1—C11—C10	123.2 (2)	C24—C25—H7	120.2 (18)
N1—C11—H20	117.1 (14)	C27—C26—C25	119.5 (3)
C10—C11—H20	119.7 (15)	C27—C26—H14	120.4 (18)
C17—C12—C13	118.3 (2)	C25—C26—H14	120.0 (18)
C17—C12—C9	121.5 (2)	C26—C27—C28	120.0 (3)
C13—C12—C9	120.2 (2)	C26—C27—H4	120.2 (16)
C14—C13—C12	121.3 (3)	C28—C27—H4	119.7 (16)
C14—C13—H12	117.4 (17)	C27—C28—C23	121.3 (2)
C12—C13—H12	121.1 (17)	C27—C28—H9	119.7 (14)
C15—C14—C13	120.2 (3)	C23—C28—H9	119.0 (14)
C15—C14—H18	119 (2)

(comp4) phloroglucinol bis(2-hydroxy-pyridine)

Crystal data

C6H6O3·2(C5H5NO)	F(000) = 664
Mr = 316.31	Dx = 1.369 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.7275 (3) Å	Cell parameters from 4785 reflections
b = 19.8281 (10) Å	θ = 2–25°
c = 11.3080 (6) Å	µ = 0.10 mm^−1
β = 117.679 (2)°	T = 295 K
V = 1534.35 (13) Å^3	Prismatic, colourless
Z = 4	0.28 × 0.20 × 0.11 mm

Data collection

Nonius Kappa CCD diffractometer	1170 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.079
Graphite monochromator	θmax = 25.0°, θmin = 2.9°
φ scans and ω scans	h = −9→9
4785 measured reflections	k = −21→23
2693 independent reflections	l = −13→13

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0789P)^2 + 0.0425P] where P = (Fo^2 + 2Fc^2)/3
2693 reflections	(Δ/σ)max = 0.001
232 parameters	Δρmax = 0.27 e Å^−3
3 restraints	Δρmin = −0.29 e Å^−3

Special details

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.

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 > 2sigma(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
O1	−0.0061 (4)	0.17925 (18)	−0.1301 (4)	0.0549 (9)
O2	0.4644 (4)	0.13677 (17)	−0.2866 (3)	0.0526 (9)
O3	0.6118 (4)	0.28927 (17)	0.0640 (3)	0.0555 (9)
O4	−0.1817 (4)	0.07418 (17)	−0.3138 (3)	0.0526 (9)
O5	0.2712 (4)	0.02526 (17)	−0.4014 (3)	0.0584 (10)
N1	−0.2678 (5)	−0.0361 (2)	−0.3541 (4)	0.0493 (10)
H1N	−0.2749	−0.0317	−0.4354	0.059*
N2	0.1910 (5)	−0.0855 (2)	−0.4308 (4)	0.0469 (10)
H2N	0.1840	−0.0829	−0.5124	0.056*
C1	0.1720 (6)	0.1892 (2)	−0.1258 (4)	0.0380 (11)
C2	0.2250 (6)	0.1558 (2)	−0.2116 (5)	0.0395 (11)
C3	0.4063 (6)	0.1678 (2)	−0.2018 (4)	0.0392 (11)
C4	0.5350 (7)	0.2127 (2)	−0.1104 (4)	0.0438 (12)
C5	0.4791 (6)	0.2453 (2)	−0.0262 (4)	0.0400 (11)
C6	0.2982 (6)	0.2347 (2)	−0.0313 (4)	0.0402 (11)
C7	−0.2205 (5)	0.0188 (3)	−0.2741 (5)	0.0435 (12)
C8	−0.2189 (6)	0.0088 (3)	−0.1492 (5)	0.0561 (14)
H8	−0.1920	0.0448	−0.0905	0.067*
C9	−0.2564 (7)	−0.0527 (4)	−0.1154 (5)	0.0687 (16)
H9	−0.2530	−0.0587	−0.0328	0.082*
C10	−0.2996 (7)	−0.1072 (3)	−0.2008 (6)	0.0697 (16)
H10	−0.3242	−0.1496	−0.1767	0.084*
C11	−0.3050 (7)	−0.0970 (3)	−0.3184 (6)	0.0625 (15)
H11	−0.3351	−0.1329	−0.3777	0.075*
C12	0.2389 (6)	−0.0292 (3)	−0.3552 (5)	0.0449 (12)
C13	0.2487 (7)	−0.0369 (3)	−0.2291 (5)	0.0573 (13)
H13	0.2789	0.0001	−0.1724	0.069*
C14	0.2150 (7)	−0.0970 (3)	−0.1891 (6)	0.0674 (15)
H14	0.2263	−0.1011	−0.1038	0.081*
C15	0.1642 (7)	−0.1528 (3)	−0.2710 (6)	0.0678 (16)
H15	0.1386	−0.1940	−0.2433	0.081*
C16	0.1533 (6)	−0.1454 (3)	−0.3916 (6)	0.0563 (14)
H16	0.1191	−0.1821	−0.4493	0.068*
H1	0.253 (6)	0.261 (2)	0.026 (4)	0.063 (13)*
H2	0.655 (5)	0.2220 (18)	−0.102 (3)	0.034 (11)*
H3	0.143 (5)	0.130 (2)	−0.281 (4)	0.043 (13)*
H1O	−0.062 (6)	0.1494 (18)	−0.183 (4)	0.057 (17)*
H2O	0.381 (6)	0.103 (2)	−0.326 (5)	0.10 (2)*
H3O	0.551 (7)	0.308 (2)	0.100 (5)	0.09 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0493 (19)	0.058 (3)	0.066 (3)	−0.0083 (17)	0.0340 (18)	−0.018 (2)
O2	0.066 (2)	0.049 (2)	0.061 (2)	−0.0050 (17)	0.0443 (19)	−0.0087 (19)
O3	0.0557 (19)	0.056 (2)	0.056 (2)	−0.0118 (17)	0.0274 (17)	−0.0192 (19)
O4	0.0591 (19)	0.047 (2)	0.057 (2)	−0.0028 (16)	0.0317 (17)	−0.0046 (18)
O5	0.083 (2)	0.044 (2)	0.057 (2)	−0.0052 (17)	0.0399 (18)	−0.0075 (18)
N1	0.061 (2)	0.040 (3)	0.046 (3)	−0.0037 (19)	0.024 (2)	−0.007 (2)
N2	0.054 (2)	0.043 (3)	0.045 (3)	0.0026 (18)	0.0246 (19)	−0.005 (2)
C1	0.039 (2)	0.039 (3)	0.042 (3)	0.005 (2)	0.024 (2)	0.002 (2)
C2	0.046 (3)	0.036 (3)	0.038 (3)	−0.001 (2)	0.020 (2)	−0.004 (3)
C3	0.053 (3)	0.032 (3)	0.043 (3)	0.006 (2)	0.031 (2)	0.001 (2)
C4	0.046 (3)	0.046 (3)	0.049 (3)	−0.005 (2)	0.030 (2)	−0.004 (3)
C5	0.047 (3)	0.034 (3)	0.035 (3)	−0.008 (2)	0.016 (2)	−0.004 (2)
C6	0.049 (3)	0.035 (3)	0.040 (3)	−0.001 (2)	0.024 (2)	−0.004 (2)
C7	0.037 (2)	0.049 (4)	0.042 (3)	0.004 (2)	0.017 (2)	0.005 (3)
C8	0.054 (3)	0.071 (4)	0.036 (3)	0.001 (3)	0.014 (2)	−0.006 (3)
C9	0.076 (4)	0.083 (5)	0.049 (4)	0.003 (3)	0.030 (3)	0.025 (4)
C10	0.081 (4)	0.052 (4)	0.069 (4)	−0.005 (3)	0.030 (3)	0.014 (4)
C11	0.076 (3)	0.045 (4)	0.065 (4)	−0.008 (3)	0.032 (3)	−0.001 (3)
C12	0.051 (3)	0.039 (3)	0.048 (3)	0.005 (2)	0.025 (2)	−0.004 (3)
C13	0.079 (3)	0.048 (4)	0.055 (4)	0.005 (3)	0.040 (3)	−0.003 (3)
C14	0.088 (4)	0.069 (5)	0.058 (4)	0.010 (3)	0.045 (3)	0.000 (4)
C15	0.087 (4)	0.055 (4)	0.079 (4)	0.008 (3)	0.053 (3)	0.020 (4)
C16	0.056 (3)	0.033 (3)	0.079 (4)	0.001 (2)	0.030 (3)	−0.003 (3)

Geometric parameters (Å, º)

O1—C1	1.369 (4)	C4—H2	0.91 (4)
O1—H1O	0.811 (19)	C5—C6	1.389 (5)
O2—C3	1.378 (5)	C6—H1	1.01 (4)
O2—H2O	0.90 (2)	C7—C8	1.421 (6)
O3—C5	1.372 (5)	C8—C9	1.349 (7)
O3—H3O	0.84 (2)	C8—H8	0.9300
O4—C7	1.273 (5)	C9—C10	1.382 (7)
O5—C12	1.273 (5)	C9—H9	0.9300
N1—C11	1.346 (6)	C10—C11	1.326 (6)
N1—C7	1.353 (6)	C10—H10	0.9300
N1—H1N	0.9000	C11—H11	0.9300
N2—C16	1.346 (5)	C12—C13	1.401 (6)
N2—C12	1.349 (5)	C13—C14	1.344 (6)
N2—H2N	0.9000	C13—H13	0.9300
C1—C2	1.384 (6)	C14—C15	1.377 (7)
C1—C6	1.392 (6)	C14—H14	0.9300
C2—C3	1.374 (6)	C15—C16	1.335 (6)
C2—H3	0.90 (4)	C15—H15	0.9300
C3—C4	1.377 (6)	C16—H16	0.9300
C4—C5	1.374 (5)
C1—O1—H1O	108 (3)	N1—C7—C8	115.2 (5)
C3—O2—H2O	107 (3)	C9—C8—C7	120.3 (5)
C5—O3—H3O	104 (4)	C9—C8—H8	119.8
C11—N1—C7	123.4 (4)	C7—C8—H8	119.8
C11—N1—H1N	118.3	C8—C9—C10	121.5 (5)
C7—N1—H1N	118.3	C8—C9—H9	119.3
C16—N2—C12	124.0 (4)	C10—C9—H9	119.3
C16—N2—H2N	118.0	C11—C10—C9	117.8 (5)
C12—N2—H2N	118.0	C11—C10—H10	121.1
O1—C1—C2	121.7 (4)	C9—C10—H10	121.1
O1—C1—C6	117.1 (4)	C10—C11—N1	121.7 (5)
C2—C1—C6	121.2 (4)	C10—C11—H11	119.1
C3—C2—C1	118.9 (4)	N1—C11—H11	119.1
C3—C2—H3	116 (2)	O5—C12—N2	119.4 (4)
C1—C2—H3	124 (2)	O5—C12—C13	125.6 (5)
C4—C3—C2	121.7 (4)	N2—C12—C13	115.1 (5)
C4—C3—O2	117.1 (4)	C14—C13—C12	120.8 (5)
C2—C3—O2	121.1 (4)	C14—C13—H13	119.6
C3—C4—C5	118.3 (4)	C12—C13—H13	119.6
C3—C4—H2	124 (2)	C13—C14—C15	121.7 (5)
C5—C4—H2	118 (2)	C13—C14—H14	119.2
O3—C5—C4	116.6 (4)	C15—C14—H14	119.2
O3—C5—C6	121.1 (4)	C16—C15—C14	117.6 (5)
C4—C5—C6	122.3 (4)	C16—C15—H15	121.2
C5—C6—C1	117.5 (4)	C14—C15—H15	121.2
C5—C6—H1	122 (2)	C15—C16—N2	120.8 (5)
C1—C6—H1	120 (2)	C15—C16—H16	119.6
O4—C7—N1	119.6 (4)	N2—C16—H16	119.6
O4—C7—C8	125.2 (5)

(comp5) bis(phloroglucinol) tris(2,3,5,6- tetramethylpyrazine)

Crystal data

3(C8H12N2)·2(C6H6O3)	F(000) = 1416
Mr = 660.80	Dx = 1.208 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.6225 (4) Å	Cell parameters from 14448 reflections
b = 13.5010 (3) Å	θ = 2–27°
c = 17.2314 (5) Å	µ = 0.08 mm^−1
β = 90.235 (1)°	T = 295 K
V = 3634.44 (16) Å^3	Prismatic, colourless
Z = 4	0.24 × 0.20 × 0.17 mm

Data collection

Nonius Kappa CCD diffractometer	3828 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
Graphite monochromator	θmax = 27.0°, θmin = 2.7°
φ scans and ω scans	h = −19→19
14448 measured reflections	k = −17→15
7827 independent reflections	l = −21→22

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.226	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0841P)^2 + 1.9639P] where P = (Fo^2 + 2Fc^2)/3
7827 reflections	(Δ/σ)max = 0.001
481 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

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.

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 > 2sigma(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
O1	0.40166 (15)	−0.10850 (15)	0.15660 (13)	0.0571 (6)
O2	0.45966 (19)	0.24044 (16)	0.17019 (17)	0.0776 (9)
O3	0.59614 (16)	0.01249 (19)	0.34117 (14)	0.0644 (7)
O4	0.90089 (16)	0.30811 (19)	0.65992 (14)	0.0686 (7)
O5	1.09688 (18)	0.43087 (17)	0.84165 (15)	0.0679 (7)
O6	1.04735 (19)	0.08123 (16)	0.82509 (16)	0.0787 (9)
N1	0.27570 (15)	−0.04353 (17)	0.04887 (14)	0.0446 (6)
N2	0.17021 (16)	0.04487 (19)	−0.05771 (15)	0.0520 (7)
N3	0.32850 (19)	0.2768 (2)	0.05617 (16)	0.0603 (7)
N4	0.22234 (17)	0.36981 (19)	−0.04792 (14)	0.0517 (7)
N5	0.68189 (16)	0.13618 (18)	0.44919 (14)	0.0470 (6)
N6	0.80153 (16)	0.18612 (19)	0.55999 (15)	0.0520 (7)
C1	0.44235 (18)	−0.0277 (2)	0.18765 (16)	0.0409 (7)
C2	0.42711 (19)	0.0674 (2)	0.16079 (17)	0.0439 (7)
C3	0.47062 (19)	0.1455 (2)	0.19562 (17)	0.0461 (7)
C4	0.52735 (19)	0.1311 (2)	0.25633 (17)	0.0444 (7)
C5	0.54145 (18)	0.0346 (2)	0.28147 (16)	0.0443 (7)
C6	0.50051 (19)	−0.0453 (2)	0.24711 (17)	0.0454 (7)
C7	0.20601 (19)	0.0057 (2)	0.07250 (16)	0.0453 (7)
C8	0.15288 (19)	0.0507 (2)	0.01784 (18)	0.0472 (7)
C9	0.23997 (19)	−0.0047 (2)	−0.08068 (17)	0.0484 (7)
C10	0.29372 (18)	−0.0487 (2)	−0.02661 (17)	0.0441 (7)
C11	0.1885 (3)	0.0092 (3)	0.15753 (19)	0.0748 (11)
H11A	0.2232	0.0597	0.1811	0.090*
H11B	0.2019	−0.0538	0.1804	0.090*
H11C	0.1292	0.0241	0.1658	0.090*
C12	0.0745 (2)	0.1068 (3)	0.0411 (2)	0.0793 (12)
H12A	0.0885	0.1512	0.0828	0.095*
H12B	0.0313	0.0611	0.0580	0.095*
H12C	0.0535	0.1440	−0.0024	0.095*
C13	0.2567 (3)	−0.0096 (4)	−0.1660 (2)	0.0855 (13)
H13A	0.2206	0.0371	−0.1925	0.103*
H13B	0.2445	−0.0752	−0.1845	0.103*
H13C	0.3156	0.0060	−0.1757	0.103*
C14	0.3736 (2)	−0.1027 (3)	−0.0492 (2)	0.0737 (11)
H14A	0.4197	−0.0832	−0.0155	0.088*
H14B	0.3879	−0.0868	−0.1019	0.088*
H14C	0.3644	−0.1728	−0.0447	0.088*
C15	0.2584 (2)	0.3246 (2)	0.08067 (18)	0.0568 (8)
C16	0.2051 (2)	0.3714 (2)	0.02806 (19)	0.0527 (8)
C17	0.2921 (2)	0.3220 (2)	−0.07226 (18)	0.0538 (8)
C18	0.3460 (2)	0.2751 (3)	−0.0194 (2)	0.0578 (8)
C19	0.2424 (3)	0.3247 (4)	0.1663 (2)	0.0993 (15)
H19A	0.2600	0.2623	0.1879	0.119*
H19B	0.1825	0.3345	0.1758	0.119*
H19C	0.2745	0.3772	0.1902	0.119*
C20	0.1251 (3)	0.4251 (3)	0.0522 (3)	0.0847 (12)
H20A	0.0837	0.3781	0.0704	0.102*
H20B	0.1021	0.4606	0.0087	0.102*
H20C	0.1386	0.4709	0.0931	0.102*
C21	0.3090 (3)	0.3226 (4)	−0.1579 (2)	0.0869 (13)
H21A	0.2578	0.3413	−0.1852	0.104*
H21B	0.3264	0.2577	−0.1742	0.104*
H21C	0.3537	0.3693	−0.1691	0.104*
C22	0.4246 (3)	0.2192 (4)	−0.0444 (3)	0.0970 (14)
H22A	0.4159	0.1496	−0.0362	0.116*
H22B	0.4730	0.2411	−0.0144	0.116*
H22C	0.4350	0.2314	−0.0984	0.116*
C23	0.66676 (19)	0.1194 (2)	0.52448 (17)	0.0473 (7)
C24	0.7271 (2)	0.1453 (2)	0.58038 (17)	0.0513 (8)
C25	0.8164 (2)	0.2025 (2)	0.48493 (18)	0.0505 (8)
C26	0.75551 (19)	0.1785 (2)	0.42840 (17)	0.0475 (7)
C27	0.5830 (2)	0.0724 (3)	0.5445 (2)	0.0811 (12)
H27A	0.5480	0.0678	0.4987	0.097*
H27B	0.5543	0.1119	0.5827	0.097*
H27C	0.5929	0.0072	0.5649	0.097*
C28	0.7122 (3)	0.1303 (4)	0.6656 (2)	0.0921 (15)
H28A	0.6530	0.1146	0.6741	0.110*
H28B	0.7266	0.1898	0.6931	0.110*
H28C	0.7473	0.0768	0.6840	0.110*
C29	0.8998 (2)	0.2490 (4)	0.4643 (2)	0.0943 (15)
H29A	0.9005	0.2638	0.4098	0.113*
H29B	0.9456	0.2040	0.4764	0.113*
H29C	0.9072	0.3090	0.4934	0.113*
C30	0.7684 (3)	0.1977 (3)	0.34423 (19)	0.0768 (11)
H30A	0.7160	0.1850	0.3166	0.092*
H30B	0.8125	0.1549	0.3249	0.092*
H30C	0.7849	0.2655	0.3368	0.092*
C31	0.95858 (18)	0.2859 (2)	0.71735 (17)	0.0452 (7)
C32	0.9985 (2)	0.3660 (2)	0.75195 (18)	0.0512 (8)
C33	1.05828 (19)	0.3497 (2)	0.80988 (17)	0.0450 (7)
C34	1.07649 (19)	0.2548 (2)	0.83448 (17)	0.0441 (7)
C35	1.03450 (19)	0.1755 (2)	0.80026 (17)	0.0459 (7)
C36	0.9758 (2)	0.1906 (2)	0.74074 (18)	0.0476 (8)
H1O	0.360 (3)	−0.091 (3)	0.115 (3)	0.112 (15)*
H2O	0.423 (2)	0.241 (3)	0.137 (2)	0.069 (12)*
H3O	0.616 (3)	0.063 (3)	0.367 (3)	0.106 (16)*
H4O	0.877 (2)	0.253 (3)	0.638 (2)	0.075 (12)*
H5O	1.135 (3)	0.409 (3)	0.872 (2)	0.079 (13)*
H6O	1.098 (4)	0.075 (4)	0.867 (4)	0.16 (2)*
H1	0.560 (2)	0.191 (2)	0.2769 (17)	0.054 (8)*
H2	0.391 (2)	0.084 (2)	0.1187 (19)	0.058 (9)*
H3	0.512 (2)	−0.115 (3)	0.2672 (19)	0.069 (10)*
H4	1.118 (2)	0.242 (2)	0.8718 (19)	0.058 (9)*
H5	0.986 (2)	0.430 (2)	0.7343 (18)	0.058 (9)*
H6	0.956 (2)	0.139 (3)	0.717 (2)	0.068 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0606 (14)	0.0490 (12)	0.0614 (15)	−0.0054 (10)	−0.0283 (12)	0.0002 (10)
O2	0.098 (2)	0.0458 (14)	0.088 (2)	−0.0010 (12)	−0.0538 (18)	0.0026 (12)
O3	0.0693 (16)	0.0662 (16)	0.0573 (15)	−0.0037 (12)	−0.0342 (12)	0.0038 (12)
O4	0.0737 (17)	0.0706 (16)	0.0611 (16)	−0.0127 (13)	−0.0399 (13)	0.0133 (12)
O5	0.0835 (18)	0.0521 (14)	0.0680 (16)	−0.0149 (12)	−0.0371 (14)	0.0060 (11)
O6	0.095 (2)	0.0447 (13)	0.096 (2)	0.0027 (12)	−0.0529 (16)	0.0014 (12)
N1	0.0368 (14)	0.0571 (15)	0.0397 (15)	0.0047 (11)	−0.0062 (11)	0.0003 (11)
N2	0.0465 (15)	0.0656 (17)	0.0438 (16)	0.0079 (12)	−0.0077 (12)	0.0073 (12)
N3	0.0669 (19)	0.0659 (18)	0.0481 (18)	0.0063 (15)	−0.0161 (14)	0.0031 (13)
N4	0.0496 (16)	0.0638 (17)	0.0415 (16)	−0.0049 (13)	−0.0116 (13)	0.0022 (12)
N5	0.0432 (15)	0.0592 (16)	0.0386 (14)	−0.0087 (11)	−0.0076 (11)	−0.0010 (11)
N6	0.0447 (15)	0.0682 (17)	0.0429 (15)	−0.0138 (12)	−0.0126 (12)	0.0020 (12)
C1	0.0378 (15)	0.0504 (17)	0.0346 (15)	−0.0033 (12)	−0.0037 (12)	−0.0006 (12)
C2	0.0410 (17)	0.0524 (18)	0.0382 (16)	0.0031 (13)	−0.0092 (13)	0.0006 (13)
C3	0.0477 (18)	0.0443 (17)	0.0463 (17)	0.0038 (13)	−0.0071 (14)	−0.0016 (13)
C4	0.0378 (16)	0.0528 (18)	0.0425 (17)	−0.0047 (13)	−0.0060 (13)	−0.0057 (13)
C5	0.0377 (16)	0.0593 (19)	0.0357 (16)	−0.0001 (13)	−0.0085 (13)	0.0008 (13)
C6	0.0443 (17)	0.0507 (18)	0.0412 (17)	−0.0021 (14)	−0.0101 (14)	0.0031 (13)
C7	0.0399 (16)	0.0585 (18)	0.0375 (17)	0.0047 (14)	−0.0024 (13)	0.0002 (13)
C8	0.0407 (17)	0.0541 (18)	0.0467 (19)	0.0065 (13)	−0.0029 (14)	−0.0003 (13)
C9	0.0426 (17)	0.0627 (19)	0.0400 (17)	0.0008 (14)	−0.0025 (14)	0.0012 (14)
C10	0.0370 (16)	0.0521 (17)	0.0432 (18)	0.0014 (13)	−0.0016 (13)	−0.0033 (13)
C11	0.072 (3)	0.111 (3)	0.042 (2)	0.020 (2)	0.0028 (18)	−0.0025 (19)
C12	0.062 (2)	0.098 (3)	0.078 (3)	0.036 (2)	−0.002 (2)	−0.005 (2)
C13	0.083 (3)	0.134 (4)	0.040 (2)	0.015 (3)	−0.002 (2)	0.004 (2)
C14	0.057 (2)	0.102 (3)	0.063 (2)	0.025 (2)	0.0049 (18)	−0.009 (2)
C15	0.066 (2)	0.064 (2)	0.0406 (18)	−0.0013 (17)	−0.0088 (16)	0.0002 (15)
C16	0.054 (2)	0.0572 (19)	0.047 (2)	−0.0040 (15)	−0.0058 (16)	−0.0048 (14)
C17	0.0479 (19)	0.070 (2)	0.0433 (19)	−0.0093 (16)	−0.0063 (15)	−0.0035 (15)
C18	0.051 (2)	0.068 (2)	0.054 (2)	0.0015 (16)	−0.0099 (16)	−0.0068 (16)
C19	0.117 (4)	0.141 (4)	0.040 (2)	0.009 (3)	0.001 (2)	0.005 (2)
C20	0.072 (3)	0.100 (3)	0.082 (3)	0.016 (2)	−0.002 (2)	−0.017 (2)
C21	0.077 (3)	0.137 (4)	0.047 (2)	−0.005 (3)	−0.001 (2)	−0.007 (2)
C22	0.072 (3)	0.124 (4)	0.095 (3)	0.029 (3)	−0.008 (2)	−0.022 (3)
C23	0.0408 (17)	0.0603 (19)	0.0407 (18)	−0.0138 (13)	−0.0064 (13)	0.0034 (13)
C24	0.0497 (19)	0.0649 (19)	0.0393 (18)	−0.0168 (15)	−0.0043 (14)	0.0048 (14)
C25	0.0416 (17)	0.069 (2)	0.0407 (18)	−0.0133 (14)	−0.0021 (14)	0.0004 (14)
C26	0.0392 (17)	0.0644 (19)	0.0388 (17)	−0.0072 (14)	−0.0004 (13)	−0.0009 (13)
C27	0.058 (2)	0.125 (3)	0.060 (2)	−0.043 (2)	−0.0045 (19)	0.008 (2)
C28	0.100 (3)	0.139 (4)	0.037 (2)	−0.050 (3)	−0.015 (2)	0.015 (2)
C29	0.054 (2)	0.158 (4)	0.071 (3)	−0.049 (3)	−0.003 (2)	0.006 (3)
C30	0.072 (3)	0.115 (3)	0.044 (2)	−0.023 (2)	0.0021 (18)	0.0046 (19)
C31	0.0391 (16)	0.0581 (18)	0.0384 (16)	−0.0050 (13)	−0.0089 (13)	0.0057 (13)
C32	0.056 (2)	0.0519 (19)	0.0456 (18)	−0.0072 (15)	−0.0172 (15)	0.0103 (14)
C33	0.0469 (17)	0.0445 (16)	0.0436 (17)	−0.0056 (13)	−0.0064 (14)	0.0016 (13)
C34	0.0374 (16)	0.0543 (18)	0.0404 (17)	−0.0007 (13)	−0.0130 (13)	0.0032 (13)
C35	0.0437 (17)	0.0480 (17)	0.0460 (17)	0.0009 (13)	−0.0099 (14)	0.0009 (13)
C36	0.0473 (18)	0.0521 (19)	0.0432 (18)	−0.0062 (14)	−0.0105 (14)	−0.0040 (14)

Geometric parameters (Å, º)

O1—C1	1.370 (3)	C14—H14A	0.9600
O1—H1O	0.99 (5)	C14—H14B	0.9600
O2—C3	1.365 (4)	C14—H14C	0.9600
O2—H2O	0.81 (4)	C15—C16	1.381 (4)
O3—C5	1.368 (3)	C15—C19	1.498 (5)
O3—H3O	0.87 (5)	C16—C20	1.505 (5)
O4—C31	1.369 (3)	C17—C18	1.390 (4)
O4—H4O	0.91 (4)	C17—C21	1.500 (5)
O5—C33	1.365 (3)	C18—C22	1.505 (5)
O5—H5O	0.85 (4)	C19—H19A	0.9600
O6—C35	1.358 (4)	C19—H19B	0.9600
O6—H6O	1.07 (6)	C19—H19C	0.9600
N1—C10	1.334 (4)	C20—H20A	0.9600
N1—C7	1.340 (4)	C20—H20B	0.9600
N2—C8	1.333 (4)	C20—H20C	0.9600
N2—C9	1.340 (4)	C21—H21A	0.9600
N3—C18	1.332 (4)	C21—H21B	0.9600
N3—C15	1.341 (4)	C21—H21C	0.9600
N4—C17	1.336 (4)	C22—H22A	0.9600
N4—C16	1.338 (4)	C22—H22B	0.9600
N5—C26	1.334 (4)	C22—H22C	0.9600
N5—C23	1.339 (4)	C23—C24	1.390 (4)
N6—C25	1.333 (4)	C23—C27	1.496 (4)
N6—C24	1.336 (4)	C24—C28	1.501 (4)
C1—C2	1.385 (4)	C25—C26	1.397 (4)
C1—C6	1.387 (4)	C25—C29	1.490 (4)
C2—C3	1.390 (4)	C26—C30	1.488 (4)
C2—H2	0.94 (3)	C27—H27A	0.9600
C3—C4	1.382 (4)	C27—H27B	0.9600
C4—C5	1.391 (4)	C27—H27C	0.9600
C4—H1	1.01 (3)	C28—H28A	0.9600
C5—C6	1.386 (4)	C28—H28B	0.9600
C6—H3	1.02 (3)	C28—H28C	0.9600
C7—C8	1.393 (4)	C29—H29A	0.9600
C7—C11	1.492 (4)	C29—H29B	0.9600
C8—C12	1.496 (4)	C29—H29C	0.9600
C9—C10	1.386 (4)	C30—H30A	0.9600
C9—C13	1.496 (5)	C30—H30B	0.9600
C10—C14	1.499 (4)	C30—H30C	0.9600
C11—H11A	0.9600	C31—C36	1.374 (4)
C11—H11B	0.9600	C31—C32	1.382 (4)
C11—H11C	0.9600	C32—C33	1.382 (4)
C12—H12A	0.9600	C32—H5	0.94 (3)
C12—H12B	0.9600	C33—C34	1.379 (4)
C12—H12C	0.9600	C34—C35	1.385 (4)
C13—H13A	0.9600	C34—H4	0.93 (3)
C13—H13B	0.9600	C35—C36	1.388 (4)
C13—H13C	0.9600	C36—H6	0.86 (4)
C1—O1—H1O	113 (3)	C15—C19—H19A	109.5
C3—O2—H2O	109 (3)	C15—C19—H19B	109.5
C5—O3—H3O	115 (3)	H19A—C19—H19B	109.5
C31—O4—H4O	112 (2)	C15—C19—H19C	109.5
C33—O5—H5O	106 (3)	H19A—C19—H19C	109.5
C35—O6—H6O	113 (3)	H19B—C19—H19C	109.5
C10—N1—C7	119.8 (2)	C16—C20—H20A	109.5
C8—N2—C9	119.1 (3)	C16—C20—H20B	109.5
C18—N3—C15	119.2 (3)	H20A—C20—H20B	109.5
C17—N4—C16	118.8 (3)	C16—C20—H20C	109.5
C26—N5—C23	119.2 (2)	H20A—C20—H20C	109.5
C25—N6—C24	118.6 (3)	H20B—C20—H20C	109.5
O1—C1—C2	121.9 (3)	C17—C21—H21A	109.5
O1—C1—C6	117.0 (3)	C17—C21—H21B	109.5
C2—C1—C6	121.1 (3)	H21A—C21—H21B	109.5
C1—C2—C3	118.4 (3)	C17—C21—H21C	109.5
C1—C2—H2	125.0 (19)	H21A—C21—H21C	109.5
C3—C2—H2	116.5 (19)	H21B—C21—H21C	109.5
O2—C3—C4	117.0 (3)	C18—C22—H22A	109.5
O2—C3—C2	120.9 (3)	C18—C22—H22B	109.5
C4—C3—C2	122.1 (3)	H22A—C22—H22B	109.5
C3—C4—C5	117.9 (3)	C18—C22—H22C	109.5
C3—C4—H1	118.1 (17)	H22A—C22—H22C	109.5
C5—C4—H1	123.8 (17)	H22B—C22—H22C	109.5
O3—C5—C6	115.9 (3)	N5—C23—C24	120.5 (3)
O3—C5—C4	122.5 (3)	N5—C23—C27	116.9 (3)
C6—C5—C4	121.6 (3)	C24—C23—C27	122.6 (3)
C5—C6—C1	118.8 (3)	N6—C24—C23	120.7 (3)
C5—C6—H3	119.3 (19)	N6—C24—C28	116.9 (3)
C1—C6—H3	121.8 (19)	C23—C24—C28	122.4 (3)
N1—C7—C8	119.6 (3)	N6—C25—C26	121.1 (3)
N1—C7—C11	117.8 (3)	N6—C25—C29	117.2 (3)
C8—C7—C11	122.6 (3)	C26—C25—C29	121.7 (3)
N2—C8—C7	120.8 (3)	N5—C26—C25	119.8 (3)
N2—C8—C12	117.5 (3)	N5—C26—C30	117.1 (3)
C7—C8—C12	121.7 (3)	C25—C26—C30	123.0 (3)
N2—C9—C10	120.5 (3)	C23—C27—H27A	109.5
N2—C9—C13	117.3 (3)	C23—C27—H27B	109.5
C10—C9—C13	122.3 (3)	H27A—C27—H27B	109.5
N1—C10—C9	120.2 (3)	C23—C27—H27C	109.5
N1—C10—C14	117.3 (3)	H27A—C27—H27C	109.5
C9—C10—C14	122.5 (3)	H27B—C27—H27C	109.5
C7—C11—H11A	109.5	C24—C28—H28A	109.5
C7—C11—H11B	109.5	C24—C28—H28B	109.5
H11A—C11—H11B	109.5	H28A—C28—H28B	109.5
C7—C11—H11C	109.5	C24—C28—H28C	109.5
H11A—C11—H11C	109.5	H28A—C28—H28C	109.5
H11B—C11—H11C	109.5	H28B—C28—H28C	109.5
C8—C12—H12A	109.5	C25—C29—H29A	109.5
C8—C12—H12B	109.5	C25—C29—H29B	109.5
H12A—C12—H12B	109.5	H29A—C29—H29B	109.5
C8—C12—H12C	109.5	C25—C29—H29C	109.5
H12A—C12—H12C	109.5	H29A—C29—H29C	109.5
H12B—C12—H12C	109.5	H29B—C29—H29C	109.5
C9—C13—H13A	109.5	C26—C30—H30A	109.5
C9—C13—H13B	109.5	C26—C30—H30B	109.5
H13A—C13—H13B	109.5	H30A—C30—H30B	109.5
C9—C13—H13C	109.5	C26—C30—H30C	109.5
H13A—C13—H13C	109.5	H30A—C30—H30C	109.5
H13B—C13—H13C	109.5	H30B—C30—H30C	109.5
C10—C14—H14A	109.5	O4—C31—C36	123.0 (3)
C10—C14—H14B	109.5	O4—C31—C32	115.8 (3)
H14A—C14—H14B	109.5	C36—C31—C32	121.2 (3)
C10—C14—H14C	109.5	C31—C32—C33	119.3 (3)
H14A—C14—H14C	109.5	C31—C32—H5	119.4 (19)
H14B—C14—H14C	109.5	C33—C32—H5	121.2 (19)
N3—C15—C16	120.3 (3)	O5—C33—C34	122.2 (3)
N3—C15—C19	116.7 (3)	O5—C33—C32	117.3 (3)
C16—C15—C19	123.0 (4)	C34—C33—C32	120.5 (3)
N4—C16—C15	120.8 (3)	C33—C34—C35	119.3 (3)
N4—C16—C20	116.7 (3)	C33—C34—H4	122.2 (19)
C15—C16—C20	122.5 (3)	C35—C34—H4	118.4 (19)
N4—C17—C18	120.5 (3)	O6—C35—C34	121.4 (3)
N4—C17—C21	117.0 (3)	O6—C35—C36	117.8 (3)
C18—C17—C21	122.6 (3)	C34—C35—C36	120.8 (3)
N3—C18—C17	120.4 (3)	C31—C36—C35	118.8 (3)
N3—C18—C22	117.3 (3)	C31—C36—H6	123 (2)
C17—C18—C22	122.3 (3)	C35—C36—H6	118 (2)