Stimuli-responsive aggregation-induced fluorescence in a series of bi­phenyl-based Knoevenagel products: effects of substituent active methyl­ene groups on π–π interactions

A series of three bi­phenyl-based Knoevenagel products (denoted 1a, 1b, 1c) with active methyl­ene groups has been synthesized. Compounds 1a and 1b show strong solid-state fluorescence, whereas 1c displays low emission. Effects of substituent groups in condensed phase packing of the molecules have been investigated and correlated with their photophysical properties. Interestingly, compound 1a exhibits mechano­fluoro­chromism with emission color changes from yellow to green (wavelength shift of 40 nm) after mechanical grinding. Furthermore, fluorescence of 1a and 1b is turned off under alkaline conditions, making them potential candidates for aggregation-enhanced emission-based pH sensors.

Computing details

For all structures, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXL2016/6 (Sheldrick, 2016); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2016); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

(1a)

Crystal data

C16H10N2	Dx = 1.275 Mg m^−3
Mr = 230.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 1955 reflections
a = 24.316 (6) Å	θ = 2.3–21.6°
b = 3.9011 (10) Å	µ = 0.08 mm^−1
c = 25.297 (7) Å	T = 296 K
V = 2399.7 (10) Å^3	Needle, yellow
Z = 8	0.25 × 0.10 × 0.07 mm
F(000) = 960

Data collection

Bruker APEX-II CCD diffractometer	3008 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.055
φ and ω scans	θmax = 26.6°, θmin = 1.6°
Absorption correction: multi-scan Bruker AXS SADABS program	h = −29→30
	k = −4→4
11085 measured reflections	l = −26→31
4535 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.077	w = 1/[σ^2(Fo^2) + (0.094P)^2 + 0.3649P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.196	(Δ/σ)max = 0.029
S = 1.07	Δρmax = 0.39 e Å^−3
4535 reflections	Δρmin = −0.26 e Å^−3
325 parameters	Absolute structure: Flack x determined using 946 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
1 restraint	Absolute structure parameter: −2.8 (10)

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
C1	0.4350 (3)	0.7422 (13)	0.8957 (3)	0.0302 (16)
C2	0.4906 (3)	0.6898 (17)	0.9117 (3)	0.0409 (17)
H2	0.515639	0.595017	0.888091	0.049*
C3	0.5072 (3)	0.7758 (16)	0.9606 (3)	0.0384 (18)
H3	0.543815	0.739079	0.969685	0.046*
C4	0.4722 (2)	0.9172 (14)	0.9981 (2)	0.0346 (13)
C5	0.4180 (2)	0.9759 (17)	0.9828 (3)	0.0433 (16)
H5	0.393609	1.074794	1.006662	0.052*
C6	0.4002 (3)	0.8900 (18)	0.9333 (3)	0.0429 (16)
H6	0.363696	0.931457	0.924284	0.051*
C7	0.4910 (2)	0.9982 (14)	1.0523 (2)	0.0380 (15)
C8	0.5441 (3)	1.1260 (18)	1.0618 (3)	0.0479 (17)
H8	0.568021	1.159058	1.033515	0.057*
C9	0.5613 (3)	1.203 (2)	1.1120 (4)	0.059 (2)
H9	0.596111	1.295145	1.117388	0.070*
C10	0.5270 (3)	1.144 (2)	1.1549 (4)	0.061 (2)
H10	0.538831	1.189801	1.189134	0.073*
C11	0.4733 (3)	1.011 (2)	1.1454 (3)	0.058 (2)
H11	0.449629	0.969104	1.173553	0.070*
C12	0.4564 (3)	0.9433 (19)	1.0943 (3)	0.0491 (17)
H12	0.421169	0.859722	1.088332	0.059*
C13	0.4116 (2)	0.6409 (16)	0.8468 (2)	0.0385 (14)
H13	0.375076	0.707282	0.842635	0.046*
C14	0.4321 (2)	0.4663 (15)	0.8049 (3)	0.0379 (14)
C15	0.4869 (3)	0.346 (2)	0.8000 (3)	0.0462 (17)
C16	0.3974 (2)	0.3796 (19)	0.7613 (3)	0.0455 (16)
C17	0.3174 (3)	0.1997 (16)	0.2625 (3)	0.0371 (17)
C18	0.3539 (2)	0.3387 (17)	0.2272 (3)	0.0426 (15)
H18	0.390639	0.362630	0.236629	0.051*
C19	0.3365 (3)	0.4447 (17)	0.1772 (3)	0.0437 (16)
H19	0.361883	0.536583	0.153641	0.052*
C20	0.2818 (2)	0.4151 (15)	0.1621 (3)	0.0387 (15)
C21	0.2446 (3)	0.2769 (15)	0.1988 (3)	0.0358 (18)
H21	0.207791	0.249680	0.189557	0.043*
C22	0.2623 (2)	0.1816 (17)	0.2483 (3)	0.0410 (18)
H22	0.236739	0.103275	0.272878	0.049*
C23	0.2637 (2)	0.5186 (15)	0.1085 (2)	0.0379 (15)
C24	0.2980 (3)	0.4719 (18)	0.0652 (3)	0.0465 (16)
H24	0.332719	0.376398	0.070015	0.056*
C25	0.2814 (3)	0.566 (2)	0.0149 (3)	0.059 (2)
H25	0.304963	0.533012	−0.013615	0.071*
C26	0.2313 (4)	0.703 (2)	0.0069 (4)	0.061 (2)
H26	0.220758	0.769159	−0.026907	0.073*
C27	0.1955 (3)	0.7474 (17)	0.0490 (4)	0.049 (2)
H27	0.160671	0.838709	0.043491	0.059*
C28	0.2123 (3)	0.6537 (18)	0.0996 (3)	0.0482 (17)
H28	0.188313	0.682989	0.127844	0.058*
C29	0.3398 (2)	0.0767 (16)	0.3127 (3)	0.0429 (16)
H29	0.377141	0.120898	0.317042	0.051*
C30	0.3167 (2)	−0.0883 (15)	0.3538 (3)	0.0408 (15)
C31	0.3504 (3)	−0.2037 (17)	0.3981 (3)	0.0450 (17)
C32	0.2595 (3)	−0.1916 (19)	0.3582 (3)	0.0482 (19)
N1	0.3702 (3)	0.3032 (17)	0.7257 (3)	0.065 (2)
N2	0.5309 (3)	0.2468 (16)	0.7949 (4)	0.066 (2)
N3	0.3765 (3)	−0.2855 (17)	0.4306 (4)	0.065 (2)
N4	0.2160 (3)	−0.2705 (19)	0.3631 (3)	0.071 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.032 (3)	0.021 (3)	0.038 (4)	−0.001 (2)	0.006 (3)	0.006 (2)
C2	0.035 (4)	0.052 (4)	0.036 (5)	0.004 (3)	0.004 (3)	−0.002 (3)
C3	0.031 (4)	0.040 (4)	0.044 (5)	0.004 (3)	−0.007 (3)	0.001 (3)
C4	0.038 (3)	0.026 (3)	0.040 (4)	0.003 (3)	0.001 (3)	0.004 (3)
C5	0.037 (3)	0.045 (4)	0.048 (4)	0.011 (3)	0.000 (3)	−0.006 (3)
C6	0.035 (3)	0.047 (4)	0.046 (4)	0.006 (3)	0.002 (3)	−0.001 (3)
C7	0.039 (4)	0.025 (3)	0.050 (4)	0.005 (2)	−0.001 (3)	−0.003 (3)
C8	0.041 (4)	0.051 (4)	0.051 (5)	0.005 (3)	0.000 (3)	0.005 (4)
C9	0.048 (4)	0.059 (5)	0.068 (7)	−0.002 (4)	−0.014 (4)	−0.006 (4)
C10	0.061 (5)	0.070 (5)	0.053 (5)	0.015 (4)	−0.015 (4)	−0.009 (4)
C11	0.067 (5)	0.059 (5)	0.048 (5)	0.015 (4)	0.004 (4)	0.000 (3)
C12	0.050 (4)	0.054 (4)	0.044 (4)	0.001 (3)	−0.001 (3)	0.002 (3)
C13	0.035 (3)	0.039 (4)	0.041 (4)	−0.002 (3)	0.002 (3)	0.009 (3)
C14	0.036 (3)	0.034 (3)	0.044 (4)	−0.004 (3)	0.002 (3)	0.005 (3)
C15	0.044 (4)	0.053 (4)	0.041 (5)	0.009 (3)	0.004 (3)	−0.011 (3)
C16	0.033 (3)	0.046 (4)	0.058 (5)	−0.001 (3)	−0.002 (3)	−0.004 (4)
C17	0.037 (3)	0.038 (4)	0.036 (5)	0.002 (3)	−0.001 (3)	−0.008 (3)
C18	0.022 (3)	0.055 (4)	0.051 (4)	−0.003 (3)	0.006 (3)	−0.004 (3)
C19	0.040 (3)	0.044 (4)	0.047 (4)	−0.006 (3)	0.011 (3)	−0.003 (3)
C20	0.042 (3)	0.028 (3)	0.047 (4)	0.000 (3)	0.006 (3)	−0.005 (3)
C21	0.023 (3)	0.037 (4)	0.047 (6)	0.002 (2)	0.010 (3)	0.001 (3)
C22	0.026 (3)	0.054 (4)	0.043 (5)	0.001 (3)	0.011 (3)	0.000 (3)
C23	0.041 (3)	0.028 (3)	0.045 (4)	−0.006 (3)	0.002 (3)	−0.002 (3)
C24	0.045 (4)	0.046 (4)	0.049 (4)	0.002 (3)	0.006 (3)	0.000 (3)
C25	0.071 (5)	0.055 (5)	0.052 (5)	0.001 (4)	0.011 (4)	0.010 (3)
C26	0.075 (5)	0.058 (5)	0.051 (5)	−0.005 (4)	−0.013 (4)	0.006 (4)
C27	0.048 (4)	0.043 (4)	0.057 (6)	0.006 (3)	−0.009 (4)	0.001 (3)
C28	0.042 (4)	0.054 (4)	0.049 (5)	0.007 (3)	0.002 (3)	0.001 (4)
C29	0.032 (3)	0.034 (4)	0.062 (5)	0.002 (3)	0.007 (3)	−0.009 (3)
C30	0.040 (3)	0.032 (3)	0.050 (4)	0.006 (3)	0.004 (3)	−0.003 (3)
C31	0.049 (4)	0.044 (4)	0.042 (4)	0.001 (3)	−0.004 (3)	−0.002 (3)
C32	0.035 (4)	0.062 (5)	0.048 (5)	0.009 (3)	0.000 (3)	0.007 (3)
N1	0.056 (4)	0.083 (5)	0.056 (5)	0.000 (3)	−0.015 (4)	−0.007 (4)
N2	0.043 (4)	0.079 (5)	0.075 (6)	0.014 (3)	−0.001 (4)	−0.009 (3)
N3	0.051 (4)	0.069 (5)	0.076 (6)	0.009 (3)	−0.014 (4)	0.010 (3)
N4	0.042 (4)	0.105 (7)	0.068 (6)	−0.006 (3)	0.009 (4)	0.026 (4)

Geometric parameters (Å, º)

C1—C6	1.396 (9)	C17—C18	1.372 (9)
C1—C13	1.419 (10)	C17—C22	1.388 (9)
C1—C2	1.427 (9)	C17—C29	1.464 (10)
C2—C3	1.342 (10)	C18—C19	1.397 (9)
C2—H2	0.9300	C18—H18	0.9300
C3—C4	1.390 (9)	C19—C20	1.388 (8)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.392 (8)	C20—C21	1.404 (9)
C4—C7	1.480 (8)	C20—C23	1.482 (9)
C5—C6	1.369 (9)	C21—C22	1.376 (10)
C5—H5	0.9300	C21—H21	0.9300
C6—H6	0.9300	C22—H22	0.9300
C7—C12	1.373 (9)	C23—C28	1.375 (9)
C7—C8	1.405 (9)	C23—C24	1.390 (8)
C8—C9	1.371 (11)	C24—C25	1.384 (9)
C8—H8	0.9300	C24—H24	0.9300
C9—C10	1.387 (13)	C25—C26	1.345 (10)
C9—H9	0.9300	C25—H25	0.9300
C10—C11	1.427 (11)	C26—C27	1.386 (13)
C10—H10	0.9300	C26—H26	0.9300
C11—C12	1.380 (9)	C27—C28	1.392 (11)
C11—H11	0.9300	C27—H27	0.9300
C12—H12	0.9300	C28—H28	0.9300
C13—C14	1.354 (9)	C29—C30	1.345 (9)
C13—H13	0.9300	C29—H29	0.9300
C14—C15	1.420 (9)	C30—C32	1.453 (9)
C14—C16	1.428 (10)	C30—C31	1.459 (10)
C15—N2	1.144 (8)	C31—N3	1.088 (9)
C16—N1	1.158 (9)	C32—N4	1.109 (8)
C6—C1—C13	117.8 (6)	C18—C17—C22	118.4 (7)
C6—C1—C2	116.1 (7)	C18—C17—C29	117.0 (6)
C13—C1—C2	126.0 (6)	C22—C17—C29	124.6 (6)
C3—C2—C1	120.7 (7)	C17—C18—C19	120.7 (6)
C3—C2—H2	119.6	C17—C18—H18	119.6
C1—C2—H2	119.6	C19—C18—H18	119.6
C2—C3—C4	122.9 (6)	C20—C19—C18	121.0 (6)
C2—C3—H3	118.5	C20—C19—H19	119.5
C4—C3—H3	118.5	C18—C19—H19	119.5
C3—C4—C5	117.1 (6)	C19—C20—C21	117.9 (6)
C3—C4—C7	121.9 (5)	C19—C20—C23	120.9 (5)
C5—C4—C7	121.0 (5)	C21—C20—C23	121.2 (6)
C6—C5—C4	121.0 (6)	C22—C21—C20	120.2 (6)
C6—C5—H5	119.5	C22—C21—H21	119.9
C4—C5—H5	119.5	C20—C21—H21	119.9
C5—C6—C1	122.2 (6)	C21—C22—C17	121.6 (7)
C5—C6—H6	118.9	C21—C22—H22	119.2
C1—C6—H6	118.9	C17—C22—H22	119.2
C12—C7—C8	119.1 (6)	C28—C23—C24	117.8 (6)
C12—C7—C4	119.6 (5)	C28—C23—C20	121.7 (6)
C8—C7—C4	121.2 (6)	C24—C23—C20	120.5 (6)
C9—C8—C7	121.0 (7)	C25—C24—C23	121.0 (6)
C9—C8—H8	119.5	C25—C24—H24	119.5
C7—C8—H8	119.5	C23—C24—H24	119.5
C8—C9—C10	120.4 (8)	C26—C25—C24	120.5 (7)
C8—C9—H9	119.8	C26—C25—H25	119.7
C10—C9—H9	119.8	C24—C25—H25	119.7
C9—C10—C11	118.6 (8)	C25—C26—C27	120.2 (8)
C9—C10—H10	120.7	C25—C26—H26	119.9
C11—C10—H10	120.7	C27—C26—H26	119.9
C12—C11—C10	119.9 (7)	C26—C27—C28	119.3 (7)
C12—C11—H11	120.0	C26—C27—H27	120.4
C10—C11—H11	120.0	C28—C27—H27	120.3
C7—C12—C11	120.9 (6)	C23—C28—C27	121.2 (7)
C7—C12—H12	119.6	C23—C28—H28	119.4
C11—C12—H12	119.6	C27—C28—H28	119.4
C14—C13—C1	132.4 (6)	C30—C29—C17	132.2 (6)
C14—C13—H13	113.8	C30—C29—H29	113.9
C1—C13—H13	113.8	C17—C29—H29	113.9
C13—C14—C15	125.5 (6)	C29—C30—C32	126.3 (6)
C13—C14—C16	120.4 (5)	C29—C30—C31	120.5 (6)
C15—C14—C16	114.1 (6)	C32—C30—C31	113.1 (6)
N2—C15—C14	178.4 (9)	N3—C31—C30	178.3 (8)
N1—C16—C14	178.4 (8)	N4—C32—C30	178.0 (9)

(1b)

Crystal data

C18H15NO2	Z = 4
Mr = 277.31	F(000) = 584
Triclinic, P1	Dx = 1.250 Mg m^−3
a = 7.7437 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.8797 (9) Å	Cell parameters from 7988 reflections
c = 16.2007 (11) Å	θ = 2.5–26.0°
α = 108.298 (3)°	µ = 0.08 mm^−1
β = 102.962 (3)°	T = 296 K
γ = 94.992 (4)°	Needle, colorless
V = 1473.21 (17) Å^3	0.19 × 0.14 × 0.11 mm

Data collection

Bruker APEX-II CCD diffractometer	4020 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
φ and ω scans	θmax = 26.1°, θmin = 1.4°
Absorption correction: multi-scan Bruker AXS SADABS program	h = −9→9
	k = −15→13
15452 measured reflections	l = −17→19
5786 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.049	w = 1/[σ^2(Fo^2) + (0.0833P)^2 + 0.2424P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.163	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.21 e Å^−3
5786 reflections	Δρmin = −0.22 e Å^−3
382 parameters	Extinction correction: SHELXL-2016/6 (Sheldrick 2016), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0038 (15)

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
C1	0.4144 (2)	0.52633 (13)	0.78027 (11)	0.0453 (4)
C2	0.4087 (3)	0.63775 (15)	0.82229 (12)	0.0599 (5)
H2	0.451082	0.668846	0.884721	0.072*
C3	0.3425 (3)	0.70303 (14)	0.77437 (12)	0.0579 (5)
H3	0.339057	0.776821	0.805070	0.069*
C4	0.2804 (2)	0.66126 (13)	0.68086 (11)	0.0438 (4)
C5	0.2061 (2)	0.73055 (13)	0.62844 (12)	0.0464 (4)
C6	0.2455 (3)	0.84554 (16)	0.66313 (15)	0.0706 (6)
H6	0.321142	0.880515	0.720882	0.085*
C7	0.1745 (4)	0.90934 (17)	0.61351 (18)	0.0821 (7)
H7	0.203414	0.986304	0.638154	0.099*
C8	0.0625 (3)	0.86028 (18)	0.52887 (16)	0.0730 (6)
H8	0.013738	0.903304	0.495979	0.088*
C9	0.0228 (3)	0.74745 (18)	0.49309 (15)	0.0683 (5)
H9	−0.051939	0.713231	0.435045	0.082*
C10	0.0929 (3)	0.68359 (15)	0.54236 (13)	0.0588 (5)
H10	0.062985	0.606715	0.516894	0.071*
C11	0.2918 (2)	0.55049 (13)	0.63862 (11)	0.0480 (4)
H11	0.255249	0.520513	0.575992	0.058*
C12	0.3555 (2)	0.48415 (13)	0.68649 (11)	0.0478 (4)
H12	0.359122	0.410361	0.655907	0.057*
C13	0.4821 (2)	0.46321 (14)	0.83742 (11)	0.0506 (4)
H13	0.536727	0.506406	0.897274	0.061*
C14	0.4799 (2)	0.35464 (14)	0.81936 (11)	0.0471 (4)
C15	0.5649 (2)	0.31544 (15)	0.89391 (12)	0.0531 (4)
C16	0.6407 (3)	0.16025 (17)	0.93265 (14)	0.0772 (6)
H16A	0.768060	0.190343	0.956880	0.093*
H16B	0.584090	0.179228	0.981859	0.093*
C17	0.6153 (5)	0.0408 (2)	0.8908 (2)	0.1146 (11)
H17A	0.489052	0.011130	0.870459	0.172*
H17B	0.673463	0.009473	0.933939	0.172*
H17C	0.666445	0.022717	0.840358	0.172*
C18	0.3979 (3)	0.27084 (14)	0.73328 (12)	0.0522 (4)
C19	0.8292 (2)	0.49552 (13)	0.70817 (11)	0.0442 (4)
C20	0.9553 (2)	0.54089 (14)	0.79141 (12)	0.0532 (4)
H20	0.995206	0.617158	0.815445	0.064*
C21	1.0223 (2)	0.47474 (14)	0.83892 (12)	0.0542 (4)
H21	1.106697	0.507396	0.894496	0.065*
C22	0.9668 (2)	0.36018 (13)	0.80581 (11)	0.0452 (4)
C23	1.0369 (2)	0.28975 (14)	0.85800 (12)	0.0514 (4)
C24	1.0936 (3)	0.33176 (18)	0.95157 (14)	0.0669 (5)
H24	1.093138	0.406179	0.981748	0.080*
C25	1.1506 (3)	0.2650 (2)	1.00037 (17)	0.0851 (7)
H25	1.188179	0.294435	1.063006	0.102*
C26	1.1520 (4)	0.1549 (2)	0.9566 (2)	0.0947 (8)
H26	1.188256	0.109550	0.989630	0.114*
C27	1.0999 (4)	0.1120 (2)	0.8644 (2)	0.0911 (8)
H27	1.102019	0.037692	0.834804	0.109*
C28	1.0443 (3)	0.17903 (16)	0.81514 (16)	0.0688 (5)
H28	1.011499	0.149612	0.752475	0.083*
C29	0.8408 (2)	0.31500 (13)	0.72280 (12)	0.0524 (4)
H29	0.799864	0.238837	0.699203	0.063*
C30	0.7747 (2)	0.38087 (14)	0.67436 (11)	0.0507 (4)
H30	0.692262	0.348029	0.618190	0.061*
C31	0.7510 (2)	0.55820 (13)	0.65272 (11)	0.0457 (4)
H31	0.680260	0.514548	0.595592	0.055*
C32	0.7630 (2)	0.66783 (13)	0.66955 (11)	0.0464 (4)
C33	0.6671 (2)	0.70753 (14)	0.59736 (11)	0.0469 (4)
C34	0.6084 (3)	0.86674 (15)	0.56080 (12)	0.0602 (5)
H34A	0.478526	0.846088	0.543027	0.072*
H34B	0.652029	0.842186	0.507379	0.072*
C35	0.6623 (4)	0.98976 (17)	0.60648 (16)	0.0875 (8)
H35A	0.791001	1.008961	0.623431	0.131*
H35B	0.618980	1.012743	0.659383	0.131*
H35C	0.611432	1.026445	0.565911	0.131*
C36	0.8614 (3)	0.75165 (14)	0.75273 (12)	0.0576 (5)
N1	0.3304 (3)	0.20326 (13)	0.66545 (11)	0.0749 (5)
N2	0.9404 (3)	0.81920 (14)	0.81881 (12)	0.0895 (7)
O1	0.56116 (18)	0.20697 (10)	0.86540 (8)	0.0612 (4)
O2	0.6296 (2)	0.37596 (12)	0.96995 (9)	0.0799 (5)
O3	0.68838 (17)	0.81697 (9)	0.62557 (8)	0.0547 (3)
O4	0.58288 (19)	0.64713 (10)	0.52346 (8)	0.0644 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0484 (9)	0.0432 (9)	0.0409 (8)	0.0079 (7)	0.0067 (7)	0.0132 (7)
C2	0.0776 (13)	0.0488 (10)	0.0404 (9)	0.0110 (9)	0.0014 (9)	0.0075 (8)
C3	0.0751 (12)	0.0372 (9)	0.0515 (10)	0.0117 (8)	0.0075 (9)	0.0077 (8)
C4	0.0430 (8)	0.0391 (8)	0.0468 (9)	0.0043 (7)	0.0096 (7)	0.0140 (7)
C5	0.0481 (9)	0.0404 (9)	0.0550 (10)	0.0078 (7)	0.0166 (8)	0.0203 (7)
C6	0.0880 (15)	0.0452 (10)	0.0715 (13)	0.0093 (10)	0.0089 (11)	0.0195 (9)
C7	0.1039 (18)	0.0442 (11)	0.1058 (19)	0.0184 (11)	0.0264 (15)	0.0354 (12)
C8	0.0808 (15)	0.0701 (14)	0.0908 (16)	0.0299 (12)	0.0284 (13)	0.0504 (13)
C9	0.0724 (13)	0.0702 (13)	0.0691 (13)	0.0199 (11)	0.0109 (10)	0.0366 (11)
C10	0.0645 (11)	0.0482 (10)	0.0624 (11)	0.0099 (9)	0.0076 (9)	0.0238 (9)
C11	0.0592 (10)	0.0414 (9)	0.0392 (8)	0.0071 (8)	0.0071 (7)	0.0126 (7)
C12	0.0582 (10)	0.0363 (8)	0.0447 (9)	0.0095 (7)	0.0087 (8)	0.0112 (7)
C13	0.0565 (10)	0.0510 (10)	0.0401 (9)	0.0114 (8)	0.0063 (7)	0.0139 (7)
C14	0.0507 (9)	0.0505 (10)	0.0395 (9)	0.0109 (8)	0.0068 (7)	0.0177 (7)
C15	0.0574 (10)	0.0522 (10)	0.0451 (10)	0.0096 (8)	0.0030 (8)	0.0177 (8)
C16	0.0912 (16)	0.0673 (13)	0.0659 (13)	0.0158 (12)	−0.0100 (11)	0.0339 (11)
C17	0.158 (3)	0.0688 (16)	0.110 (2)	0.0329 (17)	−0.0044 (19)	0.0457 (15)
C18	0.0658 (11)	0.0453 (10)	0.0467 (10)	0.0094 (8)	0.0072 (8)	0.0229 (8)
C19	0.0479 (9)	0.0428 (9)	0.0450 (9)	0.0092 (7)	0.0133 (7)	0.0184 (7)
C20	0.0562 (10)	0.0383 (9)	0.0581 (10)	0.0019 (8)	0.0022 (8)	0.0176 (8)
C21	0.0556 (10)	0.0472 (10)	0.0509 (10)	0.0046 (8)	−0.0012 (8)	0.0167 (8)
C22	0.0464 (9)	0.0438 (9)	0.0481 (9)	0.0095 (7)	0.0121 (7)	0.0195 (7)
C23	0.0469 (9)	0.0524 (10)	0.0605 (11)	0.0109 (8)	0.0108 (8)	0.0286 (8)
C24	0.0713 (13)	0.0701 (13)	0.0636 (12)	0.0176 (10)	0.0097 (10)	0.0333 (10)
C25	0.0874 (16)	0.1055 (19)	0.0774 (15)	0.0277 (14)	0.0110 (12)	0.0565 (14)
C26	0.0909 (17)	0.104 (2)	0.116 (2)	0.0344 (15)	0.0144 (16)	0.0795 (18)
C27	0.0947 (18)	0.0664 (14)	0.123 (2)	0.0301 (13)	0.0168 (16)	0.0507 (14)
C28	0.0732 (13)	0.0558 (11)	0.0798 (14)	0.0180 (10)	0.0114 (11)	0.0310 (10)
C29	0.0625 (11)	0.0349 (8)	0.0539 (10)	0.0052 (8)	0.0070 (8)	0.0137 (7)
C30	0.0575 (10)	0.0451 (9)	0.0428 (9)	0.0077 (8)	0.0035 (8)	0.0131 (7)
C31	0.0506 (9)	0.0449 (9)	0.0436 (9)	0.0081 (7)	0.0111 (7)	0.0188 (7)
C32	0.0530 (9)	0.0468 (9)	0.0438 (9)	0.0105 (8)	0.0133 (7)	0.0207 (7)
C33	0.0541 (10)	0.0464 (9)	0.0445 (9)	0.0108 (8)	0.0143 (8)	0.0200 (8)
C34	0.0757 (13)	0.0553 (11)	0.0503 (10)	0.0152 (9)	0.0033 (9)	0.0274 (8)
C35	0.1162 (19)	0.0546 (12)	0.0825 (15)	0.0138 (12)	−0.0070 (14)	0.0348 (11)
C36	0.0822 (13)	0.0420 (9)	0.0489 (10)	0.0125 (9)	0.0092 (9)	0.0214 (8)
N1	0.1111 (15)	0.0502 (9)	0.0491 (9)	0.0028 (9)	−0.0036 (9)	0.0178 (8)
N2	0.1392 (19)	0.0496 (10)	0.0608 (11)	0.0097 (11)	−0.0067 (11)	0.0180 (9)
O1	0.0754 (9)	0.0507 (7)	0.0520 (7)	0.0136 (6)	−0.0023 (6)	0.0226 (6)
O2	0.1106 (12)	0.0647 (9)	0.0464 (8)	0.0161 (8)	−0.0112 (7)	0.0166 (7)
O3	0.0738 (8)	0.0438 (7)	0.0460 (7)	0.0128 (6)	0.0053 (6)	0.0212 (5)
O4	0.0839 (9)	0.0515 (7)	0.0479 (7)	0.0078 (7)	−0.0003 (6)	0.0171 (6)

Geometric parameters (Å, º)

C1—C2	1.391 (2)	C19—C20	1.389 (2)
C1—C12	1.393 (2)	C19—C30	1.392 (2)
C1—C13	1.457 (2)	C19—C31	1.457 (2)
C2—C3	1.371 (2)	C20—C21	1.377 (2)
C2—H2	0.9300	C20—H20	0.9300
C3—C4	1.390 (2)	C21—C22	1.392 (2)
C3—H3	0.9300	C21—H21	0.9300
C4—C11	1.396 (2)	C22—C29	1.386 (2)
C4—C5	1.481 (2)	C22—C23	1.481 (2)
C5—C10	1.382 (3)	C23—C24	1.389 (3)
C5—C6	1.387 (2)	C23—C28	1.389 (3)
C6—C7	1.385 (3)	C24—C25	1.377 (3)
C6—H6	0.9300	C24—H24	0.9300
C7—C8	1.363 (3)	C25—C26	1.374 (4)
C7—H7	0.9300	C25—H25	0.9300
C8—C9	1.362 (3)	C26—C27	1.368 (4)
C8—H8	0.9300	C26—H26	0.9300
C9—C10	1.380 (2)	C27—C28	1.382 (3)
C9—H9	0.9300	C27—H27	0.9300
C10—H10	0.9300	C28—H28	0.9300
C11—C12	1.375 (2)	C29—C30	1.383 (2)
C11—H11	0.9300	C29—H29	0.9300
C12—H12	0.9300	C30—H30	0.9300
C13—C14	1.333 (2)	C31—C32	1.342 (2)
C13—H13	0.9300	C31—H31	0.9300
C14—C18	1.432 (2)	C32—C36	1.430 (2)
C14—C15	1.494 (2)	C32—C33	1.494 (2)
C15—O2	1.195 (2)	C33—O4	1.2002 (19)
C15—O1	1.322 (2)	C33—O3	1.3206 (19)
C16—C17	1.448 (3)	C34—O3	1.4475 (19)
C16—O1	1.450 (2)	C34—C35	1.498 (3)
C16—H16A	0.9700	C34—H34A	0.9700
C16—H16B	0.9700	C34—H34B	0.9700
C17—H17A	0.9600	C35—H35A	0.9600
C17—H17B	0.9600	C35—H35B	0.9600
C17—H17C	0.9600	C35—H35C	0.9600
C18—N1	1.141 (2)	C36—N2	1.143 (2)
C2—C1—C12	117.12 (15)	C20—C19—C31	125.19 (15)
C2—C1—C13	117.71 (15)	C30—C19—C31	117.27 (15)
C12—C1—C13	125.17 (15)	C21—C20—C19	121.05 (15)
C3—C2—C1	121.93 (16)	C21—C20—H20	119.5
C3—C2—H2	119.0	C19—C20—H20	119.5
C1—C2—H2	119.0	C20—C21—C22	121.63 (16)
C2—C3—C4	121.39 (15)	C20—C21—H21	119.2
C2—C3—H3	119.3	C22—C21—H21	119.2
C4—C3—H3	119.3	C29—C22—C21	117.27 (15)
C3—C4—C11	116.58 (15)	C29—C22—C23	121.35 (15)
C3—C4—C5	121.88 (14)	C21—C22—C23	121.36 (15)
C11—C4—C5	121.54 (14)	C24—C23—C28	117.86 (17)
C10—C5—C6	116.55 (16)	C24—C23—C22	120.98 (16)
C10—C5—C4	121.49 (15)	C28—C23—C22	121.14 (17)
C6—C5—C4	121.95 (16)	C25—C24—C23	121.1 (2)
C7—C6—C5	121.3 (2)	C25—C24—H24	119.5
C7—C6—H6	119.3	C23—C24—H24	119.5
C5—C6—H6	119.3	C26—C25—C24	120.0 (2)
C8—C7—C6	120.6 (2)	C26—C25—H25	120.0
C8—C7—H7	119.7	C24—C25—H25	120.0
C6—C7—H7	119.7	C27—C26—C25	120.0 (2)
C9—C8—C7	119.16 (19)	C27—C26—H26	120.0
C9—C8—H8	120.4	C25—C26—H26	120.0
C7—C8—H8	120.4	C26—C27—C28	120.1 (2)
C8—C9—C10	120.5 (2)	C26—C27—H27	120.0
C8—C9—H9	119.8	C28—C27—H27	120.0
C10—C9—H9	119.8	C27—C28—C23	120.9 (2)
C9—C10—C5	121.90 (18)	C27—C28—H28	119.6
C9—C10—H10	119.0	C23—C28—H28	119.6
C5—C10—H10	119.0	C30—C29—C22	121.33 (15)
C12—C11—C4	122.23 (15)	C30—C29—H29	119.3
C12—C11—H11	118.9	C22—C29—H29	119.3
C4—C11—H11	118.9	C29—C30—C19	121.17 (15)
C11—C12—C1	120.69 (15)	C29—C30—H30	119.4
C11—C12—H12	119.7	C19—C30—H30	119.4
C1—C12—H12	119.7	C32—C31—C19	131.35 (16)
C14—C13—C1	131.58 (16)	C32—C31—H31	114.3
C14—C13—H13	114.2	C19—C31—H31	114.3
C1—C13—H13	114.2	C31—C32—C36	124.82 (15)
C13—C14—C18	124.84 (15)	C31—C32—C33	118.79 (15)
C13—C14—C15	118.57 (15)	C36—C32—C33	116.38 (14)
C18—C14—C15	116.58 (14)	O4—C33—O3	124.93 (15)
O2—C15—O1	124.57 (16)	O4—C33—C32	123.95 (15)
O2—C15—C14	123.43 (16)	O3—C33—C32	111.12 (14)
O1—C15—C14	112.00 (14)	O3—C34—C35	106.54 (15)
C17—C16—O1	108.84 (18)	O3—C34—H34A	110.4
C17—C16—H16A	109.9	C35—C34—H34A	110.4
O1—C16—H16A	109.9	O3—C34—H34B	110.4
C17—C16—H16B	109.9	C35—C34—H34B	110.4
O1—C16—H16B	109.9	H34A—C34—H34B	108.6
H16A—C16—H16B	108.3	C34—C35—H35A	109.5
C16—C17—H17A	109.5	C34—C35—H35B	109.5
C16—C17—H17B	109.5	H35A—C35—H35B	109.5
H17A—C17—H17B	109.5	C34—C35—H35C	109.5
C16—C17—H17C	109.5	H35A—C35—H35C	109.5
H17A—C17—H17C	109.5	H35B—C35—H35C	109.5
H17B—C17—H17C	109.5	N2—C36—C32	179.4 (2)
N1—C18—C14	178.7 (2)	C15—O1—C16	116.46 (14)
C20—C19—C30	117.54 (14)	C33—O3—C34	116.85 (13)

(1c)

Crystal data

C19H16O4	Dx = 1.291 Mg m^−3
Mr = 308.32	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 1855 reflections
a = 9.221 (2) Å	θ = 2.5–26.4°
b = 9.847 (2) Å	µ = 0.09 mm^−1
c = 34.947 (6) Å	T = 296 K
V = 3173.1 (11) Å^3	Block, yellow
Z = 8	0.29 × 0.14 × 0.12 mm
F(000) = 1296

Data collection

Bruker APEX-II CCD diffractometer	1579 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.076
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan Bruker AXS SADABS program	h = −10→4
	k = −11→11
9956 measured reflections	l = −34→36
2666 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.083	w = 1/[σ^2(Fo^2) + (0.1085P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.219	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.49 e Å^−3
2666 reflections	Δρmin = −0.40 e Å^−3
211 parameters	Extinction correction: SHELXL-2016/6 (Sheldrick 2016), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.044 (5)

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
C1	0.0997 (4)	0.1684 (3)	0.16936 (9)	0.0399 (10)
C2	0.0467 (5)	0.2609 (4)	0.19616 (11)	0.0525 (11)
H2	0.001824	0.339663	0.187504	0.063*
C3	0.0586 (5)	0.2397 (4)	0.23505 (11)	0.0541 (12)
H3	0.019757	0.303231	0.251852	0.065*
C4	0.1269 (4)	0.1263 (4)	0.24954 (10)	0.0429 (10)
C5	0.1403 (4)	0.1015 (4)	0.29128 (11)	0.0463 (10)
C6	0.0397 (6)	0.1547 (4)	0.31684 (12)	0.0691 (14)
H6	−0.035760	0.208283	0.307691	0.083*
C7	0.0500 (7)	0.1291 (5)	0.35575 (13)	0.0860 (18)
H7	−0.018567	0.165176	0.372400	0.103*
C8	0.1606 (7)	0.0511 (6)	0.36976 (13)	0.0778 (16)
H8	0.166926	0.033643	0.395859	0.093*
C9	0.2609 (6)	−0.0007 (5)	0.34553 (13)	0.0745 (15)
H9	0.336788	−0.052792	0.355123	0.089*
C10	0.2512 (5)	0.0235 (5)	0.30611 (12)	0.0644 (13)
H10	0.320381	−0.013318	0.289755	0.077*
C11	0.1818 (5)	0.0337 (4)	0.22304 (11)	0.0564 (12)
H11	0.229173	−0.043623	0.231838	0.068*
C12	0.1677 (5)	0.0534 (4)	0.18431 (12)	0.0586 (13)
H12	0.204465	−0.011541	0.167606	0.070*
C13	0.0787 (4)	0.2020 (4)	0.12939 (10)	0.0418 (10)
H13	0.042312	0.289302	0.126168	0.050*
C14	0.0987 (4)	0.1383 (3)	0.09587 (10)	0.0385 (9)
C15	0.0632 (5)	0.2181 (4)	0.06143 (10)	0.0441 (10)
C16	0.2281 (5)	0.0700 (4)	0.02827 (10)	0.0455 (10)
C17	0.1414 (5)	−0.0042 (4)	0.09000 (11)	0.0465 (10)
C18	0.2297 (5)	0.0065 (5)	−0.01085 (11)	0.0650 (13)
H18A	0.136116	−0.031726	−0.016266	0.097*
H18B	0.301692	−0.063908	−0.011630	0.097*
H18C	0.252298	0.074399	−0.029624	0.097*
C19	0.3703 (4)	0.1304 (4)	0.04038 (11)	0.0510 (11)
H19A	0.400940	0.196167	0.021788	0.076*
H19B	0.441805	0.059837	0.042293	0.076*
H19C	0.359171	0.173733	0.064810	0.076*
O1	0.1853 (3)	−0.0365 (2)	0.05428 (7)	0.0515 (8)
O2	0.1308 (4)	−0.0946 (3)	0.11254 (8)	0.0715 (11)
O3	−0.0126 (3)	0.3171 (3)	0.06076 (7)	0.0634 (9)
O4	0.1162 (3)	0.1719 (3)	0.02771 (6)	0.0496 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.044 (2)	0.032 (2)	0.044 (2)	−0.0002 (17)	0.0048 (18)	−0.0025 (17)
C2	0.073 (3)	0.027 (2)	0.057 (3)	0.006 (2)	−0.005 (2)	0.0001 (18)
C3	0.083 (3)	0.039 (2)	0.041 (2)	−0.003 (2)	0.009 (2)	−0.0082 (18)
C4	0.043 (2)	0.039 (2)	0.046 (2)	−0.0070 (19)	0.0070 (18)	0.0028 (18)
C5	0.050 (3)	0.043 (2)	0.046 (3)	−0.012 (2)	0.004 (2)	−0.0004 (19)
C6	0.091 (4)	0.054 (3)	0.063 (3)	0.015 (3)	0.012 (3)	0.000 (2)
C7	0.143 (6)	0.072 (3)	0.043 (3)	0.009 (4)	0.025 (3)	0.001 (3)
C8	0.110 (5)	0.081 (4)	0.043 (3)	−0.017 (3)	0.003 (3)	0.009 (3)
C9	0.068 (4)	0.101 (4)	0.054 (3)	−0.008 (3)	−0.012 (3)	0.015 (3)
C10	0.049 (3)	0.088 (3)	0.056 (3)	−0.003 (3)	−0.003 (2)	0.006 (2)
C11	0.063 (3)	0.058 (3)	0.049 (3)	0.025 (2)	0.003 (2)	0.003 (2)
C12	0.066 (3)	0.065 (3)	0.045 (3)	0.023 (2)	0.009 (2)	−0.002 (2)
C13	0.044 (3)	0.033 (2)	0.049 (2)	0.0026 (17)	0.0029 (18)	−0.0006 (18)
C14	0.043 (2)	0.032 (2)	0.041 (2)	0.0005 (17)	0.0037 (17)	0.0039 (17)
C15	0.050 (3)	0.040 (2)	0.043 (2)	−0.003 (2)	0.0002 (19)	−0.0023 (19)
C16	0.054 (3)	0.033 (2)	0.050 (2)	−0.0069 (19)	0.0061 (19)	−0.0031 (18)
C17	0.060 (3)	0.034 (2)	0.046 (2)	−0.0071 (19)	0.005 (2)	0.002 (2)
C18	0.071 (3)	0.066 (3)	0.058 (3)	−0.017 (2)	0.015 (2)	−0.019 (2)
C19	0.050 (3)	0.038 (2)	0.066 (3)	−0.0030 (19)	0.008 (2)	−0.0008 (19)
O1	0.068 (2)	0.0313 (15)	0.0551 (17)	−0.0073 (13)	0.0168 (14)	−0.0052 (12)
O2	0.118 (3)	0.0352 (17)	0.0608 (18)	−0.0001 (17)	0.0168 (17)	0.0095 (15)
O3	0.076 (2)	0.0542 (19)	0.0599 (19)	0.0273 (17)	−0.0019 (15)	0.0071 (14)
O4	0.0535 (18)	0.0541 (17)	0.0410 (16)	0.0017 (14)	−0.0029 (13)	0.0016 (12)

Geometric parameters (Å, º)

C1—C2	1.394 (5)	C11—H11	0.9300
C1—C12	1.396 (5)	C12—H12	0.9300
C1—C13	1.448 (5)	C13—C14	1.342 (5)
C2—C3	1.380 (5)	C13—H13	0.9300
C2—H2	0.9300	C14—C17	1.472 (5)
C3—C4	1.378 (5)	C14—C15	1.474 (5)
C3—H3	0.9300	C15—O3	1.200 (4)
C4—C11	1.395 (5)	C15—O4	1.354 (4)
C4—C5	1.484 (5)	C16—O4	1.439 (5)
C5—C10	1.380 (6)	C16—O1	1.443 (4)
C5—C6	1.390 (6)	C16—C19	1.501 (5)
C6—C7	1.386 (6)	C16—C18	1.504 (5)
C6—H6	0.9300	C17—O2	1.192 (4)
C7—C8	1.368 (7)	C17—O1	1.350 (4)
C7—H7	0.9300	C18—H18A	0.9600
C8—C9	1.353 (7)	C18—H18B	0.9600
C8—H8	0.9300	C18—H18C	0.9600
C9—C10	1.401 (6)	C19—H19A	0.9600
C9—H9	0.9300	C19—H19B	0.9600
C10—H10	0.9300	C19—H19C	0.9600
C11—C12	1.373 (5)
C2—C1—C12	115.8 (3)	C11—C12—H12	119.1
C2—C1—C13	116.9 (3)	C1—C12—H12	119.1
C12—C1—C13	127.3 (3)	C14—C13—C1	135.8 (3)
C3—C2—C1	122.3 (3)	C14—C13—H13	112.1
C3—C2—H2	118.8	C1—C13—H13	112.1
C1—C2—H2	118.8	C13—C14—C17	127.2 (3)
C4—C3—C2	121.4 (4)	C13—C14—C15	115.7 (3)
C4—C3—H3	119.3	C17—C14—C15	117.0 (3)
C2—C3—H3	119.3	O3—C15—O4	117.8 (3)
C3—C4—C11	116.8 (3)	O3—C15—C14	125.3 (3)
C3—C4—C5	122.2 (3)	O4—C15—C14	116.8 (3)
C11—C4—C5	121.0 (3)	O4—C16—O1	108.6 (3)
C10—C5—C6	117.6 (4)	O4—C16—C19	110.7 (3)
C10—C5—C4	121.5 (4)	O1—C16—C19	110.4 (3)
C6—C5—C4	121.0 (4)	O4—C16—C18	106.6 (3)
C7—C6—C5	121.1 (5)	O1—C16—C18	105.8 (3)
C7—C6—H6	119.5	C19—C16—C18	114.4 (3)
C5—C6—H6	119.5	O2—C17—O1	117.4 (3)
C8—C7—C6	120.3 (5)	O2—C17—C14	126.7 (4)
C8—C7—H7	119.8	O1—C17—C14	115.7 (3)
C6—C7—H7	119.8	C16—C18—H18A	109.5
C9—C8—C7	119.8 (5)	C16—C18—H18B	109.5
C9—C8—H8	120.1	H18A—C18—H18B	109.5
C7—C8—H8	120.1	C16—C18—H18C	109.5
C8—C9—C10	120.5 (5)	H18A—C18—H18C	109.5
C8—C9—H9	119.8	H18B—C18—H18C	109.5
C10—C9—H9	119.8	C16—C19—H19A	109.5
C5—C10—C9	120.8 (4)	C16—C19—H19B	109.5
C5—C10—H10	119.6	H19A—C19—H19B	109.5
C9—C10—H10	119.6	C16—C19—H19C	109.5
C12—C11—C4	121.8 (4)	H19A—C19—H19C	109.5
C12—C11—H11	119.1	H19B—C19—H19C	109.5
C4—C11—H11	119.1	C17—O1—C16	119.6 (3)
C11—C12—C1	121.7 (4)	C15—O4—C16	118.7 (3)