Effect of a halogen bond on the crystal structure of terphenyldi­carb­oxy­lic acid derivatives

The syntheses and structures of di­methyl [1¹,2¹:2⁴,3¹-terphenyl]-1⁴,3⁴-di­carboxyl­ate (1), di­methyl 2²,2⁵-di­iodo­[1¹,2¹:2⁴,3¹-terphenyl]-1⁴,3⁴-di­carboxyl­ate (2), potassium [1¹,2¹:2⁴,3¹-terphenyl]-1⁴,3⁴-di­carboxyl­ate (3) and di­methyl [1,1′-bi­phenyl]-4,4′-di­carboxyl­ate (4) are reported. Neighboring phenyl rings in compounds 1, 3 and 4 have a planar structure (torsion angles are 0.6–4.1°) and the molecules are packed into regular layers. In the structure of the iodinated derivative of terphenyldi­carb­oxy­lic acid (2), the middle benzene ring of the terphenyl fragment is rotated relative to the other rings by 64° due to the repulsion between the protons and the iodine atoms of neighboring rings. The formation of halogen bonds between iodine and oxygen atoms of the carbonyl group leads to the movement of molecules of one layer into another layer and the loss of layered structure. Potassium [1¹,2¹:2⁴,3¹-terphenyl]-1⁴,3⁴-di­carboxyl­ate (3) forms crystals with an ionic structure. The coordination number of the potassium cation is eight and the resulting coordination polyhedron is a distorted square antiprism. Dianions in the potassium salt crystal are packed in layers similar to the layers in the di­methyl ethers 1 and 4. Salt 3 has high thermal stability to 500°C.

Computing details

(1)

Crystal data

C22H18O4	Dx = 1.421 Mg m^−3
Mr = 346.36	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 2973 reflections
a = 7.2034 (3) Å	θ = 2.4–79.8°
b = 5.9610 (2) Å	µ = 0.79 mm^−1
c = 37.6935 (12) Å	T = 100 K
V = 1618.54 (10) Å^3	Plate, clear colourless
Z = 4	0.14 × 0.12 × 0.02 mm
F(000) = 728

Data collection

XtaLAB Synergy, Single source at home/near, HyPix diffractometer	1530 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1358 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.028
Detector resolution: 10.0000 pixels mm^-1	θmax = 70.0°, θmin = 2.3°
ω scans	h = −7→8
Absorption correction: multi-scan CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −7→5
Tmin = 0.865, Tmax = 1.000	l = −39→45
5265 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.186	w = 1/[σ^2(Fo^2) + (0.0975P)^2 + 2.0199P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1530 reflections	Δρmax = 0.62 e Å^−3
119 parameters	Δρmin = −0.38 e Å^−3
0 restraints

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
O1	0.5623 (2)	0.3433 (3)	0.31907 (4)	0.0260 (5)
O2	0.4419 (3)	0.6611 (3)	0.29650 (4)	0.0327 (5)
C1	0.5055 (3)	0.6421 (4)	0.35849 (5)	0.0193 (5)
C2	0.4318 (3)	0.8540 (4)	0.36526 (6)	0.0207 (5)
H2	0.383598	0.940965	0.346255	0.025*
C3	0.4283 (3)	0.9389 (4)	0.39939 (6)	0.0195 (5)
H3	0.374999	1.082333	0.403482	0.023*
C4	0.5014 (3)	0.8182 (3)	0.42811 (5)	0.0171 (5)
C5	0.5760 (3)	0.6049 (4)	0.42072 (5)	0.0181 (5)
H5	0.625774	0.518023	0.439591	0.022*
C6	0.5787 (3)	0.5188 (4)	0.38670 (6)	0.0188 (5)
H6	0.630614	0.374748	0.382473	0.023*
C7	0.4992 (3)	0.5555 (4)	0.32156 (6)	0.0216 (5)
C8	0.5505 (3)	0.2450 (4)	0.28423 (6)	0.0285 (6)
H8A	0.628913	0.329917	0.267761	0.043*
H8B	0.421501	0.249134	0.276020	0.043*
H8C	0.593210	0.088990	0.285205	0.043*
C9	0.5011 (2)	0.9102 (3)	0.46469 (5)	0.0160 (5)
C10	0.5846 (3)	0.7970 (4)	0.49315 (5)	0.0184 (5)
H10	0.643955	0.657268	0.488902	0.022*
C11	0.5830 (3)	0.8832 (4)	0.52725 (6)	0.0180 (5)
H11	0.640368	0.800214	0.545759	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0324 (9)	0.0217 (8)	0.0241 (8)	0.0060 (6)	−0.0019 (6)	−0.0031 (6)
O2	0.0460 (11)	0.0300 (9)	0.0220 (9)	0.0077 (8)	−0.0043 (7)	0.0020 (7)
C1	0.0164 (10)	0.0199 (10)	0.0215 (11)	−0.0019 (8)	−0.0005 (8)	0.0002 (8)
C2	0.0205 (11)	0.0206 (10)	0.0212 (10)	0.0007 (8)	−0.0015 (8)	0.0019 (8)
C3	0.0175 (10)	0.0173 (10)	0.0236 (11)	0.0019 (8)	0.0006 (8)	−0.0002 (8)
C4	0.0106 (9)	0.0182 (10)	0.0225 (11)	−0.0011 (8)	0.0007 (7)	0.0011 (8)
C5	0.0127 (10)	0.0189 (10)	0.0228 (11)	−0.0004 (8)	−0.0016 (7)	0.0019 (8)
C6	0.0152 (10)	0.0163 (10)	0.0250 (11)	0.0015 (7)	0.0008 (8)	−0.0009 (8)
C7	0.0200 (10)	0.0221 (11)	0.0226 (11)	0.0001 (9)	0.0022 (8)	−0.0008 (9)
C8	0.0342 (12)	0.0272 (12)	0.0240 (11)	0.0027 (10)	−0.0011 (9)	−0.0071 (9)
C9	0.0087 (9)	0.0166 (10)	0.0226 (10)	−0.0008 (8)	−0.0001 (7)	0.0004 (8)
C10	0.0141 (9)	0.0173 (10)	0.0239 (11)	0.0026 (7)	0.0009 (7)	−0.0002 (8)
C11	0.0133 (10)	0.0182 (10)	0.0224 (10)	0.0020 (8)	−0.0008 (7)	0.0016 (8)

Geometric parameters (Å, º)

O1—C7	1.348 (3)	C5—H5	0.9500
O1—C8	1.441 (3)	C5—C6	1.381 (3)
O2—C7	1.208 (3)	C6—H6	0.9500
C1—C2	1.394 (3)	C8—H8A	0.9800
C1—C6	1.396 (3)	C8—H8B	0.9800
C1—C7	1.485 (3)	C8—H8C	0.9800
C2—H2	0.9500	C9—C10	1.403 (3)
C2—C3	1.382 (3)	C9—C11^i	1.406 (3)
C3—H3	0.9500	C10—H10	0.9500
C3—C4	1.402 (3)	C10—C11	1.384 (3)
C4—C5	1.409 (3)	C11—H11	0.9500
C4—C9	1.484 (3)
C7—O1—C8	115.19 (17)	O1—C7—C1	112.40 (18)
C2—C1—C6	118.79 (19)	O2—C7—O1	123.4 (2)
C2—C1—C7	118.34 (19)	O2—C7—C1	124.2 (2)
C6—C1—C7	122.86 (19)	O1—C8—H8A	109.5
C1—C2—H2	119.7	O1—C8—H8B	109.5
C3—C2—C1	120.6 (2)	O1—C8—H8C	109.5
C3—C2—H2	119.7	H8A—C8—H8B	109.5
C2—C3—H3	119.2	H8A—C8—H8C	109.5
C2—C3—C4	121.6 (2)	H8B—C8—H8C	109.5
C4—C3—H3	119.2	C10—C9—C4	122.17 (18)
C3—C4—C5	116.97 (19)	C10—C9—C11^i	116.2 (2)
C3—C4—C9	121.83 (19)	C11^i—C9—C4	121.67 (19)
C5—C4—C9	121.20 (19)	C9—C10—H10	119.1
C4—C5—H5	119.2	C11—C10—C9	121.87 (19)
C6—C5—C4	121.62 (19)	C11—C10—H10	119.1
C6—C5—H5	119.2	C9^i—C11—H11	119.0
C1—C6—H6	119.8	C10—C11—C9^i	122.0 (2)
C5—C6—C1	120.42 (19)	C10—C11—H11	119.0
C5—C6—H6	119.8
C1—C2—C3—C4	1.3 (3)	C5—C4—C9—C11^i	−176.08 (17)
C2—C1—C6—C5	0.7 (3)	C6—C1—C2—C3	−1.1 (3)
C2—C1—C7—O1	−175.48 (17)	C6—C1—C7—O1	3.3 (3)
C2—C1—C7—O2	3.6 (3)	C6—C1—C7—O2	−177.6 (2)
C2—C3—C4—C5	−1.0 (3)	C7—C1—C2—C3	177.68 (19)
C2—C3—C4—C9	178.85 (18)	C7—C1—C6—C5	−178.08 (18)
C3—C4—C5—C6	0.5 (3)	C8—O1—C7—O2	−2.3 (3)
C3—C4—C9—C10	−175.81 (18)	C8—O1—C7—C1	176.78 (18)
C3—C4—C9—C11^i	4.1 (3)	C9—C4—C5—C6	−179.32 (18)
C4—C5—C6—C1	−0.4 (3)	C9—C10—C11—C9^i	−0.5 (3)
C4—C9—C10—C11	−179.64 (18)	C11^i—C9—C10—C11	0.5 (3)
C5—C4—C9—C10	4.0 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

(2)

Crystal data

C22H16I2O4	F(000) = 572
Mr = 598.15	Dx = 2.001 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.4580 (3) Å	Cell parameters from 4289 reflections
b = 14.6955 (5) Å	θ = 4.3–32.3°
c = 9.7079 (4) Å	µ = 3.19 mm^−1
β = 111.084 (5)°	T = 100 K
V = 992.75 (7) Å^3	Prism, clear colourless
Z = 2	0.28 × 0.24 × 0.18 mm

Data collection

SuperNova, Dual, Cu at home/near, Atlas diffractometer	2282 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2165 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.018
Detector resolution: 10.3829 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −9→7
Absorption correction: multi-scan CrysAlisPro 1.171.41.95a (Rigaku Oxford Diffraction, 2021) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −19→17
Tmin = 0.727, Tmax = 1.000	l = −8→12
5135 measured 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)] = 0.024	w = 1/[σ^2(Fo^2) + (0.0261P)^2 + 2.5099P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.062	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 1.91 e Å^−3
2282 reflections	Δρmin = −0.66 e Å^−3
129 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0015 (4)
Primary atom site location: dual

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
I1	0.78106 (3)	0.53813 (2)	0.12200 (2)	0.01672 (9)
O1	0.1948 (3)	0.87799 (14)	0.3065 (2)	0.0190 (4)
O2	0.0125 (3)	0.75271 (15)	0.2430 (3)	0.0211 (5)
C1	0.3474 (4)	0.7331 (2)	0.3330 (3)	0.0145 (5)
C2	0.5293 (4)	0.7671 (2)	0.4120 (3)	0.0159 (5)
H2	0.544992	0.829369	0.440387	0.019*
C3	0.6879 (4)	0.7102 (2)	0.4494 (3)	0.0152 (5)
H3	0.811955	0.733370	0.504538	0.018*
C4	0.6663 (4)	0.6188 (2)	0.4063 (3)	0.0134 (5)
C5	0.4834 (4)	0.5851 (2)	0.3268 (3)	0.0165 (6)
H5	0.467621	0.523122	0.296896	0.020*
C6	0.3248 (4)	0.6416 (2)	0.2912 (3)	0.0168 (6)
H6	0.200286	0.618079	0.238335	0.020*
C7	0.8377 (4)	0.55792 (19)	0.4507 (3)	0.0133 (5)
C8	0.9051 (4)	0.51537 (19)	0.3503 (3)	0.0132 (5)
C9	1.0645 (4)	0.45816 (19)	0.3991 (3)	0.0140 (5)
H9	1.107452	0.429517	0.328847	0.017*
C10	0.1804 (4)	0.7964 (2)	0.2944 (3)	0.0158 (6)
C11	−0.1552 (5)	0.8113 (2)	0.1916 (4)	0.0269 (7)
H11A	−0.146903	0.850977	0.112987	0.040*
H11B	−0.160371	0.848577	0.273790	0.040*
H11C	−0.271445	0.773897	0.153339	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01561 (12)	0.01899 (13)	0.01278 (12)	0.00220 (7)	0.00175 (8)	0.00138 (7)
O1	0.0225 (10)	0.0127 (10)	0.0215 (11)	0.0037 (8)	0.0077 (9)	0.0005 (8)
O2	0.0135 (10)	0.0155 (10)	0.0337 (13)	0.0048 (8)	0.0077 (9)	0.0011 (9)
C1	0.0156 (13)	0.0145 (13)	0.0139 (13)	0.0036 (10)	0.0059 (10)	0.0027 (11)
C2	0.0190 (14)	0.0115 (12)	0.0169 (14)	0.0008 (10)	0.0058 (11)	−0.0006 (11)
C3	0.0128 (12)	0.0160 (13)	0.0152 (13)	−0.0019 (10)	0.0031 (10)	−0.0016 (11)
C4	0.0122 (12)	0.0146 (13)	0.0129 (13)	0.0020 (10)	0.0039 (10)	0.0023 (11)
C5	0.0155 (13)	0.0112 (13)	0.0208 (15)	0.0000 (10)	0.0040 (11)	0.0001 (11)
C6	0.0122 (12)	0.0165 (14)	0.0198 (15)	−0.0001 (10)	0.0033 (11)	0.0003 (11)
C7	0.0108 (12)	0.0120 (12)	0.0154 (14)	−0.0006 (10)	0.0026 (10)	0.0009 (11)
C8	0.0117 (12)	0.0140 (12)	0.0113 (13)	−0.0012 (10)	0.0012 (10)	0.0011 (10)
C9	0.0124 (13)	0.0150 (13)	0.0138 (14)	0.0002 (10)	0.0038 (10)	−0.0014 (10)
C10	0.0174 (13)	0.0183 (14)	0.0123 (13)	0.0027 (11)	0.0061 (10)	0.0019 (11)
C11	0.0177 (15)	0.0278 (17)	0.0336 (19)	0.0098 (13)	0.0072 (13)	0.0006 (15)

Geometric parameters (Å, º)

I1—C8	2.099 (3)	C4—C7	1.492 (4)
O1—C10	1.205 (4)	C5—H5	0.9500
O2—C10	1.334 (4)	C5—C6	1.383 (4)
O2—C11	1.451 (4)	C6—H6	0.9500
C1—C2	1.390 (4)	C7—C8	1.395 (4)
C1—C6	1.397 (4)	C7—C9^i	1.396 (4)
C1—C10	1.491 (4)	C8—C9	1.392 (4)
C2—H2	0.9500	C9—H9	0.9500
C2—C3	1.387 (4)	C11—H11A	0.9800
C3—H3	0.9500	C11—H11B	0.9800
C3—C4	1.398 (4)	C11—H11C	0.9800
C4—C5	1.395 (4)
C10—O2—C11	114.8 (2)	C8—C7—C4	123.7 (3)
C2—C1—C6	119.9 (3)	C8—C7—C9^i	118.0 (3)
C2—C1—C10	118.4 (3)	C9^i—C7—C4	118.3 (3)
C6—C1—C10	121.7 (3)	C7—C8—I1	122.2 (2)
C1—C2—H2	120.1	C9—C8—I1	117.0 (2)
C3—C2—C1	119.9 (3)	C9—C8—C7	120.7 (3)
C3—C2—H2	120.1	C7^i—C9—H9	119.4
C2—C3—H3	119.8	C8—C9—C7^i	121.3 (3)
C2—C3—C4	120.4 (3)	C8—C9—H9	119.4
C4—C3—H3	119.8	O1—C10—O2	123.6 (3)
C3—C4—C7	119.7 (2)	O1—C10—C1	124.0 (3)
C5—C4—C3	119.4 (3)	O2—C10—C1	112.3 (2)
C5—C4—C7	120.8 (3)	O2—C11—H11A	109.5
C4—C5—H5	119.9	O2—C11—H11B	109.5
C6—C5—C4	120.2 (3)	O2—C11—H11C	109.5
C6—C5—H5	119.9	H11A—C11—H11B	109.5
C1—C6—H6	119.9	H11A—C11—H11C	109.5
C5—C6—C1	120.2 (3)	H11B—C11—H11C	109.5
C5—C6—H6	119.9
I1—C8—C9—C7^i	177.1 (2)	C5—C4—C7—C8	64.8 (4)
C1—C2—C3—C4	0.8 (4)	C5—C4—C7—C9^i	−114.6 (3)
C2—C1—C6—C5	−0.8 (4)	C6—C1—C2—C3	−0.1 (4)
C2—C1—C10—O1	12.2 (5)	C6—C1—C10—O1	−167.6 (3)
C2—C1—C10—O2	−168.6 (3)	C6—C1—C10—O2	11.7 (4)
C2—C3—C4—C5	−0.7 (4)	C7—C4—C5—C6	177.6 (3)
C2—C3—C4—C7	−178.5 (3)	C7—C8—C9—C7^i	−0.4 (5)
C3—C4—C5—C6	−0.2 (4)	C9^i—C7—C8—I1	−176.9 (2)
C3—C4—C7—C8	−117.4 (3)	C9^i—C7—C8—C9	0.4 (4)
C3—C4—C7—C9^i	63.1 (4)	C10—C1—C2—C3	−179.8 (3)
C4—C5—C6—C1	1.0 (5)	C10—C1—C6—C5	178.9 (3)
C4—C7—C8—I1	3.6 (4)	C11—O2—C10—O1	4.4 (4)
C4—C7—C8—C9	−179.0 (3)	C11—O2—C10—C1	−174.9 (3)

Symmetry code: (i) −x+2, −y+1, −z+1.

(3)

Crystal data

C20H13KO4	F(000) = 736
Mr = 356.40	Dx = 1.618 Mg m^−3
Monoclinic, I2/a	Cu Kα radiation, λ = 1.54184 Å
a = 6.0126 (1) Å	Cell parameters from 2893 reflections
b = 6.9783 (2) Å	θ = 2.5–69.0°
c = 34.9410 (7) Å	µ = 3.40 mm^−1
β = 93.359 (2)°	T = 100 K
V = 1463.53 (6) Å^3	Prism, clear colourless
Z = 4	0.07 × 0.06 × 0.03 mm

Data collection

SuperNova, Single source at offset/far, HyPix3000 diffractometer	1366 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	1331 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.010
Detector resolution: 10.0000 pixels mm^-1	θmax = 69.1°, θmin = 2.5°
ω scans	h = −7→6
Absorption correction: multi-scan CrysAlisPro 1.171.41.104a (Rigaku Oxford Diffraction, 2021) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −8→7
Tmin = 0.901, Tmax = 1.000	l = −42→40
3516 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0518P)^2 + 1.1166P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max < 0.001
1366 reflections	Δρmax = 0.27 e Å^−3
116 parameters	Δρmin = −0.27 e Å^−3
0 restraints

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
K1	0.750000	0.70369 (6)	0.500000	0.01442 (16)
O1	0.38249 (16)	0.62101 (14)	0.45426 (3)	0.0140 (2)
O2	0.14599 (15)	0.85388 (14)	0.46875 (2)	0.0129 (2)
H2	0.250000	0.850 (7)	0.500000	0.087 (14)*
C1	0.1310 (2)	0.74168 (19)	0.40474 (4)	0.0099 (3)
C2	−0.0745 (2)	0.82853 (19)	0.39612 (4)	0.0113 (3)
H2A	−0.152438	0.886250	0.415994	0.014*
C3	−0.1665 (2)	0.8315 (2)	0.35868 (4)	0.0111 (3)
H3	−0.307978	0.889307	0.353395	0.013*
C4	−0.0539 (2)	0.75048 (19)	0.32860 (4)	0.0093 (3)
C5	0.1553 (2)	0.66757 (19)	0.33762 (4)	0.0108 (3)
H5	0.236951	0.614671	0.317686	0.013*
C6	0.2455 (2)	0.66134 (19)	0.37514 (4)	0.0111 (3)
H6	0.385890	0.601959	0.380639	0.013*
C7	−0.1536 (2)	0.74993 (19)	0.28844 (4)	0.0094 (3)
C8	−0.0395 (2)	0.67590 (19)	0.25786 (4)	0.0113 (3)
H8	0.105417	0.624000	0.262775	0.014*
C9	−0.1329 (2)	0.67650 (19)	0.22058 (4)	0.0108 (3)
H9	−0.049761	0.625645	0.200628	0.013*
C10	0.2305 (2)	0.73392 (19)	0.44511 (4)	0.0107 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0090 (2)	0.0199 (3)	0.0141 (2)	0.000	−0.00129 (15)	0.000
O1	0.0123 (5)	0.0188 (5)	0.0106 (5)	0.0033 (4)	−0.0038 (3)	0.0005 (4)
O2	0.0132 (5)	0.0190 (5)	0.0063 (4)	0.0024 (4)	−0.0011 (3)	−0.0009 (4)
C1	0.0117 (6)	0.0103 (6)	0.0073 (6)	−0.0024 (5)	−0.0017 (5)	0.0011 (5)
C2	0.0120 (6)	0.0133 (6)	0.0087 (6)	−0.0001 (5)	0.0018 (5)	−0.0001 (5)
C3	0.0104 (6)	0.0131 (6)	0.0096 (6)	0.0012 (5)	−0.0013 (5)	0.0007 (5)
C4	0.0110 (6)	0.0086 (6)	0.0081 (6)	−0.0022 (5)	−0.0004 (5)	0.0011 (5)
C5	0.0118 (6)	0.0126 (6)	0.0080 (6)	−0.0003 (5)	0.0012 (5)	−0.0007 (5)
C6	0.0092 (6)	0.0122 (6)	0.0116 (6)	−0.0002 (5)	−0.0013 (5)	0.0006 (5)
C7	0.0117 (6)	0.0084 (6)	0.0080 (6)	−0.0025 (5)	−0.0003 (5)	0.0007 (5)
C8	0.0100 (6)	0.0132 (6)	0.0105 (6)	0.0010 (5)	−0.0004 (5)	0.0000 (5)
C9	0.0114 (6)	0.0129 (6)	0.0081 (6)	0.0003 (5)	0.0006 (5)	−0.0003 (5)
C10	0.0096 (6)	0.0135 (6)	0.0089 (6)	−0.0033 (5)	−0.0002 (5)	0.0014 (5)

Geometric parameters (Å, º)

K1—K1^i	4.1376 (6)	C1—C10	1.5007 (17)
K1—K1^ii	4.1376 (6)	C2—H2A	0.9500
K1—O1^i	2.9106 (10)	C2—C3	1.3901 (18)
K1—O1	2.7122 (9)	C3—H3	0.9500
K1—O1^iii	2.9106 (10)	C3—C4	1.4019 (19)
K1—O1^iv	2.7121 (9)	C4—C5	1.4039 (19)
K1—O2^v	3.3220 (11)	C4—C7	1.4932 (17)
K1—O2^vi	3.3220 (11)	C5—H5	0.9500
K1—O2^vii	2.8748 (10)	C5—C6	1.3895 (18)
K1—O2^viii	2.8748 (10)	C6—H6	0.9500
O1—C10	1.2344 (17)	C7—C8	1.4017 (19)
O2—H2	1.2266 (17)	C7—C9^ix	1.4014 (19)
O2—C10	1.3000 (17)	C8—H8	0.9500
C1—C2	1.3933 (19)	C8—C9	1.3878 (18)
C1—C6	1.3930 (19)	C9—H9	0.9500
K1^i—K1—K1^ii	93.201 (17)	O2^v—K1—O2^vi	43.32 (3)
O1^iv—K1—K1^i	114.88 (2)	O2^vii—K1—O2^vi	71.36 (2)
O1^iii—K1—K1^i	71.78 (2)	O2^viii—K1—O2^v	71.36 (2)
O1^i—K1—K1^i	40.790 (19)	K1—O1—K1^i	94.69 (3)
O1^iii—K1—K1^ii	40.790 (19)	C10—O1—K1^i	114.63 (8)
O1—K1—K1^i	44.52 (2)	C10—O1—K1	125.59 (9)
O1—K1—K1^ii	114.88 (2)	K1^x—O2—K1^v	110.98 (3)
O1^iv—K1—K1^ii	44.52 (2)	K1^v—O2—H2	70 (2)
O1^i—K1—K1^ii	71.78 (2)	K1^x—O2—H2	92.5 (8)
O1^iii—K1—O1^i	77.75 (4)	C10—O2—K1^x	111.70 (8)
O1^iv—K1—O1	155.43 (4)	C10—O2—K1^v	137.24 (8)
O1^iv—K1—O1^iii	85.30 (3)	C10—O2—H2	110.6 (15)
O1—K1—O1^iii	75.56 (2)	C2—C1—C10	121.24 (12)
O1^iv—K1—O1^i	75.56 (2)	C6—C1—C2	119.01 (12)
O1—K1—O1^i	85.31 (3)	C6—C1—C10	119.76 (12)
O1^iv—K1—O2^v	82.69 (3)	C1—C2—H2A	119.7
O1—K1—O2^viii	68.72 (3)	C3—C2—C1	120.58 (12)
O1—K1—O2^v	121.51 (3)	C3—C2—H2A	119.7
O1^iv—K1—O2^vii	68.72 (3)	C2—C3—H3	119.4
O1—K1—O2^vii	121.20 (3)	C2—C3—C4	121.11 (12)
O1—K1—O2^vi	82.69 (3)	C4—C3—H3	119.4
O1^iii—K1—O2^v	148.40 (3)	C3—C4—C5	117.60 (12)
O1^iv—K1—O2^viii	121.20 (3)	C3—C4—C7	121.40 (12)
O1^i—K1—O2^vi	148.40 (2)	C5—C4—C7	121.00 (12)
O1^iii—K1—O2^vi	126.54 (2)	C4—C5—H5	119.3
O1^iv—K1—O2^vi	121.51 (3)	C6—C5—C4	121.31 (12)
O1^i—K1—O2^v	126.54 (2)	C6—C5—H5	119.3
O2^viii—K1—K1^i	68.44 (2)	C1—C6—H6	119.8
O2^v—K1—K1^i	139.584 (18)	C5—C6—C1	120.36 (12)
O2^viii—K1—K1^ii	150.28 (2)	C5—C6—H6	119.8
O2^v—K1—K1^ii	121.049 (17)	C8—C7—C4	122.01 (12)
O2^vii—K1—K1^ii	68.443 (19)	C9^ix—C7—C4	121.48 (12)
O2^vi—K1—K1^ii	139.584 (18)	C9^ix—C7—C8	116.51 (12)
O2^vi—K1—K1^i	121.049 (17)	C7—C8—H8	119.2
O2^vii—K1—K1^i	150.28 (2)	C9—C8—C7	121.68 (13)
O2^vii—K1—O1^i	138.74 (3)	C9—C8—H8	119.2
O2^vii—K1—O1^iii	79.39 (3)	C7^ix—C9—H9	119.1
O2^viii—K1—O1^i	79.39 (3)	C8—C9—C7^ix	121.80 (12)
O2^viii—K1—O1^iii	138.74 (3)	C8—C9—H9	119.1
O2^viii—K1—O2^vi	69.02 (3)	O1—C10—O2	123.88 (12)
O2^vii—K1—O2^viii	137.24 (4)	O1—C10—C1	120.98 (12)
O2^vii—K1—O2^v	69.02 (3)	O2—C10—C1	115.14 (11)
K1—O1—C10—O2	−42.16 (18)	C3—C4—C7—C8	177.58 (13)
K1^i—O1—C10—O2	73.88 (14)	C3—C4—C7—C9^ix	−2.5 (2)
K1^i—O1—C10—C1	−106.62 (11)	C4—C5—C6—C1	−1.4 (2)
K1—O1—C10—C1	137.35 (10)	C4—C7—C8—C9	−179.77 (12)
K1^v—O2—C10—O1	87.61 (16)	C5—C4—C7—C8	−3.2 (2)
K1^x—O2—C10—O1	−95.94 (13)	C5—C4—C7—C9^ix	176.70 (12)
K1^x—O2—C10—C1	84.53 (11)	C6—C1—C2—C3	1.4 (2)
K1^v—O2—C10—C1	−91.92 (13)	C6—C1—C10—O1	−17.34 (19)
C1—C2—C3—C4	−1.1 (2)	C6—C1—C10—O2	162.21 (12)
C2—C1—C6—C5	−0.1 (2)	C7—C4—C5—C6	−177.62 (12)
C2—C1—C10—O1	162.83 (13)	C7—C8—C9—C7^ix	−0.4 (2)
C2—C1—C10—O2	−17.62 (18)	C9^ix—C7—C8—C9	0.3 (2)
C2—C3—C4—C5	−0.4 (2)	C10—C1—C2—C3	−178.79 (12)
C2—C3—C4—C7	178.87 (12)	C10—C1—C6—C5	−179.98 (12)
C3—C4—C5—C6	1.65 (19)

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

(4)

Crystal data

C16H14O4	Dx = 1.427 Mg m^−3
Mr = 270.27	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 3954 reflections
a = 7.1094 (2) Å	θ = 3.0–77.9°
b = 5.9629 (2) Å	µ = 0.85 mm^−1
c = 29.6773 (8) Å	T = 100 K
V = 1258.10 (6) Å^3	Prism, clear colourless
Z = 4	0.14 × 0.1 × 0.04 mm
F(000) = 568

Data collection

XtaLAB Synergy, Single source at home/near, HyPix diffractometer	1175 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1049 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.025
Detector resolution: 10.0000 pixels mm^-1	θmax = 70.0°, θmin = 3.0°
ω scans	h = −8→8
Absorption correction: multi-scan CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −4→7
Tmin = 0.612, Tmax = 1.000	l = −35→35
6315 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0523P)^2 + 0.4708P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1175 reflections	Δρmax = 0.21 e Å^−3
92 parameters	Δρmin = −0.22 e Å^−3
0 restraints

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
O1	0.56210 (12)	0.51698 (14)	0.33793 (3)	0.0237 (3)
O2	0.44337 (13)	0.19867 (15)	0.30917 (3)	0.0283 (3)
C1	0.50609 (15)	0.2190 (2)	0.38798 (4)	0.0176 (3)
C2	0.58016 (15)	0.3431 (2)	0.42369 (4)	0.0180 (3)
H2	0.632592	0.487130	0.418254	0.022*
C3	0.57747 (15)	0.2570 (2)	0.46701 (4)	0.0176 (3)
H3	0.629102	0.343418	0.490895	0.021*
C4	0.50065 (15)	0.04589 (19)	0.47658 (4)	0.0163 (3)
C5	0.42659 (15)	−0.07655 (19)	0.44026 (4)	0.0180 (3)
H5	0.372938	−0.220013	0.445611	0.022*
C6	0.43027 (15)	0.0079 (2)	0.39674 (4)	0.0190 (3)
H6	0.380674	−0.078939	0.372677	0.023*
C7	0.50040 (16)	0.3056 (2)	0.34097 (4)	0.0195 (3)
C8	0.55047 (18)	0.6156 (2)	0.29324 (4)	0.0262 (3)
H8A	0.633992	0.534248	0.272680	0.039*
H8B	0.588825	0.773327	0.294663	0.039*
H8C	0.420752	0.605834	0.282246	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0311 (5)	0.0212 (5)	0.0188 (5)	−0.0046 (4)	−0.0018 (3)	0.0042 (3)
O2	0.0403 (5)	0.0262 (5)	0.0183 (5)	−0.0058 (4)	−0.0033 (4)	−0.0009 (4)
C1	0.0153 (6)	0.0197 (6)	0.0179 (6)	0.0022 (4)	0.0010 (4)	−0.0009 (5)
C2	0.0163 (5)	0.0163 (6)	0.0213 (6)	0.0000 (4)	0.0005 (4)	0.0004 (5)
C3	0.0156 (6)	0.0185 (6)	0.0187 (6)	0.0002 (4)	−0.0003 (4)	−0.0028 (5)
C4	0.0127 (5)	0.0176 (6)	0.0187 (6)	0.0026 (4)	0.0012 (4)	−0.0012 (5)
C5	0.0173 (6)	0.0158 (6)	0.0208 (6)	−0.0011 (4)	0.0004 (4)	−0.0001 (5)
C6	0.0180 (6)	0.0198 (6)	0.0192 (6)	0.0000 (4)	−0.0001 (4)	−0.0032 (5)
C7	0.0177 (6)	0.0203 (6)	0.0204 (6)	0.0009 (4)	0.0015 (4)	−0.0006 (5)
C8	0.0328 (7)	0.0258 (7)	0.0200 (7)	−0.0021 (5)	−0.0017 (5)	0.0068 (5)

Geometric parameters (Å, º)

O1—C7	1.3378 (15)	C3—C4	1.4015 (16)
O1—C8	1.4531 (15)	C4—C4^i	1.494 (2)
O2—C7	1.2089 (15)	C4—C5	1.4043 (16)
C1—C2	1.3958 (17)	C5—H5	0.9500
C1—C6	1.3940 (17)	C5—C6	1.3864 (17)
C1—C7	1.4881 (16)	C6—H6	0.9500
C2—H2	0.9500	C8—H8A	0.9800
C2—C3	1.3844 (17)	C8—H8B	0.9800
C3—H3	0.9500	C8—H8C	0.9800
C7—O1—C8	115.11 (9)	C6—C5—C4	121.27 (11)
C2—C1—C7	122.57 (11)	C6—C5—H5	119.4
C6—C1—C2	118.88 (11)	C1—C6—H6	119.7
C6—C1—C7	118.53 (11)	C5—C6—C1	120.61 (11)
C1—C2—H2	119.9	C5—C6—H6	119.7
C3—C2—C1	120.22 (11)	O1—C7—C1	112.41 (10)
C3—C2—H2	119.9	O2—C7—O1	123.65 (11)
C2—C3—H3	119.1	O2—C7—C1	123.93 (11)
C2—C3—C4	121.78 (11)	O1—C8—H8A	109.5
C4—C3—H3	119.1	O1—C8—H8B	109.5
C3—C4—C4^i	121.33 (13)	O1—C8—H8C	109.5
C3—C4—C5	117.23 (11)	H8A—C8—H8B	109.5
C5—C4—C4^i	121.43 (13)	H8A—C8—H8C	109.5
C4—C5—H5	119.4	H8B—C8—H8C	109.5
C1—C2—C3—C4	−0.34 (17)	C4—C5—C6—C1	−0.77 (17)
C2—C1—C6—C5	0.69 (16)	C6—C1—C2—C3	−0.15 (16)
C2—C1—C7—O1	−4.03 (16)	C6—C1—C7—O1	174.40 (9)
C2—C1—C7—O2	177.21 (11)	C6—C1—C7—O2	−4.36 (18)
C2—C3—C4—C4^i	179.69 (12)	C7—C1—C2—C3	178.28 (10)
C2—C3—C4—C5	0.27 (16)	C7—C1—C6—C5	−177.80 (10)
C3—C4—C5—C6	0.28 (16)	C8—O1—C7—O2	1.98 (16)
C4^i—C4—C5—C6	−179.14 (12)	C8—O1—C7—C1	−176.78 (9)

Symmetry code: (i) −x+1, −y, −z+1.