Methyl 3,4-bis­(cyclo­propyl­meth­oxy)benzoate

The title compound, C₁₆H₂₀O₄, was obtained unintentionally as the byproduct of an attempted synthesis of methyl 3-(cyclo­propyl­meth­oxy)-4-hy­droxy­benzoate. In the crystal, the mol­ecules are linked by inter­molecular C—H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.114
• Data-to-parameter ratio = 21.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.00
PLAT734_ALERT_1_C Contact Calc  3.4682(19), Rep    3.468(4) ......       2.11 su-Ra
              O(1) -C(13)   1.555   2.566                    #         42
PLAT734_ALERT_1_C Contact Calc    3.509(2), Rep    3.509(7) ......       3.50 su-Ra
              C(8) -C(12)   1.555   4.765                    #         42
PLAT734_ALERT_1_C Contact Calc  3.4070(18), Rep    3.407(4) ......       2.22 su-Ra
              C(12)-O(3)    1.555   1.655                    #         42
PLAT734_ALERT_1_C Contact Calc    3.578(2), Rep    3.578(5) ......       2.50 su-Ra
              C(12)-C(8)    1.555   4.664                    #         42
PLAT734_ALERT_1_C Contact Calc    3.509(2), Rep    3.509(5) ......       2.50 su-Ra
              C(12)-C(8)    1.555   4.764                    #         42
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4

Alert level G
REFLT03_ALERT_4_G  ALERT: MoKa measured Friedel data cannot be used to
                   determine absolute structure in a light-atom
                   study EXCEPT under VERY special conditions.
                   It is preferred that Friedel data is merged in such cases.
           From the CIF: _diffrn_reflns_theta_max           29.10
           From the CIF: _reflns_number_total               3852
           Count of symmetry unique reflns         2254
           Completeness (_total/calc)            170.90%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1598
           Fraction of Friedel pairs measured     0.709
           Are heavy atom types Z>Si present         no

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   1 ALERT level G = General information/check it is not something unexpected

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Roflumilast is an effective phosphodiesterase-4 inhibitor (PDE4 inhibitor), which can be used in the treatment of asthma, inflammation, bronchitis, allergy and other disorders related to immune system, heart and kidney. During the development of our own PDE4 inhibitors, roflumilast was synthesized as the positive control in the bioactivity screening, and the title compound,methyl 3,4-bis(cyclopropylmethoxy)benzoate, was a byproduct during preparation of the intermediate methyl 3-(cyclopropylmethoxy)-4-hydroxybenzoate.The crystallographic analysis of the title compound is done to confirm the chemical structure of the title compound. In the title compound, all bond lengths and angles are normal and in a good agreement with those reported previously (Hou, et al., 2010). In the crystal structure, the hydroxy groups are involved in the formation of intermolecular C—H···O hydrogen bonds(Tab 1), which link the molecules related by translation along axis b into one-dimensional chains.

Related literature

For the preparation, see: Bose et al. (2005). For a similar structure, see: Hou et al. (2010).

S2. Experimental

A mixture of 3,4-dihydroxy methyl benzoate (1.68 g, 10 mmol) and potassium carbonate (2.76 g, 20 mmol) in acetone (50 ml) was added with a solution of cyclopropyl methyl bromide (1.35 g, 10 mmol) in acetone (50 ml). The reaction mixture was stirred at 40 °C for 18 h, and then was filtered. The filtrate was evaporated on a rotary evaporator to get the dried solid, which was then purified by flash column chromatography to obtain methyl 3-(cyclopropylmethoxy)-4-hydroxybenzoate, methyl 4-(cyclopropylmethoxy)-3-hydroxybenzoate, and the title compound methyl 3,4-bis(cyclopropylmethoxy)benzoate(Bose, et al.,2005).

Crystals suitable for X-ray diffraction were obtained through slow evaporation of a solution of the pure title compound in ethyl acetate/n-hexane (1/10 by volume).

S3. Refinement

H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and refined as riding, with U_iso(H) = 1.2 U_eq of the parent atom.

Computing details

Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: CrystalClear-SM Expert (Rigaku, 2009); data reduction: CrystalClear-SM Expert (Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2009); software used to prepare material for publication: CrystalStructure (Rigaku, 2009).

Figures

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids, and H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. The packing of the title compound, showing the one-dimensional structure,with intermolecular hydrogen bonds (dashed lines); for clarity H atoms have been omitted.

Methyl 3,4-bis(cyclopropylmethoxy)benzoate

Crystal data

C16H20O4	F(000) = 592.00
Mr = 276.33	Dx = 1.278 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6064 reflections
a = 4.9018 (8) Å	θ = 1.3–31.4°
b = 15.543 (2) Å	µ = 0.09 mm^−1
c = 18.846 (2) Å	T = 113 K
V = 1435.9 (3) Å^3	Prism, colorless
Z = 4	0.22 × 0.20 × 0.18 mm

Data collection

Rigaku Saturn724 CCD diffractometer	3300 reflections with F^2 > 2.0σ(F^2)
Detector resolution: 14.222 pixels mm^-1	Rint = 0.034
ω scans	θmax = 29.1°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −6→6
Tmin = 0.891, Tmax = 0.984	k = −21→21
20068 measured reflections	l = −25→25
3852 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0778P)^2] where P = (Fo^2 + 2Fc^2)/3
3852 reflections	(Δ/σ)max = 0.001
182 parameters	Δρmax = 0.57 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3
Primary atom site location: structure-invariant direct methods

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
O(1)	0.3872 (2)	0.69719 (7)	0.66936 (5)	0.0321
O(2)	0.6968 (2)	0.59026 (7)	0.66908 (5)	0.0306
O(3)	0.7825 (2)	0.48335 (5)	0.42141 (5)	0.0209
O(4)	0.4320 (2)	0.56811 (6)	0.34625 (4)	0.0250
C(1)	0.4862 (3)	0.62225 (8)	0.56094 (7)	0.0192
C(2)	0.6558 (3)	0.56094 (8)	0.52884 (7)	0.0184
C(3)	0.6319 (3)	0.54351 (8)	0.45719 (6)	0.0174
C(4)	0.4378 (3)	0.58918 (8)	0.41612 (7)	0.0193
C(5)	0.2695 (3)	0.64967 (8)	0.44863 (7)	0.0213
C(6)	0.2930 (3)	0.66574 (8)	0.52102 (7)	0.0211
C(7)	0.5139 (3)	0.64194 (8)	0.63788 (7)	0.0216
C(8)	0.7487 (4)	0.60502 (11)	0.74361 (7)	0.0406
C(9)	0.9395 (3)	0.42507 (8)	0.46452 (6)	0.0199
C(10)	1.0118 (3)	0.34763 (8)	0.42075 (7)	0.0205
C(11)	1.2662 (3)	0.29938 (9)	0.44212 (8)	0.0262
C(12)	1.2614 (3)	0.35005 (9)	0.37423 (7)	0.0246
C(13)	0.2283 (3)	0.61039 (9)	0.30217 (7)	0.0302
C(14)	0.2718 (4)	0.57919 (10)	0.22787 (7)	0.0330
C(15)	0.5052 (4)	0.61632 (12)	0.18752 (10)	0.0442
C(16)	0.2225 (4)	0.64137 (13)	0.16830 (8)	0.0428
H(2)	0.7878	0.5312	0.5565	0.022*
H(5)	0.1381	0.6800	0.4213	0.026*
H(6)	0.1765	0.7066	0.5431	0.025*
H(8A)	0.5750	0.6078	0.7693	0.049*
H(8B)	0.8469	0.6595	0.7495	0.049*
H(8C)	0.8593	0.5578	0.7626	0.049*
H(9A)	0.8319	0.4073	0.5065	0.024*
H(9B)	1.1078	0.4538	0.4813	0.024*
H(10)	0.8558	0.3120	0.4033	0.025*
H(11A)	1.3747	0.3225	0.4821	0.031*
H(11B)	1.2633	0.2358	0.4386	0.031*
H(12A)	1.2558	0.3176	0.3291	0.030*
H(12B)	1.3671	0.4043	0.3725	0.030*
H(13A)	0.2504	0.6736	0.3045	0.036*
H(13B)	0.0423	0.5955	0.3186	0.036*
H(14)	0.2271	0.5175	0.2183	0.040*
H(15A)	0.6201	0.6597	0.2118	0.053*
H(15B)	0.6047	0.5779	0.1546	0.053*
H(16A)	0.1462	0.6184	0.1235	0.051*
H(16B)	0.1615	0.7002	0.1807	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O(1)	0.0398	0.0311	0.0253	0.0080	0.0001	−0.0084
O(2)	0.0391	0.0348	0.0179	0.0103	−0.0046	−0.0070
O(3)	0.0251	0.0207	0.0170	0.0073	−0.0011	0.0001
O(4)	0.0346	0.0232	0.0170	0.0084	−0.0041	0.0008
C(1)	0.0205	0.0176	0.0194	−0.0020	0.0025	−0.0008
C(2)	0.0171	0.0187	0.0194	−0.0004	−0.0002	−0.0003
C(3)	0.0192	0.0152	0.0178	0.0006	0.0017	−0.0000
C(4)	0.0228	0.0182	0.0170	−0.0013	−0.0017	0.0020
C(5)	0.0222	0.0188	0.0229	0.0010	−0.0014	0.0024
C(6)	0.0213	0.0185	0.0235	0.0012	0.0042	−0.0012
C(7)	0.0243	0.0197	0.0208	−0.0031	0.0009	−0.0025
C(8)	0.0575	0.0441	0.0202	0.0155	−0.0122	−0.0113
C(9)	0.0213	0.0205	0.0179	0.0038	−0.0004	0.0030
C(10)	0.0189	0.0203	0.0222	0.0011	0.0009	0.0013
C(11)	0.0251	0.0244	0.0291	0.0071	0.0026	0.0046
C(12)	0.0247	0.0255	0.0236	0.0017	0.0060	0.0002
C(13)	0.0337	0.0335	0.0235	0.0069	−0.0052	0.0038
C(14)	0.0389	0.0350	0.0251	0.0013	−0.0049	0.0053
C(15)	0.0457	0.0498	0.0371	0.0028	0.0038	0.0098
C(16)	0.0510	0.0542	0.0230	0.0148	−0.0043	0.0114

Geometric parameters (Å, º)

O(1)—C(7)	1.2143 (17)	C(15)—C(16)	1.484 (3)
O(2)—C(7)	1.3397 (11)	C(2)—H(2)	0.950
O(2)—C(8)	1.4458 (19)	C(5)—H(5)	0.950
O(3)—C(3)	1.3692 (14)	C(6)—H(6)	0.950
O(3)—C(9)	1.4397 (10)	C(8)—H(8A)	0.980
O(4)—C(4)	1.3572 (17)	C(8)—H(8B)	0.980
O(4)—C(13)	1.4558 (13)	C(8)—H(8C)	0.980
C(1)—C(2)	1.4017 (18)	C(9)—H(9A)	0.990
C(1)—C(6)	1.3856 (15)	C(9)—H(9B)	0.990
C(1)—C(7)	1.488 (3)	C(10)—H(10)	1.000
C(2)—C(3)	1.382 (3)	C(11)—H(11A)	0.990
C(3)—C(4)	1.4169 (14)	C(11)—H(11B)	0.990
C(4)—C(5)	1.3930 (18)	C(12)—H(12A)	0.990
C(5)—C(6)	1.392 (3)	C(12)—H(12B)	0.990
C(9)—C(10)	1.502 (2)	C(13)—H(13A)	0.990
C(10)—C(11)	1.5098 (14)	C(13)—H(13B)	0.990
C(10)—C(12)	1.506 (2)	C(14)—H(14)	1.000
C(11)—C(12)	1.5026 (17)	C(15)—H(15A)	0.990
C(13)—C(14)	1.497 (3)	C(15)—H(15B)	0.990
C(14)—C(15)	1.490 (3)	C(16)—H(16A)	0.990
C(14)—C(16)	1.5009 (15)	C(16)—H(16B)	0.990
O(1)···C(6)	2.875 (2)	H(6)···C(1)^viii	3.4340
O(1)···C(8)	2.6738 (14)	H(6)···C(2)^iv	3.4221
O(2)···C(2)	2.6895 (19)	H(6)···C(4)^viii	3.4694
O(3)···O(4)	2.5873 (12)	H(6)···C(5)^viii	2.9995
O(3)···C(12)	3.2546 (14)	H(6)···C(6)^viii	2.9886
O(4)···C(15)	3.1046 (16)	H(6)···H(2)^iv	3.3350
C(1)···C(4)	2.787 (3)	H(6)···H(5)^viii	3.2433
C(2)···C(5)	2.7880 (15)	H(6)···H(5)^i	2.9456
C(2)···C(9)	2.804 (2)	H(6)···H(6)^viii	3.2354
C(3)···C(6)	2.7955 (18)	H(6)···H(6)^i	3.2354
C(5)···C(13)	2.834 (3)	H(8A)···O(3)^ii	3.2735
O(1)···C(13)^i	3.468 (4)	H(8A)···C(10)^ii	2.9685
O(2)···C(15)^ii	3.545 (2)	H(8A)···C(12)^ii	2.6574
O(3)···C(5)^iii	3.556 (2)	H(8A)···C(14)^ix	3.4558
O(3)···C(12)^iv	3.407 (2)	H(8A)···H(8C)^iv	3.5954
O(4)···C(12)^iv	3.5306 (19)	H(8A)···H(10)^ii	2.8381
C(2)···C(6)^iii	3.526 (3)	H(8A)···H(12A)^ii	2.2901
C(3)···C(5)^iii	3.538 (3)	H(8A)···H(12B)^ii	2.9188
C(5)···O(3)^iv	3.556 (3)	H(8A)···H(12B)^v	3.3617
C(5)···C(3)^iv	3.538 (3)	H(8A)···H(13B)^ix	3.3436
C(6)···C(2)^iv	3.526 (3)	H(8A)···H(14)^ix	2.6278
C(8)···C(12)^ii	3.578 (3)	H(8A)···H(16B)^i	3.1585
C(8)···C(12)^v	3.509 (7)	H(8B)···O(1)^iii	3.1047
C(12)···O(3)^iii	3.407 (4)	H(8B)···C(12)^v	3.0389
C(12)···O(4)^iii	3.531 (3)	H(8B)···C(16)^i	3.5151
C(12)···C(8)^vi	3.578 (5)	H(8B)···H(10)^ii	3.0967
C(12)···C(8)^vii	3.509 (5)	H(8B)···H(12A)^ii	3.3323
C(13)···O(1)^viii	3.468 (3)	H(8B)···H(12A)^v	2.4836
C(15)···O(2)^vi	3.545 (3)	H(8B)···H(12B)^v	2.8849
C(15)···C(16)^iii	3.556 (4)	H(8B)···H(13A)^i	2.8266
C(16)···C(15)^iv	3.556 (3)	H(8B)···H(14)^ii	3.5027
O(1)···H(6)	2.5982	H(8B)···H(15A)^i	3.1979
O(1)···H(8A)	2.5145	H(8B)···H(16B)^i	2.7043
O(1)···H(8B)	2.7752	H(8C)···O(3)^ii	3.1385
O(2)···H(2)	2.3550	H(8C)···O(4)^ii	2.7133
O(3)···H(2)	2.6517	H(8C)···C(12)^v	3.1519
O(3)···H(10)	2.7092	H(8C)···C(13)^ii	3.3878
O(3)···H(12B)	3.2512	H(8C)···C(14)^ii	2.8694
O(4)···H(5)	2.6652	H(8C)···C(15)^ii	3.1254
O(4)···H(14)	2.7276	H(8C)···H(8A)^iii	3.5954
O(4)···H(15A)	3.0496	H(8C)···H(10)^ii	3.4987
C(1)···H(5)	3.2624	H(8C)···H(12A)^v	2.9798
C(2)···H(6)	3.2736	H(8C)···H(12B)^v	2.5373
C(2)···H(9A)	2.5735	H(8C)···H(13B)^ix	3.2663
C(2)···H(9B)	2.9122	H(8C)···H(14)^ix	3.2138
C(3)···H(5)	3.2890	H(8C)···H(14)^ii	2.4852
C(3)···H(9A)	2.5109	H(8C)···H(15A)^ii	3.5154
C(3)···H(9B)	2.7551	H(8C)···H(15B)^ii	2.9371
C(4)···H(2)	3.2784	H(9A)···C(11)^iv	3.4606
C(4)···H(6)	3.2707	H(9A)···C(11)^x	3.3711
C(4)···H(13A)	2.6440	H(9A)···C(15)^ii	3.5231
C(4)···H(13B)	2.6731	H(9A)···H(11A)^iv	2.6402
C(5)···H(13A)	2.7429	H(9A)···H(11A)^x	3.5855
C(5)···H(13B)	2.8201	H(9A)···H(11B)^x	2.4769
C(6)···H(2)	3.2707	H(9A)···H(12B)^iv	3.4008
C(7)···H(2)	2.6681	H(9A)···H(15B)^ii	2.8173
C(7)···H(6)	2.6334	H(9A)···H(16A)^ix	3.2426
C(7)···H(8A)	2.5499	H(9A)···H(16A)^ii	3.4014
C(7)···H(8B)	2.6766	H(9B)···O(3)^iii	3.5250
C(7)···H(8C)	3.1783	H(9B)···O(4)^iii	3.4870
C(9)···H(2)	2.5055	H(9B)···C(1)^iii	3.5419
C(9)···H(11A)	2.6830	H(9B)···C(2)^iii	3.2847
C(9)···H(11B)	3.3775	H(9B)···C(3)^iii	2.9578
C(9)···H(12A)	3.4221	H(9B)···C(4)^iii	2.9243
C(9)···H(12B)	2.7392	H(9B)···C(5)^iii	3.2049
C(11)···H(9A)	2.9697	H(9B)···C(6)^iii	3.4973
C(11)···H(9B)	2.6293	H(9B)···H(15B)^ii	3.4627
C(12)···H(9A)	3.3820	H(9B)···H(16A)^ii	3.1460
C(12)···H(9B)	2.6912	H(10)···C(8)^vi	3.3147
C(13)···H(5)	2.5315	H(10)···C(11)^iv	2.9874
C(13)···H(15A)	2.6793	H(10)···C(11)^x	3.4165
C(13)···H(15B)	3.3759	H(10)···C(12)^iv	3.0231
C(13)···H(16A)	3.3933	H(10)···C(16)^xi	3.0002
C(13)···H(16B)	2.7007	H(10)···H(8A)^vi	2.8381
C(15)···H(13A)	2.6862	H(10)···H(8B)^vi	3.0967
C(15)···H(13B)	3.3697	H(10)···H(8C)^vi	3.4987
C(16)···H(13A)	2.6193	H(10)···H(11A)^iv	2.7913
C(16)···H(13B)	3.0514	H(10)···H(11A)^x	3.0070
H(2)···H(9A)	2.1545	H(10)···H(11B)^iv	3.2057
H(2)···H(9B)	2.4315	H(10)···H(11B)^x	3.1032
H(5)···H(6)	2.3396	H(10)···H(12A)^iv	3.2582
H(5)···H(13A)	2.2709	H(10)···H(12B)^iv	2.8516
H(5)···H(13B)	2.3861	H(10)···H(16A)^xi	3.0514
H(9A)···H(10)	2.4474	H(10)···H(16B)^xi	2.3527
H(9A)···H(11A)	3.0045	H(11A)···O(3)^iii	3.3990
H(9B)···H(10)	2.9237	H(11A)···C(9)^iii	3.2119
H(9B)···H(11A)	2.4243	H(11A)···C(10)^iii	3.3530
H(9B)···H(11B)	3.5652	H(11A)···C(10)^xii	3.2863
H(9B)···H(12B)	2.5324	H(11A)···C(11)^xii	3.0519
H(10)···H(11A)	2.9497	H(11A)···C(16)^ii	3.5854
H(10)···H(11B)	2.4153	H(11A)···H(9A)^iii	2.6402
H(10)···H(12A)	2.4108	H(11A)···H(9A)^xii	3.5855
H(10)···H(12B)	2.9459	H(11A)···H(10)^iii	2.7913
H(11A)···H(12A)	2.9435	H(11A)···H(10)^xii	3.0070
H(11A)···H(12B)	2.4248	H(11A)···H(11A)^x	3.3981
H(11B)···H(12A)	2.4247	H(11A)···H(11A)^xii	3.3981
H(11B)···H(12B)	2.9436	H(11A)···H(11B)^x	3.4694
H(13A)···H(14)	2.9227	H(11A)···H(11B)^xii	2.5855
H(13A)···H(15A)	2.5272	H(11A)···H(16A)^ii	2.8206
H(13A)···H(16A)	3.5547	H(11B)···C(9)^xii	3.2146
H(13A)···H(16B)	2.4089	H(11B)···C(10)^xii	3.1923
H(13B)···H(14)	2.4211	H(11B)···C(11)^x	3.3599
H(13B)···H(16B)	3.1209	H(11B)···C(11)^xii	3.3805
H(14)···H(15A)	2.9345	H(11B)···C(15)^xiii	3.2233
H(14)···H(15B)	2.3983	H(11B)···C(16)^xi	3.4476
H(14)···H(16A)	2.4103	H(11B)···C(16)^xiii	3.5454
H(14)···H(16B)	2.9445	H(11B)···H(9A)^xii	2.4769
H(15A)···H(16A)	2.9283	H(11B)···H(10)^iii	3.2057
H(15A)···H(16B)	2.4063	H(11B)···H(10)^xii	3.1032
H(15B)···H(16A)	2.4063	H(11B)···H(11A)^x	2.5855
H(15B)···H(16B)	2.9283	H(11B)···H(11A)^xii	3.4694
O(1)···H(5)^i	2.8414	H(11B)···H(11B)^x	3.3990
O(1)···H(8B)^iv	3.1047	H(11B)···H(11B)^xii	3.3990
O(1)···H(12A)^ii	3.0988	H(11B)···H(15A)^xiii	3.1240
O(1)···H(13A)^i	2.7280	H(11B)···H(15B)^xiii	3.0867
O(1)···H(13B)^i	3.3183	H(11B)···H(16A)^xi	2.9551
O(1)···H(14)^ix	3.5071	H(11B)···H(16B)^xi	3.1149
O(1)···H(15A)^viii	3.4180	H(12A)···O(1)^vi	3.0988
O(1)···H(16B)^i	3.5118	H(12A)···C(8)^vi	3.1867
O(2)···H(14)^ix	2.8256	H(12A)···C(8)^vii	3.1528
O(2)···H(14)^ii	3.4119	H(12A)···C(15)^xiii	3.3551
O(2)···H(15B)^ii	2.8026	H(12A)···H(8A)^vi	2.2901
O(3)···H(5)^iii	3.5191	H(12A)···H(8B)^vi	3.3323
O(3)···H(8A)^vi	3.2735	H(12A)···H(8B)^vii	2.4836
O(3)···H(8C)^vi	3.1385	H(12A)···H(8C)^vii	2.9798
O(3)···H(9B)^iv	3.5250	H(12A)···H(10)^iii	3.2582
O(3)···H(11A)^iv	3.3990	H(12A)···H(15A)^xiii	2.6428
O(3)···H(12B)^iv	2.5506	H(12A)···H(16B)^xi	2.7473
O(3)···H(13B)^iii	2.9009	H(12A)···H(16B)^xiii	3.3943
O(4)···H(8C)^vi	2.7133	H(12B)···O(3)^iii	2.5506
O(4)···H(9B)^iv	3.4870	H(12B)···O(4)^iii	2.6136
O(4)···H(12B)^iv	2.6136	H(12B)···C(3)^iii	2.9854
O(4)···H(13B)^iii	3.0664	H(12B)···C(4)^iii	3.0090
C(1)···H(5)^i	3.1796	H(12B)···C(8)^vii	3.0774
C(1)···H(6)^i	3.4340	H(12B)···C(9)^iii	3.3140
C(1)···H(9B)^iv	3.5419	H(12B)···C(10)^iii	3.4040
C(2)···H(6)^iii	3.4221	H(12B)···C(13)^iii	3.5333
C(2)···H(9B)^iv	3.2847	H(12B)···H(8A)^vi	2.9188
C(2)···H(15B)^ii	3.4133	H(12B)···H(8A)^vii	3.3617
C(3)···H(5)^iii	3.3346	H(12B)···H(8B)^vii	2.8849
C(3)···H(9B)^iv	2.9578	H(12B)···H(8C)^vii	2.5373
C(3)···H(12B)^iv	2.9854	H(12B)···H(9A)^iii	3.4008
C(3)···H(13B)^iii	3.3947	H(12B)···H(10)^iii	2.8516
C(4)···H(6)^i	3.4694	H(12B)···H(13B)^iii	3.5216
C(4)···H(9B)^iv	2.9243	H(12B)···H(14)^iii	3.4659
C(4)···H(12B)^iv	3.0090	H(13A)···O(1)^viii	2.7280
C(4)···H(13B)^iii	3.4883	H(13A)···C(7)^viii	3.2771
C(5)···H(6)^i	2.9995	H(13A)···C(8)^viii	3.5579
C(5)···H(9B)^iv	3.2049	H(13A)···H(8B)^viii	2.8266
C(6)···H(2)^iv	3.3092	H(13A)···H(15A)^iv	3.5566
C(6)···H(5)^i	3.1287	H(13B)···O(1)^viii	3.3183
C(6)···H(6)^i	2.9886	H(13B)···O(3)^iv	2.9009
C(6)···H(9B)^iv	3.4973	H(13B)···O(4)^iv	3.0664
C(7)···H(5)^i	3.0449	H(13B)···C(3)^iv	3.3947
C(7)···H(13A)^i	3.2771	H(13B)···C(4)^iv	3.4883
C(7)···H(14)^ix	3.1360	H(13B)···H(8A)^xiv	3.3436
C(8)···H(10)^ii	3.3147	H(13B)···H(8C)^xiv	3.2663
C(8)···H(12A)^ii	3.1867	H(13B)···H(12B)^iv	3.5216
C(8)···H(12A)^v	3.1528	H(13B)···H(15A)^iv	3.0552
C(8)···H(12B)^v	3.0774	H(14)···O(1)^xiv	3.5071
C(8)···H(13A)^i	3.5579	H(14)···O(2)^xiv	2.8256
C(8)···H(14)^ix	3.0483	H(14)···O(2)^vi	3.4119
C(8)···H(14)^ii	3.2335	H(14)···C(7)^xiv	3.1360
C(8)···H(15B)^ii	3.3790	H(14)···C(8)^xiv	3.0483
C(8)···H(16B)^i	3.3736	H(14)···C(8)^vi	3.2335
C(9)···H(11A)^iv	3.2119	H(14)···H(8A)^xiv	2.6278
C(9)···H(11B)^x	3.2146	H(14)···H(8B)^vi	3.5027
C(9)···H(12B)^iv	3.3140	H(14)···H(8C)^xiv	3.2138
C(9)···H(15B)^ii	3.5885	H(14)···H(8C)^vi	2.4852
C(10)···H(8A)^vi	2.9685	H(14)···H(12B)^iv	3.4659
C(10)···H(11A)^iv	3.3530	H(14)···H(15B)^iv	3.4109
C(10)···H(11A)^x	3.2863	H(15A)···O(1)^i	3.4180
C(10)···H(11B)^x	3.1923	H(15A)···C(12)^xv	3.4231
C(10)···H(12B)^iv	3.4040	H(15A)···C(13)^iii	3.5184
C(10)···H(16B)^xi	3.1033	H(15A)···C(14)^iii	3.4443
C(11)···H(9A)^iii	3.4606	H(15A)···C(16)^iii	3.0775
C(11)···H(9A)^xii	3.3711	H(15A)···H(8B)^viii	3.1979
C(11)···H(10)^iii	2.9874	H(15A)···H(8C)^vi	3.5154
C(11)···H(10)^xii	3.4165	H(15A)···H(11B)^xv	3.1240
C(11)···H(11A)^x	3.0519	H(15A)···H(12A)^xv	2.6428
C(11)···H(11B)^x	3.3805	H(15A)···H(13A)^iii	3.5566
C(11)···H(11B)^xii	3.3599	H(15A)···H(13B)^iii	3.0552
C(11)···H(16B)^xi	3.4832	H(15A)···H(16A)^iii	3.1351
C(12)···H(8A)^vi	2.6574	H(15A)···H(16B)^iii	2.7897
C(12)···H(8B)^vii	3.0389	H(15B)···O(2)^vi	2.8026
C(12)···H(8C)^vii	3.1519	H(15B)···C(2)^vi	3.4133
C(12)···H(10)^iii	3.0231	H(15B)···C(8)^vi	3.3790
C(12)···H(15A)^xiii	3.4231	H(15B)···C(9)^vi	3.5885
C(12)···H(16B)^xi	3.2856	H(15B)···C(14)^iii	3.5496
C(13)···H(8C)^vi	3.3878	H(15B)···C(16)^iii	3.1951
C(13)···H(12B)^iv	3.5333	H(15B)···H(2)^vi	2.5642
C(13)···H(15A)^iv	3.5184	H(15B)···H(8C)^vi	2.9371
C(14)···H(8A)^xiv	3.4558	H(15B)···H(9A)^vi	2.8173
C(14)···H(8C)^vi	2.8694	H(15B)···H(9B)^vi	3.4627
C(14)···H(15A)^iv	3.4443	H(15B)···H(11B)^xv	3.0867
C(14)···H(15B)^iv	3.5496	H(15B)···H(14)^iii	3.4109
C(15)···H(2)^vi	3.5201	H(15B)···H(16A)^iii	2.7897
C(15)···H(8C)^vi	3.1254	H(15B)···H(16B)^iii	3.3623
C(15)···H(9A)^vi	3.5231	H(16A)···C(15)^iv	3.3656
C(15)···H(11B)^xv	3.2233	H(16A)···H(2)^xiv	3.3954
C(15)···H(12A)^xv	3.3551	H(16A)···H(9A)^xiv	3.2426
C(15)···H(16A)^iii	3.3656	H(16A)···H(9A)^vi	3.4014
C(15)···H(16B)^iii	3.4736	H(16A)···H(9B)^vi	3.1460
C(16)···H(8B)^viii	3.5151	H(16A)···H(10)^xvi	3.0514
C(16)···H(10)^xvi	3.0002	H(16A)···H(11A)^vi	2.8206
C(16)···H(11A)^vi	3.5854	H(16A)···H(11B)^xvi	2.9551
C(16)···H(11B)^xvi	3.4476	H(16A)···H(15A)^iv	3.1351
C(16)···H(11B)^xv	3.5454	H(16A)···H(15B)^iv	2.7897
C(16)···H(15A)^iv	3.0775	H(16B)···O(1)^viii	3.5118
C(16)···H(15B)^iv	3.1951	H(16B)···C(8)^viii	3.3736
H(2)···C(6)^iii	3.3092	H(16B)···C(10)^xvi	3.1033
H(2)···C(15)^ii	3.5201	H(16B)···C(11)^xvi	3.4832
H(2)···H(6)^iii	3.3350	H(16B)···C(12)^xvi	3.2856
H(2)···H(15B)^ii	2.5642	H(16B)···C(15)^iv	3.4736
H(2)···H(16A)^ix	3.3954	H(16B)···H(8A)^viii	3.1585
H(5)···O(1)^viii	2.8414	H(16B)···H(8B)^viii	2.7043
H(5)···O(3)^iv	3.5191	H(16B)···H(10)^xvi	2.3527
H(5)···C(1)^viii	3.1796	H(16B)···H(11B)^xvi	3.1149
H(5)···C(3)^iv	3.3346	H(16B)···H(12A)^xvi	2.7473
H(5)···C(6)^viii	3.1287	H(16B)···H(12A)^xv	3.3943
H(5)···C(7)^viii	3.0449	H(16B)···H(15A)^iv	2.7897
H(5)···H(6)^viii	2.9456	H(16B)···H(15B)^iv	3.3623
H(5)···H(6)^i	3.2433
C(7)—O(2)—C(8)	116.68 (12)	H(8A)—C(8)—H(8B)	109.475
C(3)—O(3)—C(9)	116.11 (9)	H(8A)—C(8)—H(8C)	109.468
C(4)—O(4)—C(13)	117.33 (10)	H(8B)—C(8)—H(8C)	109.472
C(2)—C(1)—C(6)	120.17 (12)	O(3)—C(9)—H(9A)	109.948
C(2)—C(1)—C(7)	120.42 (11)	O(3)—C(9)—H(9B)	109.953
C(6)—C(1)—C(7)	119.40 (11)	C(10)—C(9)—H(9A)	109.961
C(1)—C(2)—C(3)	120.30 (12)	C(10)—C(9)—H(9B)	109.956
O(3)—C(3)—C(2)	124.69 (11)	H(9A)—C(9)—H(9B)	108.328
O(3)—C(3)—C(4)	115.80 (10)	C(9)—C(10)—H(10)	116.366
C(2)—C(3)—C(4)	119.50 (11)	C(11)—C(10)—H(10)	116.367
O(4)—C(4)—C(3)	115.03 (11)	C(12)—C(10)—H(10)	116.375
O(4)—C(4)—C(5)	125.26 (12)	C(10)—C(11)—H(11A)	117.777
C(3)—C(4)—C(5)	119.71 (12)	C(10)—C(11)—H(11B)	117.773
C(4)—C(5)—C(6)	120.21 (12)	C(12)—C(11)—H(11A)	117.769
C(1)—C(6)—C(5)	120.09 (12)	C(12)—C(11)—H(11B)	117.772
O(1)—C(7)—O(2)	123.48 (12)	H(11A)—C(11)—H(11B)	114.909
O(1)—C(7)—C(1)	125.10 (12)	C(10)—C(12)—H(12A)	117.744
O(2)—C(7)—C(1)	111.42 (11)	C(10)—C(12)—H(12B)	117.746
O(3)—C(9)—C(10)	108.69 (9)	C(11)—C(12)—H(12A)	117.745
C(9)—C(10)—C(11)	116.52 (11)	C(11)—C(12)—H(12B)	117.747
C(9)—C(10)—C(12)	119.44 (11)	H(12A)—C(12)—H(12B)	114.871
C(11)—C(10)—C(12)	59.78 (9)	O(4)—C(13)—H(13A)	110.344
C(10)—C(11)—C(12)	59.97 (9)	O(4)—C(13)—H(13B)	110.344
C(10)—C(12)—C(11)	60.25 (9)	C(14)—C(13)—H(13A)	110.360
O(4)—C(13)—C(14)	106.85 (12)	C(14)—C(13)—H(13B)	110.358
C(13)—C(14)—C(15)	117.46 (14)	H(13A)—C(13)—H(13B)	108.585
C(13)—C(14)—C(16)	117.91 (14)	C(13)—C(14)—H(14)	116.594
C(15)—C(14)—C(16)	59.51 (12)	C(15)—C(14)—H(14)	116.598
C(14)—C(15)—C(16)	60.61 (12)	C(16)—C(14)—H(14)	116.603
C(14)—C(16)—C(15)	59.89 (12)	C(14)—C(15)—H(15A)	117.706
C(1)—C(2)—H(2)	119.856	C(14)—C(15)—H(15B)	117.711
C(3)—C(2)—H(2)	119.846	C(16)—C(15)—H(15A)	117.702
C(4)—C(5)—H(5)	119.900	C(16)—C(15)—H(15B)	117.720
C(6)—C(5)—H(5)	119.892	H(15A)—C(15)—H(15B)	114.826
C(1)—C(6)—H(6)	119.947	C(14)—C(16)—H(16A)	117.785
C(5)—C(6)—H(6)	119.960	C(14)—C(16)—H(16B)	117.794
O(2)—C(8)—H(8A)	109.469	C(15)—C(16)—H(16A)	117.781
O(2)—C(8)—H(8B)	109.474	C(15)—C(16)—H(16B)	117.788
O(2)—C(8)—H(8C)	109.470	H(16A)—C(16)—H(16B)	114.905
C(8)—O(2)—C(7)—O(1)	−2.4 (2)	C(2)—C(3)—C(4)—O(4)	179.31 (11)
C(8)—O(2)—C(7)—C(1)	177.99 (12)	C(2)—C(3)—C(4)—C(5)	−1.41 (19)
C(3)—O(3)—C(9)—C(10)	160.99 (10)	O(4)—C(4)—C(5)—C(6)	179.71 (12)
C(9)—O(3)—C(3)—C(2)	11.35 (17)	C(3)—C(4)—C(5)—C(6)	0.5 (2)
C(9)—O(3)—C(3)—C(4)	−167.98 (11)	C(4)—C(5)—C(6)—C(1)	0.7 (2)
C(4)—O(4)—C(13)—C(14)	177.72 (12)	O(3)—C(9)—C(10)—C(11)	153.94 (11)
C(13)—O(4)—C(4)—C(3)	177.39 (11)	O(3)—C(9)—C(10)—C(12)	85.31 (14)
C(13)—O(4)—C(4)—C(5)	−1.83 (19)	C(9)—C(10)—C(11)—C(12)	−110.19 (13)
C(2)—C(1)—C(6)—C(5)	−1.01 (19)	C(9)—C(10)—C(12)—C(11)	105.34 (13)
C(6)—C(1)—C(2)—C(3)	0.09 (19)	C(11)—C(10)—C(12)—C(11)	0.0
C(2)—C(1)—C(7)—O(1)	175.66 (13)	C(12)—C(10)—C(11)—C(12)	0.0
C(2)—C(1)—C(7)—O(2)	−4.76 (17)	C(10)—C(11)—C(12)—C(10)	0.0
C(7)—C(1)—C(2)—C(3)	−179.24 (12)	O(4)—C(13)—C(14)—C(15)	−76.77 (16)
C(6)—C(1)—C(7)—O(1)	−3.7 (2)	O(4)—C(13)—C(14)—C(16)	−144.94 (14)
C(6)—C(1)—C(7)—O(2)	175.90 (12)	C(13)—C(14)—C(15)—C(16)	−107.83 (16)
C(7)—C(1)—C(6)—C(5)	178.33 (12)	C(13)—C(14)—C(16)—C(15)	107.08 (17)
C(1)—C(2)—C(3)—O(3)	−178.20 (12)	C(15)—C(14)—C(16)—C(15)	0.0
C(1)—C(2)—C(3)—C(4)	1.11 (19)	C(16)—C(14)—C(15)—C(16)	0.0
O(3)—C(3)—C(4)—O(4)	−1.31 (17)	C(14)—C(15)—C(16)—C(14)	0.0
O(3)—C(3)—C(4)—C(5)	177.96 (11)

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x+3/2, −y+1, z+1/2; (iii) x+1, y, z; (iv) x−1, y, z; (v) −x+5/2, −y+1, z+1/2; (vi) −x+3/2, −y+1, z−1/2; (vii) −x+5/2, −y+1, z−1/2; (viii) x−1/2, −y+3/2, −z+1; (ix) −x+1/2, −y+1, z+1/2; (x) x−1/2, −y+1/2, −z+1; (xi) −x+1, y−1/2, −z+1/2; (xii) x+1/2, −y+1/2, −z+1; (xiii) −x+2, y−1/2, −z+1/2; (xiv) −x+1/2, −y+1, z−1/2; (xv) −x+2, y+1/2, −z+1/2; (xvi) −x+1, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O3^iii	0.99	2.55	3.4073 (18)	145

Symmetry code: (iii) x+1, y, z.