3,9-Di­methoxy-6a,11a-di­hydro-6H-benzo­[4,5]­furo­[3,2-c]­chromene-4,10-diol monohydrate

In the title compound, also known as 4,10-di­hydroxy-3,9-di­methoxy­pterocarpan monohydrate and melilotocarpan D monohydrate, C₁₇H₁₆O₆·H₂O, and the tetra­hydro­pyran ring adopts a distorted envelope conformation and tetra­hydro­furan ring displays an envelope conformation. The chroman moiety and benzo­furan ring system are inclined at an angle of 45.81 (5)°. The molecular structure is stabilized by O—H...O intramolecular interactions. In the crystal structure, the O—H...O intermolecular hydrogen bonds link the mol­ecules to form networks parallel to the ac plane; these are interconnected along the b axis by C—H...O interactions.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.038
• wR factor = 0.095
• Data-to-parameter ratio = 8.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           30.49
         From the CIF: _reflns_number_total               2412
         Count of symmetry unique reflns         2533
         Completeness (_total/calc)             95.22%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present           no
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.

---

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SHELXTL (Siemens, 1996) and SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: PLATON and SHELXL97.

3,9-Dimethoxy-6a,11a-dihydro-6H-benzo[4,5]furo[3,2-c]chromene-4,10-diol monohydrate

Crystal data

C17H16O6·H2O	F(000) = 352
Mr = 334.31	Dx = 1.391 Mg m^−3
Monoclinic, P21	Melting point = 428–430 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.9036 (2) Å	Cell parameters from 105 reflections
b = 12.3647 (3) Å	θ = 2.2–30.5°
c = 9.5054 (1) Å	µ = 0.11 mm^−1
β = 100.454 (1)°	T = 295 K
V = 797.92 (3) Å^3	Plate, colourless
Z = 2	0.3 × 0.3 × 0.1 mm

Data collection

Bruker SMART CCD diffractometer	2412 independent reflections
Radiation source: fine-focus sealed tube	2036 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 30.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→9
Tmin = 0.962, Tmax = 0.986	k = −17→17
5907 measured reflections	l = −10→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)] = 0.038	Hydrogen site location: difference Fourier map
wR(F^2) = 0.095	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0498P)^2 + 0.0697P] where P = (Fo^2 + 2Fc^2)/3
2412 reflections	(Δ/σ)max = 0.001
289 parameters	Δρmax = 0.17 e Å^−3
1 restraint	Δρmin = −0.18 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
C1	−0.2422 (3)	0.5334 (2)	0.3087 (2)	0.0412 (5)
H1	−0.251 (4)	0.529 (3)	0.409 (3)	0.051 (8)*
C2	−0.3715 (3)	0.6006 (2)	0.2186 (3)	0.0408 (5)
H2	−0.460 (5)	0.639 (3)	0.254 (3)	0.050 (8)*
C3	−0.3576 (3)	0.60943 (17)	0.0744 (2)	0.0358 (4)
O3	−0.4788 (3)	0.66976 (16)	−0.02575 (18)	0.0485 (4)
C3'	−0.6290 (6)	0.7316 (4)	0.0191 (4)	0.0714 (10)
H3'A	−0.726 (6)	0.687 (4)	0.057 (5)	0.087 (13)*
H3'B	−0.566 (5)	0.784 (3)	0.092 (4)	0.072 (11)*
H3'C	−0.691 (7)	0.772 (4)	−0.056 (5)	0.096 (14)*
C4	−0.2100 (3)	0.55288 (17)	0.0223 (2)	0.0320 (4)
O4	−0.1988 (2)	0.56457 (15)	−0.11943 (16)	0.0404 (4)
H4	−0.094 (5)	0.547 (3)	−0.133 (3)	0.056 (9)*
C4A	−0.0812 (3)	0.48569 (17)	0.1137 (2)	0.0323 (4)
O5	0.0530 (2)	0.43102 (15)	0.05049 (16)	0.0442 (4)
C6	0.2204 (4)	0.3904 (2)	0.1495 (2)	0.0433 (5)
H6A	0.289 (4)	0.344 (3)	0.097 (3)	0.055 (8)*
H6B	0.300 (4)	0.447 (2)	0.186 (3)	0.039 (7)*
C6A	0.1607 (4)	0.32531 (18)	0.2700 (3)	0.0412 (5)
H6C	0.086 (5)	0.261 (3)	0.232 (3)	0.053 (8)*
C6B	0.3393 (4)	0.30549 (18)	0.3848 (2)	0.0377 (5)
C7	0.4971 (4)	0.23542 (19)	0.3929 (3)	0.0442 (5)
H7	0.502 (4)	0.182 (3)	0.317 (3)	0.057 (9)*
C8	0.6550 (4)	0.24471 (18)	0.5077 (3)	0.0403 (5)
H8	0.764 (4)	0.199 (3)	0.517 (3)	0.047 (8)*
C9	0.6543 (3)	0.32578 (17)	0.6091 (2)	0.0334 (4)
O9	0.8041 (2)	0.34654 (15)	0.72279 (18)	0.0447 (4)
C9'	0.9776 (4)	0.2813 (3)	0.7380 (3)	0.0490 (6)
H9'A	1.068 (5)	0.307 (3)	0.823 (3)	0.058 (9)*
H9'B	0.939 (5)	0.207 (4)	0.741 (4)	0.072 (10)*
H9'C	1.041 (5)	0.290 (3)	0.652 (4)	0.068 (10)*
C10	0.4926 (3)	0.39682 (17)	0.6031 (2)	0.0322 (4)
O10	0.4845 (3)	0.47394 (14)	0.70506 (18)	0.0460 (4)
H10	0.599 (5)	0.493 (3)	0.754 (3)	0.053 (8)*
C10A	0.3382 (3)	0.38446 (16)	0.4890 (2)	0.0328 (4)
O11	0.1733 (2)	0.45040 (13)	0.46465 (15)	0.0381 (4)
C11A	0.0320 (3)	0.39450 (19)	0.3505 (2)	0.0363 (4)
H11A	−0.047 (4)	0.350 (2)	0.401 (3)	0.035 (6)*
C11B	−0.0959 (3)	0.47511 (17)	0.2584 (2)	0.0340 (4)
O1W	0.1125 (4)	0.5613 (2)	0.7443 (3)	0.0690 (6)
H1W	0.220 (10)	0.581 (6)	0.791 (7)	0.15 (3)*
H2W	0.126 (13)	0.521 (9)	0.664 (11)	0.25 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0369 (10)	0.0528 (14)	0.0351 (11)	−0.0009 (10)	0.0094 (8)	−0.0001 (9)
C2	0.0347 (10)	0.0483 (13)	0.0410 (12)	0.0056 (9)	0.0111 (9)	−0.0046 (9)
C3	0.0315 (9)	0.0363 (10)	0.0391 (11)	0.0006 (8)	0.0050 (8)	−0.0021 (8)
O3	0.0452 (9)	0.0562 (11)	0.0439 (10)	0.0203 (8)	0.0077 (7)	0.0038 (8)
C3'	0.0633 (19)	0.084 (2)	0.070 (2)	0.040 (2)	0.0191 (17)	0.011 (2)
C4	0.0306 (8)	0.0338 (10)	0.0303 (9)	−0.0026 (8)	0.0022 (7)	−0.0053 (8)
O4	0.0377 (7)	0.0521 (9)	0.0308 (7)	0.0111 (8)	0.0047 (6)	−0.0003 (7)
C4A	0.0290 (8)	0.0334 (10)	0.0336 (9)	−0.0008 (8)	0.0032 (7)	−0.0050 (8)
O5	0.0437 (8)	0.0551 (10)	0.0317 (7)	0.0177 (8)	0.0016 (6)	−0.0043 (7)
C6	0.0393 (11)	0.0524 (14)	0.0360 (11)	0.0136 (11)	0.0012 (9)	−0.0058 (10)
C6A	0.0446 (12)	0.0315 (10)	0.0419 (12)	−0.0001 (9)	−0.0071 (9)	−0.0058 (9)
C6B	0.0420 (11)	0.0310 (10)	0.0369 (11)	0.0008 (8)	−0.0017 (9)	−0.0011 (8)
C7	0.0529 (14)	0.0323 (10)	0.0439 (12)	0.0090 (10)	−0.0006 (10)	−0.0064 (9)
C8	0.0439 (12)	0.0324 (11)	0.0433 (12)	0.0096 (9)	0.0048 (9)	0.0021 (9)
C9	0.0329 (9)	0.0325 (10)	0.0338 (10)	0.0040 (8)	0.0035 (7)	0.0042 (8)
O9	0.0374 (8)	0.0474 (9)	0.0445 (9)	0.0127 (7)	−0.0051 (6)	−0.0040 (7)
C9'	0.0402 (12)	0.0570 (16)	0.0470 (14)	0.0174 (12)	0.0008 (10)	0.0033 (12)
C10	0.0344 (9)	0.0304 (9)	0.0315 (9)	0.0039 (8)	0.0056 (7)	0.0000 (8)
O10	0.0409 (8)	0.0494 (10)	0.0428 (8)	0.0151 (7)	−0.0052 (7)	−0.0138 (7)
C10A	0.0327 (9)	0.0330 (10)	0.0319 (10)	0.0031 (8)	0.0035 (8)	0.0024 (8)
O11	0.0344 (7)	0.0438 (9)	0.0340 (7)	0.0085 (7)	0.0000 (6)	−0.0042 (6)
C11A	0.0329 (9)	0.0393 (11)	0.0342 (10)	−0.0049 (9)	−0.0008 (8)	0.0043 (9)
C11B	0.0298 (9)	0.0371 (11)	0.0335 (9)	−0.0039 (8)	0.0015 (7)	−0.0001 (8)
O1W	0.0549 (11)	0.0826 (16)	0.0757 (15)	0.0063 (13)	0.0286 (11)	−0.0065 (14)

Geometric parameters (Å, º)

C1—C2	1.394 (3)	C6A—H6C	0.98 (3)
C1—C11B	1.394 (3)	C6B—C7	1.383 (3)
C1—H1	0.97 (3)	C6B—C10A	1.392 (3)
C2—C3	1.396 (3)	C7—C8	1.400 (4)
C2—H2	0.89 (3)	C7—H7	0.99 (3)
C3—O3	1.369 (3)	C8—C9	1.391 (3)
C3—C4	1.399 (3)	C8—H8	0.93 (3)
O3—C3'	1.415 (3)	C9—O9	1.378 (3)
C3'—H3'A	0.99 (5)	C9—C10	1.414 (3)
C3'—H3'B	0.99 (4)	O9—C9'	1.429 (3)
C3'—H3'C	0.91 (5)	C9'—H9'A	0.98 (3)
C4—O4	1.371 (2)	C9'—H9'B	0.96 (4)
C4—C4A	1.398 (3)	C9'—H9'C	1.01 (4)
O4—H4	0.79 (3)	C10—O10	1.368 (3)
C4A—O5	1.370 (2)	C10—C10A	1.384 (3)
C4A—C11B	1.404 (3)	O10—H10	0.87 (3)
O5—C6	1.442 (3)	C10A—O11	1.385 (2)
C6—C6A	1.517 (4)	O11—C11A	1.491 (3)
C6—H6A	0.95 (3)	C11A—C11B	1.503 (3)
C6—H6B	0.92 (3)	C11A—H11A	0.96 (3)
C6A—C6B	1.511 (3)	O1W—H1W	0.83 (7)
C6A—C11A	1.534 (3)	O1W—H2W	0.93 (11)
C2—C1—C11B	121.4 (2)	C7—C6B—C6A	132.3 (2)
C2—C1—H1	119.4 (18)	C10A—C6B—C6A	106.92 (19)
C11B—C1—H1	119.2 (18)	C6B—C7—C8	119.1 (2)
C1—C2—C3	119.9 (2)	C6B—C7—H7	121.0 (18)
C1—C2—H2	120 (2)	C8—C7—H7	119.8 (18)
C3—C2—H2	120 (2)	C9—C8—C7	119.9 (2)
O3—C3—C2	125.69 (19)	C9—C8—H8	118.4 (18)
O3—C3—C4	114.75 (18)	C7—C8—H8	121.6 (18)
C2—C3—C4	119.55 (19)	O9—C9—C8	125.55 (19)
C3—O3—C3'	118.3 (2)	O9—C9—C10	113.01 (18)
O3—C3'—H3'A	113 (3)	C8—C9—C10	121.44 (19)
O3—C3'—H3'B	108 (2)	C9—O9—C9'	118.07 (19)
H3'A—C3'—H3'B	111 (3)	O9—C9'—H9'A	107.4 (19)
O3—C3'—H3'C	109 (3)	O9—C9'—H9'B	108 (2)
H3'A—C3'—H3'C	110 (4)	H9'A—C9'—H9'B	115 (3)
H3'B—C3'—H3'C	106 (4)	O9—C9'—H9'C	110 (2)
O4—C4—C4A	122.05 (17)	H9'A—C9'—H9'C	109 (3)
O4—C4—C3	118.03 (18)	H9'B—C9'—H9'C	107 (3)
C4A—C4—C3	119.92 (17)	O10—C10—C10A	120.49 (18)
C4—O4—H4	110 (2)	O10—C10—C9	122.55 (18)
O5—C4A—C4	115.14 (17)	C10A—C10—C9	116.95 (18)
O5—C4A—C11B	123.94 (18)	C10—O10—H10	115 (2)
C4—C4A—C11B	120.91 (18)	C10—C10A—O11	123.97 (18)
C4A—O5—C6	114.29 (16)	C10—C10A—C6B	122.16 (18)
O5—C6—C6A	112.5 (2)	O11—C10A—C6B	113.84 (18)
O5—C6—H6A	106.5 (18)	C10A—O11—C11A	104.96 (15)
C6A—C6—H6A	108.4 (19)	O11—C11A—C11B	110.74 (18)
O5—C6—H6B	109.8 (17)	O11—C11A—C6A	105.08 (16)
C6A—C6—H6B	110.2 (16)	C11B—C11A—C6A	114.31 (18)
H6A—C6—H6B	109 (2)	O11—C11A—H11A	104.9 (15)
C6B—C6A—C6	109.4 (2)	C11B—C11A—H11A	110.2 (15)
C6B—C6A—C11A	101.60 (17)	C6A—C11A—H11A	111.1 (15)
C6—C6A—C11A	110.01 (19)	C1—C11B—C4A	118.25 (19)
C6B—C6A—H6C	116.2 (19)	C1—C11B—C11A	121.94 (19)
C6—C6A—H6C	110.5 (17)	C4A—C11B—C11A	119.56 (19)
C11A—C6A—H6C	108.6 (18)	H1W—O1W—H2W	112 (7)
C7—C6B—C10A	120.3 (2)
C11B—C1—C2—C3	0.8 (4)	C8—C9—C10—O10	176.9 (2)
C1—C2—C3—O3	177.9 (2)	O9—C9—C10—C10A	177.63 (19)
C1—C2—C3—C4	−1.8 (3)	C8—C9—C10—C10A	−2.2 (3)
C2—C3—O3—C3'	1.8 (4)	O10—C10—C10A—O11	3.6 (3)
C4—C3—O3—C3'	−178.4 (3)	C9—C10—C10A—O11	−177.20 (19)
O3—C3—C4—O4	1.2 (3)	O10—C10—C10A—C6B	−178.7 (2)
C2—C3—C4—O4	−179.1 (2)	C9—C10—C10A—C6B	0.5 (3)
O3—C3—C4—C4A	−177.93 (19)	C7—C6B—C10A—C10	0.4 (3)
C2—C3—C4—C4A	1.8 (3)	C6A—C6B—C10A—C10	−173.3 (2)
O4—C4—C4A—O5	−1.4 (3)	C7—C6B—C10A—O11	178.3 (2)
C3—C4—C4A—O5	177.65 (19)	C6A—C6B—C10A—O11	4.6 (3)
O4—C4—C4A—C11B	−179.96 (19)	C10—C10A—O11—C11A	−168.9 (2)
C3—C4—C4A—C11B	−0.9 (3)	C6B—C10A—O11—C11A	13.2 (2)
C4—C4A—O5—C6	161.4 (2)	C10A—O11—C11A—C11B	−149.01 (18)
C11B—C4A—O5—C6	−20.1 (3)	C10A—O11—C11A—C6A	−25.1 (2)
C4A—O5—C6—C6A	51.5 (3)	C6B—C6A—C11A—O11	26.9 (2)
O5—C6—C6A—C6B	−168.24 (19)	C6—C6A—C11A—O11	−88.9 (2)
O5—C6—C6A—C11A	−57.4 (3)	C6B—C6A—C11A—C11B	148.56 (19)
C6—C6A—C6B—C7	−76.0 (3)	C6—C6A—C11A—C11B	32.7 (3)
C11A—C6A—C6B—C7	167.7 (3)	C2—C1—C11B—C4A	0.1 (3)
C6—C6A—C6B—C10A	96.7 (2)	C2—C1—C11B—C11A	−174.1 (2)
C11A—C6A—C6B—C10A	−19.5 (2)	O5—C4A—C11B—C1	−178.5 (2)
C10A—C6B—C7—C8	0.3 (4)	C4—C4A—C11B—C1	−0.1 (3)
C6A—C6B—C7—C8	172.2 (2)	O5—C4A—C11B—C11A	−4.1 (3)
C6B—C7—C8—C9	−2.0 (4)	C4—C4A—C11B—C11A	174.31 (18)
C7—C8—C9—O9	−176.8 (2)	O11—C11A—C11B—C1	−71.0 (2)
C7—C8—C9—C10	3.0 (3)	C6A—C11A—C11B—C1	170.5 (2)
C8—C9—O9—C9'	1.2 (3)	O11—C11A—C11B—C4A	114.8 (2)
C10—C9—O9—C9'	−178.6 (2)	C6A—C11A—C11B—C4A	−3.6 (3)
O9—C9—C10—O10	−3.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5	0.79 (3)	2.34 (3)	2.709 (2)	110 (3)
O10—H10···O9	0.87 (3)	2.35 (3)	2.691 (2)	103 (2)
O1W—H2W···O11	0.93 (11)	2.16 (11)	3.086 (3)	171 (9)
O1W—H1W···O10	0.83 (7)	2.51 (7)	2.872 (3)	108 (6)
O1W—H2W···O10	0.93 (9)	2.50 (9)	2.872 (2)	104 (6)
O10—H10···O4^i	0.87 (3)	1.89 (3)	2.738 (2)	163 (3)
O4—H4···O1W^ii	0.79 (3)	2.01 (3)	2.703 (3)	147 (3)
C7—H7···O10^iii	0.99 (3)	2.58 (4)	3.373 (3)	138 (2)

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