Four inter­penetrating hydrogen-bonded three-dimensional networks in divanillin

The crystal structure of divainillin (systematic name: 6,6′-dihy­droxy-5,5′-di­meth­oxy-[1,1′-biphen­yl]-3,3′-dicarbaldehyde), C₁₆H₁₄O₆, was determined from laboratory powder X-ray diffraction data using the software EXPO2013 (direct methods) and WinPSSP (direct-space approach). Divanillin mol­ecules crystallize in the ortho­rhom­bic space group Pba2 (No. 32), with two mol­ecules per unit cell (Z′ = ). Each divanillin mol­ecule, with twofold symmetry, is linked through strong alcohol–aldehyde hydrogen bonds to four equivalent mol­ecules, defining a three-dimensional hydrogen-bonding network, with rings made up of six divanillin units (a diamond-like arrangement). Each mol­ecule is also connected through π–π inter­actions to a translation-equivalent mol­ecule along c. Four consecutive mol­ecules stacked along [001] belong to four different three-dimensional hydrogen-bonding networks defining a quadruple array of inter­penetrating networks. This complex hydrogen-bonding array is proposed as an explanation for the aging process experienced by divanillin powders.

Computing details

Program(s) used to solve structure: direct methods; program(s) used to refine structure: GSAS.

6,6'-Dihydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-3,3'-dicarbaldehyde

Crystal data

C16H14O6	V = 674.79 (1) Å^3
Mr = 302.28	Z = 2
Orthorhombic, Pba2	Dx = 1.488 Mg m^−3
Hall symbol: P 2 -2ab	CuKα1, CuKα2 radiation, λ = 1.540598, 1.544426 Å
a = 12.28767 (11) Å	T = 293 K
b = 13.97200 (18) Å	light yellow
c = 3.93043 (4) Å	flat_sheet, 20 × 0.5 mm

Data collection

Rigaku ULTIMA IV diffractometer	Data collection mode: reflection, θ-θ geometry
Radiation source: sealed X-ray tube	Scan method: step
Curved Ge crystal monochromator	2θmin = 4.994°, 2θmax = 108.104°, 2θstep = 0.01°
Specimen mounting: Glass sample holder with a 20x20x0.5 mm indentation for the sample

Refinement

Least-squares matrix: full	116 parameters
Rp = 0.035	56 restraints
Rwp = 0.049	H-atom parameters not defined?
Rexp = 0.022	(Δ/σ)max = 0.02
R(F^2) = 0.05040	Background function: GSAS Background function number 7 with 36 terms. Linear interpolation 1: 746.117 2: 636.840 3: 820.260 4: 1087.66 5: 1340.36 6: 1694.77 7: 1939.95 8: 1780.04 9: 1470.80 10: 1469.09 11: 1171.58 12: 1220.23 13: 1099.08 14: 1133.77 15: 1082.14 16: 1040.03 17: 920.035 18: 960.677 19: 942.495 20: 867.667 21: 833.747 22: 817.667 23: 803.239 24: 778.713 25: 734.737 26: 743.098 27: 717.039 28: 697.800 29: 637.240 30: 613.791 31: 574.878 32: 571.899 33: 544.400 34: 538.892 35: 514.075 36: 523.654
10312 data points	Preferred orientation correction: March-Dollase AXIS 1 Ratio= 0.77078 h= 1.000 k= 0.000 l= 0.000 Prefered orientation correction range: Min= 0.67671, Max= 2.18374
Profile function: CW Profile function number 3 with 19 terms pseudo-Voigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. #1(GU) = 280.285 #2(GV) = -19.927 #3(GW) = 18.038 #4(GP) = 0.000 #5(LX) = 5.378 #6(LY) = 0.000 #7(S/L) = 0.0295 #8(H/L) = 0.0301 #9(trns) = 8.98 #10(shft)= 0.0000 #11(stec)= 0.00 #12(ptec)= 0.00 #13(sfec)= 0.00 #14(L11) = 0.026 #15(L22) = -0.035 #16(L33) = 2.037 #17(L12) = -0.015 #18(L13) = 0.214 #19(L23) = -0.135 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0

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

	x	y	z	Uiso*/Ueq
O1	0.13485 (8)	0.31375 (11)	0.8931 (7)	0.0784 (8)*
O2	0.20440 (9)	0.64551 (12)	0.2917 (7)	0.0663 (8)*
O3	0.42399 (10)	0.64420 (7)	0.2402 (5)	0.0707 (7)*
C1	0.27806 (12)	0.41290 (11)	0.6785 (6)	0.0470 (13)*
C2	0.21080 (10)	0.48780 (17)	0.5520 (9)	0.0493 (11)*
C3	0.26177 (13)	0.56830 (16)	0.4107 (11)	0.0598 (13)*
C4	0.37574 (11)	0.57070 (11)	0.4036 (6)	0.0607 (14)*
C5	0.44038 (11)	0.49460 (17)	0.5	0.0375 (12)*
C6	0.38971 (11)	0.41765 (11)	0.6453 (6)	0.0532 (13)*
C7	0.23099 (9)	0.32760 (9)	0.8444 (6)	0.0808 (14)*
C8	0.08772 (11)	0.64343 (8)	0.3383 (3)	0.0567 (9)*
H2	0.13565 (13)	0.4859 (6)	0.579 (2)	0.0592 (13)*
H3	0.4013 (4)	0.70692 (13)	0.2997 (15)	0.0848 (9)*
H6	0.4332 (2)	0.37013 (16)	0.7397 (10)	0.0638 (15)*
H7	0.2795 (2)	0.27727 (16)	0.9036 (16)	0.0969 (16)*
H8A	0.0593 (3)	0.70318 (13)	0.2656 (12)	0.0681 (11)*
H8B	0.0718 (4)	0.6328 (5)	0.5720 (4)	0.0681 (11)*
H8C	0.0553 (3)	0.59394 (16)	0.2069 (7)	0.0681 (11)*

Geometric parameters (Å, º)

C3—C2	1.402 (4)	C7—C1	1.477 (2)
C3—C4	1.401 (2)	C7—O1	1.2124 (16)
C3—O2	1.371 (3)	C7—H7	0.951 (3)
C2—C3	1.402 (4)	O1—C7	1.2124 (16)
C2—C1	1.423 (3)	C8—O2	1.4456 (18)
C2—H2	0.930 (2)	C8—H8A	0.949 (3)
C1—C2	1.423 (3)	C8—H8B	0.951 (3)
C1—C6	1.380 (2)	C8—H8C	0.951 (3)
C1—C7	1.477 (2)	H6—C6	0.929 (3)
C6—C1	1.380 (2)	H2—C2	0.930 (2)
C6—C5	1.367 (3)	H8A—C8	0.949 (3)
C6—H6	0.929 (3)	H8A—H8B	1.562 (6)
C5—C6	1.367 (3)	H8A—H8C	1.545 (3)
C5—C5^i	1.473 (3)	H8B—C8	0.951 (3)
C5—C4	1.380 (3)	H8B—H8A	1.562 (6)
C4—C3	1.401 (2)	H8B—H8C	1.548 (4)
C4—C5	1.380 (3)	H8C—C8	0.951 (3)
C4—O3	1.349 (2)	H8C—H8A	1.545 (3)
O3—C4	1.349 (2)	H8C—H8B	1.548 (4)
O3—H3	0.949 (3)	H7—C7	0.951 (3)
O2—C3	1.371 (3)	H3—O3	0.949 (3)
O2—C8	1.4456 (18)
C2—C3—C4	118.3 (2)	C3—C4—C5	123.45 (17)
C2—C3—O2	122.46 (15)	C3—C4—O3	117.85 (18)
C4—C3—O2	119.2 (2)	C5—C4—O3	117.67 (13)
C3—C2—C1	117.96 (13)	C4—O3—H3	117.2 (3)
C3—C2—H2	120.7 (5)	C3—O2—C8	116.80 (16)
C1—C2—H2	121.1 (6)	C1—C7—O1	125.47 (15)
C2—C1—C6	120.60 (16)	C1—C7—H7	117.4 (2)
C2—C1—C7	121.35 (13)	O1—C7—H7	117.0 (2)
C6—C1—C7	118.04 (14)	O2—C8—H8A	108.0 (3)
C1—C6—C5	122.01 (15)	O2—C8—H8B	109.2 (4)
C1—C6—H6	119.9 (2)	O2—C8—H8C	111.2 (3)
C5—C6—H6	117.9 (2)	H8A—C8—H8B	110.6 (5)
C6—C5—C5^i	122.2 (2)	H8A—C8—H8C	108.8 (3)
C6—C5—C4	117.29 (13)	H8B—C8—H8C	109.0 (4)
C5^i—C5—C4	119.6 (2)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1^ii	0.949 (3)	2.231 (5)	2.828 (2)	120.0 (5)

Symmetry code: (ii) −x+1/2, y+1/2, z−1.