Two furan-2,5-di­carb­oxy­lic acid solvates crystallized from di­methyl­formamide and dimethyl sulfoxide

Furan-2,5-di­carb­oxy­lic acid (FDCA) has been ranked among the top 12 bio-based building-block chemicals by the Department of Energy in the US. The mol­ecule was first synthesized in 1876, but large-scale production has only become possible since the development of modern bio- and chemical catalysis techniques. The structures of two FDCA solvates, namely, FDCA di­methyl­formamide (DMF) disolvate, C₆H₄O₅·2C₃H₇NO, (I), and FDCA dimethyl sulfoxide (DMSO) monosolvate, C₆H₄O₅·C₂H₆OS, (II), are reported. Solvate (I) crystallizes in the ortho­rhom­bic Pbcn space group and solvate (II) crystallizes in the triclinic P space group. In (I), hydrogen bonds form between the carbonyl O atom in DMF and a hydroxy H atom in FDCA. Whilst in (II), the O atom in one DMSO mol­ecule hydrogen bonds with hydroxy H atoms in two FDCA mol­ecules. Combined with inter­molecular S...O inter­actions, FDCA mol­ecules form a two-dimensional network coordinated by DMSO.

Computing details

For both structures, data collection: APEX2 (Bruker, 2010). Cell refinement: APEX2 (Bruker, 2010) for (I); APEX2 and SAINT (Bruker, 2010) for (II). For both structures, data reduction: APEX2 and SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS2015 (Sheldrick, 2015a). Program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b) for (I); SHELXL2015 (Sheldrick, 2015b) for (II). For both structures, molecular graphics: OLEX2 (Dolomanov et al., 2009), Mercury (Macrae et al., 2008) and Marvin (ChemAxon, 2018); software used to prepare material for publication: APEX2 (Bruker, 2010), SHELXL2015 (Sheldrick, 2015b), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Furan-2,5-dicarboxylic acid dimethylformamide disolvate (I)

Crystal data

C6H4O5·2C3H7NO	Dx = 1.324 Mg m^−3
Mr = 302.28	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 3053 reflections
a = 7.5583 (7) Å	θ = 2.6–23.5°
b = 12.7016 (11) Å	µ = 0.11 mm^−1
c = 15.7903 (14) Å	T = 150 K
V = 1515.9 (2) Å^3	Prism, colourless
Z = 4	0.19 × 0.15 × 0.05 mm
F(000) = 640

Data collection

Bruker SMART APEXII CCD diffractometer	1574 independent reflections
Radiation source: sealed tube	1242 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 8.333 pixels mm^-1	θmax = 26.5°, θmin = 2.6°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	k = −15→15
Tmin = 0.905, Tmax = 0.995	l = −19→19
15185 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	All H-atom parameters refined
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.006P)^2 + 0.632P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
1574 reflections	Δρmax = 0.17 e Å^−3
133 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL2017 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0025 (6)

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	1.000000	0.58236 (8)	0.250000	0.0300 (3)
H1	0.8481 (17)	0.3572 (10)	0.2881 (8)	0.035 (4)*
C1	0.91710 (17)	0.41487 (9)	0.27058 (8)	0.0307 (3)
C2	0.87185 (16)	0.51732 (9)	0.28191 (7)	0.0286 (3)
C3	0.71524 (17)	0.56764 (9)	0.31968 (8)	0.0324 (3)
O2	0.69092 (12)	0.66197 (7)	0.32117 (6)	0.0423 (3)
O3	0.60801 (14)	0.49647 (7)	0.35065 (7)	0.0480 (3)
H3	0.504 (3)	0.5251 (15)	0.3738 (12)	0.093 (7)*
O4	0.33028 (12)	0.56295 (7)	0.42123 (6)	0.0439 (3)
C4	0.26531 (18)	0.64791 (10)	0.39776 (9)	0.0347 (3)
H4	0.3123 (18)	0.6863 (11)	0.3475 (9)	0.044 (4)*
N5	0.13253 (14)	0.69539 (8)	0.43592 (7)	0.0343 (3)
C6	0.0592 (2)	0.79398 (12)	0.40392 (12)	0.0485 (4)
H61	0.126 (2)	0.8152 (13)	0.3542 (11)	0.068 (5)*
H62	−0.066 (3)	0.7834 (13)	0.3884 (10)	0.068 (5)*
H63	0.068 (2)	0.8482 (14)	0.4489 (11)	0.065 (5)*
C7	0.0510 (2)	0.65109 (14)	0.51110 (11)	0.0489 (4)
H71	0.117 (2)	0.5881 (14)	0.5279 (10)	0.064 (5)*
H72	0.052 (2)	0.7064 (14)	0.5575 (11)	0.076 (6)*
H73	−0.072 (2)	0.6331 (13)	0.4989 (10)	0.067 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0336 (6)	0.0223 (6)	0.0341 (7)	0.000	0.0021 (5)	0.000
C1	0.0376 (7)	0.0233 (6)	0.0311 (7)	−0.0019 (5)	0.0036 (5)	0.0013 (5)
C2	0.0338 (6)	0.0241 (6)	0.0278 (6)	−0.0023 (5)	0.0007 (5)	0.0024 (5)
C3	0.0360 (7)	0.0277 (7)	0.0334 (7)	0.0019 (5)	0.0009 (5)	0.0018 (5)
O2	0.0448 (5)	0.0251 (5)	0.0570 (6)	0.0065 (4)	0.0081 (5)	0.0021 (4)
O3	0.0456 (6)	0.0288 (5)	0.0697 (7)	0.0025 (4)	0.0260 (5)	0.0042 (5)
O4	0.0433 (5)	0.0352 (5)	0.0531 (6)	0.0089 (4)	0.0116 (5)	0.0008 (4)
C4	0.0369 (7)	0.0330 (7)	0.0343 (7)	−0.0035 (6)	0.0004 (6)	−0.0038 (6)
N5	0.0358 (6)	0.0313 (6)	0.0359 (6)	0.0039 (5)	−0.0012 (5)	−0.0003 (5)
C6	0.0470 (9)	0.0383 (8)	0.0601 (11)	0.0076 (7)	−0.0049 (8)	0.0064 (8)
C7	0.0494 (10)	0.0467 (9)	0.0505 (10)	0.0124 (8)	0.0147 (8)	0.0060 (8)

Geometric parameters (Å, º)

O1—C2	1.3691 (13)	C4—N5	1.3168 (16)
O1—C2^i	1.3692 (13)	C4—H4	0.996 (14)
C1—C2	1.3574 (16)	N5—C7	1.4512 (18)
C1—C1^i	1.412 (2)	N5—C6	1.4597 (18)
C1—H1	0.941 (13)	C6—H61	0.970 (18)
C2—C3	1.4716 (17)	C6—H62	0.985 (18)
C3—O2	1.2124 (14)	C6—H63	0.991 (17)
C3—O3	1.3088 (15)	C7—H71	0.980 (17)
O3—H3	0.94 (2)	C7—H72	1.015 (18)
O4—C4	1.2422 (16)	C7—H73	0.979 (18)
C2—O1—C2^i	105.77 (12)	C4—N5—C6	121.59 (13)
C2—C1—C1^i	106.52 (7)	C7—N5—C6	117.03 (12)
C2—C1—H1	124.6 (8)	N5—C6—H61	108.8 (10)
C1^i—C1—H1	128.9 (8)	N5—C6—H62	109.5 (10)
C1—C2—O1	110.59 (11)	H61—C6—H62	109.4 (14)
C1—C2—C3	132.26 (11)	N5—C6—H63	108.8 (10)
O1—C2—C3	117.14 (10)	H61—C6—H63	110.6 (14)
O2—C3—O3	125.55 (12)	H62—C6—H63	109.8 (14)
O2—C3—C2	123.99 (11)	N5—C7—H71	108.7 (10)
O3—C3—C2	110.46 (10)	N5—C7—H72	108.5 (10)
C3—O3—H3	113.3 (12)	H71—C7—H72	111.4 (14)
O4—C4—N5	124.24 (13)	N5—C7—H73	109.5 (10)
O4—C4—H4	121.4 (8)	H71—C7—H73	110.4 (14)
N5—C4—H4	114.3 (8)	H72—C7—H73	108.3 (14)
C4—N5—C7	121.37 (12)
C1^i—C1—C2—O1	0.09 (17)	O1—C2—C3—O2	2.86 (18)
C1^i—C1—C2—C3	179.15 (13)	C1—C2—C3—O3	3.7 (2)
C2^i—O1—C2—C1	−0.04 (7)	O1—C2—C3—O3	−177.30 (10)
C2^i—O1—C2—C3	−179.26 (13)	O4—C4—N5—C7	0.7 (2)
C1—C2—C3—O2	−176.15 (14)	O4—C4—N5—C6	−178.45 (13)

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4	0.94 (2)	1.59 (2)	2.5223 (13)	173.2 (19)

Furan-2,5-dicarboxylic acid dimethyl sulfoxide monosolvate (II)

Crystal data

C6H4O5·C2H6OS	Z = 2
Mr = 234.22	F(000) = 244
Triclinic, P1	Dx = 1.560 Mg m^−3
a = 6.3129 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.9099 (9) Å	Cell parameters from 2660 reflections
c = 13.0901 (17) Å	θ = 3.2–28.2°
α = 80.5164 (17)°	µ = 0.33 mm^−1
β = 77.3664 (17)°	T = 150 K
γ = 63.8260 (16)°	Plate, colourless
V = 498.53 (11) Å^3	0.17 × 0.15 × 0.04 mm

Data collection

Bruker SMART APEXII CCD diffractometer	2044 independent reflections
Radiation source: sealed tube	1894 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 26.5°, θmin = 1.6°
Absorption correction: multi-scan (TWINABS; Krause et al., 2015)	h = −7→7
Tmin = 0.847, Tmax = 0.987	k = −8→8
2044 measured reflections	l = 0→16

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)] = 0.024	Hydrogen site location: difference Fourier map
wR(F^2) = 0.051	All H-atom parameters refined
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0057P)^2 + 0.3718P] where P = (Fo^2 + 2Fc^2)/3
2044 reflections	(Δ/σ)max < 0.001
177 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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.

Refinement. Refined as a 2-component twin but 180 deg rotation around 001 axis in reciprocal space, yielding 0.9098:0.0902 (9) component ratio.

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

	x	y	z	Uiso*/Ueq
O1	0.08991 (17)	0.41577 (17)	0.24448 (8)	0.0214 (2)
S1	0.07863 (6)	0.45030 (6)	0.12667 (3)	0.01795 (9)
C1	0.3126 (3)	0.2149 (3)	0.07023 (13)	0.0224 (3)
H1A	0.460 (3)	0.189 (3)	0.0900 (14)	0.028 (5)*
H1B	0.318 (3)	0.244 (3)	−0.0039 (15)	0.033 (5)*
H1C	0.270 (3)	0.098 (3)	0.0972 (14)	0.028 (5)*
C2	0.1993 (3)	0.6431 (3)	0.07744 (14)	0.0268 (3)
H2A	0.086 (4)	0.777 (3)	0.1041 (16)	0.042 (6)*
H2B	0.218 (3)	0.654 (3)	0.0013 (15)	0.030 (5)*
H2C	0.348 (3)	0.596 (3)	0.1017 (14)	0.030 (5)*
O11	0.65361 (18)	0.56009 (17)	0.35203 (8)	0.0218 (2)
H11	0.794 (4)	0.518 (3)	0.3177 (17)	0.047 (6)*
O12	0.57910 (18)	0.77573 (17)	0.20352 (8)	0.0245 (2)
C11	0.5112 (2)	0.7081 (2)	0.28978 (11)	0.0184 (3)
C12	0.2568 (2)	0.7818 (2)	0.33674 (11)	0.0180 (3)
O25	0.10056 (17)	0.93437 (16)	0.27591 (8)	0.0183 (2)
C13	0.1377 (3)	0.7310 (2)	0.42851 (12)	0.0220 (3)
H13	0.205 (3)	0.635 (3)	0.4811 (14)	0.025 (4)*
C14	−0.1092 (3)	0.8591 (2)	0.42580 (12)	0.0220 (3)
H14	−0.239 (3)	0.861 (3)	0.4763 (14)	0.027 (5)*
C15	−0.1224 (2)	0.9787 (2)	0.33226 (11)	0.0180 (3)
C16	−0.3208 (2)	1.1374 (2)	0.27925 (11)	0.0186 (3)
O61	−0.53223 (18)	1.17145 (18)	0.33764 (8)	0.0228 (2)
H61	−0.637 (4)	1.248 (3)	0.3064 (16)	0.043 (6)*
O62	−0.29003 (18)	1.22351 (17)	0.19237 (8)	0.0241 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0147 (5)	0.0284 (6)	0.0152 (5)	−0.0045 (4)	−0.0019 (4)	−0.0002 (4)
S1	0.01411 (17)	0.02032 (17)	0.01631 (17)	−0.00464 (13)	−0.00323 (13)	0.00009 (13)
C1	0.0191 (8)	0.0211 (8)	0.0200 (8)	−0.0023 (6)	−0.0023 (6)	−0.0023 (6)
C2	0.0315 (9)	0.0278 (9)	0.0233 (9)	−0.0157 (7)	−0.0031 (7)	−0.0008 (7)
O11	0.0132 (5)	0.0268 (6)	0.0189 (5)	−0.0041 (4)	−0.0026 (4)	0.0024 (4)
O12	0.0184 (5)	0.0249 (5)	0.0210 (6)	−0.0042 (4)	−0.0006 (4)	0.0043 (4)
C11	0.0171 (7)	0.0178 (7)	0.0185 (7)	−0.0052 (6)	−0.0040 (5)	−0.0017 (6)
C12	0.0170 (7)	0.0176 (7)	0.0177 (7)	−0.0047 (6)	−0.0058 (5)	−0.0006 (5)
O25	0.0131 (5)	0.0209 (5)	0.0169 (5)	−0.0046 (4)	−0.0024 (4)	0.0015 (4)
C13	0.0191 (7)	0.0251 (8)	0.0179 (7)	−0.0066 (6)	−0.0045 (6)	0.0026 (6)
C14	0.0173 (7)	0.0278 (8)	0.0178 (7)	−0.0084 (6)	−0.0009 (6)	−0.0001 (6)
C15	0.0140 (7)	0.0212 (7)	0.0180 (7)	−0.0068 (6)	−0.0008 (5)	−0.0033 (6)
C16	0.0162 (7)	0.0199 (7)	0.0200 (7)	−0.0072 (6)	−0.0040 (5)	−0.0022 (6)
O61	0.0127 (5)	0.0288 (6)	0.0202 (6)	−0.0037 (4)	−0.0032 (4)	0.0022 (5)
O62	0.0195 (5)	0.0298 (6)	0.0209 (6)	−0.0102 (5)	−0.0052 (4)	0.0056 (5)

Geometric parameters (Å, º)

O1—S1	1.5336 (10)	C11—C12	1.472 (2)
S1—C2	1.7802 (17)	C12—C13	1.353 (2)
S1—C1	1.7811 (15)	C12—O25	1.3667 (16)
C1—H1A	0.953 (18)	O25—C15	1.3633 (17)
C1—H1B	0.954 (19)	C13—C14	1.418 (2)
C1—H1C	0.951 (19)	C13—H13	0.908 (17)
C2—H2A	0.95 (2)	C14—C15	1.356 (2)
C2—H2B	0.972 (19)	C14—H14	0.930 (18)
C2—H2C	0.957 (19)	C15—C16	1.4732 (19)
O11—C11	1.3238 (17)	C16—O62	1.2115 (18)
O11—H11	0.84 (2)	C16—O61	1.3256 (17)
O12—C11	1.2118 (17)	O61—H61	0.79 (2)
O1—S1—C2	104.53 (7)	O11—C11—C12	112.26 (12)
O1—S1—C1	105.94 (7)	C13—C12—O25	110.77 (12)
C2—S1—C1	100.26 (8)	C13—C12—C11	134.23 (13)
S1—C1—H1A	109.8 (10)	O25—C12—C11	115.00 (12)
S1—C1—H1B	105.9 (11)	C15—O25—C12	105.88 (11)
H1A—C1—H1B	111.5 (15)	C12—C13—C14	106.34 (13)
S1—C1—H1C	106.4 (10)	C12—C13—H13	126.0 (11)
H1A—C1—H1C	110.4 (14)	C14—C13—H13	127.6 (11)
H1B—C1—H1C	112.6 (15)	C15—C14—C13	106.26 (13)
S1—C2—H2A	106.7 (12)	C15—C14—H14	125.7 (11)
S1—C2—H2B	107.3 (10)	C13—C14—H14	128.1 (11)
H2A—C2—H2B	110.4 (15)	C14—C15—O25	110.75 (12)
S1—C2—H2C	108.6 (11)	C14—C15—C16	134.29 (13)
H2A—C2—H2C	111.1 (16)	O25—C15—C16	114.93 (12)
H2B—C2—H2C	112.4 (15)	O62—C16—O61	125.09 (13)
C11—O11—H11	106.5 (14)	O62—C16—C15	123.00 (13)
O12—C11—O11	124.71 (13)	O61—C16—C15	111.90 (12)
O12—C11—C12	123.03 (13)	C16—O61—H61	111.1 (15)
O12—C11—C12—C13	179.01 (16)	C13—C14—C15—O25	−0.07 (17)
O11—C11—C12—C13	−0.5 (2)	C13—C14—C15—C16	178.07 (16)
O12—C11—C12—O25	−0.3 (2)	C12—O25—C15—C14	0.07 (16)
O11—C11—C12—O25	−179.78 (12)	C12—O25—C15—C16	−178.46 (12)
C13—C12—O25—C15	−0.05 (16)	C14—C15—C16—O62	−178.39 (16)
C11—C12—O25—C15	179.44 (12)	O25—C15—C16—O62	−0.3 (2)
O25—C12—C13—C14	0.00 (17)	C14—C15—C16—O61	1.2 (2)
C11—C12—C13—C14	−179.34 (16)	O25—C15—C16—O61	179.33 (12)
C12—C13—C14—C15	0.04 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O1^i	0.84 (2)	1.78 (2)	2.6279 (14)	177 (2)
O61—H61···O1^ii	0.79 (2)	1.87 (2)	2.6587 (15)	173 (2)

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