Synthesis and crystal structure of pyrroloquinoline quinol (PQQH₂) and pyrroloquinoline quinone (PQQ)

Pyrroloquinoline quinone (PQQ) is a water-soluble quinone compound first identified as a cofactor of alcohol- and glucose-dehydrogenases (ADH and GDH) in bacteria. For example, in the process of ADH reaction, alcohol is oxidized to the corresponding aldehyde, and inversely PQQ is reduced to pyrroloquinoline quinol (PQQH₂). PQQ and PQQH₂ molecules play an important role as a cofactor in ADH and GDH reactions. However, crystal structure analysis has not been performed for PQQ and PQQH₂. In the present study, the synthesis of PQQH₂ powder crystals was performed under air, by utilizing vitamin C as a reducing agent. By reacting a trihydrate of disodium salt of PQQ (PQQNa₂·3H₂O) with excess vitamin C in H₂O at 293 and 343 K, yellowish brown and black powder crystals of PQQH₂ having different properties were obtained in high yield, respectively. The former was PQQH₂ trihydrate (PQQH₂·3H₂O) and the latter was PQQH₂ anhydrate (PQQH₂). Furthermore, sodium-free red PQQ powder crystal (a monohydrate of PQQ, PQQ·H₂O) was prepared by the reaction of PQQNa₂·3H₂O with HCl in H₂O. Single crystals of PQQH₂ and PQQ were prepared from Me₂SO/CH₃CN mixed solvent, and we have succeeded in the crystal structure analyses of PQQH₂ and PQQ for the first time.

Computing details

For both compounds, data collection: CrystalClear (Rigaku Inc., 2008); cell refinement: CrystalClear (Rigaku Inc., 2008); data reduction: CrystalClear (Rigaku Inc., 2008); program(s) used to solve structure: SIR2011 (Burla, et al., 2012); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2016); molecular graphics: CrystalStructure 4.2.4 (Rigaku, 2016); software used to prepare material for publication: CrystalStructure 4.2.4 (Rigaku, 2016).

(I)

Crystal data

2(C7H4NO4)·2(C2H6OS)·C2H3N	Dx = 1.536 Mg m^−3
Mr = 529.53	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, Pnma	Cell parameters from 6974 reflections
a = 14.563 (5) Å	θ = 2.2–31.2°
b = 6.748 (2) Å	µ = 0.30 mm^−1
c = 23.299 (9) Å	T = 100 K
V = 2289.6 (14) Å^3	Needle, orange
Z = 4	0.24 × 0.03 × 0.02 mm
F(000) = 1104

Data collection

Rigaku Saturn724 diffractometer	2990 independent reflections
Radiation source: Varimax 50 kV 24 mA Rotating anode	2846 reflections with I > 2σ(I)
Detector resolution: 7.111 pixels mm^-1	Rint = 0.051
ω scans	θmax = 28.0°, θmin = 2.2°
Absorption correction: multi-scan REQAB (Rigaku, 1998)	h = −19→19
Tmin = 0.912, Tmax = 0.994	k = −8→8
38156 measured reflections	l = −30→30

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)] = 0.060	Hydrogen site location: mixed
wR(F^2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 3.2P] where P = (Fo^2 + 2Fc^2)/3
2990 reflections	(Δ/σ)max = 0.001
267 parameters	Δρmax = 0.48 e Å^−3
236 restraints	Δρmin = −0.36 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.95984 (15)	0.250000	0.25191 (9)	0.0413 (6)
O2	1.11256 (15)	0.250000	0.25846 (9)	0.0310 (5)
H2O	1.099 (3)	0.250000	0.2922 (18)	0.037*
O3	1.23564 (13)	0.250000	0.02383 (9)	0.0251 (5)
H3O	1.257 (2)	0.250000	−0.0141 (16)	0.030*
O4	1.14103 (14)	0.250000	−0.07778 (9)	0.0290 (5)
H4O	1.110 (3)	0.250000	−0.1046 (17)	0.035*
O5	0.74435 (14)	0.250000	−0.15150 (9)	0.0316 (5)
O6	0.88455 (14)	0.250000	−0.18742 (8)	0.0246 (4)
H6O	0.945 (3)	0.250000	−0.1763 (16)	0.030*
O7	0.79196 (14)	0.250000	0.11706 (8)	0.0301 (5)
O8	0.68979 (15)	0.250000	0.04710 (9)	0.0430 (7)
H8O	0.654 (3)	0.250000	0.076 (2)	0.052*
N1	0.97079 (16)	0.250000	0.13227 (9)	0.0195 (5)
H1N	0.913 (2)	0.250000	0.1430 (15)	0.023*
C2	1.04677 (19)	0.250000	0.16660 (11)	0.0207 (5)
C3	1.12426 (18)	0.250000	0.13281 (11)	0.0197 (5)
H3	1.186186	0.250000	0.145626	0.024*
C3A	1.09347 (17)	0.250000	0.07514 (11)	0.0178 (5)
C4	1.14201 (18)	0.250000	0.02226 (12)	0.0199 (5)
C5	1.09317 (18)	0.250000	−0.02786 (11)	0.0188 (5)
C5A	0.99512 (18)	0.250000	−0.02736 (11)	0.0165 (5)
N6	0.95695 (15)	0.250000	−0.08022 (9)	0.0171 (4)
C7	0.86636 (18)	0.250000	−0.08423 (11)	0.0182 (5)
C8	0.80810 (18)	0.250000	−0.03693 (11)	0.0190 (5)
H8	0.743438	0.250000	−0.042315	0.023*
C9	0.84439 (18)	0.250000	0.01811 (11)	0.0169 (5)
C9A	0.94206 (18)	0.250000	0.02498 (11)	0.0169 (5)
C1A	0.99642 (18)	0.250000	0.07598 (11)	0.0169 (5)
C10	1.0344 (2)	0.250000	0.22905 (12)	0.0241 (6)
C11	0.82666 (19)	0.250000	−0.14344 (11)	0.0216 (6)
C12	0.77507 (18)	0.250000	0.06616 (12)	0.0218 (6)
S1S	1.13174 (5)	0.250000	−0.23528 (3)	0.0292 (2)
C1S	1.20922 (16)	0.4481 (4)	−0.22216 (10)	0.0391 (6)
H1SA	1.231636	0.440347	−0.182567	0.047*
H1SB	1.177551	0.574682	−0.227969	0.047*
H1SC	1.261229	0.438661	−0.248715	0.047*
O1S	1.06649 (16)	0.250000	−0.18464 (10)	0.0490 (8)
S2S	0.46451 (11)	0.3252 (3)	0.11996 (11)	0.0298 (4)	0.3586 (15)
C2SA	0.4619 (5)	0.3930 (14)	0.0459 (3)	0.0472 (19)	0.3586 (15)
H2SA	0.483050	0.530048	0.041575	0.071*	0.3586 (15)
H2SB	0.398899	0.381654	0.031369	0.071*	0.3586 (15)
H2SC	0.502147	0.304519	0.024005	0.071*	0.3586 (15)
C2SB	0.3990 (12)	0.105 (2)	0.1158 (7)	0.040 (3)	0.3586 (15)
H2SD	0.436074	−0.000002	0.098375	0.060*	0.3586 (15)
H2SE	0.344287	0.128674	0.092247	0.060*	0.3586 (15)
H2SF	0.380215	0.064818	0.154468	0.060*	0.3586 (15)
O2S	0.56169 (16)	0.230 (2)	0.12930 (11)	0.0312 (14)	0.3586 (15)
S3S	0.4719 (2)	0.250000	0.08417 (17)	0.0343 (9)	0.244 (2)
C3S	0.3985 (19)	0.058 (3)	0.1078 (12)	0.035 (4)	0.244 (2)
H3SA	0.407724	−0.059548	0.083778	0.052*	0.244 (2)
H3SB	0.334506	0.101626	0.104859	0.052*	0.244 (2)
H3SC	0.412674	0.025548	0.147816	0.052*	0.244 (2)
O3S	0.56169 (16)	0.230 (2)	0.12930 (11)	0.0312 (14)	0.1221 (12)
S4S	0.4585 (15)	0.250000	0.120 (2)	0.034 (3)	0.039 (3)
C4S	0.415 (4)	0.439 (9)	0.072 (3)	0.038 (6)	0.039 (3)
H4SA	0.435174	0.569824	0.086014	0.057*	0.039 (3)
H4SB	0.348115	0.434026	0.071526	0.057*	0.039 (3)
H4SC	0.439364	0.416935	0.033572	0.057*	0.039 (3)
O4S	0.56169 (16)	0.230 (2)	0.12930 (11)	0.0312 (14)	0.0193 (14)
N1S	1.3585 (2)	0.250000	−0.07550 (13)	0.0440 (8)
C5S	1.3906 (2)	0.250000	−0.11983 (14)	0.0360 (8)
C6S	1.4333 (2)	0.250000	−0.17659 (14)	0.0401 (9)
H6SA	1.432224	0.115440	−0.192397	0.060*	0.5
H6SB	1.497004	0.295357	−0.173343	0.060*	0.5
H6SC	1.399285	0.339203	−0.202085	0.060*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0236 (11)	0.083 (2)	0.0178 (10)	0.000	−0.0041 (8)	0.000
O2	0.0229 (10)	0.0516 (14)	0.0184 (10)	0.000	−0.0074 (8)	0.000
O3	0.0125 (9)	0.0402 (12)	0.0227 (10)	0.000	−0.0007 (7)	0.000
O4	0.0178 (10)	0.0528 (15)	0.0163 (9)	0.000	0.0032 (7)	0.000
O5	0.0195 (10)	0.0566 (15)	0.0188 (10)	0.000	−0.0025 (8)	0.000
O6	0.0222 (10)	0.0373 (12)	0.0143 (9)	0.000	0.0000 (7)	0.000
O7	0.0202 (10)	0.0563 (15)	0.0138 (9)	0.000	−0.0008 (7)	0.000
O8	0.0172 (10)	0.095 (2)	0.0171 (10)	0.000	0.0027 (8)	0.000
N1	0.0159 (11)	0.0295 (13)	0.0131 (10)	0.000	−0.0021 (8)	0.000
C2	0.0208 (13)	0.0263 (14)	0.0151 (12)	0.000	−0.0052 (10)	0.000
C3	0.0181 (12)	0.0214 (13)	0.0197 (12)	0.000	−0.0066 (10)	0.000
C3A	0.0160 (12)	0.0188 (13)	0.0185 (12)	0.000	−0.0024 (9)	0.000
C4	0.0153 (12)	0.0219 (13)	0.0223 (13)	0.000	−0.0016 (10)	0.000
C5	0.0155 (12)	0.0238 (14)	0.0170 (12)	0.000	0.0017 (9)	0.000
C5A	0.0170 (12)	0.0170 (12)	0.0157 (11)	0.000	−0.0007 (9)	0.000
N6	0.0184 (10)	0.0195 (11)	0.0134 (10)	0.000	−0.0012 (8)	0.000
C7	0.0181 (12)	0.0209 (13)	0.0157 (12)	0.000	−0.0023 (9)	0.000
C8	0.0161 (12)	0.0224 (13)	0.0184 (12)	0.000	−0.0024 (9)	0.000
C9	0.0172 (12)	0.0187 (12)	0.0148 (11)	0.000	0.0000 (9)	0.000
C9A	0.0175 (12)	0.0177 (12)	0.0156 (12)	0.000	−0.0015 (9)	0.000
C1A	0.0189 (12)	0.0168 (12)	0.0151 (11)	0.000	−0.0027 (9)	0.000
C10	0.0234 (13)	0.0315 (15)	0.0174 (12)	0.000	−0.0044 (10)	0.000
C11	0.0195 (12)	0.0296 (15)	0.0157 (12)	0.000	0.0006 (10)	0.000
C12	0.0163 (12)	0.0295 (15)	0.0197 (12)	0.000	−0.0002 (10)	0.000
S1S	0.0175 (3)	0.0544 (5)	0.0159 (3)	0.000	0.0012 (2)	0.000
C1S	0.0306 (11)	0.0483 (15)	0.0382 (12)	0.0033 (11)	0.0020 (9)	−0.0138 (11)
O1S	0.0205 (11)	0.108 (2)	0.0187 (11)	0.000	0.0036 (9)	0.000
S2S	0.0205 (7)	0.0445 (9)	0.0243 (8)	−0.0046 (7)	−0.0048 (6)	0.0045 (11)
C2SA	0.040 (3)	0.073 (5)	0.029 (3)	−0.019 (3)	−0.016 (3)	0.026 (3)
C2SB	0.017 (4)	0.068 (7)	0.036 (5)	−0.010 (5)	−0.012 (3)	0.003 (5)
O2S	0.0175 (10)	0.051 (4)	0.0252 (10)	−0.001 (2)	0.0026 (8)	0.000 (2)
S3S	0.0211 (14)	0.052 (2)	0.0296 (19)	0.000	−0.0010 (12)	0.000
C3S	0.026 (6)	0.039 (7)	0.040 (8)	−0.010 (5)	−0.013 (5)	−0.004 (5)
O3S	0.0175 (10)	0.051 (4)	0.0252 (10)	−0.001 (2)	0.0026 (8)	0.000 (2)
S4S	0.026 (4)	0.049 (5)	0.028 (5)	0.000	−0.005 (4)	0.000
C4S	0.032 (9)	0.051 (10)	0.032 (9)	−0.005 (9)	−0.005 (9)	0.003 (9)
O4S	0.0175 (10)	0.051 (4)	0.0252 (10)	−0.001 (2)	0.0026 (8)	0.000 (2)
N1S	0.0285 (14)	0.075 (2)	0.0284 (14)	0.000	0.0039 (12)	0.000
C5S	0.0232 (14)	0.059 (2)	0.0261 (15)	0.000	−0.0015 (12)	0.000
C6S	0.0293 (16)	0.067 (3)	0.0243 (15)	0.000	0.0032 (13)	0.000

Geometric parameters (Å, º)

O1—C10	1.209 (4)	S1S—C1S^i	1.776 (3)
O2—C10	1.329 (3)	C1S—H1SA	0.9800
O2—H2O	0.81 (4)	C1S—H1SB	0.9800
O3—C4	1.364 (3)	C1S—H1SC	0.9800
O3—H3O	0.94 (4)	S2S—O2S	1.569 (6)
O4—C5	1.356 (3)	S2S—C2SB	1.768 (11)
O4—H4O	0.77 (4)	S2S—C2SA	1.786 (6)
O5—C11	1.213 (3)	C2SA—H2SA	0.9800
O6—C11	1.327 (3)	C2SA—H2SB	0.9800
O6—H6O	0.91 (4)	C2SA—H2SC	0.9800
O7—C12	1.211 (3)	C2SB—H2SD	0.9800
O8—C12	1.319 (3)	C2SB—H2SE	0.9800
O8—H8O	0.86 (5)	C2SB—H2SF	0.9800
N1—C1A	1.364 (3)	S3S—O3S	1.684 (4)
N1—C2	1.365 (3)	S3S—O3S^i	1.684 (4)
N1—H1N	0.88 (4)	S3S—C3S	1.767 (16)
C2—C3	1.376 (4)	S3S—C3S^i	1.767 (16)
C2—C10	1.466 (4)	C3S—H3SA	0.9800
C3—C3A	1.417 (4)	C3S—H3SB	0.9800
C3—H3	0.9500	C3S—H3SC	0.9800
C3A—C1A	1.413 (4)	O3S—O3S^i	0.27 (3)
C3A—C4	1.420 (4)	S4S—O4S	1.525 (19)
C4—C5	1.367 (4)	S4S—C4S^i	1.81 (2)
C5—C5A	1.428 (4)	S4S—C4S	1.81 (2)
C5A—N6	1.351 (3)	C4S—H4SA	0.9800
C5A—C9A	1.444 (3)	C4S—H4SB	0.9800
N6—C7	1.322 (3)	C4S—H4SC	0.9800
C7—C8	1.391 (4)	N1S—C5S	1.133 (4)
C7—C11	1.496 (4)	C5S—C6S	1.462 (4)
C8—C9	1.387 (3)	C6S—H6SA	0.9800
C8—H8	0.9500	C6S—H6SB	0.9800
C9—C9A	1.431 (4)	C6S—H6SC	0.9800
C9—C12	1.508 (4)	C6S—H6SA^i	0.980 (11)
C9A—C1A	1.428 (3)	C6S—H6SB^i	0.98 (2)
S1S—O1S	1.515 (2)	C6S—H6SC^i	0.98 (3)
S1S—C1S	1.776 (3)
C10—O2—H2O	107 (3)	S1S—C1S—H1SC	109.5
C4—O3—H3O	108 (2)	H1SA—C1S—H1SC	109.5
C5—O4—H4O	113 (3)	H1SB—C1S—H1SC	109.5
C11—O6—H6O	113 (2)	O2S—S2S—C2SB	98.7 (8)
C12—O8—H8O	108 (3)	O2S—S2S—C2SA	105.0 (3)
C1A—N1—C2	110.0 (2)	C2SB—S2S—C2SA	98.6 (6)
C1A—N1—H1N	122 (2)	S2S—C2SA—H2SA	109.5
C2—N1—H1N	128 (2)	S2S—C2SA—H2SB	109.5
N1—C2—C3	109.2 (2)	H2SA—C2SA—H2SB	109.5
N1—C2—C10	118.8 (2)	S2S—C2SA—H2SC	109.5
C3—C2—C10	132.0 (2)	H2SA—C2SA—H2SC	109.5
C2—C3—C3A	106.4 (2)	H2SB—C2SA—H2SC	109.5
C2—C3—H3	126.8	S2S—C2SB—H2SD	109.5
C3A—C3—H3	126.8	S2S—C2SB—H2SE	109.5
C1A—C3A—C3	107.7 (2)	H2SD—C2SB—H2SE	109.5
C1A—C3A—C4	120.6 (2)	S2S—C2SB—H2SF	109.5
C3—C3A—C4	131.7 (2)	H2SD—C2SB—H2SF	109.5
O3—C4—C5	122.9 (2)	H2SE—C2SB—H2SF	109.5
O3—C4—C3A	118.3 (2)	O3S—S3S—C3S	102.6 (11)
C5—C4—C3A	118.8 (2)	O3S^i—S3S—C3S	109.5 (11)
O4—C5—C4	117.7 (2)	S3S—C3S—H3SA	109.5
O4—C5—C5A	121.4 (2)	S3S—C3S—H3SB	109.5
C4—C5—C5A	120.9 (2)	H3SA—C3S—H3SB	109.5
N6—C5A—C5	113.8 (2)	S3S—C3S—H3SC	109.5
N6—C5A—C9A	123.3 (2)	H3SA—C3S—H3SC	109.5
C5—C5A—C9A	122.8 (2)	H3SB—C3S—H3SC	109.5
C7—N6—C5A	118.4 (2)	O3S^i—O3S—S3S	85.5 (5)
N6—C7—C8	123.5 (2)	O4S—S4S—C4S	119 (3)
N6—C7—C11	116.8 (2)	C4S^i—S4S—C4S	90 (5)
C8—C7—C11	119.7 (2)	S4S—C4S—H4SA	109.5
C9—C8—C7	120.0 (2)	S4S—C4S—H4SB	109.5
C9—C8—H8	120.0	H4SA—C4S—H4SB	109.5
C7—C8—H8	120.0	S4S—C4S—H4SC	109.5
C8—C9—C9A	118.8 (2)	H4SA—C4S—H4SC	109.5
C8—C9—C12	115.6 (2)	H4SB—C4S—H4SC	109.5
C9A—C9—C12	125.6 (2)	N1S—C5S—C6S	179.1 (4)
C1A—C9A—C9	130.1 (2)	C5S—C6S—H6SA	109.5
C1A—C9A—C5A	114.0 (2)	C5S—C6S—H6SB	109.5
C9—C9A—C5A	115.9 (2)	H6SA—C6S—H6SB	109.5
N1—C1A—C3A	106.7 (2)	C5S—C6S—H6SC	109.5
N1—C1A—C9A	130.4 (2)	H6SA—C6S—H6SC	109.5
C3A—C1A—C9A	122.9 (2)	H6SB—C6S—H6SC	109.5
O1—C10—O2	122.8 (3)	C5S—C6S—H6SA^i	109.5 (2)
O1—C10—C2	123.2 (3)	H6SA—C6S—H6SA^i	135.8
O2—C10—C2	114.0 (2)	H6SB—C6S—H6SA^i	75.8
O5—C11—O6	120.5 (2)	H6SC—C6S—H6SA^i	36.4
O5—C11—C7	121.6 (2)	C5S—C6S—H6SB^i	109.5 (4)
O6—C11—C7	117.8 (2)	H6SA—C6S—H6SB^i	75.8
O7—C12—O8	121.4 (3)	H6SB—C6S—H6SB^i	36.4
O7—C12—C9	126.2 (2)	H6SC—C6S—H6SB^i	135.8
O8—C12—C9	112.4 (2)	H6SA^i—C6S—H6SB^i	109.5
O1S—S1S—C1S	105.34 (10)	C5S—C6S—H6SC^i	109.5 (7)
O1S—S1S—C1S^i	105.34 (10)	H6SA—C6S—H6SC^i	36.4
C1S—S1S—C1S^i	97.67 (17)	H6SB—C6S—H6SC^i	135.8
S1S—C1S—H1SA	109.5	H6SC—C6S—H6SC^i	75.8
S1S—C1S—H1SB	109.5	H6SA^i—C6S—H6SC^i	109.5
H1SA—C1S—H1SB	109.5	H6SB^i—C6S—H6SC^i	109.5
C1A—N1—C2—C3	0.000 (1)	C12—C9—C9A—C5A	180.0
C1A—N1—C2—C10	180.000 (1)	N6—C5A—C9A—C1A	180.0
N1—C2—C3—C3A	0.000 (1)	C5—C5A—C9A—C1A	0.0
C10—C2—C3—C3A	180.000 (1)	N6—C5A—C9A—C9	0.0
C2—C3—C3A—C1A	0.000 (1)	C5—C5A—C9A—C9	180.0
C2—C3—C3A—C4	180.000 (1)	C2—N1—C1A—C3A	0.000 (1)
C1A—C3A—C4—O3	180.0	C2—N1—C1A—C9A	180.000 (1)
C3—C3A—C4—O3	0.000 (1)	C3—C3A—C1A—N1	0.000 (1)
C1A—C3A—C4—C5	0.0	C4—C3A—C1A—N1	180.000 (1)
C3—C3A—C4—C5	180.000 (1)	C3—C3A—C1A—C9A	180.000 (1)
O3—C4—C5—O4	0.0	C4—C3A—C1A—C9A	0.000 (1)
C3A—C4—C5—O4	180.0	C9—C9A—C1A—N1	0.000 (1)
O3—C4—C5—C5A	180.0	C5A—C9A—C1A—N1	180.0
C3A—C4—C5—C5A	0.0	C9—C9A—C1A—C3A	180.0
O4—C5—C5A—N6	0.0	C5A—C9A—C1A—C3A	0.0
C4—C5—C5A—N6	180.0	N1—C2—C10—O1	0.000 (1)
O4—C5—C5A—C9A	180.0	C3—C2—C10—O1	180.000 (1)
C4—C5—C5A—C9A	0.0	N1—C2—C10—O2	180.000 (1)
C5—C5A—N6—C7	180.0	C3—C2—C10—O2	0.000 (1)
C9A—C5A—N6—C7	0.0	N6—C7—C11—O5	180.000 (1)
C5A—N6—C7—C8	0.000 (1)	C8—C7—C11—O5	0.000 (1)
C5A—N6—C7—C11	180.000 (1)	N6—C7—C11—O6	0.000 (1)
N6—C7—C8—C9	0.0	C8—C7—C11—O6	180.000 (1)
C11—C7—C8—C9	180.000 (1)	C8—C9—C12—O7	180.0
C7—C8—C9—C9A	0.0	C9A—C9—C12—O7	0.0
C7—C8—C9—C12	180.0	C8—C9—C12—O8	0.0
C8—C9—C9A—C1A	180.0	C9A—C9—C12—O8	180.0
C12—C9—C9A—C1A	0.0	C3S—S3S—O3S—O3S^i	−140.5 (8)
C8—C9—C9A—C5A	0.0	C3S^i—S3S—O3S—O3S^i	−41.2 (9)

Symmetry code: (i) x, −y+1/2, z.

(II)

Crystal data

C14H6N2O8·3(C2H6OS)	Dx = 1.532 Mg m^−3
Mr = 564.59	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, P212121	Cell parameters from 7223 reflections
a = 6.901 (5) Å	θ = 2.2–31.3°
b = 12.371 (8) Å	µ = 0.37 mm^−1
c = 28.674 (18) Å	T = 100 K
V = 2448 (3) Å^3	Block, orange
Z = 4	0.05 × 0.05 × 0.02 mm
F(000) = 1176

Data collection

Rigaku Saturn724 diffractometer	5885 independent reflections
Radiation source: Varimax 50 kV 24 mA Rotating anode	4968 reflections with I > 2σ(I)
Detector resolution: 7.111 pixels mm^-1	Rint = 0.077
ω scans	θmax = 28.0°, θmin = 2.2°
Absorption correction: multi-scan REQAB (Rigaku, 1998)	h = −9→9
Tmin = 0.910, Tmax = 0.993	k = −16→16
41911 measured reflections	l = −37→37

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.070	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.185	w = 1/[σ^2(Fo^2) + (0.0801P)^2 + 4.9734P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5885 reflections	Δρmax = 1.43 e Å^−3
337 parameters	Δρmin = −0.78 e Å^−3
0 restraints	Absolute structure: Flack x determined using 1648 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.12 (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.

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

	x	y	z	Uiso*/Ueq
N1	0.9440 (7)	0.8466 (4)	−0.05934 (17)	0.0218 (10)
H1N	0.914 (10)	0.906 (6)	−0.039 (2)	0.026*
C2	0.9653 (9)	0.8499 (4)	−0.10737 (18)	0.0218 (11)
C3	0.9869 (9)	0.7459 (4)	−0.12347 (17)	0.0206 (10)
H3	1.004371	0.724012	−0.154950	0.025*
C3A	0.9777 (8)	0.6775 (4)	−0.08356 (17)	0.0190 (10)
C4	0.9825 (9)	0.5605 (4)	−0.08101 (17)	0.0203 (10)
C5	0.9453 (8)	0.5134 (4)	−0.03123 (19)	0.0220 (11)
C5A	0.9399 (8)	0.5897 (4)	0.01008 (18)	0.0194 (10)
N6	0.9387 (7)	0.5391 (4)	0.05150 (16)	0.0218 (9)
C7	0.9494 (8)	0.6010 (4)	0.08993 (18)	0.0204 (11)
C8	0.9599 (8)	0.7140 (4)	0.08793 (19)	0.0215 (11)
H8	0.972814	0.754651	0.115863	0.026*
C9	0.9516 (8)	0.7667 (4)	0.04513 (19)	0.0210 (11)
C9A	0.9441 (8)	0.7031 (4)	0.00378 (19)	0.0194 (10)
C1A	0.9501 (8)	0.7430 (4)	−0.04392 (19)	0.0209 (11)
C10	0.9588 (9)	0.9563 (5)	−0.1305 (2)	0.0276 (13)
C11	0.9544 (9)	0.5438 (5)	0.13669 (19)	0.0264 (13)
C12	0.9484 (8)	0.8898 (4)	0.04803 (19)	0.0216 (11)
O1	0.9249 (9)	1.0384 (4)	−0.10878 (17)	0.0431 (13)
O2	0.9909 (8)	0.9506 (3)	−0.17610 (13)	0.0281 (8)
H2O	0.990325	1.013111	−0.187500	0.042*
O3	1.0089 (8)	0.4989 (3)	−0.11352 (13)	0.0288 (9)
O4	0.9196 (7)	0.4173 (3)	−0.02732 (15)	0.0274 (9)
O5	0.9234 (8)	0.4468 (3)	0.14038 (15)	0.0332 (11)
O6	0.9905 (8)	0.6094 (3)	0.17141 (13)	0.0291 (9)
H6O	0.990604	0.574423	0.196522	0.044*
O7	0.8509 (6)	0.9449 (3)	0.02061 (14)	0.0257 (9)
O8	1.0449 (7)	0.9278 (3)	0.08221 (15)	0.0318 (11)
H8O	1.001782	0.989128	0.089298	0.048*
S1S	0.9985 (3)	1.23776 (12)	−0.17812 (5)	0.0329 (4)
C1SA	0.8146 (18)	1.3285 (11)	−0.1955 (5)	0.108 (6)
H1SA	0.688111	1.300080	−0.186011	0.130*
H1SB	0.817547	1.336838	−0.229521	0.130*
H1SC	0.836177	1.398896	−0.180755	0.130*
C1SB	1.1942 (17)	1.3168 (10)	−0.1962 (5)	0.092 (5)
H1SD	1.175788	1.338065	−0.228833	0.111*
H1SE	1.314305	1.275098	−0.193257	0.111*
H1SF	1.202378	1.381684	−0.176680	0.111*
O1S	0.9905 (8)	1.1426 (3)	−0.21235 (13)	0.0329 (10)
S2S	1.0039 (3)	0.40255 (14)	0.25892 (5)	0.0349 (4)
C2SA	0.8094 (11)	0.3687 (7)	0.2970 (3)	0.0402 (18)
H2SA	0.821868	0.409741	0.326042	0.048*
H2SB	0.813356	0.291118	0.303868	0.048*
H2SC	0.685925	0.386517	0.281949	0.048*
C2SB	1.1931 (10)	0.3767 (7)	0.2993 (3)	0.0385 (17)
H2SD	1.174405	0.421349	0.327172	0.046*
H2SE	1.318079	0.394221	0.284954	0.046*
H2SF	1.191343	0.300123	0.308118	0.046*
O2S	0.9969 (9)	0.5214 (4)	0.25197 (15)	0.0396 (11)
S3S	0.9899 (3)	1.19353 (10)	0.05375 (5)	0.0253 (3)
C3SA	0.7711 (10)	1.2660 (6)	0.0640 (2)	0.0304 (14)
H3SA	0.780417	1.304637	0.093730	0.036*
H3SB	0.662183	1.215165	0.065177	0.036*
H3SC	0.750100	1.317939	0.038695	0.036*
C3SB	1.1622 (10)	1.2955 (5)	0.0647 (3)	0.0321 (14)
H3SD	1.292778	1.264513	0.063289	0.039*
H3SE	1.139876	1.326264	0.095709	0.039*
H3SF	1.149846	1.352457	0.041106	0.039*
O3S	1.0051 (8)	1.1197 (3)	0.09775 (13)	0.0292 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.024 (2)	0.017 (2)	0.024 (2)	−0.0024 (18)	0.0016 (18)	0.0032 (18)
C2	0.027 (3)	0.017 (2)	0.022 (2)	0.001 (2)	−0.002 (2)	0.0006 (19)
C3	0.024 (3)	0.019 (2)	0.019 (2)	0.000 (2)	0.001 (2)	0.0011 (18)
C3A	0.020 (3)	0.019 (2)	0.018 (2)	0.002 (2)	−0.004 (2)	0.0005 (18)
C4	0.024 (3)	0.019 (2)	0.018 (2)	0.001 (2)	−0.002 (2)	−0.0015 (18)
C5	0.025 (3)	0.018 (2)	0.022 (3)	0.002 (2)	−0.001 (2)	−0.002 (2)
C5A	0.020 (2)	0.018 (2)	0.020 (2)	−0.0003 (19)	0.0008 (19)	0.0016 (19)
N6	0.024 (2)	0.019 (2)	0.023 (2)	−0.0022 (18)	−0.0005 (18)	0.0005 (18)
C7	0.023 (3)	0.018 (2)	0.020 (2)	0.001 (2)	0.000 (2)	0.0023 (19)
C8	0.022 (3)	0.021 (2)	0.022 (2)	−0.002 (2)	0.005 (2)	−0.002 (2)
C9	0.022 (3)	0.018 (2)	0.023 (3)	0.001 (2)	−0.001 (2)	0.000 (2)
C9A	0.017 (2)	0.017 (2)	0.024 (2)	0.0007 (19)	0.001 (2)	−0.003 (2)
C1A	0.023 (3)	0.014 (2)	0.025 (3)	−0.002 (2)	−0.002 (2)	0.000 (2)
C10	0.032 (3)	0.023 (3)	0.028 (3)	0.004 (2)	0.008 (2)	0.004 (2)
C11	0.031 (3)	0.027 (3)	0.022 (2)	−0.001 (2)	0.000 (2)	0.004 (2)
C12	0.029 (3)	0.014 (2)	0.022 (2)	0.003 (2)	0.003 (2)	0.0006 (19)
O1	0.067 (4)	0.026 (2)	0.037 (2)	0.013 (2)	0.016 (2)	0.006 (2)
O2	0.038 (2)	0.0217 (18)	0.0248 (18)	−0.002 (2)	0.002 (2)	0.0037 (14)
O3	0.038 (2)	0.0247 (19)	0.0236 (18)	−0.001 (2)	0.001 (2)	−0.0071 (14)
O4	0.037 (2)	0.0177 (19)	0.027 (2)	−0.0019 (17)	−0.0022 (18)	−0.0025 (16)
O5	0.052 (3)	0.020 (2)	0.027 (2)	0.000 (2)	0.000 (2)	0.0025 (17)
O6	0.043 (3)	0.0227 (19)	0.0214 (17)	−0.002 (2)	−0.002 (2)	0.0032 (14)
O7	0.029 (2)	0.021 (2)	0.027 (2)	0.0032 (16)	−0.0031 (17)	−0.0016 (17)
O8	0.046 (3)	0.0165 (19)	0.033 (2)	0.0039 (18)	−0.013 (2)	−0.0047 (16)
S1S	0.0401 (9)	0.0298 (7)	0.0289 (7)	−0.0069 (8)	−0.0017 (8)	0.0033 (5)
C1SA	0.083 (9)	0.098 (10)	0.144 (12)	0.052 (8)	−0.064 (8)	−0.085 (9)
C1SB	0.078 (8)	0.070 (8)	0.129 (11)	−0.045 (6)	0.057 (7)	−0.056 (8)
O1S	0.048 (3)	0.0250 (19)	0.0251 (18)	−0.008 (2)	−0.001 (2)	0.0046 (15)
S2S	0.0341 (8)	0.0470 (9)	0.0235 (6)	−0.0043 (8)	−0.0032 (7)	0.0115 (6)
C2SA	0.034 (4)	0.047 (4)	0.040 (4)	−0.005 (3)	−0.007 (3)	0.013 (4)
C2SB	0.031 (3)	0.055 (5)	0.030 (4)	−0.001 (3)	0.001 (3)	0.012 (3)
O2S	0.052 (3)	0.040 (2)	0.027 (2)	−0.003 (3)	−0.004 (2)	0.0009 (17)
S3S	0.0304 (7)	0.0186 (6)	0.0267 (6)	−0.0023 (6)	0.0001 (7)	−0.0035 (5)
C3SA	0.027 (3)	0.029 (3)	0.035 (3)	0.001 (3)	0.000 (3)	0.001 (3)
C3SB	0.028 (3)	0.023 (3)	0.045 (4)	0.001 (3)	−0.001 (3)	−0.006 (3)
O3S	0.042 (2)	0.0189 (18)	0.0265 (19)	0.000 (2)	−0.004 (2)	−0.0004 (14)

Geometric parameters (Å, º)

N1—C1A	1.356 (7)	O6—H6O	0.8400
N1—C2	1.386 (7)	O8—H8O	0.8400
N1—H1N	0.96 (7)	S1S—O1S	1.533 (4)
C2—C3	1.375 (7)	S1S—C1SB	1.746 (10)
C2—C10	1.474 (8)	S1S—C1SA	1.766 (11)
C3—C3A	1.425 (7)	C1SA—H1SA	0.9800
C3—H3	0.9500	C1SA—H1SB	0.9800
C3A—C1A	1.409 (7)	C1SA—H1SC	0.9800
C3A—C4	1.449 (7)	C1SB—H1SD	0.9800
C4—O3	1.217 (6)	C1SB—H1SE	0.9800
C4—C5	1.563 (7)	C1SB—H1SF	0.9800
C5—O4	1.207 (7)	S2S—O2S	1.484 (5)
C5—C5A	1.515 (7)	S2S—C2SB	1.775 (7)
C5A—N6	1.342 (7)	S2S—C2SA	1.780 (8)
C5A—C9A	1.415 (7)	C2SA—H2SA	0.9800
N6—C7	1.343 (7)	C2SA—H2SB	0.9800
C7—C8	1.401 (7)	C2SA—H2SC	0.9800
C7—C11	1.516 (7)	C2SB—H2SD	0.9800
C8—C9	1.391 (8)	C2SB—H2SE	0.9800
C8—H8	0.9500	C2SB—H2SF	0.9800
C9—C9A	1.424 (7)	S3S—O3S	1.561 (4)
C9—C12	1.525 (7)	S3S—C3SB	1.762 (7)
C9A—C1A	1.455 (8)	S3S—C3SA	1.780 (7)
C10—O1	1.215 (8)	C3SA—H3SA	0.9800
C10—O2	1.327 (7)	C3SA—H3SB	0.9800
C11—O5	1.223 (7)	C3SA—H3SC	0.9800
C11—O6	1.308 (7)	C3SB—H3SD	0.9800
C12—O7	1.239 (7)	C3SB—H3SE	0.9800
C12—O8	1.275 (7)	C3SB—H3SF	0.9800
O2—H2O	0.8400
C1A—N1—C2	110.4 (5)	C11—O6—H6O	109.5
C1A—N1—H1N	122 (4)	C12—O8—H8O	109.5
C2—N1—H1N	127 (4)	O1S—S1S—C1SB	105.5 (4)
C3—C2—N1	108.5 (5)	O1S—S1S—C1SA	106.3 (4)
C3—C2—C10	133.4 (5)	C1SB—S1S—C1SA	96.6 (7)
N1—C2—C10	118.1 (5)	S1S—C1SA—H1SA	109.5
C2—C3—C3A	106.3 (4)	S1S—C1SA—H1SB	109.5
C2—C3—H3	126.8	H1SA—C1SA—H1SB	109.5
C3A—C3—H3	126.8	S1S—C1SA—H1SC	109.5
C1A—C3A—C3	108.2 (4)	H1SA—C1SA—H1SC	109.5
C1A—C3A—C4	122.5 (5)	H1SB—C1SA—H1SC	109.5
C3—C3A—C4	129.2 (5)	S1S—C1SB—H1SD	109.5
O3—C4—C3A	126.1 (5)	S1S—C1SB—H1SE	109.5
O3—C4—C5	119.4 (5)	H1SD—C1SB—H1SE	109.5
C3A—C4—C5	114.5 (4)	S1S—C1SB—H1SF	109.5
O4—C5—C5A	122.5 (5)	H1SD—C1SB—H1SF	109.5
O4—C5—C4	118.4 (5)	H1SE—C1SB—H1SF	109.5
C5A—C5—C4	119.1 (4)	O2S—S2S—C2SB	106.9 (4)
N6—C5A—C9A	125.1 (5)	O2S—S2S—C2SA	106.9 (4)
N6—C5A—C5	113.7 (5)	C2SB—S2S—C2SA	96.4 (3)
C9A—C5A—C5	121.2 (5)	S2S—C2SA—H2SA	109.5
C5A—N6—C7	117.4 (5)	S2S—C2SA—H2SB	109.5
N6—C7—C8	122.5 (5)	H2SA—C2SA—H2SB	109.5
N6—C7—C11	117.5 (5)	S2S—C2SA—H2SC	109.5
C8—C7—C11	120.0 (5)	H2SA—C2SA—H2SC	109.5
C9—C8—C7	120.1 (5)	H2SB—C2SA—H2SC	109.5
C9—C8—H8	119.9	S2S—C2SB—H2SD	109.5
C7—C8—H8	119.9	S2S—C2SB—H2SE	109.5
C8—C9—C9A	118.5 (5)	H2SD—C2SB—H2SE	109.5
C8—C9—C12	114.9 (5)	S2S—C2SB—H2SF	109.5
C9A—C9—C12	126.6 (5)	H2SD—C2SB—H2SF	109.5
C5A—C9A—C9	116.3 (5)	H2SE—C2SB—H2SF	109.5
C5A—C9A—C1A	117.2 (5)	O3S—S3S—C3SB	103.3 (3)
C9—C9A—C1A	126.5 (5)	O3S—S3S—C3SA	102.6 (3)
N1—C1A—C3A	106.5 (5)	C3SB—S3S—C3SA	100.5 (3)
N1—C1A—C9A	128.8 (5)	S3S—C3SA—H3SA	109.5
C3A—C1A—C9A	124.5 (5)	S3S—C3SA—H3SB	109.5
O1—C10—O2	125.6 (5)	H3SA—C3SA—H3SB	109.5
O1—C10—C2	121.4 (5)	S3S—C3SA—H3SC	109.5
O2—C10—C2	113.0 (5)	H3SA—C3SA—H3SC	109.5
O5—C11—O6	125.1 (5)	H3SB—C3SA—H3SC	109.5
O5—C11—C7	122.0 (5)	S3S—C3SB—H3SD	109.5
O6—C11—C7	112.8 (5)	S3S—C3SB—H3SE	109.5
O7—C12—O8	124.7 (5)	H3SD—C3SB—H3SE	109.5
O7—C12—C9	121.5 (5)	S3S—C3SB—H3SF	109.5
O8—C12—C9	113.7 (5)	H3SD—C3SB—H3SF	109.5
C10—O2—H2O	109.5	H3SE—C3SB—H3SF	109.5
C1A—N1—C2—C3	−0.3 (7)	N6—C5A—C9A—C1A	178.4 (5)
C1A—N1—C2—C10	178.9 (5)	C5—C5A—C9A—C1A	1.1 (8)
N1—C2—C3—C3A	0.1 (7)	C8—C9—C9A—C5A	1.8 (8)
C10—C2—C3—C3A	−179.0 (6)	C12—C9—C9A—C5A	−177.2 (5)
C2—C3—C3A—C1A	0.1 (7)	C8—C9—C9A—C1A	−174.8 (5)
C2—C3—C3A—C4	176.5 (6)	C12—C9—C9A—C1A	6.2 (9)
C1A—C3A—C4—O3	−178.7 (6)	C2—N1—C1A—C3A	0.4 (6)
C3—C3A—C4—O3	5.3 (11)	C2—N1—C1A—C9A	176.4 (5)
C1A—C3A—C4—C5	2.6 (8)	C3—C3A—C1A—N1	−0.3 (6)
C3—C3A—C4—C5	−173.3 (6)	C4—C3A—C1A—N1	−177.0 (5)
O3—C4—C5—O4	−9.2 (9)	C3—C3A—C1A—C9A	−176.5 (5)
C3A—C4—C5—O4	169.6 (5)	C4—C3A—C1A—C9A	6.8 (9)
O3—C4—C5—C5A	171.7 (6)	C5A—C9A—C1A—N1	175.9 (5)
C3A—C4—C5—C5A	−9.5 (8)	C9—C9A—C1A—N1	−7.5 (9)
O4—C5—C5A—N6	11.2 (8)	C5A—C9A—C1A—C3A	−8.8 (8)
C4—C5—C5A—N6	−169.7 (5)	C9—C9A—C1A—C3A	167.9 (6)
O4—C5—C5A—C9A	−171.2 (5)	C3—C2—C10—O1	175.0 (7)
C4—C5—C5A—C9A	7.8 (8)	N1—C2—C10—O1	−4.1 (9)
C9A—C5A—N6—C7	−2.6 (8)	C3—C2—C10—O2	−4.3 (10)
C5—C5A—N6—C7	174.9 (5)	N1—C2—C10—O2	176.6 (5)
C5A—N6—C7—C8	0.5 (8)	N6—C7—C11—O5	−9.9 (9)
C5A—N6—C7—C11	−178.1 (5)	C8—C7—C11—O5	171.5 (6)
N6—C7—C8—C9	2.7 (9)	N6—C7—C11—O6	171.5 (5)
C11—C7—C8—C9	−178.7 (5)	C8—C7—C11—O6	−7.2 (8)
C7—C8—C9—C9A	−3.7 (8)	C8—C9—C12—O7	−143.3 (6)
C7—C8—C9—C12	175.4 (5)	C9A—C9—C12—O7	35.7 (9)
N6—C5A—C9A—C9	1.4 (8)	C8—C9—C12—O8	33.0 (7)
C5—C5A—C9A—C9	−175.9 (5)	C9A—C9—C12—O8	−148.0 (6)