4,4'-Bipyridinium bis(3,5-di­carboxy­benzoate) benzene-1,3,5-tri­carboxyl­ic acid hexahydrate

The asymmetric unit of the title compound, C₁₀H₁₀N₂²⁺·2C₉H₅O₆^-·C₉H₆O₆·6H₂O, consists of half of a bipyridinium cation, one singly deprotonated 3,5-di­carboxy­benzoate anion, one half of a benzene-1,3,5-tri­carboxyl­ic acid mol­ecule and three water mol­ecules that are linked by hydrogen bonds into a network structure. The two halves of the bipyridinium cation are related by an inversion centre and those of the benzene-1,3,5-tri­carboxyl­ic acid mol­ecule by twofold rotation.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.072
• wR factor = 0.157
• Data-to-parameter ratio = 11.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H9     ..  H12A    ..       1.50 Ang.
PLAT420_ALERT_2_B D-H Without Acceptor       O10    -   H10B   ...          ?

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.06
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.30

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C37 H38 N2 O24
            Atom count from _chemical_formula_moiety:C37 H38 N2 O14

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

---

Computing details

Data collection: SMART (Siemens, 1997); cell refinement: SAINT (Siemens, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

4,4'-Bipyridinium bis(3,5-dicarboxybenzoate) benzene-1,3,5-tricarboxylic acid hexahydrate

Crystal data

C10H10N2^2+·2C9H5O^6^−·C9H6O6·6H2O	F(000) = 1864
Mr = 894.69	Dx = 1.541 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -c2yc	Cell parameters from 3430 reflections
a = 10.9217 (7) Å	θ = 1.9–25.1°
b = 21.5274 (17) Å	µ = 0.13 mm^−1
c = 16.4036 (11) Å	T = 298 K
β = 91.037 (1)°	Prism, yellow
V = 3856.1 (5) Å^3	0.39 × 0.20 × 0.14 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3430 independent reflections
Radiation source: fine-focus sealed tube	3246 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 25.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.97, Tmax = 0.98	k = −25→25
10107 measured reflections	l = −14→19

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)] = 0.072	Hydrogen site location: geom & difmap
wR(F^2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.22	w = 1/[σ^2(Fo^2) + (0.0505P)^2 + 7.1401P] where P = (Fo^2 + 2Fc^2)/3
3430 reflections	(Δ/σ)max = 0.001
308 parameters	Δρmax = 0.26 e Å^−3
6 restraints	Δρmin = −0.27 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	Occ. (<1)
C1	0.7011 (2)	0.54548 (12)	0.31196 (15)	0.0302 (6)
C2	0.6567 (2)	0.52281 (12)	0.23812 (15)	0.0308 (6)
H2	0.6511	0.4801	0.2301	0.037*
C3	0.6203 (2)	0.56282 (12)	0.17611 (15)	0.0295 (6)
C4	0.6287 (2)	0.62666 (12)	0.18816 (15)	0.0303 (6)
H4	0.6048	0.6538	0.1467	0.036*
C5	0.6727 (2)	0.65003 (12)	0.26218 (15)	0.0309 (6)
C6	0.7084 (2)	0.60897 (13)	0.32359 (15)	0.0311 (6)
H6	0.7375	0.6244	0.3732	0.037*
C7	0.7411 (3)	0.50168 (13)	0.37913 (16)	0.0356 (6)
C8	0.5708 (2)	0.53654 (13)	0.09845 (15)	0.0315 (6)
C9	0.6822 (3)	0.71804 (13)	0.27893 (17)	0.0381 (7)
C10	0.5000	0.01441 (17)	0.2500	0.0309 (8)
H10	0.5000	−0.0288	0.2500	0.037*
C11	0.4522 (2)	0.04629 (12)	0.18321 (15)	0.0299 (6)
C12	0.4528 (2)	0.11068 (12)	0.18330 (15)	0.0310 (6)
H12	0.4215	0.1322	0.1385	0.037*
C13	0.5000	0.14322 (17)	0.2500	0.0302 (8)
C14	0.5000	0.21204 (19)	0.2500	0.0392 (10)
C15	0.3982 (3)	0.00942 (13)	0.11398 (16)	0.0342 (6)
C16	0.4449 (4)	0.15520 (17)	0.9546 (2)	0.0625 (10)
H16	0.4558	0.1142	0.9383	0.075*
C17	0.3303 (4)	0.17690 (15)	0.9684 (2)	0.0560 (9)
H17	0.2633	0.1506	0.9616	0.067*
C18	0.3122 (3)	0.23763 (13)	0.99228 (16)	0.0413 (7)
C19	0.4161 (4)	0.27441 (16)	1.0008 (2)	0.0562 (9)
H19	0.4080	0.3157	1.0167	0.067*
C20	0.5285 (4)	0.25129 (19)	0.9865 (2)	0.0677 (11)
H20	0.5972	0.2766	0.9921	0.081*
H10A	0.737 (5)	0.3924 (13)	0.050 (3)	0.101*
H11A	0.688 (5)	0.893 (2)	0.213 (2)	0.101*
H11B	0.653 (5)	0.890 (2)	0.291 (2)	0.101*
O1	0.5584 (2)	0.47989 (9)	0.09028 (12)	0.0478 (6)
O2	0.5413 (2)	0.57603 (9)	0.04248 (12)	0.0484 (6)
H2A	0.5131	0.5576	0.0027	0.073*
O3	0.6434 (3)	0.75311 (10)	0.21786 (14)	0.0569 (7)
H3	0.6487	0.7898	0.2309	0.085*
O4	0.7216 (3)	0.73839 (10)	0.34260 (14)	0.0629 (7)
O5	0.7741 (2)	0.52706 (10)	0.44551 (12)	0.0536 (6)
O6	0.7398 (3)	0.44521 (10)	0.36727 (13)	0.0594 (7)
O7	0.3905 (2)	−0.04722 (10)	0.11805 (12)	0.0514 (6)
O8	0.3603 (2)	0.04188 (9)	0.05282 (12)	0.0472 (6)
H8	0.3393	0.0187	0.0155	0.071*
O9	0.4470 (3)	0.23946 (11)	0.19157 (16)	0.0664 (8)
H9	0.4922	0.2664	0.1736	0.100*	0.50
O10	0.7287 (3)	0.35565 (14)	0.0483 (2)	0.0812 (9)
O11	0.6689 (5)	0.87131 (13)	0.2512 (2)	0.1117 (15)
O12	0.4832 (7)	0.36164 (18)	0.1670 (4)	0.182 (3)
N1	0.5410 (3)	0.19191 (14)	0.96419 (17)	0.0600 (8)
H1	0.6130	0.1773	0.9559	0.072*
H12B	0.457 (4)	0.3964 (15)	0.158 (3)	0.090*
H10B	0.701 (5)	0.349 (2)	0.093 (2)	0.090*
H12A	0.444 (4)	0.3313 (18)	0.179 (3)	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0322 (14)	0.0340 (14)	0.0241 (13)	0.0043 (11)	−0.0038 (11)	0.0004 (11)
C2	0.0355 (15)	0.0292 (14)	0.0275 (14)	0.0028 (11)	−0.0037 (11)	0.0014 (11)
C3	0.0305 (14)	0.0337 (14)	0.0243 (13)	−0.0007 (11)	−0.0032 (11)	0.0013 (11)
C4	0.0328 (15)	0.0332 (14)	0.0247 (13)	0.0025 (11)	−0.0026 (11)	0.0041 (11)
C5	0.0319 (14)	0.0340 (14)	0.0267 (13)	0.0004 (11)	−0.0012 (11)	0.0014 (11)
C6	0.0329 (15)	0.0372 (15)	0.0232 (13)	0.0001 (12)	−0.0045 (11)	−0.0009 (11)
C7	0.0442 (17)	0.0343 (16)	0.0282 (14)	0.0092 (13)	−0.0040 (12)	0.0030 (12)
C8	0.0349 (15)	0.0349 (16)	0.0244 (13)	0.0008 (12)	−0.0046 (11)	0.0022 (11)
C9	0.0484 (18)	0.0345 (15)	0.0314 (15)	0.0002 (13)	0.0018 (13)	−0.0014 (12)
C10	0.032 (2)	0.0287 (19)	0.032 (2)	0.000	−0.0019 (16)	0.000
C11	0.0296 (14)	0.0367 (15)	0.0233 (13)	0.0011 (11)	−0.0031 (11)	0.0004 (11)
C12	0.0338 (15)	0.0359 (15)	0.0230 (13)	−0.0001 (12)	−0.0060 (11)	0.0042 (11)
C13	0.032 (2)	0.033 (2)	0.0259 (18)	0.000	−0.0025 (15)	0.000
C14	0.053 (3)	0.033 (2)	0.032 (2)	0.000	−0.0040 (19)	0.000
C15	0.0395 (16)	0.0363 (16)	0.0268 (14)	0.0010 (12)	−0.0038 (12)	−0.0040 (12)
C16	0.083 (3)	0.0407 (19)	0.064 (2)	−0.0006 (19)	0.005 (2)	0.0022 (17)
C17	0.071 (2)	0.0345 (17)	0.062 (2)	−0.0088 (17)	0.0018 (18)	−0.0039 (15)
C18	0.072 (2)	0.0289 (15)	0.0231 (13)	−0.0091 (14)	−0.0047 (14)	0.0044 (11)
C19	0.076 (3)	0.0380 (18)	0.055 (2)	−0.0132 (18)	0.0016 (18)	−0.0057 (15)
C20	0.073 (3)	0.067 (3)	0.063 (2)	−0.019 (2)	0.000 (2)	−0.007 (2)
O1	0.0746 (16)	0.0352 (12)	0.0329 (11)	−0.0042 (10)	−0.0170 (10)	−0.0014 (9)
O2	0.0757 (16)	0.0410 (12)	0.0277 (11)	−0.0015 (11)	−0.0234 (10)	0.0030 (9)
O3	0.0897 (18)	0.0329 (11)	0.0476 (13)	0.0038 (12)	−0.0127 (12)	0.0050 (10)
O4	0.108 (2)	0.0386 (12)	0.0419 (13)	−0.0046 (13)	−0.0151 (13)	−0.0073 (10)
O5	0.0882 (18)	0.0429 (12)	0.0287 (11)	0.0089 (12)	−0.0252 (11)	0.0004 (9)
O6	0.106 (2)	0.0359 (12)	0.0357 (12)	0.0165 (12)	−0.0167 (12)	0.0032 (9)
O7	0.0785 (17)	0.0361 (12)	0.0388 (12)	0.0026 (11)	−0.0199 (11)	−0.0062 (9)
O8	0.0730 (15)	0.0414 (12)	0.0264 (10)	−0.0057 (11)	−0.0206 (10)	−0.0016 (9)
O9	0.098 (2)	0.0405 (14)	0.0599 (16)	−0.0011 (13)	−0.0263 (15)	0.0147 (11)
O10	0.083 (2)	0.0566 (17)	0.104 (2)	−0.0124 (16)	−0.0047 (19)	−0.0137 (18)
O11	0.233 (5)	0.0354 (15)	0.068 (2)	−0.001 (2)	0.047 (3)	0.0027 (13)
O12	0.327 (8)	0.054 (2)	0.162 (4)	−0.026 (4)	−0.080 (5)	0.022 (3)
N1	0.068 (2)	0.062 (2)	0.0508 (17)	0.0027 (16)	0.0000 (15)	0.0063 (15)

Geometric parameters (Å, º)

C1—C6	1.382 (4)	C14—O9^i	1.258 (3)
C1—C2	1.386 (4)	C14—O9	1.258 (3)
C1—C7	1.509 (4)	C15—O7	1.224 (3)
C2—C3	1.385 (4)	C15—O8	1.285 (3)
C2—H2	0.9300	C16—N1	1.321 (5)
C3—C4	1.391 (4)	C16—C17	1.359 (5)
C3—C8	1.487 (3)	C16—H16	0.9300
C4—C5	1.392 (4)	C17—C18	1.380 (4)
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.390 (4)	C18—C19	1.389 (5)
C5—C9	1.493 (4)	C18—C18^ii	1.485 (7)
C6—H6	0.9300	C19—C20	1.350 (5)
C7—O6	1.231 (3)	C19—H19	0.9300
C7—O5	1.265 (3)	C20—N1	1.337 (5)
C8—O1	1.234 (3)	C20—H20	0.9300
C8—O2	1.288 (3)	O2—H2A	0.8200
C9—O4	1.205 (4)	O3—H3	0.8200
C9—O3	1.318 (4)	O8—H8	0.8200
C10—C11	1.387 (3)	O9—H9	0.8200
C10—C11^i	1.387 (3)	O10—H10A	0.80 (3)
C10—H10	0.9300	O10—H10B	0.81 (3)
C11—C12	1.386 (4)	O11—H11A	0.81 (3)
C11—C15	1.498 (4)	O11—H11B	0.79 (3)
C12—C13	1.390 (3)	O12—H12B	0.81 (3)
C12—H12	0.9300	O12—H12A	0.81 (3)
C13—C12^i	1.390 (3)	N1—H1	0.8600
C13—C14	1.481 (5)
C6—C1—C2	119.2 (2)	C13—C12—H12	119.8
C6—C1—C7	120.1 (2)	C12—C13—C12^i	119.5 (3)
C2—C1—C7	120.7 (2)	C12—C13—C14	120.26 (17)
C3—C2—C1	120.9 (2)	C12^i—C13—C14	120.26 (17)
C3—C2—H2	119.5	O9^i—C14—O9	124.0 (4)
C1—C2—H2	119.5	O9^i—C14—C13	118.0 (2)
C2—C3—C4	119.5 (2)	O9—C14—C13	118.0 (2)
C2—C3—C8	119.2 (2)	O7—C15—O8	124.3 (2)
C4—C3—C8	121.3 (2)	O7—C15—C11	120.9 (2)
C3—C4—C5	120.1 (2)	O8—C15—C11	114.9 (2)
C3—C4—H4	119.9	N1—C16—C17	120.5 (3)
C5—C4—H4	119.9	N1—C16—H16	119.8
C6—C5—C4	119.3 (2)	C17—C16—H16	119.8
C6—C5—C9	118.2 (2)	C16—C17—C18	120.7 (3)
C4—C5—C9	122.5 (2)	C16—C17—H17	119.7
C1—C6—C5	120.9 (2)	C18—C17—H17	119.7
C1—C6—H6	119.5	C17—C18—C19	116.6 (3)
C5—C6—H6	119.5	C17—C18—C18^ii	121.6 (4)
O6—C7—O5	124.4 (3)	C19—C18—C18^ii	121.8 (3)
O6—C7—C1	120.0 (2)	C20—C19—C18	121.1 (3)
O5—C7—C1	115.6 (2)	C20—C19—H19	119.4
O1—C8—O2	123.3 (2)	C18—C19—H19	119.4
O1—C8—C3	120.4 (2)	N1—C20—C19	119.8 (4)
O2—C8—C3	116.2 (2)	N1—C20—H20	120.1
O4—C9—O3	123.7 (3)	C19—C20—H20	120.1
O4—C9—C5	122.6 (3)	C8—O2—H2A	109.5
O3—C9—C5	113.7 (2)	C9—O3—H3	109.5
C11—C10—C11^i	120.7 (3)	C15—O8—H8	109.5
C11—C10—H10	119.7	C14—O9—H9	109.5
C11^i—C10—H10	119.7	H10A—O10—H10B	101 (5)
C12—C11—C10	119.5 (2)	H11A—O11—H11B	116 (5)
C12—C11—C15	122.2 (2)	H12B—O12—H12A	127 (5)
C10—C11—C15	118.3 (2)	C16—N1—C20	121.3 (4)
C11—C12—C13	120.4 (2)	C16—N1—H1	119.3
C11—C12—H12	119.8	C20—N1—H1	119.3
C6—C1—C2—C3	0.4 (4)	C4—C5—C9—O3	1.0 (4)
C7—C1—C2—C3	−179.7 (2)	C11^i—C10—C11—C12	0.25 (18)
C1—C2—C3—C4	0.0 (4)	C11^i—C10—C11—C15	−178.0 (3)
C1—C2—C3—C8	−178.8 (2)	C10—C11—C12—C13	−0.5 (4)
C2—C3—C4—C5	−0.3 (4)	C15—C11—C12—C13	177.7 (2)
C8—C3—C4—C5	178.5 (2)	C11—C12—C13—C12^i	0.25 (18)
C3—C4—C5—C6	0.2 (4)	C11—C12—C13—C14	−179.75 (18)
C3—C4—C5—C9	−179.2 (3)	C12—C13—C14—O9^i	−174.0 (2)
C2—C1—C6—C5	−0.5 (4)	C12^i—C13—C14—O9^i	6.0 (2)
C7—C1—C6—C5	179.5 (3)	C12—C13—C14—O9	6.0 (2)
C4—C5—C6—C1	0.3 (4)	C12^i—C13—C14—O9	−174.0 (2)
C9—C5—C6—C1	179.6 (3)	C12—C11—C15—O7	−174.4 (3)
C6—C1—C7—O6	−176.7 (3)	C10—C11—C15—O7	3.8 (4)
C2—C1—C7—O6	3.4 (4)	C12—C11—C15—O8	4.5 (4)
C6—C1—C7—O5	3.6 (4)	C10—C11—C15—O8	−177.2 (2)
C2—C1—C7—O5	−176.4 (3)	N1—C16—C17—C18	0.2 (6)
C2—C3—C8—O1	2.4 (4)	C16—C17—C18—C19	0.3 (5)
C4—C3—C8—O1	−176.4 (3)	C16—C17—C18—C18^ii	−180.0 (3)
C2—C3—C8—O2	−178.5 (3)	C17—C18—C19—C20	−0.2 (5)
C4—C3—C8—O2	2.8 (4)	C18^ii—C18—C19—C20	−179.9 (4)
C6—C5—C9—O4	1.5 (5)	C18—C19—C20—N1	−0.4 (6)
C4—C5—C9—O4	−179.1 (3)	C17—C16—N1—C20	−0.9 (6)
C6—C5—C9—O3	−178.4 (3)	C19—C20—N1—C16	1.0 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O7^iii	0.80 (3)	2.38 (4)	2.955 (4)	130 (5)
O10—H10A···O5^iv	0.80 (3)	2.48 (4)	3.081 (4)	134 (5)
O11—H11A···O6^v	0.81 (3)	1.91 (3)	2.716 (4)	170 (5)
O11—H11B···O7^vi	0.79 (3)	2.07 (3)	2.854 (4)	169 (5)
O2—H2A···O1^vii	0.82	1.88	2.700 (3)	176
O3—H3···O11	0.82	1.80	2.616 (4)	175
O8—H8···O5^viii	0.82	1.66	2.476 (3)	171
O9—H9···O12	0.82	2.06	2.691 (4)	134
N1—H1···O10^ix	0.86	1.87	2.727 (5)	173
O12—H12A···O9	0.81 (3)	1.99 (4)	2.691 (4)	145 (5)
O12—H12B···O1	0.81 (3)	2.39 (4)	2.963 (5)	128 (4)
O12—H12B···O6^i	0.81 (3)	2.42 (4)	3.072 (7)	137 (4)

Symmetry codes: (i) −x+1, y, −z+1/2; (iii) x+1/2, y+1/2, z; (iv) x, −y+1, z−1/2; (v) −x+3/2, y+1/2, −z+1/2; (vi) −x+1, y+1, −z+1/2; (vii) −x+1, −y+1, −z; (viii) x−1/2, −y+1/2, z−1/2; (ix) −x+3/2, −y+1/2, −z+1.