Hydro­gen-bonding patterns in 4,4′-bipyridinium bis(3-carboxy-4-hydroxy­benzene­sulfonate) dihydrate

In the title compound, C₁₀H₁₀N₂²⁺·2C₇H₅O₆S⁻·2H₂O, 4,4′-bi­pyridine is centrosymmetric and protonated at both N atoms. The inversion-related hydrogen-bonded supramol­ecular chains (made up of water mol­ecules and sulfonate motifs arranged in an alternating manner) are cross-linked by 4,4′-bipyridinium cations via N—H...O (sulfonate) hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• R factor = 0.047
• wR factor = 0.131
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: PLATON.

4,4'-bipyridinium bis(3-carboxy-4-hydroxy-benzenesulfonate) dihydrate

Crystal data

C10H10N2^2+·2C7H5O6S^−·2H2O	F(000) = 652
Mr = 628.59	Dx = 1.636 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2 y b c	Cell parameters from 50 reflections
a = 7.086 (2) Å	θ = 4.9–69.9°
b = 16.669 (3) Å	µ = 2.62 mm^−1
c = 10.915 (3) Å	T = 293 K
β = 98.13 (3)°	Plate-like crystal, colourless
V = 1276.3 (6) Å^3	0.31 × 0.23 × 0.17 mm
Z = 2

Data collection

Enraf–Nonius CAD-4 diffractometer	2126 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 69.9°, θmin = 4.9°
ω–2θ scans	h = −8→8
Absorption correction: psi scan (North et al., 1968)	k = −4→20
Tmin = 0.477, Tmax = 0.638	l = 0→13
2541 measured reflections	1 standard reflections every 100 reflections
2404 independent reflections	intensity decay: none

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
2418 reflections	(Δ/σ)max = 0.001
200 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.97 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
N1	0.8536 (3)	0.14294 (12)	0.08234 (17)	0.0419 (6)
C8	0.8943 (3)	0.06615 (16)	0.1039 (2)	0.0453 (7)
C9	0.7563 (3)	0.00847 (13)	0.0745 (2)	0.0387 (6)
C10	0.5744 (3)	0.03067 (11)	0.01895 (16)	0.0268 (5)
C11	0.5379 (3)	0.11196 (13)	0.0006 (2)	0.0405 (7)
C12	0.6796 (4)	0.16718 (13)	0.0337 (2)	0.0448 (8)
S1	0.27780 (6)	0.20168 (3)	0.67410 (4)	0.0254 (2)
O1	0.4764 (2)	0.21818 (10)	0.72011 (16)	0.0458 (5)
O2	0.1765 (2)	0.16621 (9)	0.76824 (13)	0.0356 (5)
O3	0.1808 (2)	0.27201 (8)	0.61562 (15)	0.0371 (5)
O4	0.1772 (2)	−0.10899 (8)	0.62249 (14)	0.0363 (5)
O5	0.2159 (2)	−0.14566 (8)	0.43054 (14)	0.0358 (4)
O6	0.2868 (3)	−0.03506 (10)	0.27263 (13)	0.0436 (5)
C1	0.2768 (2)	0.12942 (11)	0.55549 (16)	0.0232 (5)
C2	0.2445 (2)	0.04944 (11)	0.57844 (17)	0.0244 (5)
C3	0.2468 (2)	−0.00802 (11)	0.48568 (17)	0.0237 (5)
C4	0.2838 (3)	0.01651 (11)	0.36836 (17)	0.0270 (5)
C5	0.3180 (3)	0.09722 (12)	0.34573 (18)	0.0301 (6)
C6	0.3135 (3)	0.15301 (11)	0.43828 (18)	0.0284 (5)
C7	0.2114 (3)	−0.09337 (11)	0.50955 (18)	0.0257 (5)
O1W	0.8513 (2)	0.25846 (9)	0.32300 (15)	0.0392 (5)
H1	0.94820	0.17710	0.09800	0.0500*
H8	1.01650	0.05120	0.13910	0.0540*
H9	0.78440	−0.04530	0.09150	0.0460*
H11	0.41710	0.12900	−0.03420	0.0490*
H12	0.65430	0.22170	0.02220	0.0540*
H2	0.22100	0.03370	0.65660	0.0290*
H4	0.15700	−0.16400	0.63100	0.0440*
H5	0.34370	0.11330	0.26820	0.0360*
H6	0.33500	0.20680	0.42270	0.0340*
H6A	0.26310	−0.07800	0.29990	0.079 (12)*
H1W	0.95590	0.28300	0.29800	0.0470*
H2W	0.75190	0.27060	0.26300	0.0470*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0459 (11)	0.0431 (11)	0.0377 (10)	−0.0251 (8)	0.0095 (8)	−0.0096 (8)
C8	0.0383 (11)	0.0516 (14)	0.0421 (13)	−0.0129 (10)	−0.0074 (9)	−0.0032 (10)
C9	0.0391 (11)	0.0316 (10)	0.0418 (12)	−0.0065 (9)	−0.0068 (9)	0.0032 (9)
C10	0.0324 (10)	0.0237 (9)	0.0242 (9)	−0.0054 (8)	0.0033 (7)	−0.0010 (7)
C11	0.0387 (11)	0.0259 (10)	0.0561 (14)	−0.0032 (8)	0.0037 (10)	0.0010 (9)
C12	0.0541 (14)	0.0264 (11)	0.0558 (14)	−0.0119 (9)	0.0139 (11)	−0.0038 (10)
S1	0.0235 (3)	0.0214 (3)	0.0302 (3)	0.0037 (2)	−0.0002 (2)	−0.0058 (2)
O1	0.0272 (8)	0.0532 (9)	0.0544 (10)	0.0006 (7)	−0.0034 (7)	−0.0235 (8)
O2	0.0432 (8)	0.0327 (8)	0.0325 (8)	0.0063 (6)	0.0104 (6)	−0.0029 (6)
O3	0.0416 (8)	0.0216 (7)	0.0477 (9)	0.0087 (6)	0.0052 (7)	−0.0012 (6)
O4	0.0512 (9)	0.0224 (7)	0.0373 (8)	−0.0025 (6)	0.0128 (6)	0.0039 (6)
O5	0.0455 (8)	0.0220 (7)	0.0398 (8)	0.0023 (6)	0.0062 (6)	−0.0052 (6)
O6	0.0734 (11)	0.0305 (8)	0.0275 (7)	0.0016 (7)	0.0092 (7)	−0.0072 (6)
C1	0.0237 (8)	0.0193 (8)	0.0258 (9)	0.0034 (6)	0.0004 (7)	−0.0019 (7)
C2	0.0248 (8)	0.0224 (9)	0.0258 (9)	0.0024 (7)	0.0030 (7)	0.0004 (7)
C3	0.0235 (8)	0.0208 (9)	0.0264 (9)	0.0017 (6)	0.0026 (7)	−0.0002 (7)
C4	0.0312 (9)	0.0255 (9)	0.0235 (9)	0.0033 (7)	0.0008 (7)	−0.0017 (7)
C5	0.0375 (10)	0.0299 (10)	0.0230 (9)	−0.0002 (8)	0.0042 (8)	0.0034 (7)
C6	0.0333 (10)	0.0209 (9)	0.0295 (9)	−0.0011 (7)	−0.0004 (7)	0.0029 (7)
C7	0.0239 (8)	0.0208 (8)	0.0319 (9)	0.0023 (6)	0.0018 (7)	0.0001 (7)
O1W	0.0326 (7)	0.0338 (8)	0.0505 (9)	−0.0011 (6)	0.0031 (6)	0.0150 (7)

Geometric parameters (Å, º)

S1—C1	1.7676 (19)	C10—C11	1.389 (3)
S1—O3	1.4595 (15)	C11—C12	1.372 (3)
S1—O1	1.4520 (16)	C8—H8	0.9303
S1—O2	1.4592 (16)	C9—H9	0.9311
O4—C7	1.316 (2)	C11—H11	0.9304
O5—C7	1.230 (2)	C12—H12	0.9314
O6—C4	1.356 (2)	C1—C2	1.382 (3)
O4—H4	0.9347	C1—C6	1.398 (3)
O6—H6A	0.8020	C2—C3	1.396 (3)
O1W—H1W	0.9211	C3—C4	1.404 (3)
O1W—H2W	0.9140	C3—C7	1.474 (3)
N1—C8	1.326 (3)	C4—C5	1.395 (3)
N1—C12	1.334 (3)	C5—C6	1.377 (3)
N1—H1	0.8777	C2—H2	0.9298
C8—C9	1.377 (3)	C5—H5	0.9299
C9—C10	1.395 (3)	C6—H6	0.9292
C10—C10^i	1.485 (3)
S1···H6^ii	3.0892	C5···C7^iv	3.483 (3)
S1···H1W^iii	2.8230	C6···C7^iv	3.479 (3)
S1···H1^iii	3.1111	C7···C2^xi	3.319 (3)
O1···C12^ii	3.270 (3)	C7···C5^iv	3.483 (3)
O1···O1W^ii	2.762 (2)	C7···O1W^iv	3.368 (3)
O1···O5^iv	3.152 (2)	C7···C1^xi	3.484 (3)
O1W···O2^v	2.763 (2)	C7···C6^iv	3.479 (3)
O1W···N1	3.259 (3)	C8···C9^xii	3.582 (3)
O1W···O5^vi	3.173 (2)	C8···O4^iv	3.180 (3)
O1W···O1^vii	2.762 (2)	C8···O3^v	3.368 (3)
O1W···O4^iv	2.576 (2)	C9···O2^iv	3.379 (3)
O1W···C12^ii	3.016 (3)	C9···C8^xii	3.582 (3)
O1W···C7^iv	3.368 (3)	C12···O5^vi	3.217 (3)
O2···O1W^iii	2.763 (2)	C12···O1^vii	3.270 (3)
O2···C9^iv	3.379 (3)	C12···O1W^vii	3.016 (3)
O3···C8^iii	3.368 (3)	C4···H8^x	2.9738
O3···N1^iii	2.698 (3)	C5···H8^x	2.9794
O3···C5^ii	3.364 (3)	C7···H6A	2.3819
O4···O1W^iv	2.576 (2)	C9···H11^i	2.6079
O4···C8^iv	3.180 (3)	C9···H2^iv	3.0002
O5···O1^iv	3.152 (2)	C11···H9^i	2.6099
O5···O1W^viii	3.173 (2)	C12···H2W	3.0225
O5···C12^viii	3.217 (3)	H1···O3^v	1.8394
O5···O6	2.620 (2)	H1···S1^v	3.1111
O6···O5	2.620 (2)	H1W···O2^v	1.8465
O1···H2W^ii	1.9511	H1W···O3^v	2.8706
O1···H6^ii	2.8432	H1W···S1^v	2.8230
O1···H12^ii	2.8337	H1W···O5^vi	2.8740
O1W···H12^ii	2.7648	H1W···H4^iv	2.3131
O1W···H4^iv	1.6562	H2···O2	2.5636
O2···H11^ix	2.6271	H2···O4	2.4206
O2···H6^ii	2.8371	H2···C9^iv	3.0002
O2···H9^iv	2.5224	H2W···C12	3.0225
O2···H2	2.5636	H2W···O5^vi	2.5689
O2···H1W^iii	1.8465	H2W···O1^vii	1.9511
O3···H1W^iii	2.8706	H2W···H4^iv	2.1683
O3···H1^iii	1.8394	H4···H2W^iv	2.1683
O3···H5^ii	2.6865	H4···H1W^iv	2.3131
O3···H6	2.7314	H4···O1W^iv	1.6562
O4···H2	2.4206	H5···O3^vii	2.6865
O5···H6A	1.8847	H6···O2^vii	2.8371
O5···H1W^viii	2.8740	H6···O1^vii	2.8433
O5···H12^viii	2.4220	H6···O3	2.7314
O5···H2W^viii	2.5689	H6···S1^vii	3.0892
O6···H8^x	2.6591	H6A···O5	1.8847
N1···O3^v	2.698 (3)	H6A···C7	2.3819
N1···O1W	3.259 (3)	H8···C4^xiii	2.9738
C1···C7^xi	3.484 (3)	H8···C5^xiii	2.9794
C2···C7^xi	3.319 (3)	H8···O6^xiii	2.6591
C2···C4^iv	3.488 (3)	H9···H11^i	2.0307
C2···C3^xi	3.521 (2)	H9···C11^i	2.6099
C3···C3^xi	3.565 (2)	H9···O2^iv	2.5224
C3···C3^iv	3.568 (2)	H11···H9^i	2.0307
C3···C2^xi	3.521 (2)	H11···C9^i	2.6079
C3···C4^iv	3.482 (3)	H11···O2^xiv	2.6271
C4···C3^iv	3.482 (3)	H12···O5^vi	2.4220
C4···C2^iv	3.488 (3)	H12···O1^vii	2.8337
C5···O3^vii	3.364 (3)	H12···O1W^vii	2.7648
O2—S1—C1	106.75 (9)	C12—C11—H11	119.96
O3—S1—C1	105.91 (9)	C11—C12—H12	119.95
O1—S1—C1	106.60 (9)	N1—C12—H12	119.90
O1—S1—O2	112.48 (10)	S1—C1—C6	119.79 (14)
O1—S1—O3	111.87 (10)	C2—C1—C6	119.64 (17)
O2—S1—O3	112.66 (9)	S1—C1—C2	120.56 (14)
C7—O4—H4	109.78	C1—C2—C3	120.77 (17)
C4—O6—H6A	104.65	C2—C3—C4	119.00 (17)
H1W—O1W—H2W	105.09	C2—C3—C7	120.96 (17)
C8—N1—C12	121.9 (2)	C4—C3—C7	120.05 (17)
C12—N1—H1	121.22	O6—C4—C3	122.94 (17)
C8—N1—H1	116.79	C3—C4—C5	120.12 (17)
N1—C8—C9	120.2 (2)	O6—C4—C5	116.93 (17)
C8—C9—C10	119.9 (2)	C4—C5—C6	119.92 (18)
C9—C10—C10^i	120.97 (18)	C1—C6—C5	120.55 (18)
C10^i—C10—C11	121.42 (19)	O4—C7—O5	122.91 (17)
C9—C10—C11	117.61 (19)	O4—C7—C3	114.53 (16)
C10—C11—C12	120.1 (2)	O5—C7—C3	122.56 (18)
N1—C12—C11	120.1 (2)	C3—C2—H2	119.60
C9—C8—H8	119.88	C1—C2—H2	119.63
N1—C8—H8	119.89	C4—C5—H5	120.02
C8—C9—H9	120.07	C6—C5—H5	120.06
C10—C9—H9	120.03	C1—C6—H6	119.71
C10—C11—H11	119.91	C5—C6—H6	119.74
O1—S1—C1—C6	−77.83 (16)	C2—C1—C6—C5	−0.1 (3)
O2—S1—C1—C6	161.74 (15)	S1—C1—C2—C3	−178.90 (12)
O3—S1—C1—C6	41.46 (16)	S1—C1—C6—C5	178.36 (16)
O1—S1—C1—C2	100.62 (14)	C6—C1—C2—C3	−0.4 (2)
O2—S1—C1—C2	−19.81 (15)	C1—C2—C3—C4	0.4 (2)
O3—S1—C1—C2	−140.08 (13)	C1—C2—C3—C7	−179.67 (16)
C12—N1—C8—C9	0.9 (3)	C2—C3—C4—C5	0.1 (3)
C8—N1—C12—C11	−2.1 (3)	C2—C3—C7—O5	−178.62 (18)
N1—C8—C9—C10	1.6 (3)	C2—C3—C4—O6	−179.29 (18)
C8—C9—C10—C10^i	177.17 (19)	C2—C3—C7—O4	0.5 (3)
C8—C9—C10—C11	−2.9 (3)	C7—C3—C4—C5	−179.77 (19)
C9—C10—C10^i—C9^i	180.0 (2)	C4—C3—C7—O4	−179.56 (17)
C9—C10—C11—C12	1.7 (3)	C4—C3—C7—O5	1.3 (3)
C11—C10—C10^i—C9^i	0.0 (3)	C7—C3—C4—O6	0.8 (3)
C11—C10—C10^i—C11^i	−180.0 (2)	C3—C4—C5—C6	−0.7 (3)
C9—C10—C10^i—C11^i	0.0 (3)	O6—C4—C5—C6	178.8 (2)
C10^i—C10—C11—C12	−178.35 (19)	C4—C5—C6—C1	0.7 (3)
C10—C11—C12—N1	0.8 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^v	0.88	1.84	2.698 (3)	165
O1W—H1W···O2^v	0.92	1.85	2.763 (2)	173
O1W—H2W···O5^vi	0.91	2.57	3.173 (2)	124
O1W—H2W···O1^vii	0.91	1.95	2.762 (2)	147
O4—H4···O1W^iv	0.93	1.66	2.576 (2)	167
O6—H6A···O5	0.80	1.88	2.620 (2)	152
C2—H2···O2	0.93	2.56	2.932 (2)	104
C9—H9···O2^iv	0.93	2.52	3.379 (3)	153
C12—H12···O5^vi	0.93	2.42	3.217 (3)	143

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