Bis­(tetraethyl­ammonium) 2,2′-bi­pyridine-4,4′-di­carboxyl­ate tetrahydrate

The title compound, 2C₈H₂₀N⁺·C₁₂H₆N₂O₄²⁻·4H₂O, which is one of the precursors of the dye for DSC (dye-sensitized solar cells), consists of tetraethyl­ammonium cations, 2,2′-bi­pyridine-4,4′-di­carboxyl­ate anions and water mol­ecules. The anion has a centre of symmetry and the pyridine ring is inclined to the carboxyl­ate group by 7.9 (3)°. A two-dimensional network is formed through intermolecular O—H...O hydrogen bonds between water mol­ecules and the carboxyl­ate groups of the anions.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.059
• wR factor = 0.187
• Data-to-parameter ratio = 19.5

checkCIF/PLATON results

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Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         C6
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        N12
PLAT250_ALERT_2_C Large U3/U1 ratio for average U(i,j) tensor ....       2.67

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART-W2K/NT (Bruker, 2003); cell refinement: SMART-W2K/NT; data reduction: SAINT-W2K/NT (Bruker, 2003); program(s) used to solve structure: SHELXTL-NT (Bruker, 2003); program(s) used to refine structure: SHELXTL-NT; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL-NT.

Bis(tetraethylammonium) 2,2'-bipyridine-4,4'-dicarboxylate tetrahydrate

Crystal data

2C8H20N^+·C12H6N2O4^2^−·4H2O	F(000) = 628
Mr = 574.76	Dx = 1.161 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3258 reflections
a = 10.740 (2) Å	θ = 2.7–26.1°
b = 7.5172 (15) Å	µ = 0.08 mm^−1
c = 20.398 (4) Å	T = 297 K
β = 93.40 (3)°	Needle, colourless
V = 1643.9 (6) Å^3	0.51 × 0.22 × 0.21 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3924 independent reflections
Radiation source: fine-focus sealed tube	2868 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 8.366 pixels mm^-1	θmax = 28.0°, θmin = 1.9°
φ and ω scans	h = −14→12
Absorption correction: empirical (using intensity measurements) (SADABS; Scheldrick, 1996)	k = −9→9
Tmin = 0.976, Tmax = 0.982	l = −26→24
11634 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.1096P)^2 + 0.1896P] where P = (Fo^2 + 2Fc^2)/3
3924 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental. none

Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

$1 1 - x, -0.5 + y, 0.5 - z

- 7.1037 (0.0047) x - 0.8070 (0.0050) y - 14.2732 (0.0086) z = 0.0431 (0.0100)

* 0.0046 (0.0011) N1_$1 * -0.0056 (0.0010) C1_$1 * 0.0023 (0.0010) C2_$1 * 0.0019 (0.0011) C3_$1 * -0.0029 (0.0012) C4_$1 * -0.0003 (0.0012) C5_$1

Rms deviation of fitted atoms = 0.0034

7.1037 (0.0047) x - 0.8070 (0.0051) y + 14.2732 (0.0087) z = 13.8799 (0.0106)

Angle to previous plane (with approximate e.s.d.) = 12.3 (0.1)

* 0.0046 (0.0011) N1 * -0.0056 (0.0010) C1 * 0.0023 (0.0010) C2 * 0.0019 (0.0011) C3 * -0.0029 (0.0012) C4 * -0.0003 (0.0012) C5

Rms deviation of fitted atoms = 0.0034

6.4731 (0.0233) x + 0.0356 (0.0220) y + 15.4856 (0.0365) z = 15.6782 (0.0439)

Angle to previous plane (with approximate e.s.d.) = 7.9 (0.3)

* 0.0000 (0.0000) O1 * 0.0000 (0.0000) C6 * 0.0000 (0.0000) O2

Rms deviation of fitted atoms = 0.0000

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
N1	0.94168 (12)	0.69262 (17)	0.04085 (7)	0.0468 (3)
C1	0.95390 (12)	0.52034 (18)	0.02458 (7)	0.0361 (3)
C2	0.88453 (12)	0.38600 (18)	0.05172 (7)	0.0367 (3)
C3	0.79853 (13)	0.42740 (19)	0.09693 (7)	0.0388 (3)
C4	0.78513 (15)	0.6057 (2)	0.11323 (8)	0.0472 (4)
C5	0.85781 (15)	0.7313 (2)	0.08447 (9)	0.0513 (4)
C6	0.72243 (15)	0.2816 (2)	0.12765 (8)	0.0463 (4)
O1	0.75180 (16)	0.12661 (16)	0.11620 (9)	0.0865 (6)
O2	0.63897 (13)	0.32739 (17)	0.16271 (8)	0.0709 (4)
H2	0.8961	0.2683	0.0394	0.044*
H4	0.7277	0.6399	0.1432	0.057*
H5	0.8479	0.8499	0.0961	0.062*
N12	0.24920 (13)	0.0412 (2)	0.12718 (7)	0.0550 (4)
C11	0.27263 (19)	−0.0851 (3)	0.18496 (10)	0.0672 (5)
C12	0.1844 (3)	−0.2391 (4)	0.18647 (14)	0.0965 (8)
C13	0.3465 (2)	0.1874 (3)	0.13466 (11)	0.0726 (6)
C14	0.3427 (3)	0.3201 (3)	0.07911 (15)	0.0985 (9)
C15	0.1185 (2)	0.1180 (4)	0.12676 (13)	0.0854 (7)
C16	0.0893 (3)	0.2131 (5)	0.18866 (18)	0.1219 (12)
C17	0.2574 (2)	−0.0569 (3)	0.06324 (10)	0.0781 (6)
C18	0.3837 (3)	−0.1429 (4)	0.05483 (14)	0.1043 (9)
H11A	0.3569	−0.1309	0.1840	0.081*
H11B	0.2676	−0.0179	0.2253	0.081*
H12A	0.1008	−0.1957	0.1889	0.145*
H12B	0.2060	−0.3117	0.2242	0.145*
H12C	0.1900	−0.3087	0.1473	0.145*
H13A	0.3351	0.2506	0.1753	0.087*
H13B	0.4285	0.1330	0.1383	0.087*
H14A	0.3528	0.2590	0.0384	0.148*
H14B	0.4090	0.4048	0.0865	0.148*
H14C	0.2640	0.3811	0.0770	0.148*
H15A	0.1074	0.2004	0.0903	0.103*
H15B	0.0590	0.0222	0.1192	0.103*
H16A	0.0972	0.1319	0.2250	0.183*
H16B	0.0055	0.2581	0.1844	0.183*
H16C	0.1464	0.3102	0.1962	0.183*
H17A	0.2398	0.0256	0.0273	0.094*
H17B	0.1937	−0.1485	0.0604	0.094*
H18A	0.4477	−0.0538	0.0586	0.156*
H18B	0.3838	−0.1979	0.0124	0.156*
H18C	0.3992	−0.2314	0.0883	0.156*
O3	0.49461 (12)	0.59825 (19)	0.19880 (7)	0.0611 (4)
O4	0.63296 (15)	−0.08433 (18)	0.20773 (8)	0.0731 (5)
H3A	0.549 (2)	0.521 (3)	0.1853 (10)	0.071 (6)*
H3B	0.544 (2)	0.689 (3)	0.2054 (12)	0.081 (7)*
H4B	0.5915 (18)	−0.010 (3)	0.2341 (10)	0.062 (6)*
H4A	0.664 (2)	−0.016 (4)	0.1802 (14)	0.103 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0523 (7)	0.0331 (6)	0.0574 (8)	0.0015 (5)	0.0220 (6)	−0.0037 (5)
C1	0.0371 (7)	0.0326 (7)	0.0391 (7)	0.0046 (5)	0.0076 (5)	−0.0007 (5)
C2	0.0395 (7)	0.0297 (6)	0.0416 (7)	0.0041 (5)	0.0086 (5)	−0.0019 (5)
C3	0.0407 (7)	0.0345 (7)	0.0420 (7)	0.0033 (5)	0.0096 (6)	−0.0006 (5)
C4	0.0507 (8)	0.0382 (8)	0.0550 (9)	0.0039 (6)	0.0239 (7)	−0.0052 (6)
C5	0.0577 (9)	0.0314 (7)	0.0675 (10)	0.0015 (6)	0.0267 (8)	−0.0085 (7)
C6	0.0534 (9)	0.0362 (7)	0.0515 (9)	0.0012 (6)	0.0205 (7)	−0.0003 (6)
O1	0.1164 (12)	0.0333 (6)	0.1183 (13)	0.0030 (7)	0.0784 (11)	0.0021 (7)
O2	0.0746 (8)	0.0443 (7)	0.0995 (11)	0.0019 (6)	0.0532 (8)	0.0017 (6)
N12	0.0548 (8)	0.0544 (8)	0.0541 (8)	0.0000 (6)	−0.0123 (6)	0.0034 (6)
C11	0.0634 (11)	0.0777 (13)	0.0597 (11)	0.0094 (10)	−0.0041 (9)	0.0129 (10)
C12	0.0973 (18)	0.0944 (18)	0.0967 (18)	−0.0118 (15)	−0.0031 (15)	0.0356 (15)
C13	0.0746 (12)	0.0651 (12)	0.0758 (13)	−0.0097 (10)	−0.0167 (10)	−0.0053 (10)
C14	0.112 (2)	0.0681 (15)	0.112 (2)	−0.0314 (14)	−0.0241 (16)	0.0173 (13)
C15	0.0605 (12)	0.1001 (18)	0.0936 (17)	0.0126 (11)	−0.0130 (11)	0.0243 (14)
C16	0.095 (2)	0.147 (3)	0.124 (2)	0.060 (2)	0.0126 (17)	0.002 (2)
C17	0.1071 (17)	0.0697 (13)	0.0558 (11)	−0.0170 (13)	−0.0098 (11)	−0.0016 (9)
C18	0.145 (3)	0.0911 (18)	0.0790 (16)	0.0155 (18)	0.0279 (16)	−0.0129 (14)
O3	0.0553 (7)	0.0499 (7)	0.0802 (9)	0.0044 (6)	0.0229 (6)	−0.0017 (6)
O4	0.0943 (11)	0.0396 (7)	0.0899 (11)	−0.0045 (7)	0.0437 (9)	0.0013 (7)

Geometric parameters (Å, º)

C1—N1	1.3452 (19)	C13—H13B	0.9700
C1—C2	1.389 (2)	C14—H14A	0.9600
C1—C1^i	1.482 (3)	C14—H14B	0.9600
C2—C3	1.3788 (19)	C14—H14C	0.9600
C2—H2	0.9300	C15—C16	1.500 (4)
C3—C4	1.391 (2)	C15—N12	1.517 (3)
C3—C6	1.524 (2)	C15—H15A	0.9700
C4—C5	1.378 (2)	C15—H15B	0.9700
C4—H4	0.9300	C16—H16A	0.9600
C5—N1	1.3353 (19)	C16—H16B	0.9600
C5—H5	0.9300	C16—H16C	0.9600
C6—O2	1.2286 (19)	C17—N12	1.506 (3)
C6—O1	1.2331 (19)	C17—C18	1.521 (4)
C11—C12	1.498 (3)	C17—H17A	0.9700
C11—N12	1.523 (2)	C17—H17B	0.9700
C11—H11A	0.9700	C18—H18A	0.9600
C11—H11B	0.9700	C18—H18B	0.9600
C12—H12A	0.9600	C18—H18C	0.9600
C12—H12B	0.9600	O3—H3A	0.88 (2)
C12—H12C	0.9600	O3—H3B	0.87 (3)
C13—C14	1.509 (3)	O4—H4B	0.91 (2)
C13—N12	1.518 (3)	O4—H4A	0.84 (3)
C13—H13A	0.9700
N1—C1—C2	122.62 (12)	C16—C15—N12	114.6 (2)
N1—C1—C1^i	116.37 (15)	C16—C15—H15A	108.6
N1—C5—C4	123.79 (14)	C17—C18—H18A	109.5
N1—C5—H5	118.1	C17—C18—H18B	109.5
C1—C2—H2	120.0	C17—C18—H18C	109.5
C2—C1—C1^i	121.01 (15)	C17—N12—C15	106.45 (17)
C2—C3—C4	117.41 (13)	C17—N12—C13	111.49 (17)
C2—C3—C6	120.63 (13)	C17—N12—C11	110.46 (16)
C3—C2—C1	119.92 (13)	C18—C17—H17A	108.8
C3—C2—H2	120.0	C18—C17—H17B	108.8
C3—C4—H4	120.4	N12—C11—H11A	108.5
C4—C3—C6	121.95 (13)	N12—C11—H11B	108.5
C4—C5—H5	118.1	N12—C13—H13A	108.6
C5—C4—C3	119.29 (13)	N12—C13—H13B	108.6
C5—C4—H4	120.4	N12—C17—C18	113.84 (19)
C5—N1—C1	116.97 (13)	N12—C17—H17A	108.8
O1—C6—C3	116.89 (13)	N12—C17—H17B	108.8
O2—C6—O1	125.35 (15)	N12—C15—H15A	108.6
O2—C6—C3	117.75 (13)	N12—C15—H15B	108.6
C11—C12—H12A	109.5	H11A—C11—H11B	107.5
C11—C12—H12B	109.5	H12A—C12—H12B	109.5
C11—C12—H12C	109.5	H12A—C12—H12C	109.5
C12—C11—N12	114.98 (17)	H12B—C12—H12C	109.5
C12—C11—H11A	108.5	H13A—C13—H13B	107.6
C12—C11—H11B	108.5	H14A—C14—H14B	109.5
C13—C14—H14A	109.5	H14A—C14—H14C	109.5
C13—C14—H14B	109.5	H14B—C14—H14C	109.5
C13—C14—H14C	109.5	H15A—C15—H15B	107.6
C13—N12—C11	107.00 (14)	H16A—C16—H16B	109.5
C14—C13—N12	114.56 (18)	H16A—C16—H16C	109.5
C14—C13—H13A	108.6	H16B—C16—H16C	109.5
C14—C13—H13B	108.6	H17A—C17—H17B	107.7
C15—C16—H16A	109.5	H18A—C18—H18B	109.5
C15—C16—H16B	109.5	H18A—C18—H18C	109.5
C15—C16—H16C	109.5	H18B—C18—H18C	109.5
C15—N12—C13	110.86 (17)	H4B—O4—H4A	105 (2)
C15—N12—C11	110.62 (16)	H3A—O3—H3B	99 (2)
C16—C15—H15B	108.6
N1—C1—C2—C3	0.4 (2)	C6—C3—C4—C5	179.11 (16)
C1^i—C1—C2—C3	−179.42 (15)	C18—C17—N12—C15	179.7 (2)
C1—C2—C3—C4	0.2 (2)	C18—C17—N12—C13	58.7 (3)
C1—C2—C3—C6	−179.46 (13)	C18—C17—N12—C11	−60.1 (2)
C1^i—C1—N1—C5	179.18 (15)	C16—C15—N12—C17	176.7 (2)
C2—C3—C4—C5	−0.5 (2)	C16—C15—N12—C13	−61.9 (3)
C2—C3—C6—O2	−173.14 (16)	C16—C15—N12—C11	56.7 (3)
C2—C3—C6—O1	8.3 (2)	C14—C13—N12—C17	55.6 (3)
C2—C1—N1—C5	−0.7 (2)	C14—C13—N12—C15	−62.9 (3)
C3—C4—C5—N1	0.3 (3)	C14—C13—N12—C11	176.4 (2)
C4—C3—C6—O2	7.2 (2)	C12—C11—N12—C17	−58.9 (2)
C4—C3—C6—O1	−171.33 (18)	C12—C11—N12—C15	58.7 (3)
C4—C5—N1—C1	0.3 (3)	C12—C11—N12—C13	179.6 (2)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1	0.84 (3)	1.97 (3)	2.813 (2)	174 (3)
O3—H3A···O2	0.88 (2)	1.82 (2)	2.688 (2)	168 (2)
O3—H3B···O4^ii	0.87 (3)	1.95 (3)	2.811 (2)	169 (2)
O4—H4B···O3^iii	0.91 (2)	1.88 (2)	2.776 (2)	167 (2)

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