Bis(3-picolinium) chloranilate dihydrate

In the title compound, 2 C₆H₈N⁺·C₆Cl₂O₄²⁻·2H₂O, the chloranilate and 3-picolinium (3-methyl­pyridinium) ions are connected by N—H...O hydrogen bonds to give a centrosymmetric chloranilate–3-picolinium 1:2 unit. The structure consists of layers of the 1:2 units, and water mol­ecules link the layers through O—H...O and C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 301 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.038
• wR factor = 0.104
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT052_ALERT_1_A (Proper) Absorption Correction Method Missing ..          ?

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
PLAT333_ALERT_2_C Large Average Benzene C-C Dist.  C1     -C3_a          1.44 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C3_a   ...       1.54 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C6 H8 N

   1 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

   4 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: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997–1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

(I)

Crystal data

2C6H8N^+·C6Cl2O4^2^−·2H2O	F(000) = 448.00
Mr = 431.27	Dx = 1.422 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 9.212 (6) Å	θ = 11.6–12.0°
b = 7.349 (2) Å	µ = 0.36 mm^−1
c = 15.045 (4) Å	T = 301 K
β = 98.52 (3)°	Prism, purple
V = 1007.4 (8) Å^3	0.40 × 0.30 × 0.15 mm
Z = 2

Data collection

Rigaku AFC-5R diffractometer	1521 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.014
Graphite monochromator	θmax = 27.5°, θmin = 2.7°
ω–2θ scans	h = −2→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
Tmin = 0.879, Tmax = 0.948	l = −19→19
3034 measured reflections	3 standard reflections every 97 reflections
2320 independent reflections	intensity decay: 0.9%

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0474P)^2 + 0.191P] where P = (Fo^2 + 2Fc^2)/3
2320 reflections	(Δ/σ)max = 0.01
140 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Experimental. The scan width was (1.37 + 0.30tanθ)° with an ω scan speed of 6° per minute (up to 4 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

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
Cl	0.51250 (6)	0.47787 (9)	0.29090 (3)	0.0571 (2)
O1	0.25959 (15)	0.3953 (2)	0.38805 (9)	0.0546 (4)
O2	0.74710 (15)	0.6000 (2)	0.43714 (9)	0.0527 (4)
O3	0.8470 (2)	0.7181 (3)	0.27802 (13)	0.0737 (6)
N	0.0011 (2)	0.2695 (3)	0.46111 (14)	0.0521 (5)
C1	0.3751 (2)	0.4425 (3)	0.43616 (12)	0.0377 (4)
C2	0.5061 (2)	0.4892 (3)	0.40537 (12)	0.0384 (4)
C3	0.62987 (19)	0.5501 (2)	0.46204 (12)	0.0371 (4)
C4	−0.0661 (2)	0.2227 (3)	0.53024 (15)	0.0513 (5)
C5	−0.2008 (2)	0.1392 (3)	0.51637 (16)	0.0517 (5)
C6	−0.2613 (2)	0.1055 (3)	0.42840 (17)	0.0598 (6)
C7	−0.1900 (3)	0.1568 (4)	0.35898 (17)	0.0656 (7)
C8	−0.0573 (2)	0.2402 (3)	0.37649 (16)	0.0598 (6)
C9	−0.2769 (3)	0.0863 (4)	0.5940 (2)	0.0837 (9)
H1	0.082 (3)	0.317 (4)	0.470 (2)	0.091 (10)*
H2	−0.0212	0.2470	0.5886	0.062*
H3	−0.3516	0.0472	0.4162	0.072*
H4	−0.2322	0.1347	0.2999	0.079*
H5	−0.0081	0.2763	0.3297	0.072*
H6	−0.2935	−0.0427	0.5928	0.126*
H7	−0.3692	0.1487	0.5895	0.126*
H8	−0.2167	0.1190	0.6493	0.126*
H9	0.798 (4)	0.688 (4)	0.313 (2)	0.097 (12)*
H10	0.791 (4)	0.760 (5)	0.229 (2)	0.118 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0461 (3)	0.0881 (4)	0.0362 (2)	−0.0046 (3)	0.00284 (19)	−0.0016 (3)
O1	0.0370 (8)	0.0807 (11)	0.0441 (8)	−0.0147 (7)	−0.0003 (6)	−0.0105 (7)
O2	0.0365 (7)	0.0772 (10)	0.0445 (8)	−0.0148 (7)	0.0061 (6)	0.0006 (7)
O3	0.0506 (10)	0.1230 (17)	0.0471 (9)	−0.0085 (11)	0.0061 (8)	0.0177 (10)
N	0.0299 (9)	0.0521 (11)	0.0722 (12)	−0.0031 (8)	0.0004 (8)	−0.0028 (9)
C1	0.0318 (9)	0.0388 (10)	0.0409 (9)	−0.0001 (8)	−0.0002 (7)	−0.0032 (8)
C2	0.0334 (9)	0.0461 (11)	0.0347 (8)	0.0009 (8)	0.0016 (7)	−0.0009 (8)
C3	0.0311 (9)	0.0386 (10)	0.0411 (9)	0.0007 (8)	0.0038 (7)	0.0013 (8)
C4	0.0481 (12)	0.0491 (12)	0.0528 (12)	0.0078 (10)	−0.0052 (10)	−0.0030 (10)
C5	0.0444 (12)	0.0426 (12)	0.0688 (14)	0.0075 (9)	0.0110 (10)	0.0086 (10)
C6	0.0355 (11)	0.0599 (14)	0.0810 (17)	−0.0095 (10)	−0.0009 (11)	−0.0009 (12)
C7	0.0504 (13)	0.0836 (18)	0.0581 (14)	−0.0012 (13)	−0.0072 (11)	−0.0083 (13)
C8	0.0470 (12)	0.0737 (16)	0.0605 (14)	0.0011 (12)	0.0139 (10)	0.0036 (12)
C9	0.091 (2)	0.0755 (18)	0.093 (2)	0.0147 (16)	0.0416 (17)	0.0241 (16)

Geometric parameters (Å, º)

Cl—C2	1.7339 (19)	C4—C5	1.372 (3)
O1—C1	1.244 (2)	C4—H2	0.93
O2—C3	1.249 (2)	C5—C6	1.380 (3)
O3—H9	0.77 (3)	C5—C9	1.499 (3)
O3—H10	0.88 (4)	C6—C7	1.367 (3)
N—C8	1.324 (3)	C6—H3	0.93
N—C4	1.332 (3)	C7—C8	1.358 (3)
N—H1	0.81 (3)	C7—H4	0.93
C1—C2	1.398 (3)	C8—H5	0.93
C1—C3^i	1.540 (3)	C9—H6	0.96
C2—C3	1.392 (3)	C9—H7	0.96
C3—C1^i	1.540 (3)	C9—H8	0.96
O1···O3^ii	2.859 (3)	O2···C8^iii	3.400 (3)
O1···N	2.917 (3)	O3···C8^iv	3.243 (4)
O1···C8	3.115 (3)	O3···C4^i	3.295 (4)
O2···N^i	2.755 (3)	C3···C5^iii	3.441 (3)
O2···O3	2.826 (3)	C3···C6^iii	3.477 (3)
O2···C4^i	3.185 (3)
H9—O3—H10	110 (3)	C4—C5—C9	120.9 (2)
C8—N—C4	122.6 (2)	C6—C5—C9	122.1 (2)
C8—N—H1	117 (2)	C7—C6—C5	120.8 (2)
C4—N—H1	120 (2)	C7—C6—H3	119.6
O1—C1—C2	125.56 (18)	C5—C6—H3	119.6
O1—C1—C3^i	116.07 (16)	C8—C7—C6	119.8 (2)
C2—C1—C3^i	118.37 (16)	C8—C7—H4	120.1
C3—C2—C1	123.00 (17)	C6—C7—H4	120.1
C3—C2—Cl	118.59 (15)	N—C8—C7	119.1 (2)
C1—C2—Cl	118.38 (14)	N—C8—H5	120.5
O2—C3—C2	125.19 (18)	C7—C8—H5	120.5
O2—C3—C1^i	116.25 (16)	C5—C9—H6	109.5
C2—C3—C1^i	118.56 (16)	C5—C9—H7	109.5
N—C4—C5	120.7 (2)	H6—C9—H7	109.5
N—C4—H2	119.6	C5—C9—H8	109.5
C5—C4—H2	119.6	H6—C9—H8	109.5
C4—C5—C6	117.0 (2)	H7—C9—H8	109.5
O1—C1—C2—C3	176.56 (19)	C8—N—C4—C5	0.6 (3)
C3^i—C1—C2—C3	−3.1 (3)	N—C4—C5—C6	0.5 (3)
O1—C1—C2—Cl	−1.2 (3)	N—C4—C5—C9	−180.0 (2)
C3^i—C1—C2—Cl	179.16 (13)	C4—C5—C6—C7	−1.1 (3)
C1—C2—C3—O2	−177.06 (19)	C9—C5—C6—C7	179.4 (2)
Cl—C2—C3—O2	0.7 (3)	C5—C6—C7—C8	0.7 (4)
C1—C2—C3—C1^i	3.1 (3)	C4—N—C8—C7	−1.0 (4)
Cl—C2—C3—C1^i	−179.16 (13)	C6—C7—C8—N	0.4 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1···O1	0.82 (3)	2.26 (3)	2.917 (3)	137 (3)
N—H1···O2^i	0.82 (3)	2.04 (3)	2.755 (3)	147 (3)
O3—H9···O2	0.78 (3)	2.09 (3)	2.826 (3)	158 (3)
O3—H10···O1^iv	0.89 (3)	2.02 (3)	2.859 (3)	158 (3)
C4—H2···O3^i	0.93	2.39	3.295 (4)	164
C8—H5···O3^ii	0.93	2.39	3.243 (4)	152

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