2,2′-(p-Phenyl­enediimino)dipyridinium dichloride hexa­hydrate

In the crystal structure of the title compound, C₁₆H₁₆N₄²⁺·2C l⁻·6H₂O, the 2,2′-(p-phenyl­enediimino)­dipyrid­inium cation has inversion symmetry. The chloride ions and water mol­ecules are linked via O—H...O and O—H...Cl⁻ hydrogen bonds into an infinite two-dimensional network parallel to the (001) plane. The cations, as fourfold hydrogen-bond donors, connect neighbouring [Cl⁻·(H₂O)₃]_∞ anionic networks into polymeric three-dimensional hydrogen-bonded assemblies.

Key indicators

• Single-crystal X-ray study
• T = 170 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.101
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          6
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          5
              Cl

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2000); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989); software used to prepare material for publication: SHELXL97.

2,2'-(p-Phenylenediimino)dipyridinium dichloride hexahydrate

Crystal data

C16H16N4^2+·2Cl^−·6H2O	Z = 1
Mr = 443.32	F(000) = 234
Triclinic, P1	Dx = 1.326 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 8.287 (1) Å	Cell parameters from 3148 reflections
b = 8.3104 (10) Å	θ = 4–50°
c = 9.1906 (12) Å	µ = 0.33 mm^−1
α = 65.572 (12)°	T = 170 K
β = 89.03 (1)°	Block, colourless
γ = 75.472 (10)°	0.40 × 0.40 × 0.40 mm
V = 555.14 (14) Å^3

Data collection

Kuma KM4CCD κ-geometry diffractometer	1757 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 25.0°, θmin = 2.5°
ω scans	h = −9→9
3011 measured reflections	k = −8→9
1942 independent reflections	l = −7→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Only H-atom displacement parameters refined
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0572P)^2 + 0.1307P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1942 reflections	Δρmax = 0.21 e Å^−3
142 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.064 (10)

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.47095 (6)	0.69261 (6)	−0.37170 (5)	0.0521 (2)
O1W	0.91574 (17)	0.76384 (19)	0.24879 (17)	0.0567 (4)
H1WA	0.8521	0.8009	0.3085	0.064 (7)*
H1WB	1.0151	0.7191	0.2946	0.081 (8)*
O2W	0.74753 (17)	0.8964 (2)	0.45752 (18)	0.0625 (4)
H2WA	0.6696	0.8491	0.5016	0.085 (9)*
H2WB	0.6987	1.0101	0.4233	0.084 (8)*
O3W	1.2306 (2)	0.6093 (3)	0.4144 (2)	0.0921 (6)
H3WA	1.3052	0.5368	0.3892	0.103 (10)*
H3WB	1.2783	0.6573	0.4607	0.100 (10)*
N1	0.84355 (16)	0.51561 (18)	0.15843 (16)	0.0378 (3)
H1	0.8421	0.6114	0.1811	0.050 (5)*
N2	0.63319 (18)	0.68630 (18)	−0.05458 (17)	0.0419 (4)
H2	0.5890	0.6865	−0.1434	0.051 (5)*
C2	0.74674 (19)	0.5294 (2)	0.03585 (19)	0.0358 (4)
C3	0.7710 (2)	0.3748 (2)	0.0016 (2)	0.0442 (4)
H3	0.7052	0.3873	−0.0893	0.043 (5)*
C4	0.8864 (3)	0.2162 (2)	0.0954 (2)	0.0528 (5)
H4	0.9027	0.1149	0.0667	0.076 (7)*
C5	0.9808 (2)	0.2050 (3)	0.2259 (2)	0.0561 (5)
H5	1.0663	0.0967	0.2914	0.066 (6)*
C6	0.9575 (2)	0.3561 (2)	0.2536 (2)	0.0469 (4)
H6	1.0150	0.3633	0.3396	0.051 (5)*
C7	0.57099 (18)	0.8438 (2)	−0.02286 (19)	0.0346 (4)
C8	0.5463 (2)	1.0151 (2)	−0.14945 (18)	0.0381 (4)
H8	0.5795	1.0269	−0.2532	0.041 (5)*
C9	0.5243 (2)	0.8280 (2)	0.12679 (19)	0.0385 (4)
H9	0.5375	0.7099	0.2148	0.042 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0556 (3)	0.0532 (3)	0.0520 (3)	−0.0122 (2)	0.0034 (2)	−0.0279 (2)
O1W	0.0517 (8)	0.0581 (8)	0.0702 (9)	−0.0110 (6)	0.0024 (7)	−0.0387 (7)
O2W	0.0499 (8)	0.0557 (9)	0.0730 (10)	−0.0029 (7)	0.0018 (7)	−0.0249 (7)
O3W	0.0505 (9)	0.1292 (16)	0.1248 (16)	0.0013 (9)	−0.0109 (9)	−0.0943 (14)
N1	0.0353 (7)	0.0325 (7)	0.0443 (7)	−0.0067 (5)	0.0032 (6)	−0.0163 (6)
N2	0.0464 (8)	0.0365 (7)	0.0424 (8)	−0.0011 (6)	−0.0048 (6)	−0.0217 (6)
C2	0.0351 (8)	0.0335 (8)	0.0399 (8)	−0.0094 (6)	0.0088 (6)	−0.0167 (7)
C3	0.0495 (10)	0.0386 (9)	0.0510 (10)	−0.0140 (7)	0.0119 (8)	−0.0243 (8)
C4	0.0598 (12)	0.0336 (9)	0.0659 (12)	−0.0100 (8)	0.0212 (9)	−0.0240 (8)
C5	0.0505 (11)	0.0381 (10)	0.0617 (12)	0.0004 (8)	0.0085 (9)	−0.0108 (9)
C6	0.0375 (9)	0.0441 (10)	0.0483 (10)	−0.0033 (7)	0.0013 (7)	−0.0133 (8)
C7	0.0305 (7)	0.0335 (8)	0.0396 (8)	−0.0031 (6)	−0.0026 (6)	−0.0182 (7)
C8	0.0395 (8)	0.0402 (9)	0.0314 (8)	−0.0049 (7)	0.0010 (6)	−0.0152 (7)
C9	0.0412 (9)	0.0319 (8)	0.0354 (8)	−0.0055 (6)	0.0012 (6)	−0.0099 (6)

Geometric parameters (Å, º)

O1W—H1WA	0.8500	C3—C4	1.361 (3)
O1W—H1WB	0.8500	C3—H3	0.9600
O2W—H2WA	0.8500	C4—C5	1.401 (3)
O2W—H2WB	0.8500	C4—H4	0.9600
O3W—H3WA	0.8500	C5—C6	1.349 (3)
O3W—H3WB	0.8500	C5—H5	0.9600
N1—C2	1.343 (2)	C6—H6	0.9600
N1—C6	1.362 (2)	C7—C9	1.384 (2)
N1—H1	0.8999	C7—C8	1.384 (2)
N2—C2	1.338 (2)	C8—C9^i	1.387 (2)
N2—C7	1.4264 (19)	C8—H8	0.9600
N2—H2	0.9001	C9—C8^i	1.387 (2)
C2—C3	1.411 (2)	C9—H9	0.9600
H1WA—O1W—H1WB	108.7	C5—C4—H4	121.8
H2WA—O2W—H2WB	101.2	C6—C5—C4	118.49 (17)
H3WA—O3W—H3WB	108.9	C6—C5—H5	119.0
C2—N1—C6	122.08 (15)	C4—C5—H5	122.4
C2—N1—H1	123.0	C5—C6—N1	121.01 (17)
C6—N1—H1	114.8	C5—C6—H6	125.3
C2—N2—C7	128.24 (13)	N1—C6—H6	113.7
C2—N2—H2	113.6	C9—C7—C8	120.19 (14)
C7—N2—H2	118.1	C9—C7—N2	121.54 (14)
N2—C2—N1	121.28 (14)	C8—C7—N2	118.09 (14)
N2—C2—C3	120.54 (15)	C7—C8—C9^i	120.17 (14)
N1—C2—C3	118.15 (15)	C7—C8—H8	120.6
C4—C3—C2	119.70 (17)	C9^i—C8—H8	119.3
C4—C3—H3	122.5	C7—C9—C8^i	119.64 (15)
C2—C3—H3	117.7	C7—C9—H9	121.1
C3—C4—C5	120.49 (16)	C8^i—C9—H9	119.3
C3—C4—H4	117.7
C7—N2—C2—N1	−13.8 (3)	C4—C5—C6—N1	0.8 (3)
C7—N2—C2—C3	168.02 (16)	C2—N1—C6—C5	1.6 (3)
C6—N1—C2—N2	178.72 (15)	C2—N2—C7—C9	−45.1 (2)
C6—N1—C2—C3	−3.0 (2)	C2—N2—C7—C8	139.67 (17)
N2—C2—C3—C4	−179.64 (16)	C9—C7—C8—C9^i	0.4 (3)
N1—C2—C3—C4	2.1 (2)	N2—C7—C8—C9^i	175.73 (14)
C2—C3—C4—C5	0.2 (3)	C8—C7—C9—C8^i	−0.4 (3)
C3—C4—C5—C6	−1.6 (3)	N2—C7—C9—C8^i	−175.56 (14)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2W	0.85	1.94	2.779 (2)	168
O1W—H1WB···O3W	0.85	1.91	2.759 (2)	175
O2W—H2WA···Cl1^ii	0.85	2.35	3.1957 (17)	175
O2W—H2WB···Cl1^i	0.85	2.37	3.2067 (16)	168
O3W—H3WA···Cl1^iii	0.85	2.36	3.1986 (17)	169
O3W—H3WB···Cl1^iv	0.85	2.39	3.2036 (17)	161
N1—H1···O1W	0.90	1.85	2.7121 (18)	160
N2—H2···Cl1	0.90	2.31	3.2056 (15)	179

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