N,N′-Bis(3-pyridiniometh­yl)-4,4′-benzidinediium tetra­chloride dihydrate

In the title compound, C₂₄H₂₆N₄⁴⁺·4Cl⁻·2H₂O, the cation possesses a crystallographically imposed centre of symmetry. The crystal structure is stabilized by inter­molecular N—H...Cl, N—H...O and O—H...Cl hydrogen bonds, and by π–π stacking inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.034
• wR factor = 0.102
• Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.25
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000)         300 Deg.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 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
   1 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
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

N,N'-Bis(3-pyridiniomethyl)-4,4'-benzidinediium tetrachloride dihydrate

Crystal data

C24H26N4^4+·4Cl^−·2H2O	Z = 1
Mr = 548.32	F(000) = 286
Triclinic, P1	Dx = 1.377 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9764 (17) Å	Cell parameters from 2395 reflections
b = 9.1437 (18) Å	θ = 2.4–25.4°
c = 9.5321 (18) Å	µ = 0.48 mm^−1
α = 63.838 (3)°	T = 273 K
β = 78.558 (3)°	Prism, colourless
γ = 70.586 (3)°	0.21 × 0.17 × 0.14 mm
V = 661.1 (2) Å^3

Data collection

Bruker SMART APEX II CCD area-detector diffractometer	2395 independent reflections
Radiation source: fine-focus sealed tube	2254 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans	θmax = 25.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→10
Tmin = 0.907, Tmax = 0.936	k = −11→11
6382 measured reflections	l = −11→11

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0602P)^2 + 0.1961P] where P = (Fo^2 + 2Fc^2)/3
2395 reflections	(Δ/σ)max < 0.001
162 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.18 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
C1	0.29594 (19)	0.4568 (2)	0.88845 (19)	0.0349 (4)
H1	0.3716	0.5106	0.8781	0.042*
N2	0.23685 (16)	0.37193 (17)	1.03007 (16)	0.0377 (3)
H2	0.2699	0.3684	1.1105	0.045*
C3	0.1280 (2)	0.2918 (2)	1.0523 (2)	0.0428 (4)
H3	0.0904	0.2327	1.1532	0.051*
C4	0.0728 (2)	0.2973 (2)	0.9271 (2)	0.0469 (4)
H4	−0.0038	0.2433	0.9411	0.056*
C5	0.1320 (2)	0.3844 (2)	0.7777 (2)	0.0409 (4)
H5	0.0954	0.3884	0.6910	0.049*
C6	0.24525 (19)	0.4652 (2)	0.75755 (18)	0.0331 (3)
C7	0.31881 (19)	0.5535 (2)	0.59914 (18)	0.0367 (4)
H7A	0.4262	0.5472	0.6102	0.044*
H7B	0.3240	0.4954	0.5335	0.044*
C8	0.30339 (19)	0.8204 (2)	0.36685 (18)	0.0335 (4)
C9	0.4142 (2)	0.8985 (2)	0.35521 (19)	0.0409 (4)
H9	0.4376	0.9042	0.4431	0.049*
C10	0.4913 (2)	0.9692 (2)	0.21075 (19)	0.0393 (4)
H10	0.5665	1.0225	0.2028	0.047*
C11	0.45858 (17)	0.96202 (18)	0.07760 (17)	0.0292 (3)
C12	0.3445 (2)	0.8823 (2)	0.09431 (19)	0.0392 (4)
H12	0.3198	0.8760	0.0072	0.047*
C13	0.2672 (2)	0.8122 (2)	0.2375 (2)	0.0410 (4)
H13	0.1911	0.7597	0.2465	0.049*
N1	0.22775 (16)	0.73607 (17)	0.52057 (15)	0.0343 (3)
H1A	0.1286	0.7424	0.5084	0.041*
H1B	0.2217	0.7901	0.5817	0.041*
O1W	0.06598 (18)	0.2552 (2)	0.5187 (2)	0.0604 (4)
Cl1	0.17635 (5)	0.89076 (6)	0.75802 (5)	0.04437 (16)
Cl2	0.34066 (6)	0.38621 (7)	0.29976 (5)	0.05127 (17)
H1WA	0.108 (3)	0.156 (3)	0.578 (3)	0.066 (8)*
H1WB	0.132 (4)	0.282 (4)	0.447 (4)	0.095 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0352 (8)	0.0388 (8)	0.0312 (8)	−0.0160 (7)	0.0008 (6)	−0.0116 (7)
N2	0.0433 (8)	0.0417 (8)	0.0258 (7)	−0.0138 (6)	−0.0017 (6)	−0.0106 (6)
C3	0.0446 (9)	0.0419 (9)	0.0317 (9)	−0.0170 (8)	0.0049 (7)	−0.0055 (7)
C4	0.0469 (10)	0.0511 (10)	0.0434 (10)	−0.0291 (8)	0.0005 (8)	−0.0101 (8)
C5	0.0460 (9)	0.0470 (10)	0.0345 (9)	−0.0224 (8)	−0.0026 (7)	−0.0139 (7)
C6	0.0349 (8)	0.0357 (8)	0.0276 (8)	−0.0131 (6)	0.0014 (6)	−0.0110 (6)
C7	0.0378 (8)	0.0452 (9)	0.0272 (8)	−0.0178 (7)	0.0045 (6)	−0.0131 (7)
C8	0.0374 (8)	0.0379 (8)	0.0241 (7)	−0.0177 (7)	0.0049 (6)	−0.0093 (6)
C9	0.0483 (9)	0.0579 (11)	0.0248 (8)	−0.0290 (8)	0.0020 (7)	−0.0157 (7)
C10	0.0436 (9)	0.0533 (10)	0.0287 (8)	−0.0308 (8)	0.0025 (7)	−0.0128 (7)
C11	0.0314 (7)	0.0301 (7)	0.0244 (8)	−0.0119 (6)	0.0004 (6)	−0.0080 (6)
C12	0.0505 (9)	0.0519 (10)	0.0247 (8)	−0.0300 (8)	0.0030 (7)	−0.0149 (7)
C13	0.0483 (9)	0.0542 (10)	0.0318 (9)	−0.0340 (8)	0.0054 (7)	−0.0163 (8)
N1	0.0377 (7)	0.0437 (8)	0.0244 (7)	−0.0214 (6)	0.0059 (5)	−0.0124 (6)
O1W	0.0447 (8)	0.0614 (10)	0.0608 (10)	−0.0198 (7)	−0.0050 (7)	−0.0079 (8)
Cl1	0.0526 (3)	0.0527 (3)	0.0361 (3)	−0.0283 (2)	0.00553 (18)	−0.0189 (2)
Cl2	0.0597 (3)	0.0667 (3)	0.0392 (3)	−0.0325 (2)	−0.0030 (2)	−0.0212 (2)

Geometric parameters (Å, º)

C1—N2	1.331 (2)	C8—C13	1.374 (2)
C1—C6	1.374 (2)	C8—N1	1.4696 (19)
C1—H1	0.9300	C9—C10	1.388 (2)
N2—C3	1.339 (2)	C9—H9	0.9300
N2—H2	0.8600	C10—C11	1.391 (2)
C3—C4	1.356 (3)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.391 (2)
C4—C5	1.387 (2)	C11—C11^i	1.491 (3)
C4—H4	0.9300	C12—C13	1.379 (2)
C5—C6	1.383 (2)	C12—H12	0.9300
C5—H5	0.9300	C13—H13	0.9300
C6—C7	1.501 (2)	N1—H1A	0.9000
C7—N1	1.499 (2)	N1—H1B	0.9000
C7—H7A	0.9700	O1W—H1WA	0.83 (3)
C7—H7B	0.9700	O1W—H1WB	0.82 (3)
C8—C9	1.367 (2)
N2—C1—C6	120.06 (15)	C9—C8—N1	119.90 (14)
N2—C1—H1	120.0	C13—C8—N1	119.22 (14)
C6—C1—H1	120.0	C8—C9—C10	119.28 (15)
C1—N2—C3	122.67 (15)	C8—C9—H9	120.4
C1—N2—H2	118.7	C10—C9—H9	120.4
C3—N2—H2	118.7	C9—C10—C11	121.46 (15)
N2—C3—C4	119.67 (16)	C9—C10—H10	119.3
N2—C3—H3	120.2	C11—C10—H10	119.3
C4—C3—H3	120.2	C10—C11—C12	117.44 (14)
C3—C4—C5	119.24 (17)	C10—C11—C11^i	121.45 (17)
C3—C4—H4	120.4	C12—C11—C11^i	121.11 (17)
C5—C4—H4	120.4	C13—C12—C11	121.31 (15)
C6—C5—C4	120.08 (16)	C13—C12—H12	119.3
C6—C5—H5	120.0	C11—C12—H12	119.3
C4—C5—H5	120.0	C8—C13—C12	119.70 (15)
C1—C6—C5	118.27 (15)	C8—C13—H13	120.1
C1—C6—C7	119.56 (15)	C12—C13—H13	120.1
C5—C6—C7	122.11 (15)	C8—N1—C7	111.30 (12)
N1—C7—C6	112.34 (13)	C8—N1—H1A	109.4
N1—C7—H7A	109.1	C7—N1—H1A	109.4
C6—C7—H7A	109.1	C8—N1—H1B	109.4
N1—C7—H7B	109.1	C7—N1—H1B	109.4
C6—C7—H7B	109.1	H1A—N1—H1B	108.0
H7A—C7—H7B	107.9	H1WA—O1W—H1WB	105 (3)
C9—C8—C13	120.80 (15)
C6—C1—N2—C3	0.1 (2)	C8—C9—C10—C11	−0.1 (3)
C1—N2—C3—C4	−0.7 (3)	C9—C10—C11—C12	0.5 (3)
N2—C3—C4—C5	0.8 (3)	C9—C10—C11—C11^i	179.99 (18)
C3—C4—C5—C6	−0.4 (3)	C10—C11—C12—C13	−0.3 (3)
N2—C1—C6—C5	0.3 (2)	C11^i—C11—C12—C13	−179.82 (18)
N2—C1—C6—C7	−176.83 (14)	C9—C8—C13—C12	0.6 (3)
C4—C5—C6—C1	−0.2 (3)	N1—C8—C13—C12	−176.17 (16)
C4—C5—C6—C7	176.88 (16)	C11—C12—C13—C8	−0.2 (3)
C1—C6—C7—N1	−93.48 (18)	C9—C8—N1—C7	−90.05 (19)
C5—C6—C7—N1	89.5 (2)	C13—C8—N1—C7	86.71 (19)
C13—C8—C9—C10	−0.4 (3)	C6—C7—N1—C8	179.13 (13)
N1—C8—C9—C10	176.31 (15)

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
N1—H1B···Cl1	0.90	2.16	3.0514 (15)	169
N1—H1A···O1W^ii	0.90	1.81	2.706 (2)	177
O1W—H1WA···Cl1^iii	0.83 (3)	2.23 (3)	3.0476 (19)	169 (2)
N2—H2···Cl2^iv	0.86	2.11	2.9701 (16)	174
O1W—H1WB···Cl2	0.82 (3)	2.31 (3)	3.0964 (18)	161 (3)

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