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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o734.
Published online 2008 March 20. doi:  10.1107/S160053680800723X
PMCID: PMC2961067

Bis(4,4′-methyl­enedianilinium) naphthalene-1,5-disulfonate dihydrate

Abstract

The asymmetric unit of the title salt, C13H16N2 2+·C10H6O6S2 2−·2H2O, consists of one dication located on a general position, half each of two centrosymmetric dianions, and two uncoordinated water mol­ecules in general positions. In the dication, the dihedral angle between the benzene rings is 74.67 (6)°. The cations and anions inter­act through N—H(...)O hydrogen bonds. The NH3 + functional groups are also involved in N—H(...)O hydrogen bonds with the water mol­ecules, forming an infinite three-dimensional framework in the crystal structure.

Related literature

For related literature, see: Wang & Wei (2007 [triangle]).

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Object name is e-64-0o734-scheme1.jpg

Experimental

Crystal data

  • C13H16N2 2+·C10H6O6S2 2−·2H2O
  • M r = 522.58
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o734-efi1.jpg
  • a = 7.9652 (6) Å
  • b = 10.9135 (8) Å
  • c = 13.8158 (10) Å
  • α = 87.429 (1)°
  • β = 85.820 (1)°
  • γ = 83.262 (1)°
  • V = 1188.72 (15) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 296 (2) K
  • 0.13 × 0.10 × 0.08 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.966, T max = 0.978
  • 12513 measured reflections
  • 4644 independent reflections
  • 3999 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.117
  • S = 1.08
  • 4644 reflections
  • 334 parameters
  • 30 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: SMART (Bruker, 2003 [triangle]); cell refinement: SAINT-Plus (Bruker, 2003 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800723X/bh2163sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800723X/bh2163Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

This work continues our previous synthetic and structural studies of supramolecular interactions in aromatic molecular salts and adducts (Wang & Wei, 2007). Herein we report the structure of the title salt, (I).

The title complex, (I), consists of one crystallographically independent 4,4'-diphenylmethylendiammonium dication, two water molecules and two independent half naphthalene-1,5-disulfonate dianions. In the dication, the dihedral angle between benzene rings is 74.67 (6)°, and central C1—C7—C1A angle is 112.23 (16)° (Fig. 1). Each dianion is placed on an inversion centre. The 4,4'-diphenylmethylendiammonium dication interact with two naphthalene-1,5-disulfonate dianions through N—H···O hydrogen bonds. These units are further linked by water molecules into an infinite three-dimensional framework by hydrogen bonds (Fig. 2).

Experimental

A 5 ml e thanol solution of 4,4'-methylene-bis(benzenamine) (0.5 mmol, 0.10 g) was added to an aqueous solution (25 ml) of naphthalene-1,5-disulfonic acid (0.50 mmol, 0.15 g). The mixture was stirred for 10 min. at 373 K. The solution was filtered, and the filtrate was allowed to stand at room temperature. After several days, colourless crystals suitable for X-ray diffraction were obtained.

Refinement

H atoms for water molecules O1W and O2W were located in a difference map and refined with a geometry regularized through restrictions for distances: O—H = 0.85 (1) and H···H = 1.34 (1) Å. In order to reduce isotropic displacement parameters for water H atoms, SIMU restraints (similar Uij components; Sheldrick, 2008) were applied for water molecules. Other H atoms were placed in calculated positions with bond lengths fixed to N—H = 0.89, C—H = 0.93 (aromatic CH) and C—H = 0.97 Å (methylene CH2 group) and were refined as riding atoms, with Uiso(H) = 1.5 Ueq(carrier N) or Uiso(H) = 1.2 Ueq(carrier C).

Figures

Fig. 1.
The structure of (I) including the asymmetric unit (labeled atoms) and anions completed through symmetry operators: unlabeled atoms in the C10 anion are related to labeled atoms by symmetry code -x + 1, -y, -z + 1; unlabeled atoms in the C16 anion are ...
Fig. 2.
The crystal packing of (I). Hydrogen bonds are shown as dashed lines. For clarity, H atoms not involved in hydrogen bonds are omitted.

Crystal data

C13H16N22+·C10H6O6S22–·2H2OZ = 2
Mr = 522.58F000 = 548
Triclinic, P1Dx = 1.460 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.9652 (6) ÅCell parameters from 3560 reflections
b = 10.9135 (8) Åθ = 2.3–28.5º
c = 13.8158 (10) ŵ = 0.28 mm1
α = 87.429 (1)ºT = 296 (2) K
β = 85.820 (1)ºBlock, colourless
γ = 83.262 (1)º0.13 × 0.10 × 0.08 mm
V = 1188.72 (15) Å3

Data collection

Bruker SMART APEX CCD area-detector diffractometer4644 independent reflections
Radiation source: fine-focus sealed tube3999 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
T = 296(2) Kθmax = 26.0º
ω scansθmin = 1.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)h = −9→9
Tmin = 0.966, Tmax = 0.978k = −13→13
12513 measured reflectionsl = −17→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.117  w = 1/[σ2(Fo2) + (0.0622P)2 + 0.4195P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
4644 reflectionsΔρmax = 0.30 e Å3
334 parametersΔρmin = −0.30 e Å3
30 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.40383 (6)0.31683 (4)0.49763 (3)0.04147 (14)
S20.37003 (7)0.28607 (4)0.09053 (4)0.04796 (16)
N10.4334 (2)0.52270 (16)0.28512 (13)0.0515 (4)
H1A0.41070.44780.30630.077*
H1B0.48500.55710.33020.077*
H1C0.50060.51660.23080.077*
N1A−0.0574 (3)1.33594 (17)0.21344 (16)0.0635 (5)
H1A10.05161.33760.19470.095*
H1A2−0.07721.36270.27360.095*
H1A3−0.12071.38450.17340.095*
O10.4100 (2)0.32750 (13)0.60152 (11)0.0566 (4)
O20.5575 (2)0.34399 (13)0.44339 (12)0.0595 (4)
O30.2547 (2)0.38716 (13)0.46064 (14)0.0666 (5)
O40.5241 (2)0.33961 (14)0.05942 (14)0.0723 (5)
O50.3092 (2)0.31235 (14)0.18981 (12)0.0669 (5)
O60.2382 (2)0.31961 (13)0.02363 (12)0.0615 (4)
O1W0.2991 (2)0.49532 (17)0.87440 (13)0.0664 (4)
H1WA0.358 (3)0.541 (2)0.9040 (17)0.079 (5)*
H1WB0.273 (4)0.4416 (19)0.9181 (15)0.085 (5)*
O2W0.0816 (3)0.5858 (2)0.59992 (18)0.0880 (6)
H2WA0.171 (2)0.538 (2)0.610 (2)0.088 (5)*
H2WB0.014 (3)0.542 (2)0.578 (3)0.111 (5)*
C1−0.0257 (2)0.74496 (17)0.22988 (14)0.0439 (4)
C20.0752 (3)0.68758 (19)0.15493 (14)0.0485 (5)
H20.04090.69790.09190.058*
C30.2255 (3)0.61548 (18)0.17187 (14)0.0457 (4)
H30.29240.57830.12090.055*
C40.2745 (2)0.59965 (16)0.26548 (14)0.0404 (4)
C50.1767 (3)0.65344 (17)0.34204 (14)0.0450 (4)
H50.21100.64110.40500.054*
C60.0275 (3)0.72579 (18)0.32417 (14)0.0466 (4)
H6−0.03880.76240.37560.056*
C7−0.1870 (3)0.8271 (2)0.21082 (17)0.0532 (5)
H7A−0.27440.81010.26060.064*
H7B−0.22480.80810.14860.064*
C80.3828 (2)0.15788 (15)0.48048 (12)0.0361 (4)
C90.2418 (2)0.13005 (17)0.43965 (14)0.0434 (4)
H90.15970.19310.42170.052*
C100.2200 (3)0.00641 (18)0.42456 (15)0.0459 (4)
H100.1227−0.01170.39740.055*
C110.6604 (2)0.08693 (16)0.55070 (13)0.0410 (4)
H110.67640.16800.56200.049*
C120.5117 (2)0.06267 (15)0.50798 (11)0.0330 (4)
C130.4159 (2)0.12309 (16)0.08655 (13)0.0387 (4)
C140.4905 (2)0.06601 (15)0.00027 (13)0.0342 (4)
C150.5455 (2)0.13320 (16)−0.08410 (14)0.0424 (4)
H150.53510.2190−0.08390.051*
C160.6129 (3)0.07474 (18)−0.16519 (15)0.0521 (5)
H160.64670.1208−0.21990.062*
C170.3680 (3)0.05438 (18)0.16698 (14)0.0503 (5)
H170.32250.09350.22300.060*
C1A−0.1634 (2)0.96266 (19)0.21010 (14)0.0461 (4)
C2A−0.2043 (3)1.0326 (2)0.29072 (17)0.0642 (6)
H2A−0.25450.99660.34610.077*
C3A−0.1734 (3)1.1542 (2)0.29229 (18)0.0649 (6)
H3A−0.20181.19900.34800.078*
C4A−0.1006 (3)1.20806 (19)0.21109 (16)0.0508 (5)
C5A−0.0614 (4)1.1428 (2)0.12952 (18)0.0773 (8)
H5A−0.01331.18000.07400.093*
C6A−0.0929 (4)1.0208 (2)0.12897 (17)0.0735 (7)
H6A−0.06600.97700.07260.088*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0483 (3)0.0258 (2)0.0497 (3)−0.00183 (18)−0.0032 (2)−0.00024 (18)
S20.0611 (3)0.0264 (2)0.0561 (3)−0.0029 (2)−0.0017 (2)−0.00822 (19)
N10.0616 (11)0.0389 (9)0.0524 (10)0.0040 (8)−0.0110 (8)0.0015 (7)
N1A0.0630 (12)0.0455 (10)0.0768 (13)0.0069 (9)0.0045 (10)0.0060 (9)
O10.0774 (10)0.0408 (8)0.0526 (9)−0.0095 (7)−0.0006 (7)−0.0113 (6)
O20.0672 (10)0.0366 (7)0.0731 (10)−0.0118 (7)0.0141 (8)0.0023 (7)
O30.0683 (10)0.0322 (7)0.0996 (13)0.0047 (7)−0.0284 (9)0.0023 (7)
O40.0768 (11)0.0421 (8)0.1011 (14)−0.0221 (8)0.0043 (10)−0.0137 (8)
O50.0972 (13)0.0412 (8)0.0606 (10)0.0018 (8)0.0009 (9)−0.0181 (7)
O60.0727 (10)0.0348 (7)0.0754 (11)0.0048 (7)−0.0159 (8)0.0043 (7)
O1W0.0779 (11)0.0591 (10)0.0653 (10)−0.0166 (8)−0.0188 (9)0.0083 (8)
O2W0.0815 (14)0.0805 (14)0.1024 (16)−0.0080 (11)0.0011 (12)−0.0227 (12)
C10.0446 (10)0.0385 (10)0.0500 (11)−0.0097 (8)−0.0055 (8)0.0018 (8)
C20.0612 (12)0.0451 (11)0.0396 (10)−0.0037 (9)−0.0107 (9)0.0003 (8)
C30.0595 (12)0.0370 (10)0.0398 (10)−0.0013 (8)−0.0025 (9)−0.0042 (8)
C40.0503 (11)0.0273 (8)0.0441 (10)−0.0058 (7)−0.0062 (8)0.0004 (7)
C50.0588 (12)0.0392 (10)0.0382 (10)−0.0089 (9)−0.0079 (8)0.0021 (8)
C60.0523 (11)0.0438 (10)0.0432 (10)−0.0066 (9)0.0027 (8)−0.0036 (8)
C70.0434 (11)0.0549 (12)0.0615 (13)−0.0049 (9)−0.0071 (9)0.0006 (10)
C80.0441 (10)0.0274 (8)0.0360 (9)−0.0027 (7)−0.0007 (7)0.0002 (7)
C90.0471 (10)0.0346 (9)0.0478 (10)0.0008 (8)−0.0091 (8)0.0008 (8)
C100.0455 (11)0.0415 (10)0.0527 (11)−0.0062 (8)−0.0142 (9)−0.0031 (8)
C110.0474 (10)0.0323 (9)0.0446 (10)−0.0075 (7)−0.0060 (8)−0.0039 (7)
C120.0404 (9)0.0287 (8)0.0293 (8)−0.0037 (7)0.0013 (7)−0.0004 (6)
C130.0451 (10)0.0274 (8)0.0432 (10)−0.0016 (7)−0.0041 (8)−0.0038 (7)
C140.0343 (9)0.0268 (8)0.0416 (9)−0.0028 (6)−0.0057 (7)−0.0012 (7)
C150.0490 (11)0.0273 (8)0.0497 (11)−0.0032 (7)0.0008 (8)0.0021 (7)
C160.0668 (13)0.0393 (10)0.0462 (11)−0.0011 (9)0.0083 (10)0.0084 (8)
C170.0665 (13)0.0398 (10)0.0414 (10)0.0027 (9)0.0042 (9)−0.0033 (8)
C1A0.0366 (10)0.0529 (11)0.0465 (11)0.0030 (8)−0.0043 (8)0.0057 (9)
C2A0.0727 (15)0.0602 (14)0.0555 (13)−0.0088 (12)0.0233 (11)0.0015 (10)
C3A0.0736 (16)0.0576 (14)0.0583 (14)0.0000 (12)0.0213 (12)−0.0067 (11)
C4A0.0478 (11)0.0427 (11)0.0570 (12)0.0091 (9)0.0008 (9)0.0079 (9)
C5A0.120 (2)0.0620 (15)0.0465 (13)−0.0132 (15)0.0164 (14)0.0118 (11)
C6A0.111 (2)0.0629 (15)0.0436 (12)−0.0113 (14)0.0155 (13)−0.0026 (11)

Geometric parameters (Å, °)

S1—O21.4417 (16)C7—H7A0.9700
S1—O31.4495 (15)C7—H7B0.9700
S1—O11.4501 (15)C8—C91.364 (3)
S1—C81.7900 (17)C8—C121.432 (2)
S2—O41.4496 (17)C9—C101.407 (3)
S2—O51.4507 (17)C9—H90.9300
S2—O61.4531 (17)C10—C11i1.360 (3)
S2—C131.7759 (17)C10—H100.9300
N1—C41.470 (2)C11—C10i1.360 (3)
N1—H1A0.8900C11—C121.418 (3)
N1—H1B0.8900C11—H110.9300
N1—H1C0.8900C12—C12i1.431 (3)
N1A—C4A1.478 (3)C13—C171.369 (3)
N1A—H1A10.8900C13—C141.428 (2)
N1A—H1A20.8900C14—C151.419 (3)
N1A—H1A30.8900C14—C14ii1.431 (3)
O1W—H1WA0.860 (10)C15—C161.359 (3)
O1W—H1WB0.854 (10)C15—H150.9300
O2W—H2WA0.847 (10)C16—C17ii1.401 (3)
O2W—H2WB0.840 (10)C16—H160.9300
C1—C21.389 (3)C17—C16ii1.401 (3)
C1—C61.399 (3)C17—H170.9300
C1—C71.510 (3)C1A—C2A1.376 (3)
C2—C31.382 (3)C1A—C6A1.379 (3)
C2—H20.9300C2A—C3A1.379 (3)
C3—C41.375 (3)C2A—H2A0.9300
C3—H30.9300C3A—C4A1.366 (3)
C4—C51.378 (3)C3A—H3A0.9300
C5—C61.379 (3)C4A—C5A1.358 (3)
C5—H50.9300C5A—C6A1.384 (4)
C6—H60.9300C5A—H5A0.9300
C7—C1A1.512 (3)C6A—H6A0.9300
O2—S1—O3112.14 (10)H7A—C7—H7B107.9
O2—S1—O1113.15 (10)C9—C8—C12120.94 (16)
O3—S1—O1112.19 (10)C9—C8—S1118.27 (14)
O2—S1—C8106.96 (8)C12—C8—S1120.78 (13)
O3—S1—C8106.27 (9)C8—C9—C10120.28 (17)
O1—S1—C8105.51 (8)C8—C9—H9119.9
O4—S2—O5113.54 (11)C10—C9—H9119.9
O4—S2—O6111.67 (11)C11i—C10—C9120.71 (18)
O5—S2—O6111.49 (11)C11i—C10—H10119.6
O4—S2—C13107.67 (9)C9—C10—H10119.6
O5—S2—C13106.25 (9)C10i—C11—C12121.09 (17)
O6—S2—C13105.67 (9)C10i—C11—H11119.5
C4—N1—H1A109.5C12—C11—H11119.5
C4—N1—H1B109.5C11—C12—C12i118.75 (19)
H1A—N1—H1B109.5C11—C12—C8123.03 (15)
C4—N1—H1C109.5C12i—C12—C8118.22 (19)
H1A—N1—H1C109.5C17—C13—C14121.41 (16)
H1B—N1—H1C109.5C17—C13—S2117.57 (14)
C4A—N1A—H1A1109.5C14—C13—S2120.91 (13)
C4A—N1A—H1A2109.5C15—C14—C13123.46 (15)
H1A1—N1A—H1A2109.5C15—C14—C14ii118.9 (2)
C4A—N1A—H1A3109.5C13—C14—C14ii117.66 (19)
H1A1—N1A—H1A3109.5C16—C15—C14121.31 (17)
H1A2—N1A—H1A3109.5C16—C15—H15119.3
H1WA—O1W—H1WB103.5 (14)C14—C15—H15119.3
H2WA—O2W—H2WB106.2 (15)C15—C16—C17ii120.51 (18)
C2—C1—C6117.94 (19)C15—C16—H16119.7
C2—C1—C7121.48 (18)C17ii—C16—H16119.7
C6—C1—C7120.57 (19)C13—C17—C16ii120.20 (18)
C3—C2—C1121.54 (18)C13—C17—H17119.9
C3—C2—H2119.2C16ii—C17—H17119.9
C1—C2—H2119.2C2A—C1A—C6A116.8 (2)
C4—C3—C2118.83 (19)C2A—C1A—C7122.09 (19)
C4—C3—H3120.6C6A—C1A—C7121.1 (2)
C2—C3—H3120.6C1A—C2A—C3A122.3 (2)
C3—C4—C5121.45 (18)C1A—C2A—H2A118.8
C3—C4—N1119.68 (18)C3A—C2A—H2A118.8
C5—C4—N1118.87 (17)C4A—C3A—C2A119.3 (2)
C4—C5—C6119.20 (18)C4A—C3A—H3A120.4
C4—C5—H5120.4C2A—C3A—H3A120.4
C6—C5—H5120.4C5A—C4A—C3A120.2 (2)
C5—C6—C1121.03 (19)C5A—C4A—N1A119.9 (2)
C5—C6—H6119.5C3A—C4A—N1A119.9 (2)
C1—C6—H6119.5C4A—C5A—C6A120.0 (2)
C1—C7—C1A112.23 (16)C4A—C5A—H5A120.0
C1—C7—H7A109.2C6A—C5A—H5A120.0
C1A—C7—H7A109.2C1A—C6A—C5A121.5 (2)
C1—C7—H7B109.2C1A—C6A—H6A119.3
C1A—C7—H7B109.2C5A—C6A—H6A119.3

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···O1iii0.891.912.770 (2)162
N1A—H1A1···O5iv0.892.032.897 (3)163
N1—H1C···O1Wiii0.892.072.948 (3)167
N1A—H1A2···O2Wv0.891.862.739 (3)171
N1A—H1A3···O1Wv0.891.952.807 (3)161
O1W—H1WA···O4iii0.860 (10)1.801 (10)2.645 (2)166 (2)
O1W—H1WB···O6vi0.854 (10)1.957 (11)2.807 (2)174 (3)
N1—H1A···O20.892.463.007 (2)120
N1—H1A···O50.892.472.996 (2)118
N1—H1A···O30.892.493.125 (3)129
O2W—H2WA···O2iii0.847 (10)2.68 (3)3.072 (3)110 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2163).

References

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