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In the title hydrated mol­ecular salt, C12H14N2+·2C7H4NO4·2H2O, the complete cation is generated by a crystallographic twofold axis running perpendicular to the central C—C bond. The components give rise to an infinite three-dimensional framework via inter­molecular N—H...O and O—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048994/hb2569sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048994/hb2569Isup2.hkl
Contains datablock I

CCDC reference: 667348

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.045
  • wR factor = 0.121
  • Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT731_ALERT_1_C Bond Calc 0.83(3), Rep 0.825(10) ...... 3.00 su-Ra O5 -H5B 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.83(3), Rep 0.825(10) ...... 3.00 su-Ra O5 -H5B 1.555 1.555
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 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 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

This work continues our previous synthetic and structural studies of supramolecular salts (Wei, 2007). Herein we present the crystal structure of the title salt, (I).

The title salt contains one (1,1'-biphenyl)-4,4'-diammonium dication (with the complete molecule generated from the asymmetry atoms by 2-fold symmetry), one 2-nitrobenzoate anion and one crystallization water molecule (Fig. 1). Interestingly, these components are organized into an infinite two-dimensional network in (100) via intermolecular N—H···O and O—H···O hydrogen bonds (Table 1). Further hydrogen bonds link the planes into an infinite three-dimensional framework (Fig. 2).

Related literature top

For related literature, see: Wei (2007).

Experimental top

A 5-ml ethanol soloution of (1,1'-biphenyl)-4,4'-diamine (0.5 mmol, 0.090 g) was added to an aqueous solution (20 ml) of 2-nitrobenzoic acid (1.0 mmol, 0.210 g). The mixture was stirred for 10 minutes at 373 K. The solution was filtered, and the filtrate was kept at the room temperature. After 3 d, colourless blocks of (I) were obtained.

Refinement top

The water H atoms were located in a difference map and refined isotropically with O—H = 0.82 (1) Å and H···H = 1.34 (1) Å. All remaining H atoms were positioned geometrically with C—H = 0.93 Å and N—H = 0.89 Å, and refined as riding with Uiso(H) = 1.2Ueq(C, N).

Structure description top

This work continues our previous synthetic and structural studies of supramolecular salts (Wei, 2007). Herein we present the crystal structure of the title salt, (I).

The title salt contains one (1,1'-biphenyl)-4,4'-diammonium dication (with the complete molecule generated from the asymmetry atoms by 2-fold symmetry), one 2-nitrobenzoate anion and one crystallization water molecule (Fig. 1). Interestingly, these components are organized into an infinite two-dimensional network in (100) via intermolecular N—H···O and O—H···O hydrogen bonds (Table 1). Further hydrogen bonds link the planes into an infinite three-dimensional framework (Fig. 2).

For related literature, see: Wei (2007).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003.

Figures top
[Figure 1] Fig. 1. The molecular structure unit of (I). Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. Unlabeled atoms in the N2 cation are related to labeled atoms by (-x, y, 1/2 - z).
[Figure 2] Fig. 2. Crystal packing of (I). Hydrogen bonds are shown as dashed lines. For clarity, H atoms not involved in hydrogen bonds are omitted.
1,1'-Biphenyl-4,4'-diammonium bis(2-nitrobenzoate) dihydrate top
Crystal data top
C12H14N22+·2C7H4NO4·2H2OF(000) = 1160
Mr = 554.51Dx = 1.474 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2540 reflections
a = 29.411 (10) Åθ = 2.3–27.8°
b = 6.731 (6) ŵ = 0.12 mm1
c = 13.511 (6) ÅT = 298 K
β = 110.91 (2)°Block, colorless
V = 2499 (3) Å30.15 × 0.10 × 0.08 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer
2185 independent reflections
Radiation source: fine-focus sealed tube1386 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.062
ω scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
h = 3434
Tmin = 0.983, Tmax = 0.991k = 84
5946 measured reflectionsl = 1516
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difmap and geom
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.121 w = 1/[σ2(Fo2) + (0.0609P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max < 0.001
2185 reflectionsΔρmax = 0.20 e Å3
190 parametersΔρmin = 0.20 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0029 (5)
Crystal data top
C12H14N22+·2C7H4NO4·2H2OV = 2499 (3) Å3
Mr = 554.51Z = 4
Monoclinic, C2/cMo Kα radiation
a = 29.411 (10) ŵ = 0.12 mm1
b = 6.731 (6) ÅT = 298 K
c = 13.511 (6) Å0.15 × 0.10 × 0.08 mm
β = 110.91 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer
2185 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
1386 reflections with I > 2σ(I)
Tmin = 0.983, Tmax = 0.991Rint = 0.062
5946 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0453 restraints
wR(F2) = 0.121H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.20 e Å3
2185 reflectionsΔρmin = 0.20 e Å3
190 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
N20.17925 (6)0.6702 (3)0.43129 (13)0.0362 (5)
H2A0.18830.77900.47090.043*
H2B0.18790.56310.47240.043*
H2C0.19370.66780.38360.043*
C80.02670 (7)0.6736 (3)0.27712 (15)0.0317 (5)
C90.04800 (8)0.6479 (3)0.38501 (16)0.0395 (6)
H90.02820.63070.42490.047*
C100.09734 (7)0.6471 (3)0.43505 (17)0.0399 (6)
H100.11080.63080.50810.048*
C110.12677 (7)0.6702 (3)0.37748 (15)0.0301 (5)
C120.10755 (8)0.6939 (3)0.27140 (16)0.0380 (5)
H120.12780.70760.23240.046*
C130.05784 (7)0.6975 (3)0.22153 (17)0.0391 (6)
H130.04480.71650.14860.047*
O10.20236 (5)0.0065 (2)0.55407 (10)0.0438 (4)
O20.20105 (5)0.3356 (2)0.55937 (11)0.0422 (4)
O30.10450 (6)0.1729 (3)0.54010 (12)0.0624 (5)
O40.03547 (6)0.1668 (3)0.41844 (13)0.0690 (6)
N10.07935 (6)0.1705 (3)0.44818 (14)0.0384 (5)
C10.15299 (7)0.1746 (3)0.40264 (15)0.0290 (5)
C20.10279 (7)0.1757 (3)0.36982 (15)0.0298 (5)
C30.07362 (7)0.1805 (3)0.26614 (15)0.0354 (5)
H30.03990.18230.24680.042*
C40.09457 (8)0.1827 (3)0.19041 (16)0.0425 (6)
H40.07510.18640.11900.051*
C50.14405 (8)0.1796 (3)0.21997 (17)0.0455 (6)
H50.15820.17940.16840.055*
C60.17296 (7)0.1768 (3)0.32460 (16)0.0384 (5)
H60.20660.17630.34350.046*
C70.18748 (7)0.1723 (3)0.51510 (15)0.0327 (5)
O50.22537 (7)0.3304 (3)0.78346 (15)0.0677 (6)
H5A0.2185 (10)0.337 (5)0.7192 (8)0.105 (13)*
H5B0.2483 (8)0.406 (4)0.8133 (17)0.099 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N20.0350 (10)0.0391 (10)0.0321 (10)0.0017 (8)0.0091 (8)0.0001 (8)
C80.0355 (11)0.0287 (11)0.0308 (11)0.0001 (9)0.0118 (9)0.0007 (10)
C90.0386 (12)0.0512 (14)0.0318 (12)0.0013 (11)0.0164 (10)0.0006 (11)
C100.0397 (13)0.0501 (15)0.0270 (11)0.0038 (11)0.0084 (10)0.0017 (10)
C110.0308 (11)0.0244 (11)0.0313 (11)0.0010 (9)0.0066 (9)0.0002 (9)
C120.0351 (12)0.0457 (14)0.0351 (12)0.0000 (10)0.0146 (10)0.0062 (11)
C130.0382 (13)0.0470 (14)0.0295 (11)0.0006 (11)0.0087 (10)0.0030 (10)
O10.0495 (9)0.0399 (10)0.0303 (8)0.0061 (8)0.0000 (7)0.0033 (7)
O20.0475 (9)0.0372 (9)0.0318 (8)0.0027 (7)0.0016 (7)0.0023 (7)
O30.0518 (10)0.1070 (16)0.0290 (9)0.0001 (10)0.0155 (8)0.0046 (10)
O40.0327 (10)0.1222 (17)0.0561 (11)0.0020 (10)0.0209 (8)0.0071 (11)
N10.0352 (11)0.0479 (12)0.0340 (11)0.0011 (9)0.0144 (9)0.0027 (9)
C10.0319 (11)0.0280 (11)0.0249 (10)0.0011 (9)0.0076 (9)0.0001 (9)
C20.0322 (11)0.0307 (11)0.0272 (11)0.0012 (9)0.0116 (9)0.0007 (9)
C30.0298 (11)0.0387 (12)0.0327 (12)0.0026 (10)0.0050 (9)0.0000 (10)
C40.0427 (13)0.0547 (15)0.0252 (11)0.0080 (12)0.0061 (10)0.0020 (11)
C50.0473 (14)0.0613 (16)0.0320 (12)0.0053 (12)0.0190 (11)0.0011 (12)
C60.0294 (11)0.0512 (14)0.0345 (12)0.0038 (11)0.0114 (10)0.0015 (11)
C70.0313 (11)0.0376 (13)0.0276 (11)0.0002 (11)0.0088 (9)0.0001 (11)
O50.0542 (12)0.1079 (17)0.0425 (11)0.0330 (12)0.0192 (9)0.0181 (11)
Geometric parameters (Å, º) top
N2—C111.453 (2)O3—N11.198 (2)
N2—H2A0.8900O4—N11.207 (2)
N2—H2B0.8900N1—C21.455 (2)
N2—H2C0.8902C1—C61.378 (3)
C8—C91.377 (3)C1—C21.382 (3)
C8—C131.386 (3)C1—C71.496 (3)
C8—C8i1.477 (4)C2—C31.357 (3)
C9—C101.365 (3)C3—C41.370 (3)
C9—H90.9300C3—H30.9300
C10—C111.363 (3)C4—C51.365 (3)
C10—H100.9300C4—H40.9300
C11—C121.349 (3)C5—C61.365 (3)
C12—C131.374 (3)C5—H50.9300
C12—H120.9300C6—H60.9300
C13—H130.9300O5—H5A0.819 (10)
O1—C71.245 (2)O5—H5B0.825 (10)
O2—C71.247 (2)
C11—N2—H2A109.7O3—N1—C2118.44 (17)
C11—N2—H2B109.1O4—N1—C2119.08 (18)
H2A—N2—H2B109.5C6—C1—C2116.92 (18)
C11—N2—H2C109.6C6—C1—C7117.24 (17)
H2A—N2—H2C109.5C2—C1—C7125.84 (17)
H2B—N2—H2C109.5C3—C2—C1122.73 (18)
C9—C8—C13116.70 (19)C3—C2—N1117.55 (18)
C9—C8—C8i121.8 (2)C1—C2—N1119.72 (17)
C13—C8—C8i121.5 (2)C2—C3—C4118.96 (19)
C10—C9—C8121.8 (2)C2—C3—H3120.5
C10—C9—H9119.1C4—C3—H3120.5
C8—C9—H9119.1C5—C4—C3119.88 (19)
C11—C10—C9119.75 (19)C5—C4—H4120.1
C11—C10—H10120.1C3—C4—H4120.1
C9—C10—H10120.1C4—C5—C6120.53 (19)
C12—C11—C10120.59 (18)C4—C5—H5119.7
C12—C11—N2119.94 (17)C6—C5—H5119.7
C10—C11—N2119.47 (17)C5—C6—C1120.97 (19)
C11—C12—C13119.47 (19)C5—C6—H6119.5
C11—C12—H12120.3C1—C6—H6119.5
C13—C12—H12120.3O1—C7—O2125.68 (19)
C12—C13—C8121.70 (19)O1—C7—C1116.56 (18)
C12—C13—H13119.2O2—C7—C1117.60 (18)
C8—C13—H13119.2H5A—O5—H5B109.5 (16)
O3—N1—O4122.47 (18)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1ii0.891.862.744 (3)176
N2—H2B···O20.891.882.772 (3)176
N2—H2C···O5iii0.891.902.786 (2)178
O5—H5A···O20.82 (1)2.03 (1)2.852 (3)177 (3)
O5—H5B···O1iv0.83 (1)1.98 (1)2.722 (3)149 (2)
Symmetry codes: (ii) x, y+1, z; (iii) x, y+1, z1/2; (iv) x+1/2, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC12H14N22+·2C7H4NO4·2H2O
Mr554.51
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)29.411 (10), 6.731 (6), 13.511 (6)
β (°) 110.91 (2)
V3)2499 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.15 × 0.10 × 0.08
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2001)
Tmin, Tmax0.983, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
5946, 2185, 1386
Rint0.062
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.121, 0.96
No. of reflections2185
No. of parameters190
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.20, 0.20

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON (Spek, 2003.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.891.862.744 (3)175.6
N2—H2B···O20.891.882.772 (3)175.5
N2—H2C···O5ii0.891.902.786 (2)178.4
O5—H5A···O20.819 (10)2.034 (10)2.852 (3)177 (3)
O5—H5B···O1iii0.825 (10)1.980 (14)2.722 (3)149 (2)
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z1/2; (iii) x+1/2, y+1/2, z+3/2.
 

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