Bis(N,N′-diphenyl­benzamidinium) fumarate

Orola, L.; Veidis, M.V.

doi:10.1107/S1600536810017708

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1597

doi:10.1107/S1600536810017708

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Bis(N,N′-diphenylbenzamidinium) fumarate

Liana Orola ^a and Mikelis V. Veidis ^a ^*

^aUniversity of Latvia, Kr. Valdemara 48, Riga, LV 1013, Latvia
^*Correspondence e-mail: veidis@lu.lv

(Received 24 March 2010; accepted 13 May 2010; online 9 June 2010)

The crystal structure of the title compound, 2C₁₉H₁₇N₂⁺·C₄H₂O₄²⁻, consists of centrosymmetric trimers built up of two crystallographically independent N,N′-diphenylbenzamidinium cations and one fumarate dianion, which is located on a centre of inversion. The components of the trimers are linked by N—H⋯O hydrogen bonding. In the cation, the outer rings make dihedral angles of 53.66 (5) and 78.38 (5)° with the central ring. The two outer rings make a dihdral angle of 81.49 (5)°.

Related literature

For the structure of N,N′-diphenylbenzamidine, see: Alcock et al. (1988 ) and for the structure of N,N′-diphenylbenzamidinium nitrate, see: Barker et al. (1999 ). For metal complexes of N,N′-diphenylbenzamidine, see: Davies et al. (2001 ); Jiang et al. (2005 ); Cotton et al. (1996 , 1997 ).

Experimental

Crystal data

2C₁₉H₁₇N₂⁺·C₄H₂O₄²⁻
M_r = 330.39
Monoclinic, P 2₁ /n
a = 10.5972 (3) Å
b = 8.8275 (3) Å
c = 18.7710 (7) Å
β = 102.346 (1)°
V = 1715.36 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 120 K
0.72 × 0.61 × 0.44 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (APEX2; Bruker, 2006 ) T_min = 0.95, T_max = 0.96
41010 measured reflections
5009 independent reflections
4976 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.107
S = 1.00
4876 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N19—H4⋯O3	0.88	1.79	2.673 (1)	178
N12—H9⋯O4	0.90	1.74	2.634 (2)	172

Data collection: APEX2 (Bruker, 2006); cell refinement: SMART (Bruker, 2006); data reduction: SMART; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810017708/nc2180sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810017708/nc2180Isup2.hkl

checkCIF report

Comment top

N,N'-Diphenylbenzamidine is widely used as a ligand in metal complexes and can act as a bridging (Jiang et al., 2005) or a bidentate (Davies et al., 2001) ligand. An important feature of many complexes with bridging bonding mode is metal-metal bond formation in dinuclear compounds (Cotton et al., 1997; Cotton et al., 1996). The crystal structure of N,N'-diphenylbenzamidine (Alcock et al., 1988) and its nitrate salt (Barker et al., 1999) have been reported previously. As part of an investigation of cocrystal synthesis, the N,N'-diphenylbenzamidine fumarate salt was obtained and the crystal and molecular structure was determined to identify the product. The asymmetric unit consist of one N,N'-diphenylbenzamidinium cation and half a fumarate dianion, which is located on a centre of inversion (Fig. 1). In the title compound there is a small difference in conformation of amidinium cation compared to N,N'-diphenylbenzamidine nitrate. In the amidinium cation the plane of the central phenyl ring is twisted by 53.7° and 78.4° with respect to the plane of the terminal phenyl rings 1 and 2 (Fig. 1). These values are slightly different from that in N,N'-diphenylbenzamidine nitrate in which a dihedral angle of 65.8° is observed (Barker et al., 1999). In the crystal structure of the title compound the amidinium cations are connected by the fumarate dianions via intermolecular N–H···O hydrogen bonds into trimers that are located on centres of inversion (Fig. 2 and Table 1).

Related literature top

For the structure of N,N'-diphenylbenzamidine, see: Alcock et al. (1988) and for the structure of N,N'-diphenylbenzamidinium nitrate, see: Barker et al. (1999). For metal complexes of N,N'-diphenylbenzamidine, see: Davies et al. (2001); Jiang et al. (2005); Cotton et al. (1996, 1997).

Experimental top

The title compound was prepared by dissolving N,N'-diphenylbenzamidine (0.054 g, 0.2 mmol) and fumaric acid (0.012 g, 0.1 mmol) in 5 ml of hot ethanol. Slow evaporation of the solution resulted in the formation of colorless prisms.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SMART (Bruker, 2006); data reduction: SMART (Bruker, 2006); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures top

	Fig. 1. The molecular structure of the title compound with labelling and displacement ellipsoids at the 50% probability level (symmetry code for equivalent atoms: i = -x+2, -y, -z+2). 1 and 2 distinguish the two independent terminal rings.
	Fig. 2. Crystal structure of the title compound with view of the trimers (hydrogen bonding is indicated by dashed lines).

Bis(N,N'-diphenylbenzamidinium) fumarate top

Crystal data top

2C₁₉H₁₇N₂⁺·C₄H₂O₄²⁻	F(000) = 696.00
M_r = 330.39	D_x = 1.279 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9851 reflections
a = 10.5972 (3) Å	θ = 3–30°
b = 8.8275 (3) Å	µ = 0.08 mm⁻¹
c = 18.7710 (7) Å	T = 120 K
β = 102.346 (1)°	Prism fragment, colorless
V = 1715.36 (10) Å³	0.72 × 0.61 × 0.44 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	5009 independent reflections
Radiation source: fine-focus sealed tube	4876 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 30.0°, θ_min = 2.0°
Absorption correction: multi-scan (APEX2; Bruker, 2006)	h = −14→14
T_min = 0.95, T_max = 0.96	k = 0→12
41010 measured reflections	l = 0→26

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F²) + ( 0.06P)² + 0.63P] where P = (max(F_o²,0) + 2F_c²)/3
wR(F²) = 0.107	(Δ/σ)_max = 0.001
S = 1.00	Δρ_max = 0.37 e Å⁻³
4976 reflections	Δρ_min = −0.21 e Å⁻³
226 parameters

Crystal data top

2C₁₉H₁₇N₂⁺·C₄H₂O₄²⁻	V = 1715.36 (10) Å³
M_r = 330.39	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.5972 (3) Å	µ = 0.08 mm⁻¹
b = 8.8275 (3) Å	T = 120 K
c = 18.7710 (7) Å	0.72 × 0.61 × 0.44 mm
β = 102.346 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	5009 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2006)	4876 reflections with I > 2σ(I)
T_min = 0.95, T_max = 0.96	R_int = 0.020
41010 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.00	Δρ_max = 0.37 e Å⁻³
4976 reflections	Δρ_min = −0.21 e Å⁻³
226 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.94300 (8)	0.03374 (10)	0.99406 (5)	0.0188
C2	0.86998 (8)	0.07821 (10)	0.91958 (5)	0.0172
O3	0.91578 (6)	0.04194 (8)	0.86516 (3)	0.0213
O4	0.76557 (6)	0.14853 (8)	0.91690 (4)	0.0229
C5	0.63464 (8)	0.08298 (9)	0.73154 (4)	0.0158
C6	0.53733 (8)	0.06749 (10)	0.66218 (4)	0.0155
C7	0.53685 (9)	−0.06272 (10)	0.62033 (5)	0.0202
C8	0.43586 (9)	−0.08628 (12)	0.56046 (5)	0.0247
C9	0.33852 (9)	0.02100 (12)	0.54165 (5)	0.0239
C10	0.34143 (8)	0.15261 (11)	0.58227 (5)	0.0220
C11	0.44042 (8)	0.17580 (10)	0.64315 (5)	0.0189
N12	0.59750 (7)	0.09379 (9)	0.79444 (4)	0.0177
C13	0.47079 (8)	0.07070 (10)	0.80659 (4)	0.0171
C14	0.43162 (9)	0.16661 (11)	0.85652 (5)	0.0223
C15	0.30805 (10)	0.15224 (13)	0.87010 (5)	0.0268
C16	0.22460 (9)	0.04177 (14)	0.83488 (5)	0.0282
C17	0.26682 (10)	−0.05734 (13)	0.78741 (6)	0.0285
C18	0.39004 (9)	−0.04455 (11)	0.77341 (5)	0.0230
N19	0.76104 (7)	0.08174 (9)	0.73401 (4)	0.0182
C20	0.82262 (8)	0.11807 (10)	0.67587 (4)	0.0173
C21	0.77945 (8)	0.23541 (10)	0.62732 (5)	0.0200
C22	0.84978 (9)	0.27416 (11)	0.57528 (5)	0.0232
C23	0.96279 (10)	0.19753 (12)	0.57190 (5)	0.0259
C24	1.00596 (10)	0.08164 (13)	0.62091 (6)	0.0305
C25	0.93605 (9)	0.04137 (12)	0.67293 (6)	0.0260
H11	0.9043	0.0548	1.0339	0.0224*
H91	0.2695	0.0056	0.4998	0.0277*
H101	0.2769	0.2275	0.5692	0.0264*
H111	0.4430	0.2649	0.6712	0.0230*
H141	0.4887	0.2423	0.8804	0.0269*
H151	0.2816	0.2217	0.9032	0.0324*
H161	0.1385	0.0352	0.8434	0.0313*
H171	0.2125	−0.1372	0.7639	0.0336*
H211	0.7042	0.2873	0.6302	0.0239*
H221	0.8201	0.3536	0.5423	0.0286*
H231	1.0108	0.2256	0.5354	0.0309*
H241	1.0854	0.0287	0.6200	0.0370*
H251	0.9653	−0.0391	0.7075	0.0301*
H3	0.6030	−0.1359	0.6324	0.0240*
H4	0.8118	0.0660	0.7773	0.0225*
H8	0.4178	−0.1146	0.7427	0.0269*
H9	0.6581	0.1188	0.8341	0.0217*
H12	0.4343	−0.1762	0.5325	0.0293*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0190 (4)	0.0215 (4)	0.0147 (3)	−0.0001 (3)	0.0011 (3)	0.0002 (3)
C2	0.0163 (4)	0.0173 (4)	0.0164 (4)	0.0003 (3)	−0.0002 (3)	−0.0025 (3)
O3	0.0175 (3)	0.0294 (3)	0.0162 (3)	0.0017 (2)	0.0017 (2)	0.0008 (2)
O4	0.0186 (3)	0.0281 (3)	0.0196 (3)	−0.0029 (2)	−0.0010 (2)	0.0042 (2)
C5	0.0146 (3)	0.0169 (4)	0.0154 (3)	0.0006 (3)	0.0024 (3)	0.0014 (3)
C6	0.0138 (3)	0.0185 (4)	0.0141 (3)	0.0008 (3)	0.0026 (3)	0.0001 (3)
C7	0.0201 (4)	0.0209 (4)	0.0195 (4)	−0.0020 (3)	0.0037 (3)	0.0023 (3)
C8	0.0252 (4)	0.0269 (5)	0.0212 (4)	−0.0069 (3)	0.0035 (3)	−0.0027 (4)
C9	0.0197 (4)	0.0322 (5)	0.0180 (4)	0.0005 (3)	−0.0001 (3)	−0.0046 (3)
C10	0.0156 (4)	0.0261 (4)	0.0225 (4)	0.0048 (3)	0.0002 (3)	0.0010 (3)
C11	0.0166 (4)	0.0193 (4)	0.0200 (4)	0.0000 (3)	0.0021 (3)	0.0018 (3)
N12	0.0132 (3)	0.0248 (4)	0.0148 (3)	−0.0010 (3)	0.0024 (2)	0.0001 (3)
C13	0.0141 (3)	0.0228 (4)	0.0147 (3)	0.0021 (3)	0.0035 (3)	0.0011 (3)
C14	0.0222 (4)	0.0268 (4)	0.0192 (4)	−0.0026 (3)	0.0070 (3)	−0.0005 (3)
C15	0.0256 (5)	0.0334 (5)	0.0245 (4)	−0.0005 (4)	0.0125 (4)	0.0035 (4)
C16	0.0187 (4)	0.0434 (6)	0.0246 (4)	0.0046 (4)	0.0090 (3)	−0.0010 (4)
C17	0.0233 (4)	0.0391 (6)	0.0246 (4)	−0.0023 (4)	0.0083 (4)	−0.0108 (4)
C18	0.0223 (4)	0.0271 (4)	0.0212 (4)	−0.0030 (3)	0.0085 (3)	−0.0048 (3)
N19	0.0134 (3)	0.0260 (4)	0.0149 (3)	0.0024 (3)	0.0026 (2)	0.0023 (3)
C20	0.0147 (3)	0.0212 (4)	0.0161 (4)	−0.0003 (3)	0.0036 (3)	0.0000 (3)
C21	0.0189 (4)	0.0208 (4)	0.0207 (4)	0.0010 (3)	0.0049 (3)	0.0026 (3)
C22	0.0249 (4)	0.0241 (4)	0.0210 (4)	0.0036 (3)	0.0058 (3)	−0.0007 (3)
C23	0.0245 (4)	0.0315 (5)	0.0244 (4)	0.0019 (4)	0.0111 (3)	−0.0022 (4)
C24	0.0221 (4)	0.0375 (6)	0.0357 (5)	0.0076 (4)	0.0148 (4)	0.0074 (4)
C25	0.0196 (4)	0.0315 (5)	0.0288 (5)	0.0092 (4)	0.0093 (3)	0.0077 (4)

Geometric parameters (Å, º) top

C1—C1ⁱ	1.3223 (17)	C14—C15	1.3924 (13)
C1—C2	1.4982 (11)	C14—H141	0.947
C1—H11	0.944	C15—C16	1.3857 (15)
C2—O3	1.2625 (11)	C15—H151	0.957
C2—O4	1.2603 (11)	C16—C17	1.3892 (15)
C5—C6	1.4842 (11)	C16—H161	0.961
C5—N12	1.3255 (10)	C17—C18	1.3906 (13)
C5—N19	1.3304 (10)	C17—H171	0.956
C6—C7	1.3917 (12)	C18—H8	0.935
C6—C11	1.3926 (12)	N19—C20	1.4228 (11)
C7—C8	1.3919 (13)	N19—H4	0.884
C7—H3	0.944	C20—C21	1.3908 (12)
C8—C9	1.3892 (14)	C20—C25	1.3909 (12)
C8—H12	0.950	C21—C22	1.3922 (12)
C9—C10	1.3864 (14)	C21—H211	0.931
C9—H91	0.962	C22—C23	1.3886 (14)
C10—C11	1.3912 (12)	C22—H221	0.943
C10—H101	0.945	C23—C24	1.3864 (15)
C11—H111	0.944	C23—H231	0.969
N12—C13	1.4239 (10)	C24—C25	1.3922 (13)
N12—H9	0.901	C24—H241	0.966
C13—C14	1.3907 (12)	C25—H251	0.967
C13—C18	1.3882 (12)

C1ⁱ—C1—C2	123.12 (10)	C15—C14—H141	120.5
C1ⁱ—C1—H11	119.4	C14—C15—C16	120.40 (9)
C2—C1—H11	117.5	C14—C15—H151	118.6
C1—C2—O3	118.51 (8)	C16—C15—H151	121.0
C1—C2—O4	116.12 (8)	C15—C16—C17	119.28 (9)
O3—C2—O4	125.36 (8)	C15—C16—H161	119.7
C6—C5—N12	120.33 (7)	C17—C16—H161	121.0
C6—C5—N19	122.37 (7)	C16—C17—C18	120.95 (9)
N12—C5—N19	117.26 (7)	C16—C17—H171	121.1
C5—C6—C7	119.29 (7)	C18—C17—H171	118.0
C5—C6—C11	119.85 (8)	C17—C18—C13	119.23 (9)
C7—C6—C11	120.58 (8)	C17—C18—H8	119.7
C6—C7—C8	119.25 (8)	C13—C18—H8	121.1
C6—C7—H3	121.1	C5—N19—C20	126.50 (7)
C8—C7—H3	119.7	C5—N19—H4	116.3
C7—C8—C9	120.28 (9)	C20—N19—H4	116.8
C7—C8—H12	119.4	N19—C20—C21	122.00 (8)
C9—C8—H12	120.4	N19—C20—C25	117.56 (8)
C8—C9—C10	120.23 (8)	C21—C20—C25	120.17 (8)
C8—C9—H91	120.3	C20—C21—C22	119.49 (8)
C10—C9—H91	119.4	C20—C21—H211	119.6
C9—C10—C11	119.95 (8)	C22—C21—H211	120.9
C9—C10—H101	120.9	C21—C22—C23	120.57 (9)
C11—C10—H101	119.1	C21—C22—H221	119.3
C6—C11—C10	119.66 (8)	C23—C22—H221	120.1
C6—C11—H111	119.9	C22—C23—C24	119.65 (9)
C10—C11—H111	120.5	C22—C23—H231	119.7
C5—N12—C13	127.02 (7)	C24—C23—H231	120.6
C5—N12—H9	117.3	C23—C24—C25	120.28 (9)
C13—N12—H9	115.7	C23—C24—H241	120.7
N12—C13—C14	116.64 (8)	C25—C24—H241	119.1
N12—C13—C18	123.03 (8)	C24—C25—C20	119.83 (9)
C14—C13—C18	120.29 (8)	C24—C25—H251	121.0
C13—C14—C15	119.73 (9)	C20—C25—H251	119.2
C13—C14—H141	119.8

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N19—H4···O3	0.88	1.79	2.673 (1)	178
N12—H9···O4	0.90	1.74	2.634 (2)	172

Experimental details

Crystal data
Chemical formula	2C₁₉H₁₇N₂⁺·C₄H₂O₄²⁻
M_r	330.39
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	10.5972 (3), 8.8275 (3), 18.7710 (7)
β (°)	102.346 (1)
V (Å³)	1715.36 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.72 × 0.61 × 0.44

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (APEX2; Bruker, 2006)
T_min, T_max	0.95, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	41010, 5009, 4876
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.107, 1.00
No. of reflections	4976
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.21

Computer programs: APEX2 (Bruker, 2006), SMART (Bruker, 2006), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N19—H4···O3	0.884	1.790	2.673 (1)	177.8
N12—H9···O4	0.901	1.739	2.634 (2)	172.2

Acknowledgements

We thank the US National Science Foundation for the partial support of this work through grant CHE-0521047 (to Brandeis University) for the purchase of a new X-ray diffractometer, and Professor Bruce M. Foxman for assistance with the data collection.

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