Bis[2-(4-amino-phen-yl)-4,5-dihydro-1H-imidazol-3-ium] dichloride monohydrate.

The asymmetric unit of the title compound, 2C(9)H(12)N(3) (+)·2Cl(-)·H(2)O, comprises two mol-ecules, two chloride anions and one mol-ecule of crystal water. In the imidazolinium ring, the protonation contributes to delocalization of the positive charge over the two C-N bonds. Both chloride anions are acceptors of four hydrogen bonds in a flattened tetra-hedron environment. The donors are NH(2) groups, the NH groups of the imidazolinium rings and the water mol-ecule. These hydrogen bonds and N-H⋯O(H(2)O) hydrogen bonds form a three-dimensional network.

Related literature

For background and the biological activity of aromatic amidines, see: Chen et al. (2010 ▶); Hu et al. (2009 ▶); Del Poeta et al. (1998 ▶); Baraldi et al. (2004 ▶); Jarak et al. (2011 ▶); Neidle (2001 ▶); Stolić et al. (2011 ▶). For the synthesis, see Widra et al. (1990 ▶). For related compounds see: Jarak et al. (2005 ▶); Legrand et al. (2008 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶);

Experimental

Crystal data

2C9H12N3 +·2Cl−·H2O

M = 413.35

Orthorhombic,

a = 10.5307 (2) Å

b = 17.9659 (4) Å

c = 22.4290 (5) Å

V = 4243.42 (16) Å3

Z = 8

Cu Kα radiation

μ = 2.91 mm−1

T = 293 K

0.4 × 0.05 × 0.04 mm

Data collection

Oxford Xcalibur Nova R Ruby diffractometer

Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2010 ▶) T min = 0.389, T max = 0.892

13695 measured reflections

4375 independent reflections

3054 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.116

S = 1.00

4375 reflections

348 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.13 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811050070/bq2316sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050070/bq2316Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811050070/bq2316Isup3.cml

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

2C9H12N3+·2Cl−·H2O	F(000) = 1744
Mr = 413.35	Dx = 1.294 Mg m−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4375 reflections
a = 10.5307 (2) Å	θ = 3.2–76.0°
b = 17.9659 (4) Å	µ = 2.91 mm−1
c = 22.4290 (5) Å	T = 293 K
V = 4243.42 (16) Å3	Prism, colourless
Z = 8	0.4 × 0.05 × 0.04 mm

Oxford Xcalibur Nova R Ruby diffractometer	3054 reflections with I > 2σ(I)
CCD detector, ω scans	Rint = 0.030
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2010)	θmax = 76.2°, θmin = 3.9°
Tmin = 0.389, Tmax = 0.892	h = −10→13
13695 measured reflections	k = −22→18
4375 independent reflections	l = −12→27

Refinement on F2	3 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.045	w = 1/[σ2(Fo2) + (0.0664P)2 + 0.1666P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.116	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.24 e Å−3
4375 reflections	Δρmin = −0.13 e Å−3
348 parameters

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.

	x	y	z	Uiso*/Ueq
C1A	0.15472 (18)	0.24466 (12)	0.46353 (9)	0.0591 (4)
C2A	0.2329 (2)	0.20468 (13)	0.50240 (9)	0.0677 (5)
H2A	0.2799	0.1647	0.488	0.081*
C3A	0.2413 (2)	0.22367 (13)	0.56166 (9)	0.0649 (5)
H3A	0.2947	0.1966	0.5866	0.078*
C4A	0.17150 (17)	0.28251 (10)	0.58513 (8)	0.0529 (4)
C5A	0.09206 (18)	0.32174 (11)	0.54635 (9)	0.0590 (4)
H5A	0.0434	0.3609	0.561	0.071*
C6A	0.08469 (19)	0.30346 (12)	0.48693 (9)	0.0630 (5)
H6A	0.032	0.3309	0.4619	0.076*
C7A	0.17897 (17)	0.30141 (10)	0.64793 (8)	0.0536 (4)
C8A	0.2419 (2)	0.29987 (16)	0.74592 (10)	0.0797 (6)
H811	0.3175	0.3238	0.7616	0.096*
H812	0.2177	0.2594	0.7722	0.096*
C9A	0.1344 (2)	0.35524 (14)	0.73860 (10)	0.0759 (6)
H911	0.0625	0.3423	0.7636	0.091*
H912	0.1618	0.4054	0.7481	0.091*
N1A	0.1465 (2)	0.22627 (13)	0.40482 (8)	0.0825 (6)
H11	0.0974	0.2511	0.3815	0.099*
H12	0.1904	0.1898	0.391	0.099*
N2A	0.26224 (17)	0.27362 (11)	0.68540 (8)	0.0705 (5)
H2C	0.3218	0.2434	0.6753	0.085*
N3A	0.10317 (17)	0.34793 (10)	0.67552 (8)	0.0671 (4)
H3C	0.0421	0.3714	0.6584	0.081*
C1B	0.7185 (2)	0.49540 (12)	0.38839 (10)	0.0699 (5)
C2B	0.7994 (2)	0.48300 (13)	0.43669 (11)	0.0726 (6)
H2B	0.8718	0.4542	0.4314	0.087*
C3B	0.7741 (2)	0.51242 (13)	0.49165 (10)	0.0677 (5)
H3B	0.8288	0.5024	0.5232	0.081*
C4B	0.66745 (19)	0.55730 (11)	0.50120 (9)	0.0597 (4)
C5B	0.5881 (2)	0.57082 (13)	0.45265 (11)	0.0679 (5)
H5B	0.5171	0.601	0.4577	0.082*
C6B	0.6124 (2)	0.54067 (14)	0.39764 (11)	0.0738 (6)
H6B	0.5576	0.5505	0.3661	0.089*
C7B	0.64277 (17)	0.58804 (11)	0.55951 (10)	0.0593 (5)
C8B	0.6543 (2)	0.60604 (14)	0.66131 (11)	0.0752 (6)
H821	0.7238	0.632	0.6807	0.09*
H822	0.6143	0.5728	0.6897	0.09*
C9B	0.5585 (2)	0.66057 (15)	0.63481 (12)	0.0809 (7)
H921	0.4744	0.6527	0.6512	0.097*
H922	0.5839	0.7117	0.6419	0.097*
N1B	0.7415 (2)	0.46400 (14)	0.33459 (10)	0.0947 (7)
H21	0.8067	0.4359	0.3298	0.114*
H22	0.6908	0.4722	0.3053	0.114*
N2B	0.69789 (18)	0.56590 (11)	0.60876 (8)	0.0702 (5)
H2D	0.7541	0.5312	0.6099	0.084*
N3B	0.56234 (18)	0.64252 (11)	0.57148 (9)	0.0762 (5)
H3D	0.5174	0.6648	0.5449	0.091*
Cl1	0.33702 (5)	0.08741 (3)	0.36842 (2)	0.06847 (16)
Cl2	0.48675 (5)	0.16106 (3)	0.68365 (3)	0.08017 (19)
O1	0.4366 (2)	0.99224 (11)	0.26032 (8)	0.0905 (5)
H1A	0.461 (3)	0.9475 (12)	0.2776 (14)	0.136*
H1B	0.396 (3)	1.0191 (15)	0.2913 (12)	0.136*

	U11	U22	U33	U12	U13	U23
C1A	0.0660 (10)	0.0683 (11)	0.0431 (10)	−0.0008 (9)	0.0021 (9)	0.0024 (9)
C2A	0.0789 (12)	0.0720 (13)	0.0522 (12)	0.0194 (10)	0.0007 (10)	−0.0040 (10)
C3A	0.0728 (11)	0.0716 (12)	0.0503 (11)	0.0160 (10)	−0.0065 (9)	−0.0001 (9)
C4A	0.0563 (9)	0.0563 (10)	0.0461 (10)	−0.0010 (8)	0.0003 (8)	0.0006 (8)
C5A	0.0666 (10)	0.0577 (10)	0.0527 (11)	0.0084 (9)	0.0027 (9)	0.0007 (8)
C6A	0.0677 (10)	0.0707 (12)	0.0506 (11)	0.0092 (10)	−0.0040 (9)	0.0071 (9)
C7A	0.0588 (9)	0.0527 (9)	0.0492 (10)	−0.0024 (8)	−0.0012 (8)	0.0008 (8)
C8A	0.0945 (15)	0.0948 (17)	0.0499 (12)	0.0214 (13)	−0.0123 (11)	−0.0105 (11)
C9A	0.0898 (14)	0.0868 (15)	0.0511 (12)	0.0187 (13)	−0.0059 (11)	−0.0109 (11)
N1A	0.1041 (14)	0.0982 (15)	0.0453 (10)	0.0272 (12)	−0.0067 (10)	−0.0056 (9)
N2A	0.0768 (10)	0.0855 (12)	0.0491 (10)	0.0234 (9)	−0.0076 (8)	−0.0075 (8)
N3A	0.0762 (10)	0.0756 (11)	0.0496 (10)	0.0201 (9)	−0.0077 (8)	−0.0088 (8)
C1B	0.0866 (13)	0.0648 (12)	0.0582 (12)	−0.0045 (11)	0.0046 (11)	0.0040 (10)
C2B	0.0807 (13)	0.0690 (13)	0.0682 (14)	0.0124 (11)	0.0058 (11)	0.0054 (11)
C3B	0.0758 (12)	0.0672 (12)	0.0601 (13)	0.0098 (10)	−0.0006 (10)	0.0069 (10)
C4B	0.0647 (10)	0.0540 (10)	0.0606 (12)	−0.0013 (9)	0.0017 (9)	0.0084 (9)
C5B	0.0686 (11)	0.0669 (12)	0.0684 (14)	0.0044 (10)	−0.0027 (10)	0.0054 (10)
C6B	0.0821 (13)	0.0794 (15)	0.0600 (13)	−0.0002 (12)	−0.0092 (11)	0.0080 (11)
C7B	0.0587 (9)	0.0559 (10)	0.0634 (12)	0.0002 (8)	0.0003 (9)	0.0057 (9)
C8B	0.0797 (13)	0.0808 (15)	0.0652 (14)	0.0153 (12)	0.0023 (11)	−0.0055 (11)
C9B	0.0854 (14)	0.0821 (15)	0.0753 (16)	0.0220 (13)	0.0018 (13)	−0.0069 (12)
N1B	0.1131 (15)	0.1059 (17)	0.0651 (13)	0.0179 (14)	−0.0007 (12)	−0.0067 (12)
N2B	0.0787 (10)	0.0727 (11)	0.0592 (10)	0.0204 (9)	−0.0019 (9)	−0.0008 (8)
N3B	0.0819 (11)	0.0759 (11)	0.0707 (12)	0.0247 (10)	−0.0048 (10)	0.0015 (9)
Cl1	0.0833 (3)	0.0644 (3)	0.0577 (3)	−0.0134 (2)	0.0066 (2)	−0.0012 (2)
Cl2	0.0760 (3)	0.0766 (3)	0.0879 (4)	0.0119 (3)	0.0061 (3)	0.0194 (3)
O1	0.1249 (14)	0.0828 (11)	0.0637 (10)	0.0098 (11)	0.0000 (10)	0.0030 (8)

C1A—N1A	1.360 (3)	C1B—C2B	1.396 (3)
C1A—C6A	1.391 (3)	C1B—C6B	1.397 (3)
C1A—C2A	1.398 (3)	C2B—C3B	1.367 (3)
C2A—C3A	1.375 (3)	C2B—H2B	0.93
C2A—H2A	0.93	C3B—C4B	1.399 (3)
C3A—C4A	1.391 (3)	C3B—H3B	0.93
C3A—H3A	0.93	C4B—C5B	1.394 (3)
C4A—C5A	1.398 (3)	C4B—C7B	1.443 (3)
C4A—C7A	1.451 (3)	C5B—C6B	1.372 (3)
C5A—C6A	1.375 (3)	C5B—H5B	0.93
C5A—H5A	0.93	C6B—H6B	0.93
C6A—H6A	0.93	C7B—N2B	1.310 (3)
C7A—N3A	1.311 (2)	C7B—N3B	1.322 (3)
C7A—N2A	1.313 (2)	C8B—N2B	1.456 (3)
C8A—N2A	1.453 (3)	C8B—C9B	1.527 (3)
C8A—C9A	1.516 (3)	C8B—H821	0.97
C8A—H811	0.97	C8B—H822	0.97
C8A—H812	0.97	C9B—N3B	1.458 (3)
C9A—N3A	1.458 (3)	C9B—H921	0.97
C9A—H911	0.97	C9B—H922	0.97
C9A—H912	0.97	N1B—H21	0.86
N1A—H11	0.86	N1B—H22	0.86
N1A—H12	0.86	N2B—H2D	0.86
N2A—H2C	0.86	N3B—H3D	0.86
N3A—H3C	0.86	O1—H1A	0.928 (17)
C1B—N1B	1.354 (3)	O1—H1B	0.947 (17)
N1A—C1A—C6A	121.06 (19)	N1B—C1B—C6B	121.2 (2)
N1A—C1A—C2A	121.1 (2)	C2B—C1B—C6B	117.7 (2)
C6A—C1A—C2A	117.84 (19)	C3B—C2B—C1B	121.3 (2)
C3A—C2A—C1A	120.9 (2)	C3B—C2B—H2B	119.4
C3A—C2A—H2A	119.6	C1B—C2B—H2B	119.4
C1A—C2A—H2A	119.6	C2B—C3B—C4B	121.1 (2)
C2A—C3A—C4A	121.37 (19)	C2B—C3B—H3B	119.4
C2A—C3A—H3A	119.3	C4B—C3B—H3B	119.4
C4A—C3A—H3A	119.3	C5B—C4B—C3B	117.5 (2)
C3A—C4A—C5A	117.64 (18)	C5B—C4B—C7B	122.24 (19)
C3A—C4A—C7A	121.11 (17)	C3B—C4B—C7B	120.26 (19)
C5A—C4A—C7A	121.23 (17)	C6B—C5B—C4B	121.5 (2)
C6A—C5A—C4A	121.10 (19)	C6B—C5B—H5B	119.3
C6A—C5A—H5A	119.4	C4B—C5B—H5B	119.3
C4A—C5A—H5A	119.4	C5B—C6B—C1B	120.8 (2)
C5A—C6A—C1A	121.15 (19)	C5B—C6B—H6B	119.6
C5A—C6A—H6A	119.4	C1B—C6B—H6B	119.6
C1A—C6A—H6A	119.4	N2B—C7B—N3B	109.7 (2)
N3A—C7A—N2A	110.29 (18)	N2B—C7B—C4B	124.63 (18)
N3A—C7A—C4A	125.06 (17)	N3B—C7B—C4B	125.64 (19)
N2A—C7A—C4A	124.64 (18)	N2B—C8B—C9B	102.17 (19)
N2A—C8A—C9A	102.81 (17)	N2B—C8B—H821	111.3
N2A—C8A—H811	111.2	C9B—C8B—H821	111.3
C9A—C8A—H811	111.2	N2B—C8B—H822	111.3
N2A—C8A—H812	111.2	C9B—C8B—H822	111.3
C9A—C8A—H812	111.2	H821—C8B—H822	109.2
H811—C8A—H812	109.1	N3B—C9B—C8B	102.61 (18)
N3A—C9A—C8A	102.38 (17)	N3B—C9B—H921	111.2
N3A—C9A—H911	111.3	C8B—C9B—H921	111.2
C8A—C9A—H911	111.3	N3B—C9B—H922	111.2
N3A—C9A—H912	111.3	C8B—C9B—H922	111.2
C8A—C9A—H912	111.3	H921—C9B—H922	109.2
H911—C9A—H912	109.2	C1B—N1B—H21	120
C1A—N1A—H11	120	C1B—N1B—H22	120
C1A—N1A—H12	120	H21—N1B—H22	120
H11—N1A—H12	120	C7B—N2B—C8B	113.13 (18)
C7A—N2A—C8A	112.10 (18)	C7B—N2B—H2D	123.4
C7A—N2A—H2C	124	C8B—N2B—H2D	123.4
C8A—N2A—H2C	124	C7B—N3B—C9B	112.36 (19)
C7A—N3A—C9A	112.22 (17)	C7B—N3B—H3D	123.8
C7A—N3A—H3C	123.9	C9B—N3B—H3D	123.8
C9A—N3A—H3C	123.9	H1A—O1—H1B	105 (2)
N1B—C1B—C2B	121.1 (2)
N1A—C1A—C2A—C3A	179.7 (2)	N1B—C1B—C2B—C3B	−177.6 (2)
C6A—C1A—C2A—C3A	−0.8 (3)	C6B—C1B—C2B—C3B	1.7 (4)
C1A—C2A—C3A—C4A	0.7 (4)	C1B—C2B—C3B—C4B	−1.3 (4)
C2A—C3A—C4A—C5A	0.1 (3)	C2B—C3B—C4B—C5B	0.0 (3)
C2A—C3A—C4A—C7A	178.9 (2)	C2B—C3B—C4B—C7B	−179.8 (2)
C3A—C4A—C5A—C6A	−0.9 (3)	C3B—C4B—C5B—C6B	0.8 (3)
C7A—C4A—C5A—C6A	−179.66 (19)	C7B—C4B—C5B—C6B	−179.5 (2)
C4A—C5A—C6A—C1A	0.9 (3)	C4B—C5B—C6B—C1B	−0.3 (4)
N1A—C1A—C6A—C5A	179.4 (2)	N1B—C1B—C6B—C5B	178.4 (2)
C2A—C1A—C6A—C5A	0.0 (3)	C2B—C1B—C6B—C5B	−0.9 (3)
C3A—C4A—C7A—N3A	−169.1 (2)	C5B—C4B—C7B—N2B	165.7 (2)
C5A—C4A—C7A—N3A	9.6 (3)	C3B—C4B—C7B—N2B	−14.6 (3)
C3A—C4A—C7A—N2A	10.2 (3)	C5B—C4B—C7B—N3B	−14.6 (3)
C5A—C4A—C7A—N2A	−171.1 (2)	C3B—C4B—C7B—N3B	165.2 (2)
N2A—C8A—C9A—N3A	4.1 (3)	N2B—C8B—C9B—N3B	0.3 (3)
N3A—C7A—N2A—C8A	2.6 (3)	N3B—C7B—N2B—C8B	0.8 (3)
C4A—C7A—N2A—C8A	−176.8 (2)	C4B—C7B—N2B—C8B	−179.5 (2)
C9A—C8A—N2A—C7A	−4.3 (3)	C9B—C8B—N2B—C7B	−0.7 (3)
N2A—C7A—N3A—C9A	0.5 (3)	N2B—C7B—N3B—C9B	−0.6 (3)
C4A—C7A—N3A—C9A	179.9 (2)	C4B—C7B—N3B—C9B	179.7 (2)
C8A—C9A—N3A—C7A	−3.1 (3)	C8B—C9B—N3B—C7B	0.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11···Cl2i	0.86	2.45	3.296 (2)	170.
N1A—H12···Cl1	0.86	2.45	3.304 (2)	170.
N1B—H21···Cl2ii	0.86	2.59	3.448 (2)	174.
N1B—H22···O1iii	0.86	2.02	2.882 (3)	177.
N2A—H2C···Cl2	0.86	2.29	3.1113 (18)	160
N2B—H2D···Cl1ii	0.86	2.35	3.1615 (19)	157.
N3A—H3C···Cl1i	0.86	2.36	3.1900 (17)	162.
O1—H1A···Cl2iv	0.93 (2)	2.21 (2)	3.1329 (19)	178 (3)
O1—H1B···Cl1v	0.95 (2)	2.21 (2)	3.147 (2)	170 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H11⋯Cl2i	0.86	2.45	3.296 (2)	170
N1A—H12⋯Cl1	0.86	2.45	3.304 (2)	170
N1B—H21⋯Cl2ii	0.86	2.59	3.448 (2)	174
N1B—H22⋯O1iii	0.86	2.02	2.882 (3)	177
N2A—H2C⋯Cl2	0.86	2.29	3.1113 (18)	160
N2B—H2D⋯Cl1ii	0.86	2.35	3.1615 (19)	157
N3A—H3C⋯Cl1i	0.86	2.36	3.1900 (17)	162
O1—H1A⋯Cl2iv	0.93 (2)	2.21 (2)	3.1329 (19)	178 (3)
O1—H1B⋯Cl1v	0.95 (2)	2.21 (2)	3.147 (2)	170 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .