4-Nitro-anilinium triiodide monohydrate.

In the title compound, C(6)H(7)N(2)O(2) (+)·I(3) (-)·H(2)O, the triiodide anions form two-dimensional sheets along the a and c axes. These sheets are separated by the 4-nitro-anilinium cations and water mol-ecules, which form part of an extended hydrogen-bonded chain with the triiodide along the c axis, represented by the graph set C(3) (3)(14). The second important hydrogen-bonding inter-action is between the nitro group, the water mol-ecule and the anilinium group, which forms an R(2) (2)(6) ring and may be the reason for the deviation of the torsion angle between the benzene ring and the nitro group from 180 to 163.2 (4)°. These two strong hydrogen-bonding inter-actions also cause the benzene rings to pack off-centre from one another, with an edge-on-edge π-π stacking distance of 3.634 (6) Å and a centroid-centroid separation of 4.843 (2) Å.

Related literature

For structures of 4-nitro­anilinine-monohalide salts, see: Lemmerer & Billing (2006 ▶) (bromine) and Ploug-Sørensen & Andersen (1982 ▶) (chlorine). For other amine-based triiodide salts, see: Tebbe & Loukili (1998 ▶). For a triiodide salt containing a tetra­phenyl­phospho­nium cation, see: Parvez et al. (1996 ▶). For structure-properties relationships in trihalides, see: Shibaeva & Yagubskii (2004 ▶). For graph-set analysis, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C6H7N2O2 +·I3 −·H2O

M = 537.85

Monoclinic,

a = 4.8429 (9) Å

b = 14.701 (3) Å

c = 18.346 (3) Å

β = 91.916 (3)°

V = 1305.4 (4) Å3

Z = 4

Mo Kα radiation

μ = 7.17 mm−1

T = 298 K

0.54 × 0.31 × 0.11 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer

Absorption correction: integration (XPREP; Bruker, 1999 ▶) T min = 0.113, T max = 0.506

8741 measured reflections

3150 independent reflections

2461 reflections with I > 2σ(I)

R int = 0.068

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.081

S = 1.05

3150 reflections

137 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.71 e Å−3

Δρmin = −1.42 e Å−3

Data collection: SMART-NT (Bruker, 1998 ▶); cell refinement: SMART-NT; data reduction: SAINT-Plus (Bruker, 1999 ▶); program(s) used to solve structure: XS in SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810014674/zs2032sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014674/zs2032Isup2.hkl

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

C6H7N2O2+·I3−·H2O	F(000) = 968
Mr = 537.85	Dx = 2.737 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9074 reflections
a = 4.8429 (9) Å	θ = 2.6–28.3°
b = 14.701 (3) Å	µ = 7.17 mm−1
c = 18.346 (3) Å	T = 298 K
β = 91.916 (3)°	Plate, black
V = 1305.4 (4) Å3	0.54 × 0.31 × 0.11 mm
Z = 4

Bruker SMART 1K CCD area-detector diffractometer	2461 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.068
Absorption correction: integration (XPREP; Bruker, 1999)	θmax = 28°, θmin = 1.8°
Tmin = 0.113, Tmax = 0.506	h = −6→4
8741 measured reflections	k = −19→18
3150 independent reflections	l = −24→24

Refinement on F2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0374P)2 + 0.3561P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.034	(Δ/σ)max = 0.001
wR(F2) = 0.081	Δρmax = 0.71 e Å−3
S = 1.05	Δρmin = −1.42 e Å−3
3150 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
137 parameters	Extinction coefficient: 0.0166 (6)
0 restraints

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 1999a)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
C1	0.4993 (8)	0.2871 (3)	0.2902 (2)	0.0404 (8)
C2	0.6434 (9)	0.3443 (3)	0.3357 (2)	0.0491 (10)
H2	0.7771	0.383	0.3179	0.059*
C3	0.5861 (9)	0.3433 (3)	0.4094 (2)	0.0482 (10)
H3	0.6779	0.3822	0.442	0.058*
C4	0.3913 (8)	0.2838 (3)	0.4328 (2)	0.0410 (9)
C5	0.2464 (9)	0.2267 (3)	0.3873 (2)	0.0502 (10)
H5	0.1157	0.187	0.4053	0.06*
C6	0.2991 (9)	0.2293 (3)	0.3129 (2)	0.0481 (10)
H6	0.2006	0.1928	0.2798	0.058*
N1	0.5625 (8)	0.2874 (3)	0.21247 (18)	0.0494 (9)
N2	0.3444 (8)	0.2797 (3)	0.51204 (17)	0.0574 (10)
H2A	0.1948	0.2464	0.5199	0.086*
H2B	0.3198	0.3357	0.529	0.086*
H2C	0.4903	0.2545	0.5349	0.086*
O1	0.3995 (8)	0.2526 (3)	0.16900 (17)	0.0692 (10)
O2	0.7804 (8)	0.3222 (3)	0.19569 (19)	0.0774 (11)
O3	0.8528 (8)	0.3133 (2)	0.04409 (18)	0.0583 (8)
H3A	0.878 (14)	0.316 (5)	0.0917 (12)	0.11 (3)*
H3B	0.800 (13)	0.366 (3)	0.024 (3)	0.11 (2)*
I1	0.33289 (8)	0.50637 (2)	0.091253 (18)	0.06519 (14)
I2	0.22677 (6)	0.531920 (18)	0.244438 (16)	0.04997 (12)
I3	0.12058 (7)	0.55190 (2)	0.402108 (17)	0.06257 (14)

	U11	U22	U33	U12	U13	U23
C1	0.047 (2)	0.045 (2)	0.0290 (18)	0.0061 (17)	0.0020 (16)	−0.0012 (16)
C2	0.055 (3)	0.051 (2)	0.041 (2)	−0.0106 (19)	0.003 (2)	0.0007 (18)
C3	0.057 (3)	0.055 (2)	0.0320 (19)	−0.003 (2)	−0.0039 (18)	−0.0060 (18)
C4	0.043 (2)	0.051 (2)	0.0292 (18)	0.0095 (17)	0.0039 (16)	0.0001 (16)
C5	0.049 (3)	0.062 (3)	0.041 (2)	−0.005 (2)	0.0075 (19)	0.002 (2)
C6	0.049 (2)	0.054 (2)	0.041 (2)	−0.0027 (19)	0.0015 (19)	−0.0070 (19)
N1	0.057 (2)	0.057 (2)	0.0341 (18)	0.0053 (18)	0.0045 (17)	−0.0046 (16)
N2	0.056 (2)	0.083 (3)	0.0341 (18)	−0.002 (2)	0.0071 (16)	−0.0006 (19)
O1	0.078 (2)	0.090 (3)	0.0390 (17)	−0.009 (2)	−0.0025 (16)	−0.0066 (17)
O2	0.072 (2)	0.115 (3)	0.0463 (19)	−0.020 (2)	0.0136 (17)	−0.008 (2)
O3	0.066 (2)	0.067 (2)	0.0433 (18)	−0.0040 (17)	0.0108 (16)	−0.0020 (16)
I1	0.0854 (3)	0.0619 (2)	0.0487 (2)	0.00069 (17)	0.00906 (17)	0.00064 (14)
I2	0.0543 (2)	0.04402 (18)	0.05185 (19)	0.00195 (12)	0.00491 (13)	−0.00021 (12)
I3	0.0680 (2)	0.0673 (2)	0.0529 (2)	−0.00435 (15)	0.01033 (16)	−0.01723 (15)

C1—C2	1.361 (6)	C6—H6	0.93
C1—C6	1.365 (6)	N1—O1	1.216 (5)
C1—N1	1.468 (5)	N1—O2	1.221 (5)
C2—C3	1.389 (5)	N2—H2A	0.89
C2—H2	0.93	N2—H2B	0.89
C3—C4	1.366 (6)	N2—H2C	0.89
C3—H3	0.93	O3—H3A	0.88 (2)
C4—C5	1.362 (6)	O3—H3B	0.89 (5)
C4—N2	1.480 (5)	I1—I2	2.8982 (6)
C5—C6	1.398 (6)	I2—I3	2.9694 (6)
C5—H5	0.93
C2—C1—C6	123.6 (4)	C1—C6—C5	118.0 (4)
C2—C1—N1	118.3 (4)	C1—C6—H6	121
C6—C1—N1	118.1 (4)	C5—C6—H6	121
C1—C2—C3	118.4 (4)	O1—N1—O2	123.9 (4)
C1—C2—H2	120.8	O1—N1—C1	118.9 (4)
C3—C2—H2	120.8	O2—N1—C1	117.1 (4)
C4—C3—C2	118.4 (4)	C4—N2—H2A	109.5
C4—C3—H3	120.8	C4—N2—H2B	109.5
C2—C3—H3	120.8	H2A—N2—H2B	109.5
C5—C4—C3	123.3 (4)	C4—N2—H2C	109.5
C5—C4—N2	119.0 (4)	H2A—N2—H2C	109.5
C3—C4—N2	117.7 (4)	H2B—N2—H2C	109.5
C4—C5—C6	118.4 (4)	H3A—O3—H3B	114 (6)
C4—C5—H5	120.8	I1—I2—I3	178.209 (14)
C6—C5—H5	120.8
C6—C1—C2—C3	0.7 (7)	C2—C1—C6—C5	−2.3 (7)
N1—C1—C2—C3	−179.3 (4)	N1—C1—C6—C5	177.7 (4)
C1—C2—C3—C4	1.2 (7)	C4—C5—C6—C1	2.0 (6)
C2—C3—C4—C5	−1.5 (7)	C2—C1—N1—O1	−164.1 (4)
C2—C3—C4—N2	176.4 (4)	C6—C1—N1—O1	15.9 (6)
C3—C4—C5—C6	−0.2 (7)	C2—C1—N1—O2	16.7 (6)
N2—C4—C5—C6	−178.0 (4)	C6—C1—N1—O2	−163.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3i	0.89	1.94	2.824 (5)	173
N2—H2B···I3ii	0.89	3.01	3.731 (4)	139
N2—H2C···O1iii	0.89	2.52	2.922 (5)	108
N2—H2C···O3iii	0.89	2.02	2.860 (5)	157
O3—H3A···O2	0.88 (2)	1.98 (3)	2.818 (5)	158 (6)
O3—H3B···I1iv	0.89 (5)	2.88 (5)	3.722 (3)	157 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3i	0.89	1.94	2.824 (5)	173
N2—H2B⋯I3ii	0.89	3.01	3.731 (4)	139
N2—H2C⋯O1iii	0.89	2.52	2.922 (5)	108
N2—H2C⋯O3iii	0.89	2.02	2.860 (5)	157
O3—H3A⋯O2	0.88 (2)	1.98 (3)	2.818 (5)	158 (6)
O3—H3B⋯I1iv	0.89 (5)	2.88 (5)	3.722 (3)	157 (4)

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