Crystal structure of 4-{2-[4-(di-methyl-amino)-phen-yl]diazen-1-yl}-1-methyl-pyridinium iodide.

The mol-ecular geometry of the ionic title compound, C14H17N4 (+)·I(-) or DAZOP(+)·I(-), is essentially featureless. Regarding the crystal structure, in addition to the obvious cation-anion Coulombic inter-actions, the packing is mostly directed by non-covalent inter-actions involving both ring systems, as well as the iodide anion. It consists of cationic mol-ecules aligned along [101] and disposed in an anti-parallel fashion while linked into π-bonded dimeric entities by a stacking contact involving symmetry-related phenyl rings, with a centroid-centroid distance of 3.468 (3) Å and a slippage of 0.951 Å. The dimers are, in addition, sustained by a number of C-H⋯I and I⋯π (I⋯centroid = 3.876 Å) inter-actions involving the anion. Finally, inter-dimeric contacts are of the C-H⋯I and C-H⋯π types.

Related literature

For the synthesis of precursors, see: Li et al. (1995 ▸). For spectroscopic properties of the title compound, see: Gonbeau et al. (1999 ▸). For general infomation on non-linear optical materials, see: Coradin et al. (1997 ▸); Mestechkin (2001 ▸); Nunzi et al. (2008 ▸). For general infomation on new photonic materials, see: Yu et al. (2013 ▸). For related structures, see: Cristian et al. (2004 ▸); Evans et al. (2001 ▸); Xu et al. (2012 ▸).

Experimental

Crystal data

C14H17N4 +·I−

M = 368.21

Monoclinic,

a = 18.0508 (14) Å

b = 7.2790 (5) Å

c = 11.3760 (9) Å

β = 98.929 (7)°

V = 1476.60 (19) Å3

Z = 4

Mo Kα radiation

μ = 2.16 mm−1

T = 296 K

0.14 × 0.08 × 0.03 mm

Data collection

Agilent Xcalibur Sapphire3 Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2009 ▸) T min = 0.908, T max = 1.000

5694 measured reflections

2591 independent reflections

1642 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.065

S = 0.78

2591 reflections

175 parameters

132 restraints

H-atom parameters constrained

Δρmax = 1.00 e Å−3

Δρmin = −0.51 e Å−3

Data collection: CrysAlis PRO (Agilent, 2009 ▸); cell refinement: CrysAlis PRO); data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I, shelx. DOI: 10.1107/S2056989015023646/bg2576sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023646/bg2576Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015023646/bg2576Isup3.cml

Click here for additional data file.

x y z . DOI: 10.1107/S2056989015023646/bg2576fig1.tif

The mol­ecular structure of (I),showing the atom-labelling scheme as well as the dimer formation. Displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i): 1 − x, 1 − y, 2 − z.

CCDC reference: 1441443

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H17N4+·I−	F(000) = 728
Mr = 368.21	Dx = 1.656 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.0508 (14) Å	Cell parameters from 2009 reflections
b = 7.2790 (5) Å	θ = 2.3–29.8°
c = 11.3760 (9) Å	µ = 2.16 mm−1
β = 98.929 (7)°	T = 296 K
V = 1476.60 (19) Å3	Plate, orange
Z = 4	0.14 × 0.08 × 0.03 mm

Agilent Xcalibur Sapphire3 Gemini diffractometer	2591 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1642 reflections with I > 2σ(I)
Detector resolution: 16.0267 pixels mm-1	Rint = 0.048
ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2009)	h = −21→17
Tmin = 0.908, Tmax = 1.000	k = −6→8
5694 measured reflections	l = −13→10

Refinement on F2	132 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035	H-atom parameters constrained
wR(F2) = 0.065	w = 1/[σ2(Fo2) + (0.0256P)2] where P = (Fo2 + 2Fc2)/3
S = 0.78	(Δ/σ)max = 0.001
2591 reflections	Δρmax = 1.00 e Å−3
175 parameters	Δρmin = −0.51 e Å−3

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
C1	0.7113 (3)	0.4360 (7)	0.9607 (5)	0.0253 (13)
H1A	0.7574	0.4185	1.0140	0.038*
H1B	0.6980	0.5639	0.9585	0.038*
H1C	0.7173	0.3960	0.8824	0.038*
C2	0.6716 (3)	0.2294 (6)	1.1152 (5)	0.0200 (13)
H2A	0.7244	0.2417	1.1432	0.030*
H2B	0.6593	0.1018	1.1030	0.030*
H2C	0.6439	0.2796	1.1732	0.030*
N3	0.6522 (2)	0.3295 (6)	1.0020 (4)	0.0184 (9)
C4	0.5810 (3)	0.3369 (6)	0.9457 (4)	0.0129 (9)
C5	0.5610 (3)	0.4377 (6)	0.8383 (4)	0.0152 (9)
H5A	0.5978	0.5008	0.8058	0.018*
C6	0.5211 (3)	0.2442 (6)	0.9920 (5)	0.0141 (10)
H6A	0.5316	0.1782	1.0627	0.017*
C7	0.4886 (3)	0.4430 (6)	0.7824 (4)	0.0155 (10)
H7A	0.4773	0.5105	0.7125	0.019*
C8	0.4502 (3)	0.2522 (6)	0.9340 (5)	0.0152 (10)
H8A	0.4127	0.1908	0.9660	0.018*
C9	0.4305 (3)	0.3502 (6)	0.8265 (4)	0.0131 (9)
N10	0.3607 (2)	0.3636 (5)	0.7569 (4)	0.0180 (9)
N11	0.3082 (2)	0.2693 (5)	0.7907 (4)	0.0215 (9)
C12	0.2413 (3)	0.2902 (7)	0.7100 (4)	0.0198 (10)
C13	0.2268 (3)	0.4246 (7)	0.6216 (5)	0.0219 (11)
H13A	0.2625	0.5145	0.6150	0.026*
C14	0.1827 (3)	0.1655 (7)	0.7185 (5)	0.0220 (11)
H14A	0.1880	0.0799	0.7799	0.026*
C15	0.1614 (3)	0.4251 (7)	0.5455 (5)	0.0211 (11)
H15A	0.1527	0.5167	0.4881	0.025*
C16	0.1185 (3)	0.1683 (7)	0.6385 (5)	0.0226 (10)
H16A	0.0813	0.0819	0.6441	0.027*
N17	0.1081 (2)	0.2955 (6)	0.5508 (4)	0.0184 (8)
C18	0.0410 (3)	0.2872 (7)	0.4591 (5)	0.0260 (13)
H18A	0.0347	0.4024	0.4178	0.039*
H18B	−0.0023	0.2629	0.4961	0.039*
H18C	0.0469	0.1908	0.4037	0.039*
I1	0.10101 (2)	0.68987 (5)	0.81084 (3)	0.02305 (12)

	U11	U22	U33	U12	U13	U23
C1	0.0259 (19)	0.028 (3)	0.022 (3)	−0.0084 (19)	0.004 (2)	0.003 (2)
C2	0.018 (3)	0.021 (3)	0.0204 (17)	−0.001 (2)	0.0039 (14)	0.0044 (16)
N3	0.0204 (12)	0.016 (2)	0.0187 (16)	−0.0011 (11)	0.0036 (10)	0.0014 (15)
C4	0.0196 (12)	0.009 (2)	0.0116 (15)	0.0006 (11)	0.0060 (10)	−0.0040 (14)
C5	0.0206 (11)	0.013 (2)	0.0132 (15)	0.0011 (13)	0.0063 (11)	−0.0014 (15)
C6	0.0208 (13)	0.010 (2)	0.0125 (18)	−0.0006 (11)	0.0069 (10)	−0.0044 (15)
C7	0.0208 (11)	0.012 (2)	0.015 (2)	0.0010 (12)	0.0056 (10)	−0.0012 (17)
C8	0.0212 (13)	0.009 (2)	0.0159 (15)	−0.0013 (13)	0.0056 (12)	−0.0028 (14)
C9	0.0213 (11)	0.005 (2)	0.0140 (15)	0.0020 (11)	0.0076 (11)	−0.0056 (13)
N10	0.0219 (11)	0.017 (2)	0.0161 (17)	0.0021 (11)	0.0066 (10)	−0.0039 (14)
N11	0.0231 (11)	0.022 (2)	0.0211 (18)	0.0007 (11)	0.0073 (11)	−0.0010 (14)
C12	0.0221 (12)	0.0215 (19)	0.0178 (17)	0.0026 (12)	0.0092 (12)	−0.0038 (15)
C13	0.0215 (18)	0.024 (2)	0.0211 (19)	0.0008 (14)	0.0074 (14)	−0.0008 (16)
C14	0.0211 (13)	0.023 (2)	0.023 (2)	0.0027 (14)	0.0053 (13)	0.0022 (16)
C15	0.0223 (16)	0.019 (2)	0.023 (2)	0.0016 (13)	0.0062 (13)	−0.0021 (16)
C16	0.0214 (16)	0.024 (2)	0.0232 (18)	0.0021 (14)	0.0048 (14)	0.0031 (16)
N17	0.0208 (15)	0.0174 (17)	0.0178 (17)	0.0030 (13)	0.0056 (12)	−0.0027 (13)
C18	0.0255 (18)	0.027 (3)	0.024 (2)	−0.0005 (19)	0.0002 (16)	0.001 (2)
I1	0.0222 (2)	0.0228 (2)	0.0241 (2)	−0.0007 (2)	0.00320 (14)	−0.0028 (2)

C1—N3	1.454 (6)	C8—H8A	0.9300
C1—H1A	0.9600	C9—N10	1.383 (6)
C1—H1B	0.9600	N10—N11	1.277 (5)
C1—H1C	0.9600	N11—C12	1.408 (6)
C2—N3	1.474 (6)	C12—C13	1.398 (7)
C2—H2A	0.9600	C12—C14	1.408 (7)
C2—H2B	0.9600	C13—C15	1.351 (7)
C2—H2C	0.9600	C13—H13A	0.9300
N3—C4	1.344 (6)	C14—C16	1.358 (7)
C4—C5	1.423 (7)	C14—H14A	0.9300
C4—C6	1.442 (6)	C15—N17	1.355 (6)
C5—C7	1.361 (6)	C15—H15A	0.9300
C5—H5A	0.9300	C16—N17	1.352 (6)
C6—C8	1.348 (7)	C16—H16A	0.9300
C6—H6A	0.9300	N17—C18	1.471 (6)
C7—C9	1.405 (6)	C18—H18A	0.9600
C7—H7A	0.9300	C18—H18B	0.9600
C8—C9	1.413 (7)	C18—H18C	0.9600
N3—C1—H1A	109.5	N10—C9—C7	115.2 (4)
N3—C1—H1B	109.5	N10—C9—C8	128.0 (5)
H1A—C1—H1B	109.5	C7—C9—C8	116.8 (5)
N3—C1—H1C	109.5	N11—N10—C9	116.2 (4)
H1A—C1—H1C	109.5	N10—N11—C12	110.4 (4)
H1B—C1—H1C	109.5	C13—C12—N11	126.2 (5)
N3—C2—H2A	109.5	C13—C12—C14	116.2 (5)
N3—C2—H2B	109.5	N11—C12—C14	117.6 (5)
H2A—C2—H2B	109.5	C15—C13—C12	120.6 (5)
N3—C2—H2C	109.5	C15—C13—H13A	119.7
H2A—C2—H2C	109.5	C12—C13—H13A	119.7
H2B—C2—H2C	109.5	C16—C14—C12	121.1 (5)
C4—N3—C1	121.2 (4)	C16—C14—H14A	119.5
C4—N3—C2	121.1 (4)	C12—C14—H14A	119.5
C1—N3—C2	117.3 (4)	C13—C15—N17	121.7 (5)
N3—C4—C5	121.8 (4)	C13—C15—H15A	119.1
N3—C4—C6	121.5 (4)	N17—C15—H15A	119.1
C5—C4—C6	116.7 (5)	N17—C16—C14	120.7 (5)
C7—C5—C4	120.9 (5)	N17—C16—H16A	119.6
C7—C5—H5A	119.6	C14—C16—H16A	119.6
C4—C5—H5A	119.6	C16—N17—C15	119.4 (5)
C8—C6—C4	120.7 (5)	C16—N17—C18	120.0 (4)
C8—C6—H6A	119.7	C15—N17—C18	120.6 (4)
C4—C6—H6A	119.7	N17—C18—H18A	109.5
C5—C7—C9	122.4 (5)	N17—C18—H18B	109.5
C5—C7—H7A	118.8	H18A—C18—H18B	109.5
C9—C7—H7A	118.8	N17—C18—H18C	109.5
C6—C8—C9	122.5 (5)	H18A—C18—H18C	109.5
C6—C8—H8A	118.7	H18B—C18—H18C	109.5
C9—C8—H8A	118.7
C1—N3—C4—C5	4.8 (7)	C8—C9—N10—N11	−3.6 (7)
C2—N3—C4—C5	178.0 (4)	C9—N10—N11—C12	−177.8 (4)
C1—N3—C4—C6	−174.6 (4)	N10—N11—C12—C13	−14.3 (7)
C2—N3—C4—C6	−1.4 (7)	N10—N11—C12—C14	166.1 (4)
N3—C4—C5—C7	179.8 (4)	N11—C12—C13—C15	176.8 (5)
C6—C4—C5—C7	−0.8 (7)	C14—C12—C13—C15	−3.6 (7)
N3—C4—C6—C8	−179.6 (4)	C13—C12—C14—C16	5.2 (7)
C5—C4—C6—C8	1.0 (7)	N11—C12—C14—C16	−175.2 (5)
C4—C5—C7—C9	−0.3 (7)	C12—C13—C15—N17	−0.8 (8)
C4—C6—C8—C9	−0.1 (7)	C12—C14—C16—N17	−2.3 (8)
C5—C7—C9—N10	−177.6 (4)	C14—C16—N17—C15	−2.2 (7)
C5—C7—C9—C8	1.1 (7)	C14—C16—N17—C18	174.9 (5)
C6—C8—C9—N10	177.6 (4)	C13—C15—N17—C16	3.9 (7)
C6—C8—C9—C7	−0.9 (7)	C13—C15—N17—C18	−173.3 (5)
C7—C9—N10—N11	175.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···I1i	0.96	3.09	4.042 (6)	173
C2—H2A···I1i	0.96	3.15	4.102 (5)	169
C15—H15A···I1ii	0.93	2.99	3.907 (5)	171
C7—H7A···Cg2iii	0.93	2.71	3.505 (5)	143

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C12–C16/N17 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯I1i	0.96	3.09	4.042 (6)	173
C2—H2A⋯I1i	0.96	3.15	4.102 (5)	169
C15—H15A⋯I1ii	0.93	2.99	3.907 (5)	171
C7—H7A⋯Cg2iii	0.93	2.71	3.505 (5)	143

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