1-Di­methyl­amino-3-di­methyl­iminio-2-(p-methoxy­phenyl)­prop-1-ene perchlorate

The title compound, C₁₄H₂₁N₂O⁺·ClO₄^-, is an organic non-linear optical material. It crystallizes in the monoclinic space group P2₁ and exhibits second-harmonic generation equivalent to that of urea. The structural study shows extensive electron delocalization in the vinamidinium moiety. The dihedral angle between the vinamidinium moiety and the benzene ring is 81.6 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.113
• Data-to-parameter ratio = 16.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         N2
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        Cl1
PLAT410_ALERT_2_C Short Intra H...H Contact  H1     ..  H3      ..       1.99 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.33
           From the CIF: _reflns_number_total               3404
           Count of symmetry unique reflns         1989
           Completeness (_total/calc)            171.14%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1415
           Fraction of Friedel pairs measured     0.711
           Are heavy atom types Z>Si present          yes

   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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

1-Dimethylamino-3-dimethyliminio-2-(p-methoxyphenyl)prop-1-ene perchlorate

Crystal data

C14H21N2O^+·ClO4^−	F(000) = 352
Mr = 332.79	Dx = 1.315 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 8589 reflections
a = 7.295 (2) Å	θ = 2.3–27.4°
b = 13.117 (3) Å	µ = 0.25 mm^−1
c = 8.793 (2) Å	T = 293 K
β = 92.228 (5)°	Prism, pale yellow
V = 840.7 (4) Å^3	0.3 × 0.2 × 0.1 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	2910 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 27.3°, θmin = 2.3°
φ and ω scans	h = −9→8
8565 measured reflections	k = −16→16
3404 independent reflections	l = −11→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0634P)^2 + 0.0303P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3404 reflections	Δρmax = 0.17 e Å^−3
204 parameters	Δρmin = −0.13 e Å^−3
1 restraint	Absolute structure: Flack (1983); 1577 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (6)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.27289 (8)	0.90408 (4)	0.94298 (7)	0.06917 (19)
O1	0.1574 (5)	0.8754 (3)	1.0572 (3)	0.1317 (11)
O2	0.2413 (5)	1.0055 (2)	0.9029 (4)	0.1359 (11)
O3	0.4567 (4)	0.8873 (4)	0.9781 (5)	0.1554 (14)
O4	0.2229 (4)	0.8448 (3)	0.8110 (3)	0.1131 (8)
O5	0.8308 (3)	0.66330 (17)	0.7480 (2)	0.0834 (6)
N1	0.2710 (3)	0.57731 (18)	0.1773 (2)	0.0681 (6)
N2	0.1303 (3)	0.34506 (18)	0.5870 (3)	0.0709 (6)
C1	0.2042 (4)	0.5057 (2)	0.2623 (3)	0.0640 (6)
H1	0.1113	0.4677	0.2142	0.077*
C2	0.2465 (3)	0.47522 (19)	0.4129 (3)	0.0588 (6)
C3	0.1350 (3)	0.3965 (2)	0.4585 (3)	0.0638 (6)
H3	0.0474	0.3762	0.3851	0.077*
C4	0.3981 (3)	0.52261 (19)	0.5080 (3)	0.0562 (5)
C5	0.3632 (3)	0.59848 (19)	0.6110 (3)	0.0576 (5)
H5	0.2424	0.6176	0.6255	0.069*
C6	0.5030 (3)	0.6473 (2)	0.6938 (3)	0.0602 (6)
H6	0.4756	0.6988	0.7621	0.072*
C7	0.6829 (3)	0.6193 (2)	0.6747 (3)	0.0627 (6)
C8	0.7201 (4)	0.5426 (3)	0.5734 (3)	0.0766 (8)
H8	0.8408	0.5228	0.5600	0.092*
C9	0.5793 (4)	0.4948 (2)	0.4913 (3)	0.0690 (7)
H9	0.6067	0.4429	0.4237	0.083*
C10	0.2121 (6)	0.5828 (3)	0.0161 (4)	0.0990 (11)
H10A	0.1108	0.5373	−0.0031	0.149*
H10B	0.3121	0.5635	−0.0457	0.149*
H10C	0.1749	0.6513	−0.0085	0.149*
C11	0.4171 (4)	0.6488 (2)	0.2220 (4)	0.0789 (8)
H11A	0.3976	0.6736	0.3229	0.118*
H11B	0.4161	0.7050	0.1522	0.118*
H11C	0.5335	0.6147	0.2205	0.118*
C12	−0.0107 (6)	0.2679 (3)	0.6047 (4)	0.1107 (13)
H12A	−0.0787	0.2591	0.5100	0.166*
H12B	−0.0923	0.2891	0.6817	0.166*
H12C	0.0460	0.2044	0.6343	0.166*
C13	0.2541 (5)	0.3596 (3)	0.7200 (4)	0.0931 (10)
H13A	0.3569	0.4003	0.6922	0.140*
H13B	0.2968	0.2944	0.7564	0.140*
H13C	0.1899	0.3935	0.7987	0.140*
C14	0.7938 (5)	0.7280 (3)	0.8734 (4)	0.0837 (8)
H14A	0.9072	0.7534	0.9175	0.125*
H14B	0.7305	0.6899	0.9485	0.125*
H14C	0.7187	0.7841	0.8388	0.125*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0655 (3)	0.0669 (3)	0.0754 (4)	−0.0042 (3)	0.0073 (2)	0.0043 (3)
O1	0.160 (3)	0.143 (3)	0.0958 (17)	−0.037 (2)	0.0484 (16)	−0.0009 (16)
O2	0.154 (3)	0.0753 (16)	0.182 (3)	0.0012 (16)	0.050 (2)	0.0129 (18)
O3	0.0841 (17)	0.201 (4)	0.179 (3)	0.011 (2)	−0.0228 (17)	−0.007 (3)
O4	0.126 (2)	0.1233 (19)	0.0905 (16)	−0.0041 (16)	0.0084 (14)	−0.0155 (15)
O5	0.0644 (11)	0.0971 (14)	0.0883 (14)	−0.0110 (10)	−0.0044 (10)	−0.0101 (11)
N1	0.0759 (14)	0.0759 (15)	0.0529 (11)	0.0057 (11)	0.0075 (10)	0.0020 (10)
N2	0.0843 (15)	0.0675 (13)	0.0618 (12)	−0.0084 (11)	0.0142 (10)	−0.0067 (11)
C1	0.0698 (14)	0.0709 (16)	0.0514 (12)	−0.0004 (12)	0.0036 (10)	−0.0103 (11)
C2	0.0622 (13)	0.0638 (14)	0.0505 (12)	0.0000 (11)	0.0041 (10)	−0.0070 (10)
C3	0.0681 (13)	0.0711 (15)	0.0527 (12)	−0.0085 (14)	0.0082 (9)	−0.0120 (13)
C4	0.0586 (12)	0.0617 (13)	0.0486 (11)	0.0008 (10)	0.0060 (9)	−0.0025 (10)
C5	0.0531 (12)	0.0643 (13)	0.0557 (12)	0.0055 (10)	0.0068 (10)	−0.0013 (11)
C6	0.0658 (14)	0.0643 (14)	0.0508 (12)	0.0008 (11)	0.0054 (11)	−0.0075 (10)
C7	0.0585 (13)	0.0704 (15)	0.0594 (14)	−0.0030 (11)	0.0037 (11)	−0.0008 (12)
C8	0.0512 (13)	0.094 (2)	0.0847 (19)	0.0124 (13)	0.0072 (12)	−0.0105 (15)
C9	0.0649 (14)	0.0735 (17)	0.0690 (15)	0.0082 (12)	0.0078 (12)	−0.0190 (13)
C10	0.132 (3)	0.105 (3)	0.0593 (17)	−0.002 (2)	0.0005 (18)	0.0153 (17)
C11	0.085 (2)	0.0778 (18)	0.0746 (17)	−0.0006 (15)	0.0140 (15)	0.0120 (14)
C12	0.146 (3)	0.101 (2)	0.088 (2)	−0.055 (2)	0.032 (2)	−0.006 (2)
C13	0.112 (3)	0.091 (2)	0.0745 (19)	−0.0077 (18)	−0.0143 (17)	0.0182 (17)
C14	0.092 (2)	0.0770 (18)	0.081 (2)	−0.0223 (15)	−0.0091 (15)	−0.0112 (15)

Geometric parameters (Å, º)

Cl1—O3	1.382 (3)	C6—C7	1.380 (4)
Cl1—O1	1.388 (3)	C6—H6	0.93
Cl1—O2	1.393 (3)	C7—C8	1.377 (4)
Cl1—O4	1.433 (3)	C8—C9	1.383 (4)
O5—C7	1.363 (3)	C8—H8	0.93
O5—C14	1.426 (4)	C9—H9	0.93
N1—C1	1.307 (3)	C10—H10A	0.96
N1—C11	1.462 (4)	C10—H10B	0.96
N1—C10	1.467 (4)	C10—H10C	0.96
N2—C3	1.317 (3)	C11—H11A	0.96
N2—C12	1.456 (4)	C11—H11B	0.96
N2—C13	1.462 (4)	C11—H11C	0.96
C1—C2	1.406 (4)	C12—H12A	0.96
C1—H1	0.93	C12—H12B	0.96
C2—C3	1.383 (4)	C12—H12C	0.96
C2—C4	1.496 (3)	C13—H13A	0.96
C3—H3	0.93	C13—H13B	0.96
C4—C5	1.376 (3)	C13—H13C	0.96
C4—C9	1.384 (3)	C14—H14A	0.96
C5—C6	1.387 (3)	C14—H14B	0.96
C5—H5	0.93	C14—H14C	0.96
O3—Cl1—O1	114.0 (2)	C7—C8—H8	119.7
O3—Cl1—O2	111.0 (3)	C9—C8—H8	119.7
O1—Cl1—O2	110.0 (2)	C8—C9—C4	121.2 (2)
O3—Cl1—O4	108.0 (2)	C8—C9—H9	119.4
O1—Cl1—O4	107.25 (19)	C4—C9—H9	119.4
O2—Cl1—O4	106.2 (2)	N1—C10—H10A	109.5
C7—O5—C14	116.6 (2)	N1—C10—H10B	109.5
C1—N1—C11	126.2 (2)	H10A—C10—H10B	109.5
C1—N1—C10	119.2 (3)	N1—C10—H10C	109.5
C11—N1—C10	114.3 (3)	H10A—C10—H10C	109.5
C3—N2—C12	119.4 (2)	H10B—C10—H10C	109.5
C3—N2—C13	125.7 (2)	N1—C11—H11A	109.5
C12—N2—C13	114.9 (3)	N1—C11—H11B	109.5
N1—C1—C2	132.1 (2)	H11A—C11—H11B	109.5
N1—C1—H1	113.9	N1—C11—H11C	109.5
C2—C1—H1	113.9	H11A—C11—H11C	109.5
C3—C2—C1	112.1 (2)	H11B—C11—H11C	109.5
C3—C2—C4	125.3 (2)	N2—C12—H12A	109.5
C1—C2—C4	122.6 (2)	N2—C12—H12B	109.5
N2—C3—C2	131.8 (2)	H12A—C12—H12B	109.5
N2—C3—H3	114.1	N2—C12—H12C	109.5
C2—C3—H3	114.1	H12A—C12—H12C	109.5
C5—C4—C9	117.5 (2)	H12B—C12—H12C	109.5
C5—C4—C2	121.1 (2)	N2—C13—H13A	109.5
C9—C4—C2	121.3 (2)	N2—C13—H13B	109.5
C4—C5—C6	121.9 (2)	H13A—C13—H13B	109.5
C4—C5—H5	119.0	N2—C13—H13C	109.5
C6—C5—H5	119.0	H13A—C13—H13C	109.5
C7—C6—C5	119.8 (2)	H13B—C13—H13C	109.5
C7—C6—H6	120.1	O5—C14—H14A	109.5
C5—C6—H6	120.1	O5—C14—H14B	109.5
O5—C7—C8	116.3 (2)	H14A—C14—H14B	109.5
O5—C7—C6	124.6 (2)	O5—C14—H14C	109.5
C8—C7—C6	119.1 (2)	H14A—C14—H14C	109.5
C7—C8—C9	120.5 (2)	H14B—C14—H14C	109.5
C11—N1—C1—C2	−0.1 (5)	C9—C4—C5—C6	1.2 (4)
C10—N1—C1—C2	172.8 (3)	C2—C4—C5—C6	−176.3 (2)
N1—C1—C2—C3	178.1 (3)	C4—C5—C6—C7	−0.6 (4)
N1—C1—C2—C4	−3.2 (5)	C14—O5—C7—C8	−168.1 (3)
C12—N2—C3—C2	177.2 (3)	C14—O5—C7—C6	12.9 (4)
C13—N2—C3—C2	−1.3 (5)	C5—C6—C7—O5	178.8 (2)
C1—C2—C3—N2	178.7 (3)	C5—C6—C7—C8	−0.2 (4)
C4—C2—C3—N2	−0.1 (5)	O5—C7—C8—C9	−178.7 (3)
C3—C2—C4—C5	−83.8 (3)	C6—C7—C8—C9	0.4 (4)
C1—C2—C4—C5	97.7 (3)	C7—C8—C9—C4	0.3 (5)
C3—C2—C4—C9	98.9 (3)	C5—C4—C9—C8	−1.0 (4)
C1—C2—C4—C9	−79.7 (3)	C2—C4—C9—C8	176.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11C···O2^i	0.96	2.46	3.341 (5)	152

Symmetry code: (i) −x+1, y−1/2, −z+1.