4-(Di­methyl­amino)­pyridinium 2-butoxy-3-di­cyano­methyl­ene-4-oxo­cyclo­but-1-en-1-olate

In the crystal structure of the title compound, C₇H₁₁N₂⁺·C₁₁H₉N₂O₃^-, both the cation and the anion lie on a mirror plane. Three C atoms of the butyl group are disordered over two positions related by this plane. The bond-length analysis shows that the surplus negative charge of the anion is delocalized between the cyclo­butene ring and the di­cyano­methyl­ene group. The 4-di­methyl­amino­pyridinium cation has an intermediate aromatic-quinoid structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.101
• Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT220_ALERT_2_A Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       5.48 Ratio
PLAT241_ALERT_2_A Check High   U(eq) as Compared to Neighbors  for        C10
PLAT242_ALERT_2_A Check Low    U(eq) as Compared to Neighbors  for         C9

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         47 Perc.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT215_ALERT_3_C Disordered C10     has ADP max/min Ratio .......       3.20
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors  for         C8
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       3.13
PLAT301_ALERT_3_C Main Residue  Disorder .........................      16.00 Perc.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C5     -   C7     ...       1.41 Ang.

   3 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

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Computing details

Data collection: P3 (Siemens,1989); cell refinement: P3; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX routine CIF_UPDATE (Farrugia, 1999).

4-(Dimethylamino)pyridinium 2-butoxy-3-dicyanomethylene-4-oxocyclobut-1-en-1-olate

Crystal data

C7H11N2^+·C11H9N2O3^−	F(000) = 360
Mr = 340.38	Dx = 1.22 Mg m^−3
Monoclinic, P21/m	Melting point: 414 K
Hall symbol: -P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 11.513 (3) Å	Cell parameters from 24 reflections
b = 6.7830 (17) Å	θ = 11–13°
c = 12.176 (3) Å	µ = 0.09 mm^−1
β = 102.94 (2)°	T = 293 K
V = 926.7 (4) Å^3	Needle, yellow
Z = 2	0.4 × 0.1 × 0.1 mm

Data collection

Siemens P3/PC diffractometer	Rint = 0.097
Radiation source: fine-focus sealed tube	θmax = 26.1°, θmin = 2.8°
Graphite monochromator	h = −14→13
θ–2θ scans	k = 0→8
2053 measured reflections	l = 0→15
1962 independent reflections	2 standard reflections every 98 reflections
916 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0522P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.101	(Δ/σ)max = 0.004
S = 0.82	Δρmax = 0.11 e Å^−3
1962 reflections	Δρmin = −0.09 e Å^−3
163 parameters

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	Occ. (<1)
O1	0.04301 (13)	0.25	0.71435 (14)	0.1384 (11)
O2	−0.02009 (14)	0.25	0.43758 (14)	0.1318 (10)
O3	0.26312 (13)	0.25	0.45191 (12)	0.0974 (7)
N1	0.52749 (18)	0.25	0.67206 (18)	0.0871 (7)
N2	0.31703 (18)	0.25	0.93482 (18)	0.0986 (8)
N3	0.49110 (17)	0.25	0.39996 (18)	0.0776 (6)
H3N	0.4503	0.25	0.4511	0.093*
N4	0.68525 (15)	0.25	0.15751 (15)	0.0722 (6)
C1	0.10021 (18)	0.25	0.63430 (19)	0.0873 (9)
C2	0.06976 (19)	0.25	0.5123 (2)	0.0973 (10)
C3	0.20091 (18)	0.25	0.51960 (19)	0.0733 (8)
C4	0.22288 (17)	0.25	0.64159 (16)	0.0630 (6)
C5	0.32583 (15)	0.25	0.72704 (16)	0.0584 (6)
C6	0.4371 (2)	0.25	0.69918 (18)	0.0614 (6)
C7	0.32092 (18)	0.25	0.8421 (2)	0.0687 (7)
C8	−0.0876 (2)	0.25	0.6795 (3)	0.183 (2)
H8A	−0.1173	0.1166	0.6648	0.219*	0.5
H8B	−0.1139	0.3277	0.6116	0.219*	0.5
C9	−0.1327 (4)	0.3395 (12)	0.7762 (5)	0.175 (5)	0.5
H9A	−0.2186	0.3544	0.7551	0.211*	0.5
H9B	−0.0975	0.4687	0.7944	0.211*	0.5
C10	−0.0984 (5)	0.2035 (15)	0.8778 (5)	0.301 (9)	0.5
H10A	−0.1228	0.2625	0.9416	0.361*	0.5
H10B	−0.0125	0.1878	0.8975	0.361*	0.5
C11	−0.1570 (10)	0.0018 (15)	0.8533 (15)	0.320 (7)	0.5
H11A	−0.1366	−0.079	0.9196	0.48*	0.5
H11B	−0.1294	−0.06	0.793	0.48*	0.5
H11C	−0.242	0.0174	0.832	0.48*	0.5
C12	0.4358 (2)	0.25	0.2922 (2)	0.0762 (7)
H12	0.3529	0.25	0.273	0.091*
C13	0.49713 (18)	0.25	0.20888 (19)	0.0679 (6)
H13	0.4559	0.25	0.1339	0.082*
C14	0.62283 (17)	0.25	0.23549 (18)	0.0587 (6)
C15	0.67665 (19)	0.25	0.35230 (18)	0.0660 (6)
H15	0.7593	0.25	0.3754	0.079*
C16	0.6110 (2)	0.25	0.42975 (19)	0.0728 (7)
H16	0.6487	0.25	0.5057	0.087*
C17	0.6289 (2)	0.25	0.03579 (18)	0.0870 (8)
H17A	0.6119	0.3832	0.0105	0.13*	0.5
H17B	0.556	0.1759	0.0231	0.13*	0.5
H17C	0.6821	0.1909	−0.0052	0.13*	0.5
C18	0.81543 (19)	0.25	0.1853 (2)	0.0982 (10)
H18A	0.8439	0.3828	0.1985	0.147*	0.5
H18B	0.8441	0.1946	0.1238	0.147*	0.5
H18C	0.8438	0.1725	0.2519	0.147*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0492 (9)	0.294 (3)	0.0700 (11)	0	0.0085 (8)	0
O2	0.0556 (9)	0.248 (3)	0.0769 (11)	0	−0.0179 (9)	0
O3	0.0615 (10)	0.166 (2)	0.0627 (10)	0	0.0105 (8)	0
N1	0.0599 (12)	0.0984 (19)	0.0954 (16)	0	0.0011 (11)	0
N2	0.0912 (15)	0.133 (2)	0.0601 (13)	0	−0.0081 (11)	0
N3	0.0715 (12)	0.0898 (17)	0.0770 (14)	0	0.0284 (11)	0
N4	0.0588 (10)	0.1011 (17)	0.0542 (12)	0	0.0073 (9)	0
C1	0.0462 (12)	0.159 (3)	0.0542 (14)	0	0.0059 (10)	0
C2	0.0524 (13)	0.166 (3)	0.0657 (16)	0	−0.0042 (12)	0
C3	0.0486 (12)	0.110 (2)	0.0611 (15)	0	0.0113 (11)	0
C4	0.0492 (11)	0.0838 (18)	0.0500 (13)	0	−0.0020 (9)	0
C5	0.0421 (10)	0.0830 (17)	0.0454 (13)	0	−0.0001 (8)	0
C6	0.0545 (13)	0.0579 (15)	0.0619 (14)	0	−0.0079 (11)	0
C7	0.0534 (12)	0.0812 (19)	0.0606 (16)	0	−0.0104 (10)	0
C8	0.0488 (15)	0.408 (8)	0.090 (2)	0	0.0147 (14)	0
C9	0.064 (2)	0.271 (16)	0.194 (7)	0.013 (4)	0.034 (3)	−0.014 (6)
C10	0.124 (4)	0.69 (3)	0.095 (4)	0.141 (13)	0.035 (3)	−0.011 (14)
C11	0.257 (12)	0.304 (17)	0.357 (15)	−0.083 (10)	−0.018 (11)	−0.019 (12)
C12	0.0530 (12)	0.083 (2)	0.0907 (19)	0	0.0132 (13)	0
C13	0.0587 (13)	0.0727 (17)	0.0662 (14)	0	0.0008 (11)	0
C14	0.0535 (12)	0.0615 (15)	0.0558 (13)	0	0.0008 (10)	0
C15	0.0559 (12)	0.0816 (18)	0.0600 (14)	0	0.0117 (11)	0
C16	0.0723 (15)	0.0816 (19)	0.0608 (14)	0	0.0069 (12)	0
C17	0.0775 (15)	0.122 (2)	0.0545 (14)	0	−0.0006 (11)	0
C18	0.0537 (12)	0.162 (3)	0.0789 (17)	0	0.0151 (11)	0

Geometric parameters (Å, º)

O1—C1	1.293 (3)	C9—H9A	0.97
O1—C8	1.468 (3)	C9—H9B	0.97
O2—C2	1.215 (2)	C10—C11	1.525 (5)
O3—C3	1.207 (2)	C10—H10A	0.97
N1—C6	1.160 (3)	C10—H10B	0.97
N2—C7	1.140 (3)	C11—H11A	0.96
N3—C12	1.324 (3)	C11—H11B	0.96
N3—C16	1.346 (3)	C11—H11C	0.96
N3—H3N	0.86	C12—C13	1.360 (3)
N4—C14	1.313 (2)	C12—H12	0.93
N4—C17	1.479 (3)	C13—C14	1.410 (3)
N4—C18	1.461 (3)	C13—H13	0.93
C1—C2	1.448 (3)	C14—C15	1.418 (3)
C1—C4	1.395 (3)	C15—C16	1.334 (3)
C2—C3	1.493 (3)	C15—H15	0.93
C3—C4	1.450 (3)	C16—H16	0.93
C4—C5	1.391 (2)	C17—H17A	0.96
C5—C6	1.396 (3)	C17—H17B	0.96
C5—C7	1.414 (3)	C17—H17C	0.96
C8—C9	1.515 (4)	C18—H18A	0.96
C8—H8A	0.97	C18—H18B	0.96
C8—H8B	0.97	C18—H18C	0.96
C9—C10	1.523 (5)
C1—O1—C8	116.37 (19)	C11—C10—H10A	109.4
C12—N3—C16	120.2 (2)	C9—C10—H10B	109.4
C12—N3—H3N	119.9	C11—C10—H10B	109.4
C16—N3—H3N	119.9	H10A—C10—H10B	108
C14—N4—C18	122.14 (18)	C10—C11—H11A	109.5
C14—N4—C17	122.43 (17)	C10—C11—H11B	109.5
C18—N4—C17	115.43 (19)	H11A—C11—H11B	109.5
O1—C1—C4	129.1 (2)	C10—C11—H11C	109.5
O1—C1—C2	136.58 (19)	H11A—C11—H11C	109.5
C4—C1—C2	94.27 (18)	H11B—C11—H11C	109.5
O2—C2—C1	137.6 (2)	N3—C12—C13	121.6 (2)
O2—C2—C3	136.5 (2)	N3—C12—H12	119.2
C1—C2—C3	85.95 (17)	C13—C12—H12	119.2
O3—C3—C4	134.87 (18)	C12—C13—C14	120.4 (2)
O3—C3—C2	134.9 (2)	C12—C13—H13	119.8
C4—C3—C2	90.19 (17)	C14—C13—H13	119.8
C5—C4—C1	136.8 (2)	N4—C14—C13	122.25 (19)
C5—C4—C3	133.65 (18)	N4—C14—C15	122.57 (18)
C1—C4—C3	89.59 (16)	C13—C14—C15	115.2 (2)
C4—C5—C6	119.50 (18)	C16—C15—C14	121.3 (2)
C4—C5—C7	121.63 (18)	C16—C15—H15	119.4
C6—C5—C7	118.87 (17)	C14—C15—H15	119.4
N1—C6—C5	177.6 (2)	C15—C16—N3	121.2 (2)
N2—C7—C5	180.0 (2)	C15—C16—H16	119.4
O1—C8—C9	106.4 (2)	N3—C16—H16	119.4
O1—C8—H8A	110.4	N4—C17—H17A	109.5
C9—C8—H8A	110.4	N4—C17—H17B	109.5
O1—C8—H8B	110.4	H17A—C17—H17B	109.5
C9—C8—H8B	110.4	N4—C17—H17C	109.5
H8A—C8—H8B	108.6	H17A—C17—H17C	109.5
C8—C9—C10	108.5 (5)	H17B—C17—H17C	109.5
C8—C9—H9A	110	N4—C18—H18A	109.5
C10—C9—H9A	110	N4—C18—H18B	109.5
C8—C9—H9B	110	H18A—C18—H18B	109.5
C10—C9—H9B	110	N4—C18—H18C	109.5
H9A—C9—H9B	108.4	H18A—C18—H18C	109.5
C9—C10—C11	111.2 (10)	H18B—C18—H18C	109.5
C9—C10—H10A	109.4
C8—O1—C1—C4	180	C3—C4—C5—C6	0
C8—O1—C1—C2	0	C1—C4—C5—C7	0
O1—C1—C2—O2	0	C3—C4—C5—C7	180
C4—C1—C2—O2	180	C1—O1—C8—C9	−155.3 (3)
O1—C1—C2—C3	180	O1—C8—C9—C10	−64.9 (5)
C4—C1—C2—C3	0	C8—C9—C10—C11	−62.2 (7)
O2—C2—C3—O3	0	C16—N3—C12—C13	0
C1—C2—C3—O3	180	N3—C12—C13—C14	0
O2—C2—C3—C4	180	C18—N4—C14—C13	180
C1—C2—C3—C4	0	C17—N4—C14—C13	0
O1—C1—C4—C5	0	C18—N4—C14—C15	0
C2—C1—C4—C5	180	C17—N4—C14—C15	180
O1—C1—C4—C3	180	C12—C13—C14—N4	180
C2—C1—C4—C3	0	C12—C13—C14—C15	0
O3—C3—C4—C5	0	N4—C14—C15—C16	180
C2—C3—C4—C5	180	C13—C14—C15—C16	0
O3—C3—C4—C1	180	C14—C15—C16—N3	0
C2—C3—C4—C1	0	C12—N3—C16—C15	0
C1—C4—C5—C6	180

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O3	0.86	2.16	2.834 (2)	135