An ortho­rhom­bic polymorph of 3,5-bis­[4-(dimethyl­amino)benzyl­idene]-1-methyl-4-piperidone

The title compound, C₂₄H₂₉N₃O, is an ortho­rhom­bic modification of the known monoclinic polymorph. In the crystal structure, weak C—H...N and C—H...O hydrogen bonds help to establish a non-centrosymmetric packing arrangement.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.052
• wR factor = 0.112
• Data-to-parameter ratio = 10.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

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           27.88
           From the CIF: _reflns_number_total               2629
           Count of symmetry unique reflns         2633
           Completeness (_total/calc)             99.85%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2001); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.

3,5-bis[4-(dimethylamino)benzylidene]-1-methyl-4-piperidone

Crystal data

C24H29N3O	Dx = 1.212 Mg m^−3
Mr = 375.50	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 123 reflections
a = 12.0395 (17) Å	θ = 4–24°
b = 22.298 (3) Å	µ = 0.08 mm^−1
c = 7.6686 (11) Å	T = 100 K
V = 2058.7 (5) Å^3	Needle, red
Z = 4	0.20 × 0.08 × 0.05 mm
F(000) = 808

Data collection

Bruker SMART APEXII CCD diffractometer	2629 independent reflections
Radiation source: fine-focus sealed tube	1447 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
ω scans	θmax = 27.9°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −15→15
Tmin = 0.985, Tmax = 0.996	k = −29→29
26503 measured reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.041P)^2] where P = (Fo^2 + 2Fc^2)/3
2629 reflections	(Δ/σ)max < 0.001
258 parameters	Δρmax = 0.20 e Å^−3
1 restraint	Δρmin = −0.26 e Å^−3

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	0.2415 (2)	0.42984 (12)	0.4979 (4)	0.0359 (7)
N1	0.5577 (2)	0.45962 (13)	0.4256 (4)	0.0238 (8)
N2	0.3038 (2)	0.79625 (14)	0.2929 (4)	0.0280 (8)
N3	0.5224 (3)	0.09857 (15)	0.2387 (5)	0.0356 (9)
C1	0.6771 (3)	0.47116 (17)	0.4101 (6)	0.0321 (10)
H1A	0.6961	0.5076	0.4749	0.048*
H1B	0.6965	0.4764	0.2869	0.048*
H1C	0.7186	0.4371	0.4581	0.048*
C2	0.4937 (3)	0.50984 (17)	0.3572 (5)	0.0252 (9)
H2A	0.5052	0.5130	0.2297	0.030*
H2B	0.5196	0.5476	0.4115	0.030*
C3	0.3712 (3)	0.50100 (17)	0.3953 (5)	0.0238 (9)
C4	0.3332 (3)	0.43957 (18)	0.4330 (5)	0.0270 (10)
C5	0.4073 (3)	0.38888 (17)	0.3804 (5)	0.0248 (9)
C6	0.5263 (3)	0.40422 (17)	0.3365 (5)	0.0268 (9)
H6A	0.5759	0.3712	0.3737	0.032*
H6B	0.5343	0.4094	0.2089	0.032*
C7	0.2945 (3)	0.54520 (16)	0.4028 (5)	0.0272 (9)
H7A	0.2223	0.5321	0.4353	0.033*
C8	0.3027 (3)	0.60912 (17)	0.3700 (5)	0.0244 (9)
C9	0.2164 (3)	0.64587 (17)	0.4304 (5)	0.0281 (10)
H9A	0.1554	0.6278	0.4888	0.034*
C10	0.2165 (3)	0.70706 (17)	0.4087 (5)	0.0268 (9)
H10A	0.1571	0.7302	0.4547	0.032*
C11	0.3035 (3)	0.73571 (17)	0.3190 (5)	0.0245 (9)
C12	0.3894 (3)	0.69901 (17)	0.2549 (5)	0.0258 (9)
H12A	0.4493	0.7169	0.1931	0.031*
C13	0.3887 (3)	0.63775 (17)	0.2796 (5)	0.0258 (9)
H13A	0.4481	0.6144	0.2342	0.031*
C14	0.3638 (3)	0.33314 (17)	0.3837 (5)	0.0284 (10)
H14A	0.2886	0.3317	0.4212	0.034*
C15	0.4106 (3)	0.27477 (17)	0.3405 (5)	0.0248 (9)
C16	0.3565 (3)	0.22405 (17)	0.4067 (5)	0.0305 (10)
H16A	0.2915	0.2295	0.4750	0.037*
C17	0.3937 (3)	0.16654 (19)	0.3770 (5)	0.0334 (10)
H17A	0.3558	0.1337	0.4289	0.040*
C18	0.4868 (3)	0.15565 (19)	0.2710 (6)	0.0292 (10)
C19	0.5400 (3)	0.20648 (19)	0.1992 (5)	0.0277 (10)
H19A	0.6028	0.2010	0.1259	0.033*
C20	0.5025 (3)	0.26418 (18)	0.2335 (5)	0.0286 (10)
H20A	0.5402	0.2973	0.1830	0.034*
C21	0.2064 (3)	0.83255 (17)	0.3379 (6)	0.0330 (10)
H21A	0.1937	0.8306	0.4640	0.050*
H21B	0.1411	0.8170	0.2764	0.050*
H21C	0.2194	0.8743	0.3033	0.050*
C22	0.3947 (3)	0.82440 (18)	0.1963 (5)	0.0312 (10)
H22A	0.4648	0.8177	0.2582	0.047*
H22B	0.3808	0.8676	0.1864	0.047*
H22C	0.3993	0.8068	0.0794	0.047*
C23	0.4809 (3)	0.04787 (18)	0.3381 (6)	0.0441 (12)
H23A	0.4849	0.0571	0.4629	0.066*
H23B	0.5263	0.0124	0.3130	0.066*
H23C	0.4036	0.0399	0.3054	0.066*
C24	0.6164 (3)	0.08815 (19)	0.1227 (6)	0.0392 (11)
H24A	0.6006	0.1056	0.0080	0.059*
H24B	0.6288	0.0449	0.1104	0.059*
H24C	0.6831	0.1070	0.1716	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0321 (17)	0.0346 (17)	0.0411 (17)	0.0006 (14)	0.0100 (14)	0.0026 (15)
N1	0.0191 (16)	0.029 (2)	0.0230 (18)	0.0009 (15)	−0.0008 (15)	0.0004 (16)
N2	0.0252 (18)	0.030 (2)	0.029 (2)	0.0050 (16)	0.0059 (16)	0.0036 (16)
N3	0.0295 (19)	0.033 (2)	0.044 (2)	0.0036 (17)	0.0083 (18)	0.0014 (19)
C1	0.025 (2)	0.040 (3)	0.030 (2)	0.0032 (18)	−0.001 (2)	−0.002 (2)
C2	0.027 (2)	0.031 (2)	0.017 (2)	0.0017 (18)	0.0000 (16)	0.0022 (19)
C3	0.025 (2)	0.030 (2)	0.0160 (19)	−0.0002 (18)	−0.0010 (18)	0.0019 (19)
C4	0.023 (2)	0.036 (3)	0.022 (2)	−0.0014 (18)	0.0003 (19)	−0.0026 (19)
C5	0.024 (2)	0.032 (3)	0.018 (2)	−0.0010 (18)	−0.0003 (18)	0.0004 (18)
C6	0.026 (2)	0.034 (3)	0.020 (2)	0.0034 (19)	0.0006 (18)	−0.0036 (19)
C7	0.022 (2)	0.037 (2)	0.022 (2)	−0.0030 (19)	0.002 (2)	−0.001 (2)
C8	0.019 (2)	0.037 (2)	0.018 (2)	−0.0001 (18)	0.0044 (17)	−0.0023 (18)
C9	0.023 (2)	0.037 (3)	0.024 (2)	−0.0017 (19)	0.0048 (18)	0.000 (2)
C10	0.026 (2)	0.028 (2)	0.027 (2)	0.0033 (18)	0.0022 (19)	−0.001 (2)
C11	0.022 (2)	0.030 (2)	0.022 (2)	0.0038 (18)	−0.0016 (17)	0.0017 (18)
C12	0.022 (2)	0.036 (3)	0.019 (2)	0.0013 (19)	0.0032 (18)	0.0048 (19)
C13	0.024 (2)	0.033 (3)	0.021 (2)	0.0074 (18)	0.0020 (18)	−0.0012 (19)
C14	0.028 (2)	0.034 (3)	0.023 (2)	−0.0028 (19)	−0.0007 (18)	0.001 (2)
C15	0.024 (2)	0.029 (3)	0.021 (2)	−0.0043 (18)	0.0008 (17)	0.0006 (19)
C16	0.025 (2)	0.038 (3)	0.029 (2)	0.0000 (19)	0.005 (2)	−0.003 (2)
C17	0.031 (2)	0.041 (3)	0.029 (2)	−0.009 (2)	0.004 (2)	−0.002 (2)
C18	0.022 (2)	0.038 (3)	0.028 (2)	−0.0057 (19)	−0.0038 (19)	−0.006 (2)
C19	0.023 (2)	0.039 (3)	0.021 (2)	−0.001 (2)	0.0014 (18)	0.0013 (19)
C20	0.031 (2)	0.031 (3)	0.024 (2)	−0.004 (2)	0.0005 (19)	−0.0027 (19)
C21	0.030 (2)	0.035 (2)	0.034 (2)	0.008 (2)	0.003 (2)	−0.001 (2)
C22	0.027 (2)	0.036 (3)	0.030 (2)	0.002 (2)	0.0053 (19)	0.004 (2)
C23	0.035 (3)	0.041 (3)	0.056 (3)	0.001 (2)	0.010 (2)	0.007 (3)
C24	0.034 (3)	0.037 (3)	0.046 (3)	0.004 (2)	0.003 (2)	−0.007 (2)

Geometric parameters (Å, º)

O1—C4	1.230 (4)	C10—H10A	0.9500
N1—C2	1.457 (4)	C11—C12	1.408 (5)
N1—C6	1.461 (4)	C12—C13	1.379 (5)
N1—C1	1.465 (4)	C12—H12A	0.9500
N2—C11	1.365 (4)	C13—H13A	0.9500
N2—C22	1.462 (4)	C14—C15	1.457 (5)
N2—C21	1.466 (4)	C14—H14A	0.9500
N3—C18	1.366 (5)	C15—C20	1.397 (5)
N3—C23	1.452 (5)	C15—C16	1.401 (5)
N3—C24	1.459 (5)	C16—C17	1.377 (5)
C1—H1A	0.9800	C16—H16A	0.9500
C1—H1B	0.9800	C17—C18	1.405 (5)
C1—H1C	0.9800	C17—H17A	0.9500
C2—C3	1.516 (5)	C18—C19	1.414 (5)
C2—H2A	0.9900	C19—C20	1.389 (5)
C2—H2B	0.9900	C19—H19A	0.9500
C3—C7	1.352 (5)	C20—H20A	0.9500
C3—C4	1.473 (5)	C21—H21A	0.9800
C4—C5	1.495 (5)	C21—H21B	0.9800
C5—C14	1.349 (5)	C21—H21C	0.9800
C5—C6	1.511 (5)	C22—H22A	0.9800
C6—H6A	0.9900	C22—H22B	0.9800
C6—H6B	0.9900	C22—H22C	0.9800
C7—C8	1.451 (5)	C23—H23A	0.9800
C7—H7A	0.9500	C23—H23B	0.9800
C8—C13	1.400 (5)	C23—H23C	0.9800
C8—C9	1.402 (5)	C24—H24A	0.9800
C9—C10	1.374 (5)	C24—H24B	0.9800
C9—H9A	0.9500	C24—H24C	0.9800
C10—C11	1.407 (5)
C2—N1—C6	110.2 (3)	C13—C12—C11	121.6 (3)
C2—N1—C1	110.8 (3)	C13—C12—H12A	119.2
C6—N1—C1	111.4 (3)	C11—C12—H12A	119.2
C11—N2—C22	120.1 (3)	C12—C13—C8	121.6 (3)
C11—N2—C21	120.6 (3)	C12—C13—H13A	119.2
C22—N2—C21	118.7 (3)	C8—C13—H13A	119.2
C18—N3—C23	121.5 (3)	C5—C14—C15	132.0 (3)
C18—N3—C24	120.2 (3)	C5—C14—H14A	114.0
C23—N3—C24	117.6 (3)	C15—C14—H14A	114.0
N1—C1—H1A	109.5	C20—C15—C16	116.4 (4)
N1—C1—H1B	109.5	C20—C15—C14	126.3 (4)
H1A—C1—H1B	109.5	C16—C15—C14	117.3 (3)
N1—C1—H1C	109.5	C17—C16—C15	122.7 (4)
H1A—C1—H1C	109.5	C17—C16—H16A	118.6
H1B—C1—H1C	109.5	C15—C16—H16A	118.6
N1—C2—C3	110.2 (3)	C16—C17—C18	121.1 (4)
N1—C2—H2A	109.6	C16—C17—H17A	119.5
C3—C2—H2A	109.6	C18—C17—H17A	119.5
N1—C2—H2B	109.6	N3—C18—C17	121.1 (4)
C3—C2—H2B	109.6	N3—C18—C19	122.3 (4)
H2A—C2—H2B	108.1	C17—C18—C19	116.6 (4)
C7—C3—C4	117.2 (3)	C20—C19—C18	121.4 (4)
C7—C3—C2	125.3 (3)	C20—C19—H19A	119.3
C4—C3—C2	117.5 (3)	C18—C19—H19A	119.3
O1—C4—C3	121.5 (4)	C19—C20—C15	121.7 (4)
O1—C4—C5	120.7 (4)	C19—C20—H20A	119.1
C3—C4—C5	117.7 (3)	C15—C20—H20A	119.1
C14—C5—C4	117.4 (3)	N2—C21—H21A	109.5
C14—C5—C6	125.5 (3)	N2—C21—H21B	109.5
C4—C5—C6	117.0 (3)	H21A—C21—H21B	109.5
N1—C6—C5	109.4 (3)	N2—C21—H21C	109.5
N1—C6—H6A	109.8	H21A—C21—H21C	109.5
C5—C6—H6A	109.8	H21B—C21—H21C	109.5
N1—C6—H6B	109.8	N2—C22—H22A	109.5
C5—C6—H6B	109.8	N2—C22—H22B	109.5
H6A—C6—H6B	108.2	H22A—C22—H22B	109.5
C3—C7—C8	131.5 (3)	N2—C22—H22C	109.5
C3—C7—H7A	114.3	H22A—C22—H22C	109.5
C8—C7—H7A	114.3	H22B—C22—H22C	109.5
C13—C8—C9	116.4 (3)	N3—C23—H23A	109.5
C13—C8—C7	125.7 (3)	N3—C23—H23B	109.5
C9—C8—C7	117.8 (3)	H23A—C23—H23B	109.5
C10—C9—C8	122.7 (4)	N3—C23—H23C	109.5
C10—C9—H9A	118.7	H23A—C23—H23C	109.5
C8—C9—H9A	118.7	H23B—C23—H23C	109.5
C9—C10—C11	120.7 (4)	N3—C24—H24A	109.5
C9—C10—H10A	119.6	N3—C24—H24B	109.5
C11—C10—H10A	119.6	H24A—C24—H24B	109.5
N2—C11—C10	121.6 (3)	N3—C24—H24C	109.5
N2—C11—C12	121.4 (3)	H24A—C24—H24C	109.5
C10—C11—C12	117.0 (3)	H24B—C24—H24C	109.5
C6—N1—C2—C3	63.7 (4)	C21—N2—C11—C12	171.1 (4)
C1—N1—C2—C3	−172.6 (3)	C9—C10—C11—N2	178.6 (3)
N1—C2—C3—C7	157.3 (3)	C9—C10—C11—C12	−0.4 (6)
N1—C2—C3—C4	−20.5 (4)	N2—C11—C12—C13	−179.4 (4)
C7—C3—C4—O1	−12.4 (5)	C10—C11—C12—C13	−0.4 (6)
C2—C3—C4—O1	165.6 (4)	C11—C12—C13—C8	−0.1 (6)
C7—C3—C4—C5	164.2 (3)	C9—C8—C13—C12	1.3 (5)
C2—C3—C4—C5	−17.8 (5)	C7—C8—C13—C12	−180.0 (4)
O1—C4—C5—C14	9.2 (5)	C4—C5—C14—C15	179.4 (4)
C3—C4—C5—C14	−167.4 (3)	C6—C5—C14—C15	−3.7 (7)
O1—C4—C5—C6	−168.0 (4)	C5—C14—C15—C20	−21.5 (7)
C3—C4—C5—C6	15.5 (5)	C5—C14—C15—C16	161.0 (4)
C2—N1—C6—C5	−65.9 (4)	C20—C15—C16—C17	3.2 (6)
C1—N1—C6—C5	170.8 (3)	C14—C15—C16—C17	−179.0 (4)
C14—C5—C6—N1	−151.9 (4)	C15—C16—C17—C18	−2.7 (6)
C4—C5—C6—N1	24.9 (4)	C23—N3—C18—C17	−12.5 (6)
C4—C3—C7—C8	−178.5 (4)	C24—N3—C18—C17	177.5 (4)
C2—C3—C7—C8	3.7 (6)	C23—N3—C18—C19	168.2 (4)
C3—C7—C8—C13	17.2 (6)	C24—N3—C18—C19	−1.8 (6)
C3—C7—C8—C9	−164.1 (4)	C16—C17—C18—N3	−178.7 (4)
C13—C8—C9—C10	−2.1 (5)	C16—C17—C18—C19	0.6 (6)
C7—C8—C9—C10	179.1 (4)	N3—C18—C19—C20	180.0 (4)
C8—C9—C10—C11	1.7 (6)	C17—C18—C19—C20	0.6 (6)
C22—N2—C11—C10	−178.9 (4)	C18—C19—C20—C15	0.0 (6)
C21—N2—C11—C10	−7.9 (6)	C16—C15—C20—C19	−1.9 (5)
C22—N2—C11—C12	0.1 (5)	C14—C15—C20—C19	−179.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N1^i	0.99	2.53	3.435 (3)	152
C22—H22B···O1^ii	0.98	2.49	3.245 (3)	134

Symmetry codes: (i) −x+1, −y+1, z−1/2; (ii) −x+1/2, y+1/2, z−1/2.