Ethyl 2-[1-(ferrocenylcarbon­yl)prop-1-en-2-ylamino]-3-hydroxy­propionate dichloro­methane solvate

The title compound, [Fe(C₅H₅)(C₁₄H₁₈NO₄)]·CH₂Cl₂, has been synthesized by the reaction of ferrocenoylacetone with DL-serine ethyl ester in ethanol. Electron delocalization is observed within the enaminone moiety.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.065
• wR factor = 0.202
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.09 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.74 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C15
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Fe
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C20
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9

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

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

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S1. Comment

As a part of an investigation on the chemistry of enaminones (Shi et al., 2004; Shi, 2005), the title compound, (I), has been synthesized in the laboratory and its crystal structure is reported here.

The molecular structure of (I) is shown in Fig. 1. Within the O═C—C═ C—N enaminone group, bond lengths and angles are comparable to those found in the related compound [3-(hydroxyethyl)amino-1-ferrocenylbut-2-en-1-one], (II) (Shi et al., 2005). The smaller difference of 0.04 (1) Å between the C7—C8 and C8—C9 bond distances (Table 1) clearly indicates the electron delocalization within the enaminone group (Gilli et al., 2000). The C9—C10 bond distance closes to the typical Csp²—Csp² single-bond distance of 1.48 Å and suggests that the C10 ring is not involved in the electron delocalization system of the enaminone group. The dihedral angle of 11.8 (3)° between the enaminone plane and the C10 cyclopentadienyl ring is slightly smaller than that [15.6 (2)°] in (II).

Carbonyl atom O4 is intramolecularly and intermolecularly hydrogen bonded with the enamine and hydroxy groups (Table 2).

S2. Experimental

Ferrocenoylacetone was prepared according to the literature method (Shi et al., 2004). An ethanol solution of ferrocenoylacetone and DL-serine ethyl ester in a 1:1 ratio was refluxed for 24 h. After the removal of solvent, the resulting residue was chromatographed on a silica gel column using CH₂Cl₂/ether (2:1, v/v) as eluant. The red band was collected and further recrystallized from CH₂Cl₂/petroleum ether to afford the enaminone (32% yield, m.p. 397–398 K). Analysis calculated for C₁₉H₂₃FeNO₄: C 59.24, H 6.02, N 3.64%; found: C 60.12, H 6.31, N 3.27%. IR (KBr, cm⁻¹): 3355 (br, w, OH), 3098 (w, NH), 1741 (m, O═COEt), 1600 (vs, O═C), 1525 (s, C═C). UV (λ_max, in DMF, nm): 257.50 (B band, 0.91 × 10⁴), 335.50 (K band, 1.63 × 10⁴), 445.50 (CT band, 0.079 × 10⁴). ¹H NMR (600 MHz, CDCl₃, p.p.m.): δ 11.14 (1H, s, NH), 5.37 (1H, s, CH), 4.73, 4.38 (4H, 2s, C₅H₄), 4.29–4.31 (1H, m, CHN), 4.23–4.27 (2H, q, OCH₂Me), 4.16 (5H, s, C₅H₅), 3.98–3.99 (2H, d, CH₂), 2.03 (3H, s, CH₃), 1.29–1.31 (3H, t, CH₃).

S3. Refinement

Methyl H atoms were placed at calculated positions (C—H = 0.96 Å) and torsion refined from electron density with U_iso(H) = 1.5U_eq(C). Other H atoms were placed at calculated positions (C—H = 0.93–0.98 Å, N—H = 0.86 Å and O—H = 0.82 Å) and were treated as riding atoms during the refinement, with U_iso(H) = 1.2U_eq(carrier).

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) and OscailX (McArdle, 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and OscailX; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures

Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

Ethyl 2-[1-(ferrocenylcarbonyl)prop-1-en-2-ylamino]-3-hydroxypropionate dichloromethane solvate

Crystal data

[Fe(C5H5)(C14H18NO4)]·CH2Cl2	F(000) = 976
Mr = 470.16	Dx = 1.416 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.836 (3) Å	Cell parameters from 25 reflections
b = 22.2556 (15) Å	θ = 10–13°
c = 10.023 (2) Å	µ = 0.95 mm^−1
β = 114.11 (3)°	T = 293 K
V = 2206.3 (9) Å^3	Block, red
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	2542 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 26.0°, θmin = 1.8°
ω/2θ scans	h = −13→12
Absorption correction: empirical (using intensity measurements) ψ scan (North et al., 1968)	k = −27→0
Tmin = 0.702, Tmax = 0.821	l = 0→12
4580 measured reflections	3 standard reflections every 200 reflections
4325 independent reflections	intensity decay: 0.1%

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.202	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0984P)^2 + 1.6775P] where P = (Fo^2 + 2Fc^2)/3
4325 reflections	(Δ/σ)max < 0.001
255 parameters	Δρmax = 0.60 e Å^−3
68 restraints	Δρmin = −0.75 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
Fe	0.43007 (7)	0.33067 (4)	0.06194 (8)	0.0434 (3)
Cl1	0.2218 (4)	0.48229 (17)	0.6702 (3)	0.1599 (14)
Cl2	0.1772 (4)	0.38519 (12)	0.4686 (4)	0.1481 (13)
N	0.2765 (4)	0.5549 (2)	0.2131 (4)	0.0467 (11)
H1N	0.3299	0.5292	0.2732	0.056*
O1	0.1581 (4)	0.67980 (18)	0.3566 (5)	0.0655 (12)
O2	0.0720 (4)	0.5882 (2)	0.2945 (5)	0.0697 (12)
O3	0.4033 (4)	0.5797 (2)	0.5084 (4)	0.0636 (12)
H3	0.4721	0.5823	0.5840	0.095*
O4	0.3514 (4)	0.44327 (17)	0.2816 (4)	0.0510 (10)
C1	0.0707 (10)	0.7566 (4)	0.4583 (12)	0.125 (3)
H1A	0.1605	0.7636	0.5307	0.187*
H1B	0.0066	0.7647	0.4996	0.187*
H1C	0.0533	0.7827	0.3762	0.187*
C2	0.0576 (7)	0.6933 (3)	0.4095 (9)	0.084 (2)
H2A	0.0682	0.6670	0.4905	0.101*
H2B	−0.0315	0.6867	0.3326	0.101*
C3	0.1563 (6)	0.6248 (3)	0.3075 (6)	0.0481 (13)
C4	0.2780 (5)	0.6142 (2)	0.2699 (6)	0.0423 (12)
H4	0.2761	0.6437	0.1966	0.051*
C5	0.4086 (6)	0.6218 (3)	0.4064 (6)	0.0509 (13)
H5A	0.4864	0.6142	0.3842	0.061*
H5B	0.4153	0.6622	0.4447	0.061*
C6	0.1181 (6)	0.5780 (3)	−0.0371 (6)	0.0543 (14)
H6A	0.0571	0.5985	−0.0051	0.081*
H6B	0.0673	0.5566	−0.1259	0.081*
H6C	0.1759	0.6068	−0.0545	0.081*
C7	0.2023 (5)	0.5346 (2)	0.0783 (5)	0.0407 (11)
C8	0.2050 (5)	0.4746 (2)	0.0446 (5)	0.0417 (12)
H8	0.1543	0.4623	−0.0509	0.050*
C9	0.2814 (5)	0.4308 (2)	0.1487 (5)	0.0404 (11)
C10	0.2774 (5)	0.3680 (2)	0.1020 (5)	0.0410 (12)
C11	0.2277 (5)	0.3449 (2)	−0.0449 (6)	0.0475 (13)
H11	0.1849	0.3670	−0.1303	0.057*
C12	0.2557 (6)	0.2824 (3)	−0.0358 (6)	0.0533 (14)
H12	0.2344	0.2564	−0.1147	0.064*
C13	0.3215 (6)	0.2661 (3)	0.1131 (6)	0.0552 (14)
H13	0.3506	0.2278	0.1490	0.066*
C14	0.3352 (6)	0.3187 (2)	0.1980 (6)	0.0500 (14)
H14	0.3753	0.3206	0.2995	0.060*
C15	0.5180 (8)	0.3676 (4)	−0.0629 (9)	0.081 (2)
H15	0.4718	0.3831	−0.1564	0.098*
C16	0.5622 (7)	0.3082 (4)	−0.0286 (8)	0.0745 (19)
H16	0.5511	0.2773	−0.0948	0.089*
C17	0.6261 (6)	0.3040 (3)	0.1235 (8)	0.0706 (18)
H17	0.6651	0.2696	0.1764	0.085*
C18	0.6215 (7)	0.3607 (3)	0.1829 (8)	0.0692 (18)
H18	0.6565	0.3703	0.2818	0.083*
C19	0.5557 (7)	0.3995 (3)	0.0687 (9)	0.0750 (19)
H19	0.5392	0.4400	0.0774	0.090*
C20	0.1947 (12)	0.4618 (4)	0.4968 (10)	0.116 (3)
H20A	0.2699	0.4756	0.4760	0.139*
H20B	0.1136	0.4815	0.4288	0.139*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.0428 (4)	0.0477 (5)	0.0435 (4)	0.0000 (4)	0.0214 (3)	−0.0049 (4)
Cl1	0.213 (4)	0.184 (3)	0.109 (2)	−0.069 (3)	0.092 (2)	−0.024 (2)
Cl2	0.185 (3)	0.0938 (19)	0.227 (4)	−0.0155 (18)	0.146 (3)	0.002 (2)
N	0.050 (3)	0.049 (3)	0.037 (2)	0.006 (2)	0.014 (2)	0.001 (2)
O1	0.057 (2)	0.059 (3)	0.089 (3)	−0.006 (2)	0.038 (2)	−0.029 (2)
O2	0.053 (2)	0.068 (3)	0.092 (3)	−0.018 (2)	0.034 (2)	−0.015 (2)
O3	0.063 (3)	0.079 (3)	0.037 (2)	−0.007 (2)	0.0088 (18)	0.004 (2)
O4	0.061 (2)	0.055 (2)	0.0316 (19)	0.0084 (18)	0.0130 (17)	−0.0043 (17)
C1	0.113 (5)	0.125 (6)	0.151 (6)	0.004 (4)	0.070 (5)	−0.042 (5)
C2	0.066 (4)	0.095 (4)	0.100 (4)	0.002 (3)	0.042 (3)	−0.028 (4)
C3	0.047 (3)	0.051 (3)	0.042 (3)	−0.002 (3)	0.013 (2)	−0.003 (3)
C4	0.047 (3)	0.042 (3)	0.038 (3)	−0.001 (2)	0.018 (2)	−0.001 (2)
C5	0.046 (3)	0.053 (3)	0.054 (3)	−0.004 (3)	0.020 (3)	−0.004 (3)
C6	0.051 (3)	0.063 (4)	0.041 (3)	0.002 (3)	0.011 (3)	0.003 (3)
C7	0.037 (3)	0.047 (3)	0.038 (3)	−0.001 (2)	0.015 (2)	−0.001 (2)
C8	0.038 (3)	0.054 (3)	0.031 (2)	0.000 (2)	0.012 (2)	−0.005 (2)
C9	0.037 (3)	0.051 (3)	0.039 (3)	−0.001 (2)	0.022 (2)	−0.004 (2)
C10	0.037 (3)	0.054 (3)	0.037 (3)	0.001 (2)	0.020 (2)	0.001 (2)
C11	0.046 (2)	0.051 (3)	0.045 (2)	−0.003 (2)	0.018 (2)	−0.006 (2)
C12	0.053 (3)	0.050 (3)	0.054 (3)	−0.007 (2)	0.019 (2)	−0.013 (2)
C13	0.061 (3)	0.048 (3)	0.059 (3)	−0.004 (2)	0.026 (2)	0.004 (2)
C14	0.056 (3)	0.052 (3)	0.047 (3)	−0.008 (2)	0.026 (2)	−0.003 (2)
C15	0.072 (4)	0.103 (4)	0.082 (4)	−0.007 (3)	0.044 (3)	0.015 (3)
C16	0.069 (3)	0.089 (4)	0.080 (4)	−0.001 (3)	0.046 (3)	−0.018 (3)
C17	0.055 (3)	0.075 (4)	0.083 (4)	0.009 (3)	0.029 (3)	−0.007 (3)
C18	0.054 (3)	0.083 (4)	0.074 (3)	−0.007 (3)	0.029 (3)	−0.020 (3)
C19	0.063 (3)	0.069 (4)	0.105 (4)	−0.006 (3)	0.046 (3)	−0.004 (3)
C20	0.174 (10)	0.093 (7)	0.102 (7)	0.027 (6)	0.079 (7)	0.032 (5)

Geometric parameters (Å, º)

N—C4	1.434 (6)	C11—H11	0.9300
N—C7	1.337 (6)	C12—C13	1.413 (8)
N—H1N	0.8600	C12—H12	0.9300
O1—C2	1.425 (6)	C13—C14	1.418 (8)
O1—C3	1.316 (7)	C13—H13	0.9300
O2—C3	1.191 (7)	C14—H14	0.9300
O3—C5	1.404 (7)	C15—C16	1.400 (11)
O3—H3	0.8200	C15—C19	1.405 (10)
O4—C9	1.266 (6)	C15—H15	0.9300
C1—C2	1.479 (8)	C16—C17	1.396 (9)
C1—H1A	0.9600	C16—H16	0.9300
C1—H1B	0.9600	C17—C18	1.404 (9)
C1—H1C	0.9600	C17—H17	0.9300
C2—H2A	0.9700	C18—C19	1.378 (10)
C2—H2B	0.9700	C18—H18	0.9300
C3—C4	1.530 (7)	C19—H19	0.9300
C4—C5	1.524 (7)	C20—H20A	0.9700
C4—H4	0.9800	C20—H20B	0.9700
C5—H5A	0.9700	Fe—C15	2.030 (7)
C5—H5B	0.9700	Fe—C14	2.033 (5)
C6—C7	1.497 (7)	Fe—C10	2.033 (5)
C6—H6A	0.9600	Fe—C19	2.033 (7)
C6—H6B	0.9600	Fe—C11	2.034 (6)
C6—H6C	0.9600	Fe—C18	2.040 (7)
C7—C8	1.381 (7)	Fe—C12	2.042 (6)
C8—C9	1.421 (7)	Fe—C17	2.043 (6)
C8—H8	0.9300	Fe—C16	2.045 (6)
C9—C10	1.469 (7)	Fe—C13	2.050 (6)
C10—C14	1.425 (8)	Cl1—C20	1.703 (9)
C10—C11	1.441 (7)	Cl2—C20	1.725 (10)
C11—C12	1.419 (8)
C15—Fe—C14	163.7 (3)	H6A—C6—H6B	109.5
C15—Fe—C10	125.5 (3)	C7—C6—H6C	109.5
C14—Fe—C10	41.0 (2)	H6A—C6—H6C	109.5
C15—Fe—C19	40.4 (3)	H6B—C6—H6C	109.5
C14—Fe—C19	126.3 (3)	N—C7—C6	119.2 (5)
C10—Fe—C19	105.8 (3)	N—C7—C8	120.6 (5)
C15—Fe—C11	106.8 (3)	C6—C7—C8	120.1 (5)
C14—Fe—C11	69.0 (2)	C7—C8—C9	123.3 (5)
C10—Fe—C11	41.5 (2)	C7—C8—H8	118.4
C19—Fe—C11	117.6 (3)	C9—C8—H8	118.4
C15—Fe—C18	67.3 (3)	O4—C9—C8	122.8 (5)
C14—Fe—C18	108.3 (3)	O4—C9—C10	118.1 (5)
C10—Fe—C18	117.4 (2)	C8—C9—C10	119.1 (4)
C19—Fe—C18	39.5 (3)	C14—C10—C11	107.0 (5)
C11—Fe—C18	151.3 (3)	C14—C10—C9	124.8 (5)
C15—Fe—C12	119.5 (3)	C11—C10—C9	128.0 (5)
C14—Fe—C12	68.3 (2)	C14—C10—Fe	69.5 (3)
C10—Fe—C12	69.0 (2)	C11—C10—Fe	69.3 (3)
C19—Fe—C12	152.7 (3)	C9—C10—Fe	122.1 (3)
C11—Fe—C12	40.7 (2)	C12—C11—C10	107.7 (5)
C18—Fe—C12	166.9 (3)	C12—C11—Fe	69.9 (3)
C15—Fe—C17	67.2 (3)	C10—C11—Fe	69.2 (3)
C14—Fe—C17	120.5 (3)	C12—C11—H11	126.2
C10—Fe—C17	152.7 (2)	C10—C11—H11	126.2
C19—Fe—C17	67.0 (3)	Fe—C11—H11	126.3
C11—Fe—C17	165.6 (2)	C13—C12—C11	108.8 (5)
C18—Fe—C17	40.2 (3)	C13—C12—Fe	70.1 (3)
C12—Fe—C17	129.5 (3)	C11—C12—Fe	69.3 (3)
C15—Fe—C16	40.2 (3)	C13—C12—H12	125.6
C14—Fe—C16	154.5 (3)	C11—C12—H12	125.6
C10—Fe—C16	164.0 (3)	Fe—C12—H12	126.5
C19—Fe—C16	67.6 (3)	C12—C13—C14	107.8 (5)
C11—Fe—C16	127.2 (3)	C12—C13—Fe	69.5 (3)
C18—Fe—C16	67.5 (3)	C14—C13—Fe	69.0 (3)
C12—Fe—C16	109.7 (3)	C12—C13—H13	126.1
C17—Fe—C16	39.9 (3)	C14—C13—H13	126.1
C15—Fe—C13	154.1 (3)	Fe—C13—H13	127.0
C14—Fe—C13	40.6 (2)	C13—C14—C10	108.7 (5)
C10—Fe—C13	68.9 (2)	C13—C14—Fe	70.4 (3)
C19—Fe—C13	164.8 (3)	C10—C14—Fe	69.5 (3)
C11—Fe—C13	68.6 (2)	C13—C14—H14	125.6
C18—Fe—C13	128.9 (3)	C10—C14—H14	125.6
C12—Fe—C13	40.4 (2)	Fe—C14—H14	126.1
C17—Fe—C13	110.7 (3)	C16—C15—C19	107.9 (7)
C16—Fe—C13	121.1 (3)	C16—C15—Fe	70.5 (4)
C7—N—C4	128.0 (4)	C19—C15—Fe	69.9 (4)
C7—N—H1N	116.0	C16—C15—H15	126.0
C4—N—H1N	116.0	C19—C15—H15	126.0
C3—O1—C2	116.0 (5)	Fe—C15—H15	125.2
C5—O3—H3	109.5	C17—C16—C15	107.4 (7)
C2—C1—H1A	109.5	C17—C16—Fe	69.9 (4)
C2—C1—H1B	109.5	C15—C16—Fe	69.3 (4)
H1A—C1—H1B	109.5	C17—C16—H16	126.3
C2—C1—H1C	109.5	C15—C16—H16	126.3
H1A—C1—H1C	109.5	Fe—C16—H16	126.0
H1B—C1—H1C	109.5	C16—C17—C18	108.4 (7)
O1—C2—C1	109.9 (6)	C16—C17—Fe	70.1 (4)
O1—C2—H2A	109.7	C18—C17—Fe	69.8 (4)
C1—C2—H2A	109.7	C16—C17—H17	125.8
O1—C2—H2B	109.7	C18—C17—H17	125.8
C1—C2—H2B	109.7	Fe—C17—H17	125.8
H2A—C2—H2B	108.2	C19—C18—C17	107.9 (7)
O1—C3—O2	124.8 (5)	C19—C18—Fe	69.9 (4)
O1—C3—C4	110.7 (5)	C17—C18—Fe	70.0 (4)
O2—C3—C4	124.6 (5)	C19—C18—H18	126.1
N—C4—C5	108.3 (4)	C17—C18—H18	126.1
N—C4—C3	111.6 (4)	Fe—C18—H18	125.6
C5—C4—C3	109.9 (4)	C18—C19—C15	108.4 (7)
N—C4—H4	109.0	C18—C19—Fe	70.5 (4)
C5—C4—H4	109.0	C15—C19—Fe	69.7 (4)
C3—C4—H4	109.0	C18—C19—H19	125.8
O3—C5—C4	106.3 (4)	C15—C19—H19	125.8
O3—C5—H5A	110.5	Fe—C19—H19	125.6
C4—C5—H5A	110.5	Cl1—C20—Cl2	113.2 (5)
O3—C5—H5B	110.5	Cl1—C20—H20A	108.9
C4—C5—H5B	110.5	Cl2—C20—H20A	108.9
H5A—C5—H5B	108.7	Cl1—C20—H20B	108.9
C7—C6—H6A	109.5	Cl2—C20—H20B	108.9
C7—C6—H6B	109.5	H20A—C20—H20B	107.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4^i	0.82	1.92	2.681 (6)	154
N—H1N···O4	0.86	1.92	2.617 (6)	137
C20—H20A···O4	0.97	2.55	3.270 (10)	131

Symmetry code: (i) −x+1, −y+1, −z+1.