Literature DB >> 21589213

Piperidinium N-(ferrocenylcarbon-yl)glycinate.

Petr Stěpnička¹, Martin Zábranský, Ivana Císařová.

Abstract

The title compound, (C(5)H(12)N)[Fe(C(5)H(5))(C(8)H(7)NO(3))], resulting from neutralization of N-(ferrocenylcarbon-yl)glycine with piperidine, is built up from discrete ions that assemble into sheets via the combination of conventional and weak hydrogen bonds. The key repeating unit is constituted by two piperidium cations and two carboxylate anions that assemble into a centrosymmetric array via conventional and bifurcated N-H⋯O hydrogen bonds. The aggregates thus formed are further interlinked by N-H⋯O interactions and supportive C-H⋯O contacts into layers oriented parallel to the bc plane.

Entities: CellLine Chemical Disease Gene

Year: 2010 PMID： 21589213 PMCID： PMC3011418 DOI： 10.1107/S1600536810041747

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For an overview of bioorganometallic chemistry of ferrocene, see: Štěpnička (2008 ▶). For the first synthesis of N-(ferrocenylcarbonyl)glycine, see: Schlögl (1957 ▶) and for its use in the preparation of 2-ferrocenyl-5(4H)oxazolone and its transition metal complexes, see: Bauer et al. (1999 ▶). An alternative preparative route was described by Kraatz et al. (1997 ▶). For the crystal structures of methyl N-(ferrocenylcarbonyl)glycinate and tert-butyl N-[1′-(diphenylphosphino)ferrocene-1-carbonyl]glycinate, see: Gallagher et al. (1999 ▶) and Tauchman et al. (2009 ▶), respectively. The structure of another related compound, 1,1′-bis{N-(carboxymethylene)carbamoyl}ferrocene, was reported by Appoh et al. (2004 ▶).

Experimental

Crystal data

(C5H12N)[Fe(C5H5)(C8H7NO3)] M = 372.24 Monoclinic, a = 13.9055 (4) Å b = 7.6150 (2) Å c = 16.5968 (5) Å β = 105.780 (2)° V = 1691.21 (8) Å3 Z = 4 Mo Kα radiation μ = 0.91 mm−1 T = 150 K 0.25 × 0.22 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer 25843 measured reflections 3456 independent reflections 2960 reflections with I > 2σ(I) R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.031 wR(F 2) = 0.076 S = 1.11 3456 reflections 217 parameters H-atom parameters constrained Δρmax = 0.27 e Å−3 Δρmin = −0.29 e Å−3 Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: HKL DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810041747/dn2612sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041747/dn2612Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C₅H₁₂N)[Fe(C₅H₅)(C₈H₇NO₃)]	F(000) = 784
M_r = 372.24	D_x = 1.462 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3696 reflections
a = 13.9055 (4) Å	θ = 1.0–26.4°
b = 7.6150 (2) Å	µ = 0.91 mm⁻¹
c = 16.5968 (5) Å	T = 150 K
β = 105.780 (2)°	Plate, yellow
V = 1691.21 (8) Å³	0.25 × 0.22 × 0.15 mm
Z = 4

Nonius KappaCCD diffractometer	2960 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
horizontally mounted graphite crystal	θ_max = 26.4°, θ_min = 1.5°
Detector resolution: 9.091 pixels mm^-1	h = −17→17
ω and π scans to fill the Ewald sphere	k = −9→9
25843 measured reflections	l = −20→20
3456 independent reflections

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0234P)² + 1.3244P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
3456 reflections	Δρ_max = 0.27 e Å⁻³
217 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two least-squares 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 least-squares planes.

Refinement. Refinement of F² against all diffractions. 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 > 2σ(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.

	x	y	z	U_iso*/U_eq
Fe	0.14161 (2)	0.21877 (4)	0.174028 (17)	0.02423 (9)
O1	0.33180 (10)	0.60519 (18)	0.23818 (9)	0.0292 (3)
O2	0.45779 (10)	0.33934 (18)	0.36777 (8)	0.0276 (3)
O3	0.58097 (10)	0.53347 (18)	0.38131 (8)	0.0288 (3)
N1	0.40631 (11)	0.3748 (2)	0.19374 (10)	0.0231 (3)
H1N	0.3988	0.2730	0.1668	0.028*
C1	0.22784 (14)	0.4080 (3)	0.14255 (12)	0.0238 (4)
C2	0.13442 (14)	0.4816 (3)	0.14607 (13)	0.0286 (4)
H2	0.1258	0.5733	0.1805	0.034*
C3	0.05759 (16)	0.3900 (3)	0.08792 (14)	0.0339 (5)
H3	−0.0106	0.4109	0.0776	0.041*
C4	0.10200 (16)	0.2611 (3)	0.04804 (13)	0.0338 (5)
H4	0.0681	0.1831	0.0070	0.041*
C5	0.20758 (15)	0.2717 (3)	0.08169 (12)	0.0275 (4)
H5	0.2548	0.2020	0.0666	0.033*
C6	0.22092 (16)	0.1253 (3)	0.28749 (13)	0.0323 (5)
H6	0.2831	0.1657	0.3186	0.039*
C7	0.12645 (16)	0.1899 (3)	0.29199 (13)	0.0331 (5)
H7	0.1160	0.2795	0.3268	0.040*
C8	0.05104 (17)	0.0937 (3)	0.23426 (14)	0.0364 (5)
H8	−0.0175	0.1092	0.2244	0.044*
C9	0.09846 (17)	−0.0297 (3)	0.19440 (15)	0.0369 (5)
H9	0.0664	−0.1098	0.1536	0.044*
C10	0.20368 (17)	−0.0108 (3)	0.22739 (14)	0.0352 (5)
H10	0.2524	−0.0763	0.2121	0.042*
C11	0.32579 (14)	0.4699 (2)	0.19603 (11)	0.0225 (4)
C12	0.50438 (14)	0.4274 (3)	0.24432 (12)	0.0230 (4)
H12A	0.5197	0.5426	0.2262	0.028*
H12B	0.5536	0.3458	0.2346	0.028*
C13	0.51381 (14)	0.4337 (2)	0.33808 (12)	0.0230 (4)
N2	0.37021 (12)	0.5724 (2)	0.45421 (10)	0.0283 (4)
H2N	0.4048	0.5013	0.4277	0.034*
H3N	0.3928	0.5410	0.5148	0.034*
C21	0.39265 (16)	0.7595 (3)	0.44159 (13)	0.0329 (5)
H21A	0.3741	0.7862	0.3822	0.039*
H21B	0.4638	0.7805	0.4637	0.039*
C22	0.33498 (16)	0.8779 (3)	0.48587 (14)	0.0343 (5)
H22A	0.3467	0.9997	0.4743	0.041*
H22B	0.3590	0.8599	0.5459	0.041*
C23	0.22331 (16)	0.8399 (3)	0.45705 (13)	0.0326 (5)
H23A	0.1974	0.8728	0.3987	0.039*
H23B	0.1891	0.9095	0.4896	0.039*
C24	0.20298 (16)	0.6455 (3)	0.46742 (13)	0.0325 (5)
H24A	0.2212	0.6159	0.5265	0.039*
H24B	0.1322	0.6221	0.4446	0.039*
C25	0.26207 (15)	0.5325 (3)	0.42294 (12)	0.0297 (4)
H25A	0.2507	0.4095	0.4324	0.036*
H25B	0.2397	0.5544	0.3632	0.036*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe	0.02232 (15)	0.02174 (15)	0.02877 (16)	0.00023 (12)	0.00721 (11)	0.00277 (12)
O1	0.0284 (7)	0.0236 (7)	0.0364 (8)	0.0000 (6)	0.0102 (6)	−0.0050 (6)
O2	0.0302 (7)	0.0273 (7)	0.0278 (7)	−0.0035 (6)	0.0119 (6)	0.0000 (6)
O3	0.0303 (7)	0.0277 (8)	0.0252 (7)	−0.0055 (6)	0.0021 (6)	0.0017 (6)
N1	0.0234 (8)	0.0221 (8)	0.0238 (8)	−0.0004 (7)	0.0064 (7)	−0.0030 (7)
C1	0.0241 (10)	0.0215 (9)	0.0258 (10)	0.0010 (8)	0.0070 (8)	0.0055 (8)
C2	0.0266 (10)	0.0224 (10)	0.0379 (11)	0.0047 (8)	0.0106 (9)	0.0078 (9)
C3	0.0241 (10)	0.0334 (12)	0.0417 (12)	0.0023 (9)	0.0046 (9)	0.0138 (10)
C4	0.0303 (11)	0.0381 (12)	0.0288 (10)	−0.0063 (9)	0.0011 (9)	0.0030 (9)
C5	0.0280 (10)	0.0300 (11)	0.0249 (10)	−0.0005 (9)	0.0082 (8)	0.0007 (8)
C6	0.0330 (11)	0.0314 (12)	0.0312 (11)	0.0008 (9)	0.0064 (9)	0.0112 (9)
C7	0.0390 (12)	0.0317 (12)	0.0314 (11)	−0.0013 (10)	0.0143 (9)	0.0036 (9)
C8	0.0324 (12)	0.0377 (12)	0.0421 (12)	−0.0059 (10)	0.0152 (10)	0.0077 (10)
C9	0.0468 (13)	0.0231 (11)	0.0408 (13)	−0.0088 (10)	0.0118 (11)	0.0024 (10)
C10	0.0417 (12)	0.0241 (11)	0.0412 (13)	0.0075 (9)	0.0135 (10)	0.0098 (9)
C11	0.0263 (10)	0.0197 (9)	0.0231 (9)	−0.0006 (8)	0.0094 (8)	0.0028 (8)
C12	0.0217 (9)	0.0210 (10)	0.0272 (10)	−0.0006 (8)	0.0081 (8)	−0.0001 (8)
C13	0.0238 (9)	0.0194 (9)	0.0260 (10)	0.0042 (8)	0.0071 (8)	0.0010 (8)
N2	0.0316 (9)	0.0311 (9)	0.0234 (8)	0.0044 (8)	0.0096 (7)	−0.0014 (7)
C21	0.0315 (11)	0.0366 (12)	0.0311 (11)	−0.0042 (9)	0.0098 (9)	−0.0012 (9)
C22	0.0400 (12)	0.0276 (11)	0.0343 (11)	0.0012 (10)	0.0086 (10)	−0.0025 (9)
C23	0.0351 (11)	0.0318 (11)	0.0306 (11)	0.0091 (9)	0.0084 (9)	0.0020 (9)
C24	0.0307 (11)	0.0376 (12)	0.0302 (11)	0.0030 (9)	0.0102 (9)	0.0037 (9)
C25	0.0329 (11)	0.0304 (11)	0.0248 (10)	−0.0014 (9)	0.0061 (9)	0.0004 (9)

Fe—C5	2.0290 (19)	C7—C8	1.417 (3)
Fe—C1	2.0316 (19)	C7—H7	0.9300
Fe—C6	2.034 (2)	C8—C9	1.412 (3)
Fe—C7	2.037 (2)	C8—H8	0.9300
Fe—C4	2.038 (2)	C9—C10	1.423 (3)
Fe—C9	2.041 (2)	C9—H9	0.9300
Fe—C10	2.042 (2)	C10—H10	0.9300
Fe—C8	2.044 (2)	C12—C13	1.526 (3)
Fe—C3	2.049 (2)	C12—H12A	0.9700
Fe—C2	2.051 (2)	C12—H12B	0.9700
O1—C11	1.235 (2)	N2—C25	1.483 (3)
O2—C13	1.255 (2)	N2—C21	1.485 (3)
O3—C13	1.265 (2)	N2—H2N	0.9128
N1—C11	1.342 (2)	N2—H3N	0.9980
N1—C12	1.450 (2)	C21—C22	1.522 (3)
N1—H1N	0.8865	C21—H21A	0.9700
C1—C5	1.422 (3)	C21—H21B	0.9700
C1—C2	1.430 (3)	C22—C23	1.523 (3)
C1—C11	1.486 (3)	C22—H22A	0.9700
C2—C3	1.414 (3)	C22—H22B	0.9700
C2—H2	0.9300	C23—C24	1.525 (3)
C3—C4	1.416 (3)	C23—H23A	0.9700
C3—H3	0.9300	C23—H23B	0.9700
C4—C5	1.424 (3)	C24—C25	1.513 (3)
C4—H4	0.9300	C24—H24A	0.9700
C5—H5	0.9300	C24—H24B	0.9700
C6—C10	1.413 (3)	C25—H25A	0.9700
C6—C7	1.424 (3)	C25—H25B	0.9700
C6—H6	0.9300

C5—Fe—C1	41.00 (8)	C10—C6—C7	108.0 (2)
C5—Fe—C6	121.73 (8)	C10—C6—Fe	70.00 (12)
C1—Fe—C6	106.07 (8)	C7—C6—Fe	69.64 (12)
C5—Fe—C7	158.99 (9)	C10—C6—H6	126.0
C1—Fe—C7	123.11 (8)	C7—C6—H6	126.0
C6—Fe—C7	40.93 (9)	Fe—C6—H6	125.9
C5—Fe—C4	40.99 (8)	C8—C7—C6	108.0 (2)
C1—Fe—C4	68.76 (8)	C8—C7—Fe	69.93 (12)
C6—Fe—C4	158.79 (9)	C6—C7—Fe	69.43 (12)
C7—Fe—C4	158.97 (9)	C8—C7—H7	126.0
C5—Fe—C9	121.53 (9)	C6—C7—H7	126.0
C1—Fe—C9	157.05 (9)	Fe—C7—H7	126.2
C6—Fe—C9	68.42 (9)	C9—C8—C7	107.9 (2)
C7—Fe—C9	68.21 (9)	C9—C8—Fe	69.68 (12)
C4—Fe—C9	107.89 (9)	C7—C8—Fe	69.44 (12)
C5—Fe—C10	105.85 (9)	C9—C8—H8	126.1
C1—Fe—C10	120.62 (8)	C7—C8—H8	126.1
C6—Fe—C10	40.57 (9)	Fe—C8—H8	126.4
C7—Fe—C10	68.45 (9)	C8—C9—C10	108.3 (2)
C4—Fe—C10	123.02 (9)	C8—C9—Fe	69.88 (12)
C9—Fe—C10	40.80 (9)	C10—C9—Fe	69.63 (12)
C5—Fe—C8	158.01 (9)	C8—C9—H9	125.8
C1—Fe—C8	160.30 (9)	C10—C9—H9	125.8
C6—Fe—C8	68.62 (9)	Fe—C9—H9	126.2
C7—Fe—C8	40.63 (9)	C6—C10—C9	107.8 (2)
C4—Fe—C8	123.03 (9)	C6—C10—Fe	69.43 (12)
C9—Fe—C8	40.44 (9)	C9—C10—Fe	69.57 (12)
C10—Fe—C8	68.46 (9)	C6—C10—H10	126.1
C5—Fe—C3	68.66 (8)	C9—C10—H10	126.1
C1—Fe—C3	68.52 (8)	Fe—C10—H10	126.5
C6—Fe—C3	158.55 (9)	O1—C11—N1	122.50 (18)
C7—Fe—C3	123.40 (9)	O1—C11—C1	120.83 (17)
C4—Fe—C3	40.54 (9)	N1—C11—C1	116.63 (17)
C9—Fe—C3	124.61 (9)	N1—C12—C13	113.93 (15)
C10—Fe—C3	160.19 (9)	N1—C12—H12A	108.8
C8—Fe—C3	109.10 (9)	C13—C12—H12A	108.8
C5—Fe—C2	68.87 (8)	N1—C12—H12B	108.8
C1—Fe—C2	41.02 (7)	C13—C12—H12B	108.8
C6—Fe—C2	122.11 (9)	H12A—C12—H12B	107.7
C7—Fe—C2	108.14 (9)	O2—C13—O3	124.25 (17)
C4—Fe—C2	68.31 (9)	O2—C13—C12	119.45 (17)
C9—Fe—C2	160.71 (9)	O3—C13—C12	116.28 (16)
C10—Fe—C2	157.30 (9)	C25—N2—C21	112.28 (16)
C8—Fe—C2	124.52 (9)	C25—N2—H2N	109.1
C3—Fe—C2	40.34 (8)	C21—N2—H2N	110.0
C11—N1—C12	119.69 (16)	C25—N2—H3N	108.4
C11—N1—H1N	120.1	C21—N2—H3N	110.5
C12—N1—H1N	119.7	H2N—N2—H3N	106.3
C5—C1—C2	107.95 (18)	N2—C21—C22	109.99 (17)
C5—C1—C11	128.91 (18)	N2—C21—H21A	109.7
C2—C1—C11	123.13 (18)	C22—C21—H21A	109.7
C5—C1—Fe	69.40 (11)	N2—C21—H21B	109.7
C2—C1—Fe	70.21 (11)	C22—C21—H21B	109.7
C11—C1—Fe	125.49 (13)	H21A—C21—H21B	108.2
C3—C2—C1	107.76 (19)	C21—C22—C23	111.20 (18)
C3—C2—Fe	69.78 (12)	C21—C22—H22A	109.4
C1—C2—Fe	68.77 (11)	C23—C22—H22A	109.4
C3—C2—H2	126.1	C21—C22—H22B	109.4
C1—C2—H2	126.1	C23—C22—H22B	109.4
Fe—C2—H2	126.9	H22A—C22—H22B	108.0
C2—C3—C4	108.44 (18)	C22—C23—C24	110.71 (18)
C2—C3—Fe	69.89 (11)	C22—C23—H23A	109.5
C4—C3—Fe	69.30 (12)	C24—C23—H23A	109.5
C2—C3—H3	125.8	C22—C23—H23B	109.5
C4—C3—H3	125.8	C24—C23—H23B	109.5
Fe—C3—H3	126.6	H23A—C23—H23B	108.1
C3—C4—C5	108.16 (19)	C25—C24—C23	110.77 (17)
C3—C4—Fe	70.16 (12)	C25—C24—H24A	109.5
C5—C4—Fe	69.17 (11)	C23—C24—H24A	109.5
C3—C4—H4	125.9	C25—C24—H24B	109.5
C5—C4—H4	125.9	C23—C24—H24B	109.5
Fe—C4—H4	126.3	H24A—C24—H24B	108.1
C1—C5—C4	107.69 (18)	N2—C25—C24	110.26 (17)
C1—C5—Fe	69.60 (11)	N2—C25—H25A	109.6
C4—C5—Fe	69.85 (12)	C24—C25—H25A	109.6
C1—C5—H5	126.2	N2—C25—H25B	109.6
C4—C5—H5	126.2	C24—C25—H25B	109.6
Fe—C5—H5	126.0	H25A—C25—H25B	108.1

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O2	0.91	1.86	2.764 (2)	172
N2—H3N···O3ⁱ	1.00	1.76	2.749 (2)	172
N2—H3N···O2ⁱ	1.00	2.60	3.325 (2)	130
N1—H1N···O3ⁱⁱ	0.89	2.04	2.908 (2)	166
C5—H5···O3ⁱⁱ	0.93	2.56	3.366 (3)	146
C12—H12B···O1ⁱⁱ	0.97	2.39	3.307 (3)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O2	0.91	1.86	2.764 (2)	172
N2—H3N⋯O3ⁱ	1.00	1.76	2.749 (2)	172
N2—H3N⋯O2ⁱ	1.00	2.60	3.325 (2)	130
N1—H1N⋯O3ⁱⁱ	0.89	2.04	2.908 (2)	166
C5—H5⋯O3ⁱⁱ	0.93	2.56	3.366 (3)	146
C12—H12B⋯O1ⁱⁱ	0.97	2.39	3.307 (3)	158

Symmetry codes: (i) ; (ii) .

3 in total

Piperidinium N-(ferrocenylcarbon-yl)glycinate.

Related literature

Experimental

Crystal data

Data collection

Refinement

1. Ferrocenoyl Amino Acids: A Synthetic and Structural Study.

2. A short history of SHELX.

3. Structure validation in chemical crystallography.