N-(Fluoren-9-ylmethoxy-carbon-yl)-l-aspartic acid 4-tert-butyl ester.

The bond distances and bond angles of the title compound, C(23)H(25)NO(6), are consistent with values typically found for fluoren-9-ylmethoxy-carbonyl-protected amino acids. The conformations of the backbone and the side chain are slightly different from those of l-aspartic acid. The crystal structure exhibits two inter-molecular hydrogen bonds, forming a two-dimensional sheet structure parallel to the ab plane.

Related literature

For the crystal structures of aspartic acids, see: Dawson (1977 ▶); Sequeira et al. (1989 ▶); Flaig et al. (1998 ▶); n class="Gene">Rao (1973 ▶); Wang et al. (2007 ▶); Umadevi et al. (2003 ▶); Derissen et al. (1968 ▶); Bendeif & Jelsch (2007 ▶). For the crystal structures of N-α-fluoren-9-ylmethoxy­carbonyl-protected amino acids, see: Valle et al. (1984 ▶); Yamada, Hashizume & Shimizu (2008 ▶); Yamada, Hashizume, Shimizu & Deguchi (2008 ▶); Yamada, Hashizume, Shimizu, Ohiki & Yokoyama (2008 ▶).

Experimental

Crystal data

C23H25NO6

M = 411.44

Orthorhombic,

a = 5.7166 (4) Å

b = 11.1175 (10) Å

c = 32.083 (3) Å

V = 2039.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 90 K

0.11 × 0.05 × 0.04 mm

Data collection

Rigaku AFC-8 diffractometer with Saturn70 CCD detector

Absorption correction: none

15110 measured reflections

2722 independent reflections

2167 reflections with I > 2σ(I)

R int = 0.077

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.148

S = 1.13

2722 reflections

286 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ▶); data reduction: HKL-2000; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809037611/fj2243sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037611/fj2243Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C23H25NO6	F(000) = 872
Mr = 411.44	Dx = 1.340 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 15181 reflections
a = 5.7166 (4) Å	θ = 1.8–27.6°
b = 11.1175 (10) Å	µ = 0.10 mm−1
c = 32.083 (3) Å	T = 90 K
V = 2039.0 (3) Å3	Needle, colourless
Z = 4	0.11 × 0.05 × 0.04 mm

Rigaku AFC-8 diffractometer with Saturn70 CCD detector	2167 reflections with I > 2σ(I)
Radiation source: fine-focus rotating anode	Rint = 0.077
confocal	θmax = 27.6°, θmin = 1.9°
Detector resolution: 28.5714 pixels mm-1	h = −7→6
ω scans	k = −14→10
15110 measured reflections	l = −41→41
2722 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0694P)2 + 0.981P] where P = (Fo2 + 2Fc2)/3
2722 reflections	(Δ/σ)max < 0.001
286 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

Experimental. All Friedel pairs were merged, and all f"s of containing atoms were set to zero.

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 al 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 > 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	Uiso*/Ueq
O1	0.6301 (5)	0.4494 (2)	0.15286 (8)	0.0271 (6)
O2	0.7666 (5)	0.3298 (2)	0.10086 (7)	0.0237 (6)
O3	1.1545 (5)	0.4557 (2)	0.20322 (8)	0.0254 (6)
H3	1.2064	0.5245	0.2089	0.038*
O4	0.8720 (5)	0.5069 (2)	0.24884 (8)	0.0267 (6)
O5	0.6813 (5)	0.1857 (2)	0.28643 (7)	0.0230 (6)
O6	0.3240 (5)	0.2717 (2)	0.27449 (7)	0.0207 (6)
N1	0.6108 (6)	0.3053 (3)	0.22971 (9)	0.0221 (7)
H1	0.5004	0.3395	0.2147	0.027*
C1	0.8504 (7)	0.3115 (3)	0.21511 (11)	0.0203 (8)
H1A	0.9431	0.2511	0.2313	0.024*
C2	0.8711 (7)	0.2786 (3)	0.16889 (11)	0.0221 (8)
H2A	1.0385	0.2787	0.1610	0.027*
H2B	0.8106	0.1961	0.1648	0.027*
C3	0.7406 (7)	0.3629 (3)	0.14049 (11)	0.0205 (8)
C4	0.9549 (7)	0.4366 (3)	0.22432 (11)	0.0215 (8)
C5	0.6574 (8)	0.4001 (3)	0.06656 (11)	0.0254 (9)
C6	0.7397 (9)	0.3306 (4)	0.02814 (12)	0.0363 (11)
H6A	0.6839	0.2474	0.0298	0.054*
H6B	0.9110	0.3312	0.0270	0.054*
H6C	0.6768	0.3687	0.0030	0.054*
C7	0.7598 (8)	0.5265 (3)	0.06653 (13)	0.0309 (9)
H7A	0.9308	0.5216	0.0676	0.046*
H7B	0.7024	0.5706	0.0909	0.046*
H7C	0.7120	0.5685	0.0411	0.046*
C8	0.3951 (8)	0.3978 (4)	0.07039 (14)	0.0333 (10)
H8A	0.3481	0.4396	0.0959	0.050*
H8B	0.3410	0.3142	0.0715	0.050*
H8C	0.3253	0.4381	0.0462	0.050*
C9	0.5502 (7)	0.2491 (3)	0.26529 (11)	0.0180 (7)
C10	0.2379 (7)	0.2366 (3)	0.31542 (10)	0.0206 (8)
H10A	0.3663	0.2015	0.3322	0.025*
H10B	0.1125	0.1758	0.3126	0.025*
C11	0.1424 (7)	0.3503 (3)	0.33673 (11)	0.0199 (8)
H11	0.0232	0.3901	0.3185	0.024*
C12	0.0379 (7)	0.3219 (3)	0.37912 (11)	0.0231 (8)
C13	−0.1547 (8)	0.2505 (3)	0.38905 (11)	0.0243 (8)
H13	−0.2397	0.2099	0.3679	0.029*
C14	−0.2195 (7)	0.2401 (3)	0.43060 (12)	0.0263 (9)
H14	−0.3507	0.1918	0.4378	0.032*
C15	−0.0960 (8)	0.2990 (3)	0.46202 (12)	0.0284 (9)
H15	−0.1433	0.2903	0.4902	0.034*
C16	0.0969 (7)	0.3707 (3)	0.45224 (12)	0.0261 (9)
H16	0.1830	0.4103	0.4735	0.031*
C17	0.1598 (8)	0.3825 (3)	0.41070 (11)	0.0227 (8)
C18	0.3500 (7)	0.4533 (3)	0.39111 (11)	0.0220 (8)
C19	0.5228 (8)	0.5253 (3)	0.40880 (12)	0.0286 (9)
H19	0.5306	0.5365	0.4381	0.034*
C20	0.6843 (8)	0.5807 (3)	0.38242 (13)	0.0302 (10)
H20	0.8067	0.6279	0.3940	0.036*
C21	0.6685 (8)	0.5678 (3)	0.33946 (13)	0.0289 (9)
H21	0.7788	0.6072	0.3220	0.035*
C22	0.4919 (8)	0.4973 (3)	0.32146 (12)	0.0250 (8)
H22	0.4792	0.4901	0.2920	0.030*
C23	0.3357 (7)	0.4382 (3)	0.34766 (11)	0.0230 (8)

	U11	U22	U33	U12	U13	U23
O1	0.0316 (17)	0.0205 (13)	0.0293 (14)	0.0069 (13)	0.0030 (13)	0.0004 (10)
O2	0.0291 (16)	0.0162 (12)	0.0258 (13)	0.0015 (12)	−0.0022 (12)	0.0003 (10)
O3	0.0280 (16)	0.0139 (12)	0.0342 (14)	−0.0014 (12)	0.0038 (13)	0.0000 (10)
O4	0.0299 (17)	0.0195 (12)	0.0306 (13)	0.0004 (13)	0.0039 (13)	−0.0027 (11)
O5	0.0225 (14)	0.0157 (12)	0.0307 (13)	0.0032 (11)	0.0002 (12)	0.0030 (10)
O6	0.0205 (14)	0.0179 (12)	0.0237 (12)	−0.0001 (11)	−0.0007 (11)	0.0004 (9)
N1	0.0208 (18)	0.0186 (15)	0.0269 (15)	0.0018 (14)	−0.0007 (13)	0.0030 (12)
C1	0.0191 (19)	0.0139 (16)	0.0279 (18)	0.0013 (16)	−0.0016 (16)	0.0020 (13)
C2	0.024 (2)	0.0115 (16)	0.0305 (18)	0.0027 (15)	0.0019 (17)	0.0004 (13)
C3	0.0168 (19)	0.0160 (17)	0.0286 (19)	−0.0019 (15)	0.0021 (16)	0.0032 (14)
C4	0.023 (2)	0.0199 (17)	0.0212 (17)	0.0022 (16)	−0.0020 (16)	0.0023 (14)
C5	0.029 (2)	0.0225 (18)	0.0248 (18)	−0.0006 (17)	−0.0020 (19)	0.0034 (14)
C6	0.041 (3)	0.037 (2)	0.031 (2)	0.003 (2)	−0.001 (2)	−0.0055 (18)
C7	0.031 (2)	0.0233 (19)	0.039 (2)	0.0000 (18)	−0.003 (2)	0.0060 (16)
C8	0.024 (2)	0.031 (2)	0.045 (2)	−0.0005 (18)	−0.007 (2)	0.0090 (19)
C9	0.0171 (18)	0.0119 (16)	0.0249 (17)	−0.0016 (14)	−0.0015 (15)	−0.0022 (13)
C10	0.0212 (19)	0.0169 (16)	0.0236 (17)	0.0028 (15)	0.0000 (16)	0.0004 (13)
C11	0.021 (2)	0.0133 (16)	0.0260 (17)	0.0008 (16)	0.0001 (17)	0.0016 (13)
C12	0.028 (2)	0.0135 (16)	0.0278 (18)	0.0033 (16)	0.0004 (17)	0.0006 (14)
C13	0.025 (2)	0.0162 (17)	0.0316 (19)	0.0022 (17)	−0.0024 (18)	−0.0024 (14)
C14	0.024 (2)	0.0176 (17)	0.037 (2)	0.0013 (16)	0.0061 (18)	−0.0002 (15)
C15	0.038 (3)	0.0202 (19)	0.0270 (19)	0.0022 (18)	0.0056 (18)	0.0016 (14)
C16	0.030 (2)	0.0175 (18)	0.031 (2)	0.0028 (17)	−0.0008 (18)	−0.0040 (14)
C17	0.024 (2)	0.0139 (16)	0.0305 (19)	0.0019 (16)	−0.0001 (17)	−0.0002 (13)
C18	0.020 (2)	0.0140 (16)	0.0317 (19)	0.0006 (16)	0.0002 (17)	−0.0017 (13)
C19	0.034 (3)	0.0188 (18)	0.033 (2)	−0.0009 (17)	−0.0024 (19)	−0.0046 (15)
C20	0.030 (2)	0.0152 (18)	0.045 (2)	−0.0057 (17)	−0.001 (2)	−0.0088 (15)
C21	0.030 (2)	0.0138 (17)	0.043 (2)	−0.0010 (17)	0.008 (2)	−0.0010 (15)
C22	0.029 (2)	0.0131 (16)	0.0326 (19)	−0.0014 (17)	0.0021 (18)	−0.0015 (14)
C23	0.022 (2)	0.0122 (16)	0.035 (2)	0.0020 (16)	0.0013 (18)	0.0005 (13)

O1—C3	1.218 (4)	C8—H8C	0.9800
O2—C3	1.332 (4)	C10—C11	1.537 (5)
O2—C5	1.487 (4)	C10—H10A	0.9900
O3—C4	1.344 (5)	C10—H10B	0.9900
O3—H3	0.8400	C11—C23	1.516 (5)
O4—C4	1.206 (4)	C11—C12	1.518 (5)
O5—C9	1.232 (4)	C11—H11	1.0000
O6—C9	1.350 (5)	C12—C13	1.395 (6)
O6—C10	1.456 (4)	C12—C17	1.402 (5)
N1—C9	1.346 (4)	C13—C14	1.388 (5)
N1—C1	1.450 (5)	C13—H13	0.9500
N1—H1	0.8800	C14—C15	1.394 (6)
C1—C2	1.532 (5)	C14—H14	0.9500
C1—C4	1.542 (5)	C15—C16	1.397 (6)
C1—H1A	1.0000	C15—H15	0.9500
C2—C3	1.504 (5)	C16—C17	1.387 (5)
C2—H2A	0.9900	C16—H16	0.9500
C2—H2B	0.9900	C17—C18	1.482 (5)
C5—C8	1.504 (6)	C18—C19	1.392 (5)
C5—C7	1.522 (5)	C18—C23	1.407 (5)
C5—C6	1.529 (5)	C19—C20	1.395 (6)
C6—H6A	0.9800	C19—H19	0.9500
C6—H6B	0.9800	C20—C21	1.389 (6)
C6—H6C	0.9800	C20—H20	0.9500
C7—H7A	0.9800	C21—C22	1.402 (6)
C7—H7B	0.9800	C21—H21	0.9500
C7—H7C	0.9800	C22—C23	1.392 (5)
C8—H8A	0.9800	C22—H22	0.9500
C8—H8B	0.9800
C3—O2—C5	120.9 (3)	N1—C9—O6	110.2 (3)
C4—O3—H3	109.5	O6—C10—C11	107.5 (3)
C9—O6—C10	118.1 (3)	O6—C10—H10A	110.2
C9—N1—C1	122.6 (3)	C11—C10—H10A	110.2
C9—N1—H1	118.7	O6—C10—H10B	110.2
C1—N1—H1	118.7	C11—C10—H10B	110.2
N1—C1—C2	112.0 (3)	H10A—C10—H10B	108.5
N1—C1—C4	110.3 (3)	C23—C11—C12	102.3 (3)
C2—C1—C4	111.7 (3)	C23—C11—C10	112.0 (3)
N1—C1—H1A	107.5	C12—C11—C10	111.5 (3)
C2—C1—H1A	107.5	C23—C11—H11	110.3
C4—C1—H1A	107.5	C12—C11—H11	110.3
C3—C2—C1	113.6 (3)	C10—C11—H11	110.3
C3—C2—H2A	108.9	C13—C12—C17	120.1 (3)
C1—C2—H2A	108.9	C13—C12—C11	129.3 (3)
C3—C2—H2B	108.9	C17—C12—C11	110.6 (3)
C1—C2—H2B	108.9	C14—C13—C12	118.5 (4)
H2A—C2—H2B	107.7	C14—C13—H13	120.7
O1—C3—O2	126.0 (3)	C12—C13—H13	120.7
O1—C3—C2	123.5 (3)	C13—C14—C15	121.3 (4)
O2—C3—C2	110.5 (3)	C13—C14—H14	119.3
O4—C4—O3	124.1 (3)	C15—C14—H14	119.3
O4—C4—C1	123.8 (4)	C14—C15—C16	120.4 (4)
O3—C4—C1	112.0 (3)	C14—C15—H15	119.8
O2—C5—C8	110.4 (3)	C16—C15—H15	119.8
O2—C5—C7	108.9 (3)	C17—C16—C15	118.4 (4)
C8—C5—C7	113.5 (4)	C17—C16—H16	120.8
O2—C5—C6	101.6 (3)	C15—C16—H16	120.8
C8—C5—C6	111.3 (4)	C16—C17—C12	121.3 (4)
C7—C5—C6	110.3 (3)	C16—C17—C18	130.4 (4)
C5—C6—H6A	109.5	C12—C17—C18	108.3 (3)
C5—C6—H6B	109.5	C19—C18—C23	120.9 (4)
H6A—C6—H6B	109.5	C19—C18—C17	130.8 (3)
C5—C6—H6C	109.5	C23—C18—C17	108.3 (3)
H6A—C6—H6C	109.5	C18—C19—C20	118.4 (4)
H6B—C6—H6C	109.5	C18—C19—H19	120.8
C5—C7—H7A	109.5	C20—C19—H19	120.8
C5—C7—H7B	109.5	C21—C20—C19	120.9 (4)
H7A—C7—H7B	109.5	C21—C20—H20	119.6
C5—C7—H7C	109.5	C19—C20—H20	119.6
H7A—C7—H7C	109.5	C20—C21—C22	120.9 (4)
H7B—C7—H7C	109.5	C20—C21—H21	119.6
C5—C8—H8A	109.5	C22—C21—H21	119.6
C5—C8—H8B	109.5	C23—C22—C21	118.5 (4)
H8A—C8—H8B	109.5	C23—C22—H22	120.7
C5—C8—H8C	109.5	C21—C22—H22	120.7
H8A—C8—H8C	109.5	C22—C23—C18	120.3 (4)
H8B—C8—H8C	109.5	C22—C23—C11	129.2 (3)
O5—C9—N1	125.1 (4)	C18—C23—C11	110.4 (3)
O5—C9—O6	124.7 (3)
C9—N1—C1—C2	132.6 (3)	C12—C13—C14—C15	−0.2 (6)
C9—N1—C1—C4	−102.3 (4)	C13—C14—C15—C16	0.2 (6)
N1—C1—C2—C3	62.5 (4)	C14—C15—C16—C17	0.7 (6)
C4—C1—C2—C3	−61.9 (4)	C15—C16—C17—C12	−1.6 (6)
C5—O2—C3—O1	0.3 (6)	C15—C16—C17—C18	178.6 (4)
C5—O2—C3—C2	−179.0 (3)	C13—C12—C17—C16	1.7 (6)
C1—C2—C3—O1	0.5 (5)	C11—C12—C17—C16	−179.9 (4)
C1—C2—C3—O2	179.7 (3)	C13—C12—C17—C18	−178.5 (3)
N1—C1—C4—O4	17.0 (5)	C11—C12—C17—C18	−0.1 (4)
C2—C1—C4—O4	142.3 (4)	C16—C17—C18—C19	1.9 (7)
N1—C1—C4—O3	−165.8 (3)	C12—C17—C18—C19	−177.9 (4)
C2—C1—C4—O3	−40.5 (4)	C16—C17—C18—C23	−178.1 (4)
C3—O2—C5—C8	−63.1 (4)	C12—C17—C18—C23	2.1 (4)
C3—O2—C5—C7	62.2 (5)	C23—C18—C19—C20	−1.0 (6)
C3—O2—C5—C6	178.7 (3)	C17—C18—C19—C20	178.9 (4)
C1—N1—C9—O5	−9.2 (5)	C18—C19—C20—C21	2.2 (6)
C1—N1—C9—O6	171.1 (3)	C19—C20—C21—C22	−1.0 (6)
C10—O6—C9—O5	10.9 (5)	C20—C21—C22—C23	−1.5 (6)
C10—O6—C9—N1	−169.3 (3)	C21—C22—C23—C18	2.6 (6)
C9—O6—C10—C11	122.3 (3)	C21—C22—C23—C11	−175.1 (4)
O6—C10—C11—C23	−68.6 (4)	C19—C18—C23—C22	−1.4 (6)
O6—C10—C11—C12	177.4 (3)	C17—C18—C23—C22	178.7 (3)
C23—C11—C12—C13	176.5 (4)	C19—C18—C23—C11	176.7 (3)
C10—C11—C12—C13	−63.7 (5)	C17—C18—C23—C11	−3.2 (4)
C23—C11—C12—C17	−1.7 (4)	C12—C11—C23—C22	−179.1 (4)
C10—C11—C12—C17	118.1 (4)	C10—C11—C23—C22	61.3 (5)
C17—C12—C13—C14	−0.8 (5)	C12—C11—C23—C18	3.0 (4)
C11—C12—C13—C14	−178.8 (4)	C10—C11—C23—C18	−116.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5i	0.84	1.91	2.744 (3)	172
N1—H1···O3ii	0.88	2.39	3.213 (4)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O5i	0.84	1.91	2.744 (3)	172
N1—H1⋯O3ii	0.88	2.39	3.213 (4)	156

Symmetry codes: (i) ; (ii) .