(S)-Methyl 2-(2-iodo­benzamido)­propionate

In the title compound, C₁₁H₁₂INO₃, mol­ecules are linked into one-dimensional chains along the crystallographic a axis by strong inter­molecular N—H...O hydrogen bonds. The one-dimensional chains are additionally stabilized by weak inter­molecular C_ar—H...O inter­actions. Unlike its iodine(V) analogues, the organic chain substituent in the title iodine(I) compound is not coplanar with the aromatic core but exhibits a C—C—C—O torsion angle of 50.3 (7)°.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.038
• wR factor = 0.097
• Data-to-parameter ratio = 20.1

checkCIF/PLATON results

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Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.50 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.69 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10

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           27.49
           From the CIF: _reflns_number_total               2940
           Count of symmetry unique reflns         1738
           Completeness (_total/calc)            169.16%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1202
           Fraction of Friedel pairs measured     0.692
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     = .          S

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Iodine(V) compounds are useful reagents for numerous oxidative transformations of different organic substrates (Koposov et al., 2006; Zhdankin et al., 2005; Chung et al., 2003). The title compound represents an iodine(I) precursor for the preparation of the corresponding iodine(V) reagents. X-ray crystal structure analysis of the iodine(V) amide revealed the presence of a three-dimensional polymeric network formed by various types of intermolecular interactions. In particular, very strong intermolecular I···O bonding plays an important role in the formation of the tetrameric supramolecular motifs in the structure of the iodine(V) amide (Zhdankin et al., 2003).

We now report the structure of the (S)-2-(2-iodobenzoylamino)propionic acid methyl ester, which crystalyses in the orthorhombic P2₁2₁2₁ space group (Fig. 1). In this molecule, the amidic moiety deviates from the phenyl ring plane (the C1—C6—C7—O3 torsion angle is 50.3 (7)°), thus contrasting with the structures of corresponding iodine(V) compounds where the amidic substituent was observed within the aromatic plane. The intramolecular bond distances and angles in the presented iodine(I) molecule are almost indistinguishable from those found in the corresponding iodine(V) compounds.

The molecules of (S)-2-(2-iodobenzoylamino)propionic acid methyl ester are linked together into one-dimensional polymeric chains by strong N—H···O hydrogen bonds (Table 1) formed between amide hydrogen atoms and the carbonyl oxygen atom O3 of a neighboring molecule at (x+1, y, z), generated by a translation along a axis (Fig. 2). The one-dimensional polymeric chain is stabilized by additional weak C—H···O hydrogen bonds formed between the phenyl ring hydrogen atom H62 and the carboxylic oxygen atom O1 of a neighboring molecule at (-x + 3, y + 1/2, -z + 3/2) (Fig. 2).

Related literature

For the synthesis of the title compound, see: Zhdankin et al. (2000). For the related iodine(V) amide, see: Zhdankin et al. (2003). For other related literature, see: Koposov et al. (2006); Zhdankin et al. (2005); Chung et al. (2003).

S2. Experimental

The title compound was prepared according to a published procedure (Zhdankin et al., 2000). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a methylene chloride solution of the compound.

S3. Refinement

The amidic H atom was located in a difference density Fourier map but was ultimately positioned geometrically with a N—H distance of 0.875 Å. The other H atoms were placed in calculated positions with C—H distances of 0.930 (aromatic) and 0.980 Å (alkyl). All hydrogen atoms were refined with U_iso(H) = 1.3 U_eq of their respective carrier atom. 6 reflections with [sin theta/lambda]**2 with values smaller than 0.01 were eliminated.

Computing details

Data collection: AFC-7R Software (Rigaku, 1997); cell refinement: WinAFC (Rigaku/MSC, 2000); data reduction: TEXSAN (Rigaku/MSC, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures

	Fig. 1. Thermal ellipsoid representation of the title compound, with anisotropic displacement parameters for the non-H atoms of 50% probability.
	Fig. 2. Thermal ellipsoid representation showing the NH···O and CH···O H-bonding at 50% probability.

(S)-Methyl 2-(2-iodobenzamido)propionate

Crystal data

C11H12INO3	F(000) = 648
Mr = 333.13	Dx = 1.728 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 4.990 (3) Å	θ = 15–18°
b = 12.120 (4) Å	µ = 2.49 mm^−1
c = 21.176 (10) Å	T = 295 K
V = 1280.7 (10) Å^3	Block, colorless
Z = 4	0.30 × 0.15 × 0.10 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.035
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω/2θ scans	h = −6→6
Absorption correction: ψ scan Azimuthal absorption correction (North et al., 1968)	k = 0→15
Tmin = 0.65, Tmax = 0.78	l = 0→27
3032 measured reflections	3 standard reflections every 150 reflections
2940 independent reflections	intensity decay: 0.0%
2721 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.038	P = P(6)*max(Fo^2,0) + (1-P(6))Fc^2 Method = SHELXL97 (Sheldrick, 1997) W = 1/[Sigma^2(F*) + (P(1)p)^2 + P(2)p] P(i) are: 0.519E-01 2.03 0.333
wR(F^2) = 0.097	(Δ/σ)max = 0.001
S = 0.99	Δρmax = 0.32 e Å^−3
2934 reflections	Δρmin = −0.44 e Å^−3
146 parameters	Absolute structure: Flack (1983), with 408 Friedel pairs
0 restraints	Absolute structure parameter: −0.01 (5)
Primary atom site location: structure-invariant direct methods

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

	x	y	z	Uiso*/Ueq
I1	0.61721 (8)	0.35486 (3)	0.538896 (17)	0.0580
N1	1.1480 (9)	0.3848 (4)	0.70627 (19)	0.0502
C3	1.1280 (14)	0.6402 (5)	0.5224 (3)	0.0653
O3	0.7040 (7)	0.4075 (4)	0.6935 (2)	0.0652
C1	0.8807 (11)	0.4846 (4)	0.5611 (2)	0.0441
C8	1.1316 (13)	0.3301 (5)	0.7674 (2)	0.0600
C7	0.9335 (9)	0.4247 (4)	0.6762 (2)	0.0424
C6	0.9982 (9)	0.4959 (4)	0.6203 (2)	0.0401
C5	1.1812 (11)	0.5820 (5)	0.6293 (2)	0.0512
C4	1.2461 (13)	0.6542 (5)	0.5809 (3)	0.0617
C2	0.9463 (12)	0.5566 (5)	0.5123 (2)	0.0579
O2	1.1717 (16)	0.5073 (5)	0.8118 (3)	0.1014
C9	1.2777 (15)	0.2191 (6)	0.7664 (4)	0.0757
O1	1.386 (2)	0.3732 (6)	0.8604 (3)	0.1411
C11	1.254 (3)	0.5851 (9)	0.8601 (4)	0.1409
C10	1.2453 (17)	0.4043 (7)	0.8184 (3)	0.0753
H61	1.2598	0.5911	0.6688	0.0606*
H62	1.3668	0.7114	0.5879	0.0742*
H63	1.1732	0.6875	0.4894	0.0780*
H64	0.8672	0.5481	0.4728	0.0698*
H81	0.9424	0.3168	0.7772	0.0718*
H91	1.2646	0.1845	0.8070	0.0897*
H92	1.4629	0.2307	0.7561	0.0897*
H93	1.1970	0.1725	0.7351	0.0897*
H2	1.3076	0.3941	0.6900	0.0500*
H111	1.1864	0.6598	0.8500	0.1845*
H112	1.1811	0.5611	0.9013	0.1845*
H113	1.4524	0.5867	0.8623	0.1845*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.05217 (18)	0.05985 (19)	0.0620 (2)	−0.00088 (18)	−0.00941 (17)	−0.01249 (16)
N1	0.0281 (18)	0.077 (3)	0.046 (2)	−0.0009 (19)	−0.0024 (17)	0.0160 (19)
C3	0.072 (3)	0.070 (3)	0.053 (3)	−0.004 (4)	−0.002 (3)	0.023 (2)
O3	0.0289 (17)	0.104 (3)	0.062 (2)	−0.0042 (19)	−0.0006 (16)	0.030 (2)
C1	0.039 (2)	0.049 (2)	0.044 (2)	0.007 (2)	−0.003 (2)	−0.0040 (18)
C8	0.043 (2)	0.083 (4)	0.054 (3)	−0.007 (3)	−0.004 (2)	0.023 (3)
C7	0.029 (2)	0.056 (3)	0.042 (2)	−0.0003 (19)	0.0010 (17)	0.004 (2)
C6	0.031 (2)	0.053 (3)	0.037 (2)	0.0034 (19)	0.0016 (18)	0.0005 (19)
C5	0.048 (3)	0.060 (3)	0.046 (2)	−0.007 (2)	−0.001 (2)	−0.001 (2)
C4	0.065 (3)	0.057 (3)	0.064 (3)	−0.016 (3)	−0.001 (3)	0.006 (3)
C2	0.062 (4)	0.072 (3)	0.040 (2)	0.003 (3)	−0.007 (2)	0.005 (2)
O2	0.145 (6)	0.090 (3)	0.069 (3)	0.025 (4)	−0.025 (4)	0.000 (3)
C9	0.066 (4)	0.077 (4)	0.084 (5)	−0.007 (3)	−0.013 (3)	0.028 (4)
O1	0.217 (9)	0.121 (5)	0.085 (4)	0.031 (6)	−0.082 (5)	0.004 (3)
C11	0.234 (18)	0.112 (7)	0.077 (5)	0.014 (9)	−0.037 (7)	−0.020 (5)
C10	0.088 (5)	0.087 (5)	0.051 (3)	0.006 (4)	−0.005 (3)	0.018 (3)

Geometric parameters (Å, º)

I1—C1	2.103 (5)	C8—C10	1.516 (10)
C6—C7	1.501 (7)	C8—H81	0.980
O3—C7	1.220 (6)	C6—C5	1.401 (7)
N1—C7	1.335 (6)	C5—C4	1.385 (8)
N1—C8	1.457 (6)	C5—H61	0.930
O1—C10	1.192 (9)	C4—H62	0.930
O2—C10	1.309 (9)	C2—H64	0.930
N1—H2	0.875	O2—C11	1.451 (11)
C3—C4	1.384 (8)	C9—H91	0.960
C3—C2	1.376 (9)	C9—H92	0.960
C3—H63	0.930	C9—H93	0.960
C1—C6	1.390 (7)	C11—H111	0.990
C1—C2	1.393 (7)	C11—H112	0.990
C8—C9	1.530 (10)	C11—H113	0.990
N1—C7—O3	123.2 (5)	C6—C5—H61	119.041
O2—C10—O1	123.1 (8)	C4—C5—H61	119.422
C8—N1—C7	122.9 (4)	C5—C4—C3	119.0 (5)
C8—N1—H2	117.357	C5—C4—H62	120.359
C7—N1—H2	119.675	C3—C4—H62	120.599
C4—C3—C2	120.7 (5)	C1—C2—C3	120.1 (5)
C4—C3—H63	119.557	C1—C2—H64	119.834
C2—C3—H63	119.776	C3—C2—H64	120.069
I1—C1—C6	122.6 (4)	C11—O2—C10	117.7 (7)
I1—C1—C2	116.7 (4)	C8—C9—H91	109.869
C6—C1—C2	120.5 (5)	C8—C9—H92	109.438
N1—C8—C9	111.2 (5)	H91—C9—H92	109.476
N1—C8—C10	110.0 (5)	C8—C9—H93	109.093
C9—C8—C10	110.7 (5)	H91—C9—H93	109.476
N1—C8—H81	108.442	H92—C9—H93	109.476
C9—C8—H81	108.543	O2—C11—H111	110.118
C10—C8—H81	107.883	O2—C11—H112	109.043
N1—C7—C6	114.3 (4)	H111—C11—H112	109.475
O3—C7—C6	122.5 (4)	O2—C11—H113	109.237
C7—C6—C1	124.3 (4)	H111—C11—H113	109.476
C7—C6—C5	117.5 (4)	H112—C11—H113	109.476
C1—C6—C5	118.1 (5)	C8—C10—O2	112.6 (6)
C6—C5—C4	121.5 (5)	C8—C10—O1	124.3 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O3^i	0.88	1.99	2.801 (6)	154 (4)
C4—H62···O1^ii	0.93	2.56	3.46 (2)	161 (8)

Symmetry codes: (i) x+1, y, z; (ii) −x+3, y+1/2, −z+3/2.