Cyclo(l-tyrosyl-l-tryptophanyl) dimethylformamide solvate.

THE STRUCTURE OF THE TITLE COMPOUND [SYSTEMATIC NAME: (3S,6S)-3-(4-hydroxy-benz-yl)-6-(1H-indol-3-ylmeth-yl)piperazine-2,5-dione dimethyl-formamide solvate], C(20)H(19)N(3)O(3)·C(3)H(7)NO, contains hydrogen-bonded tapes typical for diketopiperazines. The structure is stabilized by strong inter-molecular inter-actions of the types O-H⋯O and N-H⋯O involving the dipeptide and the solvent mol-ecules. The absolute configuration was known from the starting materials.

Related literature

For related structures, see: Morris et al. (1974 ▶); Grant et al. (1999 ▶); Suguna et al. (1984 ▶); Lin & Webb (1973 ▶); Razak et al., (2000 ▶); Luo & Palmore (2002 ▶); Görbitz (1987 ▶); Görbitz & Hartviksen (2006 ▶). Solvent inclusion: Görbitz & Hersleth (2000 ▶). Cambridge Structural Database: Allen (2002 ▶).

Experimental

Crystal data

C20H19N3O3·C3H7NO

M = 422.48

Monoclinic,

a = 6.1923 (2) Å

b = 15.3873 (5) Å

c = 11.3780 (3) Å

β = 96.661 (1)°

V = 1076.81 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 105 (2) K

0.80 × 0.65 × 0.20 mm

Data collection

Siemens SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.800, T max = 0.982

9514 measured reflections

2786 independent reflections

2454 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.122

S = 1.15

2786 reflections

297 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL (Bruker, 2000 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808000640/pv2058sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000640/pv2058Isup2.hkl

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

C20H19N3O3·C3H7NO	F000 = 448
Mr = 422.48	Dx = 1.303 Mg m−3
Monoclinic, P21	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7819 reflections
a = 6.1923 (2) Å	θ = 1.8–28.3º
b = 15.3873 (5) Å	µ = 0.09 mm−1
c = 11.3780 (3) Å	T = 105 (2) K
β = 96.6610 (10)º	Block, colourless
V = 1076.81 (6) Å3	0.80 × 0.65 × 0.20 mm
Z = 2

Siemens SMART CCD diffractometer	2786 independent reflections
Radiation source: fine-focus sealed tube	2454 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
Detector resolution: 8.3 pixels mm-1	θmax = 28.3º
T = 105(2) K	θmin = 1.8º
Sets of exposures each taken over 0.3° ω rotation scans	h = −8→8
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	k = −20→20
Tmin = 0.800, Tmax = 0.982	l = −12→15
9514 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.122	w = 1/[σ2(Fo2) + (0.0645P)2 + 0.2252P] where P = (Fo2 + 2Fc2)/3
S = 1.15	(Δ/σ)max = 0.001
2786 reflections	Δρmax = 0.23 e Å−3
297 parameters	Δρmin = −0.27 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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. Data were collected by measuring three sets of exposures with the detector set at 2θ = 29°, crystal-to-detector distance 5.00 cm. Refinement of F2 against ALL reflections.

	x	y	z	Uiso*/Ueq
O1	0.1720 (3)	−0.00215 (12)	0.52224 (17)	0.0277 (4)
O2	0.6882 (4)	0.38722 (14)	0.7195 (2)	0.0378 (5)
H4	0.566 (7)	0.409 (3)	0.768 (4)	0.057*
O3	0.8442 (3)	0.11985 (12)	0.31396 (17)	0.0269 (4)
N1	0.7154 (3)	0.02668 (14)	0.44228 (19)	0.0230 (4)
H1	0.867 (5)	0.014 (2)	0.465 (3)	0.028*
N2	0.2984 (3)	0.09051 (13)	0.39160 (19)	0.0223 (4)
H2	0.162 (6)	0.101 (2)	0.369 (3)	0.027*
N3	−0.0323 (4)	0.35012 (15)	0.3555 (2)	0.0268 (4)
H3	−0.123 (6)	0.379 (3)	0.383 (3)	0.032*
C1	0.5533 (4)	−0.00266 (16)	0.5160 (2)	0.0231 (5)
H11	0.5496	−0.0676	0.5117	0.028*
C2	0.6176 (4)	0.02202 (18)	0.6471 (2)	0.0280 (5)
H21	0.5086	−0.0024	0.6951	0.034*
H22	0.7596	−0.0050	0.6747	0.034*
C3	0.6339 (4)	0.11897 (18)	0.6686 (2)	0.0269 (5)
C4	0.4638 (4)	0.16582 (19)	0.7071 (2)	0.0283 (5)
H41	0.3344	0.1361	0.7206	0.034*
C5	0.4777 (4)	0.2550 (2)	0.7265 (2)	0.0317 (6)
H51	0.3601	0.2854	0.7543	0.038*
C6	0.6650 (5)	0.29970 (19)	0.7049 (2)	0.0305 (6)
C7	0.8369 (5)	0.2541 (2)	0.6663 (3)	0.0334 (6)
H71	0.9651	0.2840	0.6515	0.040*
C8	0.8222 (4)	0.1643 (2)	0.6491 (2)	0.0307 (6)
H81	0.9417	0.1336	0.6239	0.037*
C9	0.3262 (4)	0.02939 (16)	0.4750 (2)	0.0214 (4)
C10	0.4684 (4)	0.13210 (15)	0.3333 (2)	0.0203 (4)
H101	0.4283	0.1259	0.2460	0.024*
C11	0.4861 (4)	0.23024 (15)	0.3614 (2)	0.0245 (5)
H111	0.5356	0.2378	0.4467	0.029*
H112	0.5976	0.2561	0.3164	0.029*
C12	0.2766 (4)	0.27826 (15)	0.3319 (2)	0.0219 (5)
C13	0.1520 (4)	0.31262 (17)	0.4122 (2)	0.0259 (5)
H131	0.1882	0.3108	0.4956	0.031*
C14	0.1618 (4)	0.29527 (15)	0.2171 (2)	0.0236 (5)
C15	0.2022 (5)	0.27731 (19)	0.1009 (3)	0.0312 (5)
H151	0.3336	0.2499	0.0857	0.037*
C16	0.0465 (6)	0.3004 (2)	0.0084 (3)	0.0397 (7)
H161	0.0713	0.2876	−0.0706	0.048*
C17	−0.1462 (5)	0.3422 (2)	0.0292 (3)	0.0426 (7)
H171	−0.2505	0.3565	−0.0359	0.051*
C18	−0.1877 (5)	0.36285 (19)	0.1422 (3)	0.0367 (6)
H181	−0.3178	0.3919	0.1561	0.044*
C19	−0.0318 (4)	0.33969 (16)	0.2361 (2)	0.0270 (5)
C20	0.6919 (4)	0.09162 (16)	0.3637 (2)	0.0213 (4)
O1D	0.4352 (4)	0.46196 (17)	0.8569 (2)	0.0448 (5)
N1D	0.1638 (4)	0.53136 (19)	0.9359 (2)	0.0370 (5)
C1D	0.2408 (5)	0.4758 (2)	0.8623 (3)	0.0373 (6)
H1D	0.119 (6)	0.450 (3)	0.804 (3)	0.045*
C2D	−0.0661 (6)	0.5502 (2)	0.9296 (4)	0.0509 (9)
H21D	−0.1468	0.5109	0.8726	0.076*
H22D	−0.0925	0.6104	0.9041	0.076*
H23D	−0.1147	0.5419	1.0078	0.076*
C3D	0.3101 (7)	0.5866 (5)	1.0106 (5)	0.094 (2)
H31D	0.4563	0.5613	1.0191	0.141*
H32D	0.2590	0.5916	1.0887	0.141*
H33D	0.3142	0.6444	0.9747	0.141*

	U11	U22	U33	U12	U13	U23
O1	0.0200 (8)	0.0271 (9)	0.0367 (10)	0.0003 (7)	0.0066 (7)	0.0090 (7)
O2	0.0475 (12)	0.0301 (10)	0.0363 (11)	−0.0044 (9)	0.0074 (9)	−0.0026 (8)
O3	0.0188 (8)	0.0296 (9)	0.0328 (9)	0.0005 (7)	0.0059 (7)	0.0044 (8)
N1	0.0159 (9)	0.0234 (9)	0.0304 (10)	0.0030 (7)	0.0053 (7)	0.0032 (8)
N2	0.0160 (9)	0.0208 (9)	0.0303 (10)	0.0003 (7)	0.0046 (8)	0.0045 (8)
N3	0.0237 (10)	0.0212 (10)	0.0363 (12)	0.0008 (8)	0.0071 (8)	−0.0046 (9)
C1	0.0193 (10)	0.0197 (10)	0.0310 (12)	0.0015 (9)	0.0051 (9)	0.0049 (9)
C2	0.0252 (11)	0.0301 (13)	0.0286 (12)	0.0026 (10)	0.0022 (9)	0.0064 (10)
C3	0.0248 (11)	0.0320 (13)	0.0237 (11)	−0.0006 (10)	0.0014 (9)	0.0008 (10)
C4	0.0224 (11)	0.0345 (14)	0.0278 (12)	−0.0012 (10)	0.0024 (9)	0.0005 (10)
C5	0.0277 (12)	0.0385 (15)	0.0289 (13)	0.0020 (11)	0.0036 (10)	−0.0025 (11)
C6	0.0339 (14)	0.0320 (14)	0.0251 (12)	−0.0023 (11)	0.0009 (10)	−0.0020 (10)
C7	0.0279 (13)	0.0412 (15)	0.0318 (13)	−0.0059 (11)	0.0072 (10)	−0.0049 (12)
C8	0.0213 (11)	0.0400 (15)	0.0311 (13)	0.0001 (10)	0.0038 (10)	−0.0017 (11)
C9	0.0173 (10)	0.0192 (10)	0.0276 (11)	0.0019 (8)	0.0028 (8)	0.0001 (9)
C10	0.0151 (9)	0.0192 (10)	0.0266 (11)	0.0001 (8)	0.0022 (8)	0.0030 (9)
C11	0.0204 (10)	0.0192 (11)	0.0336 (13)	−0.0017 (8)	0.0027 (9)	0.0014 (9)
C12	0.0197 (10)	0.0172 (10)	0.0292 (12)	−0.0029 (8)	0.0038 (9)	0.0011 (8)
C13	0.0265 (11)	0.0215 (11)	0.0300 (12)	−0.0035 (9)	0.0049 (9)	−0.0011 (9)
C14	0.0243 (11)	0.0170 (11)	0.0296 (12)	−0.0009 (8)	0.0038 (9)	0.0020 (9)
C15	0.0367 (14)	0.0267 (12)	0.0312 (13)	0.0018 (11)	0.0080 (10)	0.0028 (10)
C16	0.0542 (19)	0.0377 (16)	0.0263 (13)	−0.0017 (13)	0.0012 (12)	0.0041 (12)
C17	0.0484 (17)	0.0380 (16)	0.0381 (15)	0.0011 (14)	−0.0087 (13)	0.0143 (13)
C18	0.0311 (13)	0.0295 (14)	0.0477 (17)	0.0020 (11)	−0.0037 (12)	0.0063 (12)
C19	0.0272 (11)	0.0194 (11)	0.0347 (13)	−0.0022 (9)	0.0046 (10)	0.0022 (10)
C20	0.0191 (10)	0.0212 (10)	0.0234 (11)	0.0023 (8)	0.0012 (8)	−0.0019 (8)
O1D	0.0433 (12)	0.0462 (13)	0.0455 (12)	0.0077 (11)	0.0076 (10)	−0.0020 (11)
N1D	0.0350 (12)	0.0415 (13)	0.0339 (12)	0.0042 (11)	0.0012 (10)	0.0027 (11)
C1D	0.0428 (16)	0.0280 (13)	0.0403 (16)	0.0007 (11)	0.0014 (13)	0.0035 (12)
C2D	0.0373 (16)	0.0400 (18)	0.075 (3)	0.0035 (13)	0.0049 (16)	0.0045 (17)
C3D	0.046 (2)	0.145 (6)	0.086 (3)	0.009 (3)	−0.013 (2)	−0.074 (4)

O1—C9	1.247 (3)	C10—C11	1.545 (3)
O2—C6	1.363 (4)	C10—H101	1.0000
O2—H4	1.04 (5)	C11—C12	1.497 (3)
O3—C20	1.234 (3)	C11—H111	0.9900
N1—C20	1.337 (3)	C11—H112	0.9900
N1—C1	1.453 (3)	C12—C13	1.368 (4)
N1—H1	0.96 (3)	C12—C14	1.437 (4)
N2—C9	1.333 (3)	C13—H131	0.9500
N2—C10	1.456 (3)	C14—C15	1.401 (4)
N2—H2	0.87 (3)	C14—C19	1.418 (3)
N3—C19	1.369 (4)	C15—C16	1.389 (4)
N3—C13	1.371 (3)	C15—H151	0.9500
N3—H3	0.81 (4)	C16—C17	1.399 (5)
C1—C9	1.512 (3)	C16—H161	0.9500
C1—C2	1.546 (4)	C17—C18	1.378 (5)
C1—H11	1.0000	C17—H171	0.9500
C2—C3	1.513 (4)	C18—C19	1.400 (4)
C2—H21	0.9900	C18—H181	0.9500
C2—H22	0.9900	O1D—C1D	1.231 (4)
C3—C4	1.389 (4)	N1D—C1D	1.324 (4)
C3—C8	1.397 (4)	N1D—C3D	1.445 (5)
C4—C5	1.391 (4)	N1D—C2D	1.446 (4)
C4—H41	0.9500	C1D—H1D	1.03 (4)
C5—C6	1.394 (4)	C2D—H21D	0.9800
C5—H51	0.9500	C2D—H22D	0.9800
C6—C7	1.388 (4)	C2D—H23D	0.9800
C7—C8	1.397 (4)	C3D—H31D	0.9800
C7—H71	0.9500	C3D—H32D	0.9800
C8—H81	0.9500	C3D—H33D	0.9800
C10—C20	1.520 (3)
C6—O2—H4	108 (3)	C12—C11—H111	108.9
C20—N1—C1	126.1 (2)	C10—C11—H111	108.9
C20—N1—H1	110 (2)	C12—C11—H112	108.9
C1—N1—H1	120 (2)	C10—C11—H112	108.9
C9—N2—C10	126.4 (2)	H111—C11—H112	107.7
C9—N2—H2	112 (2)	C13—C12—C14	106.2 (2)
C10—N2—H2	121 (2)	C13—C12—C11	125.6 (2)
C19—N3—C13	108.7 (2)	C14—C12—C11	128.2 (2)
C19—N3—H3	122 (3)	C12—C13—N3	110.6 (2)
C13—N3—H3	129 (3)	C12—C13—H131	124.7
N1—C1—C9	113.6 (2)	N3—C13—H131	124.7
N1—C1—C2	111.3 (2)	C15—C14—C19	119.0 (2)
C9—C1—C2	110.1 (2)	C15—C14—C12	134.3 (2)
N1—C1—H11	107.2	C19—C14—C12	106.7 (2)
C9—C1—H11	107.2	C16—C15—C14	118.7 (3)
C2—C1—H11	107.2	C16—C15—H151	120.6
C3—C2—C1	113.7 (2)	C14—C15—H151	120.6
C3—C2—H21	108.8	C15—C16—C17	121.3 (3)
C1—C2—H21	108.8	C15—C16—H161	119.3
C3—C2—H22	108.8	C17—C16—H161	119.3
C1—C2—H22	108.8	C18—C17—C16	121.2 (3)
H21—C2—H22	107.7	C18—C17—H171	119.4
C4—C3—C8	117.9 (3)	C16—C17—H171	119.4
C4—C3—C2	121.6 (2)	C17—C18—C19	117.8 (3)
C8—C3—C2	120.5 (2)	C17—C18—H181	121.1
C3—C4—C5	121.8 (3)	C19—C18—H181	121.1
C3—C4—H41	119.1	N3—C19—C18	130.3 (3)
C5—C4—H41	119.1	N3—C19—C14	107.9 (2)
C4—C5—C6	119.7 (3)	C18—C19—C14	121.8 (3)
C4—C5—H51	120.1	O3—C20—N1	122.7 (2)
C6—C5—H51	120.1	O3—C20—C10	118.4 (2)
O2—C6—C7	117.7 (3)	N1—C20—C10	118.9 (2)
O2—C6—C5	123.0 (3)	C1D—N1D—C3D	120.3 (3)
C7—C6—C5	119.4 (3)	C1D—N1D—C2D	121.5 (3)
C6—C7—C8	120.3 (3)	C3D—N1D—C2D	117.3 (3)
C6—C7—H71	119.9	O1D—C1D—N1D	124.7 (3)
C8—C7—H71	119.9	O1D—C1D—H1D	123 (2)
C7—C8—C3	120.9 (3)	N1D—C1D—H1D	112 (2)
C7—C8—H81	119.6	N1D—C2D—H21D	109.5
C3—C8—H81	119.6	N1D—C2D—H22D	109.5
O1—C9—N2	122.6 (2)	H21D—C2D—H22D	109.5
O1—C9—C1	118.1 (2)	N1D—C2D—H23D	109.5
N2—C9—C1	119.3 (2)	H21D—C2D—H23D	109.5
N2—C10—C20	113.8 (2)	H22D—C2D—H23D	109.5
N2—C10—C11	111.9 (2)	N1D—C3D—H31D	109.5
C20—C10—C11	108.22 (19)	N1D—C3D—H32D	109.5
N2—C10—H101	107.5	H31D—C3D—H32D	109.5
C20—C10—H101	107.5	N1D—C3D—H33D	109.5
C11—C10—H101	107.5	H31D—C3D—H33D	109.5
C12—C11—C10	113.42 (19)	H32D—C3D—H33D	109.5
N1—C1—C2—C3	62.3 (3)	C14—C12—C13—N3	−0.2 (3)
C1—C2—C3—C4	97.5 (3)	C11—C12—C13—N3	−178.3 (2)
N2—C10—C11—C12	−55.4 (3)	C19—N3—C13—C12	0.7 (3)
C10—C11—C12—C13	109.8 (3)	C13—C12—C14—C15	179.9 (3)
C20—N1—C1—C9	16.1 (4)	C11—C12—C14—C15	−2.1 (4)
C20—N1—C1—C2	−108.9 (3)	C13—C12—C14—C19	−0.4 (3)
C9—C1—C2—C3	−64.6 (3)	C11—C12—C14—C19	177.6 (2)
C1—C2—C3—C8	−82.1 (3)	C19—C14—C15—C16	−2.7 (4)
C8—C3—C4—C5	−0.1 (4)	C12—C14—C15—C16	177.0 (3)
C2—C3—C4—C5	−179.7 (2)	C14—C15—C16—C17	1.1 (4)
C3—C4—C5—C6	1.2 (4)	C15—C16—C17—C18	0.8 (5)
C4—C5—C6—O2	178.6 (3)	C16—C17—C18—C19	−0.8 (5)
C4—C5—C6—C7	−1.2 (4)	C13—N3—C19—C18	176.7 (3)
O2—C6—C7—C8	−179.7 (3)	C13—N3—C19—C14	−1.0 (3)
C5—C6—C7—C8	0.1 (4)	C17—C18—C19—N3	−178.3 (3)
C6—C7—C8—C3	1.0 (4)	C17—C18—C19—C14	−0.9 (4)
C4—C3—C8—C7	−1.0 (4)	C15—C14—C19—N3	−179.4 (2)
C2—C3—C8—C7	178.6 (3)	C12—C14—C19—N3	0.9 (3)
C10—N2—C9—O1	178.7 (2)	C15—C14—C19—C18	2.7 (4)
C10—N2—C9—C1	−0.4 (4)	C12—C14—C19—C18	−177.1 (2)
N1—C1—C9—O1	170.0 (2)	C1—N1—C20—O3	171.3 (2)
C2—C1—C9—O1	−64.4 (3)	C1—N1—C20—C10	−9.2 (4)
N1—C1—C9—N2	−10.8 (3)	N2—C10—C20—O3	176.5 (2)
C2—C1—C9—N2	114.7 (2)	C11—C10—C20—O3	−58.4 (3)
C9—N2—C10—C20	7.7 (3)	N2—C10—C20—N1	−3.0 (3)
C9—N2—C10—C11	−115.4 (3)	C11—C10—C20—N1	122.1 (2)
C20—C10—C11—C12	178.4 (2)	C3D—N1D—C1D—O1D	5.3 (6)
C10—C11—C12—C14	−67.9 (3)	C2D—N1D—C1D—O1D	174.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.96 (3)	1.94 (3)	2.902 (3)	174 (3)
N2—H2···O3ii	0.87 (3)	2.01 (3)	2.884 (3)	178 (3)
N3—H3···O1iii	0.81 (4)	2.16 (4)	2.851 (3)	144 (3)
O2—H4···O1D	1.04 (5)	1.59 (5)	2.606 (3)	163 (4)
C1D—H1D···O2ii	1.03 (4)	2.89 (4)	3.862 (4)	158
C2D—H21D···O1Dii	0.98	2.68	3.387 (4)	129
C2D—H21D···O2ii	0.98	2.70	3.671 (4)	171
C2D—H22D···C15iii	0.98	2.66	3.602 (4)	163
C3D—H32D···C3iv	0.98	2.80	3.660 (4)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.96 (3)	1.94 (3)	2.902 (3)	174 (3)
N2—H2⋯O3ii	0.87 (3)	2.01 (3)	2.884 (3)	178 (3)
N3—H3⋯O1iii	0.81 (4)	2.16 (4)	2.851 (3)	144 (3)
O2—H4⋯O1D	1.04 (5)	1.59 (5)	2.606 (3)	163 (4)

Symmetry codes: (i) ; (ii) ; (iii) .