rac-5-Bromo-N-benzyl-isatincreatinine ethanol monosolvate.

IN THE TITLE COMPOUND [SYSTEMATIC NAME: rac-1-benzyl-5-bromo-3-hy-droxy-3-(2-imino-3-methyl-5-oxoimidazolidin-4-yl)-2,3-dihydro-1H-indol-2-one ethanol monosolvate], C(19)H(17)BrN(4)O(3)·C(2)H(5)OH, which crystallized as a racemate (RR and SS), the isatin ring is almost planar, with an r.m.s. deviations from the mean plane of 0.0276 (14) Å. The phenyl ring of the benzyl group makes a dihedral angle with the mean plane of the isatin ring of 87.40 (5)° and the dihedral angle between the imidazole and isatin rings is 58.56 (7)°. In the crystal, mol-ecules are linked into two-dimensional pleated-sheet networks in the ac plane formed by O-H⋯O, N-H⋯O and O-H⋯N hydrogen bonds; within these sheets there are R(4) (4)(10) rings that involve three mol-ecules of the title compound and a single ethanol solvent mol-ecule. In addition, there are π-π inter-actions between inversion-related benzyl groups, with an inter-planar spacing of 3.444 (3) Å.

Related literature

Background information on the biological importance of isatins has been given by Pandeya et al. (2005 ▶), and by Vine et al. (2007 ▶). For similar structures, see: Tang et al. (2009 ▶); Penthala et al. (2009a ▶,b ▶).

Experimental

Crystal data

C19H17BrN4O3·C2H6O

M = 475.34

Monoclinic,

a = 7.8384 (16) Å

b = 24.553 (5) Å

c = 10.936 (2) Å

β = 99.54 (3)°

V = 2075.6 (7) Å3

Z = 4

Mo Kα radiation

μ = 2.02 mm−1

T = 90 K

0.20 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan [SCALEPACK (Otwinowski & Minor, 1997 ▶) and XABS2 (Parkin et al., 1995 ▶)] T min = 0.689, T max = 0.824

41507 measured reflections

4752 independent reflections

4147 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.074

S = 1.05

4752 reflections

282 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.19 e Å−3

Δρmin = −0.45 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and local procedures.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681300038X/hg5279sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300038X/hg5279Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681300038X/hg5279Isup3.cml

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

C19H17BrN4O3·C2H6O	F(000) = 976
Mr = 475.34	Dx = 1.521 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 51652 reflections
a = 7.8384 (16) Å	θ = 1.0–27.5°
b = 24.553 (5) Å	µ = 2.02 mm−1
c = 10.936 (2) Å	T = 90 K
β = 99.54 (3)°	Block, colourless
V = 2075.6 (7) Å3	0.20 × 0.15 × 0.10 mm
Z = 4

Nonius KappaCCD diffractometer	4752 independent reflections
Radiation source: fine-focus sealed tube	4147 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 9.1 pixels mm-1	θmax = 27.5°, θmin = 1.7°
ω scans at fixed χ = 55°	h = −10→10
Absorption correction: multi-scan [SCALEPACK (Otwinowski & Minor, 1997) and XABS2 (Parkin et al., 1995)]	k = −31→31
Tmin = 0.689, Tmax = 0.824	l = −14→14
41507 measured 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0318P)2 + 2.2794P] where P = (Fo2 + 2Fc2)/3
4752 reflections	(Δ/σ)max = 0.002
282 parameters	Δρmax = 1.19 e Å−3
3 restraints	Δρmin = −0.45 e Å−3

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-value wR and goodness of fit S are based on F2. Conventional R-values 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-values based on F2 are statistically about twice as large as those based on F, and R-values based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Br1	0.49690 (3)	0.374439 (8)	0.816959 (17)	0.02004 (7)
O1	0.41024 (17)	0.35297 (6)	0.10785 (12)	0.0171 (3)
C1	0.4044 (2)	0.36264 (7)	0.21623 (17)	0.0130 (3)
N2	0.35261 (19)	0.41049 (6)	0.26345 (14)	0.0131 (3)
C3	0.3743 (2)	0.40838 (7)	0.39354 (17)	0.0127 (3)
C4	0.3378 (2)	0.44865 (8)	0.47375 (18)	0.0152 (4)
H4	0.2896	0.4825	0.4435	0.018*
C5	0.3745 (2)	0.43786 (8)	0.60104 (17)	0.0160 (4)
H5	0.3503	0.4646	0.6587	0.019*
C6	0.4460 (2)	0.38823 (8)	0.64338 (16)	0.0140 (4)
C7	0.4822 (2)	0.34757 (7)	0.56274 (16)	0.0129 (3)
H7	0.5311	0.3138	0.5931	0.015*
C8	0.4445 (2)	0.35808 (7)	0.43654 (17)	0.0121 (3)
O9	0.64140 (16)	0.31074 (6)	0.31688 (12)	0.0163 (3)
H9	0.7024	0.3118	0.3877	0.024*
C9	0.4680 (2)	0.32370 (7)	0.32616 (16)	0.0124 (3)
C10	0.3592 (2)	0.27084 (7)	0.31485 (16)	0.0123 (3)
H10	0.3696	0.2511	0.2364	0.015*
O11	0.07782 (17)	0.31156 (5)	0.24552 (12)	0.0169 (3)
C11	0.1692 (2)	0.28271 (7)	0.32180 (16)	0.0127 (3)
N12	0.12428 (19)	0.25919 (6)	0.42372 (14)	0.0137 (3)
N13	0.2659 (2)	0.20205 (7)	0.57992 (15)	0.0166 (3)
H13A	0.356 (3)	0.1946 (9)	0.625 (2)	0.020*
H13B	0.175 (3)	0.2005 (10)	0.608 (2)	0.020*
C13	0.2659 (2)	0.23119 (7)	0.47904 (16)	0.0128 (3)
N14	0.40463 (19)	0.23525 (6)	0.42122 (14)	0.0121 (3)
C14	0.5592 (2)	0.20123 (8)	0.44579 (18)	0.0177 (4)
H14A	0.6453	0.2187	0.5088	0.026*
H14B	0.6073	0.1967	0.3692	0.026*
H14C	0.5288	0.1655	0.4758	0.026*
C15	0.3028 (2)	0.45903 (8)	0.18962 (17)	0.0156 (4)
H15A	0.3328	0.4536	0.1060	0.019*
H15B	0.3718	0.4902	0.2282	0.019*
C16	0.1127 (2)	0.47366 (8)	0.17564 (16)	0.0146 (4)
C17	−0.0132 (3)	0.43353 (8)	0.17080 (19)	0.0197 (4)
H17	0.0203	0.3965	0.1834	0.024*
C18	−0.1880 (3)	0.44717 (8)	0.14763 (19)	0.0204 (4)
H18	−0.2733	0.4195	0.1438	0.024*
C19	−0.2373 (3)	0.50119 (8)	0.13010 (18)	0.0187 (4)
H19	−0.3564	0.5106	0.1133	0.022*
C20	−0.1119 (3)	0.54152 (8)	0.13722 (19)	0.0198 (4)
H20	−0.1454	0.5786	0.1266	0.024*
C21	0.0624 (3)	0.52780 (8)	0.15986 (18)	0.0181 (4)
H21	0.1476	0.5556	0.1646	0.022*
O1S	−0.13483 (17)	0.30418 (6)	0.53172 (13)	0.0191 (3)
H1S	−0.0600	0.2885	0.4975	0.029*
C1S	−0.0616 (3)	0.35257 (9)	0.5930 (2)	0.0249 (4)
H1S1	0.0641	0.3470	0.6199	0.030*
H1S2	−0.1143	0.3588	0.6680	0.030*
C2S	−0.0892 (3)	0.40229 (9)	0.5114 (2)	0.0300 (5)
H2S1	−0.0366	0.3965	0.4372	0.045*
H2S2	−0.0355	0.4339	0.5570	0.045*
H2S3	−0.2135	0.4088	0.4869	0.045*

	U11	U22	U33	U12	U13	U23
Br1	0.02698 (11)	0.02127 (11)	0.01143 (10)	0.00486 (8)	0.00183 (7)	−0.00050 (7)
O1	0.0183 (7)	0.0219 (7)	0.0113 (6)	−0.0017 (6)	0.0030 (5)	0.0000 (5)
C1	0.0084 (8)	0.0169 (9)	0.0139 (9)	−0.0023 (6)	0.0026 (6)	0.0011 (7)
N2	0.0139 (7)	0.0146 (7)	0.0108 (7)	−0.0001 (6)	0.0016 (6)	0.0019 (6)
C3	0.0094 (8)	0.0160 (9)	0.0125 (8)	−0.0025 (7)	0.0010 (6)	0.0011 (7)
C4	0.0140 (8)	0.0131 (8)	0.0180 (9)	0.0005 (7)	0.0014 (7)	0.0005 (7)
C5	0.0157 (9)	0.0167 (9)	0.0157 (9)	−0.0001 (7)	0.0029 (7)	−0.0033 (7)
C6	0.0130 (8)	0.0191 (9)	0.0094 (8)	−0.0015 (7)	0.0005 (7)	−0.0006 (7)
C7	0.0105 (8)	0.0151 (9)	0.0129 (8)	0.0000 (7)	0.0016 (7)	0.0012 (7)
C8	0.0081 (8)	0.0144 (8)	0.0140 (9)	−0.0019 (6)	0.0028 (6)	−0.0006 (7)
O9	0.0104 (6)	0.0260 (7)	0.0129 (6)	0.0032 (5)	0.0033 (5)	−0.0005 (5)
C9	0.0103 (8)	0.0157 (9)	0.0113 (8)	0.0014 (7)	0.0019 (6)	0.0010 (7)
C10	0.0129 (8)	0.0137 (8)	0.0102 (8)	0.0018 (7)	0.0016 (6)	0.0004 (7)
O11	0.0148 (6)	0.0168 (7)	0.0174 (7)	−0.0004 (5)	−0.0025 (5)	0.0033 (5)
C11	0.0111 (8)	0.0121 (8)	0.0138 (9)	−0.0012 (6)	−0.0006 (7)	−0.0023 (7)
N12	0.0112 (7)	0.0151 (7)	0.0144 (7)	0.0011 (6)	0.0013 (6)	0.0023 (6)
N13	0.0123 (8)	0.0232 (9)	0.0146 (8)	0.0022 (7)	0.0033 (6)	0.0049 (6)
C13	0.0123 (8)	0.0130 (8)	0.0128 (8)	−0.0010 (7)	0.0014 (7)	−0.0015 (7)
N14	0.0117 (7)	0.0134 (7)	0.0116 (7)	0.0031 (6)	0.0031 (6)	0.0025 (6)
C14	0.0159 (9)	0.0185 (9)	0.0197 (10)	0.0076 (7)	0.0063 (7)	0.0034 (7)
C15	0.0160 (9)	0.0150 (9)	0.0155 (9)	−0.0009 (7)	0.0019 (7)	0.0044 (7)
C16	0.0168 (9)	0.0173 (9)	0.0095 (8)	0.0000 (7)	0.0017 (7)	0.0019 (7)
C17	0.0192 (10)	0.0152 (9)	0.0243 (10)	0.0004 (7)	0.0026 (8)	0.0040 (8)
C18	0.0175 (9)	0.0189 (10)	0.0254 (10)	−0.0036 (8)	0.0051 (8)	0.0021 (8)
C19	0.0179 (9)	0.0234 (10)	0.0152 (9)	0.0041 (8)	0.0044 (7)	0.0023 (8)
C20	0.0232 (10)	0.0153 (9)	0.0214 (10)	0.0034 (8)	0.0055 (8)	0.0009 (7)
C21	0.0201 (9)	0.0164 (9)	0.0182 (9)	−0.0028 (8)	0.0044 (7)	−0.0006 (7)
O1S	0.0127 (6)	0.0229 (7)	0.0217 (7)	0.0024 (5)	0.0033 (5)	−0.0021 (6)
C1S	0.0218 (10)	0.0275 (11)	0.0240 (11)	0.0005 (9)	−0.0002 (8)	−0.0052 (9)
C2S	0.0239 (11)	0.0286 (12)	0.0376 (13)	−0.0076 (9)	0.0049 (10)	0.0006 (10)

Br1—C6	1.9042 (18)	C13—N14	1.349 (2)
O1—C1	1.217 (2)	N14—C14	1.460 (2)
C1—N2	1.372 (2)	C14—H14A	0.9800
C1—C9	1.552 (2)	C14—H14B	0.9800
N2—C3	1.406 (2)	C14—H14C	0.9800
N2—C15	1.456 (2)	C15—C16	1.516 (3)
C3—C4	1.383 (3)	C15—H15A	0.9900
C3—C8	1.401 (3)	C15—H15B	0.9900
C4—C5	1.399 (3)	C16—C17	1.389 (3)
C4—H4	0.9500	C16—C21	1.389 (3)
C5—C6	1.388 (3)	C17—C18	1.392 (3)
C5—H5	0.9500	C17—H17	0.9500
C6—C7	1.392 (3)	C18—C19	1.386 (3)
C7—C8	1.387 (3)	C18—H18	0.9500
C7—H7	0.9500	C19—C20	1.388 (3)
C8—C9	1.509 (2)	C19—H19	0.9500
O9—C9	1.416 (2)	C20—C21	1.389 (3)
O9—H9	0.8400	C20—H20	0.9500
C9—C10	1.546 (2)	C21—H21	0.9500
C10—N14	1.451 (2)	O1S—C1S	1.436 (3)
C10—C11	1.532 (2)	O1S—H1S	0.8400
C10—H10	1.0000	C1S—C2S	1.506 (3)
O11—C11	1.230 (2)	C1S—H1S1	0.9900
C11—N12	1.353 (2)	C1S—H1S2	0.9900
N12—C13	1.359 (2)	C2S—H2S1	0.9800
N13—C13	1.315 (2)	C2S—H2S2	0.9800
N13—H13A	0.81 (2)	C2S—H2S3	0.9800
N13—H13B	0.82 (2)
O1—C1—N2	126.51 (17)	C13—N14—C10	108.09 (14)
O1—C1—C9	125.11 (17)	C13—N14—C14	125.49 (15)
N2—C1—C9	108.24 (15)	C10—N14—C14	125.31 (15)
C1—N2—C3	110.84 (15)	N14—C14—H14A	109.5
C1—N2—C15	124.14 (16)	N14—C14—H14B	109.5
C3—N2—C15	124.60 (15)	H14A—C14—H14B	109.5
C4—C3—C8	121.89 (17)	N14—C14—H14C	109.5
C4—C3—N2	127.78 (17)	H14A—C14—H14C	109.5
C8—C3—N2	110.31 (16)	H14B—C14—H14C	109.5
C3—C4—C5	117.77 (17)	N2—C15—C16	114.75 (15)
C3—C4—H4	121.1	N2—C15—H15A	108.6
C5—C4—H4	121.1	C16—C15—H15A	108.6
C6—C5—C4	120.19 (17)	N2—C15—H15B	108.6
C6—C5—H5	119.9	C16—C15—H15B	108.6
C4—C5—H5	119.9	H15A—C15—H15B	107.6
C5—C6—C7	122.12 (17)	C17—C16—C21	119.26 (18)
C5—C6—Br1	119.66 (14)	C17—C16—C15	121.06 (17)
C7—C6—Br1	118.22 (14)	C21—C16—C15	119.56 (17)
C8—C7—C6	117.69 (17)	C16—C17—C18	120.50 (18)
C8—C7—H7	121.2	C16—C17—H17	119.7
C6—C7—H7	121.2	C18—C17—H17	119.7
C7—C8—C3	120.34 (17)	C19—C18—C17	119.93 (18)
C7—C8—C9	131.13 (17)	C19—C18—H18	120.0
C3—C8—C9	108.53 (15)	C17—C18—H18	120.0
C9—O9—H9	109.5	C18—C19—C20	119.74 (18)
O9—C9—C8	115.38 (15)	C18—C19—H19	120.1
O9—C9—C10	109.18 (14)	C20—C19—H19	120.1
C8—C9—C10	113.26 (14)	C19—C20—C21	120.23 (18)
O9—C9—C1	105.76 (14)	C19—C20—H20	119.9
C8—C9—C1	102.06 (14)	C21—C20—H20	119.9
C10—C9—C1	110.69 (14)	C20—C21—C16	120.32 (18)
N14—C10—C11	100.72 (14)	C20—C21—H21	119.8
N14—C10—C9	112.50 (14)	C16—C21—H21	119.8
C11—C10—C9	111.34 (14)	C1S—O1S—H1S	109.5
N14—C10—H10	110.6	O1S—C1S—C2S	112.79 (18)
C11—C10—H10	110.6	O1S—C1S—H1S1	109.0
C9—C10—H10	110.6	C2S—C1S—H1S1	109.0
O11—C11—N12	127.07 (17)	O1S—C1S—H1S2	109.0
O11—C11—C10	122.53 (16)	C2S—C1S—H1S2	109.0
N12—C11—C10	110.35 (15)	H1S1—C1S—H1S2	107.8
C11—N12—C13	106.12 (15)	C1S—C2S—H2S1	109.5
C13—N13—H13A	121.0 (16)	C1S—C2S—H2S2	109.5
C13—N13—H13B	117.3 (16)	H2S1—C2S—H2S2	109.5
H13A—N13—H13B	118 (2)	C1S—C2S—H2S3	109.5
N13—C13—N14	123.05 (17)	H2S1—C2S—H2S3	109.5
N13—C13—N12	122.36 (16)	H2S2—C2S—H2S3	109.5
N14—C13—N12	114.59 (16)
O1—C1—N2—C3	−175.80 (17)	C8—C9—C10—N14	−61.17 (19)
C9—C1—N2—C3	0.11 (19)	C1—C9—C10—N14	−175.10 (14)
O1—C1—N2—C15	−2.9 (3)	O9—C9—C10—C11	−178.91 (14)
C9—C1—N2—C15	172.95 (15)	C8—C9—C10—C11	51.04 (19)
C1—N2—C3—C4	179.53 (18)	C1—C9—C10—C11	−62.89 (18)
C15—N2—C3—C4	6.7 (3)	N14—C10—C11—O11	−178.92 (16)
C1—N2—C3—C8	0.7 (2)	C9—C10—C11—O11	61.6 (2)
C15—N2—C3—C8	−172.11 (16)	N14—C10—C11—N12	3.60 (19)
C8—C3—C4—C5	0.4 (3)	C9—C10—C11—N12	−115.88 (16)
N2—C3—C4—C5	−178.32 (17)	O11—C11—N12—C13	179.74 (18)
C3—C4—C5—C6	0.4 (3)	C10—C11—N12—C13	−2.93 (19)
C4—C5—C6—C7	−0.6 (3)	C11—N12—C13—N13	−178.18 (17)
C4—C5—C6—Br1	179.46 (14)	C11—N12—C13—N14	1.0 (2)
C5—C6—C7—C8	0.0 (3)	N13—C13—N14—C10	−179.41 (17)
Br1—C6—C7—C8	179.97 (13)	N12—C13—N14—C10	1.4 (2)
C6—C7—C8—C3	0.7 (3)	N13—C13—N14—C14	12.2 (3)
C6—C7—C8—C9	179.66 (17)	N12—C13—N14—C14	−167.02 (17)
C4—C3—C8—C7	−1.0 (3)	C11—C10—N14—C13	−2.85 (18)
N2—C3—C8—C7	177.94 (15)	C9—C10—N14—C13	115.79 (16)
C4—C3—C8—C9	179.88 (16)	C11—C10—N14—C14	165.59 (16)
N2—C3—C8—C9	−1.21 (19)	C9—C10—N14—C14	−75.8 (2)
C7—C8—C9—O9	−63.7 (3)	C1—N2—C15—C16	111.7 (2)
C3—C8—C9—O9	115.31 (17)	C3—N2—C15—C16	−76.5 (2)
C7—C8—C9—C10	63.1 (2)	N2—C15—C16—C17	−33.1 (3)
C3—C8—C9—C10	−117.84 (16)	N2—C15—C16—C21	150.87 (17)
C7—C8—C9—C1	−177.84 (18)	C21—C16—C17—C18	1.4 (3)
C3—C8—C9—C1	1.18 (18)	C15—C16—C17—C18	−174.63 (18)
O1—C1—C9—O9	54.1 (2)	C16—C17—C18—C19	−0.5 (3)
N2—C1—C9—O9	−121.83 (15)	C17—C18—C19—C20	−0.8 (3)
O1—C1—C9—C8	175.19 (17)	C18—C19—C20—C21	1.0 (3)
N2—C1—C9—C8	−0.78 (18)	C19—C20—C21—C16	0.0 (3)
O1—C1—C9—C10	−64.0 (2)	C17—C16—C21—C20	−1.2 (3)
N2—C1—C9—C10	120.05 (16)	C15—C16—C21—C20	174.94 (17)
O9—C9—C10—N14	68.89 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O1Si	0.84	1.87	2.694 (2)	169
N13—H13A···O11ii	0.81 (2)	2.00 (2)	2.811 (2)	171 (2)
N13—H13B···O9iii	0.82 (2)	2.36 (2)	2.933 (2)	128 (2)
N13—H13B···O1iii	0.82 (2)	2.46 (2)	3.158 (2)	144 (2)
O1S—H1S···N12	0.84	1.91	2.745 (2)	174

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9⋯O1S i	0.84	1.87	2.694 (2)	169
N13—H13A⋯O11ii	0.81 (2)	2.00 (2)	2.811 (2)	171 (2)
N13—H13B⋯O9iii	0.82 (2)	2.36 (2)	2.933 (2)	128 (2)
N13—H13B⋯O1iii	0.82 (2)	2.46 (2)	3.158 (2)	144 (2)
O1S—H1S⋯N12	0.84	1.91	2.745 (2)	174

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