10,16-Dichloro-6,20-dioxa-3,23-diaza-tetra-cyclo-[23.3.1.0.0]nona-cosa-1(29),7,9,11,14(19),15,17,25,27-nona-ene-4,22-dione methanol monosolvate.

In the title compound, C(25)H(22)Cl(2)N(2)O(4)·CH(3)OH, the macrocyclic mol-ecule adopts a slightly distorted C(2)-symmetric conformation. The macrocyclic mol-ecules are linked via N-H⋯O hydrogen bonds between the amide groups into chains extending along the [010] direction. The methanol mol-ecules bridge these chains via N-H⋯O and O-H⋯O hydrogen bonds with the formation of a two-dimensional polymeric structure parallel to (001). The methanol mol-ecule is disordered over two positions with the occupancy ratio of 9:1. The disorder of the solvent molecule is caused by weak intermolecular C-H⋯Cl hydrogen bonding.

Related literature

For application of macrocycles, see: Hayvali & Hayvali (2005 ▶); Kleinpeter et al. (1997 ▶); Jaiyu et al. (2007 ▶); Christensen et al. (1997 ▶); Alexander (1995 ▶). For the synthetic procedure, see: Ertul et al. (2009 ▶).

Experimental

Crystal data

C25H22Cl2N2O4·CH4O

M = 517.39

Orthorhombic,

a = 21.9905 (3) Å

b = 8.1864 (1) Å

c = 26.6760 (3) Å

V = 4802.29 (10) Å3

Z = 8

Cu Kα radiation

μ = 2.78 mm−1

T = 120 K

0.30 × 0.11 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur A Gemini Ultra diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.826, T max = 1.000

42959 measured reflections

4099 independent reflections

3364 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.082

S = 1.03

4099 reflections

326 parameters

4 restraints

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812007052/gk2457sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007052/gk2457Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812007052/gk2457Isup3.cml

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

C25H22Cl2N2O4·CH4O	Dx = 1.431 Mg m−3
Mr = 517.39	Melting point = 316–318 K
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6415 reflections
a = 21.9905 (3) Å	θ = 3.3–67.1°
b = 8.1864 (1) Å	µ = 2.78 mm−1
c = 26.6760 (3) Å	T = 120 K
V = 4802.29 (10) Å3	Prism, colourless
Z = 8	0.30 × 0.11 × 0.08 mm
F(000) = 2160

Oxford Diffraction Xcalibur A Gemini Ultra diffractometer	4099 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	3364 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.070
Detector resolution: 10.3784 pixels mm-1	θmax = 65.1°, θmin = 3.3°
ω scan	h = −22→25
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −9→9
Tmin = 0.826, Tmax = 1.000	l = −29→31
42959 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0358P)2 + 2.1383P] where P = (Fo2 + 2Fc2)/3
4099 reflections	(Δ/σ)max = 0.002
326 parameters	Δρmax = 0.20 e Å−3
4 restraints	Δρmin = −0.21 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-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 > σ(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. Positions of disordered groups were found from electron density maps. The disordered fragments were then placed in appropriate positions, and all distances between neighbouring atoms were fixed. Site occupancies were refined for the different parts with the same thermal parameters for same atoms in various fragments. At the end of the refinement, site occupancies were fixed at values 0.90 and 0.10 and hydrogen atoms were placed into calculated positions. All hydrogen atoms could be found from maps of difference electron density, but those, attached to carbon atoms, were placed into calculated positions. The distance between N and H atoms were restrained to 1.00 Å with σ=0.02. The isotropic temperature parameters of hydrogen atoms were calculated as 1.2*Ueq of the parent atom.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	1.11069 (2)	0.02416 (7)	0.213524 (18)	0.03911 (14)
Cl2	0.84287 (2)	−0.21013 (7)	0.147714 (18)	0.03856 (14)
O1	0.70542 (6)	0.38705 (18)	0.40933 (5)	0.0367 (3)
O2	0.80594 (5)	0.19883 (17)	0.32491 (5)	0.0305 (3)
O3	0.96571 (6)	−0.16498 (18)	0.38954 (5)	0.0322 (3)
O4	0.98144 (6)	−0.1787 (2)	0.52219 (5)	0.0406 (4)
N1	0.80833 (7)	0.38887 (19)	0.40351 (6)	0.0277 (3)
H1N2	0.8870	−0.1436	0.4391	0.033*
N2	0.89913 (7)	−0.14110 (19)	0.47251 (5)	0.0262 (3)
H1N1	0.8439	0.3425	0.3862	0.031*
C1	0.81828 (9)	0.4614 (2)	0.45255 (7)	0.0315 (4)
H1A	0.7853	0.5366	0.4597	0.038*
H1B	0.8557	0.5239	0.4517	0.038*
C2	0.75257 (8)	0.3497 (2)	0.38745 (7)	0.0266 (4)
C3	0.74788 (8)	0.2590 (2)	0.33841 (7)	0.0265 (4)
H3A	0.7195	0.1690	0.3417	0.032*
H3B	0.7329	0.3318	0.3125	0.032*
C4	0.81162 (8)	0.1097 (2)	0.28177 (6)	0.0240 (4)
C5	0.76696 (8)	0.0977 (2)	0.24538 (7)	0.0267 (4)
H5	0.7306	0.1547	0.2489	0.032*
C6	0.77682 (8)	0.0000 (2)	0.20357 (7)	0.0289 (4)
H6	0.7472	−0.0093	0.1788	0.035*
C7	0.83113 (8)	−0.0828 (2)	0.19935 (7)	0.0276 (4)
C8	0.87611 (8)	−0.0703 (2)	0.23554 (7)	0.0255 (4)
H8	0.9124	−0.1273	0.2317	0.031*
C9	0.86718 (8)	0.0266 (2)	0.27735 (7)	0.0242 (4)
C10	0.91217 (8)	0.0476 (3)	0.31990 (7)	0.0338 (5)
H10A	0.9167	0.1636	0.3263	0.041*
H10B	0.8947	−0.0011	0.3498	0.041*
C11	0.97467 (8)	−0.0239 (2)	0.31231 (7)	0.0283 (4)
C12	1.00962 (8)	0.0216 (2)	0.27119 (7)	0.0296 (4)
H12	0.9936	0.0927	0.2474	0.035*
C13	1.06813 (8)	−0.0383 (2)	0.26540 (7)	0.0298 (4)
C14	1.09288 (8)	−0.1440 (3)	0.29985 (7)	0.0317 (4)
H14	1.1320	−0.1849	0.2953	0.038*
C15	1.05893 (9)	−0.1890 (3)	0.34134 (7)	0.0313 (4)
H15	1.0753	−0.2604	0.3649	0.038*
C16	1.00041 (8)	−0.1277 (2)	0.34793 (7)	0.0275 (4)
C17	0.99810 (9)	−0.1964 (3)	0.43499 (7)	0.0345 (5)
H17A	1.0330	−0.1243	0.4370	0.041*
H17B	1.0128	−0.3081	0.4348	0.041*
C18	0.95804 (9)	−0.1705 (2)	0.48030 (7)	0.0291 (4)
C19	0.85686 (9)	−0.1157 (2)	0.51386 (7)	0.0287 (4)
H19A	0.8741	−0.1632	0.5440	0.034*
H19B	0.8194	−0.1736	0.5066	0.034*
C20	0.84194 (8)	0.0621 (2)	0.52404 (7)	0.0261 (4)
C21	0.82821 (8)	0.1118 (3)	0.57256 (7)	0.0307 (4)
H21	0.8297	0.0368	0.5987	0.037*
C22	0.81235 (9)	0.2726 (3)	0.58206 (7)	0.0350 (5)
H22	0.8037	0.3052	0.6147	0.042*
C23	0.80922 (8)	0.3850 (3)	0.54350 (8)	0.0321 (4)
H23	0.7985	0.4927	0.5503	0.039*
C24	0.82213 (8)	0.3373 (2)	0.49450 (7)	0.0271 (4)
C25	0.83856 (8)	0.1760 (2)	0.48543 (7)	0.0264 (4)
H25	0.8475	0.1435	0.4528	0.032*
O5	0.94522 (11)	0.3414 (4)	0.40875 (11)	0.0418 (7)	0.90
H1O5	0.9545	0.2931	0.4346	0.050*	0.90
C26	0.99892 (15)	0.3791 (5)	0.38117 (9)	0.0415 (7)	0.90
H26A	0.9904	0.4652	0.3578	0.050*	0.90
H26B	1.0123	0.2838	0.3633	0.050*	0.90
H26C	1.0303	0.4138	0.4039	0.050*	0.90
O5A	0.9587 (14)	0.374 (5)	0.4090 (12)	0.0418 (7)	0.10
H2O5	0.9634	0.2905	0.4254	0.050*	0.10
C26A	0.9961 (18)	0.367 (6)	0.3651 (11)	0.0415 (7)	0.10
H26D	0.9888	0.4625	0.3449	0.050*	0.10
H26E	0.9863	0.2711	0.3462	0.050*	0.10
H26F	1.0381	0.3642	0.3748	0.050*	0.10

	U11	U22	U33	U12	U13	U23
Cl1	0.0270 (2)	0.0524 (3)	0.0380 (3)	−0.0081 (2)	0.00832 (19)	−0.0091 (2)
Cl2	0.0337 (3)	0.0480 (3)	0.0339 (3)	−0.0041 (2)	0.00026 (19)	−0.0116 (2)
O1	0.0250 (7)	0.0434 (9)	0.0417 (8)	0.0047 (6)	0.0079 (6)	−0.0067 (7)
O2	0.0183 (6)	0.0437 (8)	0.0294 (7)	0.0064 (6)	0.0010 (5)	−0.0059 (6)
O3	0.0221 (6)	0.0499 (9)	0.0245 (6)	0.0021 (6)	−0.0020 (5)	−0.0013 (6)
O4	0.0343 (8)	0.0595 (10)	0.0279 (7)	0.0096 (7)	−0.0066 (6)	0.0019 (7)
N1	0.0236 (8)	0.0284 (8)	0.0311 (8)	0.0029 (7)	0.0014 (6)	0.0015 (7)
N2	0.0254 (8)	0.0302 (9)	0.0230 (7)	0.0009 (7)	−0.0009 (6)	−0.0013 (6)
C1	0.0290 (10)	0.0283 (10)	0.0372 (11)	0.0017 (8)	−0.0014 (8)	−0.0044 (8)
C2	0.0242 (9)	0.0240 (10)	0.0315 (9)	0.0042 (8)	0.0035 (8)	0.0059 (8)
C3	0.0185 (8)	0.0298 (10)	0.0313 (9)	0.0057 (8)	0.0024 (7)	0.0050 (8)
C4	0.0216 (9)	0.0264 (9)	0.0241 (9)	−0.0010 (8)	0.0028 (7)	0.0051 (7)
C5	0.0184 (9)	0.0314 (10)	0.0302 (10)	0.0002 (8)	0.0002 (7)	0.0092 (8)
C6	0.0232 (9)	0.0359 (11)	0.0276 (10)	−0.0049 (8)	−0.0033 (7)	0.0064 (8)
C7	0.0261 (9)	0.0306 (10)	0.0260 (9)	−0.0053 (8)	0.0020 (7)	0.0013 (8)
C8	0.0208 (9)	0.0279 (10)	0.0277 (9)	−0.0002 (8)	0.0029 (7)	0.0043 (8)
C9	0.0194 (8)	0.0284 (10)	0.0247 (9)	−0.0012 (8)	0.0021 (7)	0.0058 (7)
C10	0.0218 (9)	0.0515 (13)	0.0280 (10)	0.0097 (9)	−0.0010 (8)	−0.0040 (9)
C11	0.0196 (9)	0.0398 (11)	0.0256 (9)	0.0026 (8)	−0.0024 (7)	−0.0082 (8)
C12	0.0233 (9)	0.0364 (11)	0.0290 (9)	0.0024 (8)	−0.0018 (8)	−0.0056 (8)
C13	0.0212 (9)	0.0383 (11)	0.0300 (10)	−0.0042 (8)	0.0019 (7)	−0.0109 (8)
C14	0.0186 (9)	0.0406 (12)	0.0359 (10)	0.0022 (8)	−0.0019 (8)	−0.0131 (9)
C15	0.0248 (10)	0.0374 (11)	0.0317 (10)	0.0055 (8)	−0.0048 (8)	−0.0076 (8)
C16	0.0207 (9)	0.0356 (11)	0.0262 (9)	−0.0002 (8)	−0.0017 (7)	−0.0074 (8)
C17	0.0294 (10)	0.0463 (13)	0.0278 (10)	0.0091 (9)	−0.0037 (8)	−0.0014 (9)
C18	0.0291 (10)	0.0313 (11)	0.0271 (10)	0.0028 (8)	−0.0027 (8)	0.0004 (8)
C19	0.0264 (9)	0.0326 (11)	0.0270 (9)	−0.0017 (8)	0.0027 (7)	0.0020 (8)
C20	0.0177 (8)	0.0335 (10)	0.0271 (9)	−0.0020 (8)	−0.0015 (7)	−0.0035 (8)
C21	0.0236 (9)	0.0434 (12)	0.0251 (9)	−0.0008 (9)	−0.0002 (7)	0.0004 (8)
C22	0.0286 (10)	0.0494 (13)	0.0271 (10)	0.0025 (9)	0.0009 (8)	−0.0109 (9)
C23	0.0235 (9)	0.0346 (11)	0.0383 (11)	0.0034 (9)	−0.0017 (8)	−0.0098 (9)
C24	0.0176 (9)	0.0334 (11)	0.0301 (10)	−0.0008 (8)	−0.0022 (7)	−0.0048 (8)
C25	0.0215 (9)	0.0334 (11)	0.0245 (9)	−0.0007 (8)	0.0011 (7)	−0.0047 (8)
O5	0.0243 (15)	0.0620 (19)	0.0390 (8)	0.0036 (10)	−0.0010 (10)	0.0116 (10)
C26	0.0367 (13)	0.0549 (17)	0.0330 (17)	−0.0057 (12)	−0.0024 (16)	0.0023 (19)
O5A	0.0243 (15)	0.0620 (19)	0.0390 (8)	0.0036 (10)	−0.0010 (10)	0.0116 (10)
C26A	0.0367 (13)	0.0549 (17)	0.0330 (17)	−0.0057 (12)	−0.0024 (16)	0.0023 (19)

Cl1—C13	1.7470 (19)	C11—C16	1.395 (3)
Cl2—C7	1.7466 (19)	C12—C13	1.386 (3)
O1—C2	1.229 (2)	C12—H12	0.9300
O2—C4	1.368 (2)	C13—C14	1.375 (3)
O2—C3	1.415 (2)	C14—C15	1.385 (3)
O3—C16	1.381 (2)	C14—H14	0.9300
O3—C17	1.430 (2)	C15—C16	1.392 (3)
O4—C18	1.232 (2)	C15—H15	0.9300
N1—C2	1.338 (2)	C17—C18	1.511 (3)
N1—C1	1.453 (2)	C17—H17A	0.9700
N1—H1N1	0.9840	C17—H17B	0.9700
N2—C18	1.334 (2)	C19—C20	1.517 (3)
N2—C19	1.458 (2)	C19—H19A	0.9700
N2—H1N2	0.9295	C19—H19B	0.9700
C1—C24	1.514 (3)	C20—C21	1.390 (3)
C1—H1A	0.9700	C20—C25	1.391 (3)
C1—H1B	0.9700	C21—C22	1.385 (3)
C2—C3	1.507 (3)	C21—H21	0.9300
C3—H3A	0.9700	C22—C23	1.382 (3)
C3—H3B	0.9700	C22—H22	0.9300
C4—C5	1.384 (3)	C23—C24	1.394 (3)
C4—C9	1.404 (3)	C23—H23	0.9300
C5—C6	1.389 (3)	C24—C25	1.391 (3)
C5—H5	0.9300	C25—H25	0.9300
C6—C7	1.378 (3)	O5—C26	1.425 (3)
C6—H6	0.9300	O5—H1O5	0.8200
C7—C8	1.386 (3)	C26—H26A	0.9600
C8—C9	1.383 (3)	C26—H26B	0.9600
C8—H8	0.9300	C26—H26C	0.9600
C9—C10	1.516 (3)	O5A—C26A	1.430 (19)
C10—C11	1.508 (3)	O5A—H2O5	0.8200
C10—H10A	0.9700	C26A—H26D	0.9600
C10—H10B	0.9700	C26A—H26E	0.9600
C11—C12	1.390 (3)	C26A—H26F	0.9600
C4—O2—C3	118.82 (14)	C14—C13—C12	121.06 (18)
C16—O3—C17	116.49 (14)	C14—C13—Cl1	120.10 (14)
C2—N1—C1	121.63 (16)	C12—C13—Cl1	118.83 (16)
C2—N1—H1N1	119.0	C13—C14—C15	119.22 (17)
C1—N1—H1N1	117.4	C13—C14—H14	120.4
C18—N2—C19	121.82 (15)	C15—C14—H14	120.4
C18—N2—H1N2	115.1	C14—C15—C16	120.21 (19)
C19—N2—H1N2	123.0	C14—C15—H15	119.9
N1—C1—C24	113.56 (16)	C16—C15—H15	119.9
N1—C1—H1A	108.9	O3—C16—C15	122.18 (17)
C24—C1—H1A	108.9	O3—C16—C11	117.25 (16)
N1—C1—H1B	108.9	C15—C16—C11	120.58 (18)
C24—C1—H1B	108.9	O3—C17—C18	111.27 (15)
H1A—C1—H1B	107.7	O3—C17—H17A	109.4
O1—C2—N1	124.17 (18)	C18—C17—H17A	109.4
O1—C2—C3	118.49 (17)	O3—C17—H17B	109.4
N1—C2—C3	117.30 (16)	C18—C17—H17B	109.4
O2—C3—C2	109.29 (15)	H17A—C17—H17B	108.0
O2—C3—H3A	109.8	O4—C18—N2	123.83 (18)
C2—C3—H3A	109.8	O4—C18—C17	118.33 (17)
O2—C3—H3B	109.8	N2—C18—C17	117.84 (16)
C2—C3—H3B	109.8	N2—C19—C20	114.22 (15)
H3A—C3—H3B	108.3	N2—C19—H19A	108.7
O2—C4—C5	124.25 (16)	C20—C19—H19A	108.7
O2—C4—C9	114.12 (15)	N2—C19—H19B	108.7
C5—C4—C9	121.62 (17)	C20—C19—H19B	108.7
C4—C5—C6	119.53 (17)	H19A—C19—H19B	107.6
C4—C5—H5	120.2	C21—C20—C25	118.80 (18)
C6—C5—H5	120.2	C21—C20—C19	119.64 (17)
C7—C6—C5	118.96 (17)	C25—C20—C19	121.47 (16)
C7—C6—H6	120.5	C22—C21—C20	120.21 (19)
C5—C6—H6	120.5	C22—C21—H21	119.9
C6—C7—C8	121.69 (18)	C20—C21—H21	119.9
C6—C7—Cl2	119.10 (14)	C23—C22—C21	120.62 (18)
C8—C7—Cl2	119.19 (15)	C23—C22—H22	119.7
C9—C8—C7	120.19 (17)	C21—C22—H22	119.7
C9—C8—H8	119.9	C22—C23—C24	120.08 (19)
C7—C8—H8	119.9	C22—C23—H23	120.0
C8—C9—C4	118.01 (16)	C24—C23—H23	120.0
C8—C9—C10	125.23 (16)	C25—C24—C23	118.84 (18)
C4—C9—C10	116.75 (16)	C25—C24—C1	121.56 (17)
C11—C10—C9	116.76 (16)	C23—C24—C1	119.60 (18)
C11—C10—H10A	108.1	C24—C25—C20	121.43 (17)
C9—C10—H10A	108.1	C24—C25—H25	119.3
C11—C10—H10B	108.1	C20—C25—H25	119.3
C9—C10—H10B	108.1	C26—O5—H1O5	109.5
H10A—C10—H10B	107.3	C26A—O5A—H2O5	109.5
C12—C11—C16	118.45 (17)	O5A—C26A—H26D	109.5
C12—C11—C10	120.39 (18)	O5A—C26A—H26E	109.5
C16—C11—C10	121.00 (17)	H26D—C26A—H26E	109.5
C13—C12—C11	120.43 (19)	O5A—C26A—H26F	109.5
C13—C12—H12	119.8	H26D—C26A—H26F	109.5
C11—C12—H12	119.8	H26E—C26A—H26F	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O5	0.98	2.31	3.039 (3)	130
N2—H1N2···O1i	0.93	2.20	2.860 (2)	128
O5—H1O5···O4ii	0.82	2.05	2.789 (3)	150
C26A—H26F···Cl2iii	0.96	2.74	3.616 (3)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O5	0.98	2.31	3.039 (3)	130
N2—H1N2⋯O1i	0.93	2.20	2.860 (2)	128
O5—H1O5⋯O4ii	0.82	2.05	2.789 (3)	150
C26A—H26F⋯Cl2iii	0.96	2.74	3.616 (3)	149

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