1D and 2D coordination polymers with a new rigid chelating linker: diacetylenedisalicylic acid

Di­acetyl­enedisalicylic acid is a new rigid linker molecule, capable of forming strong chelate bonds with metal cations. Its monosubstituted salts with di­methyl­amine and sodium form 1D and 2D coordination polymers, whose structures were solved from single crystals, along with the di­methyl ester of di­acetyl­enedisalicylic acid. The structure of the di­methyl ester is characterized by a dense co-facial π-stacking of molecules with a dominance of van der Waals interactions between the stacks. The angle between the stack direction and the butadiyne groups does not meet the Enkelmann criterion for polymerization in a crystal. In contrast to the dimethyl ester, both salts have a rigid framework with channels filled with disordered solvent molecules. Photoluminescence spectra of the acid and its di­methyl ester have been studied. Thermal analysis of the acid confirms its high thermal stability to 286°C. The acid and its di­methyl ester are prone to polymerization on further heating followed by 50–52% mass loss, forming an amorphous carbon residue at 1000°C.

Computing details

(1)

Crystal data

C20H14O6	F(000) = 364
Mr = 350.31	Dx = 1.503 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 3.82699 (9) Å	Cell parameters from 4879 reflections
b = 35.3044 (7) Å	θ = 2.5–78.1°
c = 5.73042 (13) Å	µ = 0.94 mm^−1
β = 90.336 (2)°	T = 100 K
V = 774.22 (3) Å^3	Prism, clear yellow
Z = 2	0.22 × 0.1 × 0.08 mm

Data collection

XtaLAB Synergy, Single source at home/near, HyPix diffractometer	1474 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1356 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.033
Detector resolution: 10.0000 pixels mm^-1	θmax = 70.0°, θmin = 2.5°
ω scans	h = −4→4
Absorption correction: multi-scan CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −43→41
Tmin = 0.603, Tmax = 1.000	l = −6→6
7056 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0786P)^2 + 0.2117P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
1474 reflections	Δρmax = 0.34 e Å^−3
120 parameters	Δρmin = −0.17 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
O1	0.0856 (3)	0.67984 (2)	0.76320 (16)	0.0248 (3)
O2	0.6009 (3)	0.64716 (3)	0.15441 (16)	0.0263 (3)
H2	0.550831	0.669197	0.198165	0.039*
O3	0.3411 (3)	0.69885 (2)	0.43180 (17)	0.0277 (3)
C1	0.3117 (3)	0.63277 (3)	0.5182 (2)	0.0191 (3)
C2	0.4809 (3)	0.62192 (4)	0.3115 (2)	0.0200 (3)
C3	0.5323 (3)	0.58356 (4)	0.2641 (2)	0.0214 (3)
H3	0.644517	0.576091	0.124060	0.026*
C4	0.4209 (3)	0.55655 (4)	0.4196 (2)	0.0206 (3)
H4	0.456440	0.530520	0.385112	0.025*
C5	0.2550 (3)	0.56674 (3)	0.6291 (2)	0.0191 (3)
C6	0.2008 (3)	0.60503 (3)	0.6762 (2)	0.0189 (3)
H6	0.087875	0.612362	0.816380	0.023*
C7	0.1417 (3)	0.53813 (3)	0.7882 (2)	0.0197 (3)
C8	0.0506 (3)	0.51366 (3)	0.9228 (2)	0.0196 (3)
C9	0.2504 (3)	0.67330 (3)	0.5641 (2)	0.0209 (3)
C10	0.0188 (4)	0.71897 (4)	0.8198 (3)	0.0267 (3)
H10A	−0.138047	0.729958	0.702172	0.040*
H10B	0.239709	0.733004	0.821959	0.040*
H10C	−0.090630	0.720523	0.973668	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0335 (6)	0.0154 (5)	0.0257 (5)	0.0022 (4)	0.0050 (4)	0.0009 (3)
O2	0.0336 (6)	0.0219 (5)	0.0233 (5)	−0.0028 (4)	0.0050 (4)	0.0052 (4)
O3	0.0391 (6)	0.0165 (5)	0.0277 (5)	−0.0034 (4)	0.0039 (4)	0.0038 (4)
C1	0.0203 (6)	0.0167 (6)	0.0203 (7)	−0.0014 (5)	−0.0020 (5)	0.0012 (5)
C2	0.0195 (6)	0.0217 (7)	0.0188 (6)	−0.0024 (5)	−0.0008 (5)	0.0036 (5)
C3	0.0220 (6)	0.0235 (7)	0.0186 (6)	0.0006 (5)	0.0011 (5)	−0.0009 (5)
C4	0.0220 (6)	0.0175 (6)	0.0222 (7)	0.0011 (4)	−0.0013 (5)	−0.0016 (5)
C5	0.0202 (6)	0.0167 (6)	0.0205 (6)	−0.0006 (5)	−0.0013 (5)	0.0011 (5)
C6	0.0202 (6)	0.0182 (6)	0.0183 (6)	−0.0007 (4)	0.0004 (5)	0.0003 (4)
C7	0.0215 (6)	0.0169 (6)	0.0209 (6)	0.0011 (5)	0.0002 (5)	−0.0022 (5)
C8	0.0227 (7)	0.0153 (6)	0.0208 (7)	0.0012 (4)	0.0007 (5)	−0.0018 (5)
C9	0.0226 (6)	0.0184 (6)	0.0217 (6)	−0.0016 (5)	−0.0017 (5)	0.0019 (5)
C10	0.0328 (7)	0.0161 (7)	0.0311 (8)	0.0027 (5)	0.0030 (6)	−0.0023 (5)

Geometric parameters (Å, º)

O1—C9	1.3271 (17)	C4—H4	0.9500
O1—C10	1.4418 (15)	C4—C5	1.4078 (18)
O2—H2	0.8400	C5—C6	1.3944 (17)
O2—C2	1.3490 (15)	C5—C7	1.4299 (17)
O3—C9	1.2298 (16)	C6—H6	0.9500
C1—C2	1.4065 (18)	C7—C8	1.2109 (19)
C1—C6	1.4014 (17)	C8—C8^i	1.366 (3)
C1—C9	1.4737 (17)	C10—H10A	0.9800
C2—C3	1.3955 (19)	C10—H10B	0.9800
C3—H3	0.9500	C10—H10C	0.9800
C3—C4	1.3746 (18)
C9—O1—C10	116.48 (11)	C6—C5—C7	121.01 (11)
C2—O2—H2	109.5	C1—C6—H6	119.8
C2—C1—C9	119.29 (12)	C5—C6—C1	120.41 (12)
C6—C1—C2	119.78 (12)	C5—C6—H6	119.8
C6—C1—C9	120.93 (12)	C8—C7—C5	179.03 (14)
O2—C2—C1	122.85 (12)	C7—C8—C8^i	179.21 (17)
O2—C2—C3	117.54 (11)	O1—C9—C1	113.55 (11)
C3—C2—C1	119.61 (12)	O3—C9—O1	122.65 (11)
C2—C3—H3	119.9	O3—C9—C1	123.80 (12)
C4—C3—C2	120.18 (12)	O1—C10—H10A	109.5
C4—C3—H3	119.9	O1—C10—H10B	109.5
C3—C4—H4	119.4	O1—C10—H10C	109.5
C3—C4—C5	121.23 (11)	H10A—C10—H10B	109.5
C5—C4—H4	119.4	H10A—C10—H10C	109.5
C4—C5—C7	120.21 (11)	H10B—C10—H10C	109.5
C6—C5—C4	118.78 (11)
O2—C2—C3—C4	178.91 (11)	C6—C1—C2—C3	0.92 (18)
C1—C2—C3—C4	−0.57 (19)	C6—C1—C9—O1	−0.03 (18)
C2—C1—C6—C5	−0.43 (18)	C6—C1—C9—O3	−179.87 (12)
C2—C1—C9—O1	179.32 (11)	C7—C5—C6—C1	−179.70 (11)
C2—C1—C9—O3	−0.5 (2)	C9—C1—C2—O2	2.10 (19)
C2—C3—C4—C5	−0.3 (2)	C9—C1—C2—C3	−178.45 (11)
C3—C4—C5—C6	0.75 (19)	C9—C1—C6—C5	178.93 (11)
C3—C4—C5—C7	−179.93 (11)	C10—O1—C9—O3	−0.51 (19)
C4—C5—C6—C1	−0.40 (19)	C10—O1—C9—C1	179.65 (11)
C6—C1—C2—O2	−178.54 (11)

Symmetry code: (i) −x, −y+1, −z+2.

(3)

Crystal data

C18H9O6·C2H8N	F(000) = 768
Mr = 367.35	Dx = 1.236 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 11.5705 (2) Å	Cell parameters from 8392 reflections
b = 12.5736 (2) Å	θ = 3.8–78.6°
c = 13.5708 (2) Å	µ = 0.77 mm^−1
β = 91.271 (1)°	T = 100 K
V = 1973.83 (5) Å^3	Prism, clear yellowish colourless
Z = 4	0.13 × 0.1 × 0.08 mm

Data collection

XtaLAB Synergy, Single source at home/near, HyPix diffractometer	3741 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3337 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.026
Detector resolution: 10.0000 pixels mm^-1	θmax = 70.0°, θmin = 4.8°
ω scans	h = −14→14
Absorption correction: multi-scan CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −15→14
Tmin = 0.774, Tmax = 1.000	l = −16→16
14589 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.128	w = 1/[σ^2(Fo^2) + (0.0607P)^2 + 0.7745P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3741 reflections	Δρmax = 0.28 e Å^−3
249 parameters	Δρmin = −0.30 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.30497 (9)	0.58296 (9)	−0.00510 (7)	0.0331 (3)
O2	0.47224 (9)	0.54949 (9)	0.07468 (7)	0.0332 (3)
H2	0.487975	0.520110	0.021034	0.050*	0.5
O3	0.13148 (10)	0.65463 (10)	0.08792 (8)	0.0418 (3)
H3	0.166960	0.630428	0.039455	0.063*
O4	1.02615 (9)	0.55322 (10)	0.73755 (9)	0.0408 (3)
H4	0.971829	0.548322	0.695699	0.061*	0.5
O5	1.04815 (10)	0.59096 (11)	0.89601 (9)	0.0468 (3)
O6	0.88198 (11)	0.65202 (12)	0.99714 (8)	0.0505 (3)
H6	0.949689	0.632465	0.985304	0.076*
C1	0.31881 (12)	0.62347 (11)	0.16473 (10)	0.0260 (3)
C2	0.20258 (13)	0.65562 (12)	0.16780 (11)	0.0313 (3)
C3	0.15631 (13)	0.68925 (14)	0.25664 (11)	0.0389 (4)
H3A	0.077950	0.711599	0.258396	0.047*
C4	0.22328 (14)	0.69030 (14)	0.34178 (11)	0.0370 (4)
H4A	0.191042	0.714245	0.401606	0.044*
C5	0.33892 (12)	0.65625 (11)	0.34091 (10)	0.0283 (3)
C6	0.38461 (12)	0.62409 (11)	0.25180 (10)	0.0263 (3)
H6A	0.463032	0.601884	0.250329	0.032*
C7	0.86290 (12)	0.61587 (12)	0.82344 (10)	0.0290 (3)
C8	0.81740 (14)	0.64883 (13)	0.91359 (11)	0.0343 (3)
C9	0.70163 (14)	0.67899 (14)	0.91811 (11)	0.0373 (4)
H9	0.671070	0.701497	0.979070	0.045*
C10	0.63141 (13)	0.67642 (13)	0.83516 (11)	0.0329 (3)
H10	0.552633	0.696844	0.839406	0.040*
C11	0.67490 (12)	0.64391 (11)	0.74413 (10)	0.0274 (3)
C12	0.79042 (12)	0.61381 (11)	0.74027 (10)	0.0277 (3)
H12	0.820629	0.591246	0.679196	0.033*
C13	0.40839 (12)	0.65291 (12)	0.42954 (10)	0.0298 (3)
C14	0.46930 (12)	0.64886 (12)	0.50296 (10)	0.0293 (3)
C15	0.53963 (12)	0.64575 (12)	0.58526 (10)	0.0293 (3)
C16	0.60219 (12)	0.64362 (12)	0.65761 (10)	0.0290 (3)
C17	0.36785 (12)	0.58345 (11)	0.07081 (10)	0.0281 (3)
C18	0.98673 (13)	0.58396 (13)	0.81876 (12)	0.0345 (3)
N7	1.25505 (11)	0.50938 (12)	0.80501 (10)	0.0386 (3)
H7A	1.271291	0.529706	0.868170	0.046*
H7B	1.182408	0.532417	0.789233	0.046*
C19	1.33669 (17)	0.56152 (15)	0.73988 (14)	0.0491 (4)
H19A	1.328116	0.531930	0.673307	0.074*
H19B	1.415781	0.549474	0.764732	0.074*
H19C	1.320872	0.638067	0.737960	0.074*
C20	1.25676 (16)	0.39324 (14)	0.80011 (13)	0.0448 (4)
H20A	1.237980	0.370312	0.732620	0.067*
H20B	1.199580	0.364235	0.845045	0.067*
H20C	1.333871	0.367308	0.819390	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0352 (6)	0.0413 (6)	0.0225 (5)	0.0044 (4)	−0.0061 (4)	−0.0031 (4)
O2	0.0282 (5)	0.0457 (6)	0.0255 (5)	0.0040 (4)	−0.0011 (4)	−0.0037 (4)
O3	0.0333 (6)	0.0625 (8)	0.0287 (5)	0.0132 (5)	−0.0144 (4)	−0.0132 (5)
O4	0.0268 (5)	0.0499 (7)	0.0455 (7)	0.0005 (5)	−0.0017 (5)	0.0002 (5)
O5	0.0273 (6)	0.0739 (9)	0.0387 (6)	−0.0019 (5)	−0.0113 (5)	0.0098 (6)
O6	0.0418 (7)	0.0808 (10)	0.0280 (6)	0.0077 (6)	−0.0165 (5)	−0.0045 (6)
C1	0.0272 (7)	0.0265 (7)	0.0241 (7)	0.0006 (5)	−0.0039 (5)	−0.0008 (5)
C2	0.0293 (7)	0.0365 (8)	0.0277 (7)	0.0045 (6)	−0.0101 (6)	−0.0060 (6)
C3	0.0279 (7)	0.0539 (10)	0.0347 (8)	0.0115 (7)	−0.0071 (6)	−0.0121 (7)
C4	0.0334 (8)	0.0497 (9)	0.0276 (7)	0.0077 (7)	−0.0049 (6)	−0.0124 (7)
C5	0.0286 (7)	0.0312 (7)	0.0249 (7)	0.0001 (6)	−0.0068 (5)	−0.0018 (5)
C6	0.0244 (7)	0.0282 (7)	0.0261 (7)	0.0001 (5)	−0.0050 (5)	0.0015 (5)
C7	0.0258 (7)	0.0321 (7)	0.0288 (7)	−0.0028 (6)	−0.0058 (5)	0.0036 (6)
C8	0.0356 (8)	0.0432 (9)	0.0237 (7)	0.0005 (6)	−0.0107 (6)	0.0004 (6)
C9	0.0390 (8)	0.0493 (9)	0.0235 (7)	0.0082 (7)	−0.0044 (6)	−0.0045 (6)
C10	0.0292 (7)	0.0412 (8)	0.0281 (7)	0.0062 (6)	−0.0052 (6)	0.0001 (6)
C11	0.0285 (7)	0.0301 (7)	0.0235 (7)	−0.0014 (5)	−0.0063 (5)	0.0020 (5)
C12	0.0284 (7)	0.0308 (7)	0.0238 (7)	−0.0025 (6)	−0.0028 (5)	0.0005 (5)
C13	0.0285 (7)	0.0353 (8)	0.0256 (7)	−0.0002 (6)	−0.0031 (6)	−0.0010 (6)
C14	0.0274 (7)	0.0367 (8)	0.0238 (7)	−0.0011 (6)	−0.0028 (6)	−0.0002 (6)
C15	0.0274 (7)	0.0358 (8)	0.0247 (7)	−0.0010 (6)	−0.0028 (6)	0.0009 (6)
C16	0.0286 (7)	0.0331 (8)	0.0251 (7)	−0.0017 (6)	−0.0036 (6)	0.0007 (5)
C17	0.0305 (7)	0.0297 (7)	0.0240 (7)	−0.0003 (6)	−0.0022 (5)	0.0011 (5)
C18	0.0270 (7)	0.0399 (8)	0.0365 (8)	−0.0040 (6)	−0.0020 (6)	0.0058 (6)
N7	0.0302 (6)	0.0496 (8)	0.0362 (7)	0.0017 (6)	0.0026 (5)	−0.0157 (6)
C19	0.0553 (11)	0.0417 (10)	0.0502 (10)	−0.0061 (8)	−0.0012 (8)	0.0026 (8)
C20	0.0442 (9)	0.0432 (10)	0.0472 (10)	0.0007 (8)	0.0022 (7)	0.0089 (8)

Geometric parameters (Å, º)

O1—C17	1.2479 (17)	C7—C18	1.491 (2)
O2—H2	0.8400	C8—C9	1.395 (2)
O2—C17	1.2810 (18)	C9—H9	0.9500
O3—H3	0.8400	C9—C10	1.374 (2)
O3—C2	1.3463 (17)	C10—H10	0.9500
O4—H4	0.8400	C10—C11	1.405 (2)
O4—C18	1.263 (2)	C11—C12	1.391 (2)
O5—C18	1.2565 (19)	C11—C16	1.4293 (18)
O6—H6	0.8400	C12—H12	0.9500
O6—C8	1.3445 (17)	C13—C14	1.209 (2)
C1—C2	1.406 (2)	C14—C15	1.3678 (19)
C1—C6	1.3913 (18)	C15—C16	1.207 (2)
C1—C17	1.4940 (19)	N7—H7A	0.9100
C2—C3	1.396 (2)	N7—H7B	0.9100
C3—H3A	0.9500	N7—C19	1.463 (2)
C3—C4	1.377 (2)	N7—C20	1.462 (2)
C4—H4A	0.9500	C19—H19A	0.9800
C4—C5	1.405 (2)	C19—H19B	0.9800
C5—C6	1.391 (2)	C19—H19C	0.9800
C5—C13	1.4324 (19)	C20—H20A	0.9800
C6—H6A	0.9500	C20—H20B	0.9800
C7—C8	1.405 (2)	C20—H20C	0.9800
C7—C12	1.3914 (19)
C17—O2—H2	109.5	C10—C11—C16	120.49 (13)
C2—O3—H3	109.5	C12—C11—C10	118.38 (13)
C18—O4—H4	109.5	C12—C11—C16	121.12 (13)
C8—O6—H6	109.5	C7—C12—H12	119.1
C2—C1—C17	120.25 (12)	C11—C12—C7	121.78 (13)
C6—C1—C2	118.62 (13)	C11—C12—H12	119.1
C6—C1—C17	121.03 (12)	C14—C13—C5	178.28 (15)
O3—C2—C1	122.77 (13)	C13—C14—C15	178.87 (16)
O3—C2—C3	117.34 (13)	C16—C15—C14	179.51 (17)
C3—C2—C1	119.89 (13)	C15—C16—C11	178.38 (16)
C2—C3—H3A	119.7	O1—C17—O2	124.34 (13)
C4—C3—C2	120.55 (14)	O1—C17—C1	118.71 (13)
C4—C3—H3A	119.7	O2—C17—C1	116.92 (12)
C3—C4—H4A	119.7	O4—C18—C7	119.06 (13)
C3—C4—C5	120.55 (14)	O5—C18—O4	122.76 (14)
C5—C4—H4A	119.7	O5—C18—C7	118.17 (14)
C4—C5—C13	121.23 (13)	H7A—N7—H7B	107.6
C6—C5—C4	118.45 (13)	C19—N7—H7A	108.7
C6—C5—C13	120.31 (13)	C19—N7—H7B	108.7
C1—C6—H6A	119.0	C20—N7—H7A	108.7
C5—C6—C1	121.92 (13)	C20—N7—H7B	108.7
C5—C6—H6A	119.0	C20—N7—C19	114.23 (13)
C8—C7—C18	119.71 (13)	N7—C19—H19A	109.5
C12—C7—C8	118.75 (13)	N7—C19—H19B	109.5
C12—C7—C18	121.54 (13)	N7—C19—H19C	109.5
O6—C8—C7	122.07 (14)	H19A—C19—H19B	109.5
O6—C8—C9	118.11 (14)	H19A—C19—H19C	109.5
C9—C8—C7	119.82 (13)	H19B—C19—H19C	109.5
C8—C9—H9	119.7	N7—C20—H20A	109.5
C10—C9—C8	120.57 (14)	N7—C20—H20B	109.5
C10—C9—H9	119.7	N7—C20—H20C	109.5
C9—C10—H10	119.7	H20A—C20—H20B	109.5
C9—C10—C11	120.69 (14)	H20A—C20—H20C	109.5
C11—C10—H10	119.7	H20B—C20—H20C	109.5
O3—C2—C3—C4	178.69 (15)	C8—C7—C18—O5	−2.3 (2)
O6—C8—C9—C10	−179.46 (15)	C8—C9—C10—C11	−0.3 (3)
C1—C2—C3—C4	−0.6 (3)	C9—C10—C11—C12	0.4 (2)
C2—C1—C6—C5	−0.5 (2)	C9—C10—C11—C16	−178.61 (15)
C2—C1—C17—O1	2.6 (2)	C10—C11—C12—C7	−0.4 (2)
C2—C1—C17—O2	−175.90 (13)	C12—C7—C8—O6	179.45 (14)
C2—C3—C4—C5	−0.8 (3)	C12—C7—C8—C9	−0.2 (2)
C3—C4—C5—C6	1.6 (2)	C12—C7—C18—O4	−0.8 (2)
C3—C4—C5—C13	−177.52 (15)	C12—C7—C18—O5	177.77 (14)
C4—C5—C6—C1	−0.9 (2)	C13—C5—C6—C1	178.21 (13)
C6—C1—C2—O3	−178.00 (14)	C16—C11—C12—C7	178.60 (13)
C6—C1—C2—C3	1.3 (2)	C17—C1—C2—O3	−1.6 (2)
C6—C1—C17—O1	178.94 (13)	C17—C1—C2—C3	177.67 (14)
C6—C1—C17—O2	0.4 (2)	C17—C1—C6—C5	−176.89 (13)
C7—C8—C9—C10	0.2 (3)	C18—C7—C8—O6	−0.5 (2)
C8—C7—C12—C11	0.3 (2)	C18—C7—C8—C9	179.84 (15)
C8—C7—C18—O4	179.12 (14)	C18—C7—C12—C11	−179.74 (14)

(4)

Crystal data

C48H46N4Na2O16·C3H7NO	Z = 1
Mr = 1053.96	F(000) = 552
Triclinic, P1	Dx = 1.360 Mg m^−3
a = 9.0522 (4) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.7406 (4) Å	Cell parameters from 10007 reflections
c = 15.0867 (5) Å	θ = 3.1–77.3°
α = 71.631 (3)°	µ = 1.00 mm^−1
β = 76.965 (4)°	T = 100 K
γ = 68.737 (4)°	Prism, light yellow
V = 1287.01 (10) Å^3	0.1 × 0.07 × 0.05 mm

Data collection

XtaLAB Synergy, Single source at home/near, HyPix diffractometer	5345 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	4679 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.034
Detector resolution: 10.0000 pixels mm^-1	θmax = 80.5°, θmin = 3.1°
ω scans	h = −11→11
Absorption correction: multi-scan CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −13→9
Tmin = 0.971, Tmax = 1.000	l = −19→17
18234 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.064	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.202	w = 1/[σ^2(Fo^2) + (0.1225P)^2 + 0.7824P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
5345 reflections	Δρmax = 1.00 e Å^−3
372 parameters	Δρmin = −0.51 e Å^−3
58 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O11	0.65549 (18)	0.45098 (15)	0.41275 (10)	0.0308 (3)
O14	0.71521 (19)	1.31577 (15)	−0.42516 (10)	0.0320 (3)
H14	0.697028	1.358481	−0.480734	0.048*
O15	0.84750 (18)	1.46543 (14)	−0.45022 (10)	0.0303 (3)
O12	0.49981 (18)	0.32090 (15)	0.43590 (10)	0.0314 (3)
O16	1.04024 (19)	1.42405 (16)	−0.33526 (11)	0.0336 (4)
O13	0.3610 (2)	0.33157 (17)	0.30316 (11)	0.0375 (4)
H13	0.387848	0.303965	0.357593	0.056*
O18	0.1893 (2)	0.21893 (17)	0.51917 (13)	0.0462 (5)
O17	0.3968 (2)	0.16942 (18)	0.69737 (12)	0.0464 (4)
N1	0.3503 (3)	−0.03196 (19)	0.78528 (14)	0.0389 (5)
C14	0.9754 (3)	1.3267 (2)	−0.27849 (15)	0.0298 (4)
C7	0.5645 (2)	0.4089 (2)	0.38408 (14)	0.0267 (4)
C12	0.8003 (2)	1.1883 (2)	−0.24574 (14)	0.0277 (4)
H12	0.722927	1.164447	−0.264593	0.033*
C13	0.8617 (2)	1.29106 (19)	−0.30655 (14)	0.0259 (4)
C17	0.8064 (2)	1.36382 (19)	−0.40014 (14)	0.0265 (4)
C2	0.5990 (2)	0.5681 (2)	0.22437 (14)	0.0289 (4)
H2	0.668660	0.595927	0.247052	0.035*
N2	0.1485 (3)	0.1133 (2)	0.42373 (18)	0.0512 (6)
C1	0.5652 (3)	0.6276 (2)	0.13179 (14)	0.0304 (4)
C3	0.5324 (2)	0.4686 (2)	0.28400 (14)	0.0268 (4)
C11	0.8519 (3)	1.1201 (2)	−0.15734 (15)	0.0316 (4)
C4	0.4299 (3)	0.4269 (2)	0.25007 (15)	0.0299 (4)
C15	1.0249 (3)	1.2603 (2)	−0.18931 (15)	0.0339 (5)
H15	1.100760	1.285013	−0.169690	0.041*
C19	0.6867 (3)	0.8181 (2)	0.01689 (15)	0.0344 (5)
C16	0.9634 (3)	1.1590 (2)	−0.13007 (15)	0.0348 (5)
H16A	0.997241	1.114609	−0.069476	0.042*
C6	0.4612 (3)	0.5859 (2)	0.09919 (15)	0.0330 (5)
H6	0.436548	0.626365	0.036361	0.040*
C18	0.6332 (3)	0.7304 (2)	0.07025 (15)	0.0344 (5)
C20	0.7446 (3)	0.9207 (2)	−0.04304 (15)	0.0346 (5)
C5	0.3952 (3)	0.4877 (2)	0.15698 (16)	0.0340 (5)
H5	0.325378	0.460504	0.133926	0.041*
C21	0.7926 (3)	1.0123 (2)	−0.09577 (15)	0.0341 (5)
C25	0.1171 (3)	0.2172 (2)	0.46134 (16)	0.0371 (5)
H25	0.030357	0.297481	0.441297	0.044*
C22	0.4099 (3)	0.0747 (3)	0.76830 (18)	0.0437 (5)
H22	0.465006	0.074729	0.814912	0.052*
C23	0.2661 (4)	−0.0377 (3)	0.7177 (2)	0.0507 (6)
H23A	0.257538	0.044529	0.664525	0.076*
H23B	0.158855	−0.040718	0.747120	0.076*
H23C	0.324306	−0.120760	0.695017	0.076*
C24	0.3655 (5)	−0.1360 (3)	0.8727 (2)	0.0633 (9)
H24A	0.427897	−0.119108	0.910473	0.095*
H24B	0.419905	−0.227192	0.860424	0.095*
H24C	0.259100	−0.132826	0.907179	0.095*
C26	0.2859 (6)	−0.0088 (4)	0.4466 (4)	0.0959 (16)
H26A	0.365522	−0.014257	0.390719	0.144*
H26B	0.251932	−0.091504	0.467393	0.144*
H26C	0.332835	−0.003078	0.497138	0.144*
C27	0.0581 (7)	0.1215 (6)	0.3540 (4)	0.122 (2)
H27A	−0.037033	0.203351	0.350490	0.183*
H27B	0.025610	0.038375	0.371225	0.183*
H27C	0.124223	0.128184	0.292553	0.183*
Na1	0.30614 (10)	0.34268 (8)	0.56951 (6)	0.0309 (2)
C28	−0.0980 (16)	0.4409 (14)	−0.0004 (9)	0.069 (2)	0.5
H28	−0.111468	0.497826	−0.062471	0.083*	0.5
O19	−0.1681 (8)	0.3586 (8)	0.0285 (6)	0.111 (2)	0.5
N3	−0.0028 (7)	0.4614 (6)	0.0451 (4)	0.0670 (14)	0.5
C30	0.076 (2)	0.5656 (16)	−0.0038 (13)	0.101 (5)	0.5
H30A	0.189039	0.520035	−0.021952	0.151*	0.5
H30B	0.065801	0.622805	0.037970	0.151*	0.5
H30C	0.025169	0.624117	−0.060268	0.151*	0.5
C29	0.0257 (9)	0.3883 (7)	0.1409 (5)	0.0687 (16)	0.5
H29A	−0.043535	0.329924	0.167789	0.103*	0.5
H29B	0.002319	0.454888	0.178018	0.103*	0.5
H29C	0.137806	0.330228	0.141905	0.103*	0.5
H16	0.988 (4)	1.456 (4)	−0.386 (3)	0.060 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0372 (8)	0.0320 (7)	0.0257 (7)	−0.0152 (6)	−0.0119 (6)	−0.0002 (6)
O14	0.0426 (8)	0.0308 (7)	0.0253 (7)	−0.0166 (6)	−0.0136 (6)	0.0014 (6)
O15	0.0363 (8)	0.0254 (7)	0.0284 (7)	−0.0120 (6)	−0.0117 (6)	0.0020 (5)
O12	0.0369 (8)	0.0317 (7)	0.0262 (7)	−0.0151 (6)	−0.0075 (6)	−0.0010 (6)
O16	0.0377 (8)	0.0352 (8)	0.0302 (8)	−0.0174 (6)	−0.0104 (6)	−0.0002 (6)
O13	0.0477 (9)	0.0408 (8)	0.0308 (8)	−0.0239 (7)	−0.0093 (7)	−0.0036 (6)
O18	0.0704 (12)	0.0332 (8)	0.0441 (10)	−0.0208 (8)	−0.0249 (9)	−0.0046 (7)
O17	0.0542 (11)	0.0391 (9)	0.0377 (9)	−0.0112 (8)	−0.0072 (8)	−0.0020 (6)
N1	0.0468 (11)	0.0312 (9)	0.0331 (10)	−0.0041 (8)	−0.0137 (8)	−0.0043 (8)
C14	0.0315 (10)	0.0284 (10)	0.0277 (10)	−0.0080 (8)	−0.0069 (8)	−0.0043 (8)
C7	0.0282 (9)	0.0250 (9)	0.0247 (9)	−0.0062 (7)	−0.0062 (7)	−0.0039 (7)
C12	0.0318 (10)	0.0251 (9)	0.0242 (9)	−0.0069 (8)	−0.0061 (8)	−0.0043 (7)
C13	0.0288 (9)	0.0230 (9)	0.0230 (9)	−0.0049 (7)	−0.0073 (7)	−0.0029 (7)
C17	0.0286 (9)	0.0225 (9)	0.0260 (9)	−0.0056 (7)	−0.0083 (7)	−0.0026 (7)
C2	0.0312 (10)	0.0287 (10)	0.0260 (10)	−0.0087 (8)	−0.0074 (8)	−0.0045 (8)
N2	0.0562 (13)	0.0489 (12)	0.0568 (14)	−0.0080 (10)	−0.0142 (11)	−0.0299 (11)
C1	0.0336 (10)	0.0294 (10)	0.0250 (10)	−0.0081 (8)	−0.0061 (8)	−0.0032 (8)
C3	0.0266 (9)	0.0256 (9)	0.0254 (10)	−0.0052 (7)	−0.0060 (7)	−0.0045 (7)
C11	0.0349 (10)	0.0278 (10)	0.0260 (10)	−0.0069 (8)	−0.0060 (8)	−0.0008 (8)
C4	0.0320 (10)	0.0289 (10)	0.0288 (10)	−0.0082 (8)	−0.0070 (8)	−0.0069 (8)
C15	0.0337 (11)	0.0394 (11)	0.0286 (10)	−0.0111 (9)	−0.0107 (8)	−0.0046 (9)
C19	0.0394 (11)	0.0347 (11)	0.0260 (10)	−0.0102 (9)	−0.0102 (8)	−0.0012 (8)
C16	0.0366 (11)	0.0376 (11)	0.0253 (10)	−0.0073 (9)	−0.0116 (8)	−0.0014 (8)
C6	0.0384 (11)	0.0336 (10)	0.0246 (10)	−0.0066 (9)	−0.0106 (8)	−0.0050 (8)
C18	0.0387 (11)	0.0342 (11)	0.0260 (10)	−0.0079 (9)	−0.0091 (8)	−0.0029 (8)
C20	0.0403 (11)	0.0355 (11)	0.0250 (10)	−0.0110 (9)	−0.0098 (8)	−0.0009 (8)
C5	0.0358 (11)	0.0362 (11)	0.0327 (11)	−0.0106 (9)	−0.0114 (9)	−0.0086 (9)
C21	0.0374 (11)	0.0329 (11)	0.0272 (10)	−0.0079 (9)	−0.0080 (8)	−0.0021 (8)
C25	0.0440 (12)	0.0311 (10)	0.0356 (11)	−0.0112 (9)	−0.0066 (9)	−0.0076 (9)
C22	0.0500 (14)	0.0395 (12)	0.0389 (11)	−0.0090 (10)	−0.0138 (11)	−0.0067 (8)
C23	0.0613 (17)	0.0413 (13)	0.0507 (15)	−0.0139 (12)	−0.0152 (13)	−0.0105 (11)
C24	0.097 (3)	0.0404 (14)	0.0424 (15)	−0.0110 (15)	−0.0217 (16)	−0.0014 (12)
C26	0.094 (3)	0.068 (2)	0.125 (4)	0.025 (2)	−0.044 (3)	−0.062 (3)
C27	0.130 (4)	0.125 (4)	0.140 (5)	0.007 (3)	−0.077 (4)	−0.087 (4)
Na1	0.0406 (5)	0.0267 (4)	0.0257 (4)	−0.0134 (3)	−0.0054 (3)	−0.0028 (3)
C28	0.056 (5)	0.088 (5)	0.075 (5)	−0.004 (4)	−0.013 (4)	−0.054 (4)
O19	0.071 (4)	0.130 (5)	0.171 (7)	−0.039 (4)	0.005 (4)	−0.096 (5)
N3	0.047 (3)	0.079 (3)	0.092 (3)	0.000 (2)	−0.028 (3)	−0.053 (3)
C30	0.059 (6)	0.093 (7)	0.108 (9)	0.006 (5)	−0.007 (6)	−0.005 (6)
C29	0.059 (4)	0.063 (4)	0.086 (4)	−0.015 (3)	−0.007 (3)	−0.028 (3)

Geometric parameters (Å, º)

O11—C7	1.275 (2)	C11—C21	1.428 (3)
O11—Na1^i	2.4654 (16)	C4—C5	1.404 (3)
O14—H14	0.8400	C15—H15	0.9500
O14—C17	1.289 (2)	C15—C16	1.376 (3)
O15—C17	1.244 (2)	C19—C18	1.203 (3)
O15—Na1^ii	2.4765 (16)	C19—C20	1.372 (3)
O12—C7	1.255 (2)	C16—H16A	0.9500
O12—Na1	2.3658 (17)	C6—H6	0.9500
O16—C14	1.351 (3)	C6—C5	1.368 (3)
O16—Na1^iii	2.5154 (19)	C20—C21	1.205 (3)
O16—H16	0.90 (4)	C5—H5	0.9500
O13—H13	0.8400	C25—H25	0.9500
O13—C4	1.341 (3)	C22—H22	0.9500
O18—C25	1.210 (3)	C23—H23A	0.9800
O18—Na1	2.3411 (18)	C23—H23B	0.9800
O17—C22	1.216 (3)	C23—H23C	0.9800
O17—Na1	2.2807 (19)	C24—H24A	0.9800
N1—C22	1.367 (3)	C24—H24B	0.9800
N1—C23	1.431 (3)	C24—H24C	0.9800
N1—C24	1.432 (3)	C26—H26A	0.9800
C14—C13	1.403 (3)	C26—H26B	0.9800
C14—C15	1.398 (3)	C26—H26C	0.9800
C7—C3	1.492 (3)	C27—H27A	0.9800
C12—H12	0.9500	C27—H27B	0.9800
C12—C13	1.395 (3)	C27—H27C	0.9800
C12—C11	1.396 (3)	C28—H28	0.9500
C13—C17	1.482 (3)	C28—O19	1.189 (12)
C2—H2	0.9500	C28—N3	1.328 (11)
C2—C1	1.393 (3)	N3—C30	1.457 (12)
C2—C3	1.389 (3)	N3—C29	1.441 (8)
N2—C25	1.321 (3)	C30—H30A	0.9800
N2—C26	1.453 (4)	C30—H30B	0.9800
N2—C27	1.436 (5)	C30—H30C	0.9800
C1—C6	1.408 (3)	C29—H29A	0.9800
C1—C18	1.431 (3)	C29—H29B	0.9800
C3—C4	1.410 (3)	C29—H29C	0.9800
C11—C16	1.402 (3)
C7—O11—Na1^i	144.15 (13)	O18—C25—H25	117.2
C17—O14—H14	109.5	N2—C25—H25	117.2
C17—O15—Na1^ii	125.63 (13)	O17—C22—N1	124.2 (2)
C7—O12—Na1	127.65 (13)	O17—C22—H22	117.9
C14—O16—Na1^iii	117.40 (12)	N1—C22—H22	117.9
C14—O16—H16	103 (2)	N1—C23—H23A	109.5
Na1^iii—O16—H16	92 (2)	N1—C23—H23B	109.5
C4—O13—H13	109.5	N1—C23—H23C	109.5
C25—O18—Na1	147.53 (16)	H23A—C23—H23B	109.5
C22—O17—Na1	164.8 (2)	H23A—C23—H23C	109.5
C22—N1—C23	120.5 (2)	H23B—C23—H23C	109.5
C22—N1—C24	120.2 (2)	N1—C24—H24A	109.5
C24—N1—C23	119.3 (2)	N1—C24—H24B	109.5
O16—C14—C13	122.08 (18)	N1—C24—H24C	109.5
O16—C14—C15	118.09 (19)	H24A—C24—H24B	109.5
C15—C14—C13	119.83 (19)	H24A—C24—H24C	109.5
O11—C7—C3	118.02 (18)	H24B—C24—H24C	109.5
O12—C7—O11	123.32 (18)	N2—C26—H26A	109.5
O12—C7—C3	118.65 (18)	N2—C26—H26B	109.5
C13—C12—H12	119.8	N2—C26—H26C	109.5
C13—C12—C11	120.41 (19)	H26A—C26—H26B	109.5
C11—C12—H12	119.8	H26A—C26—H26C	109.5
C14—C13—C17	119.81 (18)	H26B—C26—H26C	109.5
C12—C13—C14	119.79 (18)	N2—C27—H27A	109.5
C12—C13—C17	120.39 (18)	N2—C27—H27B	109.5
O14—C17—C13	116.26 (17)	N2—C27—H27C	109.5
O15—C17—O14	123.24 (18)	H27A—C27—H27B	109.5
O15—C17—C13	120.49 (18)	H27A—C27—H27C	109.5
C1—C2—H2	119.5	H27B—C27—H27C	109.5
C3—C2—H2	119.5	O11^i—Na1—O15^ii	76.39 (5)
C3—C2—C1	120.98 (19)	O11^i—Na1—O16^iv	83.47 (6)
C25—N2—C26	120.0 (3)	O15^ii—Na1—O16^iv	78.07 (6)
C25—N2—C27	121.8 (3)	O12—Na1—O11^i	95.40 (6)
C27—N2—C26	118.0 (3)	O12—Na1—O15^ii	81.36 (6)
C2—C1—C6	118.94 (19)	O12—Na1—O16^iv	159.09 (6)
C2—C1—C18	121.1 (2)	O18—Na1—O11^i	156.67 (7)
C6—C1—C18	119.94 (19)	O18—Na1—O15^ii	81.00 (6)
C2—C3—C7	120.77 (18)	O18—Na1—O12	86.76 (7)
C2—C3—C4	119.44 (18)	O18—Na1—O16^iv	86.33 (7)
C4—C3—C7	119.77 (18)	O17—Na1—O11^i	105.54 (7)
C12—C11—C16	118.9 (2)	O17—Na1—O15^ii	168.08 (7)
C12—C11—C21	120.7 (2)	O17—Na1—O12	109.91 (7)
C16—C11—C21	120.46 (19)	O17—Na1—O16^iv	90.39 (6)
O13—C4—C3	123.02 (19)	O17—Na1—O18	95.43 (7)
O13—C4—C5	117.55 (19)	O19—C28—H28	116.6
C5—C4—C3	119.4 (2)	O19—C28—N3	126.7 (12)
C14—C15—H15	120.1	N3—C28—H28	116.6
C16—C15—C14	119.8 (2)	C28—N3—C30	118.3 (12)
C16—C15—H15	120.1	C28—N3—C29	123.9 (8)
C18—C19—C20	178.6 (3)	C29—N3—C30	117.8 (10)
C11—C16—H16A	119.3	N3—C30—H30A	109.5
C15—C16—C11	121.33 (19)	N3—C30—H30B	109.5
C15—C16—H16A	119.3	N3—C30—H30C	109.5
C1—C6—H6	119.6	H30A—C30—H30B	109.5
C5—C6—C1	120.74 (19)	H30A—C30—H30C	109.5
C5—C6—H6	119.6	H30B—C30—H30C	109.5
C19—C18—C1	178.0 (2)	N3—C29—H29A	109.5
C21—C20—C19	178.8 (2)	N3—C29—H29B	109.5
C4—C5—H5	119.8	N3—C29—H29C	109.5
C6—C5—C4	120.5 (2)	H29A—C29—H29B	109.5
C6—C5—H5	119.8	H29A—C29—H29C	109.5
C20—C21—C11	179.0 (2)	H29B—C29—H29C	109.5
O18—C25—N2	125.6 (2)
O11—C7—C3—C2	−0.6 (3)	C3—C2—C1—C6	0.3 (3)
O11—C7—C3—C4	−178.74 (18)	C3—C2—C1—C18	179.82 (19)
O12—C7—C3—C2	178.87 (18)	C3—C4—C5—C6	0.6 (3)
O12—C7—C3—C4	0.7 (3)	C11—C12—C13—C14	−0.3 (3)
O16—C14—C13—C12	179.00 (18)	C11—C12—C13—C17	−179.68 (18)
O16—C14—C13—C17	−1.7 (3)	C15—C14—C13—C12	−0.8 (3)
O16—C14—C15—C16	−178.97 (19)	C15—C14—C13—C17	178.52 (19)
O13—C4—C5—C6	179.82 (19)	C18—C1—C6—C5	179.9 (2)
C14—C13—C17—O14	172.83 (18)	C21—C11—C16—C15	178.4 (2)
C14—C13—C17—O15	−7.2 (3)	C23—N1—C22—O17	0.0 (4)
C14—C15—C16—C11	0.3 (3)	C24—N1—C22—O17	−177.3 (3)
C7—C3—C4—O13	−1.8 (3)	C26—N2—C25—O18	−4.1 (5)
C7—C3—C4—C5	177.40 (18)	C27—N2—C25—O18	−178.7 (4)
C12—C13—C17—O14	−7.8 (3)	Na1^i—O11—C7—O12	−122.2 (2)
C12—C13—C17—O15	172.13 (18)	Na1^i—O11—C7—C3	57.2 (3)
C12—C11—C16—C15	−1.4 (3)	Na1^ii—O15—C17—O14	27.4 (3)
C13—C14—C15—C16	0.9 (3)	Na1^ii—O15—C17—C13	−152.59 (14)
C13—C12—C11—C16	1.4 (3)	Na1—O12—C7—O11	64.8 (2)
C13—C12—C11—C21	−178.34 (19)	Na1—O12—C7—C3	−114.62 (18)
C2—C1—C6—C5	−0.5 (3)	Na1^iii—O16—C14—C13	−96.2 (2)
C2—C3—C4—O13	179.99 (19)	Na1^iii—O16—C14—C15	83.6 (2)
C2—C3—C4—C5	−0.8 (3)	Na1—O18—C25—N2	136.4 (3)
C1—C2—C3—C7	−177.81 (18)	Na1—O17—C22—N1	40.0 (8)
C1—C2—C3—C4	0.4 (3)	O19—C28—N3—C30	178.5 (7)
C1—C6—C5—C4	0.1 (3)	O19—C28—N3—C29	−2.6 (17)

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