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The title compound, [(4S,4aS,5aS,6S,12aS)-2-amino­hydroxy­methyl­ene-1,2,3,4,4a,5,5a,6,11,12a-deca­hydro-6,10,12,12a-tetra­­hydroxy-6-methyl-1,3,11-trioxo­naphthacen-4-yl]­di­methyl­amm­onium chloride, C22H25N2O8+·Cl-, a well known antibiotic, has been structurally characterized from an individual coarse powder grain by use of high-intensity synchrotron radiation, in conjunction with an exercise in ab initio powder diffraction structure solution. Free refinement of all H atoms establishes the major tautomeric form of the protonated tetracycline mol­ecule without prejudice. The mol­ecule has extensive intramolecular hydrogen bonding involving most of the potential donors and acceptors, and all intermolecular hydrogen bonding uses the chloride anion as acceptor.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100010349/bm1422sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100010349/bm1422Isup2.hkl
Contains datablock I

CCDC reference: 153890

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: local programs; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 1995); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

[(4S,4aS,5aS,6R,12aS)-2-aminohydroxymethylene-1,2,3,4,4a,5,5a,6,11,12a- decahydro-6,10,12,12a-tetrahydroxy-6-methyl-1,3,11-trioxonaphthacen-4-yl] dimethylammonium chloride top
Crystal data top
C22H25N2O8+·ClDx = 1.463 Mg m3
Mr = 480.89Synchrotron radiation, λ = 0.6883 Å
Orthorhombic, P212121Cell parameters from 6452 reflections
a = 10.9300 (9) Åθ = 2.5–29.2°
b = 12.7162 (11) ŵ = 0.23 mm1
c = 15.7085 (13) ÅT = 150 K
V = 2183.3 (3) Å3Prism, yellow
Z = 40.04 × 0.03 × 0.02 mm
F(000) = 1008
Data collection top
Bruker SMART CCD
diffractometer with Oxford Cryosystems open-flow cryostat (Cosier & Glazer, 1986)
3937 reflections with I > 2σ(I)
Radiation source: Daresbury SRS station 9.8Rint = 0.047
Silicon 111 monochromatorθmax = 29.3°, θmin = 2.2°
Detector resolution: 8.192 pixels mm-1h = 148
ω rotation with narrow frames scansk = 1717
8955 measured reflectionsl = 214
4915 independent reflections
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.050 w = 1/[σ2(Fo2) + (0.0579P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.116(Δ/σ)max = 0.001
S = 0.97Δρmax = 0.57 e Å3
4915 reflectionsΔρmin = 0.24 e Å3
399 parametersExtinction correction: SHELXTL (Sheldrick, 1995), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0038 (12)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983); 1958 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.02 (8)
Special details top

Experimental. The data collection nominally covered over a quadrant of reciprocal space, by a combination of two sets of ω-scan exposures, each set with a different φ angle for the crystal and with frame widths of 0.15°. Crystal cooling was by a Cryostream device (Cosier & Glazer, 1986).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.92963 (7)0.41939 (6)0.00197 (4)0.01949 (17)
O10.0086 (3)0.3656 (3)0.43967 (14)0.0392 (7)
H10.039 (4)0.433 (4)0.435 (2)0.047 (13)*
O60.1453 (2)0.46012 (16)0.12979 (12)0.0194 (5)
H60.086 (4)0.449 (3)0.088 (2)0.045 (12)*
O110.7514 (2)0.64335 (19)0.07408 (14)0.0268 (5)
O130.3634 (2)0.71743 (18)0.18883 (13)0.0250 (5)
O140.5800 (2)0.60174 (18)0.29547 (12)0.0212 (5)
H140.565 (4)0.614 (3)0.338 (2)0.033 (11)*
O150.3506 (2)0.60822 (17)0.35612 (12)0.0198 (5)
H150.283 (4)0.580 (4)0.385 (2)0.045 (12)*
O170.1647 (2)0.50211 (18)0.38835 (12)0.0234 (5)
O190.6623 (3)0.81863 (18)0.04211 (13)0.0269 (6)
H190.734 (5)0.757 (4)0.055 (3)0.061 (14)*
N100.7465 (3)0.4488 (2)0.14281 (16)0.0193 (6)
H100.793 (4)0.464 (3)0.100 (2)0.035 (11)*
N190.4694 (3)0.8551 (2)0.08138 (17)0.0288 (7)
H19A0.475 (4)0.921 (3)0.058 (2)0.034 (10)*
H19B0.408 (4)0.833 (4)0.112 (2)0.049 (14)*
C10.0207 (3)0.3204 (3)0.36224 (18)0.0272 (8)
C20.0525 (4)0.2345 (3)0.3435 (2)0.0314 (9)
H20.111 (3)0.211 (3)0.388 (2)0.026 (9)*
C30.0436 (4)0.1888 (3)0.2657 (2)0.0302 (8)
H30.084 (4)0.134 (3)0.253 (2)0.040 (12)*
C40.0378 (3)0.2253 (3)0.2036 (2)0.0240 (7)
H40.038 (3)0.189 (3)0.148 (2)0.028 (9)*
C50.1113 (3)0.3105 (2)0.22057 (18)0.0183 (7)
C60.1962 (3)0.3609 (2)0.15436 (17)0.0178 (7)
C70.3178 (3)0.3872 (2)0.19906 (16)0.0145 (6)
H70.337 (4)0.318 (3)0.222 (2)0.028 (9)*
C80.4148 (3)0.4314 (2)0.13903 (16)0.0170 (6)
H8A0.378 (4)0.486 (3)0.107 (2)0.035 (10)*
H8B0.444 (3)0.378 (3)0.1001 (19)0.025 (9)*
C90.5241 (3)0.4766 (2)0.18811 (16)0.0141 (6)
H90.554 (3)0.423 (3)0.2292 (18)0.020 (8)*
C100.6283 (3)0.5041 (2)0.12622 (17)0.0156 (6)
H10A0.615 (3)0.482 (2)0.0715 (17)0.007 (7)*
C110.6526 (3)0.6204 (2)0.11090 (16)0.0180 (6)
C120.5579 (3)0.6923 (2)0.12673 (16)0.0170 (6)
C130.4588 (3)0.6663 (2)0.18199 (15)0.0171 (7)
C140.4828 (3)0.5705 (2)0.24083 (15)0.0150 (6)
C150.3690 (3)0.5439 (2)0.29061 (15)0.0158 (6)
C160.2940 (3)0.4624 (2)0.27178 (16)0.0149 (6)
C170.1867 (3)0.4446 (2)0.32353 (16)0.0184 (7)
C180.1060 (3)0.3578 (3)0.30253 (17)0.0187 (7)
C190.5622 (3)0.7911 (2)0.08265 (16)0.0204 (7)
C200.2161 (4)0.2919 (3)0.0769 (2)0.0246 (8)
H20A0.135 (3)0.284 (3)0.0479 (18)0.015 (8)*
H20B0.245 (4)0.225 (4)0.090 (2)0.038 (11)*
H20C0.259 (3)0.329 (3)0.034 (2)0.025 (9)*
C210.7318 (4)0.3324 (3)0.1384 (2)0.0259 (8)
H21A0.688 (4)0.311 (3)0.184 (2)0.041 (11)*
H21B0.810 (4)0.303 (3)0.1312 (19)0.019 (9)*
H21C0.698 (3)0.321 (3)0.085 (2)0.028 (10)*
C220.8096 (4)0.4811 (3)0.2228 (2)0.0308 (9)
H22A0.820 (3)0.559 (3)0.223 (2)0.028 (9)*
H22B0.885 (4)0.458 (4)0.222 (2)0.039 (12)*
H22C0.761 (4)0.457 (3)0.269 (2)0.030 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0148 (4)0.0225 (3)0.0212 (3)0.0031 (3)0.0017 (3)0.0011 (3)
O10.0359 (18)0.0553 (19)0.0265 (11)0.0166 (16)0.0098 (10)0.0003 (11)
O60.0161 (13)0.0172 (11)0.0248 (10)0.0042 (11)0.0052 (9)0.0008 (8)
O110.0167 (14)0.0226 (12)0.0412 (11)0.0041 (11)0.0086 (10)0.0072 (10)
O130.0229 (15)0.0233 (12)0.0288 (10)0.0096 (12)0.0041 (9)0.0014 (9)
O140.0140 (13)0.0322 (13)0.0174 (9)0.0055 (11)0.0032 (8)0.0005 (8)
O150.0154 (13)0.0240 (12)0.0200 (9)0.0000 (11)0.0013 (8)0.0047 (8)
O170.0180 (13)0.0292 (12)0.0229 (9)0.0002 (12)0.0037 (8)0.0026 (9)
O190.0310 (16)0.0199 (12)0.0297 (11)0.0075 (13)0.0002 (10)0.0052 (9)
N100.0132 (15)0.0194 (13)0.0254 (11)0.0001 (12)0.0046 (10)0.0042 (10)
N190.038 (2)0.0166 (14)0.0319 (14)0.0056 (15)0.0021 (13)0.0069 (11)
C10.020 (2)0.0351 (19)0.0262 (14)0.0004 (17)0.0011 (13)0.0090 (13)
C20.017 (2)0.041 (2)0.0364 (16)0.0087 (19)0.0011 (14)0.0125 (15)
C30.017 (2)0.0267 (19)0.0466 (18)0.0080 (19)0.0042 (14)0.0057 (15)
C40.013 (2)0.0218 (17)0.0373 (16)0.0003 (15)0.0020 (13)0.0007 (13)
C50.0084 (18)0.0178 (15)0.0287 (13)0.0039 (14)0.0015 (11)0.0034 (11)
C60.0169 (18)0.0154 (14)0.0211 (12)0.0025 (14)0.0004 (11)0.0015 (10)
C70.0061 (16)0.0135 (14)0.0237 (12)0.0009 (13)0.0003 (10)0.0006 (10)
C80.0124 (17)0.0177 (15)0.0209 (11)0.0008 (15)0.0022 (11)0.0034 (11)
C90.0079 (16)0.0132 (14)0.0211 (11)0.0007 (13)0.0011 (10)0.0015 (10)
C100.0074 (16)0.0173 (15)0.0220 (12)0.0014 (14)0.0008 (10)0.0011 (11)
C110.0153 (18)0.0184 (15)0.0202 (12)0.0003 (15)0.0013 (11)0.0031 (11)
C120.0172 (18)0.0133 (13)0.0206 (12)0.0003 (15)0.0011 (11)0.0006 (9)
C130.018 (2)0.0167 (14)0.0161 (11)0.0002 (15)0.0013 (11)0.0034 (10)
C140.0119 (16)0.0151 (14)0.0181 (11)0.0015 (14)0.0024 (10)0.0005 (10)
C150.0135 (17)0.0170 (15)0.0170 (11)0.0046 (14)0.0036 (10)0.0015 (10)
C160.0123 (17)0.0153 (14)0.0172 (11)0.0040 (14)0.0009 (10)0.0024 (10)
C170.0151 (18)0.0210 (16)0.0190 (12)0.0052 (15)0.0009 (10)0.0038 (10)
C180.0111 (18)0.0209 (16)0.0240 (13)0.0031 (14)0.0007 (11)0.0045 (11)
C190.026 (2)0.0143 (14)0.0209 (12)0.0055 (17)0.0036 (12)0.0000 (10)
C200.019 (2)0.0250 (19)0.0299 (15)0.0014 (18)0.0012 (13)0.0109 (13)
C210.024 (2)0.0177 (17)0.0366 (17)0.0050 (17)0.0117 (15)0.0046 (13)
C220.017 (2)0.038 (2)0.0367 (18)0.002 (2)0.0056 (15)0.0019 (15)
Geometric parameters (Å, º) top
O1—C11.352 (4)C6—C201.516 (4)
O1—H10.92 (5)C6—C71.540 (4)
O6—C61.432 (4)C7—C161.512 (4)
O6—H60.94 (4)C7—C81.526 (4)
O11—C111.260 (4)C7—H70.97 (4)
O13—C131.234 (4)C8—C91.534 (4)
O14—C141.422 (3)C8—H8A0.95 (4)
O14—H140.70 (4)C8—H8B0.97 (3)
O15—C151.330 (3)C9—C141.522 (4)
O15—H150.94 (4)C9—C101.538 (4)
O17—C171.277 (3)C9—H91.00 (3)
O19—C191.314 (4)C10—C111.521 (4)
O19—H191.13 (5)C10—H10A0.92 (3)
N10—C211.490 (4)C11—C121.403 (5)
N10—C221.490 (4)C12—C131.427 (4)
N10—C101.494 (4)C12—C191.435 (4)
N10—H100.87 (4)C13—C141.551 (4)
N19—C191.301 (5)C14—C151.507 (4)
N19—H19A0.91 (4)C15—C161.354 (4)
N19—H19B0.86 (5)C16—C171.445 (4)
C1—C21.386 (5)C17—C181.450 (5)
C1—C181.405 (4)C20—H20A1.00 (3)
C2—C31.357 (5)C20—H20B0.93 (4)
C2—H21.00 (4)C20—H20C0.95 (4)
C3—C41.400 (5)C21—H21A0.90 (4)
C3—H30.85 (4)C21—H21B0.94 (4)
C4—C51.374 (5)C21—H21C0.92 (4)
C4—H40.99 (3)C22—H22A0.99 (4)
C5—C181.422 (4)C22—H22B0.88 (5)
C5—C61.534 (4)C22—H22C0.95 (4)
C1—O1—H1107 (2)N10—C10—C9115.0 (2)
C6—O6—H6109 (3)C11—C10—C9116.8 (3)
C14—O14—H14117 (4)N10—C10—H10A99.4 (19)
C15—O15—H15105 (3)C11—C10—H10A100.0 (19)
C19—O19—H19108 (2)C9—C10—H10A113.8 (19)
C21—N10—C22111.3 (3)O11—C11—C12124.2 (3)
C21—N10—C10111.5 (3)O11—C11—C10116.6 (3)
C22—N10—C10114.7 (3)C12—C11—C10118.5 (3)
C21—N10—H10104 (3)C11—C12—C13121.1 (3)
C22—N10—H10109 (3)C11—C12—C19117.5 (3)
C10—N10—H10105 (3)C13—C12—C19121.4 (3)
C19—N19—H19A121 (3)O13—C13—C12124.9 (3)
C19—N19—H19B113 (3)O13—C13—C14120.3 (3)
H19A—N19—H19B125 (4)C12—C13—C14114.6 (3)
O1—C1—C2118.0 (3)O14—C14—C15111.5 (2)
O1—C1—C18121.4 (3)O14—C14—C9109.0 (2)
C2—C1—C18120.5 (3)C15—C14—C9110.5 (2)
C3—C2—C1119.2 (3)O14—C14—C13105.5 (2)
C3—C2—H2123 (2)C15—C14—C13110.2 (3)
C1—C2—H2117 (2)C9—C14—C13110.0 (2)
C2—C3—C4122.1 (4)O15—C15—C16123.2 (3)
C2—C3—H3122 (3)O15—C15—C14112.8 (3)
C4—C3—H3116 (3)C16—C15—C14123.9 (3)
C5—C4—C3119.9 (3)C15—C16—C17119.3 (3)
C5—C4—H4123 (2)C15—C16—C7123.0 (3)
C3—C4—H4117 (2)C17—C16—C7117.7 (3)
C4—C5—C18119.0 (3)O17—C17—C16120.8 (3)
C4—C5—C6123.4 (3)O17—C17—C18120.2 (3)
C18—C5—C6117.5 (3)C16—C17—C18119.0 (3)
O6—C6—C20110.4 (2)C1—C18—C5119.2 (3)
O6—C6—C5108.4 (3)C1—C18—C17120.6 (3)
C20—C6—C5112.9 (3)C5—C18—C17120.2 (3)
O6—C6—C7105.5 (2)N19—C19—O19118.4 (3)
C20—C6—C7111.6 (3)N19—C19—C12122.0 (3)
C5—C6—C7107.7 (2)O19—C19—C12119.6 (3)
C16—C7—C8110.7 (2)C6—C20—H20A107.5 (18)
C16—C7—C6109.5 (2)C6—C20—H20B114 (2)
C8—C7—C6113.4 (2)H20A—C20—H20B108 (3)
C16—C7—H7109 (2)C6—C20—H20C111 (2)
C8—C7—H7114 (2)H20A—C20—H20C99 (3)
C6—C7—H799 (2)H20B—C20—H20C117 (3)
C7—C8—C9111.6 (2)N10—C21—H21A109 (3)
C7—C8—H8A108 (2)N10—C21—H21B108 (2)
C9—C8—H8A109 (2)H21A—C21—H21B117 (3)
C7—C8—H8B111 (2)N10—C21—H21C104 (2)
C9—C8—H8B109 (2)H21A—C21—H21C117 (3)
H8A—C8—H8B109 (3)H21B—C21—H21C101 (3)
C14—C9—C8109.7 (2)N10—C22—H22A108.9 (19)
C14—C9—C10112.6 (2)N10—C22—H22B110 (3)
C8—C9—C10110.2 (2)H22A—C22—H22B103 (4)
C14—C9—H9106.5 (18)N10—C22—H22C108 (2)
C8—C9—H9109 (2)H22A—C22—H22C113 (3)
C10—C9—H9109.1 (19)H22B—C22—H22C115 (3)
N10—C10—C11109.5 (3)
O1—C1—C2—C3178.9 (3)C8—C9—C14—C1548.5 (3)
C18—C1—C2—C32.1 (5)C10—C9—C14—C15171.6 (2)
C1—C2—C3—C40.3 (6)C8—C9—C14—C1373.4 (3)
C2—C3—C4—C50.4 (5)C10—C9—C14—C1349.6 (3)
C3—C4—C5—C182.2 (5)O13—C13—C14—O14110.9 (3)
C3—C4—C5—C6175.4 (3)C12—C13—C14—O1464.6 (3)
C4—C5—C6—O6107.7 (3)O13—C13—C14—C159.5 (4)
C18—C5—C6—O669.9 (3)C12—C13—C14—C15175.0 (2)
C4—C5—C6—C2015.0 (4)O13—C13—C14—C9131.7 (3)
C18—C5—C6—C20167.5 (3)C12—C13—C14—C952.8 (3)
C4—C5—C6—C7138.7 (3)O14—C14—C15—O1538.9 (3)
C18—C5—C6—C743.8 (4)C9—C14—C15—O15160.3 (2)
O6—C6—C7—C1655.9 (3)C13—C14—C15—O1577.9 (3)
C20—C6—C7—C16175.9 (3)O14—C14—C15—C16140.3 (3)
C5—C6—C7—C1659.7 (3)C9—C14—C15—C1618.8 (4)
O6—C6—C7—C868.3 (3)C13—C14—C15—C16103.0 (3)
C20—C6—C7—C851.6 (4)O15—C15—C16—C171.4 (4)
C5—C6—C7—C8176.1 (3)C14—C15—C16—C17179.6 (3)
C16—C7—C8—C945.2 (3)O15—C15—C16—C7177.8 (3)
C6—C7—C8—C9168.7 (2)C14—C15—C16—C71.3 (4)
C7—C8—C9—C1464.4 (3)C8—C7—C16—C1514.4 (4)
C7—C8—C9—C10171.1 (3)C6—C7—C16—C15140.2 (3)
C21—N10—C10—C11166.9 (2)C8—C7—C16—C17166.4 (3)
C22—N10—C10—C1165.5 (3)C6—C7—C16—C1740.6 (3)
C21—N10—C10—C959.2 (3)C15—C16—C17—O172.7 (4)
C22—N10—C10—C968.4 (3)C7—C16—C17—O17176.6 (3)
C14—C9—C10—N10116.1 (3)C15—C16—C17—C18179.4 (3)
C8—C9—C10—N10121.1 (3)C7—C16—C17—C181.4 (4)
C14—C9—C10—C1114.3 (3)O1—C1—C18—C5177.2 (3)
C8—C9—C10—C11108.5 (3)C2—C1—C18—C53.8 (5)
N10—C10—C11—O1133.6 (3)O1—C1—C18—C171.9 (5)
C9—C10—C11—O11166.6 (2)C2—C1—C18—C17177.1 (3)
N10—C10—C11—C12155.6 (2)C4—C5—C18—C13.8 (5)
C9—C10—C11—C1222.6 (4)C6—C5—C18—C1173.8 (3)
O11—C11—C12—C13168.4 (3)C4—C5—C18—C17177.1 (3)
C10—C11—C12—C1321.5 (4)C6—C5—C18—C175.2 (4)
O11—C11—C12—C1914.0 (4)O17—C17—C18—C114.8 (4)
C10—C11—C12—C19156.0 (3)C16—C17—C18—C1163.1 (3)
C11—C12—C13—O13168.0 (3)O17—C17—C18—C5164.3 (3)
C19—C12—C13—O139.5 (4)C16—C17—C18—C517.8 (4)
C11—C12—C13—C1416.7 (4)C11—C12—C19—N19167.9 (3)
C19—C12—C13—C14165.8 (2)C13—C12—C19—N199.6 (4)
C8—C9—C14—O14171.4 (2)C11—C12—C19—O1912.1 (4)
C10—C9—C14—O1465.6 (3)C13—C12—C19—O19170.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O170.92 (5)1.79 (5)2.564 (4)140 (4)
O6—H6···Cl1i0.94 (4)2.25 (4)3.179 (2)174 (3)
O14—H14···O150.70 (4)2.36 (4)2.683 (3)110 (4)
O14—H14···Cl1ii0.70 (4)2.56 (4)3.195 (2)153 (4)
O15—H15···O170.94 (4)1.63 (5)2.491 (3)151 (4)
O19—H19···O111.13 (5)1.49 (5)2.484 (3)143 (4)
N10—H10···Cl10.87 (4)2.26 (4)3.053 (3)152 (3)
N19—H19A···Cl1iii0.91 (4)2.27 (4)3.157 (3)163 (4)
N19—H19B···O130.86 (5)1.97 (5)2.694 (4)141 (4)
Symmetry codes: (i) x1, y, z; (ii) x+3/2, y+1, z+1/2; (iii) x1/2, y+3/2, z.
 

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