research communications
Crystal structures of 4-methyl-2-oxo-2H-chromene-7,8-diyl diacetate and 4-methyl-2-oxo-2H-chromene-7,8-diyl bis(pent-4-ynoate)
aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
*Correspondence e-mail: lystranne.maynard@howard.edu
In the structures of the two title coumarin derivatives, C14H12O6, (1), and C20H16O6, (2), one with acetate and the other with pent-4-ynoate substituents, both the coumarin rings are almost planar. In (1), both acetate substituents are significantly rotated out of the coumarin plane to minimize steric repulsions. One acetate substituent is disordered over two equivalent conformations, with occupancies of 0.755 (17) and 0.245 (17). In (2), there are two pent-4-ynoate substituents, the C C group of one being disordered over two positions with occupancies of 0.55 (2) and 0.45 (2). One of the pent-4-ynoate substituents is in an extended conformation, while the other is in a bent conformation. In this derivative, the planar part of both pent-4-ynoate substituents deviate from the coumarin plane. The packing of (1) is dominated by π–π stacking involving the coumarin rings and weak C—H⋯O contacts link the parallel stacks in the [101] direction. In contrast, in (2) the packing is dominated by R22(24) hydrogen bonds, involving the acidic sp H atom and the oxo O atom, which link the molecules into centrosymmetric dimers. The bent conformation of one of the pent-4-ynoate substituents prevents the coumarin rings from engaging in π–π stacking.
1. Chemical context
et al., 2012), the most notable being warfarin (Holbrook et al., 2005). Modified are a type of vitamin K antagonist (Marongiu & Barcellona, 2015).
and their derivatives have wide applications in a number of diverse areas. They are used in the pharmaceutical industry as precursor reagents in the synthesis of a number of synthetic anticoagulant pharmaceuticals (BairagiIn another important application, coumarin dyes are extensively used as gain media in blue–green tunable organic dye lasers (Schäfer, 1990; Duarte & Hillman, 1990; Duarte, 2003). Coumarin tetramethyl laser dyes offer wide tunability and high laser gain (Chen et al., 1988; Duarte et al., 2006), and they are also used as the active medium in coherent OLED emitters (Duarte et al., 2005).
4-Methyl coumarin derivatives have previously been used as acetyl-group donors for post-translational modification of proteins via an acetyl–CoA independent mechanism (Raj, Singh et al., 2005; Raj, Kumari et al., 2006). Calreticulin-mediated acetylation of glutathione-S-transferase (GST) using substrate 7,8-diacetyoxy-4-methyl coumarin, DAMC (1) (systematic name: 4-methyl-2-oxo-2H-chromene-7,8-diyl diacetate) has been shown to inhibit GST activity in a spectroscopic assay (Raj, Singh et al., 2005). The of the related compound 7,8-dihydroxy-4-methylcoumarin (Kurosaki et al., 2003) has been reported. Pentynoyl probes have been used as chemical reporters to monitor protein acetylation (Bateman et al., 2013; Yang et al., 2010). For background to bio-orthogonal reactions using alkyne–azide cycloaddition, see Sletten & Bertozzi (2011) and Yang & Hang (2011).
We have synthesized a new coumarin derivative, 7,8-dipentynoyloxy-4-methyl coumarin, DPeMC (2) [systematic name: 4-methyl-2-oxo-2H chromene-7,8-diyl bis(pent-4-ynoate)] as a chemical reporter of calreticulin's acyltransferase capabilities (Singh et al., 2011). As part of this work, the crystal structures of both coumarin derivatives are presented in this article.
2. Structural commentary
This paper reports the structures of two derivatives of coumarin (systematic name; 2H-chromen-2-one), C14H12O6 (1) and C20H16O6 (2), which are to be used as chemical reporters of calreticulin's acyltransferase capabilities. These two compounds will be first discussed individually and then compared.
In the structure of (1) (Fig. 1), the coumarin ring is almost planar (r.m.s. deviation of fitted atoms = 0.0063 Å) with O2 in the plane [deviation of 0.0048 (9) Å]. Both acetate substituents are significantly rotated out of this plane to minimize steric repulsions [dihedral angle of 66.19 (7)° to the coumarin ring for O3, O4, and C11, and 79.4 (3)° for O5, C13 O6A]. One acetate substituent is disordered over two equivalent conformations with occupancies of 0.755 (17) and 0.245 (17). The metrical parameters of both the coumarin ring and acetate substituents are in the normal ranges.
In (2) (Fig. 2), the C C group of one of the pent-4-ynoate substituents is disordered over two positions with occupancies of 0.55 (2) and 0.45 (2). The coumarin ring is almost planar (r.m.s. deviation of fitted atoms = 0.0305 Å) with O2 significantly out of this plane [0.144 (2) Å] but O3 in the plane [0.063 (2) Å]. One of the pent-4-ynoate substituents is in an extended conformation (O5 to C21) while the other is in a bent conformation about C13. This can be seen from a consideration of the O3—C12—C13—C14 torsion angle of −46.3 (2)° compared to the equivalent torsion angle O5—C17—C18—C19 of 176.16 (12)°. The planar parts of both pent-4-ynoate substituents deviate from the coumarin plane but by different amounts [40.90 (15)° for O3, O4 and C12 compared to 74.07 (10)° for O5, O6 and C17]. The metrical parameters of both the coumarin ring and pent-4-ynoate substituents are in the normal ranges including the C C triple bonds [C15A C16A = 1.186 (9), C15B C16B = 1.169 (11) and C20 C21 = 1.177 (3) Å].
3. Supramolecular features
The packing of (1) is dominated by π–π stacking involving the coumarin rings [centroid–centroid distance of 3.6640 (5) Å, slippage of 1.422 Å, symmetry code 1 − x, 1 − y, 1 − z]. This can be observed in Fig. 3. In addition, there are weak C—H⋯O contacts (Table 1) involving C13 and O6A(x, 1 + y, z) as well as C6 and O2(x − 1, 1 + y, z), C15A and O2 (1 − x, −y, 2 − z) which link the parallel stacks in the [101] direction.
In contrast to (1), for (2) the packing (Fig. 4) is dominated by R22(24) hydrogen bonds (Table 2) involving the acidic sp H atom and O2 which link the molecules into centrosymmetric dimers. The bent conformation of one of the pent-4-ynoate substituents prevents the coumarin rings from engaging in π–π stacking in contrast to (1).
4. Database survey
Our group has reported a number of related structures (Jasinski & Paight, 1994, 1995; Jasinski & Woudenberg, 1994, 1995; Jasinski & Li, 2002; Jasinski et al., 1998, 2003; Butcher et al., 2007).
5. Synthesis and crystallization
7,8-Diacetoxy-4-methylcoumarin (1). 4-Methyl-2-oxo-2H-chromene-7,8-diyl diacetate (DAMC) was synthesized using a previously reported procedure (Jalal et al., 2012).
7,8-Dipentynoyloxy-4-methylcoumarin (2). 0.5 mmol 7,8-dihydroxy-4-methyl coumarin, DHMC [systematic name: 7,8-dihydroxy-4-methyl-2H-chromen-2-one], 2.5 equivalents pentynoic anhydride (Malkoch et al., 2005) and catalytic 4-dimethylaminopyridine (DMAP) was stirred for 24 h at room temperature in anhydrous THF (2 mL). Ice-cold water (25 mL) was added to the reaction flask, and the filtered crude product was washed with hexanes followed by recrystallization from ethanol to obtain small brown crystals of 4-methyl-2-oxo-2H chromene-7,8-diyl bis(pent-4-ynoate).
Spectroscopic analysis: 1H NMR (400 MHz, CDCl3): δ 7.51–7.49 (1H, d), δ 7.20–7.17 (1H, d), δ 6.29 (1H, s), δ 3.01–3.08 (2H, m, HC C), δ 2.89–2.84 (2H, t, C C—CH2), δ 2.61–2.70 (4H, m, OOC—CH2), δ 2.44 (3H, s, CH3), δ 2.09–2.11 (2H, C C-–CH2).
6. Refinement
Crystal data, data collection and structure . For (1), the H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.98 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms. One acetate substituent is disordered over two equivalent conformations with occupancies of 0.755 (17) and 0.245 (17).
details are summarized in Table 3
|
In the 2), the H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.99 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms. The C C group of one of the pent-4-ynoate substituents is disordered over two positions with occupancies of 0.55 (2) and 0.45 (2).
for (Supporting information
10.1107/S2056989016005892/hg5471sup1.cif
contains datablocks 1, 2. DOI:Structure factors: contains datablock 1. DOI: 10.1107/S2056989016005892/hg54711sup2.hkl
Structure factors: contains datablock 2. DOI: 10.1107/S2056989016005892/hg54712sup3.hkl
Supporting information file. DOI: 10.1107/S2056989016005892/hg54711sup4.cml
Coumarins and their derivatives have wide applications in a number of diverse areas. They are used in the pharmaceutical industry as precursor reagents in the synthesis of a number of synthetic anticoagulant pharmaceuticals (Bairagi et al., 2012), the most notable being warfarin (Holbrook et al., 2005). Modified
are a type of vitamin K antagonist (Marongiu & Barcellona, 2015).In another important application, coumarin dyes are extensively used as gain media in blue–green tunable organic dye lasers (Schäfer, 1990; Duarte & Hillman, 1990; Duarte, 2003). Coumarin tetramethyl laser dyes offer wide tunability and high laser gain (Chen et al., 1988; Duarte et al., 2006), and they are also used as the active medium in coherent OLED emitters (Duarte et al., 2005).
4-Methyl coumarin derivatives have previously been used as acetyl-group donors for post-translational modification of proteins via an acetyl–CoA independent mechanism (Raj, Singh et al., 2005; Raj, Kumari et al., 2006). Calreticulin-mediated acetylation of glutathione-S-transferase (GST) using substrate 7,8-diacetyoxy-4-methyl coumarin, DAMC (1) (systematic name: 4-methyl-2-oxo-2H-chromene-7,8-diyl diacetate has been shown to inhibit GST activity in a spectroscopic assay (Raj, Singh et al., 2005). Pentynoyl probes have been used as chemical reporters to monitor protein acetylation (Bateman et al., 2013; Yang et al., 2010). For background to bio-orthogonal reactions using alkyne–azide cycloaddition, see Sletten & Bertozzi (2011) and Yang & Hang 2011).
We have synthesized a new coumarin derivative, 7,8-dipentynoyloxy-4-methyl coumarin, DPeMC (2) [systematic name: 4-methyl-2-oxo-2H chromene-7,8-diyl bis(pent-4-ynoate)] as a chemical reporter of calreticulin's acyltransferase capabilities. As part of this work and as a continuation of our previous structural studies of coumarin derivatives (Jasinski & Paight, 1994, 1995; Jasinski & Woudenberg, 1994, 1995; Jasinski & Li, 2002; Jasinski et al., 1998, 2003; Butcher et al., 2007), the crystal structures of both coumarin derivatives are presented in this article.
This paper reports the structures of two derivatives of coumarin (systematic name; 2H-chromen-2-one), C14H12O6 (1) and C20H16O6 (2), which are to be used as chemical reporters of calreticulin's acyltransferase capabilities. These two compounds will be first discussed individually and then compared.
In the structure of (1) (Fig. 1), the coumarin ring is planar (r.m.s. deviation of fitted atoms = 0.0063 Å) with O2 in the plane [deviation of 0.0048 (9) Å]. Both acetate substituents are significantly rotated out of this plane to minimize steric repulsions [dihedral angle of 66.19 (7)° to the coumarin ring for O3, O4, and C11, and 79.4 (3)° for O5, C13 O6A]. One acetate substituent is disordered over two equivalent conformations with occupancies of 0.755 (17) and 0.245 (17). The metrical parameters of both the coumarin ring and acetate substituents are in the normal ranges.
By contrast with (1), in the structure of (2) (Fig. 2) there are two pent-4-ynoate substituents in place of the acetate substituents. The C≡ C group of one of the pent-4-ynoate substituents is disordered over two positions with occupancies of 0.55 (2) and 0.45 (2). The coumarin ring is planar (r.m.s. deviation of fitted atoms = 0.0305 Å) with O2 significantly out of this plane [0.144 (2) Å] but O3 in the plane [0.063 (2) Å]. One of the pent-4-ynoate substituents is in an extended conformation (O5 to C21) while the other is in a bent conformation about C13. This can be seen clearly from a consideration of the O3—C12—C13—C14 torsion angle of -46.3 (2)° compared to the equivalent torsion angle O5—C17—C18—C19 of 176.16 (12)°. The planar parts of both pent-4-ynoate substituents deviate from the coumarin plane but by different amounts [40.90 (15)° for O3, O4 and C12 compared to 74.07 (10)° for O5, O6 and C17]. The metrical parameters of both the coumarin ring and pent-4-ynoate substituents are in the normal ranges including the C≡C triple bonds [C15A≡C16A = 1.186 (9), C15B≡ C16B = 1.169 (11) and C20≡C21 = 1.177 (3) Å].
The packing of (1) is dominated by π–π stacking involving the coumarin rings [centroid–centroid distance of 3.6640 (5) Å, slippage of 1.422 Å, symmetry code 1 - x, 1 - y, 1 - z]. This can be observed in Fig. 3. In addition, there are weak C—H···O contacts involving C13 and O6A(x, 1 + y, z) as well as C6 and O2(x - 1, 1 + y, z), C15A and O2 (1 - x, -y, 2 - z) which link the parallel stacks in the [101] direction.
In contract to (1), for (2) the packing is dominated by R22(24) hydrogen bonds involving the acidic sp H atom and O2 which link the molecules into centrosymmetric dimers. The bent conformation of one of the pent-4-ynoate substituents prevents the coumarin rings from engaging in π–π stacking in contrast to (1).
The
of 7,8-dihydroxy-4-methylcoumarin (Kurosaki et al., (2003) and other related coumarin structures (Jasinski & Paight, 1994, 1995; Jasinski & Woudenberg, 1994, 1995; Jasinski & Li, 2002; Jasinski et al., 1998, 2003; Butcher et al., 2007) have been reported. For more background on calreticulin transacetylase activity, see Singh et al., (2011).7,8-Diacetoxy-4-methylcoumarin (1). 4-Methyl-2-oxo-2H-chromene-7,8-diyl diacetate (DAMC) was synthesized using a previously reported procedure (Jalal et al., 2012).
7,8-Dipentynoyloxy-4-methylcoumarin (2). 0.5 mmol 7,8-dihydroxy-4-methyl coumarin, DHMC [systematic name: 7,8-dihydroxy-4-methyl-2H-chromen-2-one], 2.5 equivalents pentynoic anhydride (Malkoch et al., 2005) and catalytic 4-dimethylaminopyridine (DMAP) was stirred for 24 h at room temperature in anhydrous THF (2 mL). Ice-cold water (25 mL) was added to the reaction flask, and the filtered crude product was washed with hexanes followed by recrystallization from ethanol to obtain small brown crystals of 4-methyl-2-oxo-2H chromene-7,8-diyl bis(pent-4-ynoate).
Spectroscopic analysis: 1H NMR (400 MHz, CDCl3): δ 7.51–7.49 (1H, d), δ 7.20–7.17 (1H, d), δ 6.29 (1H, s), δ 3.01–3.08 (2H, m, HC≡C), δ 2.89–2.84 (2H, t, C≡C—CH2), δ 2.61–2.70 (4H, m, OOC—CH2), δ 2.44 (3H, s, CH3), δ 2.09–2.11 (2H, C≡C-–CH2).
Crystal data, data collection and structure
details are summarized in Table 3. For (1), the H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.98 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms. One acetate substituent is disordered over two equivalent conformations with occupancies of 0.755 (17) and 0.245 (17).In the ≡C group of one of the pent-4-ynoate substituents is disordered over two positions with occupancies of 0.55 (2) and 0.45 (2).
for (2), the H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.99 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms. The CCoumarins and their derivatives have wide applications in a number of diverse areas. They are used in the pharmaceutical industry as precursor reagents in the synthesis of a number of synthetic anticoagulant pharmaceuticals (Bairagi et al., 2012), the most notable being warfarin (Holbrook et al., 2005). Modified
are a type of vitamin K antagonist (Marongiu & Barcellona, 2015).In another important application, coumarin dyes are extensively used as gain media in blue–green tunable organic dye lasers (Schäfer, 1990; Duarte & Hillman, 1990; Duarte, 2003). Coumarin tetramethyl laser dyes offer wide tunability and high laser gain (Chen et al., 1988; Duarte et al., 2006), and they are also used as the active medium in coherent OLED emitters (Duarte et al., 2005).
4-Methyl coumarin derivatives have previously been used as acetyl-group donors for post-translational modification of proteins via an acetyl–CoA independent mechanism (Raj, Singh et al., 2005; Raj, Kumari et al., 2006). Calreticulin-mediated acetylation of glutathione-S-transferase (GST) using substrate 7,8-diacetyoxy-4-methyl coumarin, DAMC (1) (systematic name: 4-methyl-2-oxo-2H-chromene-7,8-diyl diacetate has been shown to inhibit GST activity in a spectroscopic assay (Raj, Singh et al., 2005). Pentynoyl probes have been used as chemical reporters to monitor protein acetylation (Bateman et al., 2013; Yang et al., 2010). For background to bio-orthogonal reactions using alkyne–azide cycloaddition, see Sletten & Bertozzi (2011) and Yang & Hang 2011).
We have synthesized a new coumarin derivative, 7,8-dipentynoyloxy-4-methyl coumarin, DPeMC (2) [systematic name: 4-methyl-2-oxo-2H chromene-7,8-diyl bis(pent-4-ynoate)] as a chemical reporter of calreticulin's acyltransferase capabilities. As part of this work and as a continuation of our previous structural studies of coumarin derivatives (Jasinski & Paight, 1994, 1995; Jasinski & Woudenberg, 1994, 1995; Jasinski & Li, 2002; Jasinski et al., 1998, 2003; Butcher et al., 2007), the crystal structures of both coumarin derivatives are presented in this article.
This paper reports the structures of two derivatives of coumarin (systematic name; 2H-chromen-2-one), C14H12O6 (1) and C20H16O6 (2), which are to be used as chemical reporters of calreticulin's acyltransferase capabilities. These two compounds will be first discussed individually and then compared.
In the structure of (1) (Fig. 1), the coumarin ring is planar (r.m.s. deviation of fitted atoms = 0.0063 Å) with O2 in the plane [deviation of 0.0048 (9) Å]. Both acetate substituents are significantly rotated out of this plane to minimize steric repulsions [dihedral angle of 66.19 (7)° to the coumarin ring for O3, O4, and C11, and 79.4 (3)° for O5, C13 O6A]. One acetate substituent is disordered over two equivalent conformations with occupancies of 0.755 (17) and 0.245 (17). The metrical parameters of both the coumarin ring and acetate substituents are in the normal ranges.
By contrast with (1), in the structure of (2) (Fig. 2) there are two pent-4-ynoate substituents in place of the acetate substituents. The C≡ C group of one of the pent-4-ynoate substituents is disordered over two positions with occupancies of 0.55 (2) and 0.45 (2). The coumarin ring is planar (r.m.s. deviation of fitted atoms = 0.0305 Å) with O2 significantly out of this plane [0.144 (2) Å] but O3 in the plane [0.063 (2) Å]. One of the pent-4-ynoate substituents is in an extended conformation (O5 to C21) while the other is in a bent conformation about C13. This can be seen clearly from a consideration of the O3—C12—C13—C14 torsion angle of -46.3 (2)° compared to the equivalent torsion angle O5—C17—C18—C19 of 176.16 (12)°. The planar parts of both pent-4-ynoate substituents deviate from the coumarin plane but by different amounts [40.90 (15)° for O3, O4 and C12 compared to 74.07 (10)° for O5, O6 and C17]. The metrical parameters of both the coumarin ring and pent-4-ynoate substituents are in the normal ranges including the C≡C triple bonds [C15A≡C16A = 1.186 (9), C15B≡ C16B = 1.169 (11) and C20≡C21 = 1.177 (3) Å].
The packing of (1) is dominated by π–π stacking involving the coumarin rings [centroid–centroid distance of 3.6640 (5) Å, slippage of 1.422 Å, symmetry code 1 - x, 1 - y, 1 - z]. This can be observed in Fig. 3. In addition, there are weak C—H···O contacts involving C13 and O6A(x, 1 + y, z) as well as C6 and O2(x - 1, 1 + y, z), C15A and O2 (1 - x, -y, 2 - z) which link the parallel stacks in the [101] direction.
In contract to (1), for (2) the packing is dominated by R22(24) hydrogen bonds involving the acidic sp H atom and O2 which link the molecules into centrosymmetric dimers. The bent conformation of one of the pent-4-ynoate substituents prevents the coumarin rings from engaging in π–π stacking in contrast to (1).
The
of 7,8-dihydroxy-4-methylcoumarin (Kurosaki et al., (2003) and other related coumarin structures (Jasinski & Paight, 1994, 1995; Jasinski & Woudenberg, 1994, 1995; Jasinski & Li, 2002; Jasinski et al., 1998, 2003; Butcher et al., 2007) have been reported. For more background on calreticulin transacetylase activity, see Singh et al., (2011).7,8-Diacetoxy-4-methylcoumarin (1). 4-Methyl-2-oxo-2H-chromene-7,8-diyl diacetate (DAMC) was synthesized using a previously reported procedure (Jalal et al., 2012).
7,8-Dipentynoyloxy-4-methylcoumarin (2). 0.5 mmol 7,8-dihydroxy-4-methyl coumarin, DHMC [systematic name: 7,8-dihydroxy-4-methyl-2H-chromen-2-one], 2.5 equivalents pentynoic anhydride (Malkoch et al., 2005) and catalytic 4-dimethylaminopyridine (DMAP) was stirred for 24 h at room temperature in anhydrous THF (2 mL). Ice-cold water (25 mL) was added to the reaction flask, and the filtered crude product was washed with hexanes followed by recrystallization from ethanol to obtain small brown crystals of 4-methyl-2-oxo-2H chromene-7,8-diyl bis(pent-4-ynoate).
Spectroscopic analysis: 1H NMR (400 MHz, CDCl3): δ 7.51–7.49 (1H, d), δ 7.20–7.17 (1H, d), δ 6.29 (1H, s), δ 3.01–3.08 (2H, m, HC≡C), δ 2.89–2.84 (2H, t, C≡C—CH2), δ 2.61–2.70 (4H, m, OOC—CH2), δ 2.44 (3H, s, CH3), δ 2.09–2.11 (2H, C≡C-–CH2).
detailsCrystal data, data collection and structure
details are summarized in Table 3. For (1), the H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.98 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms. One acetate substituent is disordered over two equivalent conformations with occupancies of 0.755 (17) and 0.245 (17).In the ≡C group of one of the pent-4-ynoate substituents is disordered over two positions with occupancies of 0.55 (2) and 0.45 (2).
for (2), the H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.99 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms. The CData collection: CrysAlis PRO (Agilent, 2014) for (1); APEX2 (Bruker, 2005) for (2). Cell
CrysAlis PRO (Agilent, 2014) for (1); APEX2 (Bruker, 2005) for (2). Data reduction: CrysAlis PRO (Agilent, 2014) for (1); SAINT (Bruker, 2002) for (2). For both compounds, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Diagram of the structure and numbering scheme for (1), showing the major occupancy component only. Atomic displacement parameters are drawn at the 30% probability level. | |
Fig. 2. Diagram of the structure and numbering scheme for (2), showing the major occupancy component only. Atomic displacement parameters are drawn at the 30% probability level. | |
Fig. 3. Packing diagram for (1), viewed along the c axis, showing the parallel coumarin rings. C—H···O secondary interactions are drawn with dashed bonds. | |
Fig. 4. Packing diagram for (2), viewed along the a axis. R22(24) hydrogen bonds involving the acidic sp H and O2 atoms link the molecules into centrosymmetric dimers. C—H···O secondary interactions are drawn with dashed bonds. |
C14H12O6 | Z = 2 |
Mr = 276.24 | F(000) = 288 |
Triclinic, P1 | Dx = 1.401 Mg m−3 |
a = 7.3722 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.7235 (7) Å | Cell parameters from 1905 reflections |
c = 11.7032 (15) Å | θ = 4.4–32.8° |
α = 69.263 (10)° | µ = 0.11 mm−1 |
β = 87.519 (11)° | T = 173 K |
γ = 69.113 (10)° | The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments., colorless |
V = 654.66 (14) Å3 | 0.33 × 0.26 × 0.11 mm |
Agilent Xcalibur Eos Gemini diffractometer | 4296 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3087 reflections with I > 2σ(I) |
Detector resolution: 16.0416 pixels mm-1 | Rint = 0.036 |
ω scans | θmax = 32.7°, θmin = 3.2° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | h = −11→8 |
Tmin = 0.883, Tmax = 1.000 | k = −13→12 |
7360 measured reflections | l = −16→17 |
Refinement on F2 | 13 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.156 | w = 1/[σ2(Fo2) + (0.0738P)2 + 0.0282P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4296 reflections | Δρmax = 0.36 e Å−3 |
192 parameters | Δρmin = −0.24 e Å−3 |
C14H12O6 | γ = 69.113 (10)° |
Mr = 276.24 | V = 654.66 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.3722 (10) Å | Mo Kα radiation |
b = 8.7235 (7) Å | µ = 0.11 mm−1 |
c = 11.7032 (15) Å | T = 173 K |
α = 69.263 (10)° | 0.33 × 0.26 × 0.11 mm |
β = 87.519 (11)° |
Agilent Xcalibur Eos Gemini diffractometer | 4296 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | 3087 reflections with I > 2σ(I) |
Tmin = 0.883, Tmax = 1.000 | Rint = 0.036 |
7360 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 13 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.36 e Å−3 |
4296 reflections | Δρmin = −0.24 e Å−3 |
192 parameters |
Experimental. Absorption correction: CrysAlisPro (Agilent Technologies, 2014) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.48459 (13) | 0.24436 (11) | 0.69118 (8) | 0.0225 (2) | |
O2 | 0.67011 (16) | 0.00141 (12) | 0.66239 (10) | 0.0336 (3) | |
O3 | 0.09094 (15) | 0.73883 (12) | 0.78120 (9) | 0.0264 (2) | |
O4 | 0.20400 (17) | 0.95648 (13) | 0.68569 (10) | 0.0332 (3) | |
O5 | 0.38600 (14) | 0.41942 (12) | 0.84842 (8) | 0.0238 (2) | |
C2 | 0.54690 (19) | 0.14688 (16) | 0.61566 (13) | 0.0234 (3) | |
C3 | 0.4606 (2) | 0.22921 (16) | 0.49018 (12) | 0.0235 (3) | |
H3A | 0.5012 | 0.1646 | 0.4372 | 0.028* | |
C4 | 0.32496 (19) | 0.39359 (16) | 0.44454 (12) | 0.0203 (2) | |
C11 | 0.2429 (2) | 0.47678 (18) | 0.31289 (12) | 0.0267 (3) | |
H11A | 0.2925 | 0.3903 | 0.2729 | 0.040* | |
H11B | 0.2823 | 0.5775 | 0.2711 | 0.040* | |
H11C | 0.1003 | 0.5170 | 0.3085 | 0.040* | |
C10 | 0.26109 (18) | 0.49190 (15) | 0.52589 (11) | 0.0183 (2) | |
C5 | 0.11893 (18) | 0.66244 (15) | 0.49057 (12) | 0.0209 (3) | |
H5A | 0.0596 | 0.7197 | 0.4086 | 0.025* | |
C6 | 0.06342 (19) | 0.74874 (15) | 0.57236 (12) | 0.0225 (3) | |
H6A | −0.0339 | 0.8636 | 0.5473 | 0.027* | |
C7 | 0.15204 (19) | 0.66502 (15) | 0.69197 (12) | 0.0207 (2) | |
C8 | 0.29286 (18) | 0.49730 (15) | 0.72996 (11) | 0.0193 (2) | |
C9 | 0.34563 (17) | 0.41057 (14) | 0.64741 (12) | 0.0183 (2) | |
C12 | 0.1158 (2) | 0.89364 (16) | 0.76502 (13) | 0.0244 (3) | |
C13 | 0.0176 (3) | 0.9662 (2) | 0.85859 (16) | 0.0368 (4) | |
H13A | 0.0693 | 1.0528 | 0.8641 | 0.055* | |
H13B | 0.0421 | 0.8704 | 0.9386 | 0.055* | |
H13C | −0.1231 | 1.0232 | 0.8347 | 0.055* | |
C14 | 0.3169 (3) | 0.3042 (2) | 0.93265 (14) | 0.0376 (4) | |
O6A | 0.1945 (8) | 0.2587 (9) | 0.9046 (3) | 0.0509 (11) | 0.755 (17) |
C15A | 0.4350 (12) | 0.2219 (9) | 1.0560 (7) | 0.0572 (13) | 0.755 (17) |
H15A | 0.5502 | 0.1208 | 1.0568 | 0.086* | 0.755 (17) |
H15B | 0.3550 | 0.1827 | 1.1207 | 0.086* | 0.755 (17) |
H15C | 0.4764 | 0.3090 | 1.0706 | 0.086* | 0.755 (17) |
O6B | 0.150 (2) | 0.3148 (19) | 0.9106 (11) | 0.0509 (11) | 0.245 (17) |
C15B | 0.406 (4) | 0.265 (3) | 1.051 (2) | 0.0572 (13) | 0.245 (17) |
H15D | 0.3343 | 0.3584 | 1.0818 | 0.086* | 0.245 (17) |
H15E | 0.5415 | 0.2586 | 1.0435 | 0.086* | 0.245 (17) |
H15F | 0.4039 | 0.1523 | 1.1073 | 0.086* | 0.245 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0247 (5) | 0.0181 (4) | 0.0211 (5) | −0.0030 (3) | −0.0014 (4) | −0.0075 (3) |
O2 | 0.0349 (6) | 0.0229 (5) | 0.0345 (6) | −0.0005 (4) | 0.0013 (5) | −0.0107 (4) |
O3 | 0.0366 (5) | 0.0242 (4) | 0.0236 (5) | −0.0127 (4) | 0.0108 (4) | −0.0137 (4) |
O4 | 0.0434 (6) | 0.0334 (5) | 0.0314 (6) | −0.0202 (5) | 0.0118 (5) | −0.0162 (4) |
O5 | 0.0286 (5) | 0.0265 (4) | 0.0171 (4) | −0.0115 (4) | −0.0004 (4) | −0.0069 (3) |
C2 | 0.0247 (6) | 0.0201 (5) | 0.0263 (7) | −0.0074 (5) | 0.0053 (5) | −0.0105 (5) |
C3 | 0.0276 (6) | 0.0242 (6) | 0.0239 (7) | −0.0109 (5) | 0.0064 (5) | −0.0135 (5) |
C4 | 0.0227 (6) | 0.0237 (5) | 0.0196 (6) | −0.0125 (5) | 0.0048 (5) | −0.0099 (5) |
C11 | 0.0313 (7) | 0.0320 (7) | 0.0204 (7) | −0.0131 (6) | 0.0023 (5) | −0.0118 (5) |
C10 | 0.0194 (6) | 0.0198 (5) | 0.0178 (6) | −0.0091 (4) | 0.0025 (4) | −0.0072 (4) |
C5 | 0.0218 (6) | 0.0207 (5) | 0.0189 (6) | −0.0080 (4) | 0.0007 (5) | −0.0052 (4) |
C6 | 0.0232 (6) | 0.0183 (5) | 0.0236 (7) | −0.0056 (4) | 0.0031 (5) | −0.0070 (5) |
C7 | 0.0242 (6) | 0.0207 (5) | 0.0211 (6) | −0.0100 (5) | 0.0070 (5) | −0.0109 (5) |
C8 | 0.0217 (6) | 0.0206 (5) | 0.0163 (6) | −0.0092 (4) | 0.0009 (4) | −0.0058 (4) |
C9 | 0.0184 (5) | 0.0157 (5) | 0.0207 (6) | −0.0060 (4) | 0.0016 (4) | −0.0066 (4) |
C12 | 0.0278 (6) | 0.0237 (6) | 0.0240 (7) | −0.0082 (5) | 0.0013 (5) | −0.0122 (5) |
C13 | 0.0480 (9) | 0.0391 (8) | 0.0367 (9) | −0.0195 (7) | 0.0147 (7) | −0.0266 (7) |
C14 | 0.0538 (10) | 0.0411 (8) | 0.0212 (7) | −0.0277 (7) | 0.0018 (7) | −0.0045 (6) |
O6A | 0.076 (2) | 0.061 (2) | 0.0308 (8) | −0.053 (2) | 0.0009 (11) | −0.0047 (13) |
C15A | 0.088 (3) | 0.055 (3) | 0.0236 (12) | −0.038 (3) | −0.0136 (16) | 0.006 (2) |
O6B | 0.076 (2) | 0.061 (2) | 0.0308 (8) | −0.053 (2) | 0.0009 (11) | −0.0047 (13) |
C15B | 0.088 (3) | 0.055 (3) | 0.0236 (12) | −0.038 (3) | −0.0136 (16) | 0.006 (2) |
O1—C9 | 1.3691 (14) | C5—H5A | 0.9500 |
O1—C2 | 1.3906 (15) | C6—C7 | 1.3910 (19) |
O2—C2 | 1.2100 (16) | C6—H6A | 0.9500 |
O3—C12 | 1.3731 (15) | C7—C8 | 1.3829 (17) |
O3—C7 | 1.3916 (15) | C8—C9 | 1.3901 (17) |
O4—C12 | 1.1945 (17) | C12—C13 | 1.4898 (19) |
O5—C14 | 1.3641 (17) | C13—H13A | 0.9800 |
O5—C8 | 1.3921 (15) | C13—H13B | 0.9800 |
C2—C3 | 1.4440 (19) | C13—H13C | 0.9800 |
C3—C4 | 1.3502 (18) | C14—O6A | 1.205 (4) |
C3—H3A | 0.9500 | C14—O6B | 1.234 (14) |
C4—C10 | 1.4544 (17) | C14—C15B | 1.43 (2) |
C4—C11 | 1.4973 (19) | C14—C15A | 1.512 (7) |
C11—H11A | 0.9800 | C15A—H15A | 0.9800 |
C11—H11B | 0.9800 | C15A—H15B | 0.9800 |
C11—H11C | 0.9800 | C15A—H15C | 0.9800 |
C10—C9 | 1.4005 (18) | C15B—H15D | 0.9800 |
C10—C5 | 1.4045 (16) | C15B—H15E | 0.9800 |
C5—C6 | 1.3810 (17) | C15B—H15F | 0.9800 |
C9—O1—C2 | 120.75 (10) | C9—C8—O5 | 120.50 (11) |
C12—O3—C7 | 117.51 (10) | O1—C9—C8 | 116.45 (11) |
C14—O5—C8 | 116.43 (11) | O1—C9—C10 | 122.58 (11) |
O2—C2—O1 | 116.03 (12) | C8—C9—C10 | 120.96 (11) |
O2—C2—C3 | 126.76 (13) | O4—C12—O3 | 122.90 (12) |
O1—C2—C3 | 117.20 (11) | O4—C12—C13 | 126.98 (13) |
C4—C3—C2 | 123.15 (12) | O3—C12—C13 | 110.12 (12) |
C4—C3—H3A | 118.4 | C12—C13—H13A | 109.5 |
C2—C3—H3A | 118.4 | C12—C13—H13B | 109.5 |
C3—C4—C10 | 118.48 (12) | H13A—C13—H13B | 109.5 |
C3—C4—C11 | 121.68 (12) | C12—C13—H13C | 109.5 |
C10—C4—C11 | 119.83 (11) | H13A—C13—H13C | 109.5 |
C4—C11—H11A | 109.5 | H13B—C13—H13C | 109.5 |
C4—C11—H11B | 109.5 | O6A—C14—O5 | 122.2 (2) |
H11A—C11—H11B | 109.5 | O6B—C14—O5 | 117.7 (6) |
C4—C11—H11C | 109.5 | O6B—C14—C15B | 125.8 (15) |
H11A—C11—H11C | 109.5 | O5—C14—C15B | 107.3 (11) |
H11B—C11—H11C | 109.5 | O6A—C14—C15A | 125.4 (4) |
C9—C10—C5 | 118.01 (11) | O5—C14—C15A | 111.6 (3) |
C9—C10—C4 | 117.84 (11) | C14—C15A—H15A | 109.5 |
C5—C10—C4 | 124.15 (12) | C14—C15A—H15B | 109.5 |
C6—C5—C10 | 121.47 (12) | H15A—C15A—H15B | 109.5 |
C6—C5—H5A | 119.3 | C14—C15A—H15C | 109.5 |
C10—C5—H5A | 119.3 | H15A—C15A—H15C | 109.5 |
C5—C6—C7 | 119.04 (11) | H15B—C15A—H15C | 109.5 |
C5—C6—H6A | 120.5 | C14—C15B—H15D | 109.5 |
C7—C6—H6A | 120.5 | C14—C15B—H15E | 109.5 |
C8—C7—C6 | 121.09 (11) | H15D—C15B—H15E | 109.5 |
C8—C7—O3 | 117.00 (11) | C14—C15B—H15F | 109.5 |
C6—C7—O3 | 121.65 (11) | H15D—C15B—H15F | 109.5 |
C7—C8—C9 | 119.41 (11) | H15E—C15B—H15F | 109.5 |
C7—C8—O5 | 120.05 (11) | ||
C9—O1—C2—O2 | 180.00 (11) | O3—C7—C8—O5 | −8.72 (17) |
C9—O1—C2—C3 | 0.67 (17) | C14—O5—C8—C7 | 98.60 (15) |
O2—C2—C3—C4 | −179.19 (13) | C14—O5—C8—C9 | −83.97 (15) |
O1—C2—C3—C4 | 0.07 (19) | C2—O1—C9—C8 | 179.93 (11) |
C2—C3—C4—C10 | −0.66 (19) | C2—O1—C9—C10 | −0.79 (17) |
C2—C3—C4—C11 | 178.16 (12) | C7—C8—C9—O1 | −179.44 (10) |
C3—C4—C10—C9 | 0.54 (17) | O5—C8—C9—O1 | 3.11 (17) |
C11—C4—C10—C9 | −178.31 (11) | C7—C8—C9—C10 | 1.28 (18) |
C3—C4—C10—C5 | −178.89 (11) | O5—C8—C9—C10 | −176.18 (10) |
C11—C4—C10—C5 | 2.27 (19) | C5—C10—C9—O1 | 179.64 (10) |
C9—C10—C5—C6 | 0.16 (18) | C4—C10—C9—O1 | 0.18 (18) |
C4—C10—C5—C6 | 179.58 (11) | C5—C10—C9—C8 | −1.12 (18) |
C10—C5—C6—C7 | 0.63 (18) | C4—C10—C9—C8 | 179.42 (11) |
C5—C6—C7—C8 | −0.48 (19) | C7—O3—C12—O4 | −7.8 (2) |
C5—C6—C7—O3 | −174.49 (11) | C7—O3—C12—C13 | 171.97 (12) |
C12—O3—C7—C8 | 120.51 (13) | C8—O5—C14—O6A | 6.8 (5) |
C12—O3—C7—C6 | −65.25 (16) | C8—O5—C14—O6B | −20.6 (8) |
C6—C7—C8—C9 | −0.46 (18) | C8—O5—C14—C15B | −169.5 (13) |
O3—C7—C8—C9 | 173.82 (11) | C8—O5—C14—C15A | 177.4 (4) |
C6—C7—C8—O5 | 177.00 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···O2i | 0.95 | 2.65 | 3.3465 (17) | 130 |
C13—H13A···O6Aii | 0.98 | 2.48 | 3.451 (5) | 173 |
C15A—H15B···O2iii | 0.98 | 2.52 | 3.401 (8) | 150 |
Symmetry codes: (i) x−1, y+1, z; (ii) x, y+1, z; (iii) −x+1, −y, −z+2. |
C20H16O6 | F(000) = 736 |
Mr = 352.33 | Dx = 1.357 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.2785 (3) Å | Cell parameters from 9562 reflections |
b = 16.3785 (8) Å | θ = 2.5–30.4° |
c = 20.0502 (11) Å | µ = 0.10 mm−1 |
β = 95.992 (2)° | T = 200 K |
V = 1723.95 (16) Å3 | Rod, colourless |
Z = 4 | 0.55 × 0.14 × 0.11 mm |
Bruker Quest diffractometer | 3859 reflections with I > 2σ(I) |
ω scans | Rint = 0.035 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 30.6°, θmin = 2.5° |
Tmin = 0.658, Tmax = 0.746 | h = −7→6 |
24358 measured reflections | k = −23→23 |
5276 independent reflections | l = −28→28 |
Refinement on F2 | 13 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.142 | w = 1/[σ2(Fo2) + (0.0483P)2 + 1.0298P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
5276 reflections | Δρmax = 0.37 e Å−3 |
255 parameters | Δρmin = −0.21 e Å−3 |
C20H16O6 | V = 1723.95 (16) Å3 |
Mr = 352.33 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.2785 (3) Å | µ = 0.10 mm−1 |
b = 16.3785 (8) Å | T = 200 K |
c = 20.0502 (11) Å | 0.55 × 0.14 × 0.11 mm |
β = 95.992 (2)° |
Bruker Quest diffractometer | 5276 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3859 reflections with I > 2σ(I) |
Tmin = 0.658, Tmax = 0.746 | Rint = 0.035 |
24358 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 13 restraints |
wR(F2) = 0.142 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.37 e Å−3 |
5276 reflections | Δρmin = −0.21 e Å−3 |
255 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.4888 (2) | 0.14589 (6) | 0.70580 (6) | 0.0315 (3) | |
O2 | 0.7381 (3) | 0.03765 (8) | 0.70909 (7) | 0.0482 (4) | |
O3 | −0.0447 (2) | 0.37392 (7) | 0.67567 (6) | 0.0326 (3) | |
O4 | 0.1091 (2) | 0.50086 (8) | 0.66067 (7) | 0.0416 (3) | |
O5 | 0.0579 (2) | 0.21864 (7) | 0.64977 (5) | 0.0278 (2) | |
O6 | 0.3186 (2) | 0.22167 (8) | 0.56756 (6) | 0.0384 (3) | |
C2 | 0.7046 (3) | 0.10414 (10) | 0.73219 (8) | 0.0329 (3) | |
C3 | 0.8638 (3) | 0.14369 (10) | 0.78577 (8) | 0.0327 (3) | |
H3A | 1.0078 | 0.1150 | 0.8063 | 0.039* | |
C4 | 0.8176 (3) | 0.21931 (10) | 0.80793 (7) | 0.0289 (3) | |
C5 | 0.5425 (3) | 0.34519 (9) | 0.79035 (8) | 0.0309 (3) | |
H5A | 0.6481 | 0.3735 | 0.8240 | 0.037* | |
C6 | 0.3343 (3) | 0.38464 (10) | 0.75779 (8) | 0.0317 (3) | |
H6A | 0.2971 | 0.4395 | 0.7686 | 0.038* | |
C7 | 0.1793 (3) | 0.34264 (9) | 0.70865 (7) | 0.0272 (3) | |
C8 | 0.2314 (3) | 0.26251 (9) | 0.69265 (7) | 0.0249 (3) | |
C9 | 0.4453 (3) | 0.22431 (9) | 0.72504 (7) | 0.0253 (3) | |
C10 | 0.6024 (3) | 0.26439 (9) | 0.77514 (7) | 0.0263 (3) | |
C11 | 0.9821 (4) | 0.25697 (12) | 0.86536 (9) | 0.0394 (4) | |
H11D | 1.1244 | 0.2203 | 0.8794 | 0.056 (6)* | |
H11E | 0.8808 | 0.2659 | 0.9030 | 0.066 (7)* | |
H11F | 1.0484 | 0.3094 | 0.8512 | 0.068 (7)* | |
C12 | −0.0603 (3) | 0.45274 (10) | 0.65301 (8) | 0.0300 (3) | |
C13 | −0.3222 (3) | 0.46849 (11) | 0.61876 (10) | 0.0394 (4) | |
H13A | −0.3207 | 0.5209 | 0.5942 | 0.047* | |
H13B | −0.4420 | 0.4744 | 0.6533 | 0.047* | |
C14 | −0.4205 (4) | 0.40154 (13) | 0.56970 (11) | 0.0449 (5) | |
H14A | −0.591 (5) | 0.4172 (15) | 0.5499 (13) | 0.067 (7)* | |
H14B | −0.433 (4) | 0.3504 (13) | 0.5928 (11) | 0.042 (5)* | |
C15A | −0.280 (2) | 0.3949 (8) | 0.5166 (7) | 0.0399 (16) | 0.55 (2) |
C16A | −0.147 (3) | 0.3912 (8) | 0.4725 (6) | 0.059 (2) | 0.55 (2) |
H16A | −0.0410 | 0.3882 | 0.4371 | 0.071* | 0.55 (2) |
C15B | −0.228 (3) | 0.3822 (10) | 0.5170 (8) | 0.0399 (16) | 0.45 (2) |
C16B | −0.084 (3) | 0.3704 (10) | 0.4775 (8) | 0.059 (2) | 0.45 (2) |
H16B | 0.0337 | 0.3609 | 0.4455 | 0.071* | 0.45 (2) |
C17 | 0.1254 (3) | 0.19905 (9) | 0.58756 (7) | 0.0258 (3) | |
C18 | −0.0746 (3) | 0.14582 (10) | 0.55133 (8) | 0.0300 (3) | |
H18A | −0.2420 | 0.1734 | 0.5498 | 0.036* | |
H18B | −0.0856 | 0.0939 | 0.5762 | 0.036* | |
C19 | −0.0149 (3) | 0.12754 (10) | 0.48024 (8) | 0.0341 (4) | |
H19A | −0.0120 | 0.1794 | 0.4549 | 0.041* | |
H19B | 0.1567 | 0.1028 | 0.4819 | 0.041* | |
C20 | −0.2013 (4) | 0.07199 (10) | 0.44457 (8) | 0.0360 (4) | |
C21 | −0.3513 (4) | 0.02838 (12) | 0.41527 (10) | 0.0468 (5) | |
H21 | −0.4724 | −0.0068 | 0.3916 | 0.077 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0352 (6) | 0.0212 (5) | 0.0355 (6) | −0.0018 (4) | −0.0082 (5) | −0.0036 (4) |
O2 | 0.0545 (8) | 0.0302 (6) | 0.0553 (8) | 0.0084 (6) | −0.0157 (6) | −0.0085 (6) |
O3 | 0.0307 (6) | 0.0262 (6) | 0.0396 (6) | −0.0003 (4) | −0.0019 (5) | −0.0005 (5) |
O4 | 0.0330 (6) | 0.0369 (7) | 0.0538 (8) | −0.0062 (5) | −0.0014 (5) | 0.0089 (6) |
O5 | 0.0264 (5) | 0.0289 (5) | 0.0273 (5) | −0.0056 (4) | −0.0008 (4) | −0.0043 (4) |
O6 | 0.0324 (6) | 0.0449 (7) | 0.0383 (6) | −0.0130 (5) | 0.0061 (5) | −0.0084 (5) |
C2 | 0.0373 (9) | 0.0238 (7) | 0.0358 (8) | −0.0007 (6) | −0.0042 (7) | 0.0024 (6) |
C3 | 0.0333 (8) | 0.0288 (8) | 0.0341 (8) | −0.0035 (6) | −0.0057 (6) | 0.0062 (6) |
C4 | 0.0309 (8) | 0.0293 (7) | 0.0253 (7) | −0.0089 (6) | −0.0025 (6) | 0.0049 (6) |
C5 | 0.0413 (9) | 0.0268 (7) | 0.0233 (7) | −0.0087 (6) | −0.0024 (6) | −0.0037 (6) |
C6 | 0.0427 (9) | 0.0246 (7) | 0.0272 (7) | −0.0031 (6) | 0.0009 (6) | −0.0033 (6) |
C7 | 0.0307 (7) | 0.0258 (7) | 0.0250 (7) | −0.0014 (6) | 0.0024 (6) | 0.0006 (5) |
C8 | 0.0276 (7) | 0.0239 (7) | 0.0227 (6) | −0.0071 (6) | 0.0001 (5) | −0.0018 (5) |
C9 | 0.0312 (7) | 0.0192 (6) | 0.0249 (7) | −0.0052 (6) | 0.0001 (5) | 0.0002 (5) |
C10 | 0.0315 (7) | 0.0239 (7) | 0.0224 (7) | −0.0072 (6) | −0.0018 (5) | 0.0015 (5) |
C11 | 0.0410 (9) | 0.0414 (10) | 0.0324 (8) | −0.0080 (8) | −0.0120 (7) | 0.0010 (7) |
C12 | 0.0300 (8) | 0.0283 (8) | 0.0323 (8) | 0.0030 (6) | 0.0063 (6) | −0.0008 (6) |
C13 | 0.0309 (8) | 0.0318 (9) | 0.0544 (11) | 0.0021 (7) | −0.0004 (7) | −0.0005 (7) |
C14 | 0.0344 (9) | 0.0408 (10) | 0.0570 (12) | −0.0078 (8) | −0.0078 (8) | −0.0006 (9) |
C15A | 0.043 (4) | 0.034 (4) | 0.0394 (10) | −0.006 (3) | −0.008 (2) | −0.0004 (19) |
C16A | 0.071 (5) | 0.057 (5) | 0.051 (2) | −0.017 (3) | 0.008 (3) | −0.008 (3) |
C15B | 0.043 (4) | 0.034 (4) | 0.0394 (10) | −0.006 (3) | −0.008 (2) | −0.0004 (19) |
C16B | 0.071 (5) | 0.057 (5) | 0.051 (2) | −0.017 (3) | 0.008 (3) | −0.008 (3) |
C17 | 0.0260 (7) | 0.0229 (7) | 0.0274 (7) | 0.0005 (5) | −0.0014 (5) | −0.0015 (5) |
C18 | 0.0280 (7) | 0.0308 (8) | 0.0305 (8) | −0.0053 (6) | −0.0002 (6) | −0.0060 (6) |
C19 | 0.0399 (9) | 0.0331 (8) | 0.0282 (8) | −0.0055 (7) | −0.0009 (6) | −0.0013 (6) |
C20 | 0.0480 (10) | 0.0307 (8) | 0.0275 (8) | 0.0009 (7) | −0.0041 (7) | 0.0001 (6) |
C21 | 0.0602 (12) | 0.0379 (10) | 0.0390 (10) | −0.0072 (9) | −0.0103 (9) | −0.0037 (8) |
O1—C9 | 1.3675 (18) | C11—H11E | 0.9800 |
O1—C2 | 1.3851 (19) | C11—H11F | 0.9800 |
O2—C2 | 1.204 (2) | C12—C13 | 1.501 (2) |
O3—C12 | 1.3682 (19) | C13—C14 | 1.527 (3) |
O3—C7 | 1.3911 (19) | C13—H13A | 0.9900 |
O4—C12 | 1.189 (2) | C13—H13B | 0.9900 |
O5—C17 | 1.3705 (18) | C14—C15A | 1.364 (13) |
O5—C8 | 1.3889 (17) | C14—C15B | 1.574 (15) |
O6—C17 | 1.1931 (19) | C14—H14A | 0.98 (3) |
C2—C3 | 1.446 (2) | C14—H14B | 0.96 (2) |
C3—C4 | 1.347 (2) | C15A—C16A | 1.186 (9) |
C3—H3A | 0.9500 | C16A—H16A | 0.9500 |
C4—C10 | 1.453 (2) | C15B—C16B | 1.169 (11) |
C4—C11 | 1.501 (2) | C16B—H16B | 0.9500 |
C5—C6 | 1.379 (2) | C17—C18 | 1.497 (2) |
C5—C10 | 1.402 (2) | C18—C19 | 1.521 (2) |
C5—H5A | 0.9500 | C18—H18A | 0.9900 |
C6—C7 | 1.394 (2) | C18—H18B | 0.9900 |
C6—H6A | 0.9500 | C19—C20 | 1.470 (2) |
C7—C8 | 1.385 (2) | C19—H19A | 0.9900 |
C8—C9 | 1.391 (2) | C19—H19B | 0.9900 |
C9—C10 | 1.3977 (19) | C20—C21 | 1.177 (3) |
C11—H11D | 0.9800 | C21—H21 | 0.9500 |
C9—O1—C2 | 120.77 (12) | O3—C12—C13 | 109.55 (14) |
C12—O3—C7 | 121.60 (12) | C12—C13—C14 | 113.95 (15) |
C17—O5—C8 | 117.86 (11) | C12—C13—H13A | 108.8 |
O2—C2—O1 | 116.59 (14) | C14—C13—H13A | 108.8 |
O2—C2—C3 | 126.42 (16) | C12—C13—H13B | 108.8 |
O1—C2—C3 | 116.97 (14) | C14—C13—H13B | 108.8 |
C4—C3—C2 | 123.07 (15) | H13A—C13—H13B | 107.7 |
C4—C3—H3A | 118.5 | C15A—C14—C13 | 112.6 (6) |
C2—C3—H3A | 118.5 | C13—C14—C15B | 112.2 (7) |
C3—C4—C10 | 118.56 (14) | C15A—C14—H14A | 104.9 (16) |
C3—C4—C11 | 121.39 (15) | C13—C14—H14A | 107.9 (15) |
C10—C4—C11 | 120.05 (14) | C15B—C14—H14A | 114.3 (16) |
C6—C5—C10 | 121.75 (14) | C15A—C14—H14B | 112.2 (14) |
C6—C5—H5A | 119.1 | C13—C14—H14B | 110.5 (13) |
C10—C5—H5A | 119.1 | C15B—C14—H14B | 103.3 (14) |
C5—C6—C7 | 118.88 (14) | H14A—C14—H14B | 108.4 (19) |
C5—C6—H6A | 120.6 | C16A—C15A—C14 | 176.4 (14) |
C7—C6—H6A | 120.6 | C15A—C16A—H16A | 180.0 |
C8—C7—O3 | 114.71 (13) | C16B—C15B—C14 | 177.9 (16) |
C8—C7—C6 | 121.01 (14) | C15B—C16B—H16B | 180.0 |
O3—C7—C6 | 124.13 (14) | O6—C17—O5 | 123.07 (13) |
C7—C8—O5 | 119.98 (13) | O6—C17—C18 | 127.00 (14) |
C7—C8—C9 | 119.26 (13) | O5—C17—C18 | 109.93 (13) |
O5—C8—C9 | 120.45 (13) | C17—C18—C19 | 111.39 (13) |
O1—C9—C8 | 116.28 (12) | C17—C18—H18A | 109.4 |
O1—C9—C10 | 122.63 (14) | C19—C18—H18A | 109.4 |
C8—C9—C10 | 121.07 (13) | C17—C18—H18B | 109.4 |
C9—C10—C5 | 117.99 (14) | C19—C18—H18B | 109.4 |
C9—C10—C4 | 117.62 (14) | H18A—C18—H18B | 108.0 |
C5—C10—C4 | 124.39 (13) | C20—C19—C18 | 112.58 (14) |
C4—C11—H11D | 109.5 | C20—C19—H19A | 109.1 |
C4—C11—H11E | 109.5 | C18—C19—H19A | 109.1 |
H11D—C11—H11E | 109.5 | C20—C19—H19B | 109.1 |
C4—C11—H11F | 109.5 | C18—C19—H19B | 109.1 |
H11D—C11—H11F | 109.5 | H19A—C19—H19B | 107.8 |
H11E—C11—H11F | 109.5 | C21—C20—C19 | 179.00 (19) |
O4—C12—O3 | 124.34 (15) | C20—C21—H21 | 180.0 |
O4—C12—C13 | 126.10 (15) | ||
C9—O1—C2—O2 | −174.76 (15) | O5—C8—C9—C10 | −171.09 (13) |
C9—O1—C2—C3 | 6.7 (2) | O1—C9—C10—C5 | 179.15 (14) |
O2—C2—C3—C4 | 178.29 (18) | C8—C9—C10—C5 | −2.0 (2) |
O1—C2—C3—C4 | −3.3 (2) | O1—C9—C10—C4 | −0.8 (2) |
C2—C3—C4—C10 | −2.0 (2) | C8—C9—C10—C4 | 178.12 (13) |
C2—C3—C4—C11 | 177.73 (16) | C6—C5—C10—C9 | 0.6 (2) |
C10—C5—C6—C7 | 0.3 (2) | C6—C5—C10—C4 | −179.52 (15) |
C12—O3—C7—C8 | −141.36 (14) | C3—C4—C10—C9 | 4.1 (2) |
C12—O3—C7—C6 | 43.1 (2) | C11—C4—C10—C9 | −175.69 (14) |
C5—C6—C7—C8 | 0.3 (2) | C3—C4—C10—C5 | −175.83 (15) |
C5—C6—C7—O3 | 175.49 (14) | C11—C4—C10—C5 | 4.4 (2) |
O3—C7—C8—O5 | −3.7 (2) | C7—O3—C12—O4 | −1.9 (2) |
C6—C7—C8—O5 | 171.99 (14) | C7—O3—C12—C13 | 179.10 (14) |
O3—C7—C8—C9 | −177.27 (13) | O4—C12—C13—C14 | 134.73 (19) |
C6—C7—C8—C9 | −1.6 (2) | O3—C12—C13—C14 | −46.3 (2) |
C17—O5—C8—C7 | 111.09 (16) | C12—C13—C14—C15A | −64.6 (6) |
C17—O5—C8—C9 | −75.36 (17) | C12—C13—C14—C15B | −53.0 (7) |
C2—O1—C9—C8 | 176.26 (14) | C8—O5—C17—O6 | −4.2 (2) |
C2—O1—C9—C10 | −4.8 (2) | C8—O5—C17—C18 | 174.99 (12) |
C7—C8—C9—O1 | −178.55 (13) | O6—C17—C18—C19 | −4.7 (2) |
O5—C8—C9—O1 | 7.9 (2) | O5—C17—C18—C19 | 176.16 (13) |
C7—C8—C9—C10 | 2.5 (2) | C17—C18—C19—C20 | 177.12 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13B···O4i | 0.99 | 2.43 | 3.244 (2) | 139 |
C18—H18A···O6i | 0.99 | 2.51 | 3.482 (2) | 167 |
Symmetry code: (i) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···O2i | 0.95 | 2.65 | 3.3465 (17) | 130.2 |
C13—H13A···O6Aii | 0.98 | 2.48 | 3.451 (5) | 173.1 |
C15A—H15B···O2iii | 0.98 | 2.52 | 3.401 (8) | 149.8 |
Symmetry codes: (i) x−1, y+1, z; (ii) x, y+1, z; (iii) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13B···O4i | 0.99 | 2.43 | 3.244 (2) | 139.3 |
C18—H18A···O6i | 0.99 | 2.51 | 3.482 (2) | 166.8 |
Symmetry code: (i) x−1, y, z. |
Experimental details
(1) | (2) | |
Crystal data | ||
Chemical formula | C14H12O6 | C20H16O6 |
Mr | 276.24 | 352.33 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 173 | 200 |
a, b, c (Å) | 7.3722 (10), 8.7235 (7), 11.7032 (15) | 5.2785 (3), 16.3785 (8), 20.0502 (11) |
α, β, γ (°) | 69.263 (10), 87.519 (11), 69.113 (10) | 90, 95.992 (2), 90 |
V (Å3) | 654.66 (14) | 1723.95 (16) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.10 |
Crystal size (mm) | 0.33 × 0.26 × 0.11 | 0.55 × 0.14 × 0.11 |
Data collection | ||
Diffractometer | Agilent Xcalibur Eos Gemini | Bruker Quest |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2014) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.883, 1.000 | 0.658, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7360, 4296, 3087 | 24358, 5276, 3859 |
Rint | 0.036 | 0.035 |
(sin θ/λ)max (Å−1) | 0.759 | 0.716 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.156, 1.04 | 0.057, 0.142, 1.07 |
No. of reflections | 4296 | 5276 |
No. of parameters | 192 | 255 |
No. of restraints | 13 | 13 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.24 | 0.37, −0.21 |
Computer programs: CrysAlis PRO (Agilent, 2014), APEX2 (Bruker, 2005), SAINT (Bruker, 2002), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors wish to acknowledge the assistance of Dr Matthias Zeller in the collection of diffraction data and NSF Grant DMR 1337296 for funds to purchase the X-ray diffractometer. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the Gemini–E X-ray diffractometer. RJB is grateful for the NSF award 1205608, Partnership for Reduced Dimensional Materials, for partial funding of this research as well as the Howard University Nanoscience Facility access to liquid nitrogen. LAM wishes to acknowledge that this material is based upon work supported by the National Science Foundation under Howard University ADVANCE Institutional Transformation (HU ADVANCE-IT) Grant No. 1208880.
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