Structure and hydrogen bonding in 2,4-dihydroxybenzoic acid at 90, 100, 110 and 150 K; a theoretical and single-crystal X-ray diffraction study

Parkin, A.; Adam, M.; Cooper, R.I.; Middlemiss, D.S.; Wilson, C.C.

doi:10.1107/S0108768106055212

Structure and hydrogen bonding in 2,4-dihydroxybenzoic acid at 90, 100, 110 and 150 K; a theoretical and single-crystal X-ray diffraction study

A. Parkin, M. Adam, R. I. Cooper, D. S. Middlemiss and C. C. Wilson

A new polymorph of 2,4-dihydroxybenzoic acid is reported. The structure was characterized by multiple-temperature X-ray diffraction and solid-state DFT computations. The material shows a geometric pattern of hydrogen bonding consistent with cooperativity between the intermolecular carboxylic acid dimer and intramolecular hydrogen bonds. The presence of proton disorder within this hydrogen-bond system, which would support such a cooperative model, was not fully ruled out by the initial X-ray studies. However, solid-state calculations on the three possible end-point tautomers indicate that the dominant crystallographically observed configuration is substantially lower in energy than the other tautomers (by at least 9 kJ mol^-1), indicating that no disorder should be expected. It is therefore concluded that no disorder is observed either in the intra- or intermolecular hydrogen bonds of the title compound and that the cooperativity between the hydrogen bonds is not present within the temperature range studied.

Keywords: hydrogen bonding; single-crystal X-ray diffraction; polymorphism; solid-state computations; cooperative disorder.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768106055212/bs5037sup1.cif Contains datablocks 90k, 100k, 110k, 150k
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768106055212/bs503790ksup2.hkl Contains datablock 90k
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768106055212/bs5037100ksup3.hkl Contains datablock 100k
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768106055212/bs5037110ksup4.hkl Contains datablock 110k
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768106055212/bs5037150ksup5.hkl Contains datablock 150k

CCDC references: 245900; 245901; 245902; 245903

Computing details top

For all compounds, data collection: COLLECT (Nonius BV, 1997); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1996); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1996); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al. 2003); molecular graphics: CAMERON (Watkin et al. 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al. 2003).

Figures top

(90k) 2,4-dihydroxybenzoic acid top

Crystal data top

C₇H₆O₄	F(000) = 320
M_r = 154.12	D_x = 1.583 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 3.6686 (5) Å	Cell parameters from 10028 reflections
b = 22.333 (3) Å	θ = 0–35°
c = 8.0046 (11) Å	µ = 0.13 mm⁻¹
β = 99.630 (3)°	T = 90 K
V = 646.58 (15) Å³	Plate, colourless
Z = 4	0.80 × 0.30 × 0.08 mm

Data collection top

Nonius Kappa CCD diffractometer	1301 reflections with I > 2.00s(I)
Graphite monochromator	R_int = 0.047
ϕ & ω scans	θ_max = 33.8°, θ_min = 1.8°
Absorption correction: multi-scan SORTAV (Blessing)	h = −5→5
T_min = 0.96, T_max = 0.99	k = −30→25
5714 measured reflections	l = −12→10
2022 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.054	P = P(6)max(F_o²,0) + (1-P(6))F_c² Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma²(F) + (P(1)p)² + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.322E-01 0.690 0.00 0.00 0.00 0.333
wR(F²) = 0.132	(Δ/σ)_max = 0.000164
S = 0.96	Δρ_max = 0.71 e Å⁻³
2019 reflections	Δρ_min = −0.83 e Å⁻³
107 parameters	Extinction correction: Larson 1970 Crystallographic Computing eq 22
0 restraints	Extinction coefficient: 12 (7)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₇H₆O₄	V = 646.58 (15) Å³
M_r = 154.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.6686 (5) Å	µ = 0.13 mm⁻¹
b = 22.333 (3) Å	T = 90 K
c = 8.0046 (11) Å	0.80 × 0.30 × 0.08 mm
β = 99.630 (3)°

Data collection top

Nonius Kappa CCD diffractometer	2022 independent reflections
Absorption correction: multi-scan SORTAV (Blessing)	1301 reflections with I > 2.00s(I)
T_min = 0.96, T_max = 0.99	R_int = 0.047
5714 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.71 e Å⁻³
2019 reflections	Δρ_min = −0.83 e Å⁻³
107 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.3016 (5)	0.09421 (8)	0.7174 (2)	0.0136
C2	0.3938 (5)	0.15429 (8)	0.7589 (2)	0.0135
O2	0.3800 (4)	0.17744 (6)	0.91619 (17)	0.0182
C3	0.5016 (5)	0.19267 (8)	0.6389 (2)	0.0144
C4	0.5175 (5)	0.17137 (8)	0.4772 (2)	0.0144
O4	0.6182 (4)	0.20656 (6)	0.35487 (18)	0.0179
C5	0.4250 (5)	0.11172 (8)	0.4325 (2)	0.0157
C6	0.3196 (5)	0.07420 (8)	0.5523 (2)	0.0143
C7	0.1800 (5)	0.05422 (8)	0.8407 (2)	0.0142
O8	0.1500 (4)	0.07026 (6)	0.98746 (17)	0.0179
O9	0.1034 (4)	−0.00118 (6)	0.78791 (18)	0.0183
H31	0.5677	0.2352	0.6689	0.0170*
H51	0.4378	0.0967	0.3160	0.0195*
H61	0.2535	0.0317	0.5214	0.0179*
H4	0.682 (9)	0.2419 (15)	0.397 (4)	0.052 (9)*
H81	0.0734	0.0440	1.0596	0.070 (11)*	0.0000
H82	0.2057	0.1081	1.0210	0.028 (9)*	0.3000
H9	0.0264	−0.0281	0.8581	0.070 (11)*
H2	0.3101	0.1540	0.9968	0.031 (9)*	0.7000

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0134 (9)	0.0120 (9)	0.0161 (9)	0.0000 (7)	0.0043 (7)	0.0011 (7)
C2	0.0131 (9)	0.0143 (9)	0.0133 (8)	0.0011 (7)	0.0030 (7)	−0.0005 (7)
O2	0.0277 (8)	0.0137 (7)	0.0142 (7)	−0.0018 (6)	0.0065 (6)	−0.0021 (5)
C3	0.0151 (9)	0.0114 (9)	0.0174 (9)	−0.0002 (6)	0.0045 (7)	0.0020 (7)
C4	0.0128 (8)	0.0150 (9)	0.0159 (9)	0.0008 (7)	0.0038 (7)	0.0055 (7)
O4	0.0245 (8)	0.0150 (7)	0.0156 (7)	−0.0011 (6)	0.0078 (6)	0.0022 (5)
C5	0.0154 (9)	0.0164 (9)	0.0159 (9)	0.0000 (7)	0.0038 (7)	−0.0019 (7)
C6	0.0149 (9)	0.0127 (9)	0.0158 (9)	0.0004 (7)	0.0036 (7)	−0.0003 (7)
C7	0.0131 (9)	0.0142 (9)	0.0153 (8)	0.0009 (7)	0.0021 (7)	0.0018 (7)
O8	0.0253 (8)	0.0143 (7)	0.0148 (7)	−0.0026 (6)	0.0052 (6)	0.0001 (5)
O9	0.0264 (8)	0.0107 (6)	0.0189 (7)	−0.0041 (6)	0.0074 (6)	−0.0006 (5)

Geometric parameters (Å, º) top

C1—C2	1.410 (3)	O4—H4	0.88 (3)
C1—C6	1.406 (3)	C5—C6	1.377 (3)
C1—C7	1.456 (3)	C5—H51	1.000
C2—O2	1.370 (2)	C6—H61	1.000
C2—C3	1.393 (3)	C7—O8	1.251 (2)
O2—H2	0.900	C7—O9	1.322 (2)
C3—C4	1.389 (3)	O8—H81	0.900
C3—H31	1.000	O8—H82	0.900
C4—O4	1.354 (2)	O9—H9	0.900
C4—C5	1.406 (3)

C2—C1—C6	118.48 (16)	C4—C5—C6	118.91 (17)
C2—C1—C7	120.85 (16)	C4—C5—H51	120.546
C6—C1—C7	120.64 (17)	C6—C5—H51	120.538
C1—C2—O2	122.12 (16)	C1—C6—C5	121.57 (17)
C1—C2—C3	120.51 (17)	C1—C6—H61	119.105
O2—C2—C3	117.38 (17)	C5—C6—H61	119.328
C2—O2—H2	119.895	C1—C7—O8	123.12 (17)
C2—C3—C4	119.51 (17)	C1—C7—O9	115.49 (16)
C2—C3—H31	120.279	O8—C7—O9	121.39 (17)
C4—C3—H31	120.209	C7—O8—H81	120.139
C3—C4—O4	122.28 (17)	C7—O8—H82	119.860
C3—C4—C5	121.02 (17)	H81—O8—H82	120.000
O4—C4—C5	116.70 (17)	C7—O9—H9	119.839
C4—O4—H4	109 (2)

(100k) 2,4-dihydroxybenzoic acid top

Crystal data top

C₇H₆O₄	F(000) = 320
M_r = 154.12	D_x = 1.580 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 3.6721 (5) Å	Cell parameters from 14033 reflections
b = 22.341 (3) Å	θ = 0–33°
c = 8.007 (1) Å	µ = 0.13 mm⁻¹
β = 99.602 (3)°	T = 100 K
V = 647.68 (15) Å³	Plate, colourless
Z = 4	0.80 × 0.30 × 0.08 mm

Data collection top

Nonius Kappa CCD diffractometer	1139 reflections with I > 2.00s(I)
Graphite monochromator	R_int = 0.040
ϕ & ω scans	θ_max = 33.1°, θ_min = 1.8°
Absorption correction: multi-scan SORTAV (Blessing)	h = −5→5
T_min = 0.96, T_max = 0.99	k = −28→25
7727 measured reflections	l = −12→11
1963 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.123	P = P(6)max(F_o²,0) + (1-P(6))F_c² Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma²(F) + (P(1)p)² + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.384E-01 0.163 0.00 0.00 0.00 0.333
S = 0.95	(Δ/σ)_max = 0.000110
1963 reflections	Δρ_max = 0.81 e Å⁻³
106 parameters	Δρ_min = −0.76 e Å⁻³
0 restraints

Crystal data top

C₇H₆O₄	V = 647.68 (15) Å³
M_r = 154.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.6721 (5) Å	µ = 0.13 mm⁻¹
b = 22.341 (3) Å	T = 100 K
c = 8.007 (1) Å	0.80 × 0.30 × 0.08 mm
β = 99.602 (3)°

Data collection top

Nonius Kappa CCD diffractometer	1963 independent reflections
Absorption correction: multi-scan SORTAV (Blessing)	1139 reflections with I > 2.00s(I)
T_min = 0.96, T_max = 0.99	R_int = 0.040
7727 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.81 e Å⁻³
1963 reflections	Δρ_min = −0.76 e Å⁻³
106 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.3011 (5)	0.09402 (8)	0.7174 (2)	0.0153
C2	0.3933 (5)	0.15417 (8)	0.7592 (2)	0.0150
O2	0.3785 (4)	0.17742 (6)	0.91572 (17)	0.0209
C3	0.4999 (5)	0.19273 (8)	0.6393 (2)	0.0164
C4	0.5163 (5)	0.17131 (8)	0.4777 (2)	0.0162
O4	0.6170 (4)	0.20646 (6)	0.35488 (18)	0.0208
C5	0.4249 (5)	0.11185 (8)	0.4331 (2)	0.0172
C6	0.3194 (5)	0.07439 (8)	0.5524 (2)	0.0165
C7	0.1804 (5)	0.05405 (8)	0.8411 (2)	0.0163
O8	0.1489 (4)	0.07032 (6)	0.98718 (16)	0.0203
O9	0.1041 (4)	−0.00109 (6)	0.78805 (17)	0.0207
H31	0.5660	0.2353	0.6693	0.0170*
H51	0.4378	0.0968	0.3165	0.0195*
H61	0.2534	0.0319	0.5215	0.0179*
H4	0.677 (7)	0.2412 (13)	0.395 (3)	0.048 (8)*
H81	0.0722	0.0441	1.0593	0.027 (8)*	0.2500
H82	0.2045	0.1082	1.0207	0.036 (9)*	0.2000
H9	0.0272	−0.0280	0.8583	0.027 (8)*	0.7500
H2	0.3086	0.1540	0.9963	0.038 (9)*	0.8000

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0149 (9)	0.0148 (9)	0.0165 (9)	0.0003 (7)	0.0036 (7)	0.0002 (7)
C2	0.0150 (9)	0.0158 (9)	0.0145 (9)	0.0012 (7)	0.0035 (7)	−0.0018 (7)
O2	0.0320 (8)	0.0163 (7)	0.0159 (7)	−0.0008 (6)	0.0085 (6)	−0.0014 (5)
C3	0.0164 (9)	0.0134 (9)	0.0197 (9)	−0.0005 (7)	0.0041 (8)	0.0003 (7)
C4	0.0137 (9)	0.0171 (10)	0.0181 (10)	0.0017 (7)	0.0036 (7)	0.0039 (7)
O4	0.0282 (8)	0.0174 (7)	0.0185 (7)	−0.0029 (6)	0.0083 (6)	0.0025 (6)
C5	0.0176 (10)	0.0200 (10)	0.0146 (9)	−0.0008 (8)	0.0044 (8)	−0.0014 (7)
C6	0.0166 (9)	0.0145 (9)	0.0184 (9)	−0.0005 (7)	0.0030 (8)	−0.0012 (7)
C7	0.0145 (9)	0.0170 (10)	0.0172 (9)	0.0011 (7)	0.0025 (7)	0.0004 (7)
O8	0.0291 (8)	0.0164 (7)	0.0165 (7)	−0.0038 (6)	0.0068 (6)	0.0008 (5)
O9	0.0304 (8)	0.0125 (7)	0.0205 (7)	−0.0039 (6)	0.0078 (6)	0.0002 (5)

Geometric parameters (Å, º) top

C1—C2	1.412 (3)	O4—H4	0.85 (3)
C1—C6	1.404 (2)	C5—C6	1.374 (3)
C1—C7	1.456 (3)	C5—H51	1.000
C2—O2	1.366 (2)	C6—H61	1.000
C2—C3	1.394 (3)	C7—O8	1.249 (2)
O2—H2	0.900	C7—O9	1.318 (2)
C3—C4	1.390 (3)	O8—H81	0.900
C3—H31	1.000	O8—H82	0.900
C4—O4	1.357 (2)	O9—H9	0.900
C4—C5	1.402 (3)

C2—C1—C6	118.21 (16)	C4—C5—C6	118.90 (17)
C2—C1—C7	120.70 (16)	C4—C5—H51	120.636
C6—C1—C7	121.06 (17)	C6—C5—H51	120.467
C1—C2—O2	122.31 (16)	C1—C6—C5	121.84 (17)
C1—C2—C3	120.58 (16)	C1—C6—H61	118.768
O2—C2—C3	117.10 (16)	C5—C6—H61	119.397
C2—O2—H2	119.765	C1—C7—O8	123.01 (17)
C2—C3—C4	119.28 (17)	C1—C7—O9	115.26 (16)
C2—C3—H31	120.427	O8—C7—O9	121.73 (17)
C4—C3—H31	120.296	C7—O8—H81	119.945
C3—C4—O4	122.32 (17)	C7—O8—H82	120.047
C3—C4—C5	121.19 (17)	H81—O8—H82	120.006
O4—C4—C5	116.48 (17)	C7—O9—H9	119.690
C4—O4—H4	109.6 (18)

(110k) 2,4-dihydroxybenzoic acid top

Crystal data top

C₇H₆O₄	F(000) = 320
M_r = 154.12	D_x = 1.580 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 3.6742 (5) Å	Cell parameters from 13719 reflections
b = 22.341 (3) Å	θ = 0–33°
c = 8.0065 (10) Å	µ = 0.13 mm⁻¹
β = 99.567 (3)°	T = 110 K
V = 648.08 (15) Å³	Plate, colourless
Z = 4	0.80 × 0.30 × 0.08 mm

Data collection top

Nonius Kappa CCD diffractometer	1139 reflections with I > 2.00s(I)
Graphite monochromator	R_int = 0.036
ϕ & ω scans	θ_max = 33.1°, θ_min = 1.8°
Absorption correction: multi-scan SORTAV (Blessing)	h = −5→5
T_min = 0.96, T_max = 0.99	k = −28→25
7722 measured reflections	l = −12→11
1963 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.123	P = P(6)max(F_o²,0) + (1-P(6))F_c² Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma²(F) + (P(1)p)² + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.384E-01 0.159 0.00 0.00 0.00 0.333
S = 0.95	(Δ/σ)_max = 0.000141
1963 reflections	Δρ_max = 0.82 e Å⁻³
106 parameters	Δρ_min = −0.76 e Å⁻³
0 restraints

Crystal data top

C₇H₆O₄	V = 648.08 (15) Å³
M_r = 154.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.6742 (5) Å	µ = 0.13 mm⁻¹
b = 22.341 (3) Å	T = 110 K
c = 8.0065 (10) Å	0.80 × 0.30 × 0.08 mm
β = 99.567 (3)°

Data collection top

Nonius Kappa CCD diffractometer	1963 independent reflections
Absorption correction: multi-scan SORTAV (Blessing)	1139 reflections with I > 2.00s(I)
T_min = 0.96, T_max = 0.99	R_int = 0.036
7722 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.82 e Å⁻³
1963 reflections	Δρ_min = −0.76 e Å⁻³
106 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.3011 (5)	0.09402 (8)	0.7174 (2)	0.0153
C2	0.3933 (5)	0.15417 (8)	0.7592 (2)	0.0150
O2	0.3785 (4)	0.17743 (6)	0.91569 (17)	0.0209
C3	0.4999 (5)	0.19273 (8)	0.6393 (2)	0.0164
C4	0.5163 (5)	0.17131 (8)	0.4777 (2)	0.0161
O4	0.6170 (4)	0.20646 (6)	0.35488 (18)	0.0208
C5	0.4249 (5)	0.11185 (8)	0.4331 (2)	0.0172
C6	0.3195 (5)	0.07439 (8)	0.5524 (2)	0.0165
C7	0.1804 (5)	0.05405 (8)	0.8411 (2)	0.0162
O8	0.1489 (4)	0.07034 (6)	0.98720 (16)	0.0203
O9	0.1041 (4)	−0.00109 (6)	0.78805 (17)	0.0207
H31	0.5659	0.2353	0.6693	0.0170*
H51	0.4378	0.0968	0.3165	0.0195*
H61	0.2534	0.0319	0.5215	0.0179*
H4	0.676 (7)	0.2414 (13)	0.395 (3)	0.048 (8)*
H81	0.0722	0.0441	1.0593	0.027 (8)*	0.2500
H82	0.2045	0.1082	1.0207	0.042 (9)*	0.1500
H9	0.0272	−0.0280	0.8583	0.027 (8)*	0.7500
H2	0.3086	0.1540	0.9963	0.044 (9)*	0.8500

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0150 (9)	0.0147 (9)	0.0165 (9)	0.0003 (7)	0.0036 (7)	0.0002 (7)
C2	0.0151 (9)	0.0158 (9)	0.0145 (9)	0.0012 (7)	0.0035 (7)	−0.0018 (7)
O2	0.0321 (8)	0.0163 (7)	0.0159 (7)	−0.0008 (6)	0.0085 (6)	−0.0014 (5)
C3	0.0164 (9)	0.0134 (9)	0.0196 (9)	−0.0005 (7)	0.0041 (8)	0.0003 (7)
C4	0.0137 (9)	0.0170 (10)	0.0180 (10)	0.0016 (7)	0.0036 (7)	0.0039 (7)
O4	0.0283 (8)	0.0173 (7)	0.0184 (7)	−0.0028 (6)	0.0083 (6)	0.0025 (6)
C5	0.0176 (10)	0.0200 (10)	0.0146 (9)	−0.0008 (8)	0.0044 (8)	−0.0014 (7)
C6	0.0166 (9)	0.0144 (9)	0.0183 (9)	−0.0005 (7)	0.0030 (8)	−0.0012 (7)
C7	0.0145 (9)	0.0170 (10)	0.0172 (9)	0.0011 (7)	0.0025 (8)	0.0004 (7)
O8	0.0290 (8)	0.0166 (7)	0.0164 (7)	−0.0038 (6)	0.0069 (6)	0.0009 (5)
O9	0.0305 (8)	0.0124 (7)	0.0205 (7)	−0.0039 (6)	0.0078 (6)	0.0002 (5)

Geometric parameters (Å, º) top

C1—C2	1.412 (3)	O4—H4	0.86 (3)
C1—C6	1.404 (2)	C5—C6	1.373 (3)
C1—C7	1.456 (3)	C5—H51	1.000
C2—O2	1.366 (2)	C6—H61	1.000
C2—C3	1.393 (3)	C7—O8	1.249 (2)
O2—H2	0.900	C7—O9	1.318 (2)
C3—C4	1.390 (3)	O8—H81	0.900
C3—H31	1.000	O8—H82	0.900
C4—O4	1.357 (2)	O9—H9	0.900
C4—C5	1.402 (3)

C2—C1—C6	118.21 (16)	C4—C5—C6	118.89 (17)
C2—C1—C7	120.71 (16)	C4—C5—H51	120.648
C6—C1—C7	121.06 (17)	C6—C5—H51	120.456
C1—C2—O2	122.32 (16)	C1—C6—C5	121.83 (17)
C1—C2—C3	120.59 (16)	C1—C6—H61	118.769
O2—C2—C3	117.09 (16)	C5—C6—H61	119.402
C2—O2—H2	119.753	C1—C7—O8	122.98 (17)
C2—C3—C4	119.27 (17)	C1—C7—O9	115.26 (16)
C2—C3—H31	120.428	O8—C7—O9	121.76 (17)
C4—C3—H31	120.302	C7—O8—H81	119.918
C3—C4—O4	122.31 (17)	C7—O8—H82	120.069
C3—C4—C5	121.21 (17)	H81—O8—H82	120.011
O4—C4—C5	116.48 (17)	C7—O9—H9	119.691
C4—O4—H4	109.7 (18)

(150k) 2,4-dihydroxybenzoic acid top

Crystal data top

C₇H₆O₄	F(000) = 320
M_r = 154.12	D_x = 1.572 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 3.6854 (5) Å	Cell parameters from 13860 reflections
b = 22.367 (3) Å	θ = 0–33°
c = 8.0085 (11) Å	µ = 0.13 mm⁻¹
β = 99.448 (3)°	T = 150 K
V = 651.20 (15) Å³	Plate, colourless
Z = 4	0.80 × 0.30 × 0.08 mm

Data collection top

Nonius Kappa CCD diffractometer	1062 reflections with I > 2.00s(I)
Graphite monochromator	R_int = 0.036
ϕ & ω scans	θ_max = 33.1°, θ_min = 1.8°
Absorption correction: multi-scan SORTAV (Blessing)	h = −5→5
T_min = 0.96, T_max = 0.99	k = −30→26
7572 measured reflections	l = −12→10
1933 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.140	P = P(6)max(F_o²,0) + (1-P(6))F_c² Method = SHELXL 97 (Sheldrick, 1997) W = 1. / [Sigma²(F) + (P(1)p)² + P(2)p + P(4) + P(5)Sin(theta)] P(i) are: 0.525E-01 0.175E-01 0.00 0.00 0.00 0.333
S = 0.98	(Δ/σ)_max = 0.000119
1933 reflections	Δρ_max = 0.77 e Å⁻³
106 parameters	Δρ_min = −0.72 e Å⁻³
0 restraints

Crystal data top

C₇H₆O₄	V = 651.20 (15) Å³
M_r = 154.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.6854 (5) Å	µ = 0.13 mm⁻¹
b = 22.367 (3) Å	T = 150 K
c = 8.0085 (11) Å	0.80 × 0.30 × 0.08 mm
β = 99.448 (3)°

Data collection top

Nonius Kappa CCD diffractometer	1933 independent reflections
Absorption correction: multi-scan SORTAV (Blessing)	1062 reflections with I > 2.00s(I)
T_min = 0.96, T_max = 0.99	R_int = 0.036
7572 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.77 e Å⁻³
1933 reflections	Δρ_min = −0.72 e Å⁻³
106 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.2989 (6)	0.09413 (9)	0.7174 (3)	0.0182
C2	0.3900 (6)	0.15413 (9)	0.7587 (3)	0.0190
O2	0.3740 (5)	0.17749 (6)	0.91497 (19)	0.0262
C3	0.4964 (6)	0.19257 (9)	0.6388 (3)	0.0199
C4	0.5136 (6)	0.17132 (9)	0.4774 (3)	0.0201
O4	0.6140 (5)	0.20643 (7)	0.3553 (2)	0.0268
C5	0.4237 (6)	0.11186 (9)	0.4333 (3)	0.0219
C6	0.3185 (6)	0.07433 (9)	0.5526 (3)	0.0210
C7	0.1797 (6)	0.05416 (9)	0.8408 (3)	0.0206
O8	0.1478 (4)	0.07040 (6)	0.98682 (18)	0.0259
O9	0.1038 (4)	−0.00105 (6)	0.7881 (2)	0.0268
H31	0.5625	0.2351	0.6688	0.0170*
H51	0.4366	0.0968	0.3167	0.0195*
H61	0.2524	0.0318	0.5217	0.0179*
H4	0.679 (8)	0.2423 (15)	0.390 (4)	0.068 (11)*
H81	0.0712	0.0442	1.0589	0.040 (10)*	0.3000
H82	0.2035	0.1083	1.0203	0.060 (10)*	0.0000
H9	0.0268	−0.0280	0.8584	0.040 (10)*	0.7000
H2	0.3041	0.1541	0.9955	0.062 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0173 (10)	0.0166 (10)	0.0215 (11)	0.0002 (8)	0.0058 (8)	0.0020 (8)
C2	0.0195 (11)	0.0195 (11)	0.0181 (10)	0.0001 (8)	0.0031 (8)	−0.0010 (8)
O2	0.0414 (10)	0.0192 (8)	0.0202 (8)	−0.0019 (7)	0.0111 (7)	−0.0012 (6)
C3	0.0222 (11)	0.0146 (10)	0.0234 (11)	−0.0003 (8)	0.0050 (9)	0.0011 (8)
C4	0.0182 (10)	0.0209 (11)	0.0215 (11)	0.0003 (8)	0.0047 (9)	0.0040 (8)
O4	0.0349 (9)	0.0235 (9)	0.0235 (9)	−0.0034 (7)	0.0098 (7)	0.0042 (7)
C5	0.0221 (11)	0.0233 (11)	0.0210 (11)	0.0002 (9)	0.0058 (9)	−0.0028 (9)
C6	0.0221 (12)	0.0180 (10)	0.0233 (11)	−0.0006 (9)	0.0048 (9)	−0.0002 (8)
C7	0.0195 (11)	0.0196 (11)	0.0229 (11)	0.0009 (8)	0.0040 (9)	0.0015 (8)
O8	0.0371 (10)	0.0212 (8)	0.0211 (8)	−0.0039 (7)	0.0093 (7)	0.0016 (6)
O9	0.0392 (10)	0.0160 (8)	0.0271 (9)	−0.0066 (6)	0.0110 (7)	0.0005 (6)

Geometric parameters (Å, º) top

C1—C2	1.409 (3)	O4—H4	0.87 (3)
C1—C6	1.405 (3)	C5—C6	1.375 (3)
C1—C7	1.454 (3)	C5—H51	1.001
C2—O2	1.367 (2)	C6—H61	1.002
C2—C3	1.392 (3)	C7—O8	1.248 (2)
O2—H2	0.901	C7—O9	1.320 (2)
C3—C4	1.388 (3)	O8—H81	0.901
C3—H31	1.002	O8—H82	0.902
C4—O4	1.352 (2)	O9—H9	0.901
C4—C5	1.402 (3)

C2—C1—C6	118.26 (18)	C4—C5—C6	119.10 (19)
C2—C1—C7	120.87 (18)	C4—C5—H51	120.559
C6—C1—C7	120.86 (18)	C6—C5—H51	120.344
C1—C2—O2	122.31 (18)	C1—C6—C5	121.61 (19)
C1—C2—C3	120.63 (19)	C1—C6—H61	118.896
O2—C2—C3	117.06 (18)	C5—C6—H61	119.494
C2—O2—H2	119.645	C1—C7—O8	122.93 (19)
C2—C3—C4	119.45 (19)	C1—C7—O9	115.45 (18)
C2—C3—H31	120.391	O8—C7—O9	121.61 (18)
C4—C3—H31	120.155	C7—O8—H81	119.915
C3—C4—O4	122.29 (19)	C7—O8—H82	120.023
C3—C4—C5	120.95 (18)	H81—O8—H82	120.060
O4—C4—C5	116.76 (19)	C7—O9—H9	119.840
C4—O4—H4	113 (2)

Experimental details

	(90k)	(100k)	(110k)	(150k)
Crystal data
Chemical formula	C₇H₆O₄	C₇H₆O₄	C₇H₆O₄	C₇H₆O₄
M_r	154.12	154.12	154.12	154.12
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Monoclinic, P2₁/n
Temperature (K)	90	100	110	150
a, b, c (Å)	3.6686 (5), 22.333 (3), 8.0046 (11)	3.6721 (5), 22.341 (3), 8.007 (1)	3.6742 (5), 22.341 (3), 8.0065 (10)	3.6854 (5), 22.367 (3), 8.0085 (11)
β (°)	99.630 (3)	99.602 (3)	99.567 (3)	99.448 (3)
V (Å³)	646.58 (15)	647.68 (15)	648.08 (15)	651.20 (15)
Z	4	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.13	0.13	0.13	0.13
Crystal size (mm)	0.80 × 0.30 × 0.08	0.80 × 0.30 × 0.08	0.80 × 0.30 × 0.08	0.80 × 0.30 × 0.08

Data collection
Diffractometer	Nonius Kappa CCD diffractometer	Nonius Kappa CCD diffractometer	Nonius Kappa CCD diffractometer	Nonius Kappa CCD diffractometer
Absorption correction	Multi-scan SORTAV (Blessing)	Multi-scan SORTAV (Blessing)	Multi-scan SORTAV (Blessing)	Multi-scan SORTAV (Blessing)
T_min, T_max	0.96, 0.99	0.96, 0.99	0.96, 0.99	0.96, 0.99
No. of measured, independent and observed [I > 2.00s(I)] reflections	5714, 2022, 1301	7727, 1963, 1139	7722, 1963, 1139	7572, 1933, 1062
R_int	0.047	0.040	0.036	0.036
(sin θ/λ)_max (Å⁻¹)	0.783	0.768	0.768	0.768

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.132, 0.96	0.051, 0.123, 0.95	0.051, 0.123, 0.95	0.054, 0.140, 0.98
No. of reflections	2019	1963	1963	1933
No. of parameters	107	106	106	106
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.83	0.81, −0.76	0.82, −0.76	0.77, −0.72

Computer programs: COLLECT (Nonius BV, 1997), DENZO/SCALEPACK (Otwinowski & Minor, 1996), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al. 2003), CAMERON (Watkin et al. 1996).

Selected geometric parameters (Å, º) for (90k) top

C1—C2	1.410 (3)	C4—O4	1.354 (2)
C1—C6	1.406 (3)	C4—C5	1.406 (3)
C1—C7	1.456 (3)	C5—C6	1.377 (3)
C2—O2	1.370 (2)	C7—O8	1.251 (2)
C2—C3	1.393 (3)	C7—O9	1.322 (2)
C3—C4	1.389 (3)

C2—C1—C6	118.48 (16)	C3—C4—C5	121.02 (17)
C2—C1—C7	120.85 (16)	O4—C4—C5	116.70 (17)
C6—C1—C7	120.64 (17)	C4—C5—C6	118.91 (17)
C1—C2—O2	122.12 (16)	C1—C6—C5	121.57 (17)
C1—C2—C3	120.51 (17)	C1—C7—O8	123.12 (17)
O2—C2—C3	117.38 (17)	C1—C7—O9	115.49 (16)
C2—C3—C4	119.51 (17)	O8—C7—O9	121.39 (17)
C3—C4—O4	122.28 (17)

Selected geometric parameters (Å, º) for (100k) top

C1—C2	1.412 (3)	C4—O4	1.357 (2)
C1—C6	1.404 (2)	C4—C5	1.402 (3)
C1—C7	1.456 (3)	C5—C6	1.374 (3)
C2—O2	1.366 (2)	C7—O8	1.249 (2)
C2—C3	1.394 (3)	C7—O9	1.318 (2)
C3—C4	1.390 (3)

C2—C1—C6	118.21 (16)	C3—C4—C5	121.19 (17)
C2—C1—C7	120.70 (16)	O4—C4—C5	116.48 (17)
C6—C1—C7	121.06 (17)	C4—C5—C6	118.90 (17)
C1—C2—O2	122.31 (16)	C1—C6—C5	121.84 (17)
C1—C2—C3	120.58 (16)	C1—C7—O8	123.01 (17)
O2—C2—C3	117.10 (16)	C1—C7—O9	115.26 (16)
C2—C3—C4	119.28 (17)	O8—C7—O9	121.73 (17)
C3—C4—O4	122.32 (17)

Selected geometric parameters (Å, º) for (110k) top

C1—C2	1.412 (3)	C4—O4	1.357 (2)
C1—C6	1.404 (2)	C4—C5	1.402 (3)
C1—C7	1.456 (3)	C5—C6	1.373 (3)
C2—O2	1.366 (2)	C7—O8	1.249 (2)
C2—C3	1.393 (3)	C7—O9	1.318 (2)
C3—C4	1.390 (3)

C2—C1—C6	118.21 (16)	C3—C4—C5	121.21 (17)
C2—C1—C7	120.71 (16)	O4—C4—C5	116.48 (17)
C6—C1—C7	121.06 (17)	C4—C5—C6	118.89 (17)
C1—C2—O2	122.32 (16)	C1—C6—C5	121.83 (17)
C1—C2—C3	120.59 (16)	C1—C7—O8	122.98 (17)
O2—C2—C3	117.09 (16)	C1—C7—O9	115.26 (16)
C2—C3—C4	119.27 (17)	O8—C7—O9	121.76 (17)
C3—C4—O4	122.31 (17)

Selected geometric parameters (Å, º) for (150k) top

C1—C2	1.409 (3)	C4—O4	1.352 (2)
C1—C6	1.405 (3)	C4—C5	1.402 (3)
C1—C7	1.454 (3)	C5—C6	1.375 (3)
C2—O2	1.367 (2)	C7—O8	1.248 (2)
C2—C3	1.392 (3)	C7—O9	1.320 (2)
C3—C4	1.388 (3)

C2—C1—C6	118.26 (18)	C3—C4—C5	120.95 (18)
C2—C1—C7	120.87 (18)	O4—C4—C5	116.76 (19)
C6—C1—C7	120.86 (18)	C4—C5—C6	119.10 (19)
C1—C2—O2	122.31 (18)	C1—C6—C5	121.61 (19)
C1—C2—C3	120.63 (19)	C1—C7—O8	122.93 (19)
O2—C2—C3	117.06 (18)	C1—C7—O9	115.45 (18)
C2—C3—C4	119.45 (19)	O8—C7—O9	121.61 (18)
C3—C4—O4	122.29 (19)

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